diffraction n2 adsorption: Topics by Science.gov

Sample records for diffraction n2 adsorption

Light Hydrocarbon Adsorption Mechanisms in Two Calcium-Based Microporous Metal Organic Frameworks

DOE PAGES

Plonka, Anna M.; Chen, Xianyin; Wang, Hao; ...

2016-01-25

The adsorption mechanism of ethane, ethylene, and acetylene (C 2H n; n = 2, 4, 6) on two microporous metal organic frameworks (MOFs) is described here that is consistent with observations from single crystal and powder X-ray diffraction, calorimetric measurements, and gas adsorption isotherm measurements. Two calcium-based MOFs, designated as SBMOF-1 and SBMOF-2 (SB: Stony Brook), form three-dimensional frameworks with one-dimensional open channels. As determined from single crystal diffraction experiments, channel geometries of both SBMOF-1 and SBMOF-2 provide multiple adsorption sites for hydrocarbon molecules through C–H···π and C–H···O interactions, similarly to interactions in the molecular and protein crystals. In conclusion,more » both materials selectively adsorb C 2 hydrocarbon gases over methane as determined with IAST and breakthrough calculations as well as experimental breakthrough measurements, with C 2H 6/CH 4 selectivity as high as 74 in SBMOF-1.« less
Syntheses, structures and selective dye adsorption of five formic-based coordination polymers prepared by in-situ hydrolysis of N, N‧-dimethylformamide

NASA Astrophysics Data System (ADS)

Zhu, Zheng; Meng, Xiang-min; Zhang, Dong-mei; Zhang, Xia; Wang, Mei; Jin, Fan; Fan, Yu-hua

2017-04-01

Five functional coordination polymers (formic-based CPs) namely: {[Cu2(CHOO)3(bibp)2]·CHOO}n (1), {[Co2(CHOO)3(bibp)2]·NO3·H2O}n (2), {[Ni2(CHOO)3(bibp)2]·NO3·H2O}n (3) [Co(CHOO)2(bbibp)]n (4) and [Zn(CHOO)2(bbibp)]n (5) (bibp=4,4‧-bis(imidazolyl)biphenyl, bbibp=4,4‧-bis(benzoimidazo-1-yl)biphenyl) have been successfully hydrothermally synthesized using the in-situ hydrolysis of N, N‧-dimethylformamide (DMF) as the source of formate. All of these five polymers were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complexes 1-3 have the similar three-dimensional 3D kag topological framework built from the bibp ligand as the support member between the neighboring formic planes. Both complexes 4 and 5 have the similar one-dimensional 1D linear chain which is further assembled into 3D supermolecular structure by C-H…O hydrogen bonds. The dyes adsorption experiments have also been investigated systematically. The results show that complexes 2 and 3 exhibit high selective adsorption ability towards anionic dyes in their aqueous solution. Moreover, complex 2 displays good reversibility in the process of the dyes adsorption-release. Meanwhile, the unusual blocking phenomenon was firstly observed when complex 2 was in MO/OIV aqueous solutions with different concentration.
Selective Adsorption Resonances in the Scattering of n-H2 p-H2 n-D2 and o-D2 from Ag(111)

NASA Astrophysics Data System (ADS)

Yu, Chien-Fan; Whaley, K. Birgitta; Hogg, Charles S.; Sibener, Steven J.

1983-12-01

Diffractive and rotationally mediated selective adsorption scattering resonances are reported for n-H2 p-H2 n-D2 and o-D2 on Ag(111). Small resonance shifts and line-width differences are observed between n-H2 and p-H2 indicating a weak orientation dependence of the laterally averaged H2/Ag(111) potential. The p-H2 and o-D2 levels were used to determine the isotropic component of this potential, yielding a well depth of ~ 32 meV.
Adsorption and molecular siting of CO2, water, and other gases in the superhydrophobic, flexible pores of FMOF-1 from experiment and simulation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc00278e Click here for additional data file.

PubMed Central

Moghadam, Peyman Z.; Ivy, Joshua F.; Arvapally, Ravi K.; dos Santos, Antonio M.; Pearson, John C.; Zhang, Li; Tylianakis, Emmanouil; Ghosh, Pritha; Oswald, Iain W. H.; Kaipa, Ushasree

2017-01-01

FMOF-1 is a flexible, superhydrophobic metal–organic framework with a network of channels and side pockets decorated with –CF3 groups. CO2 adsorption isotherms measured between 278 and 313 K and up to 55 bar reveal a maximum uptake of ca. 6.16 mol kg–1 (11.0 mol L–1) and unusual isotherm shapes at the higher temperatures, suggesting framework expansion. We used neutron diffraction and molecular simulations to investigate the framework expansion behaviour and the accessibility of the small pockets to N2, O2, and CO2. Neutron diffraction in situ experiments on the crystalline powder show that CO2 molecules are favourably adsorbed at three distinct adsorption sites in the large channels of FMOF-1 and cannot access the small pockets in FMOF-1 at 290 K and oversaturated pressure at 61 bar. Stepped adsorption isotherms for N2 and O2 at 77 K can be explained by combining Monte Carlo simulations in several different crystal structures of FMOF-1 obtained from neutron and X-ray diffraction under different conditions. A similar analysis is successful for CO2 adsorption at 278 and 283 K up to ca. 30 bar; however, at 298 K and pressures above 30 bar, the results suggest even more substantial expansion of the FMOF-1 framework. The measured contact angle for water on an FMOF-1 pellet is 158°, demonstrating superhydrophobicity. Simulations and adsorption measurements also show that FMOF-1 is hydrophobic and water is not adsorbed in FMOF-1 at room temperature. Simulated mixture isotherms of CO2 in the presence of 80% relative humidity predict that water does not influence the CO2 adsorption in FMOF-1, suggesting that hydrophobic MOFs could hold promise for CO2 capture from humid gas streams. PMID:28553541
Adsorption and molecular siting of CO2, water, and other gases in the superhydrophobic, flexible pores of FMOF-1 from experiment and simulation.

PubMed

Moghadam, Peyman Z; Ivy, Joshua F; Arvapally, Ravi K; Dos Santos, Antonio M; Pearson, John C; Zhang, Li; Tylianakis, Emmanouil; Ghosh, Pritha; Oswald, Iain W H; Kaipa, Ushasree; Wang, Xiaoping; Wilson, Angela K; Snurr, Randall Q; Omary, Mohammad A

2017-05-01

FMOF-1 is a flexible, superhydrophobic metal-organic framework with a network of channels and side pockets decorated with -CF 3 groups. CO 2 adsorption isotherms measured between 278 and 313 K and up to 55 bar reveal a maximum uptake of ca. 6.16 mol kg -1 (11.0 mol L -1 ) and unusual isotherm shapes at the higher temperatures, suggesting framework expansion. We used neutron diffraction and molecular simulations to investigate the framework expansion behaviour and the accessibility of the small pockets to N 2 , O 2 , and CO 2 . Neutron diffraction in situ experiments on the crystalline powder show that CO 2 molecules are favourably adsorbed at three distinct adsorption sites in the large channels of FMOF-1 and cannot access the small pockets in FMOF-1 at 290 K and oversaturated pressure at 61 bar. Stepped adsorption isotherms for N 2 and O 2 at 77 K can be explained by combining Monte Carlo simulations in several different crystal structures of FMOF-1 obtained from neutron and X-ray diffraction under different conditions. A similar analysis is successful for CO 2 adsorption at 278 and 283 K up to ca. 30 bar; however, at 298 K and pressures above 30 bar, the results suggest even more substantial expansion of the FMOF-1 framework. The measured contact angle for water on an FMOF-1 pellet is 158°, demonstrating superhydrophobicity. Simulations and adsorption measurements also show that FMOF-1 is hydrophobic and water is not adsorbed in FMOF-1 at room temperature. Simulated mixture isotherms of CO 2 in the presence of 80% relative humidity predict that water does not influence the CO 2 adsorption in FMOF-1, suggesting that hydrophobic MOFs could hold promise for CO 2 capture from humid gas streams.
Structural characterization of framework-gas interactions in the metal-organic framework Co2(dobdc) by in situ single-crystal X-ray diffraction.

PubMed

Gonzalez, Miguel I; Mason, Jarad A; Bloch, Eric D; Teat, Simon J; Gagnon, Kevin J; Morrison, Gregory Y; Queen, Wendy L; Long, Jeffrey R

2017-06-01

The crystallographic characterization of framework-guest interactions in metal-organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH 4 , N 2 , O 2 , Ar, and P 4 adsorption in Co 2 (dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate), a metal-organic framework bearing coordinatively unsaturated cobalt(ii) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(ii) sites in the framework that no analogous molecular structures exist, demonstrating the utility of metal-organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co-CH 4 and Co-Ar interactions observed in Co 2 (dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal-CH 4 interaction and the first crystallographically characterized metal-Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(ii) sites in Co 2 (dobdc), with differential enthalpies of adsorption as weak as -17(1) kJ mol -1 (for Ar). Moreover, the structures of Co 2 (dobdc)·3.8N 2 , Co 2 (dobdc)·5.9O 2 , and Co 2 (dobdc)·2.0Ar reveal the location of secondary (N 2 , O 2 , and Ar) and tertiary (O 2 ) binding sites in Co 2 (dobdc), while high-pressure CO 2 , CO, CH 4 , N 2 , and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures.
Syntheses, structures and selective dye adsorption of five formic-based coordination polymers prepared by in-situ hydrolysis of N, N′-dimethylformamide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Zheng; Meng, Xiang-min; Zhang, Dong-mei

Five functional coordination polymers (formic-based CPs) namely: ([Cu{sub 2}(CHOO){sub 3}(bibp){sub 2}]·CHOO){sub n} (1), ([Co{sub 2}(CHOO){sub 3}(bibp){sub 2}]·NO{sub 3}·H{sub 2}O)n (2), ([Ni{sub 2}(CHOO){sub 3}(bibp){sub 2}]·NO{sub 3}·H{sub 2}O){sub n} (3) [Co(CHOO){sub 2}(bbibp)]{sub n} (4) and [Zn(CHOO){sub 2}(bbibp)]{sub n} (5) (bibp=4,4′-bis(imidazolyl)biphenyl, bbibp=4,4′-bis(benzoimidazo-1-yl)biphenyl) have been successfully hydrothermally synthesized using the in-situ hydrolysis of N, N′-dimethylformamide (DMF) as the source of formate. All of these five polymers were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complexes 1–3 have the similar three-dimensional 3D kag topological framework built from the bibp ligand as the support member betweenmore » the neighboring formic planes. Both complexes 4 and 5 have the similar one-dimensional 1D linear chain which is further assembled into 3D supermolecular structure by C–H…O hydrogen bonds. The dyes adsorption experiments have also been investigated systematically. The results show that complexes 2 and 3 exhibit high selective adsorption ability towards anionic dyes in their aqueous solution. Moreover, complex 2 displays good reversibility in the process of the dyes adsorption-release. Meanwhile, the unusual blocking phenomenon was firstly observed when complex 2 was in MO/OIV aqueous solutions with different concentration.« less
Adsorption of CO2 on amine-functionalised MCM-41: experimental and theoretical studies.

PubMed

dos Santos, Thiago Custódio; Bourrelly, Sandrine; Llewellyn, Philip L; Carneiro, José Walkimar de M; Ronconi, Célia Machado

2015-04-28

Adsorption of CO2 on MCM-41 functionalised with [3-(2-aminoethylamino)propyl]trimethoxysilane (MCM-41-N2), N(1)-(3-trimethoxysilylpropyl)diethylenetriamine (MCM-41-N3), 4-aminopyridine (MCM-41-aminopyridine), 4-(methylamino)pyridine (MCM-41-methylaminopyridine) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (MCM-41-guanidine) was investigated. The amine-functionalised materials were characterised by (29)Si and (13)C solid-state nuclear magnetic resonance, N2 adsorption/desorption isotherms, X-ray diffraction and transmission electron microscopy. CO2 adsorption at 1.0 bar and 30 °C showed that the amount of CO2 (nads/mmol g(-1)) adsorbed on MCM-41-N2 and MCM-41-N3 is approximately twice the amount adsorbed on MCM-41. For MCM-41-aminopyridine, MCM-41-methylaminopyridine and MCM-41-guanidine, the CO2 adsorption capacity was smaller than that of MCM-41 at the same conditions. The proton affinity (computed with wB97x-D/6-311++G(d,p)) of the secondary amino groups is higher than that of the primary amino groups; however, the relative stabilities of the primary and secondary carbamates are similar. The differential heat of adsorption decreases as the number of secondary amino groups increases.
Room-temperature fabrication of core-shell nano-ZnO/pollen grain biocomposite for adsorptive removal of organic dye from water

NASA Astrophysics Data System (ADS)

Tzvetkov, George; Kaneva, Nina; Spassov, Tony

2017-04-01

A new core-shell nano-ZnO/pollen grain (n-ZnO/PG) biocomposite has been successfully synthesized via simple and low-temperature two-step liquid precipitation method. The synthetic strategy consists of grafting the surface of pine pollen grains (PG) with Zn2+-organic complexes followed by a treatment in Zn(CH3COO)2/NaOH solution, thus producing a closed n-ZnO shell around the organic core, with a thickness of ∼450 nm. Scanning electron microscopy, X-ray diffraction, FTIR, XPS and UV-vis spectroscopy measurements along with N2 adsorption/desorption were used to characterize the resulting n-ZnO/PG biocomposite. The as-prepared core-shell microparticles are meso-/macro-porous with BET surface area of 25 m2 g-1 and total pore volume of 0.26 cm3 g-1. The adsorption properties of n-ZnO/PG were evaluated through adsorption of Malachite Green (MG) from aqueous medium at room temperature (25 °C). For the sake of comparison, the physico-chemical and adsorptive properties of the raw PG and pure n-ZnO were also examined. Results indicate that n-ZnO/PG is the most favorable for the adsorption of MG under the conditions used in this study. The adsorption kinetic data for PG, n-ZnO and n-ZnO/PG follow the pseudo-second order equation and the maximum adsorption capacity follows an order of n-ZnO/PG > n-ZnO > PG. For n-ZnO/PG an adsorption uptake up to 145.9 mg g-1 is observed. The as-prepared core-shell biocomposite material is a promising cost-effective and environmentally friendly adsorbent due to its textural properties, surface chemistry, adsorption capacity and recyclability.
Structural characterization of framework–gas interactions in the metal–organic framework Co 2 (dobdc) by in situ single-crystal X-ray diffraction

DOE PAGES

Gonzalez, Miguel I.; Mason, Jarad A.; Bloch, Eric D.; ...

2017-04-19

The crystallographic characterization of framework–guest interactions in metal–organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH 4, N 2, O 2, Ar, and P 4 adsorption in Co2(dobdc) (dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate), a metal–organic framework bearing coordinatively unsaturated cobalt(II) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(II) sites in the framework that no analogous molecular structures exist,more » demonstrating the utility of metal–organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co–CH 4 and Co–Ar interactions observed in Co 2(dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal–CH 4 interaction and the first crystallographically characterized metal–Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(II) sites in Co 2(dobdc), with differential enthalpies of adsorption as weak as –17(1) kJ mol –1 (for Ar). Moreover, the structures of Co 2(dobdc)·3.8N 2, Co 2(dobdc)·5.9O 2, and Co 2(dobdc)·2.0Ar reveal the location of secondary (N 2, O 2, and Ar) and tertiary (O 2) binding sites in Co 2(dobdc), while high-pressure CO 2, CO, CH 4, N 2, and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures.« less
Fabrication of magnetic biochar as a treatment medium for As(V) via pyrolysis of FeCl3-pretreated spent coffee ground.

PubMed

Cho, Dong-Wan; Yoon, Kwangsuk; Kwon, Eilhann E; Biswas, Jayanta Kumar; Song, Hocheol

2017-10-01

This study investigated the preparation of magnetic biochar from N 2 - and CO 2 -assisted pyrolysis of spent coffee ground (SCG) for use as an adsorption medium for As(V), and the effects of FeCl 3 pretreatment of SCG on the material properties and adsorption capability of the produced biochar. Pyrolysis of FeCl 3 -pretreated SCG in CO 2 atmosphere produced highly porous biochar with its surface area ∼70 times greater than that produced in N 2 condition. However, despite the small surface area, biochar produced in N 2 showed greater As(V) adsorption capability. X-ray diffraction and X-ray photoelectron spectrometer analyses identified Fe 3 C and Fe 3 O 4 as dominant mineral phases in N 2 and CO 2 conditions, with the former being much more adsorptive toward As(V). The overall results suggest functional biochar can be facilely fabricated by necessary pretreatment to expand the applicability of biochar for specific purposes. Copyright © 2017 Elsevier Ltd. All rights reserved.
New 3 D Tubular Porous Structure of an Organic-Zincophosphite Framework with Interesting Gas Adsorption and Luminescence Properties.

PubMed

Wang, Chih-Min; Lee, Li-Wei; Chang, Tsung-Yuan; Fan, Bing-Lun; Wang, Chih-Ling; Lin, Hsiu-Mei; Lu, Kuang-Lieh

2016-11-02

A new 3D tubular zinc phosphite, Zn 2 (C 22 H 22 N 8 ) 0.5 (HPO 3 ) 2 ⋅H 2 O (1), incorporating a tetradentate organic ligand was synthesized under hydro(solvo)thermal conditions and structurally characterized by single-crystal X-ray diffraction. Compound 1 is the first example of inorganic zincophosphite chains being interlinked through 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene to form a tubular porous framework with unusual organic-inorganic hybrid channels. The thermal and chemical stabilities, high capacity for CO 2 adsorption compared to that for N 2 adsorption, and interesting optical properties of LED devices fabricated using this compound were also studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Surface modification of a low cost bentonite for post-combustion CO2 capture

NASA Astrophysics Data System (ADS)

Chen, Chao; Park, Dong-Wha; Ahn, Wha-Seung

2013-10-01

A low cost bentonite was modified with PEI (polyethylenimine) through a physical impregnation method. Bentonite in its natural state and after amine modification were characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy, X-ray diffraction, N2 adsorption-desorption isotherms, and investigated for CO2 capture using a thermogravimetric analysis unit connected to a flow panel. The effect of adsorption temperature, PEI loading and CO2 partial pressure on the CO2 capture performance of the PEI-modified bentonite was examined. A cyclic CO2 adsorption-desorption test was also carried out to assess the stability of PEI-modified bentonite as a CO2 adsorbent. Bentonite in its natural state showed negligible CO2 uptake. After amine modification, the CO2 uptake increased significantly due to CO2 capture by amine species introduced via chemisorption. The PEI-modified bentonites showed high CO2 capture selectivity over N2, and exhibited excellent stability in cyclic CO2 adsorption-desorption runs.
The structure of N2 adsorbed on the rumpled NaCl(100) surface—A combined LEED and DFT-D study

NASA Astrophysics Data System (ADS)

Vogt, Jochen

2012-11-01

The structure of N2 physisorbed on the NaCl(100) single crystal surface is investigated by means of quantitative low-energy electron diffraction (LEED) in combination with dispersion corrected density functional theory (DFT-D). In the temperature range between 20 K and 45 K, a p(1 × 1) structure is observed in the LEED experiment. According to the structure analysis based on the measured diffraction spot intensity profiles, the N2 molecules are adsorbed over the topmost Na+ ions. The experimental distance of the lower nitrogen to the Na+ ion underneath is (2.55 ± 0.07) Å; the corresponding DFT-D value is 2.65 Å. The axes of the molecules are tilted (26 ± 3)° with respect to the surface normal, while in the zero Kelvin optimum structure from DFT-D, the molecules have a perpendicular orientation. The experimental monolayer heat of adsorption, deduced from a Fowler-Guggenheim kinetic model of adsorption is -(13.6 ± 1.6) kJ mol-1, including a lateral molecule-molecule interaction energy of -(2.0 ± 0.4) kJ mol-1. The zero Kelvin adsorption energy from DFT-D, including zero point energy correction, is -15.6 kJ mol-1; the molecule-molecule interaction is -2.4 kJ mol-1. While the rumpling of the NaCl(100) surface is unchanged upon adsorption of nitrogen, the best-fit root mean square thermal displacements of the ions in the topmost substrate layer are significantly reduced.
Two-step adsorption on jungle-gym-type porous coordination polymers: dependence on hydrogen-bonding capability of adsorbates, ligand-substituent effect, and temperature.

PubMed

Uemura, Kazuhiro; Yamasaki, Yukari; Onishi, Fumiaki; Kita, Hidetoshi; Ebihara, Masahiro

2010-11-01

A preliminary study of isopropanol (IPA) adsorption/desorption isotherms on a jungle-gym-type porous coordination polymer, [Zn(2)(bdc)(2)(dabco)](n) (1, H(2)bdc = 1,4-benzenedicarboxylic acid, dabco =1,4-diazabicyclo[2.2.2]octane), showed unambiguous two-step profiles via a highly shrunk intermediate framework. The results of adsorption measurements on 1, using probing gas molecules of alcohol (MeOH and EtOH) for the size effect and Me(2)CO for the influence of hydrogen bonding, show that alcohol adsorption isotherms are gradual two-step profiles, whereas the Me(2)CO isotherm is a typical type-I isotherm, indicating that a two-step adsorption/desorption is involved with hydrogen bonds. To further clarify these characteristic adsorption/desorption behaviors, selecting nitroterephthalate (bdc-NO(2)), bromoterephthalate (bdc-Br), and 2,5-dichloroterephthalate (bdc-Cl(2)) as substituted dicarboxylate ligands, isomorphous jungle-gym-type porous coordination polymers, {[Zn(2)(bdc-NO(2))(2)(dabco)]·solvents}(n) (2 ⊃ solvents), {[Zn(2)(bdc-Br)(2)(dabco)]·solvents}(n) (3 ⊃ solvents), and {[Zn(2)(bdc-Cl(2))(2)(dabco)]·solvents}(n) (4 ⊃ solvents), were synthesized and characterized by single-crystal X-ray analyses. Thermal gravimetry, X-ray powder diffraction, and N(2) adsorption at 77 K measurements reveal that [Zn(2)(bdc-NO(2))(2)(dabco)](n) (2), [Zn(2)(bdc-Br)(2)(dabco)](n) (3), and [Zn(2)(bdc-Cl(2))(2)(dabco)](n) (4) maintain their frameworks without guest molecules with Brunauer-Emmett-Teller (BET) surface areas of 1568 (2), 1292 (3), and 1216 (4) m(2) g(-1). As found in results of MeOH, EtOH, IPA, and Me(2)CO adsorption/desorption on 2-4, only MeOH adsorption on 2 shows an obvious two-step profile. Considering the substituent effects and adsorbate sizes, the hydrogen bonds, which are triggers for two-step adsorption, are formed between adsorbates and carboxylate groups at the corners in the pores, inducing wide pores to become narrow pores. Interestingly, such a two-step MeOH adsorption on 2 depends on the temperature, attributed to the small free-energy difference (ΔF(host)) between the two guest-free forms, wide and narrow pores.
Synthesis, characterization, and application of Zn(NH 3)(CO3) for selective adsorptive separation of CO2

NASA Astrophysics Data System (ADS)

Khazeni, Naasser

This study explores the potential of Zn(NH3)(CO3) for selective CO2 separation. It develops a novel, highly controllable, single-pot synthesis approach based on urea hydrolysis and solvothermal aging to increase the feasibility of synthesizing Zn(NH3)(CO3), determines the structure of Zn(NH3)(CO3) in detail through single crystal X-ray diffraction and powder X-ray diffraction analyses, and performs adsorption analyses for the compound using CO2, N 2, H2, O2, and CH4 as adsorptives. Through adsorptive characterization, a systematic adsorbent selection screening is performed to assess the potential application of Zn(NH3)(CO 3) for adsorptive separation of CO2 from an upstream gas mixture of power generation, hydrogen production, and natural gas industries. Structural analysis shows Zn(NH3)(CO3) to have an inorganic helical framework that consists of a small helix of (ZnOCO) 2 and a large helix of (ZnOCO)4 with two ammines (NH 3) pendant from every other zinc. In terms of adsorption capacity and CO2 selectivity, Zn(NH3)(CO3) adsorbed 0.550 mmole/g CO2 at 293 K and 4500 mmHg, but only 0.047 mmole/g N 2, 0.084 mmole/g H2, 0.207 mmole/g 02, and 0.060 mmole/g CH4 at the same temperature and pressure. This behavior demonstrates considerable equilibrium selectivities - 36, 31, 63, and 11 - for separating CO2 from CH4, CO2 from H 2, CO2 from N2, and CO2 from 02, respectively. During adsorption, the pendant ammines act as the gates of check-valves: applied pressure opens the gates for adsorption; and during desorption, the gates are closed, trapping the adsorbates, until a reduction of pressure to near-atmospheric levels. Therefore, Zn(NH3)(CO3) exhibits low-pressure H3 or H4 hysteresis, indicating that the Zn(NH3)(CO3) framework can achieve gas storage at near-atmospheric pressures. Additionally, the compound proves structurally stable, with an adsorption decrease of 0.8% after 20 adsorption/desorption cycles - a factor that, considered with the other characteristics of Zn(NH3)(CO 3), renders this compound a potential candidate for separating CO 2 from H2and N2. The adsorbent selection screening affirmed that Zn(NH3)(CO 3) can be a potential candidate for LFG separation using PSA, LFG separation using VSA, oxy-fuel CO2 purification using PSA, and air separation using PSA at 263K. For those applications, the low CO2 uptake by Zn(NH3)(CO3) was offset by considerable selectivity, regenerability, and adsorbent selection parameter.
Insight into the adsorption of tetracycline onto amino and amino-Fe3+ gunctionalized mesoporous silica: Effect of functionalized groups.

PubMed

Zhang, Ziyang; Li, Haiyan; Liu, Huijuan

2018-03-01

In order to study the influences of functionalized groups onto the adsorption of tetracycline, we prepared a series of amino and amino-Fe 3+ complex mesoporous silica adsorbents with diverse content of amino and Fe 3+ groups (named N,N-SBA15 and Fe-N,N-SBA15). The resulting mesoporous silica adsorbents were fully characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectrometer (FTIR) and N 2 adsorption/desorption isotherms. Furthermore, the effects of functionalized groups on the removal of TC were investigated. The results showed that the periodic ordered structure of SBA-15 was maintained after modification of amino/Fe 3+ groups. The functionalized amino groups decreased the adsorption capacity while the coordinated Fe 3+ increased the adsorption capacity. The adsorption kinetics of TC fitted pseudo-second-order model well and the equilibrium was achieved quickly. The adsorption isotherms fitted the Langmuir model well and with the Fe 3+ content increased from 3.93% to 8.26%, the Q max of the adsorbents increased from 102 to 188mmol/kg. The solution pH affected the adsorption of TC onto amino complex adsorbents slightly while influenced the adsorption onto Fe-amine complex adsorbents greatly. The adsorption of TC on SBA15 and N,N-SBA15 may be related to the formation of outer-sphere surface complexes, while the adsorption of TC onto Fe-N,N-SBA15 was mainly attributed to the inner-sphere surface complexes. This study could offer potential materials that have excellent adsorption behavior for environmental remediation and suggested useful information for the preparing other adsorbents in environmental applications. Copyright © 2017. Published by Elsevier B.V.
Adsorption/reduction of Hg(II) and Pb(II) from aqueous solutions by using bone ash/nZVI composite: effects of aging time, Fe loading quantity and co-existing ions.

PubMed

Gil, Antonio; Amiri, Mohammad Javad; Abedi-Koupai, Jahangir; Eslamian, Saeid

2018-01-01

In this research, a versatile and highly efficient method for the stabilization of nanoscale zerovalent iron particles (nZVI) on the surface of ostrich bone ash (OBA) was presented as a novel inorganic adsorbent (OBA/nZVI) for the removal of Hg(II) and Pb(II) ions from aqueous solutions, even after 1 year of storage under room conditions. The removal behavior of the OBA/nZVI was assessed as a function of the initial pH, contact time, initial pollutants concentration, temperature, amount of adsorbent, effect of competitive metal ions, and ionic strength. The synthesized adsorbent was characterized by several techniques including N 2 adsorption at - 196 °C, FT-IR spectroscopy, scanning electron microscopy, X-ray diffraction, and zeta potential. The results confirmed that the OBA is a good candidate as support of nZVI. The maxima adsorption capacity for Hg(II) and Pb(II) ions found from experimental results were 170 and 160 mg g -1 , when the loading quantities of Fe were 20%. The equilibrium sorption data obeyed a Langmuir-Freundlich isotherm type model. The kinetic data of the adsorption followed the mechanism of the pseudo-second-order model. The thermodynamic experiments indicated that the removal of metal ions were feasible, endothermic, and spontaneous. It can be found that fresh and aged OBA/nZVI maintained its usability even after five cycles in the order: fresh (OBA/nZVI)-Hg(II) > fresh (OBA/nZVI)-Pb(II) > aged (OBA/nZVI)-Hg(II) > aged (OBA/nZVI)-Pb(II), which indicate that OBA/nZVI can be regenerated as adsorbent. The existence of Fe in the OBA/nZVI was proved by SEM-EDX results and X-ray diffraction analysis also confirmed adsorption/reduction of some of the Hg(II) to Hg 0 and Pb(II) to Pb 0 .
Pentaethylenehexamine-Loaded Hierarchically Porous Silica for CO2 Adsorption

PubMed Central

Ji, Changchun; Huang, Xin; Li, Lei; Xiao, Fukui; Zhao, Ning; Wei, Wei

2016-01-01

Recently, amine-functionalized materials as a prospective chemical sorbent for post combustion CO2 capture have gained great interest. However, the amine grafting for the traditional MCM-41, SBA-15, pore-expanded MCM-41 or SBA-15 supports can cause the pore volume and specific surface area of sorbents to decrease, significantly affecting the CO2 adsorption-desorption dynamics. To overcome this issue, hierarchical porous silica with interparticle macropores and long-range ordering mesopores was prepared and impregnated with pentaethylenehexamine. The pore structure and amino functional group content of the modified silicas were analyzed by scanning electron microscope, transmission electron microscope, N2 adsorption, X-ray powder diffraction, and Fourier transform infrared spectra. Moreover, the effects of the pore structure as well as the amount of PEHA loading of the samples on the CO2 adsorption capacity were investigated in a fixed-bed adsorption system. The CO2 adsorption capacity reached 4.5 mmol CO2/(g of adsorbent) for HPS−PEHA-70 at 75 °C. Further, the adsorption capacity for HPS-PEHA-70 was steady after a total of 15 adsorption-desorption cycles. PMID:28773956
Hydrothermal synthesis, crystal structures, and enantioselective adsorption property of bis(L-histidinato)nickel(II) monohydrate

NASA Astrophysics Data System (ADS)

Ramos, Christian Paul L.; Conato, Marlon T.

2018-05-01

Despite the numerous researches in metal-organic frameworks (MOFs), there are only few reports on biologically important amino acids, histidine in particular, on its use as bridging ligand in the construction of open-framework architectures. In this work, hydrothermal synthesis was used to prepare a compound based on Ni2+ and histidine. The coordination assembly of imidazole side chain of histidine with divalent nickel ions in aqueous condition yielded purple prismatic solids. Single crystal X-ray diffraction (XRD) analysis of the product revealed structure for Ni(C6H8N3O2)2 • H2O that has a monoclinic (C2) structure with lattice parameters, a = 29.41, b = 8.27, c = 6.31 Å, β = 90.01 ˚. Circular dichroism - optical rotatory dispersion (CD-ORD), Powder X-ray diffraction (PXRD) and Fourier transform - infrared spectroscopy (FT-IR) analyses are conducted to further characterize the crystals. Enantioselective adsorption analysis using racemic mixture of 2-butanol confirmed bis(L-histidinato)nickel(II) monohydrate MOF crystal's enantioselective property preferentially favoring the adsorption of (S)-2-butanol isomer.

o-Vanillin functionalized mesoporous silica - coated magnetite nanoparticles for efficient removal of Pb(II) from water

NASA Astrophysics Data System (ADS)

Culita, Daniela C.; Simonescu, Claudia Maria; Patescu, Rodica-Elena; Dragne, Mioara; Stanica, Nicolae; Oprea, Ovidiu

2016-06-01

o-Vanillin functionalized mesoporous silica - coated magnetite (Fe3O4@MCM-41-N-oVan) was synthesized and fully characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, N2 adsorption-desorption technique and magnetic measurements. The capacity of Fe3O4@MCM-41-N-oVan to adsorb Pb(II) from aqueous solutions was evaluated in comparison with raw mesoporous silica - coated magnetite (Fe3O4@MCM-41) and amino - modified mesoporous silica coated magnetite (Fe3O4@MCM-41-NH2). The effect of adsorption process parameters such us pH, contact time, initial Pb(II) concentration was also investigated. The adsorption data were successfully fitted with the Langmuir model, exhibiting a maximum adsorption capacity of 155.71 mg/g at pH=4.4 and T=298 K. The results revealed that the adsorption rate was very high at the beginning of the adsorption process, 80-90% of the total amount of Pb(II) being removed within the first 60 min, depending on the initial concentration. The results of the present work suggest that Fe3O4@MCM-41-N-oVan is a suitable candidate for the separation of Pb(II) from contaminated water.
Adsorption properties of biomass-based activated carbon prepared with spent coffee grounds and pomelo skin by phosphoric acid activation

NASA Astrophysics Data System (ADS)

Ma, Xiaodong; Ouyang, Feng

2013-03-01

Activated carbon prepared from spent coffee grounds and pomelo skin by phosphoric acid activation had been employed as the adsorbent for ethylene and n-butane at room temperature. Prepared activated carbon was characterized by means of nitrogen adsorption-desorption, X-ray powder diffraction, scanning electron microscope and Fourier transform infrared spectroscope. It was confirmed that pore structure played an important role during the adsorption testes. Adsorption isotherms of ethylene and n-butane fitted well with Langmuir equation. The prepared samples owned better adsorption capacity for n-butane than commercial activated carbon. Isosteric heats of adsorptions at different coverage were calculated through Clausius-Clapeyron equation. Micropore filling effect was explained in a thermodynamic way.
Titanium-incorporated organic–inorganic hybrid adsorbent for improved CO{sub 2} adsorption performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiaoyun; Qin, Hongyan; Zhang, Sisi

2015-02-15

Highlights: • Titanium-incorporated organic–inorganic hybrid adsorbent was prepared. • The incorporation of Ti to the adsorbent showed significant effect. • The sorbent shows high CO{sub 2} capture capacity both in pure and diluted CO{sub 2} at RT. • The sorbent exhibits a high recycling stability after 15 cycling runs. - Abstract: The CO{sub 2} adsorption performance of acrylonitrile (AN)–tetraethylenepentamine (TEPA) adduct (hereafter referred to as TN) impregnated adsorbent was greatly enhanced by introduction of Titanium atom into the silica matrix. The adsorbents were characterized by X-ray fluorescence spectrometry (XRF), X-ray diffraction (XRD), transmission electron microscopy (TEM), N{sub 2} adsorption/desorption, UV–vismore » spectroscopy, Fourier transform infrared (FTIR) spectroscopy. The adsorption experiments together with the physicochemical characterization demonstrated that these adsorbents containing an optimal amount of Titanium (Ti/Si ≈ 0.1) remarkably reinforced the CO{sub 2} adsorption capacity and recycling stability. The highest CO{sub 2} uptakes reached 4.65 and 1.80 mmol CO{sub 2}/g adsorbent at 25 °C under 90% CO{sub 2} (CO{sub 2}/N{sub 2}, 90:10 V/V) and 1% CO{sub 2} (CO{sub 2}/N{sub 2}, 1:99 V/V) conditions for sample Ti(0.1)-DMS-TN, respectively. Repeated adsorption/desorption cycles revealed that the Ti-incorporated adsorbent showed only a tiny decrease in adsorption capacity (1.778 mmol CO{sub 2}/g adsorbent after 15 cycles, decreased by 0.95%), significantly enhanced the adsorbent recycling stability.« less
Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water.

PubMed

Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

2011-11-30

The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu(3)(BTC)(2)(H(2)O)(3)](n) (HKUST-1, BTC=benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu(3)(BTC)(2)](n) samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N(2) sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu(3)(BTC)(2)](n) exhibited remarkably high adsorption affinity (K(d)=4.73 × 10(5)mL g(-1)) and high adsorption capacity (714.29 mg g(-1)) for Hg(2+) adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg(2+) under the same condition. Copyright Â© 2011 Elsevier B.V. All rights reserved.
Nb2O5 nanowires in-situ grown on carbon fiber: A high-efficiency material for the photocatalytic reduction of Cr(VI).

PubMed

Du, Yucheng; Zhang, Shihao; Wang, Jinshu; Wu, Junshu; Dai, Hongxing

2018-04-01

Niobium oxide nanowire-deposited carbon fiber (CF) samples were prepared using a hydrothermal method with amorphous Nb 2 O 5 ·nH 2 O as precursor. The physical properties of the samples were characterized by means of numerous techniques, including X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), UV-visible spectroscopy (UV-vis), N 2 adsorption-desorption, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy. The efficiency for the removal of Cr(VI) was determined. Parameters such as pH value and initial Cr(VI) concentration could influence the Cr(VI) removal efficiency or adsorption capacity of the Nb 2 O 5 /carbon fiber sample obtained after hydrothermal treatment at 160°C for 14hr. The maximal Cr(VI) adsorption capacity of the Nb 2 O 5 nanowire/CF sample was 115mg/g. This Nb 2 O 5 /CF sample also showed excellent photocatalytic activity and stability for the reduction of Cr(VI) under UV-light irradiation: the Cr(VI) removal efficiency reached 99.9% after UV-light irradiation for 1hr and there was no significant decrease in photocatalytic performance after the use of the sample for 10 repeated cycles. Such excellent Cr(VI) adsorption capacity and photocatalytic performance was related to its high surface area, abundant surface hydroxyl groups, and good UV-light absorption ability. Copyright © 2017. Published by Elsevier B.V.
Functional kaolin supported nanoscale zero-valent iron as a Fenton-like catalyst for the degradation of Direct Black G.

PubMed

Lin, Jiajiang; Sun, Mengqiang; Liu, Xinwen; Chen, Zuliang

2017-10-01

Kaolin supported nanoscale zero-valent iron (K-nZVI) is synthesized and applied as the Fenton-like oxidation catalyst to degrade a model azo dye, Direct Black G (DBG). The characterization of K-nZVI by the high resolution transmission electronmicroscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Energy Diffraction Spectrum (EDS) and X-ray diffraction (XRD) show that kaolin as a support material not only reduces the aggregation of zero-valent iron (nZVI) but also facilitates the Fenton-like oxidation by increasing the local concentration of DBG in the vicinity of nZVI. Pseudo first-order and pseudo second-order kinetic models are employed to reveal the adsorption and degradation of the DBG using K-nZVI as the catalyst. A better fit with pseudo second-order model for the adsorption process and equal excellent fits with pseudo first-order and pseudo second-order models for the degradation process are observed; the adsorption process is found to be the rate limiting step for overall reactions. The adsorption, evaluated by isotherms and thermodynamic parameters is a spontaneous and endothermic process. High-performance liquid chromatography-mass spectrometry (LC-MS) analysis was used to test degraded products in the degradation of DGB by K-nZVI. A removal mechanism based on the adsorption and degradation is proposed, including (i) prompt adsorption of DBG onto the K-nZVI surface, and (ii) oxidation of DBG by hydroxyl radicals at the K-nZVI surface. The application of K-nZVI to treat real wastewater containing azo dyes shows excellent degradation efficiency. Copyright © 2017 Elsevier Ltd. All rights reserved.
A novel highly efficient adsorbent {[Co4(L)2(μ3-OH)2(H2O)3(4,4‧-bipy)2]·(H2O)2}n: Synthesis, crystal structure, magnetic and arsenic (V) absorption capacity

NASA Astrophysics Data System (ADS)

Zhang, Chong; Xiao, Yu; Qin, Yan; Sun, Quanchun; Zhang, Shuhua

2018-05-01

A novel highly efficient adsorbent-microporous tetranuclear Co(II)-based polymer, {[Co4(L)2(μ3-OH)2(H2O)3(4,4‧-bipy)2]·(H2O)2}n (1, H3L = 4-(N,N‧-bis(4-carboxybenzyl)amino) benzenesulfonic acid, 4,4‧-bipy = 4,4‧-bipyridine), was hydrothermally synthesized. The complex 1 is a metal-organic framework (MOF) material which was characterized by single-crystal X-ray diffraction, BET and platon software. Co-MOF (complex 1) reveals excellent adsorption property. The capacity of Co-MOF to remove arsenic As(V) from sodium arsenate aqueous solutions was investigated (The form of As(V) is AsO43-). The experimental results showed that Co-MOF had a higher stable and relatively high As(V) removal rate (> 98%) at pH 4-10. The adsorption kinetics followed a pseudo-second-order kinetic model, and the adsorption isotherm followed the Langmuir equation. Co-MOF exhibits a very high adsorption capacity of As(V) in aqueous solution (Qmax of 96.08 mg/g). Finally, the optimal adsorption conditions for the model were obtained through a Box-Behnken response surface experiment which was designed with adsorption time, dose, temperature and rotational speed of the shaker as the influencing factors to determine two-factor interaction effects. Co-MOF was further characterized using FTIR, PXRD, X-ray photoelectron spectroscopy before and after adsorption As (V). The magnetism of Co-MOF was also discussed.
Adsorption properties and photocatalytic activity of TiO2/activated carbon fiber composite

NASA Astrophysics Data System (ADS)

Yao, Shuhua; Song, Shuangping; Shi, Zhongliang

2014-06-01

Photocatalysts of titanium dioxide (TiO2) and TiO2/activated carbon fiber (TiO2/ACF) composite were prepared by sol-gel method, followed by calcining the pure TiO2 sols and the TiO2/ACF sols at 500°C for 2 h in a N2 atmosphere, respectively. These photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and N2 adsorption-desorption isotherms measurement. Batch experiments were conducted to study the adsorption property of TiO2/ACF composite using methylene blue as adsorbate. The adsorption data obtained from different batch experiments were analyzed using pseudo-second-order kinetic model, the experimental data can be adequately described by the pseudo-second-order equation. The photodecomposition behavior of TiO2/ACF was investigated in aqueous solution using methylene blue as target pollutant. It was found that methylene blue could be removed rapidly from water by TiO2/ACF, the photocatalytic decomposition was obviously improved when the photocatalyst was used. Kinetics analysis revealed that the photocatalytic decomposition reaction can be described well by a first-order rate equation.
Zinc(II) and cadmium(II) coordination polymers containing phenylenediacetate and 4,4‧-azobis(pyridine) ligands: Syntheses, structures, dye adsorption properties and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Sezer, Güneş Günay; Arıcı, Mürsel; Erucar, İlknur; Yeşilel, Okan Zafer; Özel, Handan Ucun; Gemici, Betül Tuba; Erer, Hakan

2017-11-01

Two new coordination polymers (CPs) - [Zn(μ4-ppda)(μ-abpy)0.5]n(1) and [Cd(μ3-opda)(μ-abpy)0.5(H2O)]n(2) (o/ppda = 1,2/1,4-phenylenediacetate, abpy = 4,4‧-azobis(pyridine)) - have been synthesized by using Zn(II)/Cd(II) salts in the presence of o- and p-phenylenediacetic acid and abpy under hydrothermal conditions. Their structures have been characterized by FT-IR spectroscopy, elemental analysis, X-ray powder diffraction and single crystal X-ray diffraction techniques. The structural diversities were observed depending on anionic ligands and metal centers in the synthesized complexes. Complex 1 consists of a 2-fold interpenetrated 3D+3D→3D framework with pcu topology while complex 2 has a 2D structure with sql topology. The adsorption of methylene blue (MB) was studied to examine the potential of the title CPs for removal of dyes from aqueous solution. Molecular dynamics (MD) simulations were also performed to examine diffusion of MB in 1 and 2. Thermal and optical properties of two complexes were also discussed.
Insertion of bentonite with Organometallic [Fe3O(OOC6H5)6(H2O)3(NO3).nH2O] as Adsorbent of Congo Red

NASA Astrophysics Data System (ADS)

Said, Muhammad; Paluta Utami, Hasja; Hayati, Ferlina

2018-01-01

The adsorption of Congo red using bentonite inserted organometallic has been investigated. The insertion bentonite was characterized using FT-IR Spectrophotometer, XRD and XRF analysis. The FT-IR characterization showed the higher intensity of peak wavenumber at 470.6 cm-1 for Fe3O on the ratio 1:3. While the XRD characterization showed the shift of diffraction angle of 2θ was 5.2° and has a basal spacing of 16.8 Å. In the XRF characterization, the insertion process of organometallic occurred optimally with the percentage of metal oxide reached 71.75 %. The adsorption process of bentonite inserted organometallic compound [Fe3O(OOC6H5)6(H2O)3(NO3)·nH2O] showed the adsorption rate (k) is 0.050 min-1, the largest adsorption capacity (b) at 70°C is 4.48 mol/g, the largest adsorption energy at temperature 30°C which is 6.4 kJ/mol Organometallic compounds. The value of the enthalpy (ΔH) and entropy (ΔS) decreased with increasing concentrations of the Congo red. Effect of pH on the adsorption on at pH 3 shows the biggest of number Congo red absorbed is 19.52 mg/L for insertion of bentonite.
Cesium and Strontium Retentions Governed by Aluminosilicate Gel in Alkali-Activated Cements

PubMed Central

Jang, Jeong Gook; Park, Sol Moi; Lee, Haeng Ki

2017-01-01

The present study investigates the retention mechanisms of cesium and strontium for alkali-activated cements. Retention mechanisms such as adsorption and precipitation were examined in light of chemical interactions. Batch adsorption experiments and multi-technical characterizations by using X-ray diffraction, zeta potential measurements, and the N2 gas adsorption/desorption methods were conducted for this purpose. Strontium was found to crystalize in alkali-activated cements, while no cesium-bearing crystalline phases were detected. The adsorption kinetics of alkali-activated cements having relatively high adsorption capacities were compatible with pseudo-second-order kinetic model, thereby suggesting that it is governed by complex multistep adsorption. The results provide new insight, demonstrating that characteristics of aluminosilicate gel with a highly negatively charged surface and high micropore surface area facilitated more effective immobilization of cesium and strontium in comparison with calcium silicate hydrates. PMID:28772803
Effective removal of hydrogen sulfide using 4A molecular sieve zeolite synthesized from attapulgite.

PubMed

Liu, Xinpeng; Wang, Rui

2017-03-15

In this work, 4A molecular sieve zeolite was synthesized from attapulgite (ATP) in different conditions and was applied initially for H 2 S removal. The sorbent was characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectra and N 2 adsorption/desorption. The effects of the synthesis condition and adsorption temperature were studied by dynamic adsorption experiment. The optimal adsorption temperature is 50°C. The H 2 S adsorption results have showed that the optimal synthesis conditions are as follows: the ratio of silicon to aluminum and ratio of sodium to silicon are both 1.5, the ratio of water to sodium is 30, crystallization temperature and crystallization time is 90°C, 4h, respectively. The breakthrough and saturation sulfur sorption capacities of zeolite synthesized under optimum conditions are up to nearly 10 and 15mg/g-sorbent, respectively, and the H 2 S removal rate is nearly 100%. The adsorption kinetics nonlinear fitting results show that the adsorption system follows Bingham model. These results indicate that 4A molecular sieve zeolite synthesized from attapulgite can be used for H 2 S removal promisingly. Copyright © 2016 Elsevier B.V. All rights reserved.
Adsorption of vitamin E on mesoporous titania nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shih, C.J., E-mail: cjshih@kmu.edu.tw; Lin, C.T.; Wu, S.M.

2010-07-15

Tri-block nonionic surfactant and titanium chloride were used as starting materials for the synthesis of mesoporous titania nanocrystallite powders. The main objective of the present study was to examine the synthesis of mesoporous titania nanocrystals and the adsorption of vitamin E on those nanocrystals using X-ray diffraction (XRD), transmission electron microscopy, and nitrogen adsorption and desorption isotherms. When the calcination temperature was increased to 300 {sup o}C, the reflection peaks in the XRD pattern indicated the presence of an anatase phase. The crystallinity of the nanocrystallites increased from 80% to 98.6% with increasing calcination temperature from 465 {sup o}C tomore » 500 {sup o}C. The N{sub 2} adsorption data and XRD data taken after vitamin E adsorption revealed that the vitamin E molecules were adsorbed in the mesopores of the titania nanocrystals.« less
Preparation and characterization of pitch-based nanoporous carbons for improving CO{sub 2} capture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Seul-Yi; Yoo, Hye-Min; Park, Sang Wook

2014-07-01

Pitch is considered a promising low-cost carbon precursor. However, when pitch is pyrolyzed, it forms polycrystalline graphite, which is non-porous, and therefore, not useful for CO{sub 2} adsorption. In this work, pitch was chemically activated to obtain a large specific surface area and micropore volume. Varying weight ratios of KOH (i.e., 0, 1, 2, and 3) were used as the activating agent. The characteristics of the samples were investigated using scanning electron microscopy (SEM), N{sub 2}/77 K adsorption isotherms, and X-ray diffraction (XRD). The CO{sub 2} adsorption performance was studied by isothermal adsorption/desorption measurements. The results showed that an increasemore » in specific surface areas and total pore volumes of pitch-based nanoporous carbons, resulted in an enhancement of CO{sub 2} adsorption capacity. - Graphical abstract: This is the surface morphologies of pitch precursor and pitch-derived activated carbon (AC-2). - Highlights: • Pitch is considered a promising low-cost carbon precursor. • Specific surface area: 1442 m{sup 2}/g and micropore volume: 0.504 cm{sup 3}/g. • CO{sub 2} adsorption capacity showed 203 mg/g (@ RT/1 bar)« less
Starch-g-Poly-(N, N-dimethyl acrylamide-co-acrylic acid): an efficient Cr (VI) ion binder.

PubMed

Kolya, Haradhan; Roy, Anirban; Tripathy, Tridib

2015-01-01

Synthesis of Starch-g-(Poly N, N-dimethylacrylamide-co-acrylic acid) was carried out by solution polymerization technique using potassium perdisulfate (K(2)S(2)O(8)) as the initiator. The graft copolymer was characterized by measuring molecular weight, using size exclusion chromatography (SEC), FTIR spectroscopy and X-ray diffraction (XRD) studies. The synthetic graft copolymer was used for removal of hexavalent chromium ion [Cr (VI)] from its aqueous solution. Various operating variables affecting the metal sorption such as, the amount of adsorbent, solution pH, contact time, temperature and the Cr (VI) solution concentration were extensively investigated. FTIR and UV-VIS spectroscopy, cyclic voltammetry (CV) were employed to study the metal complexation. The adsorption data could be well described by the pseudo-second-order and Langmuir isotherm model which indicate a chemisorption process. Calculation of the various thermodynamic parameters for the adsorption was also done. The negative value of free energy change (ΔG°) indicates the spontaneous nature of the adsorption. Copyright © 2014 Elsevier B.V. All rights reserved.
Synthesis and application of a new carboxylated cellulose derivative. Part I: Removal of Co(2+), Cu(2+) and Ni(2+) from monocomponent spiked aqueous solution.

PubMed

Teodoro, Filipe Simões; Ramos, Stela Nhandeyara do Carmo; Elias, Megg Madonyk Cota; Mageste, Aparecida Barbosa; Ferreira, Gabriel Max Dias; da Silva, Luis Henrique Mendes; Gil, Laurent Frédéric; Gurgel, Leandro Vinícius Alves

2016-12-01

A new carboxylated cellulose derivative (CTA) was prepared from the esterification of cellulose with 1,2,4-Benzenetricarboxylic anhydride. CTA was characterized by percent weight gain (pwg), amount of carboxylic acid groups (nCOOH), elemental analysis, FTIR, TGA, solid-state (13)C NMR, X-ray diffraction (DRX), specific surface area, pore size distribution, SEM and EDX. The best CTA synthesis condition yielded a pwg and nCOOH of 94.5% and 6.81mmolg(-1), respectively. CTA was used as an adsorbent material to remove Co(2+), Cu(2+) and Ni(2+) from monocomponent spiked aqueous solution. Adsorption studies were developed as a function of the solution pH, contact time and initial adsorbate concentration. Langmuir model better fitted the experimental adsorption data and the maximum adsorption capacities estimated by this model were 0.749, 1.487 and 1.001mmolg(-1) for Co(2+), Cu(2+) and Ni(2+), respectively. The adsorption mechanism was investigated by using isothermal titration calorimetry. The values of ΔadsH° were in the range from 5.36 to 8.09kJmol(-1), suggesting that the mechanism controlling the phenomenon is physisorption. Desorption and re-adsorption studies were also performed. Desorption and re-adsorption efficiencies were closer to 100%, allowing the recovery of both metal ions and CTA adsorbent. Copyright © 2016 Elsevier Inc. All rights reserved.
Adsorption of Paraquat Dichloride by Graphitic Carbon Nitride Synthesized from Melamine Scraps

NASA Astrophysics Data System (ADS)

Watcharenwong, A.; Kaeokan, A.; Rammaroeng, R.; Upama, P.; Kajitvichyanukul, P.

2017-07-01

In this research, graphitic carbon nitride (g-C3N4) was synthesized from useless melamine scraps. Mixture of melamine powder and urea was directly burned in the muffle furnace at 550 °C. Later as-synthesized g-C3N4 was modified with hydrochloric acid. The g-C3N4 powder was characterized by several techniques including X-ray diffraction, scanning electron microscope, and specific surface area analyser. Adsorption of the herbicide paraquat from an aqueous solution to suspended particles of g-C3N4 was investigated, taking into consideration several parameters such as initial concentration of paraquat, initial pH, and dosage of g-C3N4. The results showed that with the same amount of g-C3N4, the increase in the paraquat concentration caused the reduction in the removal efficiency and the higher the amount of g-C3N4, the less residual paraquat remained in the bulk solution. G-C3N4 showed better adsorption behaviour in the basic condition. Finally, Langmuir and Freundlich adsorption isotherms were also evaluated. Paraquat adsorption by g-C3N4 was in accordance with Langmuir more than Freundlich adsorption isotherm.
Removal of copper and nickel from water using nanocomposite of magnetic hydroxyapatite nanorods

NASA Astrophysics Data System (ADS)

Thanh, Dong Nguyen; Novák, Pavel; Vejpravova, Jana; Vu, Hong Nguyen; Lederer, Jaromír; Munshi, Tasnim

2018-06-01

A nanocomposite of magnetic hydroxyapatite was synthesized and tested as an adsorbent for the removal of copper (Cu (II)) and nickel (Ni(II)) from aqueous solution. The adsorbent was investigated using Transmission Electron Microscopy (TEM), Scanning Electron Microscopy equipped with an Energy Dispersive Spectrometer (SEM/EDS), X-ray powder diffraction (XRD) and the Brunauer-Elmet-Teller nitrogen adsorption technique (BET-N2 adsorption). Batch experiments were carried out to determine and compare the adsorption parameters of Fe3O4 and its composite with hydroxyapatite. It was found that the adsorbent is nanostructured and has a specific surface area of 101.2 m2 g-1. The Langmuir adsorption isotherm was found to be an appropriate model to describe the adsorption processes, showing the adsorption capacities of Cu(II) and Ni(II) of 48.78 mg g-1 and 29.07 mg g-1, respectively. In addition to the high adsorption capacity, the fully-adsorbed material could be easily separated from aqueous media using an external magnetic field. These results suggested that the utilization of new hydroxyapatite - Fe3O4 nanocomposite for the removal of Cu(II) and Ni(II) is a promising method in water technology.
Facile synthesis of uniform hierarchical composites CuO-CeO2 for enhanced dye removal

NASA Astrophysics Data System (ADS)

Xu, Pan; Niu, Helin; Chen, Jingshuai; Song, Jiming; Mao, Changjie; Zhang, Shengyi; Gao, Yuanhao; Chen, Changle

2016-12-01

The hierarchically shaped CuO-CeO2 composites were prepared through a facile solvothermal method without using any template. The as-prepared products were characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and N2 adsorption-desorption analysis. In the characterization, we found that CuO-CeO2 composites were showed uniform size and morphology which were consisted of the secondary nanoflakes interconnected with each other. Most interestingly, the composites showed efficient performance to remove methyl blue and Congo red dyes from water with maximum adsorption capacities of 2131.24 and 1072.09 mg g-1, respectively. In addition, because of their larger surface area and the unique hierarchical structures, the adsorption performance of the CuO-CeO2 composites is much better than the materials of CuO and CeO2.
Nanoporous active carbons at ambient conditions: a comparative study using X-ray scattering and diffraction, Raman spectroscopy and N2 adsorption

NASA Astrophysics Data System (ADS)

Shiryaev, A. A.; Voloshchuk, A. M.; Volkov, V. V.; Averin, A. A.; Artamonova, S. D.

2017-05-01

Furfural-derived sorbents and activated carbonaceous fibers were studied using Small- and Wide-angle X-ray scattering (SWAXS), X-ray diffraction and multiwavelength Raman spectroscopy after storage at ambient conditions. Correlations between structural features with degree of activation and with sorption parameters are observed for samples obtained from a common precursor and differing in duration of activation. However, the correlations are not necessarily applicable to the carbons obtained from different precursors. Using two independent approaches we show that treatment of SWAXS results should be performed with careful analysis of applicability of the Porod law to the sample under study. In general case of a pore with rough/corrugated surface deviations from the Porod law may became significant and reflect structure of the pore-carbon interface. Ignorance of these features may invalidate extraction of closed porosity values. In most cases the pore-matrix interface in the studied samples is not atomically sharp, but is characterized by 1D or 2D fluctuations of electronic density responsible for deviations from the Porod law. Intensity of the pores-related small-angle scattering correlates positively with SBET values obtained from N2 adsorption.

UiO-66-NH2/GO Composite: Synthesis, Characterization and CO2 Adsorption Performance

PubMed Central

Cao, Yan; Zhang, Hongmei; Song, Fujiao; Huang, Tao; Ji, Jiayu; Zhong, Qin; Chu, Wei; Xu, Qi

2018-01-01

In this work, a new composite materials of graphene oxide (GO)-incorporated metal-organic framework (MOF)(UiO-66-NH2/GO) were in-situ synthesized, and were found to exhibit enhanced high performances for CO2 capture. X-ray diffraction (XRD), scanning electron microscope (SEM), N2 physical adsorption, and thermogravimetric analysis (TGA) were applied to investigate the crystalline structure, pore structure, thermal stability, and the exterior morphology of the composite. We aimed to investigate the influence of the introduction of GO on the stability of the crystal skeleton and pore structure. Water, acid, and alkali resistances were tested for physical and chemical properties of the new composites. CO2 adsorption isotherms of UiO-66, UiO-66-NH2, UiO-66/GO, and UiO-66-NH2/GO were measured at 273 K, 298 K, and 318 K. The composite UiO-66-NH2/GO exhibited better optimized CO2 uptake of 6.41 mmol/g at 273 K, which was 5.1% higher than that of UiO-66/GO (6.10 mmol/g). CO2 adsorption heat and CO2/N2 selectivity were then calculated to further evaluate the CO2 adsorption performance. The results indicated that UiO-66-NH2/GO composites have a potential application in CO2 capture technologies to alleviate the increase in temperature of the earth’s atmosphere. PMID:29641476
Quinoline derivative containing monomeric and polymeric metal carboxylates: Synthesis, crystal structure and gas adsorption study over a 2D layered framework

NASA Astrophysics Data System (ADS)

Gayen, Saikat; Saha, Debraj; Koner, Subratanath

2018-06-01

A new supramolecular metal-carboxylate framework [Co(mqc)2]n (1), and another monomeric compound [Zn (mqc)2(H2O)] (2) (mqcH = 4-methoxy 2-quinolinecarboxylic acid) have been synthesized solvothermally and characterized by single crystal X-ray diffraction, elemental analysis, IR spectra, UV-vis spectra, powdered X-ray diffraction (PXRD) and thermogravimetric analysis. Compound 1 is a 2D coordination polymer, extended to a 3D porous supramolecular network having void space in between 2D layers. Compound 1 exhibits gas uptake capacity of N2, H2, CO2 and CH4 like small gas molecules in which moderately high uptake of H2 and CO2 takes place among the 2D MOFs. While the Zn variety, compound 2 features a one-dimensional chain like structure through strong intermolecular hydrogen-bonding.
Hexagonal mesoporous silica modified with copper phthalocyanine as a photocatalyst for pesticide 2,4-dichlorophenoxiacetic acid degradation.

PubMed

DeOliveira, Edimar; Neri, Cláudio R; Ribeiro, Anderson O; Garcia, Vinícius S; Costa, Leonardo L; Moura, Aline O; Prado, Alexandre G S; Serra, Osvaldo A; Iamamoto, Yassuko

2008-07-01

A new mesoporous catalyst was prepared by the reaction between 3-aminopropyltrimethoxisylane and Cu(II)-hexadecafluorophthalocyanine, followed by co-condensation of tetraethylorthosilicate around a micelle formed by n-dodecylamine. The surfactant was removed from the pores by continuous extraction with ethanol, giving the Si-CuF16Pc catalyst. This catalyst was characterized by SEM, FTIR, TGA, 29Si NMR, N2 adsorption and X-ray diffraction. SEM images confirmed that the catalyst material is formed by nanoaggregates with a diameter of 100 nm. N2 adsorption isotherms showed that Si-CuF16Pc has a surface area of approximately 200 m2 g(-1) and a porous diameter of 7.7 nm, characterizing the mesoporosity of this product. This novel material shows an excellent photocatalytic activity, degrading almost 90% of 2,4-dichlorophenoxyacetic acid (2,4-D) up to 30 min, while only approximately 40% of photodegradation was obtained in its absence.
A one-step thermal decomposition method to prepare anatase TiO2 nanosheets with improved adsorption capacities and enhanced photocatalytic activities

NASA Astrophysics Data System (ADS)

Li, Wenting; Shang, Chunli; Li, Xue

2015-12-01

Anatase TiO2 nanosheets (NSs) with high surface area have been prepared via a one-step thermal decomposition of titanium tetraisopropoxide (TTIP) in oleylamine (OM), and their adsorption capacities and photocatalytic activities are investigated by using methylene blue (MB) and methyl orange (MO) as model pollutants. During the synthesis procedure, only one type of surfactant, oleylamine (OM), is used as capping agents and no other solvents are added. Structure and properties of the TiO2 NSs were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption analysis, UV-vis spectrum, X-ray photoelectron spectroscopy (XPS) and Photoluminescence (PL) methods. The results indicate that the TiO2 NSs possess high surface area up to 378 m2 g-1. The concentration of capping agents is found to be a key factor controlling the morphology and crystalline structure of the product. Adsorption and photodegradation experiments reveal that the prepared TiO2 NSs possess high adsorption capacities of model pollutants MB and high photocatalytic activity, showing that TiO2 NSs can be used as efficient pollutant adsorbents and photocatalytic degradation catalysts of MB in wastewater treatment.
Hydroquinone and Quinone-Grafted Porous Carbons for Highly Selective CO2 Capture from Flue Gases and Natural Gas Upgrading.

PubMed

Wang, Jun; Krishna, Rajamani; Yang, Jiangfeng; Deng, Shuguang

2015-08-04

Hydroquinone and quinone functional groups were grafted onto a hierarchical porous carbon framework via the Friedel-Crafts reaction to develop more efficient adsorbents for the selective capture and removal of carbon dioxide from flue gases and natural gas. The oxygen-doped porous carbons were characterized with scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. CO2, CH4, and N2 adsorption isotherms were measured and correlated with the Langmuir model. An ideal adsorbed solution theory (IAST) selectivity for the CO2/N2 separation of 26.5 (298 K, 1 atm) was obtained on the hydroquinone-grafted carbon, which is 58.7% higher than that of the pristine porous carbon, and a CO2/CH4 selectivity value of 4.6 (298 K, 1 atm) was obtained on the quinone-grafted carbon (OAC-2), which represents a 28.4% improvement over the pristine porous carbon. The highest CO2 adsorption capacity on the oxygen-doped carbon adsorbents is 3.46 mmol g(-1) at 298 K and 1 atm. In addition, transient breakthrough simulations for CO2/CH4/N2 mixture separation were conducted to demonstrate the good separation performance of the oxygen-doped carbons in fixed bed adsorbers. Combining excellent adsorption separation properties and low heats of adsorption, the oxygen-doped carbons developed in this work appear to be very promising for flue gas treatment and natural gas upgrading.
Radioactive Cobalt(II) Removal from Aqueous Solutions Using a Reusable Nanocomposite: Kinetic, Isotherms, and Mechanistic Study

PubMed Central

Wang, Ximing; Chen, Zhangjing

2017-01-01

A lignocellulose/montmorillonite (LMT) nanocomposite was prepared as a reusable adsorbent for cobalt(II) ions, and characterized by nitrogen (N2) adsorption/desorption isotherm, X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscopy (TEM), and Fourier Transform Infrared Spectroscopy (FTIR). LMT exhibited efficient adsorption of cobalt ions (Co(II)), and the adsorbed Co(II) was readily desorbed by nitric acid (HNO3). All parameters affecting the adsorption and/or desorption of Co(II), including initial Co(II) concentration, pH value, temperature, HNO3 concentration, and time, were optimized. The kinetic data analysis showed that the adsorption followed the pseudo-second-order kinetic model and fit well into the Langmuir isotherm equation. Notably, the nanocomposite can be used four times without significantly losing adsorbent capability. The Energy-Dispersive X-ray (EDX) and FTIR spectra analysis also revealed that the adsorption mechanism may be mainly a chemical adsorption dominated process. PMID:29186794
Adsorption of aqueous Cd(II) and Pb(II) on activated carbon nanopores prepared by chemical activation of doum palm shell.

PubMed

Gaya, Umar Ibrahim; Otene, Emmanuel; Abdullah, Abdul Halim

2015-01-01

Non-uniformly sized activated carbons were derived from doum palm shell, a new precursor, by carbonization in air and activation using KOH, NaOH and ZnCl2. The activated carbon fibres were characterised by X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, particle size analysis and evaluated for Cd(II) and Pb(II) removal. The 40-50 nm size, less graphitic, mesoporous NaOH activated carbon yielded high adsorption efficiency, pointing largely to the influence surface area. The performance of the KOH based activated carbon was arguably explained for the first time in terms of crystallinity. The efficiencies of the mesoporous ZnCl2-formulated activated carbon diminished due to the presence of larger particles. Batch adsorption of divalent metals revealed dependence on adsorbent dose, agitation time, pH and adsorbate concentrations with high adsorption efficiencies at optimum operating parameters. The equilibrium profiles fitted Langmuir and Freundlich isotherms, and kinetics favoured pseudo-second order model. The study demonstrated the practicability of the removal of alarming levels of cadmium and lead ions from industrial effluents.
o-Vanillin functionalized mesoporous silica – coated magnetite nanoparticles for efficient removal of Pb(II) from water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Culita, Daniela C., E-mail: danaculita@yahoo.co.uk; Simonescu, Claudia Maria; Patescu, Rodica-Elena

2016-06-15

o-Vanillin functionalized mesoporous silica – coated magnetite (Fe{sub 3}O{sub 4}@MCM-41-N-oVan) was synthesized and fully characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, N{sub 2} adsorption–desorption technique and magnetic measurements. The capacity of Fe{sub 3}O{sub 4}@MCM-41-N-oVan to adsorb Pb(II) from aqueous solutions was evaluated in comparison with raw mesoporous silica – coated magnetite (Fe{sub 3}O{sub 4}@MCM-41) and amino – modified mesoporous silica coated magnetite (Fe{sub 3}O{sub 4}@MCM-41-NH{sub 2}). The effect of adsorption process parameters such us pH, contact time, initial Pb(II) concentration was also investigated. The adsorption data were successfully fitted with the Langmuir model, exhibiting a maximummore » adsorption capacity of 155.71 mg/g at pH=4.4 and T=298 K. The results revealed that the adsorption rate was very high at the beginning of the adsorption process, 80–90% of the total amount of Pb(II) being removed within the first 60 min, depending on the initial concentration. The results of the present work suggest that Fe{sub 3}O{sub 4}@MCM-41-N-oVan is a suitable candidate for the separation of Pb(II) from contaminated water. - Graphical abstract: A novel magnetic adsorbent based on o-vanillin functionalized mesoporous silica – coated magnetite was synthesized and fully characterized and its adsorption capacity for Pb(II) ions in aqueous solutions was evaluated. The maximum adsorption capacity for Pb(II) ions was determined to be 155.71 mg g{sup −1}. The adsorption rate was very high at the beginning of the adsorption process, 90% of the total amount of Pb(II) being removed within the first 60 min. Display Omitted.« less
Overcoming double-step CO2 adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg2(dobpdc)† †Electronic supplementary information (ESI) available: Additional experimental details, and full characterization (powder X-ray diffraction, infrared spectra, diamine loadings, dry N2 decomposition profiles, and CO2 adsorption data) for all new adsorbents. CCDC 1577354. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04266c

PubMed Central

Milner, Phillip J.; Martell, Jeffrey D.; Siegelman, Rebecca L.; Gygi, David; Weston, Simon C.

2017-01-01

Alkyldiamine-functionalized variants of the metal–organic framework Mg2(dobpdc) (dobpdc4– = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) are promising for CO2 capture applications owing to their unique step-shaped CO2 adsorption profiles resulting from the cooperative formation of ammonium carbamate chains. Primary,secondary (1°,2°) alkylethylenediamine-appended variants are of particular interest because of their low CO2 step pressures (≤1 mbar at 40 °C), minimal adsorption/desorption hysteresis, and high thermal stability. Herein, we demonstrate that further increasing the size of the alkyl group on the secondary amine affords enhanced stability against diamine volatilization, but also leads to surprising two-step CO2 adsorption/desorption profiles. This two-step behavior likely results from steric interactions between ammonium carbamate chains induced by the asymmetrical hexagonal pores of Mg2(dobpdc) and leads to decreased CO2 working capacities and increased water co-adsorption under humid conditions. To minimize these unfavorable steric interactions, we targeted diamine-appended variants of the isoreticularly expanded framework Mg2(dotpdc) (dotpdc4– = 4,4′′-dioxido-[1,1′:4′,1′′-terphenyl]-3,3′′-dicarboxylate), reported here for the first time, and the previously reported isomeric framework Mg-IRMOF-74-II or Mg2(pc-dobpdc) (pc-dobpdc4– = 3,3′-dioxidobiphenyl-4,4′-dicarboxylate, pc = para-carboxylate), which, in contrast to Mg2(dobpdc), possesses uniformally hexagonal pores. By minimizing the steric interactions between ammonium carbamate chains, these frameworks enable a single CO2 adsorption/desorption step in all cases, as well as decreased water co-adsorption and increased stability to diamine loss. Functionalization of Mg2(pc-dobpdc) with large diamines such as N-(n-heptyl)ethylenediamine results in optimal adsorption behavior, highlighting the advantage of tuning both the pore shape and the diamine size for the development of new adsorbents for carbon capture applications. PMID:29629084
Adsorption kinetics of NO on ordered mesoporous carbon (OMC) and cerium-containing OMC (Ce-OMC)

NASA Astrophysics Data System (ADS)

Chen, Jinghuan; Cao, Feifei; Chen, Songze; Ni, Mingjiang; Gao, Xiang; Cen, Kefa

2014-10-01

Ordered mesoporous carbon (OMC) and cerium-containing OMC (Ce-OMC) were prepared using evaporation-induced self-assembly (EISA) method and used to adsorb NO. N2 sorption, X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to confirm their structures. The results showed that the ordered and uniform structures were successfully synthesized and with the introduction of cerium pore properties were not significantly changed. The NO adsorption capacity of OMC was two times larger than that of activated carbon (AC). With the introduction of cerium both the adsorption capacity and the adsorption rate were improved. The effects of residence time and oxygen concentration on NO adsorption were also investigated. Oxygen played an important role in the NO adsorption (especially in the form of chemisorption) and residence time had small influence on the NO adsorption capacity. The NO adsorption kinetics was analyzed using pseudo-first-order, pseudo-second-order, Elovich equation and intraparticle diffusion models. The results indicated that the NO adsorption process can be divided into rapid adsorption period, slow adsorption period, and equilibrium adsorption period. The pseudo-second-order model was the most suitable model for NO adsorption on OMC and Ce-OMC. The rate controlling step was the intraparticle diffusion together with the adsorption reaction.
Wastewater remediation by TiO2-impregnated chitosan nano-grafts exhibited dual functionality: High adsorptivity and solar-assisted self-cleaning.

PubMed

Essawy, Amr A; Sayyah, S M; El-Nggar, A M

2017-08-01

This work provides a very infrequent and unique avenue of a novel bio-based nanografted polymeric composites achieving encouraging results in green management of dye contaminants in wastewater. A chitosan-grafted-polyN-Methylaniline (Ch-g-PNMANI) and chitosan-grafted-polyN-Methylaniline imprinted TiO 2 nanocomposites (Ch-g-PNMANI/TiO 2 ) were prepared and efficiently applied in wastewater remediation. The nanocomposites were characterized by FT-IR spectroscopy, X-ray diffraction, transmission electron microscopy, UV-Vis diffuse reflectance spectroscopy and Brunauer-Emmett-Teller surface area (BET) measurements. The prepared composites exhibit higher adsorptivity in removing remazol red RB-133 (RR RB-133) dye compared to other adsorbents reported in literature. The effects of TiO 2 loadings, initial dye concentration, contact time, and pH on dye adsorption were investigated. The maximum adsorption of dye was found at low pH values. Furthermore, Ch-g-PNMANI/TiO 2 of the optimum TiO 2 loading has higher adsorption capacity (116.3mg/g) than the pristine Ch-g-PNMANI (108.7mg/g). Moreover, the prepared adsorbents are photoactive under sunlight-irradiation. The study addresses a nanocomposite of considerable adsorption and in the same time has the fastest self-cleaning photoactivity (t 1/2 =31.5min.) under sunlight irradiation where a plausible photodegradation mechanism was proposed. Interestingly, the presented photoactive adsorbents are still effective in removing dye after five adsorption/sunlight-assisted self-cleaning photoregeneration cycles and therefore, they can be potentially applied to the rapid, "green" and low-cost remediation of RR RB-133 enriched industrial printing and dyeing wastewater. Copyright © 2017 Elsevier B.V. All rights reserved.
Fabrication of carbon/SiO2 composites from the hydrothermal carbonization process of polysaccharide and their adsorption performance.

PubMed

Li, Yinhui; Li, Kunyu; Su, Min; Ren, Yanmei; Li, Ying; Chen, Jianxin; Li, Liang

2016-11-20

In this work, carbon/SiO2 composites, using amylose and tetraethyl orthosilicate (TEOS) as raw materials, were successfully prepared by a facial hydrothermal carbonization process. The carbon/SiO2 composites were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Energy Dispersive Spectroscopy (EDS), transmission electron microscope (TEM), N2 adsorption and Thermogravimetric (TG) analysis. The composites, which were made up of amorphous SiO2 and amorphous carbon, were found to have hierarchical porous structures. The mass ratios of amylose and SiO2 and the hydrothermal carbonization time had significant effects on the morphology of the composites, which had three shapes including monodispersed spheres, porous pieces and the nano-fibers combined with nano-spheres structures. The adsorption performance of the composites was studied using Pb(2+) as simulated contaminants from water. When the mass ratio of amylose and SiO2 was 9/1, the hydrothermal time was 30h and the hydrothermal temperature was 180°C, the adsorption capacity of the composites achieved to 52mg/g. Experimental data show that adsorption kinetics of the carbon/SiO2 composites can be fitted well by the Elovich model, while the isothermal data can be perfectly described by the Langmuir adsorption model and Freundlich adsorption model. The maximum adsorption capacity of the carbon/SiO2 composites is 56.18mgg(-1). Copyright © 2016 Elsevier Ltd. All rights reserved.
Selective adsorption of thiophenic compounds from fuel over TiO2/SiO2 under UV-irradiation.

PubMed

Miao, Guang; Ye, Feiyan; Wu, Luoming; Ren, Xiaoling; Xiao, Jing; Li, Zhong; Wang, Haihui

2015-12-30

This study investigates selective adsorption of thiophenic compounds from fuel over TiO2/SiO2 under UV-irradiation. The TiO2/SiO2 adsorbents were prepared and then characterized by N2 adsorption, X-ray diffraction and X-ray photoelectron spectroscopy. Adsorption isotherms, selectivity and kinetics of TiO2/SiO2 were measured in a UV built-in batch reactor. It was concluded that (a) with the employment of UV-irradiation, high organosulfur uptake of 5.12 mg/g was achieved on the optimized 0.3TiO2/0.7SiO2 adsorbent at low sulfur concentration of 15 ppmw-S, and its adsorption selectivity over naphthalene was up to 325.5; (b) highly dispersed TiO2 served as the photocatalytic sites for DBT oxidation, while SiO2 acted as the selective adsorption sites for the corresponding oxidized DBT using TiO2 as a promoter, the two types of active sites worked cooperatively to achieve the high adsorption selectivity of TiO2/SiO2; (c) The kinetic rate-determining step for the UV photocatalysis-assisted adsorptive desulfurization (PADS) over TiO2/SiO2 was DBT oxidation; (d) consecutive adsorption-regeneration cycles suggested that the 0.3TiO2/0.7SiO2 adsorbent can be regenerated by acetonitrile washing followed with oxidative air treatment. This work demonstrated an effective PADS approach to greatly enhance adsorption capacity and selectivity of thiophenic compounds at low concentrations for deep desulfurization under ambient conditions. Copyright © 2015 Elsevier B.V. All rights reserved.
Effect of pH and Electrolytes on Adsorption of 2,4-D onto Kaolinite

NASA Astrophysics Data System (ADS)

Sharma, A.; Kawamoto, K.; Komatsu, T.; Moldrup, P.

2006-12-01

The fate and transport of pesticides in soil can be greatly influenced by adsorption onto clay minerals such as kaolinite. The ionic pesticide 2,4-D (2,4-dichlorophenoxyacetic acid) is one of the most commonly used herbicides. The purpose of this study is to investigate the effect of electrolytes and pH on the adsorption of 2,4- D onto kaolinite. The adsorption coefficient (Kd) of 2,4-D on two types of kaolinite was measured in batch experiments using water and 4 different electrolytes (0.005M CaSO4, 0.005M CaCl2, 0.01M KCl, and 0.01M NaCl). The experiments were carried out with 0.5 g kaolinite at a solid:liquid ratio of 1:20 and at different pH (1.9-6.3). The pH of the solution was controlled by addition of 0.2N of HCl. X-ray diffraction analysis of both kaolinite with and without adsorbed 2,4-D was also done to understand the location of 2,4-D adsorption. The effects of pH and electrolytes on Kd were compared and possible adsorption mechanisms were revealed for 2,4-D adsorption onto the two different types of kaolinite. The results implied that 2,4-D adsorption was higher for an electrolyte solution with monovalent cation than with divalent cation for one type of kaolinite, while no such trend was observed for the other kaolinite. The adsorption of 2,4-D increased significantly with decreasing pH for both types of kaolinite.
Gas adsorption/separation properties of metal directed self-assembly of two coordination polymers with 5-nitroisophthalate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arıcı, Mürsel; Yeşilel, Okan Zafer, E-mail: yesilel@ogu.edu.tr; Keskin, Seda

2014-02-15

Two new coordination polymers, namely, [Co(µ-nip)(µ-bpe)]{sub n} (1) and [Zn(µ-nip)(µ-bpe)]{sub n} (2) (nip: 5-nitroisophthalate, bpe: 1,2-bis(4-pyridyl)ethane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermal analysis. Moreover, atomically detailed simulation studies of complex 2 for CO{sub 2}/CH{sub 4} adsorption and separation were performed. Complex 1 consists of two dimensional (2D) (4,4) grid networks with the point symbol of 4{sup 4}.6{sup 2}. Complex 2 exhibits a 3-fold interpenetrating 3D framework with 6{sup 5}.8-dmp topology. Thermal properties of the complexes showed that both complexes were stable over 320 °C. Simulation studies demonstrated that complexmore » 2 can separate CO{sub 2} from CH{sub 4} at low pressures at 273 K. - Graphical abstract: In this study, two new coordination polymers, namely, [Co(µ-nip)(µ-bpe)]{sub n} (1) and [Zn(µ-nip)(µ-bpe)]{sub n} (2) (nip: 5-nitroisophthalate, bpe: 1,2-bis(4-pyridyl)ethane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermal analysis. Moreover, atomically detailed simulation studies of complex 2 for CO{sub 2}/CH{sub 4} adsorption and separation were performed. Complex 1 consists of two dimensional (2D) (4,4) grid networks with the point symbol of 4{sup 4}.6{sup 2}. Complex 2 exhibits a 3-fold interpenetrating 3D framework with 6{sup 5}.8-dmp topology. Simulation studies demonstrated that complex 2 can separate CO{sub 2} from CH{sub 4} at low pressures at 273 K. Display Omitted - Highlights: • Two new coordination polymers with 5-nitroisophthalate and 1,2-bis(4-pyridyl)ethane. • Atomically detailed simulation studies of the complexes. • Complex 2 can be proposed as molecular sieve to separate CO{sub 2} from CH{sub 4} at low pressures.« less
Effect of pH on the adsorption and photocatalytic degradation of sulfadimidine in Vis/g-C3N4 progress.

PubMed

Yang, Bin; Mao, Xuhui; Pi, Liu; Wu, Yixiao; Ding, Huijun; Zhang, Weihao

2017-03-01

In this study, g-C 3 N 4 was synthesized by thermal polycondensation of melamine and was characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, UV-visible diffuse reflection spectroscopy, and scanning electron microscopy. Results showed that g-C 3 N 4 degraded sulfadimidine (SMD) under visible light, in which the adsorption and photocatalytic degradation was influenced by pH. The maximum adsorption capacity was achieved at approximately pH 5. The highest degradation rate constant was obtained at strong acid and alkali. In addition, the degradation mechanism of g-C 3 N 4 was evaluated with the help of quencher agents. The intermediates, degradation pathways, and mineralization of SMD were also determined to evaluate the degradation and oxidation ability of g-C 3 N 4 .
Development of TRPN dendrimer-modified disordered mesoporous silica for CO{sub 2} capture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiaoyun; Zhang, Sisi; Qin, Hongyan

2014-08-15

Highlights: • A novel series of TRPN dendrimers are synthesized. • Structurally disordered mesoporous silica was used to develop the CO{sub 2} adsorbent. • The CO{sub 2} adsorption capacity is relatively high. • The sorbent exhibits a high stability after 12 cycling runs. • The sorbent achieves complete desorption at low temperature (60 °C). - Abstract: A novel series of tri(3-aminopropyl) amine (TRPN) dendrimers were synthesized and impregnated on structurally disordered mesoporous silica (DMS) to generate CO{sub 2} adsorbents (TS). The physicochemical and adsorption properties of the adsorbents before and after dendrimer modification were characterized by X-ray diffraction (XRD), thermogravimetricmore » analysis (TGA), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and N{sub 2} adsorption–desorption (N{sub 2}-BET) techniques. CO{sub 2} adsorption–desorption tests indicated that the sorbent demonstrates high CO{sub 2} adsorption capacity (138.1 mg g{sup −1} for G1 sample TS-G1-3CN-50 and 91.7 mg g{sup −1} for G2 sample TS-G2-6CN-50), and can completely desorb CO{sub 2} under vacuum at 60 °C. Its CO{sub 2} adsorption capacity at 25 °C increases with the amine loading, achieving the highest adsorption capacity (140.6 mg g{sup −1} for TS-G1-3CN) at 60%. The developed TS materials exhibited excellent cycling stability. After 12 consecutive adsorption–desorption runs, TS-G1-3CN-50 shows an adsorption capacity of 136.0 mg g{sup −1}, retaining 98.5% of its original value.« less
Adsorption of Cd2+ ions on plant mediated SnO2 nanoparticles

NASA Astrophysics Data System (ADS)

Haq, Sirajul; Rehman, Wajid; Waseem, Muhammad; Shahid, Muhammad; Mahfooz-ur-Rehman; Hussain Shah, Khizar; Nawaz, Mohsan

2016-10-01

Plant mediated SnO2 nanoparticles were synthesized by using SnCl4.5H2O as a precursor material. The nanoparticles were then characterized for BET surface area measurements, energy dispersive x-rays (EDX), scanning electron microscopy (SEM), UV-vis diffuse reflectance (DRS) spectra and x-rays diffraction (XRD) analysis. The successful synthesis of SnO2 nanoparticles was confirmed by EDX analysis. The particle sizes were in the range 19-27 nm whereas the crystallite size computed from XRD measurement was found to be 19.9 nm. Batch adsorption technique was employed for the removal of Cd2+ ions from aqueous solution. The sorption studies of Cd2+ ions were performed at pHs 4 and 6. The equilibrium concentration of Cd2+ ions was determined by atomic absorption spectrometer (flame mode). The uptake of Cd2+ ions was affected by initial concentration, pH and temperature of the electrolytic solution. It was observed that the adsorption of Cd2+ ions enhanced with increase in the initial concentration of Cd2+ ions whereas a decrease in the percent adsorption was detected. From the thermodynamic parameters, the adsorption process was found spontaneous and endothermic in nature. The n values confirmed 2:1 exchange mechanism between surface protons and Cd2+ ions.
Structural characterization of framework–gas interactions in the metal–organic framework Co2(dobdc) by in situ single-crystal X-ray diffraction† †Electronic supplementary information (ESI) available: Supplementary figures, crystallographic information, adsorption isotherms and fits, CCDC 1530119–1530126. For ESI and crystallographic data in CIF or other electronic format. See DOI: 10.1039/c7sc00449d Click here for additional data file. Click here for additional data file.

PubMed Central

Gonzalez, Miguel I.; Mason, Jarad A.; Bloch, Eric D.; Teat, Simon J.; Gagnon, Kevin J.; Morrison, Gregory Y.; Queen, Wendy L.

2017-01-01

The crystallographic characterization of framework–guest interactions in metal–organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH4, N2, O2, Ar, and P4 adsorption in Co2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate), a metal–organic framework bearing coordinatively unsaturated cobalt(ii) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(ii) sites in the framework that no analogous molecular structures exist, demonstrating the utility of metal–organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co–CH4 and Co–Ar interactions observed in Co2(dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal–CH4 interaction and the first crystallographically characterized metal–Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(ii) sites in Co2(dobdc), with differential enthalpies of adsorption as weak as –17(1) kJ mol–1 (for Ar). Moreover, the structures of Co2(dobdc)·3.8N2, Co2(dobdc)·5.9O2, and Co2(dobdc)·2.0Ar reveal the location of secondary (N2, O2, and Ar) and tertiary (O2) binding sites in Co2(dobdc), while high-pressure CO2, CO, CH4, N2, and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures. PMID:28966783
Adsorption of caffeine on mesoporous activated carbon fibers prepared from pineapple plant leaves.

PubMed

Beltrame, Karla K; Cazetta, André L; de Souza, Patrícia S C; Spessato, Lucas; Silva, Taís L; Almeida, Vitor C

2018-01-01

The present work reports the preparation of activated carbon fibers (ACFs) from pineapple plant leaves, and its application on caffeine (CFN) removal from aqueous solution. The preparation procedure was carried out using the H 3 PO 4 as activating agent and slow pyrolysis under N 2 atmosphere. The characterization of materials was performed from the N 2 adsorption and desorption isotherms, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy, Boehm titration and pH pzc method. ACFs showed high BET surface area value (S BET = 1031m 2 g -1 ), well-developed mesoporous structure (mesopore volume of 1.27cm³ g -1 ) and pores with average diameter (D M ) of 5.87nm. Additionally, ACFs showed features of fibrous material with predominance of acid groups on its surface. Adsorption studies indicated that the pseudo-second order kinetic and Langmuir isotherm models were that best fitted to the experimental data. The monolayer adsorption capacity was found to be 155.50mgg -1 . thermodynamic studies revealed that adsorption process is spontaneous, exothermic and occurs preferably via physisorption. The pineapple leaves are an efficient precursor for preparation of ACFs, which were successful applied as adsorbent material for removal of caffeine from the aqueous solutions. Copyright © 2017 Elsevier Inc. All rights reserved.

Improving adsorption and activation of the lipase immobilized in amino-functionalized ordered mesoporous SBA-15

NASA Astrophysics Data System (ADS)

Xu, Yun-qiang; Zhou, Guo-wei; Wu, Cui-cui; Li, Tian-duo; Song, Hong-bin

2011-05-01

Ordered mesoporous SBA-15 was prepared by hydrothermal process and was functionalized with(3-aminopropyl) triethoxysilane (APTES) by post-synthesis-grafting method. The materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive spectrometer (EDS), small-angle X-ray powder diffraction (SAXRD), N 2 adsorption-desorption and Fourier transform infrared spectroscopy (FT-IR). The results indicated that SBA-15 had a 2-dimensional hexagonal p6 mm mesoscopic structure and the mesoscopic structure was remained after the functionalization procedure. The activities of porcine pancreatic lipase (PPL) immobilized in SBA-15 by physical adsorption and in APTES functionalized SBA-15 by chemical adsorption were studied by hydrolysis of triacetin. Chemically adsorbed PPL showed higher loading amount and catalytic activity comparing with physically adsorbed PPL. The stability of immobilized PPL against thermal and pH of reaction medium was significantly improved. Recycling experiments showed that chemically adsorbed PPL exhibited better reusability than physically adsorbed PPL.
Adsorption isotherm studies of chromium (VI) from aqueous solutions using sol-gel hydrotalcite-like compounds.

PubMed

Ramos-Ramírez, Esthela; Ortega, Norma L Gutiérrez; Soto, Cesar A Contreras; Gutiérrez, Maria T Olguín

2009-12-30

In under-developed countries, industries such as paint and pigment manufacturing, leather tanning, chrome plating and textile processing, usually discharge effluents containing Cr(VI) and Cr(III) into municipal sanitary sewers. It has been reported that Cr(VI) acts as a powerful epithelial irritant and as a human carcinogen. In the present work, hydrotalcite-like compounds with a Mg/Al ratio=2 were synthesized by the sol-gel method. The hydrotalcite-like compounds and their corresponding thermally treated products were characterized by powder X-ray diffraction, infrared spectroscopy and N(2) adsorption. The hydrotalcite-like compounds and the heated solids were used as adsorbents for Cr(VI) in aqueous solutions. Adsorption isotherm studies of Cr(VI) from aqueous solution are described. The adsorbent capacity was determined using the Langmuir, Freundlich and Dubinin-Radushkevich adsorption isotherm models. The Cr(VI) adsorption isotherm data fit best to the Langmuir isotherm model. The maximum Cr(VI) uptake by hydrotalcite and the heated solids was determined using the Langmuir equation and was found to range between 26 and 29 mg Cr(VI)/g adsorbent.
Synthesis of magnetic ordered mesoporous carbon (Fe-OMC) adsorbent and its evaluation for fuel desulfurization

NASA Astrophysics Data System (ADS)

Farzin Nejad, N.; Shams, E.; Amini, M. K.

2015-09-01

In this work, magnetic ordered mesoporous carbon adsorbent was synthesized using soft templating method to adsorb sulfur from model oil (dibenzothiophene in n-hexane). Through this research, pluronic F-127, resorcinol-formaldehyde and hydrated iron nitrate were respectively used as soft template, carbon source and iron source. The adsorbent was characterized by X-ray diffraction, nitrogen adsorption-desorption isotherm and transmission electron microscopy. Nitrogen adsorption-desorption measurement revealed the high surface area (810 m2 g-1), maxima pore size of 3.3 nm and large pore volume (1.01 cm3 g-1) of the synthesized sample. The adsorbent showed a maximum adsorption capacity of 111 mg dibenzothiophene g-1 of adsorbent. Sorption process was described by the pseudo-second-order rate equation and could be better fitted by the Freundlich model, showing the heterogeneous feature of the adsorption process. In addition, the adsorption capacity of regenerated adsorbent was 78.6% of the initial level, after five regeneration cycles.
Mg-MOF-74@SBA-15 hybrids: Synthesis, characterization, and adsorption properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chakraborty, Anindita; Maji, Tapas Kumar, E-mail: tmaji@jncasr.ac.in

2014-12-01

Nanocrystals of Mg-MOF-74 have been immobilized into the mesopores of SBA-15 rods to fabricate Mg-MOF-74@SBA-15 hybrid materials. To furnish such composites, a relatively simple synthetic strategy has been adopted by direct dispersion of the metal-organic framework (MOF) precursors in SBA-15 matrix to prepare the hybrid materials in situ. The hybrid materials have been characterized using powder X-ray diffraction and several spectroscopic and microscopic techniques, which suggest growth of the MOF nanocrystals inside the SBA-15 mesopores and the composites exhibit characteristics of both the components. N{sub 2} adsorption isotherms at 77 K reveal that the composites contain additional mesopores, compared tomore » only micropores of pristine MOF nanocrystals. In addition to such combination of both micro and mesoporosity, the composites also demonstrate significant CO{sub 2} adsorption at room temperature.« less
Photocatalytic enhancement of floating photocatalyst: Layer-by-layer hybrid carbonized chitosan and Fe-N- codoped TiO2 on fly ash cenospheres

NASA Astrophysics Data System (ADS)

Song, Jingke; Wang, Xuejiang; Bu, Yunjie; Wang, Xin; Zhang, Jing; Huang, Jiayu; Ma, RongRong; Zhao, Jianfu

2017-01-01

Due to the advantage of floating on water surface, floating photocatalysts show higher rates of radical formation and collection efficiencies. And they were expected to be used for solar remediation of non-stirred and non-oxygenated reservoirs. In this research, floating fly ash cenospheres (FAC) supported layer-by- layer hybrid carbonized chitosan and Fe-N-codoped TiO2 was prepared by a simple sol-gel method. The catalysts were characterized by X-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy(DRS), nitrogen adsorption analyses for Brunauer-Emmett-Teller (BET) specific surface area. It is indicated that Fe-N codoped narrowed the material's band gap, and the layer of carbonized chitosan (Cts) increased the catalyst's adsorption capacity and the absorption ability of visible light. Comparing with Fe-N-TiO2/FAC and N-TiO2/FAC, the composite photocatalyst show excellent performance on the degradation of RhB. Photodegradation rate of RhB by Fe-N-TiO2/FAC-Cts was 0.01018 min-1, which is about 1.5 and 2.09 times higher than Fe-N-TiO2/FAC and N-TiO2/FAC under visible light irradiation in 240 min, respectively. The dye photosentization, capture of holes and electrons by Fe3+ ion, and synergistic effect of adsorption and photodegradation were attributed to the results for the improvement of photocatalytic performance. The floating photocatalyst can be reused for at least three consecutive times without any significant decrease on the degradation of Rhodamin B after each reuse.
Paraquat adsorption on NaX and Al-MCM-41.

PubMed

Rongchapo, Wina; Deekamwong, Krittanun; Loiha, Sirinuch; Prayoonpokarach, Sanchai; Wittayakun, Jatuporn

2015-01-01

The aim of this work is to determine paraquat adsorption capacity of zeolite NaX and Al-MCM-41. All adsorbents were synthesized by hydrothermal method using rice husk silica. For Al-MCM-41, aluminum (Al) was added to the synthesis gel of MCM-41 with Al content of 10, 15, 20 and 25 wt%. The faujasite framework type of NaX and mesoporous characteristic of Al-MCM-41 were confirmed by X-ray diffraction. Surface area of all adsorbents determined by N2 adsorption-desorption analysis was higher than 650 m2/g. Al content and geometry were determined by X-ray fluorescence and 27Al nuclear magnetic resonance, respectively. Morphology of Al-MCM-41 were studied by transmission electron microscopy; macropores and defects were observed. The paraquat adsorption experiments were conducted using a concentration range of 80-720 mg/L for NaX and 80-560 mg/L for Al-MCM-41. The paraquat adsorption isotherms from all adsorbents fit well with the Langmuir model. The adsorption capacity of NaX was 120 mg/g-adsorbent. Regarding Al-MCM-41, the 10% Al-MCM-41 exhibited the lowest capacity of 52 mg/g-adsorbent while the other samples had adsorption capacity of 66 mg/g-adsorbent.
Synthesis, characterization and study of arsenate adsorption from aqueous solution by {alpha}- and {delta}-phase manganese dioxide nanoadsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Mandeep; Thanh, Dong Nguyen, E-mail: Dong.Nguyen.Thanh@vscht.c; Ulbrich, Pavel

2010-12-15

Single-phase {alpha}-MnO{sub 2} nanorods and {delta}-MnO{sub 2} nano-fiber clumps were synthesized using manganese pentahydrate in an aqueous solution. These nanomaterials were characterized using the Transmission Electron Microscope (TEM), Field Emission Scanning Electron Microscope (FE-SEM), Powder X-ray diffraction (XRD) and the Brunauer-Elmet-Teller nitrogen adsorption technique (BET-N{sub 2} adsorption). The structural analysis shows that {alpha}-MnO{sub 2} (2x2 tunnel structure) has the form of needle-shaped nanorods and {delta}-MnO{sub 2} (2D-layered structure) consists of fine needle-like fibers arranged in ball-like aggregates. Batch adsorption experiments were carried out to determine the effect of pH on adsorption kinetics and adsorption capacity for the removal of As(V)more » from aqueous solution onto these two types of nanoadsorbents. The adsorption capacity of As(V) was found to be highly pH dependent. The adsorption of As(V) onto {alpha}-MnO{sub 2} reached equilibrium more rapidly with higher adsorption capacity compared to {delta}-MnO{sub 2}. -- Graphical abstract: {alpha}-MnO{sub 2} (2x2 tunnel structure) nanorods and {delta}-MnO{sub 2} (2-D layered structure) nano-fiber clumps were synthesized in a facile way in an aqueous solution and characterized by TEM, FE-SEM, XRD and BET-N{sub 2} adsorption techniques. The structural analysis shows that {alpha}-MnO{sub 2} is needle shaped nanorods and {delta}-MnO{sub 2} consists of 2-D platelets of fine needle-like fibers arranged in ball-like aggregates. Further batch experiments confirmed that both nanoadsorbents are potential candidates for the adsorption of As(V) with a capacity of 19.41 and 15.33 mg g{sup -1} for {alpha}-MnO{sub 2} and {delta}-MnO{sub 2}, respectively. The presence of As3d peak in XPS study indicates that arsenic on the surface of nanoadsorbents is in the stable form of As(V) with a percentage of arsenate onto {alpha}-MnO{sub 2} is 0.099% as compared to 0.021% onto {delta}-MnO{sub 2}, clearly indicating the higher adsorption of As(V) in case of {alpha}-MnO{sub 2} as compared to {delta}-MnO{sub 2}, which is in good agreement with the adsorption studies results. Display Omitted« less
MgO-based adsorbents for CO2 adsorption: Influence of structural and textural properties on the CO2 adsorption performance.

PubMed

Elvira, Gutiérrez-Bonilla; Francisco, Granados-Correa; Víctor, Sánchez-Mendieta; Alberto, Morales-Luckie Raúl

2017-07-01

A series of MgO-based adsorbents were prepared through solution-combustion synthesis and ball-milling process. The prepared MgO-based powders were characterized using X-ray diffraction, scanning electron microscopy, N 2 physisorption measurements, and employed as potential adsorbents for CO 2 adsorption. The influence of structural and textural properties of these adsorbents over the CO 2 adsorption behaviour was also investigated. The results showed that MgO-based products prepared by solution-combustion and ball-milling processes, were highly porous, fluffy, nanocrystalline structures in nature, which are unique physico-chemical properties that significantly contribute to enhance their CO 2 adsorption. It was found that the MgO synthesized by solution combustion process, using a molar ratio of urea to magnesium nitrate (2:1), and treated by ball-milling during 2.5hr (MgO-BM2.5h), exhibited the maximum CO 2 adsorption capacity of 1.611mmol/g at 25°C and 1atm, mainly via chemisorption. The CO 2 adsorption behaviour on the MgO-based adsorbents was correlated to their improved specific surface area, total pore volume, pore size distribution and crystallinity. The reusability of synthesized MgO-BM2.5h was confirmed by five consecutive CO 2 adsorption-desorption times, without any significant loss of performance, that supports the potential of MgO-based adsorbent. The results confirmed that the special features of MgO prepared by solution-combustion and treated by ball-milling during 2.5hr are favorable to be used as effective MgO-based adsorbent in post-combustion CO 2 capture technologies. Copyright © 2016. Published by Elsevier B.V.
A controlled release of ibuprofen by systematically tailoring the morphology of mesoporous silica materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu Fengyu; Chemistry and Pharmaceutical College, Jiamusi University, Jiamusi 154007; Zhu Guangshan

2006-07-15

A series of mesoporous silica materials with similar pore sizes, different morphologies and variable pore geometries were prepared systematically. In order to control drug release, ibuprofen was employed as a model drug and the influence of morphology and pore geometry of mesoporous silica on drug release profiles was extensively studied. The mesoporous silica and drug-loaded samples were characterized by X-ray diffraction, Fourier transform IR spectroscopy, N{sub 2} adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. It was found that the drug-loading amount was directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drugmore » release profiles could be controlled by tailoring the morphologies of mesoporous silica carriers. - Graphical abstract: The release of ibuprofen is controlled by tailoring the morphologies of mesoporous silica. The mesoporous silica and drug-loaded samples are characterized by powder X-ray diffraction, Fourier transform IR spectroscopy, N{sub 2} adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. The drug-loading amount is directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drug release profiles can be controlled by tailoring the morphologies of mesoporous silica carriers.« less
Ammonia-evaporation-induced construction of three-dimensional NiO/g-C3N4 composite with enhanced adsorption and visible light-driven photocatalytic performance

NASA Astrophysics Data System (ADS)

Tzvetkov, George; Tsvetkov, Martin; Spassov, Tony

2018-07-01

Novel visible light-driven heterostructured NiO/g-C3N4 photocatalyst has been designed and successfully prepared via ammonia-evaporation-induced method. The synthetic strategy consists of grafting the surface of g-C3N4 with Ni(NH3)62+ complex followed by its hydrolysis at lower pH to form nano-wrinkled thin film of α-Ni(OH)2. The final NiO/g-C3N4 hybrid was obtained after calcination of the Ni(OH)2/g-C3N4 precursor at 350 °C. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, FTIR, N2 adsorption/desorption, UV-vis diffuse reflectance and photoluminescence spectroscopy were used to characterize the resulting material. Our results revealed the formation of meso-/macroporous three-dimensional hierarchical honeycomb-like structure with high BET surface area (141 m2 g-1). The photocatalytic performance of the composite under visible light (λ > 400 nm) irradiation was evaluated through degradation of Malachite Green (MG) from aqueous medium at room temperature (25 °C). For the sake of comparison, the physico-chemical and photocatalytic properties of the pristine g-C3N4 and nanostructured NiO were also examined. Results indicated that NiO/g-C3N4 is much more active than pristine g-C3N4 and NiO in the photodegradation of MG. The enhanced photocatalytic performance of the composite was mainly attributed to the combination of high adsorption capacity which facilitates the direct redox reactions of dye and the efficient inhibition of photo-generated electron-hole pair recombination. Superoxide radicals (•O2-) and photo-generated holes (h+) were found to be the main active species in the process.
One-pot synthesis of binary metal organic frameworks (HKUST-1 and UiO-66) for enhanced adsorptive removal of water contaminants.

PubMed

Azhar, Muhammad Rizwan; Abid, Hussein Rasool; Sun, Hongqi; Periasamy, Vijay; Tadé, Moses O; Wang, Shaobin

2017-03-15

In this study, binary metal organic frameworks (MOFs) with HKUST-1 and UiO-66 have been synthesized in a one-pot process. The synthesized MOFs were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), N 2 adsorption, and thermogravimetric analysis (TGA). The meso-porosity and thermal stability of the binary MOFs were higher than those of single HKUST-1 or UiO-66. The synthesized MOF hybrids were then tested for adsorptive removal of methylene blue (MB) from wastewater in terms of kinetic and isothermal adsorption as compared to a commercially available activated carbon (AC). All the synthesized MOFs showed significant removal of MB under a wide range of pH. The adsorption capacities of HKUST-1 are higher than UiO-66 and commercial AC while the binary MOFs presented an even higher adsorption capacity than single MOFs. This is the first time that binary HKUST-1 and UiO-66 MOFs have been successfully synthesized and demonstrated enhanced adsorptive removal of contaminants. Copyright © 2016 Elsevier Inc. All rights reserved.
Aminopropyl-functionalized mesoporous carbon (APTMS-CMK-3) as effective phosphate adsorbent

NASA Astrophysics Data System (ADS)

Yang, Yanju; Wang, Juanjuan; Qian, Xiaoqing; Shan, Yuhua; Zhang, Haipeng

2018-01-01

Excess phosphate discharge into water bodies can lead to severe eutrophication. Adsorption has been considered as one of the most effective approaches for phosphate removal and recovery. A new aminopropyl-functionalized mesoporous carbon CMK-3 (denoted as APTMS-CMK-3) was prepared and the materials were used as adsorbents for the removal of phosphate in water. The structure, functional groups and surface charge of the materials were characterized by X-ray powder diffraction, transmission electron microscope, N2 adsorption-desorption, elemental analysis, Fourier transform infrared spectra, X-ray photoelectron spectroscopy and zeta potential measurements. The effects of contact time, initial phosphate concentration, solution pH, coexisting anions and dissolved humic acid were studied. The adsorption capacity of APTMS-CMK-3 was 38.09 mg g-1 at the equilibrium concentration of 49.06 mg L-1, and the adsorption data were well fitted with the Freundlich model. As for the reuse of APTMS-CMK-3, a relatively stable adsorption performance was observed after five adsorption-desorption cycles. Therefore, the way of grafting aminopropyl groups on the CMK-3 efficiently enhanced the capability for phosphate adsorption, indicating that it could be used as potential adsorbents for the removal of phosphate in water.
Adsorption Studies of Gadolinium ion on Graphitic Carbon Nitride

NASA Astrophysics Data System (ADS)

Kuila, S. K.; Kundu, T. K.

2018-03-01

Bulk graphitic carbon nitride (g-C3N4) is synthesized by thermal decomposition of urea and used as an adsorbent for gadolinium ion (Gd3+) from aqueous solution. Adsorption capacity of g-C3N4 is found to be influenced by initial Gd3+ concentration, solution pH and contact time. Adsorbed Gd3+is separated from g-C3N4 by ultracentrifuge. Initial and Gd ion accumulated g-C3N4 adsorbent are characterized by X-ray diffraction technique (XRD) for phase identification, UV-visible and Fourier transform infrared (FTIR) spectroscopy for adsorption characteristics and optical property, scanning electron microscopy (SEM) for morphological behaviour along with energy dispersive X-ray spectroscopy (EDS) for elemental study. HNO3(0.1M), NaOH (0.1M) and de-ionized water are used for desorption and around 97% quantitative recovery of Gd ion is observed.
Hydroisomerization of n-dodecane over Pt/Al-MCM-48 catalysts.

PubMed

Yun, Soyoung; Park, Young-Kwon; Jeong, Soon-Yong; Han, Jeongsik; Jeon, Jong-Ki

2014-04-01

The objective of this study is to evaluate the catalytic potential of Pt/Al-MCM-48 catalysts in hydroisomerization of n-dodecane. The effects of the Si/Al ratio and platinum loading on the acid characteristics of Al-MCM-48 and the catalytic performance in n-dodecane hydroisomerization were analyzed. The catalysts were characterized by X-ray diffraction, nitrogen adsorption, infrared spectroscopy of pyridine adsorption, and temperature programmed desorption of ammonia. The number of weak strength acid sites on Al-MCM-48 increased with 0.5 wt% platinum loading. The weak strength acid sites of Pt/Al-MCM-48 catalysts were ascribed to Lewis acid sites, which can be confirmed by NH3-TPD and FTIR spectra of pyridine adsorption. Iso-dodecane can be produced with high selectivity in n-dodecane hydrosisomerization over Pt/Al-MCM-48 catalysts. This is attributed to the mild acidic properties of Pt/Al-MCM-48 catalysts.
Characterization of the carbonaceous materials obtained from different agro-industrial wastes.

PubMed

Ensuncho-Muñoz, A E; Carriazo, J G

2015-01-01

This paper reports the preparation and characterization of carbonaceous materials obtained from three types of vegetable wastes provided by agricultural industries. Soft carbonization (280°C) and H3PO4-activation procedures were used to convert the agricultural wastes to carbon powders with high adsorbent capacities. This process is excellent for eliminating and exploiting the huge masses (many tons) of vegetable residues remaining after each harvest every year in several Colombian agro-industries. The powders were characterized by X-ray diffraction (XRD), IR spectroscopy, scanning electron microscopy (SEM), and N2-adsorption isotherms. XRD and IR verified the formation of carbons, and SEM showed small particles (20-500 µm) with characteristic morphology for each type of residue used and abundant cavities of different sizes. The N2-adsorption analyses showed that the carbons had high adsorption capacities with important surface area values and large pore volumes. The use of the activated carbonaceous materials as adsorbent of azo dyes (allura red and sunset yellow) from aqueous solutions was evaluated. The results showed a good adsorption capacity indicating the potentiality of these materials as pollutant adsorbents in food industry wastewaters. These results indicate that these powders can be used as potential adsorbents for different gaseous or liquid pollutants.
Synthesis, characterization and experimental investigation of Cu-BTC as CO2 adsorbent from flue gas.

PubMed

Xie, Jiangkun; Yan, Naiqiang; Qu, Zan; Yang, Shijian

2012-01-01

Porous Cu-BTC material was synthesized by the solvothermal method. Powder X-ray diffraction (PXRD) was used to test the phase purity of the synthesized material and investigate its structural stability under the influence of flue gas components. The thermal stability of the material was determined through thermal gravimetric (TG) analysis. Scanning electron microscopy (SEM) was employed to study the microstructure of the material. Cu-BTC was demonstrated not only to have high CO2 adsorption capacity but also good selectivity of CO2 over N2 by means of packed bed tests. The adsorption capacity of Cu-BTC for CO2 was about 69 mL/g at 22 degrees C. The influence of the main flue gas components on the CO2 capacity of the material were discussed as well.
Fiber optic sensors based on hybrid phenyl-silica xerogel films to detect n-hexane: determination of the isosteric enthalpy of adsorption.

PubMed

Echeverría, Jesús C; Calleja, Ignacio; Moriones, Paula; Garrido, Julián J

2017-01-01

We investigated the response of three fiber optic sensing elements prepared at pH 10 from phenyltriethoxysilane (PhTEOS) and tetraethylsilane (TEOS) mixtures with 30, 40, and 50% PhTEOS in the silicon precursor mixture. The sensing elements are referred to as Ph30, Ph40 and Ph50, respectively. The films were synthesized by the sol-gel method and affixed to the end of optical fibers by the dip-coating technique. Fourier transform infrared spectroscopy, N 2 adsorption-desorption at 77 K and X-ray diffraction analysis were used to characterize the xerogels. At a given pressure of n -hexane, the response of each sensing element decreased with temperature, indicating an exothermic process that confirmed the role of adsorption in the overall performance of the sensing elements. The isosteric adsorption enthalpies were obtained from the calibration curves at different temperatures. The magnitude of the isosteric enthalpy of n -hexane increased with the relative response and reached a plateau that stabilized at approximately -31 kJ mol -1 for Ph40 and Ph50 and at approximately -37 kJ mol -1 for Ph30. This indicates that the adsorbate-adsorbent interaction was dominant at lower relative pressure and condensation of the adsorbate on the mesopores was dominant at higher relative pressure.
Highly efficient removal of chlorotetracycline from aqueous solution using graphene oxide/TiO2 composite: Properties and mechanism

NASA Astrophysics Data System (ADS)

Li, Zhaoqian; Qi, Mengyu; Tu, Chunyan; Wang, Weiping; Chen, Jianrong; Wang, Ai-Jun

2017-12-01

The extensive usage of chlorotetracycline (CTC) has caused the persistence of antibiotic residues in aquatic environments, resulting in serious threat to human health and ecosystems. In this study, graphene oxide/titanium dioxide (GO/TiO2) nanocomposite was successfully synthesized via in situ hydrolysis of tetra-n-butyl titanate (Ti(BuO)4) to TiO2 particles on GO sheets and used as adsorbent for efficient adsorptive removal of CTC from aqueous solution. The prepared GO/TiO2 was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transformed infrared (FT-IR), Raman spectroscopy and X-ray photoelectron (XPS). Adsorption kinetics, isotherms and thermodynamics were systematically investigated to evaluate the adsorption properties of GO/TiO2. Adsorption mechanism was further analyzed by FT-IR, UV-vis and XPS. The results indicated that adsorption kinetics closely followed the pseudo-second order model; the maximum adsorption capacity determined by Langmuir model was 261.10 mg g-1 at 298 K and the thermodynamic studies revealed that the adsorption of CTC onto the GO/TiO2 was a spontaneous and endothermic process. Moreover, the interactions between CTC and GO/TiO2 were presumed to be ligand exchange between CTC and TiO2, while the π-π electron donor-acceptor interaction, hydrogen bond and cation-π bonding were constructed between CTC and GO. Finally, the prepared GO/TiO2 was successfully applied for the efficient removal of CTC from Wu River water.
Adsorbent synthesis of polypyrrole/TiO(2) for effective fluoride removal from aqueous solution for drinking water purification: Adsorbent characterization and adsorption mechanism.

PubMed

Chen, Jie; Shu, Chiajung; Wang, Ning; Feng, Jiangtao; Ma, Hongyu; Yan, Wei

2017-06-01

More than 20 countries are still suffering problems of excessive fluoride containing water, and greater than 8mg/L fluoride groundwater has been reported in some villages in China. In order to meet the challenge in the drinking water defluoridation engineering, a high efficiency and affinity defluoridation adsorbent PPy/TiO 2 composite was designed and synthetized by in-situ chemical oxidative polymerization. Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction Investigator (XRD), X-ray photoelectron spectroscopy (XPS), Thermogravimetric analysis (TG), N 2 isotherm analysis, Scanning Electron Microscopy (SEM) and Zeta potential analysis were conducted to characterize surface and textural properties of the as-prepared PPy/TiO 2 , and the possibility of fluoride adsorption was carefully estimated by adsorption isotherm and kinetic studies. Characterization investigations demonstrate the uniqueness of surface and textural properties, such as suitable specific surface area and abundant positively charged nitrogen atoms (N + ), which indicate the composite is a suitable material for the fluoride adsorption. Adsorption isotherms and kinetics follow better with Langmuir and pseudo-second-order model, respectively. The maximum adsorption capacity reaches 33.178mg/g at 25°C according to Langmuir model, and particular interest was the ability to reduce the concentration of fluoride from 11.678mg/L to 1.5mg/L for drinking water at pH of 7 within 30min. Moreover, the adsorbent can be easily recycled without the loss of adsorption capacity after six cycles, greatly highlighting its outstanding affinity to fluoride, low-cost and novel to be used in the purification of fluoride containing water for drinking. Furthermore, the adsorption mechanism was extensively investigated and discussed by FTIR investigation and batch adsorption studies including effect of pH, surface potential and thermodynamics. The adsorption is confirmed to be a spontaneous and exothermic process with decreasing entropy, which is prominently conducted through electrostatic attraction, and ionic exchange, and chelation may be also involved. Hydroxyls and positively charged nitrogen atoms play important roles in the adsorption. Copyright © 2017 Elsevier Inc. All rights reserved.
Evaluation of synthesis characterization and simulation study of magnetic nanoparticles for ammonia synthesis in MIM

NASA Astrophysics Data System (ADS)

Irfan, Muhammad; Yahya, Noorhana; Shafie, Afza; Soleimani, Hassan; Alqasem, Bilal; Rehman, Zia Ur; Qureshi, Saima

2016-11-01

It is generally understood that magnetic energy is much smaller than thermal energy which dominates the chemical equilibrium. Magnetic nanoparticles (NiO) as catalyst were synthesized by chemical reduction routes following micro emulsion method having an average size of 239 nm and 207.2 nm followed by FESEM and TEM analysis respectively. EDX analysis of nanoparticles (NPs) with 90.80 weight% Ni, 9.20 weight % O2 and 72.90 atomic% Ni, 27.10 atomic% O2 falls it into the category of formation of nickel and oxide NPs. TEM for parallel Ni EELs vs intensity is 840.0 eV to 860.0 eV and 70 to 80 respectively. TEM diffraction and fringe spacing analysis of NPs reveals the details about diffraction planes as (200), (311), (400) and lattice parameter 4.136 nm respectively. Both RAMAN spectroscopy and FTIR spectroscopy analysis of NPs elaborate the consistency between peak intensity and RAMAN shift (cm-1) as 318.74 cm-1, 522.78 cm-1, 620.28 cm-1 and 450 cm-1, 515.84 cm-1and 720.08 cm-1 respectively. The saturation magnetization (Ms) of NiO NPs was measured to be 32.524 emu/g by VSM for a specific mass of 14.1x10-3 g. Simulation study based on DFT in term of catalytic effect related to sorbents and sorbates atomistic, thermodynamic and quantum mechanical interactions including adsorption is illustrated in this article using first principal DFT simulation study. The average total energy, average total adsorption energy, average adsorption energy of H2, and N2 over NiO (111) surface are reported as 4.414 kcal/mol, 4.4145 kcal/mol, -1.671 kcal/mol, and 0.869 kcal/mol respectively. Whereas, isosteric heats of adsorption energies for H2, N2 over NiO (111) cleaved surface were calculated to 1.617kcal/mol, and -0.881 kcal/mol respectively. Ammonia synthesis carried out by MIM and peaks were detected by FTIR and yield was quantified by Kjeldahl method in few thousands μmole gcat-1 h-1.

Preparation, characterization and dye adsorption of Au nanoparticles/ZnAl layered double oxides nanocomposites

NASA Astrophysics Data System (ADS)

Zhang, Yu Xin; Hao, Xiao Dong; Kuang, Min; Zhao, Han; Wen, Zhong Quan

2013-10-01

In this work, Au/ZnAl-layer double oxides (LDO) nanocomposties were prepared through a facile calcination process of AuCl4- intercalated ZnAl-layered double hydroxides (LDHs) nanocomposites. The morphology and crystal structure of these nanocomposites were characterized by Scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), and N2 sorption analysis. By tailoring the process parameter, such as calcination temperature, heating time and the component composition, the adsorption properties of methyl orange (MO) on the Au/ZnAl-LDO nanocomposites were investigated in this work. In a typical adsorption process, it was found that 0.985 mg of MO (0.01 g L-1, 100 mL, 1 mg of MO in total) can be removed in 60 min by utilizing only 2.5 mg of Au/ZnAl-LDO (Au content, 1%) as adsorbents. Our adsorption data obtained from the Langmuir model also gave good values of the determination coefficient, and the saturated adsorption capacity of Au/ZnAl-LDO nanocomposites for MO was found to be 627.51 mg/g under ambient condition (e.g., room temperature, 1 atm). In principle, these hybrid nanostructures with higher adsorption abilities could be very promising adsorbents for wastewater treatment.
Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks.

PubMed

Elsaidi, Sameh K; Mohamed, Mona H; Simon, Cory M; Braun, Efrem; Pham, Tony; Forrest, Katherine A; Xu, Wenqian; Banerjee, Debasis; Space, Brian; Zaworotko, Michael J; Thallapally, Praveen K

2017-03-01

Dynamic and flexible metal-organic frameworks (MOFs) that respond to external stimuli, such as stress, light, heat, and the presence of guest molecules, hold promise for applications in chemical sensing, drug delivery, gas separations, and catalysis. A greater understanding of the relationship between flexible constituents in MOFs and gas adsorption may enable the rational design of MOFs with dynamic moieties and stimuli-responsive behavior. Here, we detail the effect of subtle structural changes upon the gas sorption behavior of two "SIFSIX" pillared square grid frameworks, namely SIFSIX-3-M (M = Ni, Fe). We observe a pronounced inflection in the Xe adsorption isotherm in the Ni variant. With evidence from X-ray diffraction studies, density functional theory, and molecular simulations, we attribute the inflection to a disordered to ordered transition of the rotational configurations of the pyrazine rings induced by sorbate-sorbent interactions. We also address the effect of cage size, temperature, and sorbate on the guest-induced ring rotation and the adsorption isotherms. The absence of an inflection in the Xe adsorption isotherm in SIFSIX-3-Fe and in the Kr, N 2 , and CO 2 adsorption isotherms in SIFSIX-3-Ni suggest that the inflection is highly sensitive to the match between the size of the cage and the guest molecule.
Enhanced adsorption of chromium onto activated carbon by microwave-assisted H(3)PO(4) mixed with Fe/Al/Mn activation.

PubMed

Sun, Yuanyuan; Yue, Qinyan; Mao, Yanpeng; Gao, Baoyu; Gao, Yuan; Huang, Lihui

2014-01-30

FeCl3, AlCl3 and MnCl2 were used as the assisted activation agent in activated carbon preparation by H3PO4 activation using microwave heating method. The physico-chemical properties of activated carbons were investigated by scanning electron microscope (SEM), N2 adsorption/desorption, Boehm's titration, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). To investigate the adsorption performances of chromium onto these newly developed activated carbons, a batch of experiments were performed under different adsorption conditions: solution pH, initial Cr(VI) ion concentration, contact time and co-existing ions. The results suggested that carbon with MnCl2 as assisted activation agent displayed the highest BET surface area (1332m(2)/g) and the highest pore volume (1.060cm(3)/g). FeCl3, AlCl3 and MnCl2 had successfully improved Cr(VI) adsorption and activated carbon with FeCl3 as assisted activation agent exhibited the best uptake capacity. To study the transformation of Cr(VI) in adsorption process, total chromium in the aqueous solution was also recorded. The ratio of the amount of Cr(VI) to Cr(III) on each adsorbent was explained by XPS analysis results. Both the co-existing salts (Na2SO4 and NaNO3) demonstrated promoted effects on Cr(VI) removal by four carbons. The pseudo-second-order model and Freundlich equation displayed a good correlation with adsorption data. Copyright © 2013 Elsevier B.V. All rights reserved.
Water Adsorption in Porous Metal-Organic Frameworks and Related Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Furukawa, H; Gandara, F; Zhang, YB

2014-03-19

Water adsorption in porous materials is important for many applications such as dehumidification, thermal batteries, and delivery of drinking water in remote areas. In this study, we have identified three criteria for achieving high performing porous materials for water adsorption. These criteria deal with condensation pressure of water in the pores, uptake capacity, and recyclability and water stability of the material. In search of an excellently performing porous material, we have studied and compared the water adsorption properties of 23 materials, 20 of which are metal organic frameworks (MOFs). Among the MOFs are 10 zirconium(IV) MOFs with a subset ofmore » these, MOF-801-SC (single crystal form), -802, -805, -806, -808, -812, and -841 reported for the first time. MOF-801-P (microcrystalline powder form) was reported earlier and studied here for its water adsorption properties. MOF-812 was only made and structurally characterized but not examined for water adsorption because it is a byproduct of MOF-841 synthesis. All the new zirconium MOFs are made from the Zr6O4(OH)(4)(-CO2)(n) secondary building units (n = 6, 8, 10, or 12) and variously shaped carboxyl organic linkers to make extended porous frameworks. The permanent porosity of all 23 materials was confirmed and their water adsorption measured to reveal that MOF-801-P and MOF-841 are the highest performers based on the three criteria stated above; they are water stable, do not lose capacity after five adsorption/desorption cycles, and are easily regenerated at room temperature. An X-ray single-crystal study and a powder neutron diffraction study reveal the position of the water adsorption sites in MOF-801 and highlight the importance of the intermolecular interaction between adsorbed water molecules within the pores.« less
Water adsorption in porous metal-organic frameworks and related materials.

PubMed

Furukawa, Hiroyasu; Gándara, Felipe; Zhang, Yue-Biao; Jiang, Juncong; Queen, Wendy L; Hudson, Matthew R; Yaghi, Omar M

2014-03-19

Water adsorption in porous materials is important for many applications such as dehumidification, thermal batteries, and delivery of drinking water in remote areas. In this study, we have identified three criteria for achieving high performing porous materials for water adsorption. These criteria deal with condensation pressure of water in the pores, uptake capacity, and recyclability and water stability of the material. In search of an excellently performing porous material, we have studied and compared the water adsorption properties of 23 materials, 20 of which are metal-organic frameworks (MOFs). Among the MOFs are 10 zirconium(IV) MOFs with a subset of these, MOF-801-SC (single crystal form), -802, -805, -806, -808, -812, and -841 reported for the first time. MOF-801-P (microcrystalline powder form) was reported earlier and studied here for its water adsorption properties. MOF-812 was only made and structurally characterized but not examined for water adsorption because it is a byproduct of MOF-841 synthesis. All the new zirconium MOFs are made from the Zr6O4(OH)4(-CO2)n secondary building units (n = 6, 8, 10, or 12) and variously shaped carboxyl organic linkers to make extended porous frameworks. The permanent porosity of all 23 materials was confirmed and their water adsorption measured to reveal that MOF-801-P and MOF-841 are the highest performers based on the three criteria stated above; they are water stable, do not lose capacity after five adsorption/desorption cycles, and are easily regenerated at room temperature. An X-ray single-crystal study and a powder neutron diffraction study reveal the position of the water adsorption sites in MOF-801 and highlight the importance of the intermolecular interaction between adsorbed water molecules within the pores.
Removal of phosphate from water by amine-functionalized copper ferrite chelated with La(III).

PubMed

Gu, Wei; Li, Xiaodi; Xing, Mingchao; Fang, Wenkan; Wu, Deyi

2018-04-01

Eutrophication has become a worldwide environmental problem and removing phosphorus from water/wastewater before discharge is essential. The purpose of our present study was to develop an efficient material in terms of both phosphate adsorption capacity and magnetic separability. To this end, we first compared the performances of four spinel ferrites, including magnesium, zinc, nickel and copper ferrites. Then we developed a copper ferrite-based novel magnetic adsorbent, by synthesizing 1,6-hexamethylenediamine-functionalized copper ferrite(CuFe 2 O 4 ) via a single solvothermal synthesis process followed by LaCl 3 treatment. The materials were characterized with X-ray diffraction, transmission electron microscope, vibrating sample magnetometer, Fourier transform infrared spectra and N 2 adsorption-desorption. The maximum adsorption capacity of our material, calculated from the Langmuir adsorption isotherm model, attained 32.59mg/g with a saturation magnetization of 31.32emu/g. Data of adsorption kinetics were fitted well to the psuedo-second-order model. Effects of solution pH and coexisting anions (Cl - , NO 3 - , SO 4 2- ) on phosphate adsorption were also investigated, showing that our material had good selectivity for phosphate. But OH - competed efficiently with phosphate for adsorption sites. Furthermore, increasing both NaOH concentration and temperature resulted in an enhancement of desorption efficiency. Thus NaOH solution could be used to desorb phosphate adsorbed on the material for reuse, by adopting a high NaOH concentration and/or a high temperature. Copyright © 2017 Elsevier B.V. All rights reserved.
Structural changes caused by H 2 adsorption on the Si(111)7 × 7 surface

NASA Astrophysics Data System (ADS)

Wolff, S. H.; Wagner, S.; Gibson, J. M.; Loretto, D.; Robinson, I. K.; Bean, J. C.

1990-12-01

Structural changes caused by the adsorption of molecular hydrogen adsorption onto the Si(111)7 × 7 surface reconstruction are quantified using the first structure parameter refinement on transmission electron diffraction (TED) data. We find that initial adsorption of molecular hydrogen onto the Si(111)7 × 7 surface causes a preferential decrease in the occupancy of the center adatoms. Further adsorption of hydrogen results in the breaking of the dimer bonds and the removal of the corner adatoms.
Syntheses, crystal structures, and water adsorption behaviors of jungle-gym-type porous coordination polymers containing nitro moieties

NASA Astrophysics Data System (ADS)

Uemura, Kazuhiro; Onishi, Fumiaki; Yamasaki, Yukari; Kita, Hidetoshi

2009-10-01

NO 2 containing dicarboxylate bridging ligands, nitroterephthalate (bdc-NO 2) and 2,5-dinitroterephthalate (bdc-(NO 2) 2), afford porous coordination polymers, {[Zn 2(bdc-NO 2) 2(dabco)]· solvents} n ( 2⊃ solvents) and {[Zn 2(bdc-(NO 2) 2) 2(dabco)]· solvents} n ( 3⊃ solvents). Both compounds form jungle-gym-type regularities, where a 2D square grid composed of dinuclear Zn 2 units and dicarboxylate ligands is bridged by dabco molecules to extend the 2D layers into a 3D structure. In 2⊃ solvents and 3⊃ solvents, a rectangle pore surrounded by eight Zn 2 corners contains two and four NO 2 moieties, respectively. Thermal gravimetry (TG) and X-ray powder diffraction (XRPD) measurements reveal that both compounds maintain the frameworks regularities without guest molecules and with solvents such as MeOH, EtOH, i-PrOH, and Me 2CO. Adsorption measurements reveal that dried 2 and 3 adsorb H 2O molecules to be {[Zn 2(bdc-NO 2) 2(dabco)]·4H 2O} n ( 2⊃4H 2O) and {[Zn 2(bdc-(NO 2) 2) 2(dabco)]·6H 2O} n ( 3⊃6H 2O), showing the pore hydrophilicity enhancement caused by NO 2 group introduction.
Preparation of iron oxide-impregnated spherical granular activated carbon-carbon composite and its photocatalytic removal of methylene blue in the presence of oxalic acid.

PubMed

Kadirova, Zukhra C; Hojamberdiev, Mirabbos; Katsumata, Ken-Ichi; Isobe, Toshihiro; Matsushita, Nobuhiro; Nakajima, Akira; Sharipov, Khasan; Okada, Kiyoshi

2014-01-01

The spherical granular activated carbon-carbon composites (GAC-Fe) with different iron oxide contents (Fe mass% = 0.6-10) were prepared by a pore volume impregnation method. The X-ray diffraction (XRD), scanning electron microscopy (SEM), and N2-adsorption results confirm the presence of amorphous iron oxide, pyrolytic carbon, and graphitized globular carbon nanoparticles covered with amorphous carbon in the CAG-Fe. The rate of photodegradation of methylene blue (MB) in aqueous solution under UV light in the presence of oxalic acid correlates with porosity of the prepared materials. The total MB removal includes the combination of adsorption and photodegradation without the addition of H2O2. The results of total organic carbon (TOC) analysis reveal that the decolorization of MB in aqueous solution containing oxalic acid corresponds to the decomposition of organic compounds to CO2 and H2O.
Highly efficient and selective adsorption of In{sup 3+} on pristine Zn/Al layered double hydroxide (Zn/Al-LDH) from aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnabas, Mary Jenisha; Parambadath, Surendran; Mathew, Aneesh

2016-01-15

A pristine Zn/Al-layered double hydroxide (Zn/Al-LDH) showed excellent adsorption ability and selectivity towards In{sup 3+} ions from aqueous solutions. The adsorption behaviour as a function of the contact time, solution pH, ionic strength, and amount of adsorbent under ambient conditions revealed a strong dependency on the pH and ionic strength over In{sup 3+} intake. The structure and properties of Zn/Al-LDH and In{sup 3+} adsorbed Zn/Al-LDH (In–Zn/Al-LDH) were examined carefully by X-ray diffraction, Fourier transform infrared spectroscopy, N{sub 2}-sorption/desorption, UV–vis spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent had a sufficient number of active sites that were responsible for the In{sup 3+}more » adsorption and quite stable even after the adsorption process. The selective adsorption of In{sup 3+} on Zn/Al-LDH was also observed even from a mixture containing competing ions, such as Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, and Cu{sup 2+}. The adsorption experiments showed that Zn/Al-LDH is a promising material for the pre-concentration and selective removal of In{sup 3+} from large volumes of aqueous solutions. - Highlights: • A pristine Zn/Al-layered double hydroxide showed good selectivity for In{sup 3+} ions. • The material exhibited a maximum In{sup 3+} intake of 205 mg g{sup −1} at pH 6. • The materials showed good affinity of In{sup 3+} over Cu{sup 2+} and Pb{sup 2+} from ion mixtures.« less
Evidence of Near Surface Layer Stabilization by Liquid Multilayer Adsorbed Films

NASA Astrophysics Data System (ADS)

Strange, Nicholas; Larese, J. Z.

Molecular adsorption on surfaces is fundamentally important in a variety of scientific and technological processes. Surface adsorption plays a key role in catalysis/catalytic supports, optoelectronic devices, lubrication and adhesion, wetting phenomena, and separations. We present the results of a comprehensive investigation of the first ten members of the homologous series of n-alkanes (methane-decane) adsorbed on the basal plane of hexagonal boron nitride using high-resolution, volumetric adsorption isotherm measurements (more than 30 separate temperatures per molecule). The experimentally determined heats of adsorption vs. carbon chain length follow the well-known ``odd-even'' behavior of the n-alkanes. While this may not be surprising we will illustrate additional potential surface configurations that can lead to an increase in entropy. Potential phase transitions are identified using changes in the 2D-compressibility. In addition, we describe the results of companion molecular dynamics modeling to provide microscopic insight to the wetting behavior as a function of alkane chain length and film thickness. A comparison with the behavior of the same n-alkane set on MgO and graphite will also be included. These studies can serve as the basis for developing accurate, robust models of the potential energy surfaces and can be used for future investigations of the microscopic structure and dynamics of these adsorbed films using neutron/xray diffraction and neutron spectroscopy.
Highly selective and efficient removal of lead with magnetic nano-adsorbent: Multivariate optimization, isotherm and thermodynamic studies.

PubMed

Khani, Rouhollah; Sobhani, Sara; Beyki, Mostafa Hossein

2016-03-15

2-Hydroxyethylammonium sulfonate immobilized on γ-Fe2O3 nanoparticles (γ-Fe2O3-2-HEAS) was synthesized by the reaction of n-butylsulfonated γ-Fe2O3 with ethanolamine. The structure of the resulting product was confirmed by fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD) spectrometry, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), elemental analysis, N2 adsorption-desorption and vibrating sample magnetometer (VSM) techniques. The supported ionic liquid on γ-Fe2O3 was applied as a new and green adsorbent to remove Pb(II) from aqueous solution. The effect of adsorption parameters such as pH, shaking time and amount of the adsorbent were investigated using two level three factor (2(3)) full factorial central composite design with the help of Design-Expert, Stat-Ease Inc. version 9.0 software. The significance of independent variables and their interactions were tested by means of the analysis of variance (ANOVA) with 95% confidence limits (α=0.05). The thermodynamic parameters of the adsorption process are estimated. It is found that the process is exothermic and spontaneous. The Langmuir and Freundlich models have been also applied to evaluate the removal efficiency and the data were correlated well with the Freundlich model. Copyright © 2015 Elsevier Inc. All rights reserved.
Removal of ammonium and heavy metals by cost-effective zeolite synthesized from waste quartz sand and calcium fluoride sludge.

PubMed

Zhang, Qian; Lin, Bing; Hong, Junming; Chang, Chang-Tang

2017-02-01

This study focuses on the effectiveness of zeolite (10% CF-Z [0.5]) hydrothermally synthesized from waste quartz sand and calcium fluoride (CF) for ammonium ion and heavy metal removal. Zeolite was characterized through powder X-ray diffraction, Fourier-transform infrared spectroscopy, micromeritics N 2 adsorption/desorption analysis, and field emission scanning electron microscopy. The effects of CF addition, Si/Al ratio, initial ammonium concentration, solution pH, and temperature on the adsorption of ammonium on 10% CF-Z (0.5) were further examined. Results showed that 10% CF-Z (0.5) was a single-phase zeolite A with cubic-shaped crystals and 10% CF-Z (0.5) efficiently adsorbs ammonium and heavy metals. For instance, 91% ammonium (10 mg L -1 ) and 93% lead (10 mg L -1 ) are removed. The adsorption isotherm, kinetics, and thermodynamics of ammonium adsorption on 10% CF-Z (0.5) were also theoretically analyzed. The adsorption isotherm of ammonium and lead on 10% CF-Z (0.5) in single systems indicated that Freundlich model provides the best fit for the equilibrium data, whereas pseudo-second-order model best describes the adsorption kinetics. The adsorption degree of ions on 10% CF-Z (0.5) in mixed systems exhibits the following pattern: lead > ammonium > cadmium > chromium.
Pb(II) removal from water using Fe-coated bamboo charcoal with the assistance of microwaves.

PubMed

Zhang, Zengsheng; Wang, Xuejiang; Wang, Yin; Xia, Siqing; Chen, Ling; Zhang, Yalei; Zhao, Jianfu

2013-05-01

Bamboo charcoal (BC) was used as starting material to prepare iron-modified bamboo charcoal (Fe-MBC) by its impregnation in FeCl3 and HNO3 solutions simultaneously, followed by microwave heating. The material can be used as an adsorbent for Pb(II) contaminants removal in water. The composites were prepared with Fe molar concentration of 0.5, 1.0 and 2.0 mol/L and characterized by means of N2 adsorption-desorption isotherms, X-ray diffraction spectroscopy (XRD), scanning electron microscopy coupled with energy dispersive X-ray spectrometry (SEM-EDS), Fourier transform infrared (FT-IR) and point of zero charge (pH(pzc)) measurements. Nitrogen adsorption analyses showed that the BET specific surface area and total pore volume increased with iron impregnation. The adsorbent with Fe molar concentration of 2 mol/L (2Fe-MBC) exhibited the highest surface area and produced the best pore structure. The Pb(II) adsorption process of 2Fe-MBC and BC were evaluated in batch experiments and 2Fe-MBC showed an excellent adsorption capability for removal Pb(II). The adsorption of Pb(II) strongly depended on solution pH, with maximum values at pH 5.0. The ionic strength had a significant effect on the adsorption at pH < 6.0. The adsorption isotherms followed the Langmuir isotherm model well, and the maximum adsorption capacity for Pb(II) was 200.38 mg/g for 2Fe-MBC. The adsorption processes were well fitted by a pseudo second-order kinetic model. Thermodynamic parameters showed that the adsorption of Pb(II) onto Fe-MBC was feasible, spontaneous, and exothermic under the studied conditions, and the ion exchange mechanism played an significant role. These results have important implications for the design of low-cost and effective adsorbents in the removal of Pb(II) from wastewater.
Reuse of organobentonites with a carbon dioxide responsive solvent.

PubMed

Luan, Ling-Yu; Zhang, Li; Wang, Li-Hong

2018-05-22

Synthesized organobentonite (SOB), montmorillonite (MMT), and commercial organobentonite (COB) were used as adsorbents for paraffin oil, a model pollutant in land-based oil spills and oil pipeline rupture. The characterization of clays was carried out with scanning electron microscopy (SEM), thermogravimetric analysis (TG), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). After adsorption, oil was separated from adsorbents with a carbon dioxide responsive solvent N,N-dimethylcyclohexylamine (DMCHA), and DMCHA was subsequently separated from paraffin oil upon CO 2 bubbling instead of distillation with high energy cost. The adsorption capacity of oil to SOB, MMT, and COB was 0.686, 1.124, and 1.239 g/g, respectively. It was found that the adsorption capacity and rinsed amount of the adsorbents depended on the d-spacing, which is related to surfactant content. Electrical conductivity and pH measurements suggested that the separation process occurred via two steps. Firstly, during the initial 35 min, carbonate ions coexisted with bicarbonate ions. Then, only bicarbonate ions existed after the introduction of CO 2 gas for 120 min. Thus, organobentonites were feasible for hydrocarbon adsorption and could be simply reused by an amine-based responsive solvent. This work provided a cost-effective and sustainable method of recycling of organobentonites and the responsive solvent, which can be used to deal with leaked oil and oil spills.
Mercury(II) removal from aqueous solutions and wastewaters using a novel cation exchanger derived from coconut coir pith and its recovery.

PubMed

Anirudhan, T S; Divya, L; Ramachandran, M

2008-09-15

A new adsorbent (PGCP-COOH) having carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto coconut coir pith, CP (a coir industry-based lignocellulosic residue), using potassium peroxydisulphate as an initiator and in the presence of N,N'-methylenebisacrylamide as a cross-linking agent. The adsorbent was characterized with the help of infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, and potentiometric titrations. The ability of PGCP-COOH to remove Hg(II) from aqueous solutions was assessed using batch adsorption technique under kinetic and equilibrium conditions. Adsorbent exhibits very high adsorption potential for Hg(II) and more than 99.0% removal was achieved in the pH range 5.5-8.0. Adsorption process was found to follow first-order-reversible kinetics. An increase of ionic strength of the medium caused a decrease in metal removal, indicating the occurrence of outer-sphere surface complex mechanism. The equilibrium data were fitted well by the Freundlich isotherm model (R(2)=0.99; chi(2)=1.81). The removal efficiency was tested using chlor-alkali industry wastewater. Adsorption isotherm experiments were also conducted for comparison using a commercial carboxylate-functionalized ion exchanger, Ceralite IRC-50. Regeneration experiments were tried for four cycles and results indicate a capacity loss of <9.0%.
Fabrication of N, P-codoped reduced graphene oxide and its application for organic dye removal

NASA Astrophysics Data System (ADS)

Wu, Yu; Yang, Feng; Liu, Xiaoxia; Tan, Guangqun; Xiao, Dan

2018-03-01

N, P-codoped reduced graphene oxide (PA-RGO) was synthesized from graphene oxide (GO) and phytic acid (PA) mixture with the reductant of hydrazine hydrate (N2H4) via one-pot solution method. PA can modify the surface of RGO to enhance the hydrophilicity of RGO, and supply anionic functional groups, which can complex with cationic dye via anion-cation interaction. PA-RGO with different amount doped PA were used to remove multiple organic dyes from aqueous solution. The adsorption properties of the PA-RGO-2.0 towards Rhodamine B (RhB) were investigated under various parameters such as different pH of initial solution, different dosage of the PA-RGO-2.0, shaking speed and temperature. To study structural and chemical characterization of PA-RGO-2.0, Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscope (AFM), X-ray photoelectron and spectroscopy (XPS) were used, and UV-vis spectrum was used to monitor the absorbance of adsorbate. The batch adsorption experiments of RhB on PA-RGO-2.0 showed that the RhB equilibrium capacity was about 149 mg/g. In addition, the adsorption process was well-matched with the pseudo-second-order rate model. The as-prepared composites were found to be highly selective for cationic organic dyes. The good reusability of PA-RGO indicated that the adsorbent possessed potential practical application.
A high surface area Zr(IV)-based metal–organic framework showing stepwise gas adsorption and selective dye uptake

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lv, Xiu-Liang; Tong, Minman; Huang, Hongliang

2015-03-15

Exploitation of new metal–organic framework (MOF) materials with high surface areas has been attracting great attention in related research communities due to their broad potential applications. In this work, a new Zr(IV)-based MOF, [Zr{sub 6}O{sub 4}(OH){sub 4}(eddb){sub 6}] (BUT-30, H{sub 2}eddb=4,4′-(ethyne-1,2-diyl)dibenzoic acid) has been solvothermally synthesized, characterized, and explored for gases and dyes adsorptions. Single-crystal X-ray diffraction analysis demonstrates a three-dimensional cubic framework structure of this MOF, in which each Zr{sub 6}O{sub 4}(OH){sub 4} building unit is linked by 12 linear eddb ligands. BUT-30 has been found stable up to 400 °C and has a Brunauer–Emmett–Teller (BET) surface area asmore » high as 3940.6 m{sup 2} g{sup −1} (based on the N{sub 2} adsorption at 77 K) and total pore volume of 1.55 cm{sup 3} g{sup −1}. It is more interesting that this MOF exhibits stepwise adsorption behaviors for Ar, N{sub 2}, and CO{sub 2} at low temperatures, and selective uptakes towards different ionic dyes. - Graphical abstract: A new Zr(IV)-based MOF with high surface area has been synthesized and structurally characterized, which shows stepwise gas adsorption at low temperature and selective dye uptake from solution. - Highlights: • A new Zr-based MOF was synthesized and structurally characterized. • This MOF shows a higher surface area compared with its analogous UiO-67 and 68. • This MOF shows a rare stepwise adsorption towards light gases at low temperature. • This MOF performs selective uptakes towards cationic dyes over anionic ones. • Using triple-bond spacer is confirmed feasible in enhancing MOF surface areas.« less
Postsynthetic Functionalization of Mg-MOF-74 with Tetraethylenepentamine: Structural Characterization and Enhanced CO2 Adsorption.

PubMed

Su, Xiao; Bromberg, Lev; Martis, Vladimir; Simeon, Fritz; Huq, Ashfia; Hatton, T Alan

2017-03-29

Postsynthetic functionalization of magnesium 2,5-dihydroxyterephthalate (Mg-MOF-74) with tetraethylenepentamine (TEPA) resulted in improved CO 2 adsorption performance under dry and humid conditions. XPS, elemental analysis, and neutron powder diffraction studies indicated that TEPA was incorporated throughout the MOF particle, although it coordinated preferentially with the unsaturated metal sites located in the immediate proximity to the surface. Neutron and X-ray powder diffraction analyses showed that the MOF structure was preserved after amine incorporation, with slight changes in the lattice parameters. The adsorption capacity of the functionalized amino-Mg-MOF-74 (TEPA-MOF) for CO 2 was as high as 26.9 wt % versus 23.4 wt % for the original MOF due to the extra binding sites provided by the multiunit amines. The degree of functionalization with the amines was found to be important in enhancing CO 2 adsorption, as the optimal surface coverage improved performance and stability under both pure CO 2 and CO 2 /H 2 O coadsorption, and with partially saturated surface coverage, optimal CO 2 capacity could be achieved under both wet and dry conditions by a synergistic binding of CO 2 to the amines as well as metal centers.
A facile approach to prepare porous cup-stacked carbon nanotube with high performance in adsorption of methylene blue.

PubMed

Gong, Jiang; Liu, Jie; Jiang, Zhiwei; Wen, Xin; Mijowska, Ewa; Tang, Tao; Chen, Xuecheng

2015-05-01

Novel porous cup-stacked carbon nanotube (P-CSCNT) with special stacked morphology consisting of many truncated conical graphene layers was synthesized by KOH activating CSCNT from polypropylene. The morphology, microstructure, textural property, phase structure, surface element composition and thermal stability of P-CSCNT were investigated by field-emission scanning electron microscope, transmission electron microscope (TEM), high-resolution TEM, N2 sorption, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and thermal gravimetric analysis. A part of oblique graphitic layers were etched by KOH, and many holes with a diameter of several to a doze of nanometers connecting inner tube with outside were formed, which endowed P-CSCNT with high specific surface area (558.7 m(2)/g), large pore volume (1.993 cm(3)/g) and abundant surface functional groups. Subsequently, P-CSCNT was used for adsorption of methylene blue (MB) from wastewater. Langmuir model closely fitted the adsorption results, and the maximum adsorption capacity of P-CSCNT was as high as 319.1mg/g. This was ascribed to multiple adsorption mechanisms including pore filling, hydrogen bonding, π-π and electrostatic interactions. Pseudo second-order kinetic model was more valid to describe the adsorption behavior. Besides, P-CSCNT showed good recyclablity and reusability. These results demonstrated that P-CSCNT had potential application in wastewater treatment. Copyright © 2015 Elsevier Inc. All rights reserved.

Enhancing gas adsorption and separation capacity through ligand functionalization of microporous metal-organic framework structures.

PubMed

Zhao, Yonggang; Wu, Haohan; Emge, Thomas J; Gong, Qihan; Nijem, Nour; Chabal, Yves J; Kong, Lingzhu; Langreth, David C; Liu, Hui; Zeng, Heping; Li, Jing

2011-04-26

Hydroxyl- and amino- functionalized [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O leads to two new structures, [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O (BDC=terephthalic acid, TED=triethylenediamine, BDC-OH=2-hydroxylterephthalic acid, BDC-NH(2)=2-aminoterephthalic acid). Single-crystal X-ray diffraction and powder X-ray diffraction studies confirmed that the structures of both functionalized compounds are very similar to that of their parent structure. Compound [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O can be considered a 3D porous structure with three interlacing 1D channels, whereas both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O contain only 1D open channels as a result of functionalization of the BDC ligand by the OH and NH(2) groups. A notable decrease in surface area and pore size is thus observed in both compounds. Consequently, [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O takes up the highest amount of H(2) at low temperatures. Interestingly, however, both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O show significant enhancement in CO(2) uptake at room temperature, suggesting that the strong interactions between CO(2) and the functionalized ligands, indicating that surface chemistry, rather than porosity, plays a more important role in CO(2) adsorption. A comparison of single-component CO(2), CH(4), CO, N(2), and O(2) adsorption isotherms demonstrates that the adsorption selectivity of CO(2) over other small gases is considerably enhanced through functionalization of the frameworks. Infrared absorption spectroscopic measurements and theoretical calculations are also carried out to assess the effect of functional groups on CO(2) and H(2) adsorption potentials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Grafted chromium 13-membered dioxo-macrocyclic complex into aminopropyl-based nanoporous SBA-15

NASA Astrophysics Data System (ADS)

Tarlani, Aliakbar; Joharian, Monika; Narimani, Khashayar; Muzart, Jacques; Fallah, Mahtab

2013-07-01

In a new approach, chromium (III) tetraaza dioxo ligand was grafted onto functionalized SBA-15 after four step reactions by using coordinating ability of anchored amino functionalized SBA-15. After the termination of each step, the obtained product was characterized by FT-IR, low-angle X-ray diffraction (LA-XRD), N2 adsorption-desorption isotherms (Brunauer-Emmett-Teller (BET)-Barret-Joyner-Halenda (BJH)) and thermogravimetric analysis (TGA), and used as catalyst for the efficient and regioselective alcoholysis of styrene oxide to 2-alkoxy-1-phenylethanol product at ambient temperature.
Preparation and enhanced daylight-induced photocatalytic activity of C,N,S-tridoped titanium dioxide powders.

PubMed

Zhou, Minghua; Yu, Jiaguo

2008-04-15

A simple method for preparing highly daylight-induced photoactive nanocrystalline C,N,S-tridoped TiO2 powders was developed by a solid-phase reaction. The as-prepared TiO2 powders were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra, N2 adsorption-desorption measurements and transmission electron microscopy (TEM). The photocatalytic activity was evaluated by the photocatalytic oxidation of formaldehyde under daylight irradiation in air. The results show that daylight-induced photocatalytic activities of the as-prepared TiO2 powders were improved by C,N,S-tridoping. The C,N,S-tridoped TiO2 powders exhibited stronger absorption in the near UV and visible-light region with red shift in the band-gap transition. When the molar ratio of CS(NH2)2 to xerogel TiO2 powders (prepared by hydrolysis of Ti(OC4H9)4 in distilled water) (R) was kept in 3, the daylight-induced photocatalytic activities of the as-prepared C,N,S-tridoped TiO2 powders were about more than six times greater than that of Degussa P25 and un-doped TiO2 powders. The high activities of the C,N,S-tridoped TiO2 can be attributed to the results of the synergetic effects of strong absorption in the near UV and visible-light region, red shift in adsorption edge and two phase structures of un-doped TiO2 and C,N,S-tridoped TiO2.
Ionic liquid-assisted sonochemical preparation of CeO 2 nanoparticles for CO oxidation

DOE PAGES

Alammar, Tarek; Noei, Heshmat; Wang, Yuemin; ...

2014-10-10

CeO 2 nanoparticles were synthesized via a one-step ultrasound synthesis in different kinds of ionic liquids based on bis(trifluoromethanesulfonylamide, [Tf 2N] –, in combination with various cations including 1-butyl-3-methylimidazolium ([C 4mim] +), 1-ethyl-2,3-dimethylimidazolium ([Edimim] +), butyl-pyridinium([Py 4] +), 1-butyl-1-methyl-pyrrolidinium ([Pyrr 14] +), and 2-hydroxyethyl-trimethylammonium ([N 1112OH] +). Depending on synthetic parameters, such as ionic liquid, Ce(IV) precursor, heating method, and precipitator, formed ceria exhibits different morphologies, varying from nanospheres, nanorods, nanoribbons, and nanoflowers. The morphology, crystallinity, and chemical composition of the obtained materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive X-raymore » spectroscopy (EDX), Raman spectroscopy, and N2 adsorption. The structural and electronic properties of the as-prepared CeO 2 samples were probed by CO adsorption using IR spectroscopy under ultrahigh vacuum conditions. The catalytic activities of CeO 2 nanoparticles were investigated in the oxidation of CO. CeO 2 nanospheres obtained sonochemically in [C 4mim][Tf 2N] exhibit the best performance for low-temperature CO oxidation. As a result, the superior catalytic performance of this material can be related to its mesoporous structure, small particle size, large surface area, and high number of surface oxygen vacancy sites.« less
Ultrasound-assisted preparation of a nanostructured zinc(II) amine pillar metal-organic framework as a potential sorbent for 2,4-dichlorophenol adsorption from aqueous solution.

PubMed

Abazari, Reza; Salehi, Ghazal; Mahjoub, Ali Reza

2018-09-01

Using a green and simple route with ultrasound illumination under atmospheric pressure and at room temperature, the nanosized preparation of a Zn(II) metal-organic framework, [Zn(ATA)(BPD)] ∞ (ATA = 2-aminoterephthalic acid), BPD = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene), having nano-plate shape and 3D channel framework, was considered and the product was named as compound 1. The X-ray diffraction (XRD), scanning electron microscopy (SEM), IR spectroscopy, Brunauer-Emmett-Teller (BET), and thermogravimetric analysis (TGA) were used for characterization of the synthesized micro/nano-structures. Further, impact of different sonication times and initial reagent contents on the shape and size of the micro/nano-structures was investigated. The results show that under ultrasound irradiation non-aggregated plates with uniform morphology can be obtained with content of [0.0125] M of the initial reagents in the presence of triethylamine (TEA) at 120 min. Moreover, through N 2 adsorption, effect of the preparation route on the porosity was explored. The bulk and nano-plates of compound 1 were also studied for adsorption of 2,4-dichlorophenol as a pollutant sample. Kinetic studies indicated that 2,4-dichlorophenol adsorption via MOF nano-plates are of first-order kinetics. Also, MOF nano-plates have significantly been reutilized for five times while their adsorption properties have remained unchanged. Copyright © 2018 Elsevier B.V. All rights reserved.
Evaluation of nitrate and phosphate adsorption on Al-modified biochar: Influence of Al content.

PubMed

Yin, Qianqian; Ren, Huaipu; Wang, Ruikun; Zhao, Zhenghui

2018-08-01

Biochars with different Al contents (i.e., 5, 10, 15, and 20 wt%) were prepared to evaluate their adsorption capacities for nitrate (NO 3 - ) and phosphate (PO 4 3- ) from eutrophic water. Several techniques, including N 2 adsorption-desorption, X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectrometry, were applied to characterize the physical-chemical properties of the biochars. We found that the NO 3 - and PO 4 3- adsorptions significantly improved on the Al-modified biochars because of their multifunctional and surface charge properties. In single-solute adsorption, 15 Al/BC and 20 Al/BC exhibited optimal NO 3 - and PO 4 3- adsorption capacities, respectively. In bi-solute coadsorption, the PO 4 3- adsorption on the biochar was less affected with the coexistence of NO 3 - , whereas the coexistence of PO 4 3- had a significant impact on the NO 3 - adsorption. The optimal solution pH for NO 3 - adsorption was 6, and pH < 6 was advantageous to PO 4 3- adsorption. In the kinetic study, the pseudo-second-order model could describe the NO 3 - and PO 4 3- adsorptions on biochar well, indicating that chemical adsorption was the main adsorption mechanism. The Langmuir-Freundlich model agreed well with the NO 3 - and PO 4 3- adsorptions on the biochars, and the maximum adsorption capacities for NO 3 - and PO 4 3- reached 89.58 mg/g and 57.49 mg/g, respectively. Therefore, the Al-modified biochar was a good choice for the remediation of eutrophic water. Copyright © 2018 Elsevier B.V. All rights reserved.
A combined experimental and theoretical study on ethanol conversion to propylene over Y/ZrO2 catalyst

NASA Astrophysics Data System (ADS)

Wang, Fangfang; Xia, Wei; Mu, Xichuan; Chen, Kun; Si, Huimin; Li, Zhihao

2018-05-01

ZrO2-based catalysts doped with Y were prepared by co-precipitation method. The effect of yttrium modification on the selective conversion of bio-ethanol to propylene over ZrO2 catalysts was investigated. The physical and chemical properties of the catalysts were characterized by N2 adsorption-desorption method, temperature programmed desorption and X-ray diffraction. The maximum yield of propylene reached 44.0% over 0.03Y/ZrO2 catalyst. A coordination of acid-base properties accounts for the remarkable improvement of reaction activities over Y-doped ZrO2 catalysts in this investigation. On the basis of calculation results, it can be concluded that significant charge transfer occurs as a result of introduction of Y or O-vacancy. The adsorption of ethanol and propylene on perfect t-ZrO2 (1 0 1), defect t-ZrO2 (1 0 1) and Y/ZrO2 (1 0 1) surfaces were investigated with density functional theory (DFT). The adsorption for ethanol on Y/ZrO2 (1 0 1) and defect t-ZrO2 (1 0 1) surfaces are more stable than that on perfect t-ZrO2 (1 0 1). On the defect t-ZrO2 (1 0 1) surface, ethanol dominantly absorbs at the O-vacancy site, indicating that O-vacancy becomes the favorable adsorption site. On the Y/ZrO2 (1 0 1) and defect t-ZrO2 (1 0 1) surfaces, the adsorption energy of propylene decreases, which makes propylene desorb quickly after formation.
SeO2 adsorption on CaO surface: DFT and experimental study on the adsorption of multiple SeO2 molecules

NASA Astrophysics Data System (ADS)

Fan, Yaming; Zhuo, Yuqun; Li, Liangliang

2017-10-01

SeO2 adsorption mechanisms on CaO surface were firstly investigated by both density functional theory (DFT) calculations and adsorption experiments. Adsorption of multiple SeO2 on the CaO (001) surface was investigated using slab model. Based on the results of adsorption energy and surface property, a double-layer adsorption mechanisms were proposed. In experiments, the SeO2 adsorption products were prepared in a U-shaped quartz reactor at 200 °C. The surface morphology was investigated by field emission scanning electron microscopy (FE-SEM). The superficial and total SeO2 mass fractions were measured by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES), respectively. The surface valence state and bulk structure are determined by XPS and X-Ray Diffraction (XRD). The experimental results are in good agreement with the DFT results. In conclusion, the fundamental SeO2 chemisorption mechanisms on CaO surface were suggested.
Adsorptive removal of selected pharmaceuticals by mesoporous silica SBA-15.

PubMed

Bui, Tung Xuan; Choi, Heechul

2009-09-15

The removal of five selected pharmaceuticals, viz., carbamazepine, clofibric acid, diclofenac, ibuprofen, and ketoprofen was examined by batch sorption experiments onto a synthesized mesoporous silica SBA-15. SBA-15 was synthesized and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N(2) adsorption-desorption measurement, and point of zero charge (PZC) measurement. Pharmaceutical adsorption kinetics was rapid and occurred on a scale of minutes, following a pseudo-second-order rate expression. Adsorption isotherms were best fitted by the Freundlich isotherm model. High removal rates of individual pharmaceuticals were achieved in acidic media (pH 3-5) and reached 85.2% for carbamazepine, 88.3% for diclofenac, 93.0% for ibuprofen, 94.3% for ketoprofen, and 49.0% for clofibric acid at pH 3 but decreased with increase in pH. SBA-15 also showed high efficiency for removal of a mixture of 5 pharmaceuticals. Except for clofibric acid (35.6%), the removal of pharmaceuticals in the mixture ranged from 75.2 to 89.3%. Based on adsorption and desorption results, the mechanism of the selected pharmaceuticals was found to be a hydrophilic interaction, providing valuable information for further studies to design materials for the purpose. The results of this study suggest that mesoporous-silica-based materials are promising adsorbents for removing pharmaceuticals from not only surface water but also wastewater of pharmaceutical industrial manufactures.
Photodegradation of methyl red under visible light by mesoporous carbon nitride

NASA Astrophysics Data System (ADS)

Hu, Yueyue; Zhang, Min; Xiao, Zaozao; Jiang, Tao; Yan, Bing; Li, Jian

2018-02-01

Mesoporous carbon nitride (mpg-C3N4) with tunable microstructure has been successfully prepared through a simple polymerization reaction of cyanamide by a nano hard-templating approach. The obtained materials have been characterized using X-ray diffraction (XRD), N2 adsorption, and Fourier transform infrared (FT-IR) spectroscopy. The results show that the pore diameter of the mpg-C3N4 materials can be easily tuned from 3.8 to 10.5 nm. The mpg-C3N4 materials are demonstrated to exhibit much higher visible light photocatalytic activity than that of g-C3N4 for the degradation of aqueous methyl red (MR). The high surface areas and large pore volume contributed to the efficient visible light photocatalytic activity.
Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution.

PubMed

Lei, Di; Zheng, Qianwen; Wang, Yili; Wang, Hongjie

2015-02-01

A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH2-Mn-SBA-15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganese-loaded SBA-15 (Mn-SBA-15) and used as a Cu2+ adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N2 adsorption/desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH2-Mn-SBA-15. The ordered mesoporous structure of SBA-15 was remained after modification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu2+ on NH2-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH2-Mn-SBA-15 for Cu2+ was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu2+ by NH2-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu2+. The NH2-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption-desorption experiments showed that the NH2-Mn-SBA-15 could be regenerated by acid treatment without altering its properties. Copyright © 2014. Published by Elsevier B.V.
Surface sodium lignosulphonate-immobilized sawdust particle as an efficient adsorbent for capturing Hg2+ from aqueous solution.

PubMed

Gao, Shan; Luo, Tiantian; Zhou, Qi; Luo, Wenjun; Li, Haifeng; Jing, Luru

2018-05-01

In this work, the soluble sodium lignosulphonate (LS Na ) molecules were successfully grafted onto the surface of pine sawdust (PSD) particles to obtain an efficient adsorbent (PSD-LS) for removing Hg 2+ from wastewater. In advance, the surface of sawdust particles were carboxymethylated by chloroacetic acid, the LS Na would be anchored on the surface by a heterogeneous esterification reaction occurred between the hydroxyl of LS Na and carboxyl on PSD surface. The resultant product (PSD-LS) exhibited a good adsorption performance for Hg 2+ with adsorption capacity up to 164.77 mg/g and it was characterized by scanning electron microscope (SEM), energy dispersive X-ray diffraction (EDX), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The effects of pH, contact time, adsorption temperature and initial concentration on the adsorption of Hg 2+ were investigated. Results showed that the pseudo-second-order kinetics and Langmuir isotherm model could describe the adsorption process better. In addition, the composite adsorbent has outstanding reusability with high and stable desorption rates under several continuous cycle. These findings suggested that PSD-LS was a potential adsorbent to remove hazardous metal ions from wastewater. Copyright © 2018 Elsevier Inc. All rights reserved.
Adsorption of Pb2+ ions on novel ternary nanocomposite of tin, iron and titania

NASA Astrophysics Data System (ADS)

Rehman, Mahfooz ur; Rehman, Wajid; Waseem, Muhammad; Haq, Sirajul; Hussain Shah, Khizar; Kang, Peng

2018-02-01

In this study, ternary nanocomposite (TNC) was synthesized by microemulsion method by taking Sn, Ti and Fe in (1:1:1) molar ratio. The BET surface area and pore size were measured by nitrogen adsorption method. The morphological features of TNC like particle size, elemental percentage and crystallite size were studied by scanning electron microscopy (SEM), energy dispersive x-rays (EDX) and x-rays diffraction (XRD) respectively, whereas the surface functional groups were detected by Fourier Transform Infrared (FTIR) spectroscopy. The crystallite size was found to be 11 nm, calculated from FWHM of diffraction peak with relative intensity 100%. For the thermal stability of TNC, thermogravimetric analysis (TGA) was performed. Batch adsorption tests were used for the removal of Pb2+ ions from aqueous solutions. The maximum adsorption capacity in this study was found to be 79.56 mg g-1 at 40 °C which is promising than the values reported in the literature. Based on the regression coefficient (r 2), the adsorption data was found well fitted to the Langmuir as compared to Freundlich model. The exchange of a single proton with every Pb2+ ion was calculated. Thermodynamic parameters were indicative for the sorption process to be endothermic and spontaneous.
Synthesis of nano-TiO2/diatomite composite and its photocatalytic degradation of gaseous formaldehyde

NASA Astrophysics Data System (ADS)

Zhang, Guangxin; Sun, Zhiming; Duan, Yongwei; Ma, Ruixin; Zheng, Shuilin

2017-08-01

The TiO2/diatomite composite was synthesized through a mild hydrolysis of titanyl sulfate. The prepared composite was characterized by X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis diffused reflectance spectroscopy. The results demonstrate that the anatase TiO2 nanopartilces anchored on the surface of diatomite with Ti-O-Si bonds between diatomite and TiO2. The photodegradation of gaseous formaldehyde under UV irradiation by the TiO2/diatomite composite was studied under various operating conditions, including relative humidity, illumination intensity and catalyst amount, which have significant influence on the degradation process. The TiO2/diatomite composite exhibited better photocatalytic activity than pure TiO2, which could be attributed to the favorable nanoparticles dispersibility and strong formaldehyde adsorption capacity. In addition, the composite exhibited outstanding reusability over five cycles. The TiO2/diatomite composite shows great promising application foreground in formaldehyde degradation.
Optimization of CO2 adsorption capacity and cyclical adsorption/desorption on tetraethylenepentamine-supported surface-modified hydrotalcite.

PubMed

Thouchprasitchai, Nutthavich; Pintuyothin, Nuthapol; Pongstabodee, Sangobtip

2018-03-01

The objective of this research was to investigate CO 2 adsorption capacity of tetraethylenepentamine-functionalized basic-modified calcined hydrotalcite (TEPA/b-cHT) sorbents at atmospheric pressure formed under varying TEPA loading levels, temperatures, sorbent weight to total gaseous flow rate (W/F) ratios and CO 2 concentrations in the influent gas. The TEPA/b-cHT sorbents were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectrometry (FT-IR), thermal gravimetric analysis (TGA), Brunauer-Emmet-Teller (BET) analysis of nitrogen (N 2 ) adsorption/desorption and carbon-hydrogen-nitrogen (CHN) elemental analysis. Moreover, a full 2 4 factorial design with three central points at a 95% confidence interval was used to screen important factor(s) on the CO 2 adsorption capacity. It revealed that 85.0% variation in the capacity came from the influence of four main factors and the 15.0% one was from their interactions. A face-centered central composite design response surface method (FCCCD-RSM) was then employed to optimize the condition, the maximal capacity of 5.5-6.1mmol/g was achieved when operating with a TEPA loading level of 39%-49% (W/W), temperature of 76-90°C, W/F ratio of 1.7-2.60(g·sec)/cm 3 and CO 2 concentration of 27%-41% (V/V). The model fitted sufficiently the experimental data with an error range of ±1.5%. From cyclical adsorption/desorption and selectivity at the optimal condition, the 40%TEPA/b-cHT still expressed its effective performance after eight cycles. Copyright © 2017. Published by Elsevier B.V.
Chlamydomonas angulosa (Green Alga) and Nostoc commune (Blue-Green Alga) Microalgae-Cellulose Composite Aerogel Beads: Manufacture, Physicochemical Characterization, and Cd (II) Adsorption

PubMed Central

Hwang, Kyojung; Kwon, Gu-Joong; Yang, Jiwook; Kim, Minyoung; Hwang, Won Joung; Youe, Wonjae; Kim, Dae-Young

2018-01-01

This study presents composite aerogel beads prepared by mixing dissolved cellulose with Chlamydomonas angulosa and Nostoc commune cells, respectively, at 0.1, 0.3, and 0.5% (w/w). The manufactured composites (termed regenerated cellulose (RC)), with C. angulosa (RCCA-(1, 3, and 5)), and with N. commune (RCNC-(1, 3, and 5)) were analyzed. Both RCCA-5 and RCNC-5 showed the high specific surface area to be about 261.3 and 332.8 m2·g−1. In the microstructure analysis, network structures were observed in the cross-sections of RC, RCCA-5, and RCNC-5. The pyrolysis temperature of the RCCA-5 and RCNC-5 composite aerogel beads was rapidly increased about 250 °C during the mixing of cellulose with C. angulosa and N. commune. The chemical analysis of RC, RCCA-5, and RCNC-5 showed peaks corresponding to various functional groups, such as amide, carboxyl, and hydroxyl groups from protein, lipid, and carbohydrate. RCNC-5 at pH 6 demonstrated highest Cd2+ removal rate about 90.3%, 82.1%, and 63.1% at 10, 25, and 50 ppm Cd2+, respectively. At pH 6, Cd2+ adsorption rates per unit weight of the RCNC-5 were about 0.9025, 2.0514, and 3.1547 mg/g at 10, 25, and 50 ppm, respectively. The peaks assigned to the amide, carboxyl, and hydroxyl groups in RCCA-5, RCNC-5, and RC were shifted or disappeared immediately after adsorption of Cd2+. The specific surface area, total pore volume, and mean pore diameter of composites was decreased due to adsorption of Cd2+ on the developed materials. As can be seen in the X-ray powder diffraction (XRD) spectrum, significant changes in the molecular structure of the composite aerogel beads were not observed even after adsorption of Cd2+. PMID:29621190
Acoustic cavitation induced synthesis of zirconium impregnated activated carbon for effective fluoride scavenging from water by adsorption.

PubMed

Mullick, Aditi; Neogi, Sudarsan

2018-07-01

Environmental concern associated with the side effects of high fluoride content in ground water and surface water has prompted the researchers to look for an efficient, convenient and easy method. Considering the potential of a good adsorbent, present study reports the synthesis of a composite by impregnating zirconium on powdered activated carbon (AC) using ultrasound as the tool for synthesis and applying it for fluoride adsorption from water. The nature of the composite was determined through characterization by scanning electron microscopy (SEM), energy dispersive Xray (EDX), Xray diffraction (XRD), N 2 adsorption analysis (BET) and Fourier Transform Infrared Spectroscopy (FTIR) analysis. The pH pzc (point of zero charge) of the adsorbent was found to be 5.03; with the optimum pH obtained at 4 for adsorption of strong electronegative fluoride ions. The initial fluoride concentration was varied from 2.5 up to 20 mg.L -1 and the maximum adsorption capacity of 5 mg.g -1 was obtained. A maximum fluoride removal of 94.4% was obtained for an initial concentration of 2.5 mg.L -1 within an equilibrium time of 180 min. The adsorption isotherm followed the Langmuir isotherm model indicating a monolayer adsorption process and the adsorption kinetics followed pseudo second order model. The effects of various coexisting ions (HCO 3 - , NO 3 - , SO 4 2- , Cl - ) commonly present in the water were found to have negligible impact on the process performance. Conducting the adsorption-desorption studies for five consecutive cycles for an initial fluoride concentration of 10 mg.L -1 , the removal efficiency reduced from 86.2 to 32.6%. The ultrasonic method provided an easy route to synthesize the composite in less time and significantly reduced energy consumption by more than 96% compared to the conventional method. Copyright © 2018 Elsevier B.V. All rights reserved.
Preparation of 1D Hierarchical Material Mesosilica/Pal Composite and Its Performance in the Adsorption of Methyl Orange

PubMed Central

Wu, Mei; Han, Haifeng; Ni, Lingli; Song, Daiyun; Li, Shuang; Hu, Tao; Jiang, Jinlong; Chen, Jing

2018-01-01

This paper highlights the synthesis of a one-dimensional (1D) hierarchical material mesosilica/palygorskite (Pal) composite and evaluates its adsorption performance for anionic dye methyl orange (MO) in comparison with Pal and Mobile crystalline material-41 (MCM-41). The Mesosilica/Pal composite is consisted of mesosilica coated Pal nanorods and prepared through a dual template approach using cetyltrimethyl ammonium bromide (CTAB) and Pal as soft and hard templates, respectively. The composition and structure of the resultant material was characterized by a scanning electron microscope (SEM), transmissionelectron microscopy (TEM), N2 adsorption-desorption analysis, small-angle X-Ray powder diffraction (XRD), and zeta potential measurement. Adsorption experiments were carried out with different absorbents at different contact times and pH levels. Compared with Pal and MCM-41, the mesosilica/Pal composite exhibited the best efficiency for MO adsorption. Its adsorption ratio is as high as 70.4%. Its adsorption equilibrium time is as short as 30 min. Results testify that the MO retention is promoted for the micro-mesoporous hierarchical structure and positive surface charge electrostatic interactions of the mesosilica/Pal composite. The regenerability of the mesosilica/Pal composite absorbent was also assessed. 1D morphology makes it facile to separate from aqueous solutions. It can be effortlessly recovered and reused for up to nine cycles. PMID:29361713
Production of silica gel from Tunisian sands and its adsorptive properties

NASA Astrophysics Data System (ADS)

Lazaar, K.; Hajjaji, W.; Pullar, R. C.; Labrincha, J. A.; Rocha, F.; Jamoussi, F.

2017-06-01

Thanks to its highly absorbent character, silica gel is used in several applications, such as air moisture removal, as a treatment agent for effluents. In this study, silica gels were synthesised from Tunisian sands, collected from the Fortuna and Sidi Aich Formations in northern and central Tunisia. The collected quartz sand raw materials, as well as the prepared silica gels, were characterised by different techniques, such as X-ray diffraction (XRD), X-ray fluorescence (XRF) and scanning electron microscopy (SEM). XRD patterns of quartz sands showed quartz as main phase (86.1-98%), with lower contents of potassic feldspars, along with kaolinite and calcite. These quartz sands presented relatively small quantities of Fe2O3 (0.3%-0.5%) and TiO2 (0.1%-0.6%). The synthesised silica gels exhibited pore diameters exceeding 20 Å and surface areas up to 194 m2/g, comparable with those described in the literature and commercial silica gel. N2 adsorption isotherms showed that the silica gels prepared from Tunisian sands are mesoporous materials with high adsorption capacities. To understand better their adsorbent properties and applicability on an industrial scale, these gels were tested for methylene blue (MB) absorption. Maximum decolourisation rates (up to 96% after a contact time of 180 min) occurred with products synthesised at pH 3. The adsorption mechanism fitted better with a Langmuir model, revealing a monolayer coverage process of MB molecules over the gel surface, and the adsorption kinetics of the dye on these materials is well described by the second order model. The corresponding equilibrium adsorption capacities obtained from experimental data (Qexp = 292-214 mg/g) were close to the estimated maximum adsorption capacities (Qe = 333-250 mg/g), and to that of an industrial silica gel (250 mg/g).
Recovery of indium ions by nanoscale zero-valent iron

NASA Astrophysics Data System (ADS)

Chen, Wen; Su, Yiming; Wen, Zhipan; Zhang, Yalei; Zhou, Xuefei; Dai, Chaomeng

2017-03-01

Indium and its compounds have plenty of industrial applications and high demand. Therefore, indium recovery from various industrial effluents is necessary. It was sequestered by nanoscale zero-valent iron (nZVI) whose size mainly ranged from 50 to 70 nm. Adsorption kinetics and isotherm, influence of pH, and ionic strength were thoroughly investigated. The reaction process was well fitted to a pseudo second-order model, and the maximum adsorption capacity of In(III) was 390 mg In(III)/g nZVI similar to 385 mg In(III)/g nZVI at 298 K calculated by Langmuir model. The mole ratio of Fe(II) released to In(III) immobilized was 3:2, which implied a special chemical process of co-precipitation combined Fe(OH)2 with In(OH)3. Transmission electron microscopy with an energy-disperse X-ray (TEM-EDX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize surface morphology, corrosion products, and valence state of indium precipitate formed on nanoparticles. The structural evolution changed from core-shell structure of iron oxide to sheet structure of co-precipitation, to sphere structure that hydroxide gradually dissolved as the pH decreased, and to cavity structures for the pH continually decreased. Furthermore, below pH 4.7, the In(III) enrichment was inhibited for the limited capacity of co-precipitation. Also, it was found that Ca2+ and HPO4 2- have more negative influence on In(III) recovery compared with Na+, NO3 -, HCO3 -, and SO4 2-. Therefore, the In(III) recovery can be described by a mechanism which consists of adsorption, co-precipitation, and reduction and was over 78% even after 3 cycles. The results confirmed that it was applicable to employ nZVI for In(III) immobilization.

Fiber optic sensors based on hybrid phenyl-silica xerogel films to detect n-hexane: determination of the isosteric enthalpy of adsorption

PubMed Central

Calleja, Ignacio; Moriones, Paula; Garrido, Julián J

2017-01-01

We investigated the response of three fiber optic sensing elements prepared at pH 10 from phenyltriethoxysilane (PhTEOS) and tetraethylsilane (TEOS) mixtures with 30, 40, and 50% PhTEOS in the silicon precursor mixture. The sensing elements are referred to as Ph30, Ph40 and Ph50, respectively. The films were synthesized by the sol–gel method and affixed to the end of optical fibers by the dip-coating technique. Fourier transform infrared spectroscopy, N2 adsorption–desorption at 77 K and X-ray diffraction analysis were used to characterize the xerogels. At a given pressure of n-hexane, the response of each sensing element decreased with temperature, indicating an exothermic process that confirmed the role of adsorption in the overall performance of the sensing elements. The isosteric adsorption enthalpies were obtained from the calibration curves at different temperatures. The magnitude of the isosteric enthalpy of n-hexane increased with the relative response and reached a plateau that stabilized at approximately −31 kJ mol−1 for Ph40 and Ph50 and at approximately −37 kJ mol−1 for Ph30. This indicates that the adsorbate–adsorbent interaction was dominant at lower relative pressure and condensation of the adsorbate on the mesopores was dominant at higher relative pressure. PMID:28326238
A simple method to prepare magnetic modified beer yeast and its application for cationic dye adsorption.

PubMed

Yu, Jun-Xia; Wang, Li-Yan; Chi, Ru-An; Zhang, Yue-Fei; Xu, Zhi-Gao; Guo, Jia

2013-01-01

The purpose of this research is to use a simple method to prepare magnetic modified biomass with good adsorption performances for cationic ions. The magnetic modified biomass was prepared by two steps: (1) preparation of pyromellitic dianhydride (PMDA) modified biomass in N, N-dimethylacetamide solution and (2) preparation of magnetic PMDA modified biomass by a situ co-precipitation method under the assistance of ultrasound irradiation in ammonia water. The adsorption potential of the as-prepared magnetic modified biomass was analyzed by using cationic dyes: methylene blue and basic magenta as model dyes. Optical micrograph and x-ray diffraction analyses showed that Fe(3)O(4) particles were precipitated on the modified biomass surface. The as-prepared biosorbent could be recycled easily by using an applied magnetic field. Titration analysis showed that the total concentration of the functional groups on the magnetic PMDA modified biomass was calculated to be 0.75 mmol g(-1) by using the first derivative method. The adsorption capacities (q(m)) of the magnetic PMDA modified biomass for methylene blue and basic magenta were 609.0 and 520.9 mg g(-1), respectively, according to the Langmuir equation. Kinetics experiment showed that adsorption could be completed within 150 min for both dyes. The desorption experiment showed that the magnetic sorbent could be used repeatedly after regeneration. The as-prepared magnetic modified sorbent had a potential in the dyeing industry wastewater treatment.
Nanoporous Boron Nitride as Exceptionally Thermally Stable Adsorbent: Role in Efficient Separation of Light Hydrocarbons.

PubMed

Saha, Dipendu; Orkoulas, Gerassimos; Yohannan, Samuel; Ho, Hoi Chun; Cakmak, Ercan; Chen, Jihua; Ozcan, Soydan

2017-04-26

In this work, nanoporous boron nitride sample was synthesized with a Brunauer-Emmett-Teller (BET) surface area of 1360 m 2 /g and particle size 5-7 μm. The boron nitride was characterized with X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electron microscopy (TEM and SEM). Thermogravimetric analysis (TGA) under nitrogen and air and subsequent analysis with XPS and XRD suggested that its structure is stable in air up to 800 °C and in nitrogen up to 1050 °C, which is higher than most of the common adsorbents reported so far. Nitrogen and hydrocarbon adsorption at 298 K and pressure up to 1 bar suggested that all hydrocarbon adsorption amounts were higher than that of nitrogen and the adsorbed amount of hydrocarbon increases with an increase in its molecular weight. The kinetics of adsorption data suggested that adsorption becomes slower with the increase in molecular weight of hydrocarbons. The equilibrium data suggested that that boron nitride is selective to paraffins in a paraffin-olefin mixture and hence may act as an "olefin generator". The ideal adsorbed solution theory (IAST)-based selectivity for CH 4 /N 2 , C 2 H 6 /CH 4 , and C 3 H 8 /C 3 H 6 was very high and probably higher than the majority of adsorbents reported in the literature. IAST-based calculations were also employed to simulate the binary mixture adsorption data for the gas pairs of CH 4 /N 2 , C 2 H 6 /CH 4 , C 2 H 6 /C 2 H 4 , and C 3 H 8 /C 3 H 6 . Finally, a simple mathematical model was employed to simulate the breakthrough behavior of the above-mentioned four gas pairs in a dynamic column experiment. The overall results suggest that nanoporous boron nitride can be used as a potential adsorbent for light hydrocarbon separation.
Organically functionalized mesoporous SBA-15 as sorbents for removal of selected pharmaceuticals from water.

PubMed

Bui, Tung Xuan; Kang, Seo-Young; Lee, Sang-Hyup; Choi, Heechul

2011-10-15

Mesoporous silica SBA-15 and its postfunctionalized counterparts with hydroxymethyl (HM-SBA-15), aminopropyl (AP-SBA-15), and trimethylsilyl (TMS-SBA-15) were prepared and characterized by powder X-ray diffraction, N(2) adsorption-desorption measurement, Fourier-transform infrared spectroscopy, and elemental analysis. The removal of a mixture of 12 selected pharmaceuticals was investigated by batch adsorption experiments onto SBA-15 and the grafted materials. SBA-15 showed to have moderate adsorption affinity with amino-containing (atenolol, trimethoprim) and hydrophobic pharmaceuticals, but it displayed minimal adsorption affinity toward hydrophilic compounds. HM-SBA-15 was analogous with SBA-15 in terms of the adsorption efficiency toward all pharmaceuticals. AP-SBA-15 exhibited an increase in the adsorption of two acidic compounds (clofibric acid, diclofenac) but a decrease in the adsorption of estrone and the two amino-containing compounds. Among the grafted materials, TMS-SBA-15 had the highest adsorption affinity toward most pharmaceuticals. Moreover, the adsorption of nine pharmaceuticals to TMS-SBA-15 was significantly higher than that to SBA-15; seven of which showed the removal percentages from 70.6% to 98.9% onto TMS-SBA-15. The number of pharmaceuticals showing high adsorption efficiency onto TMS-SBA-15 did not alter significantly as the pH changed in the range of 5.5-7.6. The results suggest that TMS-SBA-15 is a promising material for the removal of pharmaceuticals from aqueous phase, especially for the treatment of wastewater from drug manufacturers. Copyright © 2011 Elsevier B.V. All rights reserved.
Functionalized MIL-101 with imidazolium-based ionic liquids for the cycloaddition of CO2 and epoxides under mild condition

NASA Astrophysics Data System (ADS)

Liu, Dan; Li, Gang; Liu, Haiou

2018-01-01

A kind of multi-functional sites metal-organic framework (MOF) composite (MIL-101-IMBr) was successfully prepared by post-synthesis modification of MIL-101 with imidazolium-based ionic liquids. The ionic liquids not only functionalize as basic sites but also provide halide anions, which serve as a nucleophile in cycloaddition reaction. The prepared functional MOF materials were characterized by X-ray diffraction, fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, N2 adsorption-desorption and CO2 temperature programmed desorption. The results of fourier transform infrared spectroscopy and energy dispersive spectroscopy show that the MIL-101-IMBr composite was successfully synthesized. The N2 adsorption-desorption results clearly demonstrated that the modified composites still preserve high BET surface area and total pore volume. The composite exhibits high catalytic activity for the cycloaddition of CO2 with epoxides under mild and co-catalyst free conditions. The conversion of propylene oxide was 95.8% and the selectivity of cyclic carbonate was 97.6% under 0.8 MPa at 80 °C for 4 h. Moreover, the catalyst can be used for at least five times.
Decreasing Ni, Cu, Cd, and Zn heavy metal magnetite-bentonite nanocomposites and adsorption isotherm study

NASA Astrophysics Data System (ADS)

Eskandari, M.; Zakeri Khatir, M.; Khodadadi Darban, A.; Meshkini, M.

2018-04-01

This present study was conducted to investigate the effect of magnetite-bentonite nanocomposite on heavy metal removal from an effluent. For this purpose, magnetite-bentonite nanocomposite was prepared through the chemical method and characterized using x-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques, followed by studying the effect of produced nanocomposite on the removal of Ni2+, Cu2+, Cd2+, and Zn2+ heavy metal ions. The results showed that adsorption capacity of magnetite-bentonite nanocomposites for the studied ions is in the order of Zn2+ > Cd2+ > Cu2+ > Ni2+. Adsorption isotherms were drawn for Ni2+, Cu2+, Cd2+, and Zn2+ cations and found that cations adsorption on nanocomposite fit into Langmuir model.
Sol-Gel Synthesis of Ordered β-Cyclodextrin-Containing Silicas

NASA Astrophysics Data System (ADS)

Trofymchuk, Iryna Mykolaivna; Roik, Nadiia; Belyakova, Lyudmila

2016-03-01

New approaches for β-cyclodextrin-containing silicas synthesis were demonstrated. Materials with hexagonally ordered mesoporous structure were prepared by postsynthesis grafting and by co-condensation methods. β-Cyclodextrin activated by a N, N'-carbonyldiimidazole was employed for postsynthesis treatment of 3-aminopropyl-modified MCM-41 support as well as for sol-gel synthesis with β-cyclodextrin-containing organosilane and tetraethyl orthosilicate participation in the presence of cetyltrimethylammonium bromide. The successful incorporation of cyclic oligosaccharide moieties in silica surface layer was verified by means of FT-IR spectroscopy and chemical analysis. Obtained β-cyclodextrin-containing materials were characterized by X-ray diffraction, transmission electron microscopy, and low-temperature adsorption-desorption of nitrogen. In spite of commensurable loading of β-cyclodextrin groups attained by both proposed approaches (up to 0.028 μmol · m-2), it was found that co-condensation procedure provides uniform distribution of β-cyclodextrin functionalities in silica framework, whereas postsynthesis grafting results in modification of external surface of silica surface. Adsorption of benzene from aqueous solutions onto the surface of β-cyclodextrin-containing materials prepared by co-condensation method was studied as the function of time and equilibrium concentration. Langmuir and Freundlich models were used to evaluate adsorption processes and parameters. Adsorption experiments showed that β-cyclodextrin-containing silicas could be promising for the trace amount removal of aromatics from water.
Amazon kaolinite functionalized with diethylenetriamine moieties for U(VI) removal: thermodynamic of cation-basic interactions.

PubMed

Guerra, Denis L; Leidens, Victor L; Viana, Rúbia R; Airoldi, Claudio

2010-08-15

The compound N-[3-(trimethoxysilyl)propyl]diethylenetriamine (MPDET) was anchored onto Amazon kaolinite surface (KLT) by heterogeneous route. The modified and natural kaolinite clay samples were characterized by transmission electron microscopy (TEM), scanning electron microscopic (SEM), N(2) adsorption, powder X-ray diffraction, thermal analysis, ion exchange capacities, and nuclear magnetic nuclei of (29)Si and (13)C. The well-defined peaks obtained in the (13)C NMR spectrum in the 5.0-62.1 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The adsorption of uranyl on natural (KLT) and modified (KLT(MPDET)) kaolinite clays was investigated as a function of the solution pH, metal concentration, temperature, and ionic strength. The ability of these materials to remove U(VI) from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 4.0. The maximum number of moles adsorbed was determined to be 8.37 x 10(-3) and 13.87 x 10(-3) mmol g(-1) for KLT and KLT(MPDET) at 298 K, respectively. The energetic effects (Delta(int)H, Delta(int)G, and Delta(int)S) caused by metal cations adsorption were determined through calorimetric titrations. Copyright 2010. Published by Elsevier B.V.
Structural Variety and Adsorptive Properties of Mesoporous Silicas with Immobilized Oligosaccharide Groups

NASA Astrophysics Data System (ADS)

Trofymchuk, Iryna; Roik, Nadiia; Belyakova, Lyudmila

2017-04-01

In this research, we report on the synthesis of mesoporous silicas with various quantities of immobilized oligosaccharide groups and different pore ordering degree. The hydrothermal co-condensation of tetraethyl orthosilicate and β-cyclodextrin-containing organosilane in the presence of cetyltrimethylammonium bromide template was employed. The purpose of this investigation was to show the opportunity of increasing β-cyclodextrin content in silica matrix by changing the molar ratio of initial reagents during organosilane synthesis and to determine whether the enhancing of immobilized groups on the surface influences on model aromatic compound adsorption from water. It was prepared several β-cyclodextrin-organosilanes by modification of (3-aminopropyl)triethoxysilane with oligosaccharide (the molar composition of reaction mixtures were 1:1, 3:1, and 5:1) with using N, N'-carbonyldiimidazole as linking agent. Three types of MCM-41 materials were obtained with 0.018, 0.072, and 0.095 mmol g-1 β-cyclodextrin-group loading according to chemical analysis of silicas. The IR spectroscopy and potentiometric titration were also performed to confirm the presence of functional groups in the silica matrix. Nitrogen sorptometry experiments exhibited the decrease of high surface area (from 812 to 457 m2 g-1) and the average pore diameter (from 1.06 to 0.60 cm3 g-1) of synthesized silicas with increasing of immobilized oligosaccharide groups. The influence of β-cyclodextrin-organosilane presence on the forming of hexagonally arranged porous structure of silicas was evaluated by X-ray diffraction and TEM analyses. As the loading of oligosaccharide groups increases in obtained silicas, the (100) reflex in diffraction patterns is even less intense and broader, denoting the decrease of long-range pore ordering. Adsorption experiments were carried out to study the effect of β-cyclodextrin groups' attendance in silica matrix on benzene uptakes from aqueous solutions. Experimental kinetic curves of benzene adsorption on synthesized silicas were compared with theoretical models of Lagergren and Ho-McKay for pseudo-first and pseudo-second-order processes. Langmuir and Freundlich isotherm models were used to evaluate adsorption processes and parameters. Obtained β-cyclodextrin-containing MCM-41 silicas demonstrate adsorption level performance of known samples and could be very promising for benzene uptakes from aqueous solutions in water treatment processes.
Adsorption of alcohols on a two-dimensional SiO2 single crystal - Alcohol adsorption on silicatene

NASA Astrophysics Data System (ADS)

Nayakasinghe, M. T.; Sivapragasam, N.; Burghaus, U.

2017-12-01

The adsorption kinetics of alcohols (methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol) was studied on monoatomic, two-dimensional SiO2 single crystals (silicatene) using thermal desorption spectroscopy (TDS). Silicatene was grown on Mo(1 1 2) at ultra-high vacuum. In contrast to Mo, the alcohols physisorb molecularly on the hydrophobic SiO2/Mo surface. Zero coverage binding energies vary from 46.5 to 65.5 kJ/mol and increase with molecular size. Silicatene was characterized by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and water TDS.
Competitive adsorption of Pb2+, Cu2+, and Cd2+ ions on microporous titanosilicate ETS-10.

PubMed

Lv, Lu; Hor, Mei Peng; Su, Fabing; Zhao, X S

2005-07-01

In the present study, the competitive adsorption characteristics of binary and ternary heavy metal ions Pb2+, Cu2+, and Cd2+ on microporous titanosilicate ETS-10 were investigated in batch systems. Pure microporous titanosilicate ETS-10 was synthesized with P25 as the Ti source and characterized by the techniques of X-ray diffraction (XRD), field emission-scanning electron microscope (FESEM), nitrogen adsorption, and zeta-potential. Equilibrium and kinetic adsorption data showed that ETS-10 displays a high selectivity toward one metal in a two-component or a three-component system with an affinity order of Pb2+ > Cd2+ > Cu2+. The equilibrium behaviors of heavy metals species with stronger affinity toward ETS-10 can be described by the Langmuir equation while the adsorption kinetics of the metals can be well fitted to a pseudo-second-order (PSO) model.
Stabilization of Au Monatomic-High Islands on the (2 ×2 )-Nad Reconstructed Surface of Wurtzite AlN(0001)

NASA Astrophysics Data System (ADS)

Eydoux, Benoit; Baris, Bulent; Khoussa, Hassan; Guillermet, Olivier; Gauthier, Sébastien; Bouju, Xavier; Martrou, David

2017-10-01

Noncontact atomic force microscopy images show that gold grows on the (2 ×2 )-Nad reconstructed polar (0001) surface of AlN insulating films, in the form of large monatomic islands. High-resolution images and in situ reflection high-energy electron diffraction spectra reveal two moiré patterns from which an atomic model can be built. Density functional theory calculations confirm this model and give insight into the mechanisms that lead to the stabilization of the monolayer. Gold adsorption is accompanied, first, by a global vertical charge transfer from the AlN substrate that fulfills the electrostatic stability criterion for a polar material, and second, by lateral charge transfers that are driven by the local chemical properties of the (2 ×2 )-Nad reconstruction. These results present alternative strategies to grow metal electrodes onto nitride compounds with a better controlled interface, a crucial issue for applications.
Investigate the ultrasound energy assisted adsorption mechanism of nickel(II) ions onto modified magnetic cobalt ferrite nanoparticles: Multivariate optimization.

PubMed

Mehrabi, Fatemeh; Alipanahpour Dil, Ebrahim

2017-07-01

In present study, magnetic cobalt ferrite nanoparticles modified with (E)-N-(2-nitrobenzylidene)-2-(2-(2-nitrophenyl)imidazolidine-1-yl) ethaneamine (CoFe 2 O 4 -NPs-NBNPIEA) was synthesized and applied as novel adsorbent for ultrasound energy assisted adsorption of nickel(II) ions (Ni 2+ ) from aqueous solution. The prepared adsorbent characterized by Fourier transforms infrared spectroscopy (FT-IR), transmission electron microscope (TEM), vibrating sample magnetometer (VSM) and X-ray diffraction (XRD). The dependency of adsorption percentage to variables such as pH, initial Ni 2+ ions concentration, adsorbent mass and ultrasound time were studied with response surface methodology (RSM) by considering the desirable functions. The quadratic model between the dependent and independent variables was built. The proposed method showed good agreement between the experimental data and predictive value, and it has been successfully employed to adsorption of Ni 2+ ions from aqueous solution. Subsequently, the experimental equilibrium data at different concentration of Ni 2+ ions and 10mg amount of adsorbent mass was fitted to conventional isotherm models like Langmuir, Freundlich, Tempkin, Dubinin-Radushkevich and it was revealed that the Langmuir is best model for explanation of behavior of experimental data. In addition, conventional kinetic models such as pseudo-first and second-order, Elovich and intraparticle diffusion were applied and it was seen that pseudo-second-order equation is suitable to fit the experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.
Direct structural evidence of commensurate-to-incommensurate transition of hydrocarbon adsorption in a microporous metal organic framework

DOE PAGES

Banerjee, Debasis; Wang, Hao; Gong, Qihan; ...

2015-10-27

Here, the efficiency of physisorption-based separation of gas-mixtures depends on the selectivity of adsorbent which is directly linked to size, shape, polarizability and other physical properties of adsorbed molecules. Commensurate adsorption is an interesting and important adsorption phenomenon, where the adsorbed amount, location, and orientation of an adsorbate are commensurate with the crystal symmetry of the adsorbent. Understanding this phenomenon is important and beneficial as it can provide vital information about adsorbate–adsorbent interaction and adsorption–desorption mechanism. So far, only sporadic examples of commensurate adsorption have been reported in porous materials such as zeolites and metal organic frameworks (MOFs). In thismore » work we show for the first time direct structural evidence of commensurate-to-incommensurate transition of linear hydrocarbon molecules (C 2–C7) in a microporous MOF, by employing a number of analytical techniques including single crystal X-ray diffraction (SCXRD), in situ powder X-ray diffraction coupled with differential scanning calorimetry (PXRD-DSC), gas adsorption and molecular simulations.« less
Critical Factors Driving the High Volumetric Uptake of Methane in Cu₃(btc)₂.

PubMed

Hulvey, Zeric; Vlaisavljevich, Bess; Mason, Jarad A; Tsivion, Ehud; Dougherty, Timothy P; Bloch, Eric D; Head-Gordon, Martin; Smit, Berend; Long, Jeffrey R; Brown, Craig M

2015-08-26

A thorough experimental and computational study has been carried out to elucidate the mechanistic reasons for the high volumetric uptake of methane in the metal-organic framework Cu3(btc)2 (btc(3-) = 1,3,5-benzenetricarboxylate; HKUST-1). Methane adsorption data measured at several temperatures for Cu3(btc)2, and its isostructural analogue Cr3(btc)2, show that there is little difference in volumetric adsorption capacity when the metal center is changed. In situ neutron powder diffraction data obtained for both materials were used to locate four CD4 adsorption sites that fill sequentially. This data unequivocally shows that primary adsorption sites around, and within, the small octahedral cage in the structure are favored over the exposed Cu(2+) or Cr(2+) cations. These results are supported by an exhaustive parallel computational study, and contradict results recently reported using a time-resolved diffraction structure envelope (TRDSE) method. Moreover, the computational study reveals that strong methane binding at the open metal sites is largely due to methane-methane interactions with adjacent molecules adsorbed at the primary sites instead of an electronic interaction with the metal center. Simulated methane adsorption isotherms for Cu3(btc)2 are shown to exhibit excellent agreement with experimental isotherms, allowing for additional simulations that show that modifications to the metal center, ligand, or even tuning the overall binding enthalpy would not improve the working capacity for methane storage over that measured for Cu3(btc)2 itself.
Removal of heavy metals using bentonite supported nano-zero valent iron particles

NASA Astrophysics Data System (ADS)

Zarime, Nur Aishah; Yaacob, Wan Zuhari Wan; Jamil, Habibah

2018-04-01

This study reports the composite nanoscale zero-valent iron (nZVI) which was successfully synthesized using low cost natural clay (bentonite). Bentonite composite nZVI (B-nZVI) was introduced to reduce the agglomeration of nZVI particles, thus will used for heavy metals treatment. The synthesized material was analyzed using physical, mineralogy and morphology analysis such as Brunnaer-Emmett-Teller (BET) surface area, Field Emission Scanning Electron Microscopy (FESEM), X-Ray Diffraction (XRD), Fourier Transform Infrared (FTIR) and X-ray Photoelectron Spectroscopy (XPS). The batch adsorption test of Bentonite and B-nZVI with heavy metals solutions (Pb, Cu, Cd, Co, Ni and Zn) was also conducted to determine their effectiveness in removing heavy metals. Through Batch test, B-nZVI shows the highest adsorption capacity (qe= 50.25 mg/g) compared to bentonite (qe= 27.75 mg/g). This occurred because B-nZVI can reduce aggregation of nZVI, dispersed well in bentonite layers thus it can provide more sites for adsorbing heavy metals.
Adsorption characterization of gaseous volatile organic compound on mesoporous silica particles prepared from spent diatomaceous earth.

PubMed

Bei, Lei-Lei; Tao, Hong; Ma, Chih-Ming; Shiue, Angus; Chang, Chang-Tang

2014-04-01

This study used spent diatomaceous earth (SDE) from drink processing as source of Si and cationic surfactant (CTAB) as a template for the synthesis of mesoporous silica Materials (MSM) through hydrothermal method. The MSM was characterized by Small-angle X-ray Diffraction (SXRD), Scanning Electron Microscopy (SEM), Thermo Gravimetric Analysis (TGA), Fourier Transform Infrared (FT-IR) spectroscopy and N2 adsorption-desorption analyzer. The results showed that the surface area, pore volume and pore size was roughly ranged from 880 to 1060 m2 g(-1), 1.05 cm3 g(-1) and 4.0 nm, respectively. The properties of the synthesized MSM were also compared with those prepared from pure silica sources (MCM-41) and got almost the same characteristics. The synthesized MSM was used as adsorbent at 25 degrees C with carrier gas of air. The adsorption equilibrium revealed that adsorption capacity of MSM was 59.6, 65.7, 69.6, 84.9 mg g(-1) while the acetone concentration was 600, 800, 1000 ppm, 1600 ppm respectively. Results showed that breakthrough curves correlate to the challenge vapor concentration, adsorbent loading, and the flow rate. The results obtained in the present work demonstrated that it was feasibility of using the SDE as a potential source of silica to prepare MSM.
Catalytic wet peroxide oxidation of benzoic acid over Fe/AC catalysts: Effect of nitrogen and sulfur co-doped activated carbon.

PubMed

Qin, Hangdao; Xiao, Rong; Chen, Jing

2018-06-01

The parent activated carbon (ACP) was modified with urea and thiourea to obtain N-doped activated carbon (ACN) and N, S co-doped activated carbon (ACNS), respectively. Iron supported on activated carbon (Fe/ACP, Fe/ACN and Fe/ACNS) were prepared and worked as catalyst for catalytic wet peroxide oxidation of benzoic acid (BA). The catalysts were characterized by N 2 adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscope (TEM), and their performance was evaluated in terms of benzoic acid and TOC removal. The results indicated the doped N and S improved the adsorption capacity as well as catalytic activity of activated carbon. Besides, the catalytic activity toward benzoic acid degradation was found to be enhanced by Fe/ACNS compared to that of Fe/ACP and Fe/ACN. The enhanced catalytic performance was attributed to the presence of the nitrogen and sulfur atoms may serve to improve the relative amount of Fe 2+ on iron oxide surface and also help prevent leaching of Fe. It was also observed that the stability or reutilization of Fe/ACNS catalyst was fairly good. Copyright © 2018 Elsevier B.V. All rights reserved.
Mechanochemical solvent-free in situ synthesis of drug-loaded {Cu2(1,4-bdc)2(dabco)}n MOFs for controlled drug delivery

NASA Astrophysics Data System (ADS)

Nadizadeh, Zahra; Naimi-Jamal, M. Reza; Panahi, Leila

2018-03-01

In the present study, ibuprofen-loaded nano metal-organic frameworks (NMOFs) {Cu2(1,4-bdc)2(dabco)}n and {Cu2(1,4-bdc-NH2)2(dabco)}n (bdc=benzenedicarboxylic acid, and dabco=diazabicyclooctane) were synthesized by ball-milling at room temperature in 2 h. The produced drug-loaded Cu-NMOFs were studied as ibuprofen drug delivery system and exhibited well-defined drug release behavior, exceptionally high drug loading capacities and the ability to entrap the model drug. The loading efficiency for ibuprofen was determined about 50.54% and 50.27%, respectively. The drug release of NMOFs was also monitored, and all of the loaded drug was released in 1 day. The NMOFs were characterized by FT-IR spectroscopy, X-ray powder diffraction (XRPD), thermogravimetric analysis (TGA), SEM (scanning electron microscopy), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma (ICP), UV-vis spectroscopy and N2 adsorption porosimetry (BET&BJH).
Preparation and Characterization of Mesoporous Zirconia Made by Using a Poly (methyl methacrylate) Template

NASA Astrophysics Data System (ADS)

Duan, Guorong; Zhang, Chunxiang; Li, Aimei; Yang, Xujie; Lu, Lude; Wang, Xin

2008-03-01

Superfine powders of poly (methyl methacrylate) (PMMA) have been prepared by means of an emulsion polymerization method. These have been used as templates in the synthesis of tetragonal phase mesoporous zirconia by the sol gel method, using zirconium oxychloride and oxalic acid as raw materials. The products have been characterized by infrared spectroscopy, X-ray diffraction analysis, transmission electron microscopy, N2 adsorption-desorption isotherms, and pore size distribution. The results indicate that the average pore size was found to be 3.7 nm.

Simultaneous adsorption of Cu2+ and Acid fuchsin (AF) from aqueous solutions by CMC/bentonite composite.

PubMed

Gong, Ning; Liu, Yanping; Huang, Ruihua

2018-04-21

Carboxymethyl-chitosan (CMC)/bentonite composite was prepared by the method of membrane-forming, and characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) techniques. The simultaneous adsorption of Cu 2+ and Acid fuchsin (AF) applying CMC/bentonite composite as an adsorbent in single or binary systems was investigated. The adsorption study was conducted systematically by varying the ratio of CMC to bentonite, adsorbent dosage, initial pH value, initial Cu 2+ (or AF) concentration, contact time and the interaction of two components in binary solutions. The results showed that the presence of Cu 2+ hindered the adsorption of AF, while the presence of AF almost had no influence on the adsorption of Cu 2+ in binary systems. The adsorption data of Cu 2+ and AF were both suitable for Langmuir isotherm model, and the maximum adsorption capacities of CMC/bentonite composite, according to the Langmuir isotherm model were 81.4 mg/g for Cu 2+ and 253.2 mg/g for AF at 298 K. The pseudo-second-order model could better describe the adsorption process of Cu 2+ and AF. Thermodynamic constant values illustrated that the adsorption of Cu 2+ was endothermic, while the adsorption process of AF was exothermic. Copyright © 2018. Published by Elsevier B.V.
Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

PubMed

Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

2016-02-01

This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.
Enhanced adsorption of humic acids on ordered mesoporous carbon compared with microporous activated carbon.

PubMed

Liu, Fengling; Xu, Zhaoyi; Wan, Haiqin; Wan, Yuqiu; Zheng, Shourong; Zhu, Dongqiang

2011-04-01

Humic acids are ubiquitous in surface and underground waters and may pose potential risk to human health when present in drinking water sources. In this study, ordered mesoporous carbon was synthesized by means of a hard template method and further characterized by X-ray diffraction, N2 adsorption, transition electron microscopy, elemental analysis, and zeta-potential measurement. Batch experiments were conducted to evaluate adsorption of two humic acids from coal and soil, respectively, on the synthesized carbon. For comparison, a commercial microporous activated carbon and nonporous graphite were included as additional adsorbents; moreover, phenol was adopted as a small probe adsorbate. Pore size distribution characterization showed that the synthesized carbon had ordered mesoporous structure, whereas the activated carbon was composed mainly of micropores with a much broader pore size distribution. Accordingly, adsorption of the two humic acids was substantially lower on the activated carbon than on the synthesized carbon, because of the size-exclusion effect. In contrast, the synthesized carbon and activated carbon showed comparable adsorption for phenol when the size-exclusion effect was not in operation. Additionally, we verified by size-exclusion chromatography studies that the synthesized carbon exhibited greater adsorption for the large humic acid fraction than the activated carbon. The pH dependence of adsorption on the three carbonaceous adsorbents was also compared between the two test humic acids. The findings highlight the potential of using ordered mesoporous carbon as a superior adsorbent for the removal of humic acids. Copyright © 2011 SETAC.
A pressure-amplifying framework material with negative gas adsorption transitions.

PubMed

Krause, Simon; Bon, Volodymyr; Senkovska, Irena; Stoeck, Ulrich; Wallacher, Dirk; Többens, Daniel M; Zander, Stefan; Pillai, Renjith S; Maurin, Guillaume; Coudert, François-Xavier; Kaskel, Stefan

2016-04-21

Adsorption-based phenomena are important in gas separations, such as the treatment of greenhouse-gas and toxic-gas pollutants, and in water-adsorption-based heat pumps for solar cooling systems. The ability to tune the pore size, shape and functionality of crystalline porous coordination polymers--or metal-organic frameworks (MOFs)--has made them attractive materials for such adsorption-based applications. The flexibility and guest-molecule-dependent response of MOFs give rise to unexpected and often desirable adsorption phenomena. Common to all isothermal gas adsorption phenomena, however, is increased gas uptake with increased pressure. Here we report adsorption transitions in the isotherms of a MOF (DUT-49) that exhibits a negative gas adsorption; that is, spontaneous desorption of gas (methane and n-butane) occurs during pressure increase in a defined temperature and pressure range. A combination of in situ powder X-ray diffraction, gas adsorption experiments and simulations shows that this adsorption behaviour is controlled by a sudden hysteretic structural deformation and pore contraction of the MOF, which releases guest molecules. These findings may enable technologies using frameworks capable of negative gas adsorption for pressure amplification in micro- and macroscopic system engineering. Negative gas adsorption extends the series of counterintuitive phenomena such as negative thermal expansion and negative refractive indices and may be interpreted as an adsorptive analogue of force-amplifying negative compressibility transitions proposed for metamaterials.
Exoelectron emission from a clean, annealed magnesium single crystal during oxygen adsorption

NASA Technical Reports Server (NTRS)

Ferrante, J.

1976-01-01

Exoelectron emission was observed from a clean, annealed Mg (0001) surface during oxygen and chlorine adsorption at pressures of 6.5x10 0.00001- N/sq m and lower. the studies were performed in an ultrahigh vacuum system. The crystals were cleaned by argon ion bombardment and annealed at 300 C. Auger electron spectroscopy was used to verify surface cleanliness, and low energy electron diffraction was used to verify that the surface was annealed. The emission was found to be oxygen arrival rate dependent. Two peaks were observed in the electron emission with exposure. Evidence is presented that the formation of the second peak corresponds to oxidation of the Mg surface. No emission was observed from clean aluminum during adsorption. Results verify that electron emission occurs from a strain free surface simply upon adsorption of oxygen. A qualitative explanation for the mechanisms of emission in terms of chemical effects is presented.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Rather, Sami ullah, E-mail: rathersami@gmail.com; Taimoor, Aqeel Ahmad; Muhammad, Ayyaz

Highlights: • Hydrogen adsorption comparisons of commercial, milled, and MgH{sub 2} composite. • Hydrogen adsorption capacity and kinetics improves tremendously by CNT embedding. • Unsteady state modeling and simulation of adsorption kinetics. - Abstract: Magnesium hydride (MgH{sub 2})–carbon nanotubes (CNT) composite has been prepared by high-energy ball milling method and their experimental and kinetic hydrogen adsorption studies was assessed. Hydrogen adsorption studies were performed by Sievert’s volumetric apparatus and kinetic evaluation was conducted by surface chemistry and Langmuir–Hinshelwood–Hougen–Watson (LHHW) type mode. Powder X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) were performed. Hydrogen adsorption capacity of commercial MgH{submore » 2}, milled MgH{sub 2}, and MgH{sub 2}/CNT composite are found to be 0.04, 0.057, and 0.059 g (H{sub 2})/g (MgH{sub 2}) at 673 K and hydrogen pressure of 4.6 MPa. Addition of 5 wt% of CNTs to MgH{sub 2} proved to be very critical to enhance hydrogen adsorption as well as to improve its kinetics. It was observed that hydrogen adsorption is not in quasi-state equilibrium and is modeled using kinetic rate laws.« less
Super-microporous solid base MgO-ZrO2 composite and their application in biodiesel production

NASA Astrophysics Data System (ADS)

Su, Jiaojiao; Li, Yongfeng; Wang, Huigang; Yan, Xiaoliang; Pan, Dahai; Fan, Binbin; Li, Ruifeng

2016-10-01

The super-microporous microcrystalline MgO-ZrO2 nanomaterials (pore size 1-2 nm) was prepared successfully via a facile one-pot evaporation-induced self-assembly (EISA) method and employed in the transesterification of soybean oil and methanol. X-ray diffraction, transmission electron microscope, temperature programmed desorption of CO2, and N2 adsorption porosimetry were employed to characterize the nanocomposites. Nitrogen sorption isotherms revealed that these materials had large surface areas of more than 200 m2/g. Moreover, the sample with a Mg/Zr molar ratio of 0.5 and calcined at 400 °C showed high biodiesel yield (around 99% at 150 °C).
Influence of Crystal Expansion/Contraction on Zeolite Membrane Permeation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sorenson, Stephanie G; Payzant, E Andrew; Noble, Richard D

X-ray diffraction was used to measure the unit cell parameters of B-ZSM-5, SAPO-34, and NaA zeolite powders as a function of adsorbate loading at 303 K, and in one case, at elevated temperatures. Most adsorbates expanded the zeolite crystals below saturation loading at 303 K: n-hexane and SF6 in B-ZSM-5, methanol and CO2 in SAPO-34, and methanol in NaA zeolite. As the loadings increased, the crystals expanded more. Changes in the unit cell volumes of B-ZSM-5 and SAPO-34 zeolite powders correlated with changes in permeation through zeolite membranes defects. When the zeolite crystals expanded or contracted upon adsorption, the defectmore » sizes decreased or increased. In B-ZSM-5 membranes, the fluxes through defects decreased dramatically when n-hexane or SF6 adsorbed. In contrast, i-butane adsorption at 303 K contracted B-ZSM-5 crystals at low loadings and expanded them at higher loadings. Correspondingly, the flux through B-ZSM-5 membrane defects increased at low i-butane loadings and decreased at high loading because the defects increased in size at low loading and decreased at high loadings. At 398 K and 473 K, n-hexane expanded the B-ZSM-5 unit cell more as the temperature increased from 303 to 473 K. The silicalite-1 and B-ZSM-5 unit cell volumes expanded similarly upon n-hexane adsorption at 303 K; boron substitution had little effect on volume expansion.« less
Simultaneous adsorption of Cd²⁺ and BPA on amphoteric surfactant activated montmorillonite.

PubMed

Liu, Chongmin; Wu, Pingxiao; Zhu, Yajie; Tran, Lytuong

2016-02-01

The study mainly investigated the simultaneous adsorption of bisphenol A (BPA) and Cd(2+) from aqueous solution on octadecane-betaine modified montmorillonite (BS-Mt). The characteristics of the obtained materials were analyzed by X-ray diffraction (XRD), Fourier-transform infrared (FTIR), Specific surface area (BET) and Scanning electron microscopy/Energy disperse spectroscopy (SEM/EDS), confirming that BS-18 was successfully introduced into Mt. Also, factors including initial solution pH, initial Cd(2+)/BPA concentration, contact time and adsorbent dosage on the adsorption processes were shown to be crucial for Cd(2+) adsorption, whereas had negligible effects on BPA adsorption. In this study, we found that pseudo-second-order model fitted well with the adsorption kinetic studies for both Cd(2+) and BPA with an equilibrium time of 24 h. The Cd(2+) and BPA adsorption isotherm could be well described by Freundlich model and Langmuir model, respectively. On the basis of kinetic models, the maximum adsorption capacity of Cd(2+) in aqueous solution was slightly enhanced after modification, indicating that Cd(2+) adsorption on BS-Mt was mainly attributed to direct electrostatic attraction and the chelate reaction, while the dramatic enhancement of maximum adsorption capacity for BPA was due to the hydrophobic interaction. Copyright © 2015 Elsevier Ltd. All rights reserved.
Interaction of hydrogen chloride and water with oxide surfaces. III - Titanium dioxide

NASA Technical Reports Server (NTRS)

Siriwardane, R. V.; Wightman, J. P.

1983-01-01

The adsorption of hydrogen chloride and water vapors on five TiO2 powders in both the anatase and rutile crystalline forms was studied as a function of temperature, pressure, and outgas conditions. The adsorbents were characterized utilizing X-ray powder diffraction, scanning electron microscopy, surface area analysis, indicator method, microelectrophoresis, XPS, and infrared spectroscopy. It was found that both outgas temperature and adsorption temperature influenced the adsorption of water vapor on TiO2, while water vapor adsorption on TiO2 was completely reversible. It is argued that the number of hydroxyl groups present on the surface determines the adsorption capacity of water on the different titanium dioxides. It was found that heats of immersion in water were affected significantly by outgas temperature. Hydrogen chloride adsorption isotherms at 30 C measured on TiO2 after outgassing at 100-400 C showed that a part of the total HCl adsorbed was irreversibly adsorbed. The highest HCl adsorption capacity per unit area was exhibited by anatase, while pure rutile exhibited the lowest adsorption capacity.
Synthesis and characterization of Cu2O/TiO2 photocatalysts for H2 evolution from aqueous solution with different scavengers

NASA Astrophysics Data System (ADS)

Li, Yanping; Wang, Baowei; Liu, Sihan; Duan, Xiaofei; Hu, Zongyuan

2015-01-01

A series of Cu2O/TiO2 photocatalysts with different molar fraction of Cu2O were prepared by a facile modified ethanol-induced approach followed by a calcination process. The chemical state of copper compound was proved to be cuprous oxide by the characterization of X-ray photoelectron spectra (XPS). Furthermore, these composite oxides were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption desorption and UV-vis techniques to study the morphologies, structures, and optical properties of the as-prepared samples. The results indicated that the photocatalytic activity of n-type TiO2 was significantly enhanced by combined with p-type Cu2O, due to the efficient p-n heterojunction. The p-n heterojunction between Cu2O and TiO2 can enhance visible-light adsorption, efficiently suppress charge recombination, improve interfacial charge transfer, and especially provide plentiful reaction active sites on the surface of photocatalyst. As a consequence, the prepared 2.5-Cu2O/TiO2 photocatalyst exhibited the highest photocatalytic activity for H2 evolution rate and reached 2048.25 μmol/(g h), which is 14.48 times larger than that of pure P25. The apparent quantum yield (AQY) of the 2.5-Cu2O/TiO2 sample at 365 nm was estimated to be 4.32%. In addition, the influence of different scavengers, namely methanol, anhydrous ethanol, ethylene glycol and glycerol, on the photocatalytic activity for H2 evolution rate was discussed.
Photodegradation of gaseous acetaldehyde and methylene blue in aqueous solution with titanium dioxide-loaded activated carbon fiber polymer materials and aquatic plant ecotoxicity tests.

PubMed

Kadirova, Zukhra C; Hojamberdiev, Mirabbos; Katsumata, Ken-ichi; Isobe, Toshihiro; Matsushita, Nobuhiro; Nakajima, Akira; Okada, Kiyoshi

2014-03-01

TiO2-supported activated carbon felts (TiO2-ACFTs) were prepared by dip coating of felts composed of activated carbon fibers (ACFs) with either polyester fibers (PS-A20) and/or a polyethylene pulp (PE-W15) in a TiO2 aqueous suspension followed by calcination at 250 °C for 1 h. The as-prepared TiO2-ACFTs with 29-35 wt.% TiO2 were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and N2 adsorption. The TiO2-ACFT(PS-A20) samples with 0 and 29 wt.% TiO2 were microporous with specific surface areas (S BET) of 996 and 738 m(2)/g, respectively, whereas the TiO2-ACFT(PE-W15) samples with 0 and 35 wt.% TiO2 were mesoporous with S BET of 826 and 586 m(2)/g, respectively. Adsorption and photocatalytic activity of the as-prepared samples were evaluated by measuring adsorption in the dark and photodegradation of gaseous acetaldehyde (AcH) and methylene blue (MB) in aqueous solution under UV light. The TiO2 loading caused a considerable decrease in the S BET and MB adsorption capacity along with an increase in MB photodegradation and AcH mineralization. Lemna minor was chosen as a representative aquatic plant for ecotoxicity tests measuring detoxification of water obtained from the MB photodegradation reaction with the TiO2-ACFT samples under UV light.
Prussian blue analogues for CO(2) and SO(2) capture and separation applications.

PubMed

Thallapally, Praveen K; Motkuri, Radha Kishan; Fernandez, Carlos A; McGrail, B Peter; Behrooz, Ghorishi S

2010-06-07

Adsorption isotherms of pure gases present in flue gas including CO(2), N(2), SO(2), NO, H(2)S, and water were studied using prussian blues of chemical formula M(3)[Co(CN)(6)](2).nH(2)O (M = Co, Zn) using an HPVA-100 volumetric gas analyzer and other spectroscopic methods. All the samples were characterized, and the microporous nature of the samples was studied using the BET isotherm. These materials adsorbed 8-10 wt % of CO(2) at room temperature and 1 bar of pressure with heats of adsorption ranging from 200 to 300 Btu/lb of CO(2), which is lower than monoethanolamine (750 Btu/lb of CO(2)) at the same mass loading. At high pressures (30 bar and 298 K), these materials adsorbed approximately 20-30 wt % of CO(2), which corresponds to 3 to 5 molecules of CO(2) per formula unit. Similar gas adsorption isotherms for SO(2), H(2)S, and NO were collected using a specially constructed volumetric gas analyzer. At close to 1 bar of equilibrium pressure, these materials sorb around 2.5, 2.7, and 1.2 mmol/g of SO(2), H(2)S, and NO. In particular, the uptake of SO(2) and H(2)S in Co(3)[Co(CN)(6)](2) is quite significant since it sorbs around 10 and 4.5 wt % at 0.1 bar of pressure. The stability of prussian blues before and after trace gases was studied using a powder X-ray diffraction instrument, which confirms these materials do not decompose after exposure to trace gases.
Competitive adsorption behaviors of carbon dioxide and n-dodecane mixtures in 13X molecular sieve

NASA Astrophysics Data System (ADS)

Zhu, Chaofan; Dong, Mingzhe; Gong, Houjian

2018-01-01

The CO2 cyclic injection has been proven to be effective to enhance tight oil recovery under constant reservoir temperature and down hole pressure conditions. However, the enhance tight oil recovery mechanism was unclear, especially the adsorption of the CO2 and alkane in the surface. Therefore, it is great important to study the adsorption mechanism of CO2 and alkane mixtures in tight oil. In this study, a new experimental method and apparatus have been designed to test the change of the mole fraction of CO2 and n-C12 before and after the adsorption equilibrium. Then, the adsorption amount of CO2 and n-C12 was obtained by a mathematical method. Moreover, the adsorption character of CO2 and n-C12 mixtures in 13X molecular sieve and the effect of pressure on the adsorption and amount were studied. The results show that the adsorption of CO2 and the desorption of n-C12 follow the Langmuir adsorption. This study provides a straightforward method to experimentally determine the adsorption properties of the tight oil, which can be used to evaluate enhanced tight oil recovery by CO2 injection.
The adsorption and reaction of adenine nucleotides on montmorillonite

NASA Technical Reports Server (NTRS)

Ferris, James P.; Hagan, William J., Jr.

1986-01-01

The binding of AMP to Zn(2+)-montmorillonite is investigated in the presence of salts and Good's zwitterion buffers, PIPES and MES. The initial concentrations of nucleotide and the percent adsorbtion are used to calculate the adsorption isotherms, and the Langmuir adsorption equation is used for the analysis of data. The adsorption coefficient was found to be three times greater in the presence of 0.2 M PIPES than in its absence. In addition, basal spacings measured by X-ray diffraction were increased by the buffer. These results are interpreted in terms of a model in which the adsorption of AMP is mediated by a Zn(2+) complex of PIPES in different orientations in the interlamellar region of the montmorillonite. Mixed ligand complexes of this type are reminiscent of the complexes observed between metal ions and biological molecules in living systems.
Synthesis and visible-light photocatalytic performance of flower-like porous Bi5O7I

NASA Astrophysics Data System (ADS)

Yao, Lizhu; Shi, Lei; Wang, Fangxiao

2018-04-01

Flower-like porous Bi5O7I was successfully synthesized through an easy thermal decomposition of flower-like BiOI. And its chemical structure, morphology and optical property were thoroughly analyzed by x-ray diffraction, x-ray photoelectron spectroscopy, scanning electron microscope, energydispersive spectrometry elements mapping, transmission electron microscopy, N2 adsorption-desorption isotherm, BET, and UV–vis diffuse reflectance spectra. The visible-light photocatalytic elimination of rhodamine B (RhB) was investigated. The experimental results indicated that flower-like porous Bi5O7I exhibited enhanced photocatalytic activity for degrading RhB in comparsion of flower-like BiOI, g-C3N4 and N-doped TiO2. Additionally, the as-prepared flower-like porous Bi5O7I possessed catalytic stability after recycles.
Effect of Different Activated Carbon as Carrier on the Photocatalytic Activity of Ag-N-ZnO Photocatalyst for Methyl Orange Degradation under Visible Light Irradiation

PubMed Central

Chen, Xiaoqing; Gao, Zhenzhen; Ye, Bang-Ce

2017-01-01

In order to enhance the photodegradation of methyl orange (MO) by ZnO under visible light irradiation, ZnO nanoparticles co-doped with Ag and N and supported on activated carbon (AC) with different properties were synthesized through the sol-gel method. The prepared photocatalysts were characterized in terms of the structure and properties through X-ray diffraction, N2 adsorption-desorption, ultraviolet-visible (UV-vis), diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, photoluminescence, and electron spin resonance. The photocatalytic activities of these photocatalysts followed the order: Ag-N-ZnO/ACs > Ag-N-ZnO > N, or Ag single-doped ZnO > commercial ZnO. This result was attributed to the small particle size, large surface area, narrow band gap, and high charge separation of Ag-N-ZnO/ACs. The Ag-N-ZnO/coconut husk activated carbon (Ag-N-ZnO/CHAC) exhibited the highest degradation efficiency of 98.82% for MO under visible light irradiation. This outcome was due to the abundant pore structure of Ag-N-ZnO/CHAC, resulting in stronger adsorption than that of other Ag-N-ZnO/ACs. Moreover, the degradation of MO on photocatalysis followed first order kinetics. The reactive species ·OH and ·O2− played more important roles in the photocatalytic degradation of MO over composite photocatalyst. Ag-N-ZnO/CHAC photocatalyst exhibited higher photocatalytic activity than unsupported Ag-N-ZnO after five recycling runs. PMID:28872593
Nanoscale zerovalent iron (nZVI) supported by natural and acid-activated sepiolites: the effect of the nZVI/support ratio on the composite properties and Cd2+ adsorption.

PubMed

Habish, Amal Juma; Lazarević, Slavica; Janković-Častvan, Ivona; Jokić, Bojan; Kovač, Janez; Rogan, Jelena; Janaćković, Đorđe; Petrović, Rada

2017-01-01

Natural (SEP) and partially acid-activated (AAS) sepiolites were used to prepare composites with nanoscale zerovalent iron (nZVI) at different (SEP or AAS)/nZVI ratios in order to achieve the best nZVI dispersibility and the highest adsorption capacity for Cd 2+ . Despite the higher surface area and pore volume of AAS, better nZVI dispersibility was achieved by using SEP as the support. On the other hand, a lower oxidation degree was achieved during the synthesis using AAS. X-ray photoelectron spectroscopy (XPS) analysis of the composite with the best nZVI dispersibility, before and after Cd 2+ adsorption, confirmed that the surface of the nZVI was composed of oxidized iron species. Metallic iron was not present on the surface, but it was detected in the subsurface region after sputtering. The content of zerovalent iron decreased after Cd 2+ adsorption as a result of iron oxidation during Cd 2+ adsorption. The XPS depth profile showed that cadmium was present not only at the surface of the composite but also in the subsurface region. The adsorption isotherms for Cd 2+ confirmed that the presence of SEP and AAS decreased the agglomeration of the nZVI particles in comparison to the pure nZVI, which provided a higher adsorption capacity. The results showed that the prevention of both aggregation and oxidation during the synthesis was necessary for obtaining an SEP/AAS-nZVI composite with a high adsorption capacity, but oxidation during adsorption was beneficial for Cd 2+ removal. The formation of strong bonds between Cd 2+ and the adsorbents sites of different energy until monolayer formation was proposed according to modeling of the adsorption isotherms.
An efficient adsorption of indigo carmine dye from aqueous solution on mesoporous Mg/Fe layered double hydroxide nanoparticles prepared by controlled sol-gel route.

PubMed

Ahmed, M A; Brick, A A; Mohamed, A A

2017-05-01

A new approach for removal of indigo carmine blue (IC) dye which is extensively used in jeans manufacture was successfully performed on novel mesoporous [LDH] nanoparticles prepared by sol-gel route using CTAB as shape and pore directing agent. The physicochemical features were monitored by X-ray diffraction (XRD), Fourier transformer infra-red (FTIR), N 2 adsorption-desorption isotherm, Field emission electron microscope (FESEM) and high resolution transmission electron microscope (HRTEM). The influence of reaction parameters affecting dye adsorption including contact time, initial dye concentration, pH and temperature were investigated. Textural analysis and HRTEM images indicate the existence of mesoporous spherical nanoparticles of size = 26 nm connected to each other's and embedded large numbers of mesopores of average pore radius = 43.5 Å. A successful adsorption of IC on LDH nanoparticles of surface area = 85.6 m 2 /g at various pH with maximum adsorption capacity = 62.8 mg/g at pH = 9.5. Langmuir model is more favorable to describe the adsorption of IC rather than Freundlich model which reflecting the preferential formation of monolayer on the surface of LDH. Both film diffusion and the intraparticle diffusion affect the dye adsorption. The values of enthalpy change (ΔH) for and (ΔS) are + 28.18 and + 0.118 kJ/mol, respectively indicating that the removal process is endothermic. The results indicated that LDH nanoparticles conserved a good activity even after five consecutive cycles of reuse. Our results suggest that mesoporous LDH nanoparticles are considered a potential novel adsorbent for remediation of wastewater containing IC. Copyright © 2017 Elsevier Ltd. All rights reserved.
CuO based catalysts on modified acidic silica supports tested in the de-NOx reduction.

PubMed

Bennici, Simona; Gervasini, Antonella; Lazzarin, Marta; Ragaini, Vittorio

2005-03-01

A series of dispersed CuO catalysts supported on modified silica supports with Al2O3 (SA), TiO2 (ST), and ZrO2 (SZ) were prepared optimising the adsorption method of copper deposition assisted by ultrasound treatment, already reported in a previous paper (S. Bennici, A. Gervasini, V. Ragaini, Ultrason. Sonochem. 10 (2003) 61). The obtained catalysts were characterized in their bulk (atomic absorption, X-ray diffraction, temperature programmed reduction) and surface (N2 adsorption, X-ray photoelectron spectroscopy, scanning electron microscopy) properties. The morphology of the finished materials was not deeply modified compared with that of the relevant supports. The employed complemented techniques evidenced a well dispersed CuO phase with a copper-support interaction on the most acidic supports (SA and SZ). The catalyst performances were studied in the reaction of selective catalytic reduction of NOx with ethene in oxidizing atmosphere in a flow apparatus under variable times (0.360-0.072 s) and temperatures (200-450 degrees C). The catalysts prepared on the most acidic supports (SA and SZ) were the most active and selective towards N2 formation. They showed a particular interesting activity in the reaction of NO2 reduction besides that of NO reduction.

Synthesis and application of ion imprinting polymer coated magnetic multi-walled carbon nanotubes for selective adsorption of nickel ion

NASA Astrophysics Data System (ADS)

He, Junnan; Shang, Hongzhou; Zhang, Xing; Sun, Xiaoran

2018-01-01

A novel nickel ion imprinted polymers (IIPs) based on multi-walled carbon nanotubes (MWCNTs) were synthesized inverse emulsion system, using chitosan(CS) and acrylic acid as the functional monomers, Ni (II) as the template, and N' N-methylene bis-acrylamide as the cross-linker. The chemical structure and morphological feature of the IIPs were characterized by scanning electron microscopy (SEM), Thermogravimetry (TG), X-ray diffraction (XRD), and Fourier transform infrared spectrometer (FTIR). The studies indicated that the gel layer was well grafted on the surface of MWCNTs. Studies on the adsorption ability of the IIPs, by atomic absorption spectrophotometry, demonstrated that IIPs possessed excellent adsorption and selective ability towards Ni (II), fitting to pseudo second-order kinetic isotherms and with a maximum capacity of 19.86 mg/g, and selectivity factor of 13.09 and 4.42. The electrochemical performance of ion imprinting carbon paste electrode (CPE/IIPs) was characterized by Cyclic voltammetry (CV). Studies have shown that CPE/IIPs showed excellent electrochemical performance.
Molecular and Dissociative Adsorption of Water on (TiO 2 ) n Clusters, n = 1–4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Mingyang; Straatsma, Tjerk P.; Dixon, David A.

In the low energy structures of the (TiO 2) n(H 2O) m (n ≤ 4, m ≤ 2n) and (TiO 2) 8(H 2O) m (m = 3, 7, 8) clusters were predicted using a global geometry optimization approach, with a number of new lowest energy isomers being found. Water can molecularly or dissociatively adsorb on pure and hydrated TiO 2 clusters. Dissociative adsorption is the dominant reaction for the first two H 2O adsorption reactions for n = 1, 2, and 4, for the first three H 2O adsorption reactions for n = 3, and for the first four Hmore » 2O adsorption reactions for n = 8. As more H 2O’s are added to the hydrated (TiO 2)n cluster, dissociative adsorption becomes less exothermic as all the Ti centers become 4-coordinate. Furthermore two types of bonds can be formed between the molecularly adsorbed water and TiO 2 clusters: a Lewis acid–base Ti–O(H 2) bond or an O···H hydrogen bond. The coupled cluster CCSD(T) results show that at 0 K the H 2O adsorption energy at a 4-coordinate Ti center is ~15 kcal/mol for the Lewis acid–base molecular adsorption and ~7 kcal/mol for the H-bond molecular adsorption, in comparison to that of 8–10 kcal/mol for the dissociative adsorption. The cluster size and geometry independent dehydration reaction energy, ED, for the general reaction 2(-TiOH) → -TiOTi– + H 2O at 4-coordinate Ti centers was estimated from the aggregation reaction of nTi(OH) 4 to form the monocyclic ring cluster (TiO 3H 2) n + nH 2O. E D is estimated to be -8 kcal/mol, showing that intramolecular and intermolecular dehydration reactions are intrinsically thermodynamically allowed for the hydrated (TiO 2) n clusters with all of the Ti centers 4-coordinate, which can be hindered by cluster geometry changes caused by such processes. Finally by bending force constants for the TiOTi and OTiO bonds are determined to be 7.4 and 56.0 kcal/(mol·rad 2). Infrared vibrational spectra were calculated using density functional theory, and the new bands appearing upon water adsorption were assigned.« less
Molecular and Dissociative Adsorption of Water on (TiO 2 ) n Clusters, n = 1–4

DOE PAGES

Chen, Mingyang; Straatsma, Tjerk P.; Dixon, David A.

2015-10-20

In the low energy structures of the (TiO 2) n(H 2O) m (n ≤ 4, m ≤ 2n) and (TiO 2) 8(H 2O) m (m = 3, 7, 8) clusters were predicted using a global geometry optimization approach, with a number of new lowest energy isomers being found. Water can molecularly or dissociatively adsorb on pure and hydrated TiO 2 clusters. Dissociative adsorption is the dominant reaction for the first two H 2O adsorption reactions for n = 1, 2, and 4, for the first three H 2O adsorption reactions for n = 3, and for the first four Hmore » 2O adsorption reactions for n = 8. As more H 2O’s are added to the hydrated (TiO 2)n cluster, dissociative adsorption becomes less exothermic as all the Ti centers become 4-coordinate. Furthermore two types of bonds can be formed between the molecularly adsorbed water and TiO 2 clusters: a Lewis acid–base Ti–O(H 2) bond or an O···H hydrogen bond. The coupled cluster CCSD(T) results show that at 0 K the H 2O adsorption energy at a 4-coordinate Ti center is ~15 kcal/mol for the Lewis acid–base molecular adsorption and ~7 kcal/mol for the H-bond molecular adsorption, in comparison to that of 8–10 kcal/mol for the dissociative adsorption. The cluster size and geometry independent dehydration reaction energy, ED, for the general reaction 2(-TiOH) → -TiOTi– + H 2O at 4-coordinate Ti centers was estimated from the aggregation reaction of nTi(OH) 4 to form the monocyclic ring cluster (TiO 3H 2) n + nH 2O. E D is estimated to be -8 kcal/mol, showing that intramolecular and intermolecular dehydration reactions are intrinsically thermodynamically allowed for the hydrated (TiO 2) n clusters with all of the Ti centers 4-coordinate, which can be hindered by cluster geometry changes caused by such processes. Finally by bending force constants for the TiOTi and OTiO bonds are determined to be 7.4 and 56.0 kcal/(mol·rad 2). Infrared vibrational spectra were calculated using density functional theory, and the new bands appearing upon water adsorption were assigned.« less
Nanostructured Mn-Fe Binary Mixed Oxide: Synthesis, Characterization and Evaluation for Arsenic Removal.

PubMed

Pillewan, Pradnya; Mukherjee, Shrabanti; Bansiwal, Amit; Rayalu, Sadhana

2014-07-01

Adsorption of arsenic on bimetallic Mn and Fe mixed oxide was carried out using both field as well as simulated water. The material was synthesized using hydrothermal method and characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Langmuir and Freundlich adsorption isotherms were computed using batch adsorption studies to determine the adsorption capacity of Mn-Fe binary mixed oxide for arsenic. Adsorption capacity for MFBMO obtained from Freundlich model was found to be 2.048 mg/g for simulated water and 1.084 mg/g for field water. Mn-Fe binary mixed oxide was found to be effective adsorbent for removal of arsenic from water.
A supramolecular Tröger's base derived coordination zinc polymer for fluorescent sensing of phenolic-nitroaromatic explosives in water† †Electronic supplementary information (ESI) available: Spectroscopic (multinuclear NMR, IR HRMS) characterizations, optimized structure, TGA, powder diffraction and fluorescence titration profiles. See DOI: 10.1039/c6sc04367d Click here for additional data file.

PubMed Central

Dabadie, Charlyne; Byrne, Kevin; Savyasachi, Aramballi J.; Umadevi, Deivasigamani; Schmitt, Wolfgang; Kitchen, Jonathan A.

2017-01-01

A V-Shaped 4-amino-1,8-napthalimide derived tetracarboxylic acid linker (L; bis-[N-(1,3-benzenedicarboxylic acid)]-9,18-methano-1,8-naphthalimide-[b,f][1,5]diazocine) comprising the Tröger's base (TB) structural motif was rationally designed and synthesised to access a nitrogen-rich fluorescent supramolecular coordination polymer. By adopting the straight forward precipitation method, a new luminescent nanoscale Zn(ii) coordination polymer (TB-Zn-CP) was synthesized in quantitative yield using Zn(OAc)2·2H2O and tetraacid linker L (1 : 0.5) in DMF at room temperature. The phase-purity of as-synthesised TB-Zn-CP was confirmed by X-ray powder diffraction analysis, infra-red spectroscopy, and elemental analysis. Thermogravimetric analysis suggests that TB-Zn-CP is thermally stable up to 330 °C and the morphological features of TB-Zn-CP was analysed by SEM and AFM techniques. The N2 adsorption isotherm of thermally activated TB-Zn-CP at 77 K revealed a type-II reversible adsorption isotherm and the calculated Brunauer–Emmett–Teller (BET) surface area was found to be 72 m2 g–1. Furthermore, TB-Zn-CP displayed an excellent CO2 uptake capacity of 76 mg g–1 at 273 K and good adsorption selectivity for CO2 over N2 and H2. The aqueous suspension of as-synthesized TB-Zn-CP showed strong green fluorescence (λ max = 520 nm) characteristics due to the internal-charge transfer (ICT) transition and was used as a fluorescent sensor for the discriminative sensing of nitroaromatic explosives. The aqueous suspension of TB-Zn-CP showed the largest quenching responses with high selectivity for phenolic-nitroaromatics (4-NP, 2,4-DNP and PA) even in the concurrent presence of other potentially competing nitroaromatic analytes. The fluorescence titration studies also provide evidence that TB-Zn-CP detects picric acid as low as the parts per billion (26.3 ppb) range. Furthermore, the observed fluorescence quenching responses of TB-Zn-CP towards picric acid were highly reversible. The highly selective fluorescence quenching responses including the reversible detection efficiency make the nanoscale coordination polymer TB-Zn-CP a potential material for the discriminative fluorescent sensing of nitroaromatic explosives. PMID:28572910
Adsorption of methyl orange on mesoporous γ-Fe2O3/SiO2 nanocomposites

NASA Astrophysics Data System (ADS)

Deligeer, W.; Gao, Y. W.; Asuha, S.

2011-02-01

Mesoporous γ-Fe2O3/SiO2 nanocomposite containing 30 mol% of γ-Fe2O3 was prepared by a template-free sol-gel method, and its removal ability for methyl orange (MO) was investigated. The nanocomposite was characterized using X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscope (SEM), Fourier transform infrared (FTIR) absorption measurements, nitrogen adsorption-desorption measurements, and magnetic measurements. The synthesized γ-Fe2O3/SiO2 nanocomposite has a mesoporous structure with an average pore size of 3.5 nm and a specific surface area of 245 m2/g, and it exhibits ferrimagnetic characteristics with the maximum saturation magnetization of 20.9 emu/g. The adsorption of MO on the nanocomposite reaches the maximum adsorbed percentage of ca. 80% within a few minutes, showing that most of MO can be removed in a short time. The MO adsorption data fit well with both Langmuir and Freundlich adsorption isotherms. The maximum adsorption capacity of MO is estimated to be 476 mg/g.
Activated carbon-based magnetic TiO2 photocatalyst codoped with iodine and nitrogen for organic pollution degradation

NASA Astrophysics Data System (ADS)

Wang, Xuejiang; Song, Jingke; Huang, Jiayu; Zhang, Jing; Wang, Xin; Ma, RongRong; Wang, Jiayi; Zhao, Jianfu

2016-12-01

Magnetic photocatalyst - iodine and nitrogen codoped TiO2 based on chitosan decorated magnetic activated carbon (I-N-T/CMAC) was prepared via simple coprecipitation and sol-gel method. The characteristics of photocatalysts were investigated by X-ray diffraction (XRD), N2 adsorption-desorption isotherm, field emission scanning electron microscopy (FESEM), energy dispersive spectrometry (EDS), fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflection spectroscopy (UV-vis DRS), photoluminescence (PL) spectroscopy and vibrating sample magnetometer (VSM). It turned out that the prepared material had large surface area, enhanced absorption of visible light, and magnetically separable properties when mole ratio of I/Ti was 0.1. Iodine-nitrogen codoped magnetic photocatalyst was used for the removal of salicylic acid (SA), and the rate of adsorption reaction for SA by I0.1-N-T/CMAC followed the pseudo second-order kinetic. Under visible light irradiation, 89.71% SA with initial concentration = 30 mg/L could be removed by I0.1-N-T/CMAC, and photodegradation rate of SA on I0.1-N-T/CMAC composites was 0.0084 min-1 which is about 4 times higher than that of magnetic photocatalyst with nitrogen doped only. The effects of SA initial concentration, pH, coexisting anions and humic acid to the degradation of SA with the prepared material were also investigated. Main oxidative species in the photodegradation process are rad OH and h+.
Highly-Selective and Reversible O₂ Binding in Cr₃(1,3,5-benzenetricarboxylate)₂

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murray, Leslie J; Dinca, Mircea; Yano, Junko

2010-06-16

Reaction of Cr(CO)₆ with trimesic acid in DMF affords the metal–organic framework Cr₃(BTC)₂∙nDMF (BTC 3- = 1,3,5-benzenetricarboxylate), which is isostructural to Cu₃(BTC)₂∙3H₂O. Exchanging DMF for methanol and heating at 160 °C under dynamic vacuum for 48 h results in the desolvated framework Cr₃(BTC)₂. Nitrogen gas adsorption measurements performed at 77 K revealed a type I isotherm, indicating BET and Langmuir surface areas of 1810 and 2040 m²/g, respectively. At 298 K, the O₂ adsorption isotherm for Cr₃(BTC)₂ rises steeply to a capacity of 11 wt % at 2 mbar, while the corresponding N₂ adsorption isotherm displays very little uptake, graduallymore » rising to a capacity of 0.58 wt % at 1 bar. Accordingly, the material displays an unprecedented O₂/N₂ selectivity factor of 22. Deoxygenation of the sample could be accomplished by heating at 50 °C under vacuum for 48 h, leading to a gradually diminishing uptake capacity over the course of 15 consecutive adsorption/desorption cycles. Infrared and X-ray absorption spectra suggest formation of an O₂ adduct with partial charge transfer from the Cr II centers exposed on the surface of the framework. Neutron powder diffraction data confirm this mechanism of O₂ binding and indicate a lengthening of the Cr–Cr distance within the paddle-wheel units of the framework from 2.06(2) to 2.8(1) Å.« less
Adsorption behavior of hydrotalcite-like modified bentonite for Pb2+, Cu2+and methyl orange removal from water

NASA Astrophysics Data System (ADS)

Chen, Yu; Peng, Jingdong; Xiao, Huan; Peng, Huanjun; Bu, Lingli; Pan, Ziyu; He, Yan; Chen, Fang; Wang, Xiang; Li, Shiyu

2017-10-01

Hydrotalcite-like compound (HTlc) which contained lanthanum cation was prepared successfully. The title compound was characterized by thermogravimetry analysis, element analysis, X-ray fluorescence, Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, as well as specific surface area. The study sought to investigate the adsorption of heavy metals and dye (Pb2+, Cu2+ and methyl orange) in aqueous solution on Ben-HTlc. For optimization of adsorption behavior of the three elements, the pH value, contact time, adsorbate concentration were optimized. As for Pb2+, Cu2+ and methyl orange (MO), the single-component adsorption generally reached the maximum quantity in first 20 min and their respective adsorption capacities were 384.6 mg g-1, 156.3 mg g-1 and 333.3 mg g-1 (pH = 6.5 ± 0.1), the adsorption affinities were in the following sequence Pb2+ > MO > Cu2+. The repeated adsorption and regeneration studies showed the promising application of Ben-HTlc. The breakthrough experimental consequence had shown that the synthesized Ben-HTlc could efficiently remove heavy metals and dye from water, suggesting the potential utilization of Ben-HTlc in pollutants removal.
[Effect of humic acids on migration and transformation of NH4(+) -N in saturated aquifer].

PubMed

Meng, Qing-Jun; Zhang, Yan; Feng, Qi-Yan; Zhang, Shuang-Sheng

2011-11-01

Isothermal adsorption experiment was used to study the adsorbing process of NH4(+) -N in quartz sands under the conditions with and without humic acid; the Langmuir and Freundlich equations were used to fit the absorption result and the maximum adsorption capacity of NH4(+) -N by quarts sands was calculated. Through the soil column experiments, the concentration of NH4(+) -N, NO3(-) -N and NO2(-) -N in effluent water in the tested soil column was investigated, and the effect of humic acid on migration and transformation of NH4(+) -N in saturated aquifer was analyzed, and Pseudo-second-order Kinetics Equation and Two-step Adsorption Kinetics Rate Equation were applied to fit the kinetic processes. The results showed that both Langmuir and Freundlich models can well describe the isothermal adsorption process of NH4(+) -N on the surface of quartz sands, which means that NH4(+) -N adsorbed by the quartz sand was mainly in the form of monolayer adsorption. The humic acid could increase the adsorption capacity of NH4(+) -N on quartz sand, and the saturated adsorption capacity was 0.354 mg x g(-1) under the condition with humic acid and 0.205 mg x g(-1) with the absence of humic acid. The experiment indicated that humic acid increased the adsorption capacity of NH4(+) -N on the surface of quartz sand by increasing adsorption space in the initial stage. After saturation, humic acid influenced the migration and transformation of NH4(+) -N to NO3(-) -N and NO2(-) -N probably through providing carbon source and energy for microorganisms such as nitrifying bacteria and then resulting in lower NH4(+) -N concentration in effluent water. Both Pseudo-second-order Kinetics Equation and Two-step Adsorption Kinetics Rate Equations can well describe the process of NH4(+) -N adsorption kinetics on quartz sand (R2 = 0.997 7 and R2 = 0.998 1 with humic acid; R2 = 0.992 3 and R2 = 0.994 4 without humic acid), indicating that this process was chemical adsorption. By comparing the adsorption rate coefficient of Two-step Adsorption Kinetics Rate Equation k3 (0.247 and 0.143, respectively) and k4 (0.006 27 and 0.001 7) between the treatments with and without humic acid, it can be referred that NH4(+) -N was non-orientated adsorption on active points of the quartz sand at the initial stage, and the humic acid could increase the equilibrium adsorption quantity(q(e)) of NH4(+) -N on quartz sands.
Adsorption and photocatalytic properties of transition metal Zinc(II) complex based on 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid

NASA Astrophysics Data System (ADS)

Qiao, Yu; Ren, Shan-Shan; Liu, Li-Hui; Guan, Wei-Sheng; Li, Zhi-Min; Che, Guang-Bo; Liu, Chun-Bo; Wang, Yan-Yan; Wang, Qing-Wei; Li, Xiu-Ying; Zhu, En-Wei

2018-06-01

A new coordination polymeric zinc(II) complex, namely, [Zn2(L)(H2O)3]n·nNO3(1), (H3L = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid) has been synthesized under solvothermal conditions and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction analysis and powder X-ray diffraction. Complex 1 exhibits a three-dimensional structure with a Schläfli symbol of 44•69•82 topologies, constructed from two crystallographically independent five and six coordinated mode with metal center and connected H3L ligands. The complex has good thermal stability and excellent photoluminescent property. Furthermore, by comparing the photoluminescent and photocatalytic mutation results induced by interconversion of metal ions, we confirm that the properties mutation induced by metal ions is much controllable and obvious. In addition, the complex exhibits significantly enhanced photocatalytic activity for methylene blue (MB) under UV light irradiation (λ < 400 nm), and the degradation rate could reach 75% in 80 min. Meanwhile trapping experiments indicated that the •O2- and h+ are the main activated species.
A porous Cd(II) metal-organic framework with high adsorption selectivity for CO2 over CH4

NASA Astrophysics Data System (ADS)

Zhu, Chunlan

2017-05-01

Metal-organic frameworks (MOFs) have attracted a lot of attention in recent decades. We applied a semi-rigid four-carboxylic acid linker to assemble with Cd(II) ions to generate a novel microporous Cd(II) MOF material. Single crystal X-ray diffraction study reveals the different two dimension (2D) layers can be further packed together with an AB fashion by hydrogen bonds (O4sbnd H4⋯O7 = 1.863 Å) to construct a three dimension (3D) supermolecular architecture. The resulting sample can be synthesized under solvothermal reactions successfully, which exhibits high selectivity adsorption of CO2 over CH4 at room temperature. In addition, the obtained sample was characterized by thermal gravimetric analyses (TGA), Fourier-transform infrared spectra (FT-IR), elemental analysis (CHN) and powder X-ray diffraction (PXRD).
Elucidating the breathing of the metal-organic framework MIL-53(Sc) with ab initio molecular dynamics simulations and in situ X-ray powder diffraction experiments.

PubMed

Chen, Linjiang; Mowat, John P S; Fairen-Jimenez, David; Morrison, Carole A; Thompson, Stephen P; Wright, Paul A; Düren, Tina

2013-10-23

Ab initio molecular dynamics (AIMD) simulations have been used to predict structural transitions of the breathing metal-organic framework (MOF) MIL-53(Sc) in response to changes in temperature over the range 100-623 K and adsorption of CO2 at 0-0.9 bar at 196 K. The method has for the first time been shown to predict successfully both temperature-dependent structural changes and the structural response to variable sorbate uptake of a flexible MOF. AIMD employing dispersion-corrected density functional theory accurately simulated the experimentally observed closure of MIL-53(Sc) upon solvent removal and the transition of the empty MOF from the closed-pore phase to the very-narrow-pore phase (symmetry change from P2(1)/c to C2/c) with increasing temperature, indicating that it can directly take into account entropic as well as enthalpic effects. We also used AIMD simulations to mimic the CO2 adsorption of MIL-53(Sc) in silico by allowing the MIL-53(Sc) framework to evolve freely in response to CO2 loadings corresponding to the two steps in the experimental adsorption isotherm. The resulting structures enabled the structure determination of the two CO2-containing intermediate and large-pore phases observed by experimental synchrotron X-ray diffraction studies with increasing CO2 pressure; this would not have been possible for the intermediate structure via conventional methods because of diffraction peak broadening. Furthermore, the strong and anisotropic peak broadening observed for the intermediate structure could be explained in terms of fluctuations of the framework predicted by the AIMD simulations. Fundamental insights from the molecular-level interactions further revealed the origin of the breathing of MIL-53(Sc) upon temperature variation and CO2 adsorption. These simulations illustrate the power of the AIMD method for the prediction and understanding of the behavior of flexible microporous solids.
Drastic reduction of adsorption of CO and H2 on (111)-type Pd layers

NASA Technical Reports Server (NTRS)

Poppa, H.; Soria, F.

1983-01-01

Clean surfaces of (111)-type Pd layers, grown from the vapor phase on Mo(110) at room temperature, were used to study the adsorption of CO and H2 by temperature-programmed desorption, Auger electron spectroscopy, and low-energy electron diffraction. Mild annealing of the as-grown layers during a single desorption cycle (to about 600 K) drastically reduces the adsorption for both adsorbates. Low-dose argon-ion bombardment introduces surface imperfections which restore a high adsorption probability. The results are interpreted in terms of particular (111)-type surface structures that persist tp layer thicknesses of about four monolayers; the results raise questions with respect to the surface structure of supported thin epitaxial islands and particles of Pd and possibly also with respect to conventional methods of preparing bulk surfaces of Pd for adsorption studies.
Amino-functionalized mesoporous MCM-41 silica as an efficient adsorbent for water treatment: batch and fixed-bed column adsorption of the nitrate anion

NASA Astrophysics Data System (ADS)

Ebrahimi-Gatkash, Mehdi; Younesi, Habibollah; Shahbazi, Afsaneh; Heidari, Ava

2017-07-01

In the present study, amino-functionalized Mobil Composite Material No. 41 (MCM-41) was used as an adsorbent to remove nitrate anions from aqueous solutions. Mono-, di- and tri-amino functioned silicas (N-MCM-41, NN-MCM-41 and NNN-MCM-41) were prepared by post-synthesis grafting method. The samples were characterized by means of X-ray powder diffraction, FTIR spectroscopy, thermogravimetric analysis, scanning electron microscopy and nitrogen adsorption-desorption. The effects of pH, initial concentration of anions, and adsorbent loading were examined in batch adsorption system. Results of adsorption experiments showed that the adsorption capacity increased with increasing adsorbent loading and initial anion concentration. It was found that the Langmuir mathematical model indicated better fit to the experimental data than the Freundlich. According to the constants of the Langmuir equation, the maximum adsorption capacity for nitrate anion by N-MCM-41, NN-MCM-41 and NNN-MCM-41 was found to be 31.68, 38.58 and 36.81 mg/g, respectively. The adsorption kinetics were investigated with pseudo-first-order and pseudo-second-order model. Adsorption followed the pseudo-second-order rate kinetics. The coefficients of determination for pseudo-second-order kinetic model are >0.99. For continuous adsorption experiments, NNN-MCM-41 adsorbent was used for the removal of nitrate anion from solutions. Breakthrough curves were investigated at different bed heights, flow rates and initial nitrate anion concentrations. The Thomas and Yan models were utilized to calculate the kinetic parameters and to predict the breakthrough curves of different bed height. Results from this study illustrated the potential utility of these adsorbents for nitrate removal from water solution.
Ab Initio Cluster Calculations for the Adsorption of Small Molecules on Oxide Surfaces - from Single Molecules to Monolayers

NASA Astrophysics Data System (ADS)

Pykavy, M.; Staemmler, V.; Rittner, F.

2000-04-01

Quantum chemical ab initio cluster calculations were performed for the adsorption of small molecules on metal oxide surfaces. Two systems were studied in detail: The adsorption of N2 on the (110) surface plane of TiO2 (rutile) and the adsorption of CO on the polar (0001) surface of Cr2O3. In both cases a full five-dimensional potential for the interaction of a single molecule with the respective surface was calculated. For N2/TiO2 (110) the minimum was found for the end-on adsorption of N2 atop a coordinately unsaturated surface Ti atom, with an adsorption energy of (35 ± 5) kJ/mol. In the case of CO/Cr2O3 (0001) the CO molecule is adsorbed strongly tilted (almost side-on) along a line connecting two Cr3+ ions at the surface; the calculated adsorption energy is 22 kJ/mol. In conjunction with empirical pair potentials for the N2/N2 and CO/CO interaction in the gas phase, Monte Carlo simulations were carried out to determine adsorption isotherms and the geometric structure of adsorbed monolayers.
Facile preparation of highly-dispersed cobalt-silicon mixed oxide nanosphere and its catalytic application in cyclohexane selective oxidation

PubMed Central

2011-01-01

Highly dispersed cobalt-silicon mixed oxide [Co-SiO2] nanosphere was successfully prepared with a modified reverse-phase microemulsion method. This material was characterized in detail by X-ray diffraction, transmission electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance spectra, X-ray absorption spectroscopy near-edge structure, and N2 adsorption-desorption measurements. High valence state cobalt could be easily obtained without calcination, which is fascinating for the catalytic application for its strong oxidation ability. In the selective oxidation of cyclohexane, Co-SiO2 acted as an efficient catalyst, and good activity could be obtained under mild conditions. PMID:22067075
Facile synthesis of 2D Zn(II) coordination polymer and its crystal structure, selective removal of methylene blue and molecular simulations

NASA Astrophysics Data System (ADS)

Sezer, Güneş Günay; Yeşilel, Okan Zafer; Şahin, Onur; Arslanoğlu, Hasan; Erucar, İlknur

2017-09-01

A new coordination polymer {[Zn(μ3-ppda)(H2O)(μ-bpa)Zn(μ-ppda)(μ-bpa)]·4H2O}n (1) (ppda = 1,4-phenylenediacetate, bpa = 1,2-bis(4-pyridyl)ethane) has been synthesized by microwave-assisted reaction and characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffractions. The asymmetric unit of 1 consists of two Zn(II) ions, two bpa ligands, two ppda ligands, one coordinated and four non-coordinated water molecules. In 1, ppda2- anions are linked the adjacent Zn(II) centers to generate 1D double-stranded chains. These chains are connected into 2D sheets by the bridging bpa ligands. Atomically detailed modeling was performed to compute single and binary component adsorption isotherms of H2, CO2, CH4 and N2 in complex 1. Results showed that 1 exhibits a high adsorption selectivity towards CO2 due to its high affinity for CO2. Results of this study will be helpful to guide the microwave-assisted reaction of coordination polymers to design promising adsorbents for gas storage and gas separation applications. The luminescent property of 1 and the selective removal of dyes in 1 have been also discussed. Results showed that 1 can be a potential candidate for luminescence applications and can selectively adsorb methylene blue (MB) dye molecules.
Effect of heat treatment on the efficient adsorption of Cd2+ ions by nanosized SiO2, TiO2 and their composite

NASA Astrophysics Data System (ADS)

Waseem, M.; Muntha, S. T.; Nawaz, M.; Rehman, W.; Rehman, M. A.; Shah, K. H.

2017-01-01

In this study nanosized SiO2, TiO2 and their composite were synthesized via the oil in water (o/w) microemulsion method and their thermal treatment was performed at 378, 573, 973 and 1273 K. The physicochemical properties of the samples were studied by surface area measurements, scanning electron microscopy, Fourier transform infra-red spectroscopy and x-ray diffraction analysis. The Brunauer, Emmett and Teller surface area of all the adsorbents increases from 378 to 573 K, while it decreases upon further heat treatment. The average crystallite size decreases by heating the samples from 378 to 573 K while it increases when the adsorbents were thermally heat treated at 973 and 1273 K. The intensity of a few IR bands was reduced along with the disappearance of most of the bands at higher temperatures. The appearance of the beta-cristobalite phase in SiO2 and the rutile phase in TiO2 was confirmed from the diffraction data. The heat treated samples were subjected to preliminary adsorption of Cd2+ ions from aqueous solution at 293 K. Based on the preliminary adsorption experiments, SiO2, TiO2 and their composite heat treated at 573 K were selected for further adsorption studies. The Langmuir model was found to be fitted to the sorption data of TiO2 and the nanocomposite while the adsorption of Cd2+ ions by the SiO2 nanoparticles was explained well based on the Freundlich model. In the present study, the maximum Cd2+ adsorption capacity of SiO2, TiO2 and their composite was found to be 79.72, 98.55 and 107.17 mg g-1, respectively. The q m and K f values obtained in the present study were found to be far better than those reported in the literature. The negative values of ΔG confirm the feasibility of an adsorption process at higher temperatures. The positive values of ΔH and ΔS represent the endothermic and physical nature of the adsorption process with the increased randomness of Cd2+ ions at the solid/solution interface.
Adsorption-photodegradation of humic acid in water by using ZnO coupled TiO2/bamboo charcoal under visible light irradiation.

PubMed

Wang, Xuejiang; Wu, Zhen; Wang, Yin; Wang, Wei; Wang, Xin; Bu, Yunjie; Zhao, Jianfu

2013-11-15

ZnO coupled TiO2/bamboo charcoal (ZnO-TiO2/BC) was prepared using the sol-gel method combined with microwave irradiation. The ZnO-TiO2/BC and TiO2/BC were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), N2 adsorption (BET), and UV-vis diffuse reflectance spectroscopy (UV-vis-DRS). The ZnO dopant promoted the transformation of anatase TiO2 to rutile phase, and a significant red shift of absorption edge was brought out due to the interfacial coupling effect between ZnO and TiO2 particles. The BET specific surface area and total pore volume decreased with ZnO doping, indicating that some micropores were blocked. SEM studies indicated that ZnO was almost uniformly deposited on the surface of the ZnO-TiO2/BC. The adsorption and photocatalytic degradation experiments showed that the photo-degrade efficiency for Zno-TiO2/BC was higher than that of TiO2/BC, and for both composites, the removal efficiency of HA increased as pH decreased from 10.0 to 2.0. The degradation of HA by ZnO-TiO2/BC and TiO2/BC fitted well with the Langmuir-Hinshelwood kinetics model, and HA degradation was achieved through a synergistic mechanism of adsorption and photocatalysis. ZnO-TiO2/BC could be used as an effective and alternative photocatalyst for the treatment of water contaminated by organic pollutants. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis and crystal structure of Cd-based metal-organic framework for removal of methyl-orange from aqueous solution

NASA Astrophysics Data System (ADS)

Tella, Adedibu C.; Olawale, Margaret D.; Neuburger, Markus; Obaleye, Joshua A.

2017-11-01

A novel [Cd(INA)2(H2O)]. ISB (1) (INA = isonicotinate; ISB = isobutanol) was synthesized through the reaction between the isonicotinic acid ligand and cadmium (II) salt and characterized by elemental analysis, FTIR and UV-Visible spectroscopies, SEM and Single crystal X-ray diffraction. The crystal is orthorhombic, space group Pbca, a = 12.24(10) Å, b = 15.4646(13) Å, c = 18.8445(17) Å, V = 3569(3) Å3, Z = 8. The pentagonal bipyramid (seven coordinate) around the cadmium (II) ion is of the form CdN2O5 coordinating to four oxygen atoms from carboxylates, one oxygen atom from water molecule and two nitrogen atoms of pyridine. The structure of compound is stabilized by two hydrogen bonds namely intermolecular (O-H-O) and intramolecular type C-H-O accounting for polymeric nature of the metal-organic frameworks. 1 was studied for adsorptive removal of methyl orange (MO) from aqueous solution. Equilibrium isotherm study reveals that Langmuir model gave a better fitting result than the Freundlich model. The pseudo-second order model could be used to interpret adsorption kinetics. The maximum adsorption capacity calculated by Langmuir was 166 mg/g at 300 K. These results indicate the adsorption of MO on 1 is partly due to electrostatic interaction between methyl orange and the adsorbent. 1 could be used as adsorbent to remove methyl orange from aqueous solution.
Adsorption of heavy metals from aqueous solutions by Mg-Al-Zn mingled oxides adsorbent.

PubMed

El-Sayed, Mona; Eshaq, Gh; ElMetwally, A E

2016-10-01

In our study, Mg-Al-Zn mingled oxides were prepared by the co-precipitation method. The structure, composition, morphology and thermal stability of the synthesized Mg-Al-Zn mingled oxides were analyzed by powder X-ray diffraction, Fourier transform infrared spectrometry, N 2 physisorption, scanning electron microscopy, differential scanning calorimetry and thermogravimetry. Batch experiments were performed to study the adsorption behavior of cobalt(II) and nickel(II) as a function of pH, contact time, initial metal ion concentration, and adsorbent dose. The maximum adsorption capacity of Mg-Al-Zn mingled oxides for cobalt and nickel metal ions was 116.7 mg g -1 , and 70.4 mg g -1 , respectively. The experimental data were analyzed using pseudo-first- and pseudo-second-order kinetic models in linear and nonlinear regression analysis. The kinetic studies showed that the adsorption process could be described by the pseudo-second-order kinetic model. Experimental equilibrium data were well represented by Langmuir and Freundlich isotherm models. Also, the maximum monolayer capacity, q max , obtained was 113.8 mg g -1 , and 79.4 mg g -1 for Co(II), and Ni(II), respectively. Our results showed that Mg-Al-Zn mingled oxides can be used as an efficient adsorbent material for removal of heavy metals from industrial wastewater samples.
Synthesis, characterization, and potential application of Mn2+-intercalated bentonite in fluoride removal: adsorption modeling and mechanism evaluation

NASA Astrophysics Data System (ADS)

Mudzielwana, Rabelani; Gitari, Wilson M.; Akinyemi, Segun A.; Msagati, Titus A. M.

2017-12-01

The study synthesizes a low-cost adsorbent made from Mn2+-modified bentonite clay for groundwater defluoridation. The clays were characterized using X-ray diffraction, X-ray fluorescence, scanning electron microscopy, and Fourier transform infrared techniques. The fluoride adsorption capacity of the modified clay was evaluated using batch experiments. The adsorption kinetics results showed that the optimum fluoride (F-) uptake was achieved within the 30 min' contact time. The data fitted well to pseudo-second-order of reaction kinetics indicating that adsorption of F- occurred via chemisorption. In addition, the adsorption isotherm data fitted well to Langmuir isotherm model indicating that adsorption occurred on a mono-layered surface. Maximum F- removal of 57% was achieved from groundwater with an initial F- concentration of 5.4 mg L-1 and natural pH of 8.6 using adsorbent dosage of 1 g/100 mL. Fluoride adsorption occurred through ligands and ion exchange mechanisms. The synthesized adsorbent was successfully regenerated for up to five times. The study shows that Mn2+-intercalated bentonite clay has potential for application in defluoridation of groundwater.
[Adsorption of heavy metals on the surface of birnessite relationship with its Mn average oxidation state and adsorption sites].

PubMed

Wang, Yan; Tan, Wen-Feng; Feng, Xiong-Han; Qiu, Guo-Hong; Liu, Fan

2011-10-01

Adsorption characteristics of mineral surface for heavy metal ions are largely determined by the type and amount of surface adsorption sites. However, the effects of substructure variance in manganese oxide on the adsorption sites and adsorption characteristics remain unclear. Adsorption experiments and powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) were combined to examine the adsorption characteristics of Pb2+, Cu2+, Zn2+ and Cd2+ sequestration by birnessites with different Mn average oxidation state (AOS), and the Mn AOS dependent adsorption sites and adsorption characteristics. The results show that the maximum adsorption capacity of Pb2+, Cu2+, Zn2+ and Cd2+ increased with increasing birnessite Mn AOS. The adsorption capacity followed the order of Pb2+ > Cu2+ > Zn2+ > Cd2+. The observations suggest that there exist two sites on the surface of birnessite, i. e., high-binding-energy site (HBE site) and low-binding-energy site (LBE site). With the increase of Mn AOS for birnessites, the amount of HBE sites for heavy metal ions adsorption remarkably increased. On the other hand, variation in the amount of LBE sites was insignificant. The amount of LBE sites is much more than those of HBE sites on the surface of birnessite with low Mn AOS. Nevertheless, both amounts on the surface of birnessite with high Mn AOS are very close to each other. Therefore, the heavy metal ions adsorption capacity on birnessite is largely determined by the amount of HBE sites. On birnessite surface, adsorption of Cu2+, Zn2+, and Cd2+ mostly occurred at HBE sites. In comparison with Zn2+ and Cd2+, more Cu2+ adsorbed on the LBW sites. Pb2+ adsorption maybe occupy at both LBE sites and HBE sites simultaneously.
N-doping effectively enhances the adsorption capacity of biochar for heavy metal ions from aqueous solution.

PubMed

Yu, Wenchao; Lian, Fei; Cui, Guannan; Liu, Zhongqi

2018-02-01

N-doping was successfully employed to improve the adsorption capacity of biochar (BC) for Cu 2+ and Cd 2+ by direct annealing of crop straws in NH 3 . The surface N content of BC increased more than 20 times by N-doping; meanwhile the content of oxidized-N was gradually diminished but graphitic-N was formed and increased with increasing annealing temperature and duration time. After N-doping, a high graphitic-N percentage (46.4%) and S BET (418.7 m 2 /g) can be achieved for BC. As a result, the N-doped BC exhibited an excellent adsorption capacity for Cu 2+ (1.63 mmol g -1 ) and Cd 2+ (1.76 mmol g -1 ), which was up to 4.0 times higher than that of the original BC. Furthermore, the adsorption performance of the N-doped BC remained stable even at acidic conditions. A positive correlation can be found between adsorption capacity with the graphitic N content on BC surface. The surface chemistry of N-doped BC before and after the heavy metal ions adsorption was carefully examined by XPS and FTIR techniques, which indicated that the adsorption mechanisms mainly included cation-π bonding and complexation with graphitic-N and hydroxyl groups of carbon surfaces. Copyright © 2017 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Uemura, Kazuhiro, E-mail: k_uemura@gifu-u.ac.j; Onishi, Fumiaki; Yamasaki, Yukari

NO{sub 2} containing dicarboxylate bridging ligands, nitroterephthalate (bdc-NO{sub 2}) and 2,5-dinitroterephthalate (bdc-(NO{sub 2}){sub 2}), afford porous coordination polymers, {l_brace}[Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)].solvents{r_brace}{sub n} (2 contains solvents) and {l_brace}[Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)].solvents{r_brace}{sub n} (3 contains solvents). Both compounds form jungle-gym-type regularities, where a 2D square grid composed of dinuclear Zn{sub 2} units and dicarboxylate ligands is bridged by dabco molecules to extend the 2D layers into a 3D structure. In 2 contains solvents and 3 contains solvents, a rectangle pore surrounded by eight Zn{sub 2} corners contains two and four NO{sub 2} moieties, respectively. Thermal gravimetry (TG) and X-ray powdermore » diffraction (XRPD) measurements reveal that both compounds maintain the frameworks regularities without guest molecules and with solvents such as MeOH, EtOH, i-PrOH, and Me{sub 2}CO. Adsorption measurements reveal that dried 2 and 3 adsorb H{sub 2}O molecules to be {l_brace}[Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)].4H{sub 2}O{r_brace}{sub n} (2 contains 4H{sub 2}O) and {l_brace}[Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)].6H{sub 2}O{r_brace}{sub n} (3 contains 6H{sub 2}O), showing the pore hydrophilicity enhancement caused by NO{sub 2} group introduction. - Graphical abstract: Two hydrophilic porous coordination polymers, [Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)]{sub n} (2, bdc-NO{sub 2}=nitroterephthalate, dabco=1,4-diazabicyclo[2.2.2]octane) and [Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)]{sub n} (3, bdc-(NO{sub 2}){sub 2}=2,5-dinitroterephthalate), have been synthesized and characterized by single X-ray analyses, thermal gravimetry, and adsorption measurements.« less
Th(IV) Adsorption onto Oxidized Multi-Walled Carbon Nanotubes in the Presence of Hydroxylated Fullerene and Carboxylated Fullerene

PubMed Central

Wang, Jing; Liu, Peng; Li, Zhan; Qi, Wei; Lu, Yan; Wu, Wangsuo

2013-01-01

The adsorption of Th(IV) onto the surface of oxidized multi-walled carbon nanotubes (oMWCNTs) in the absence and presence of hydroxylated fullerene (C60(OH)n) and carboxylated fullerene (C60(C(COOH)2)n) has been investigated. C60(OH)n, C60(C(COOH)2)n and oMWCNTs have been chosen as model phases because of their representative in carbon nano-materials family. Adsorption experiments were performed by batch procedure as a function of contact time, pH, ionic strength, and temperature. The results demonstrated that the adsorption of Th(IV) was rapidly reached equilibrium and the kinetic process could be described by a pseudo-second-order rate model very well. Th(IV) adsorption on oMWCNTs was dependent on pH but independent on ionic strength. Adsorption isotherms were correlated better with the Langmuir model than with the Freundlich model. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that Th(IV) adsorption on oMWCNTs was spontaneous and endothermic. Compared with the adsorption of Th(IV) on the same oMWCNTs free of C60(OH)n or C60(C(COOH)2)n, the study of a ternary system showed the inhibition effect of C60(OH)n at high concentration on the adsorption of Th(IV) in a pH range from neutral to slightly alkaline; whereas the promotion effect of C60(C(COOH)2)n, even at its low concentration, on Th(IV) adsorption was observed in acid medium. PMID:28788324
Synthesis of Zeolite-X from Bottom Ash for H2 Adsorption

NASA Astrophysics Data System (ADS)

Kurniawan, R. Y.; Romadiansyah, T. Q.; Tsamarah, A. D.; Widiastuti, N.

2018-01-01

Zeolite-X was synthesized from bottom ash power plant waste using fusion method on air atmosphere. The fused product dissolved in demineralized water and aluminate solution was added to adjust the SiO2/Al2O3 molar ratio gel prior hydrothermal process. The synthesis results were characterized using X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Fourier Transform Infrared (FTIR). The results showed that the zeolite-X has a high crystallinity with octahedral particle. The pure-form zeolite-X then was characterized and tested for H2 gas adsorption by gravimetric method to determine the H2 gas adsorption capacity of zeolite-X from bottom ash and it was compared to synthetic zeolite-X.
Facile fabrication of transparent TiO2-C@TiO2-C free-standing film for visible-light photocatalytic application

NASA Astrophysics Data System (ADS)

Hu, Luyang; Zhang, Yumin; Zhang, Shanmei; Li, Benxia

2017-02-01

A transparent TiO2-C@TiO2-C free-standing film has been synthesized by two-step hydrothermal method and subsequent thermal annealing. The chemical composition and morphological features of the TiO2-C@TiO2-C film are characterized using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy and N2 adsorption-desorption measurement. The results indicate that the flower-like micro/nanostructure TiO2-C particle layers are intimately inhered to porous TiO2-C fibers. The fibers in film are interconnected each other to form a three-dimensional reticulate microstructure, and exhibit intense visible light absorption and high adsorptivity of dye molecules. The interaction between TiO2 and its surface carbon layer in TiO2-C particle promotes the generation of Ti-O-C bonds, which leads to effective charge transfer. Under visible-light irradiation, TiO2-C@TiO2-C film presents enhanced photocatalytic activity for degradation of methylene blue. This work may provide a new viewpoint for designing transparent photocatalytic film for promising applications in heterogeneous photocatalysis.
Uniform surface modification of diatomaceous earth with amorphous manganese oxide and its adsorption characteristics for lead ions

NASA Astrophysics Data System (ADS)

Li, Song; Li, Duanyang; Su, Fei; Ren, Yuping; Qin, Gaowu

2014-10-01

A novel method to produce composite sorbent material compromising porous diatomaceous earth (DE) and surface functionalized amorphous MnO2 is reported. Via a simple in situ redox reaction over the carbonized DE powders, a uniform layer of amorphous MnO2 was anchored onto the DE surface. The hybrid adsorbent was characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. The batch method has been employed to investigate the effects of surface coating on adsorption performance of DE. According to the equilibrium studies, the adsorption capacity of DE for adsorbing lead ions after MnO2 modification increased more than six times. And the adsorption of Pb2+ on the MnO2 surface is based on ion-exchange mechanism. The developed strategy presents a novel opportunity to prepare composite adsorbent materials by integrating nanocrystals with porous matrix.
Microwave-assisted synthesis of HKUST-1 and functionalized HKUST-1-@H3PW12O40: selective adsorption of heavy metal ions in water analyzed with synchrotron radiation.

PubMed

Zou, Fang; Yu, Runhan; Li, Rongguan; Li, Wei

2013-08-26

A simple, rapid and efficient synthesis of the metal-organic framework (MOF) HKUST-1 [Cu3(1,3,5-benzene-tri-carboxilic-acid)2] by microwave irradiation is described, which afforded a homogeneous and highly selective material. The unusually short time to complete the synthesis by microwave irradiation is mainly attributable to rapid nucleation rather than to crystal growth rate. Using this method, HKUST-1-MW (MW=microwave) could be prepared within 20 min, whereas by hydrothermal synthesis, involving conventional heating, the preparation time is 8 h. Work efficiency was improved by the good performance of the obtained HKUST-1-MW which exhibited good selective adsorption of heavy metal ions, as well as a remarkably high adsorption affinity and adsorption capacity, but no adsorption of Hg(2+) under the same experimental conditions. Of particular importance is the preservation of the structure after metal-ion adsorption, which remained virtually intact, with only a few changes in X-ray diffraction intensity and a moderate decline in surface area. Synthesis of the polyoxometalate-containing HKUST-1-MW@H3PW12O40 afforded a MOF with enhanced stability in water, due to the introduced Keggin-type phosphotungstate, which systematically occluded in the cavities constituting the walls between the mesopores. Different Cu/W ratios were investigated according to the extrusion rate of cooper ions concentration, without significant structural changes after adsorption. The MOFs obtained feature particle sizes between 10-20 μm and their structures were determined using synchrotron-based X-ray diffraction. The results of this study can be considered important for potentially wider future applications of MOFs, especially to attend environmental issues. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Water decontamination via the removal of Pb (II) using a new generation of highly energetic surface nano-material: Co(+2)Mo(+6) LDH.

PubMed

Mostafa, Mohsen S; Bakr, Al-Sayed A; El Naggar, Ahmed M A; Sultan, El-Sayed A

2016-01-01

CoMo(CO3(2-)) layered double hydroxide of a highly energetic surface, as a new LDH consisting of divalent and hexavalent cations (M(+2)/M(+6)-LDH), was prepared by a homogeneous co-precipitation method. The structure and morphology of the prepared material was confirmed by several analytical techniques namely; X-ray diffraction analysis (XRD), X-ray fluorescence (XRF), Fourier transform infra-red (FT-IR) spectroscopy, differential scanning calorimetry and thermal gravimetric analysis (DSC-TGA), N2 adsorption-desorption isotherm and scanning electron microscope (SEM). The highly energetic surface of the prepared LDH was demonstrated via the X-ray photoelectron spectroscopy (XPS). The surface energy is due to the formation of +4 surface charges in the brucite layer between Co(+2) and Mo(+6). The prepared LDH was applied as a novel adsorbent for the removal of Pb (II) from its aqueous solution at different experimental conditions of time, temperature and initial Pb (II) concentrations. The change of the Pb (II) concentrations; due to adsorption, was monitored by atomic absorption spectrophotometer (AAS). The maximum uptake of Pb (II) by the Co Mo LDH was (73.4 mg/g) at 298 K. The Pb (II) adsorption was found to follow Langmuir isotherm and pseudo second order model. The adsorption process was spontaneous and endothermic. The interference of other cations on the removal of the Pb (II) was studied. Na(+) and K(+) were found to increase the adsorption capacity of the Co Mo LDH toward Pb (II) while it was slightly decreased by the presence of Mn(+2) and Cu(+2). The synthesized LDH showed a great degree of recoverability (7 times) while completely conserving its parental morphology and adsorption capacity. The mechanism of the lead ions removal had exhibited more reliability through a surface adsorption by the coordination between the Mo(+6) of the brucite layers and the oxygen atoms of the nitrates counter ions. Copyright © 2015 Elsevier Inc. All rights reserved.
Molecular simulation of methane adsorption characteristics on coal macromolecule

NASA Astrophysics Data System (ADS)

Yang, Zhiyuan; He, Xiaoxiao; Meng, Zhuoyue; Xue, Wenying

2018-02-01

In this paper, the molecular model of anthracite named Wender2 was selected to study the adsorption behaviour of single component CH4 and the competitive adsorption of CH4/CO2, CH4/H2O and CH4/N2. The molecular model of anthracite was established by molecular simulation software (Materials Studio 8.0), and Grand Canonical Monte Carlo (GCMC) simulations were carried out to investigate the single and binary component adsorption. The effects of pressure and temperature on the adsorption position, adsorption energy and adsorption capacity were mainly discussed. The results show that for the single component adsorption, the adsorption capacity of CH4 increases rapidly with the pressure ascending, and then tends to be stable after the first step. The low temperature is favourable for the adsorption of CH4, and the high temperature promotes desorption quantity of CH4 from the coal. Adsorbent molecules are preferentially adsorbed on the edge of coal macromolecules. The order of adsorption capacity of CH4/CO2, CH4/H2O and CH4/N2 in the binary component is H2O>CO2>CH4>N2. The change of pressure has little effect on the adsorption capacity of the adsorbent in the competitive adsorption, but it has a great influence on the adsorption capacity of the adsorbent, and there is a positive correlation between them.
Adsorption of octylamine on titanium dioxide

NASA Astrophysics Data System (ADS)

Siwińska, Daria; Kołodziejczak-Radzimska, Agnieszka; Krysztafkiewicz, Andrzej; Jesionowski, Teofil

2009-05-01

Processes of adsorption and desorption of a model active substance (octylamine) on the surface of unmodified titanium dioxide (E 171) have been performed. The effects of concentration of octylamine and time of the process on the character of adsorption have been studied and the efficiency of the adsorption/desorption has been determined. The samples obtained have been studied by X-ray diffraction. The nitrogen adsorption/desorption isotherms, particle size distribution and absorption capacities of water, dibutyl phthalate and paraffin oil have been determined. The efficiency of octylamine adsorption on the surface of the titanium dioxide has been found positively correlated with the concentration of octylamine in the initial solution. The desorption of octylamine has decreased with increasing concentration of this compound adsorbed. For octylamine in low concentrations the physical adsorption has been found to dominate, which is desirable when using TiO 2 in the production of pharmaceuticals.
Synthesis and Characterization of Reduced Graphene Oxide-Supported Nanoscale Zero-Valent Iron (nZVI/rGO) Composites Used for Pb(II) Removal

PubMed Central

Fan, Mingyi; Li, Tongjun; Hu, Jiwei; Cao, Rensheng; Wu, Qing; Wei, Xionghui; Li, Lingyun; Shi, Xuedan; Ruan, Wenqian

2016-01-01

Reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were prepared by chemical deposition method and were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, N2-sorption and X-ray photoelectron spectroscopy (XPS). Operating parameters for the removal process of Pb(II) ions, such as temperature (20–40 °C), pH (3–5), initial concentration (400–600 mg/L) and contact time (20–60 min), were optimized using a quadratic model. The coefficient of determination (R2 > 0.99) obtained for the mathematical model indicates a high correlation between the experimental and predicted values. The optimal temperature, pH, initial concentration and contact time for Pb(II) ions removal in the present experiment were 21.30 °C, 5.00, 400.00 mg/L and 60.00 min, respectively. In addition, the Pb(II) removal by nZVI/rGO composites was quantitatively evaluated by using adsorption isotherms, such as Langmuir and Freundlich isotherm models, of which Langmuir isotherm gave a better correlation, and the calculated maximum adsorption capacity was 910 mg/g. The removal process of Pb(II) ions could be completed within 50 min, which was well described by the pseudo-second order kinetic model. Therefore, the nZVI/rGO composites are suitable as efficient materials for the advanced treatment of Pb(II)-containing wastewater. PMID:28773813
The studies on gas adsorption properties of MIL-53 series MOFs materials

NASA Astrophysics Data System (ADS)

Jiao, Yuqiu; Li, Zhenyu; Ma, Yue; Zhou, Guanggang; Wang, Shuangxi; Lu, Guiwu

2017-08-01

Molecular dynamics (MD), grand canonical Monte Carlo (GCMC) and ideal adsorbed solution theory (IAST) were used to study the structures and gas adsorption properties of MIL-53(M)[M=Cr, Fe, Sc, Al] metal organic framework (MOF) materials. The results show that the volumes of those MOF materials increase significantly at high temperature. By analyzing the adsorption isotherms, we found that the temperature had a paramount effect on the gas adsorption behaviors of these MOF materials. For MIL-53(Cr), the orders of the quantities of adsorbed gases were CH4>N2>CO2>H2S, CH4>H2S>CO2>N2 and CH4>CO2>H2S>N2 at 100K, 293K and 623K, respectively. We also calculated the adsorption of several combinations of two gases by MIL-53(Cr) at 293K, the results indicate that the material had selective adsorption of CH4 over CO2, H2S and N2. Our calculations provide microscopic insights into the gas adsorption performances of these MOFs and may further guide the practice of gas separation.
The Adsorption of Dextranase onto Mg/Fe-Layered Double Hydroxide: Insight into the Immobilization

PubMed Central

Ding, Yi; Liu, Le; Fang, Yaowei; Zhang, Xu; Lyu, Mingsheng; Wang, Shujun

2018-01-01

We report the adsorption of dextranase on a Mg/Fe-layered double hydroxide (Mg/Fe-LDH). We focused the effects of different buffers, pH, and amino acids. The Mg/Fe-LDH was synthesized, and adsorption experiments were performed to investigate the effects. The maximum adsorption occurred in pH 7.0 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer, and the maximum dextranase adsorption uptake was 1.38 mg/g (416.67 U/mg); histidine and phenylalanine could affect the adsorption. A histidine tag could be added to the protein to increase the adsorption significantly. The performance features and mechanism were investigated with X-ray diffraction patterns (XRD) and Fourier transform infrared spectra (FTIR). The protein could affect the crystal structure of LDH, and the enzyme was adsorbed on the LDH surface. The main interactions between the protein and LDH were electrostatic and hydrophobic. Histidine and phenylalanine could significantly affect the adsorption. The hexagonal morphology of LDH was not affected after adsorption. PMID:29562655
Oxygen adsorption on the Al0.25Ga0.75N (0001) surface: A first-principles study

NASA Astrophysics Data System (ADS)

Fu, Jiaqi; Song, Tielei; Liang, Xixia; Zhao, Guojun

2018-04-01

To understand the interaction mechanism for the oxygen adsorption on AlGaN surface, herein, we built the possible models of oxygen adsorption on Al0.25Ga0.75N (0001) surface. For different oxygen coverage, three kinds of adsorption site are considered. Then the favorable adsorption sites are characterized by first principles calculation for (2 × 2) supercell of Al0.25Ga0.75N (0001) surface. On basis of the optimal adsorption structures, our calculated results show that all the adsorption processes are exothermic, indicating that the (0001) surface orientation is active towards the adsorption of oxygen. The doping of Al is advantage to the adsorption of O atom. Additionally, the adsorption energy decreases with reducing the oxygen coverage, and the relationship between them is approximately linear. Owing to the oxygen adsorption, the surface states in the fundamental band gap are significant reduced with respect to the free Al0.25Ga0.75N (0001) surface. Moreover, the optical properties on different oxygen coverage are also discussed.
Magnetically Separable Fe3O4/SnO2/Graphene Adsorbent for Waste Water Removal

NASA Astrophysics Data System (ADS)

Paramarta, V.; Taufik, A.; Saleh, R.

2017-05-01

Our previous study conducted the SnO2 and SnO2/graphene adsorption efficiency in Methylene Blue removal from aqueous solution, however, the difficulty of adsorbent separation from the methylene blue solution limits its efficiency. Therefore, in this work, SnO2 and SnO2/graphene was combined with Fe3O4 to improve the separation process and adsorption performance for removing the organic dyes. Fe3O4/SnO2/grapheme were synthesized by using the co-precipitation method. The graphene content was varied from 1, 3, and 5 weight percent (wt%). The crystalline phase and thermal stability of the samples were characterized by using X- ray Diffraction (XRD) and Thermal Gravimetric Analysis (TGA). The adsorption ability of the samples was investigated by using significant adsorption degradation of MB observed when the graphene in Fe3O4/SnO2 nanocomposite was added. The other parameters such as pH and initial concentration have also been investigated. The reusability was also investigated to study the stability of the samples. The fitting of equilibrium adsorption capacity result indicates that the adsorption mechanism of Fe3O4/SnO2 nanocomposite with graphene tends to follow the Langmuir adsorption isotherm model.
Effect of the acid treatment conditions of kaolinite on etheramine adsorption: A comparative analysis using chemometric tools.

PubMed

Leal, Paulo Vitor Brandão; Magriotis, Zuy Maria; Sales, Priscila Ferreira de; Papini, Rísia Magriotis; Viana, Paulo Roberto de Magalhães

2017-07-15

The present work evaluated the effect of the acid treatment conditions of natural kaolinite (NK) regarding its efficiency in removing etheramine. The treatment was conducted using sulfuric acid at the concentrations of 1 mol L -1 (KA-01), 2 mol L -1 (KA-02) and 5 mol L -1 (KA-05) at 85 °C. The obtained adsorbents were characterized by X-ray fluorescence, X-ray diffraction, N 2 adsorption/desorption isotherms, zeta potential analysis and infrared spectroscopy. The Response Surface Method was used to optimize adsorption parameters (initial concentration of etheramine, adsorbent mass and pH of the solution). The results, described by means of a central composite design, were adjusted to the quadratic model. Results revealed that the adsorption was more efficient at the etheramine concentration of 400 mg L -1 , pH 10 and adsorbent mass of 0.1 g for NK and 0.2 g for KA-01, KA-02 and KA-05. The sample KA-02 presented a significant increase of etheramine removal compared to the NK sample. The adsorption kinetics conducted under optimized conditions showed that the system reached the equilibrium in approximately 30 min. The kinetic data were better adjusted to the pseudo-second order model. The isotherm data revealed that the Sips model was the most adequate one. The calculation of E ads allowed to infer that the mechanism for etheramine removal in all the evaluated samples was chemisorption. The reuse tests showed that, after four uses, the efficiency of adsorbents in removing etheramine did not suffer significant modifications, which makes the use of kaolinite to treat effluents from the reverse flotation of iron ore feasible. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lead (Pb2+) and copper (Cu2+) remediation from water using superparamagnetic maghemite (γ-Fe2O3) nanoparticles synthesized by Flame Spray Pyrolysis (FSP).

PubMed

Rajput, Shalini; Singh, Lok P; Pittman, Charles U; Mohan, Dinesh

2017-04-15

Superparamagnetic maghemite (γ-Fe 2 O 3 ) nanoparticles of controllable morphology were successfully synthesized using a flame spray pyrolysis (FSP) technique. Their physico-chemical properties, size, morphology, and surface chemistries were determined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), selected area electron diffraction patterns (SAED), SEM-EDX, scanning electron microscopy (SEM), and pH ZPC (6.3). Elemental contents before and after adsorption were identified using energy dispersive X-ray fluorescence (ED-XRF), energy dispersive X-ray analysis (EDX) and elemental mapping. Surface area (S BET 79.35m 2 /g) and size distribution analyses were conducted using a surface area analyzer and dynamic light scattering (DLS), respectively. The magnetic moment (44.5 at 300K and 50.16 at 2K) was determined using a physical properties measurement system (PPMS). The first adsorption study using γ-Fe 2 O 3 nanoparticles synthesized by FSP to successfully remediate Pb 2+ and Cu 2+ from water is reported. Batch adsorption studies were carried out. An optimum pH of 5.0 was studied for Pb 2+ and Cu 2+ removal. Pb 2+ and Cu 2+ removal mechanisms by these maghemite nanoparticles were presented. The adsorption of Pb 2+ and Cu 2+ was highly pH-dependent. The metal ion uptake was mainly governed by electrostatic attractions. Sorption kinetic data followed the pseudo-second-order model. The Freundlich, Langmuir, Redlich-Peterson, Radke and Sips adsorption isotherm models were applied to interpret equilibrium data. The Freundlich and Langmuir isotherm equations best fit the respective equilibrium data for Pb 2+ and Cu 2+ . The maximum Langmuir adsorption capacities of these maghemite nanoparticles were 68.9mg/g at 45°C for Pb 2+ and 34.0mg/g at 25 °C for Cu 2+ . Thus, these maghemite nanoparticles made by FSP were readily prepared, characterized and showed promise for remediating heavy metal ions from aqueous solutions. Copyright © 2016 Elsevier Inc. All rights reserved.
Effects of Polyethylene Glycol and Citric Acid on Preparation and Hydrodechlorination Activity of Molybdenum Phosphide

NASA Astrophysics Data System (ADS)

Liu, Xiaomeng; Lu, Shaoxiang; Xu, Hanghui; Ren, Lili

2018-07-01

Molybdenum phosphide (MoP), modified by polyethylene glycol (PEG) and citric acid (CA), exhibited 2 to 3 times superior activity than the MoP modified by CA alone. And the optimal activity temperature was reduced from 500 to 450oC. The catalyst was fully characterized by a variety of techniques including X-ray diffraction (XRD), N2 adsorption-desorption isotherm, scanning electron microscopy (SEM), transmission electron microscopy (TEM). The results showed that the addition of PEG and CA increased the surface area of MoP and decreased the particle size of MoP. Furthermore, the reaction mechanism also has been discussed by combining the activity data and characterization results.
Amine–mixed oxide hybrid materials for carbon dioxide adsorption from CO2/H2 mixture

NASA Astrophysics Data System (ADS)

Ravi, Navin; Aishah Anuar, Siti; Yusuf, Nur Yusra Mt; Isahak, Wan Nor Roslam Wan; Shahbudin Masdar, Mohd

2018-05-01

Bio-hydrogen mainly contains hydrogen and high level of carbon dioxide (CO2). High concentration of CO2 lead to a limitation especially in fuel cell application. In this study, the amine-mixed oxide hybrid materials for CO2 separation from bio-hydrogen model (50% CO2:50% H2) have been studied. Fourier-transform infrared spectroscopy (FTIR) and x-ray diffraction (XRD) characterizations showed that the amine–mixed oxide hybrid materials successfully adsorbed CO2 physically with no chemical adsorption evidence. The dry gas of CO2/H2 mixture adsorbed physically on amine–CuO–MgO hybrid material. No carbonates were detected after several times of adsorption, which indicated the good recyclability of adsorbents. The adsorbent system of diethanolamine (DEA)/15% CuO–75% MgO showed the highest CO2 adsorption capacity of 21.2 wt% due to the presence of polar substance on MgO surface, which can adsorb CO2 at ambient condition. The alcohol group of DEA can enhance the CO2 solubility on the adsorbent surface. In the 20% CuO–50% MgO adsorbent system, DEA as amine type showed a high CO2 adsorption of 19.4 wt%. The 10% amine loading system showed that the DEA adsorption system provided high CO2 adsorption. The BET analysis confirmed that a high amine loading contributed to the decrease in CO2 adsorption due to the low surface area of the adsorbent system.
Synthesis of a Ni2P/Ni12P5 bi-phase nanocomposite for the efficient catalytic reduction of 4-nitrophenol based on the unique n-n heterojunction effects.

PubMed

Tian, Feng-Yu; Hou, Dongfang; Zhang, Wei-Min; Qiao, Xiu-Qing; Li, Dong-Sheng

2017-10-24

A novel heterostructure catalyst of Ni 2 P/Ni 12 P 5 has been fabricated through a simple solvothermal method by modifying the molar ratio of the initial raw materials. The products are characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). It is found that the two phases, Ni 2 P and Ni 12 P 5 , are interlaced with one another in the as-formed nanocomposite, resulting in more interfaces. The bi-phase catalyst exhibits a markedly enhanced catalytic activity in the reduction of 4-nitrophenol, as compared to that of single Ni 2 P or Ni 12 P 5 . The enhanced catalytic activity can be attributed to the unique n-n series effects, which result in the increased ease of electron transfer over the Ni 2 P/Ni 12 P 5 bi-phase catalyst.
Investigation of Zn2+ and Cd2+ Adsorption Performanceby Different Weathering Basalts

NASA Astrophysics Data System (ADS)

Xue, Q.; Shuo, Q.; Chen, H.

2016-12-01

Geological barriers play an important role in preventing pollution of groundwater. Basalts are common geological media; however, there have not been any studies that report the effect of basalt type on the metal ion adsorption performance. In this study, we explored the metal ion (Zn2+ and Cd2+) adsorption ability of two kinds of weathering basalts: the origin weathering basalt (WB) and the eluvial deposit (ED), both of which were derived from same basaltic formation. Characteristics of the sediments were examined by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Barrett-Joyner-Halenda (BJH) measurement and the rapid potentiometric titration (RPT) method. Batch experiments were performed to evaluate the Zn2+ and Cd2+ adsorption performance of WB and ED and how adsorption was affected by contact time, initial metal ion concentration, pH and ionic strength. Despite WB and ED having similar chemical compositions, WB exhibited better adsorption than ED likely due to the fact that WB was rougher and had more small-sized spherical structures and stronger electrostatic forces. The adsorption process fit the Freundlich isotherm model well. The adsorption efficiency decreased with a decrease of pH (from 4 to 2) and with increasing ionic strength. These results suggest that a geological barrier composed of WB media might be able to effectively sequester metallic contaminants to prevent them from reaching groundwater.
Montmorillonite-supported Pd0, Fe0, Cu0 and Ag0 nanoparticles: Properties and affinity towards CO2

NASA Astrophysics Data System (ADS)

Bouazizi, Nabil; Barrimo, Diana; Nousir, Saadia; Ben Slama, Romdhane; Roy, René; Azzouz, Abdelkrim

2017-04-01

This study reports the carbon dioxide (CO2) adsorption on montmorillonite (NaMt) incorporating Cu0, Fe0, Pd0 and Ag0 as metallic nanoparticles (MNPs). The changes in structural, textural, morphological and adsorption properties of the resulting materials (NaMt-MNPs) were investigated. Electron microscopy and X-ray diffraction showed that dispersion of fine MNPs occurs mainly within the interlayer space of NaMt, producing a slight structure expansion. This was accompanied by a visible enhancement of the affinity towards CO2, as supported by thermal programmed desorption measurements. NaMt-MNPs displayed high CO2 retention capacity (CRC) of ca. 657 μmol/g for NaMt-Cu as compared to NaMt. This was explained in terms of increased number of available adsorption sites due to enlarged interlayer spaces caused by MNP insertion. The differences in CO2 adsorption capacities clearly demonstrate the key role of MNPs in improving the surface properties and adsorption capacity. The results reported herein open new prospects for clay supported metal nanoparticles as efficient adsorbents for CO2.
Adsorption properties of AlN on Si(111) surface: A density functional study

NASA Astrophysics Data System (ADS)

Yuan, Yinmei; Zuo, Ran; Mao, Keke; Tang, Binlong; Zhang, Zhou; Liu, Jun; Zhong, Tingting

2018-04-01

In the process of preparing GaN on Si substrate by MOCVD, an AlN buffer layer is very important. In this study, we conducted density functional theory calculations on the adsorption of AlN molecule on Si(111)-(2 × 2) surface, with the AlN molecule located horizontally or vertically above Si(111) surface at different adsorption sites. The calculations revealed that the lowest adsorption energy was at the N-top-Al-bridge site in the horizontal configuration, with the narrowest band gap, indicating that it was the most preferential adsorption growth status of AlN. In the vertical configurations, N adatom was more reactive and convenient to form bonds with the topmost Si atoms than Al adatom. When the N-end of the AlN molecule was located downward, the hollow site was the preferred adsorption site; when the Al-end was located downward, the bridge site was the most energetically favorable. Moreover, we investigated some electronic properties such as partial density of states, electron density difference, Mulliken populations, etc., revealing the microscale mechanism for AlN adsorption on Si(111) surface and providing theoretical support for adjusting the processing parameters during AlN or GaN production.
Removal of copper (II) ion from aqueous solution using zeolite Y synthesized from rice husk ash: Equilibrium and kinetic study

NASA Astrophysics Data System (ADS)

Tuyen, Nguyen Thi Kim; Nhan, Do Nguyen Thanh; Nhat, Trieu Thi; An, Ngo Thanh; Long, Nguyen Quang

2017-09-01

Zeolite Y was synthesized from silica of rice-husk ash using hydrothermal process. The crystalline structure FAU of zeolite Y was characterized by X-ray diffraction (XRD). Surface's area of the catalyst was determined by physic-adsorption method using BET model. The zeolite was examined for possibility of Cu2+ adsorbent by an ion-exchange mechanism. Various adsorption isotherm models, such as Langmuir, Freundlich and Dubinin-Radushkevich were tested for equilibrium study. The integration method was applied to find out the possible kinetic equation of the Cu2+ adsorption on the zeolite Y which obtained from cheap and locally available rice husk ash.
Carbon/CuO nanosphere-anchored g-C3N4 nanosheets as ternary electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Vattikuti, S. V. Prabhakar; Reddy, B. Purusottam; Byon, Chan; Shim, Jaesool

2018-06-01

Novel electrode materials for supercapacitors comprised of carbon and copper oxide (CuO) nanospheres on graphitic carbon nitride (g-C3N4) nanosheets, denoted as C/CuO@g-C3N4 are self-assembled via a one-step co-pyrolysis decomposition method. The pure g-C3N4 and C/CuO@g-C3N4 were confirmed by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), thermal gravimetric and differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS), N2 adsorption/desorption studies and Fourier-transform infrared spectroscopy (FTIR). The specific capacitance was 247.2 F g-1 in 0.5 M NaOH at a current density of 1 A g-1, and more than 92.1% of the capacitance was retained after 6000 cycles. The property enhancement was ascribed to the synergistic effects of the three components in the composite. These results suggest that C/CuO@g-C3N4 possessed an excellent cyclic stability with respect to their capacity performance as electrode materials.
Hexadimethrine-montmorillonite nanocomposite: Characterization and application as a pesticide adsorbent

NASA Astrophysics Data System (ADS)

Gámiz, B.; Hermosín, M. C.; Cornejo, J.; Celis, R.

2015-03-01

The goal of this work was to prepare and characterize a novel functional material by the modification of SAz-1 montmorillonite with the cationic polymer hexadimethrine (SA-HEXAD), and to explore the potential use of this nanocomposite as a pesticide adsorbent. Comparative preparation and characterization with the well-known hexadecyltrimethylammonium-modified SAz-1 montmorillonite (SA-HDTMA) was also assessed. The characterization was performed by elemental analysis, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), physisorption of N2, scanning electron microscopy (SEM) and Z potential measurements. The characterization and adsorption experiments showed that the extent of pesticide adsorption was markedly subjected to the structure and features of the surface of each organo-clay and also to the nature of the considered pesticide. SA-HEXAD displayed a high affinity for anionic pesticides which, presumably, were adsorbed by electrostatic attraction on positively-charged ammonium groups of the polymer not directly interacting with the clay. In contrast, SA-HDTMA displayed great adsorption of both uncharged and anionic pesticides with predominance of hydrophobic interactions. This work provided information about the surface properties of a new organic-inorganic nanohybrid material, SA-HEXAD, and its potential as an adsorbent for the removal of anionic organic pollutants from aqueous solutions.
Synthesis and photocatalytic properties of TiO{sub 2} nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, X.H.; Liang, Y.; Wang, Z.

2008-08-04

TiO{sub 2} particles, rods, flowers and sheets were prepared by hydrothermal method via adjusting the temperature, the pressure and the concentration of TiCl{sub 4}. The as-prepared TiO{sub 2} powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra and N{sub 2} adsorption-desorption measurements. It was found that pressure is the most important factor influencing the morphology of TiO{sub 2}. The photocatalytic activity of the products was evaluated by the photodegradation of aqueous brilliant red X-3B solution under UV light. Among the as-prepared nanostructures, the flower-like TiO{sub 2}more » exhibited the highest photocatalytic activity.« less
Low frequency sonochemical synthesis of nanoporous amorphous manganese dioxide (MnO2) and adsorption of remazol reactive dye

NASA Astrophysics Data System (ADS)

Hasan, Siti Zubaidah; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali

2015-09-01

Nanoporous amorphous-MnO2 was synthesized by sonochemical process (sonication) on the solid manganese (II) acetate tetrahydrate (Mn(CH3COO)2.4H2O) in 0.1 M KMnO4. The product was characterized by X-ray diffraction (XRD), morphology of the material was scanned by Field Emission Scanning Electron Microscopy (FE-SEM) and absorptions of MnO2 bonding was characterized by Fourier Transform Infra-Red Spectrometer (FT-IR). Remazol reactive dye or Red 3BS, was used in the adsorption study using nanoporous amorphous-MnO2. In batch experiment, 10 ppm of Remazol reactive dye was used and experiment was carried out at room temperature. Adsorption of Remazol dye on 0.2g synthesized nanoporous amorphous-MnO2 showed 99 - 100% decolorization.
Adsorptive separation studies of ethane-methane and methane-nitrogen systems using mesoporous carbon.

PubMed

Yuan, Bin; Wu, Xiaofei; Chen, Yingxi; Huang, Jianhan; Luo, Hongmei; Deng, Shuguang

2013-03-15

Adsorptive separations of C(2)H(6)/CH(4) and CH(4)/N(2) binary mixtures are of paramount importance from the energy and environmental points of view. A mesoporous carbon adsorbent was synthesized using a soft template method and characterized with TEM, TGA, and nitrogen adsorption/desorption. Adsorption equilibrium and kinetics of C(2)H(6), CH(4), and N(2) on the mesoporous carbon adsorbent were determined at 278, 298, and 318 K and pressures up to 100 kPa. The adsorption capacities of C(2)H(6) and CH(4) on the mesoporous carbon adsorbent at 298 K and 100 kPa are 2.20 mmol/g and 1.05 mmol/g, respectively. Both are significantly higher than those of many adsorbents including pillared clays and ETS-10 at a similar condition. The equilibrium selectivities of C(2)H(6)/CH(4) and CH(4)/N(2) at 298 K are 19.6 and 5.8, respectively. It was observed that the adsorption of C(2)H(6), CH(4), and N(2) gases on the carbon adsorbent was reversible with modest isosteric heats of adsorption, which implies that this carbon adsorbent can be easily regenerated in a cyclic adsorption process. These results suggest that the mesoporous carbon studied in this work is a promising alternative adsorbent for the separations of C(2)H(6)/CH(4) and CH(4)/N(2) gas mixtures. Copyright © 2012 Elsevier Inc. All rights reserved.
Hierarchical NiO-SiO2 composite hollow microspheres with enhanced adsorption affinity towards Congo red in water.

PubMed

Lei, Chunsheng; Zhu, Xiaofeng; Zhu, Bicheng; Yu, Jiaguo; Ho, Wingkei

2016-03-15

Hollow microspheres and hierarchical porous nanostructured materials with desired morphologies have gained remarkable attention for their potential applications in environmental technology. In this study, NiO-SiO2 hollow microspheres were prepared by co-precipitation with SiO2 and nickel salt as precursors, followed by dipping in alkaline solution and calcination. The samples were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, nitrogen adsorption, and X-ray photoelectron spectroscopy. The synthesized hollow spheres were composed of a SiO2 shell and hierarchical porous NiO nanosheets on the surface. Adsorption experiments suggested that NiO-SiO2 composite particles were powerful adsorbents for removal of Congo red from water, with a maximum adsorption capacity of 204.1 mg/g. The high specific surface areas, hollow structures, and hierarchical porous surfaces of the hollow composite particles are suitable for various applications, including adsorption of pollutants, chemical separation, and water purification. Copyright © 2015 Elsevier Inc. All rights reserved.
Magnetic graphene oxide for adsorption of organic dyes from aqueous solution

NASA Astrophysics Data System (ADS)

Drashya, Lal, Shyam; Hooda, Sunita

2018-05-01

Graphene oxide (GO), a 2-D carbon nanomaterial, large surface area, oxygen-containing groups (like: hydroxyl, epoxy and carboxyl) and excellent water dispersibility due to it is good adsorbent dye removal from pollutant water1. But it's difficult to separate GO from water after adsorption. Therefore, Iron oxide was introduced in Graphene oxide by decorating method to make separation more efficient2. We present herein a one step process to prepare Magnetic Graphene oxide (MGO). The Fourier transform infrared spectrometer (FT-IR), X-ray diffraction (XRD) and Raman Spectroscopy characterized the chemical structure of the MGO composite. The adsorption of dyes onto MGO was studied in relation to initial concentration of Dyes, contact time, adsorbent dose, temperature and pH value of solution. We have studied adsorption capacity of different dyes (Methylene blue and crystal violet) by MGO.
Adsorption of heavy metals on amine-functionalized MCM-48

NASA Astrophysics Data System (ADS)

Taba, P.; Budi, P.; Puspitasari, A. Y.

2017-04-01

The ordered mesoporous silica with cubic structure, MCM-48 was synthesized by post-synthesis under basic media using colloidal silica, cetyltrimethylammonium bromide, and Triton X-100. The modified material, NH2-MCM-48 was prepared using 3-aminopropyl trimetoxysilane (3-APTMS). X-ray diffraction and FT-IR were used to characterize the samples. The modified material was utilized for adsorption of Cu2+and Mn2+ from aqueous solution. Parameters used for studying the adsorption process were pH, time of contact, and the initial concentrations of Cu2+ and Mn2+ ions. Desorption of ions from the adsorbent was also studied using several desorbing agents. The pseudo-second order was found to be the kinetic order for the metals adsorption. The adsorption of Cu2+ and Mn2+ on NH2-MCM-48 was fixed by the Langmuir model better than the Freundlich model with the capacity of 0.52 and 0.80 mmol g-1 for Cu2+ and Mn2+, respectively. The best desorbing agents for removing the adsorbed Cu2+ and Mn2+ from the adsorbent were 1 M HNO3 and 1 M HC1, respectively.
Adsorption of H2O, H2, O2, CO, NO, and CO2 on graphene/g-C3N4 nanocomposite investigated by density functional theory

NASA Astrophysics Data System (ADS)

Wu, Hong-Zhang; Bandaru, Sateesh; Liu, Jin; Li, Li-Li; Wang, Zhenling

2018-02-01

Motivated by the photocatalytic reactions of small molecules on g-C3N4 by these insights, we sought to explore the adsorption of H2O and CO2 molecules on the graphene side and H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side of hybrid g-C3N4/graphene nanocomposite using first-principles calculations. The atomic structure and electronic properties of hybrid g-C3N4/graphene nanocomposite is explored. The adsorption of small molecules on graphene/g-C3N4 nanocomposite is thoroughly investigated. The computational studies revels that all small molecules on graphene/g-C3N4 nanocomposite are the physisorption. The adsorption characteristics of H2O and CO2 molecules on the graphene side are similar to that on graphene. The adsorption of H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side always leads to a buckle structure of graphene/g-C3N4 nanocomposite. Graphene as a substrate can significantly relax the buckle degree of g-C3N4 in g-C3N4/graphene nanocomposite.
Humidity sensing behavior of tin-loaded 3-D cubic mesoporous silica

NASA Astrophysics Data System (ADS)

Poonia, Ekta; Dahiya, Manjeet S.; Tomer, Vijay K.; Kumar, Krishan; Kumar, Sunil; Duhan, Surender

2018-07-01

The present scientific investigation deals with template synthesis of 3D-cubic mesoporous KIT-6 with in-situ loading of SnO2 to obtain a material with enhanced number of surface active sites. The structural insights have been reported through analysis of XRD, TEM, FESEM, N2 sorption and mid-IR absorption data. X-ray diffraction confirmed 3D-cubic mesoporous structure of silica with Ia 3 bar d symmetry and existence of anatase SnO2 species. A decrease in surface area on loading of SnO2 nanoparticles is revealed via analysis of N2 adsorption-desorption isotherms. Rapid response time of 15 s and super rapid recovery time of 2 s (with response > 100) have been exhibited by sensor based on sample containing 1 wt% of SnO2. Further investigation on sensing performance of nanocomposite with 1 wt% of SnO2 confirmed its ohmic behavior (with negligible V-I hysteresis), excellent cycle stability, outstanding long term stability and very low hysteresis (1.4% at 53% RH).
Investigation of the spatially anisotropic component of the laterally averaged molecular Hydrogen/Ag(111) physisorption potential

NASA Astrophysics Data System (ADS)

Whaley, K. B.; Yu, C. F.; Hogg, C. S.; Light, J. C.; Sibener, S. J.

1985-08-01

A detailed investigation of the spatially anisotropic component of the laterally averaged molecular hydrogen/Ag(111) physisorption potential is presented. Experimentally derived rotationally inelastic transition probabilities for H2, D2, and HD, taken as a function of collision energy, are compared with those resulting from close-coupled quantum scattering calculations. These calculations utilize exponential-3 and variable exponent parameterizations of the laterally averaged isotropic potential which reproduce the experimental bound state resonance spectra for p-H2 and o-D2 on Ag(111). Complementary information is obtained by analyzing the magnetic sub-level splittings for physisorbed J = 1 n-H2, using diffractive selective adsorption resonance energies calculated with first order perturbation theory. Theoretical predictions for HD/Ag(111) rotationally mediated selective adsorption resonances are also compared with previously reported experimental results, which show well resolved J-dependent energy shifts resulting in part from the orientational anisotropy of the potential. The results obtained in this study indicate that both the attractive and repulsive parts of the anisotropic potential exhibit only a weak orientation dependence, in agreement with recent theoretical predictions for this system.
Investigation of the spatially anisotropic component of the laterally averaged molecular hydrogen/Ag(111) physisorption potential

NASA Astrophysics Data System (ADS)

Whaley, K. Birgitta; Yu, Chien-fan; Hogg, C. S.; Light, John C.; Sibener, S. J.

1985-10-01

A detailed investigation of the spatially anisotropic component of the laterally averaged molecular hydrogen/Ag(111) physisorption potential is presented. Experimentally derived rotationally inelastic transition probabilities for H2, D2, and HD, taken as a function of collision energy, are compared with those resulting from close-coupled quantum scattering calculations. These calculations utilize exponential-3 and variable exponent parametrizations of the laterally averaged isotropic potential which reproduce the experimental bound state resonance spectra for p-H2 and o-D2 on Ag(111). Complementary information is obtained by analyzing the magnetic sublevel splittings for physisorbed J=1 n-H2, using diffractive selective adsorption resonance energies calculated with first order perturbation theory. Theoretical predictions for HD/Ag(111) rotationally mediated selective adsorption resonances are also compared with previously reported experimental results, which show well resolved J-dependent energy shifts resulting in part from the orientational anisotropy of the potential. The results obtained in this study indicate that both the attractive and repulsive parts of the anisotropic potential exhibit only a weak orientation dependence, in agreement with recent theoretical predictions for this system.

Solvothermal synthesis of TiO2 nanocrystals with {001} facets using titanic acid nanobelts for superior photocatalytic activity

NASA Astrophysics Data System (ADS)

Cao, Yuhui; Zong, Lanlan; Li, Qiuye; Li, Chen; Li, Junli; Yang, Jianjun

2017-01-01

Anatase TiO2 nanocrystals exposed with {001} facets were fabricated by solvothermal strategy in HF-C4H9OH mixed solution, using titanic acid nanobelts (TAN) as a precursor. The shape of TAN is a long flat plane with a high aspect ratio, and F- is easily adsorbed on the surface of the nanobelts, inducing a higher exposure of {001} facet of TiO2 nanoparticles during the structure reorganization. The exposed percentage of {001} facets could vary from 40 to 77% by adjusting the amount of HF. The as-prepared samples were characterized by transmission electron microscopy, N2 adsorption-desorption isotherms, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscope. The photocatalytic measurement showed that TiO2 nanocrystals with 77% {001} facets exhibited much superior photocatalytic activity for photodegradation of methyl orange, methylene blue, and rhodamine B. And what's more, the mineralization rate of methyl orange was as high as 96% within 60 min. The photocatalytic enhancement is due to a large amount of the high energetic {001} facets exposing, the special truncated octahedral morphology and a stronger ability for dyes adsorption.
Physicochemical properties of metal-doped activated carbons and relationship with their performance in the removal of SO2 and NO.

PubMed

Gao, Xiang; Liu, Shaojun; Zhang, Yang; Luo, Zhongyang; Cen, Kefa

2011-04-15

Several metal-doped activated carbons (Fe, Co, Ni, V, Mn, Cu and Ce) were prepared and characterized. The results of N(2) adsorption-desorption, X-ray diffraction, and X-ray photoelectron spectroscopy indicated that some metals (Cu and Fe) were partly reduced by carbon during preparation. Activity tests for the removal of SO(2) and the selective catalytic reduction of NO with ammonia were carried out. Due to different physicochemical properties, different pathways for the SO(2) removal had been put out, i.e., catalytic oxidation, direct reaction and adsorption. This classification depended on the standard reduction potentials of metal redox pairs. Samples impregnated with V, Ce and Cu showed good activity for NO reduction by NH(3), which was also ascribed to the reduction potential values of metal redox pairs. Ce seemed to be a promising alternative to V due to the higher activity in NO reduction and the nontoxic property. A metal cation which could easily convert between the two valences seemed to be crucial to the good performance of both SO(2) and NO removal, just like V and Cu. Copyright © 2011 Elsevier B.V. All rights reserved.
CO adsorption on N2-precovered NaY faujasite: a FTIR analysis of the resulting adsorbed species.

PubMed

Cairon, Olivier

2013-08-26

To productively complete the information regarding the reversible adsorption of a gas mixture on the micropores of cationic zeolites, the adsorption of the two gases N2 and CO on NaY faujasite is taken as a model case study. We analyze herein CO adsorption (77 K) on two distinct N2-precovered NaY sets (low and medium). We outline the continuous desorption of N2 adducts during CO admittance to full N2 desorption for the highest CO loadings. These features contrast with preceding results obtained for N2 loading on CO-precovered NaY. By comparing these results with the sole CO admission and combining both studies regarding the co-adsorption sets, we demonstrate the influence of the basic strength of the two gases regarding the nature of the surface-adsorbed species formed. We also propose and discuss a hypothesis regarding the formation of adsorbed mixed species having both N2 and CO as ligands. These new findings strengthen the statistical response of IR signatures as a helpful proposal for analyzing adsorbed species and their assignments. This survey completes the molecular understanding of gas-mixture adsorption that lacks experimental data to date. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Adsorption of toxic metal ion Cr(VI) from aqueous state by TiO2-MCM-41: equilibrium and kinetic studies.

PubMed

Parida, Kulamani; Mishra, Krushna Gopal; Dash, Suresh Kumar

2012-11-30

This paper deals with the immobilization of various weight percentage of TiO(2) on mesoporous MCM-41, characterization of the materials by X-ray diffraction (XRD), nitrogen adsorption-desorption, Fourier Transform Infrared (FTIR) analysis, UV-vis diffuse reflectance spectroscopy (DRS) and evaluation of the adsorption capacity toward Cr(VI) removal. It is found that the MCM-41 structure retained after loading of TiO(2) but the surface area and pore diameter decreased due to pore blockage. Adsorption of Cr(VI) from aqueous state was investigated on TiO(2)-MCM-41 by changing various parameters such as pH, metal ion concentration, and the temperature. When TiO(2) loading was more than 20 wt.%, the adsorption activity (25)TiO(2)-MCM-41 reduced significantly due to considerable decrease in the surface area. It is also observed that TiO(2) and neat MCM-41 exhibits very less Cr(VI) adsorption compared to TiO(2)-MCM-41. The adsorption of Cr(VI) onto (20)TiO(2)-MCM-41 at pH~5.5 and temperature 323 K was 91% at 100mg/L Cr(VI) metal ion concentration in 80 min. The experimental data fitted well to Langmuir and Freundlich isotherms. The adsorption of Cr(VI) on TiO(2)-MCM-41 followed a second order kinetics with higher values of intra-particle diffusion rate. Thermodynamic parameters suggested that the adsorption process is endothermic in nature and desorption studies indicated a chemisorption mode. Copyright © 2012 Elsevier B.V. All rights reserved.
Characterization of N3 dye adsorption on TiO2 using quartz-crystal microbalance with dissipation monitoring

NASA Astrophysics Data System (ADS)

Wayment-Steele, Hannah K.; Johnson, Lewis E.; Dixon, Matthew C.; Johal, Malkiat S.

2013-09-01

Understanding the kinetics of dye adsorption on semiconductors is crucial for designing dye-sensitized solar cells (DSSCs) with enhanced efficiency. Harms et al. recently applied the Quartz-Crystal Microbalance with Dissipation Monitoring (QCM-D) to study in situ dye adsorption on flat TiO2 surfaces. QCM-D measures adsorption in real time and therefore allows one to determine the kinetics of the process. In this work, we characterize the adsorption of N3, a commercial RuBipy dye, using the native oxide layer of a titanium sensor to simulate the TiO2 substrate of a DSSC. We report equilibrium constants that are in agreement with previous absorbance studies of N3 adsorption, and therefore demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption.
Competitive adsorption of Cd2+, Pb2+ and Ni2+ onto Fe3+-modified argillaceous limestone: Influence of pH, ionic strength and natural organic matters.

PubMed

He, Shuran; Li, Yongtao; Weng, Liping; Wang, Jinjin; He, Jinxian; Liu, Yonglin; Zhang, Kun; Wu, Qihong; Zhang, Yulong; Zhang, Zhen

2018-10-01

In present study, the feasibility of applying a natural adsorbent with Fe 3+ modification (Fe 3+ -modified argillaceous limestone, FAL) on the competitive adsorption of heavy metals (i.e., Cd 2+ , Pb 2+ and Ni 2+ ) was evaluated. The current results revealed an efficient adsorption on Cd 2+ , Pb 2+ and Ni 2+ in mono-metal system. Further experiments demonstrated a high selectivity of Pb 2+ during the competitive adsorption of Cd 2+ , Pb 2+ and Ni 2+ . The adsorption selectivity of the metal ions followed the order of Pb ≫ Cd > Ni. In addition, both pH and ionic strength are important factors affecting the metal adsorptions. It is interestingly that various NOMs (i.e., humic acid (HA) and glycine (Gly)) exerted different effects on the adsorption behaviors, probably due to the different affinities for Pb 2+ , Cd 2+ and Ni 2+ and the redistribution of newly-formed metal-DOM complexes. X-ray photoelectron spectroscopy (XPS) analysis together with X-ray diffraction (XRD) and energy dispersive spectrometer (EDS) analysis revealed that the metal adsorptions were mainly regulated via the synergistic mechanisms of ion exchange by Na + , Ca 2+ , and Al 3+ , precipitation to form CdCO 3 and Pb 2 (OH) 2 (CO 3 ) 2 , as well as complexes of FAL-OPb and FAL-ONi by hydroxyl groups on the surface of FAL. The application of FAL would be a promising option in leading to an efficient heavy metal removal. Copyright © 2018 Elsevier B.V. All rights reserved.
High-performance magnetic carbon materials in dye removal from aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Xiaoming, E-mail: dawn1026@163.com; Zhang, Yu; Dai, Yuan

To obtain a novel adsorbent with excellent adsorption capacity and convenient magnetic separation property, magnetic activated semi-coke was prepared by KOH activation method and further modified by FeCl{sub 3}. The surface morphology, physical structure, chemical properties and textural characteristics of unmodified semi-coke, KOH-modified semi-coke and magnetic activated semi-coke were characterized by scanning electron microscopy, X-ray powder diffraction, N{sub 2} adsorption-desorption measurement, and electronic differential system. The adsorption characteristics of the magnetic activated semi-coke were explored for the removal of methyl orang (MO), methylene blue (MB), congo red (CR), acid fuchsin (AF), and rhodamine B (RB) from aqueous solution. The effectsmore » of adsorption parameters, including adsorbent dosage, pH and contact time, were investigated by comparing the adsorption properties of the magnetic activated semi-coke to RB. The result showed that the magnetic activated semi-coke displayed excellent dispersion, convenient separation and high adsorption capacity. The adsorption experiment data indicated that the pseudosecond order model and the Langmuir model could well explain the adsorption processes of RB on the magnetic activated semi-coke, and the maximum adsorption capacity (q{sub m}) was 526.32 mg/g. The values of thermodynamic parameters (ΔG°, ΔH° and ΔS°) indicated that the adsorption process depended on the temperature of the aqueous phase, and it was spontaneous and exothermic in nature. As the addition of the magnetic activated semi-coke, the color of the solution significantly faded. Subsequently, fast aggregation of the magnetic activated semi-coke from their homogeneous dispersion in the presence of an external magnetic field could be happened. So, the magnetic activated semi-coke displayed excellent dispersion, convenient separation and high adsorption capacity. - Graphical abstract: As the addition of the magnetic activated semi-coke, the color of the solution significantly faded. Subsequently, fast aggregation of the magnetic activated semi-coke from their homogeneous dispersion in the presence of an external magnetic field could be happened. So, the magnetic activated semi-coke displayed excellent dispersion, convenient separation and high adsorption capacity. Display Omitted.« less
Decolorization of reactive dye using a photo-ferrioxalate system with brick grain-supported iron oxide.

PubMed

Cheng, Hui-Pin; Huang, Yao-Hui; Lee, Changha

2011-04-15

The photocatalytic activity of a brick grain-supported iron oxide (denoted as B1) was tested for its activity to degrade Reactive Black 5 (RB5) in the presence of oxalic acid. B1 was obtained as a solid waste from a wastewater treatment plant, and characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray powder diffraction (XRD) and N(2) adsorption/desorption isotherm analyses. The decolorization experiments were performed in a fluidized bed reactor with aeration under UV-A irradiation (λ = 365 nm). The effects of various factors such as solution pH, concentration of oxalic acid and dissolved oxygen on the decolorization of RB5 were evaluated considering the contributions of adsorption and photo-catalytic degradation. The role of dissolved iron in the removal of RB5 and the stability of B1 were also examined. In addition, the removal of TOC during the photo-catalytic reaction was monitored. Copyright © 2011 Elsevier B.V. All rights reserved.
Polyethylenimine-incorporated zeolite 13X with mesoporosity for post-combustion CO2 capture

NASA Astrophysics Data System (ADS)

Chen, Chao; Kim, Su-Sung; Cho, Won-Seung; Ahn, Wha-Seung

2015-03-01

X-type zeolite with mesoporosity (Meso-13X) was prepared by using dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride as a mesopore-generating agent, and then modified with polyethylenimine (PEI) through a physical impregnation method to form a hybrid material (Meso-13X-PEI). Meso-13X with and without PEI was characterized by X-ray powder diffraction (XRD), N2 adsorption-desorption isotherm at 77 K, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). Meso-13X-PEI exhibited higher CO2 capture capacity than PEI-modified zeolite 13X owing to its larger pore volume that accommodates more amine species inside the pore structure, and the mesoporosity also can facilitate dispersion of PEI molecules inside the pore channels. Compared to zeolite 13X, Meso-13X-PEI showed much higher CO2 capture selectivity (against N2) as well as higher CO2 capture capacity at relatively high temperature (e.g. 100 °C) and dilute CO2 concentration relevant to post-combustion conditions.
Preparation of Ice-Templated MOF-Polymer Composite Monoliths and Their Application for Wastewater Treatment with High Capacity and Easy Recycling.

PubMed

Fu, Qingshan; Wen, Lang; Zhang, Lei; Chen, Xuedan; Pun, Daniel; Ahmed, Adham; Yang, Yonghong; Zhang, Haifei

2017-10-04

An ice-templating process was used to fabricate polymer/MOF monoliths, specifically chitosan/UiO-66, as adsorbents for water treatment. The ice-templated macropores enhanced mass transport, while the monoliths could be easily recovered from solution. This was demonstrated by the adsorption of methylchlorophenoxypropionic acid (MCPP, a herbicide compound) from dilute aqueous solution. To enhance the stability, the freeze-dried monoliths were treated with NaOH solution, solvent exchanged, and dried. The treated chitosan/UiO-66 monolith achieved an adsorption capacity of 34.33 mg g -1 (a maximum theoretic value of 334 mg g -1 by the Langmuir model), closer to the capacity (36.00 mg g -1 ) of the freshly prepared UiO-66 nanoparticles and much higher than that of the NaOH-washed UiO-66 nanoparticles (18.55 mg g -1 ), by performing the tests in 60 ppm MCPP solution. The composite monolith could be easily picked up using tweezers and used for recycling tests. Over 80% of the adsorption capacity was retained after three more cycles. The powder X-ray diffraction and N 2 sorption studies suggested the crystalline structure of UiO-66 was destroyed during NaOH washing procedure. This, however, provides the potential to improve the adsorption capacity by developing methods to fabricate true polymer/MOF composites.
Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework.

PubMed

Banerjee, Debasis; Wang, Hao; Plonka, Anna M; Emge, Thomas J; Parise, John B; Li, Jing

2016-08-08

Gate-opening is a unique and interesting phenomenon commonly observed in flexible porous frameworks, where the pore characteristics and/or crystal structures change in response to external stimuli such as adding or removing guest molecules. For gate-opening that is induced by gas adsorption, the pore-opening pressure often varies for different adsorbate molecules and, thus, can be applied to selectively separate a gas mixture. The detailed understanding of this phenomenon is of fundamental importance to the design of industrially applicable gas-selective sorbents, which remains under investigated due to the lack of direct structural evidence for such systems. We report a mechanistic study of gas-induced gate-opening process of a microporous metal-organic framework, [Mn(ina)2 ] (ina=isonicotinate) associated with commensurate adsorption, by a combination of several analytical techniques including single crystal X-ray diffraction, in situ powder X-ray diffraction coupled with differential scanning calorimetry (XRD-DSC), and gas adsorption-desorption methods. Our study reveals that the pronounced and reversible gate opening/closing phenomena observed in [Mn(ina)2 ] are coupled with a structural transition that involves rotation of the organic linker molecules as a result of interaction of the framework with adsorbed gas molecules including carbon dioxide and propane. The onset pressure to open the gate correlates with the extent of such interaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
New Insights into CO2 Adsorption on Layered Double Hydroxide (LDH)-Based Nanomaterials

NASA Astrophysics Data System (ADS)

Tang, Nian; He, Tingyu; Liu, Jie; Li, Li; Shi, Han; Cen, Wanglai; Ye, Zhixiang

2018-02-01

The interlamellar spacing of layered double hydroxides (LDHs) was enlarged by dodecyl sulfonate ions firstly, and then, (3-aminopropyl)triethoxysilane (APS) was chemically grafted (APS/LDHs). The structural characteristics and thermal stability of these prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), reflectance Fourier transform infrared spectrometer (FTIR), thermogravimetric analysis (TG), and elemental analysis (EA) respectively. The CO2 adsorption performance was investigated adopting TG and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The results presented that the CO2 adsorption capacity on APS/LDHs was as high as 90 mg/g and showed no obvious reduction during a five cyclic adsorption-desorption test, indicating its superior performance stability. The DRIFTS results showed that both carbamates and weakly bounded CO2 species were generated on APS/LDHs. The weakly adsorbed species was due to the different local chemical environment for CO2 capture provided by the surface moieties of LDHs like free silanol and hydrogen bonds.
A Robust Open Framework Formed by Decavanadate Clusters and Copper(II) Complexes of Macrocyclic Polyamines: Permanent Microporosity and Catalytic Oxidation of Cycloalkanes.

PubMed

Martín-Caballero, Jagoba; San José Wéry, Ana; Reinoso, Santiago; Artetxe, Beñat; San Felices, Leire; El Bakkali, Bouchra; Trautwein, Guido; Alcañiz-Monge, Juan; Vilas, José Luis; Gutiérrez-Zorrilla, Juan M

2016-05-16

The first decavanadate-based microporous hybrid, namely, [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·10H2O (1, cyclam = 1,4,8,11-tetraazacyclotetradecane) was prepared by reaction of (VO3)(-) anions and {Cu(cyclam)}(2+) complexes in NaCl (aq) at pH 4.6-4.7 and characterized by elemental analyses, thermogravimetry, and X-ray diffraction (powder, single-crystal) techniques. Compound 1 exhibits a POMOF-like supramolecular open-framework built of covalent decavanadate/metalorganic layers with square-like voids, the stacking of which is aided by interlamellar cementing complexes and generates water-filled channels with approximate cross sections of 10.4 × 8.8 Å(2). The framework is robust enough to remain virtually unaltered upon thermal evacuation of all water molecules of hydration, as demonstrated through single-crystal X-ray diffraction studies on the anhydrous phase 1a. This permanent microporosity renders interesting functionality to 1, such as selective adsorption of CO2 over N2 and remarkable activity as heterogeneous catalyst toward the H2O2-based oxidation of the highly-stable, tricyclic alkane adamantane.
Role of oxygen adsorption in modification of optical and surface electronic properties of MoS2

NASA Astrophysics Data System (ADS)

Shakya, Jyoti; Kumar, Sanjeev; Mohanty, Tanuja

2018-04-01

In this work, the effect of surface oxidation of molybdenum disulfide (MoS2) nanosheets induced by hydrogen peroxide (H2O2) on the work function and bandgap of MoS2 has been investigated for tuning its optical and electronic properties. Transmission electron microscopy studies reveal the existence of varying morphologies of few layers of MoS2 as well as quantum dots due to the different absorbing effects of two mixed solvents on MoS2. The X-ray diffraction, electron paramagnetic resonance, and Raman studies indicate the presence of physical as well as chemical adsorption of oxygen atoms in MoS2. The photoluminescence spectra show the tuning of bandgap arising from the passivation of trapping centers leading to radiative recombination of excitons. The value of work function obtained from scanning Kelvin probe microscopy of MoS2 in mixed solvents of H2O2 and N-methyl-2-pyrrolidone increases with an increase in the concentration of H2O2. A linear relationship could be established between H2O2 content in mixed solvent and measured values of work function. This work gives the alternative route towards the commercial use of defect engineered transition metal dichalcogenide materials in diverse fields.
Adsorption characteristics of hexavalent chromium on HCB/TiO2

NASA Astrophysics Data System (ADS)

Zhang, Li; Zhang, Yonggang

2014-10-01

Sol-gel method was adopted to prepare HCB/TiO2 and its adsorption ability of hexavalent chromium, Cr(VI), and removal from aqueous solution were investigated. The samples were characterized by Power X-ray diffraction (XRD) and a transmission electron microscope (TEM) which showed that the TiO2 was deposited on the surface of HCB. FTIR was used to identify the changes of the surface functional groups before and after adsorption. Potentiometric titration method was used to characterize the zero charge (pHpzc) characteristics of the surface of HCB/TiO2 which showed more acidic functional groups containing. Batch experiments showed that initial pH, absorbent dosage, contact time and initial concentration of Cr(VI) were important parameters for the Cr(VI) adsorption studies. The Freundlich isotherm model better reflected the experimental data better. Cr(VI) adsorption process followed the pseudo-second order kinetic model, which illustrated chemical adsorption. The thermodynamic parameters, such as Gibbs free energy (ΔG), changes in enthalpy change (ΔH) and changes in entropy change (ΔS) were also evaluated. Negative value of free energy occurred at temperature range of 25-45 °C, so Cr(VI) adsorption by HCB/TiO2 is spontaneous. Desorption results showed that the adsorption capacity could maintain 80% after five cycles. The maximum adsorption capacity for Cr(VI) was at 27.33 mg g-1 in an acidic medium, of which the value is worth comparable with other low-cost adsorbents.
Synthesis and characterization of ion-imprinted resin based on carboxymethyl cellulose for selective removal of UO₂²⁺.

PubMed

Monier, M; Abdel-Latif, D A

2013-09-12

In this work, the surface ion-imprinting technique was employed for the preparation of surface ion-imprinted chelating microspheres resin based on modified salicylaldehyde-carboxymethyl cellulose (U-CMC-SAL) in presence of uranyl ions as a template and formaldehyde as a cross-linker. Various instrumental techniques such as elemental analysis, scanning electron microscope (SEM), FTIR and X-ray diffraction spectra were utilized for full characterization of the prepared polymeric samples. The prepared resin exhibited a higher capability for selective removal of UO₂²⁺ when compared to the non-imprinted resin (N-CMC-SAL). Also, different important parameters such as pH, temperature, time and initial metal ion concentration were examined in order to evaluate the optimum condition for the adsorption process. The results indicated that pH 5 was the best for the UO₂²⁺ uptake, in addition, the adsorption was exothermic in nature, follows the second-order kinetics and the adsorption isotherm showed the best fit with Langmuir isotherm model with maximum adsorption capacity of 180 ± 1 and 97 ± 1 mg/g for both U-CMC-SAL and N-CMC-SAL respectively. Desorption and regeneration were carried out using 0.5M HNO3 solution and the results confirmed that the resin keeps about 92% of its original efficiency after five consecutive adsorption-desorption operations. Copyright © 2013 Elsevier Ltd. All rights reserved.
Preparation of calcium hydroxyapatite nanoparticles using microreactor and their characteristics of protein adsorption.

PubMed

Kandori, Kazuhiko; Kuroda, Tomohiko; Togashi, Shigenori; Katayama, Erika

2011-02-03

The calcium hydroxyapatite Ca(10)(PO(4))(6)(OH)(2) (Hap) nanoparticles were prepared by using microreactor and employed these Hap nanoparticles to clarify the adsorption behavior of proteins. The size of Hap particles produced by the microreactor reduced in the order of a hardness of the reaction conditions for mixing Ca(OH)(2) and H(3)PO(4) aqueous solutions, such as flow rates of both solutions and temperature. Finally, the size of the smallest Hap nanoparticle became 2 × 15 nm(2), similar to that of BSA molecule (4 × 14 nm(2)). It is noteworthy that the smallest Hap nanoparticles still possesses rodlike shape, suggesting that particles are grown along c-axis even though the reactants mixed very rapidly in narrow channels of the microreactors. The X-ray diffraction patterns of the Hap nanoparticles revealed that the crystallinity of the materials produced by the microreactor is low. The FTIR measurement indicated that the Hap nanoparticles produced by microreactor were carbonate-substituted type B Hap, where the carbonate ions replace the phosphate ions in the crystal lattice. All the adsorption isotherms of acidic bovine serum albumin (BSA), neutral myoglobin (MGB), and basic lysozyme (LSZ) onto Hap nanoparticles from 1 × 10(-4) mol/dm(3) KCl solution were the Langmuirian type. The saturated amounts of adsorbed BSA (n(S)(BSA)) for the Hap nanoparticles produced by microreactor were decreased with decrease in the mean particle length, and finally it reduced to zero for the smallest Hap nanoparticles. Similar results were observed for the adsorption of LSZ; the saturated amounts of adsorbed LSZ (n(S)(LSZ)) also reduced to zero for the smallest Hap nanoparticles. However, in the case of MGB, the saturated mounts of adsorbed MGB (n(S)(MGB)) are also depressed with decreased in their particle size, but about half of MGB molecules still adsorbed onto the smallest Hap nanoparticles. This difference in the protein adsorption behavior was explained by the difference in the size and flexibility of three kinds of proteins. The reduction of n(S)(BSA) is due to the decrease in the fraction of C sites on the side face of each Hap nanoparticle; i.e., there is not enough area left on the nanoparticle surface to adsorb large BSA molecules even though the BSA molecules are soft and their conformations are alterable. The reduction of n(S)(LSZ) was explained by the reduction of P sites. Further, rigidity of the LSZ molecules was given another possibility of the depression of n(S)(LSZ) for the Hap nanoparticles. However, MGB molecules with small and soft structure were adsorbed on the Hap nanoparticle surface by changing their conformation. We could control the amounts of adsorbed proteins by changing the particle size of Hap in the nanometer range and kinds of proteins. These obtained results may be useful for developing biomimetic materials for bone grafts and successful surgical devices in the biochemical field.
PET-modified red mud as catalysts for oxidative desulfurization reactions.

PubMed

do Prado, Nayara T; Heitmann, Ana P; Mansur, Herman S; Mansur, Alexandra A; Oliveira, Luiz C A; de Castro, Cinthia S

2017-07-01

This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N 2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N 2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS). Copyright © 2017. Published by Elsevier B.V.
Cobalt doping of the MOF-5 framework and its effect on gas-adsorption properties.

PubMed

Botas, Juan A; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Orcajo, M Gisela

2010-04-20

Partial isomorphic substitution of Zn in IRMOF metal clusters by cobalt ions is described for the first time. Specifically, different numbers of Co(2+) ions have been incorporated during solvothermal crystallization into the Zn-based MOF-5 (IRMOF-1) framework, which is one of the most studied MOF materials. The amount of Zn that can be substituted seems to be limited, being no more than 25% of total metal content, that is, no more than one Co atom inside every metal cluster formed by four transition-metal ions, on average. Several characterization techniques, including X-ray diffraction, DR UV-visible spectroscopy, N(2) adsorption isotherms, and thermogravimetrical analysis, strongly support the effective incorporation of Co into the material framework. As-synthesized CoMOF-5 has cobalt ions in octahedral coordination, changing to tetrahedral by simple evacuation, presumably by the removal of two diethylformamide molecules per Co ion. Moreover, the H(2), CH(4), and CO(2) uptake of MOF-5 materials systematically increases with the Co content, particularly at high pressure. Such an increase is moderate anyway, considering that Co is incorporated into unexposed metal sites that are less accessible to gas molecules.
Investigation of Y/SBA Composite Molecular Sieves Morphology Control and Catalytic Performance for n-Pentane Aromatization

PubMed Central

Shi, Chun-Wei; Wu, Wen-Yuan; Li, Shuai; Bian, Xue; Zhao, Shan-lin; Pei, Ming-Yuan

2016-01-01

Using Y molecular sieve as the core, Y/SBA-15 composite molecular sieves were prepared by different crystallization methods in the paper. The growth process and morphologies of the composite molecular sieves were controlled by adjusting the synthesis factors. The structures and acidity of two kinds of composite molecular sieves were characterized by X-ray diffraction (XRD), N2 adsorption/desorption, transmission electron microscopy (TEM), and NH3-TPD. The catalysis performances of the composite molecular sieves were investigated in the aromatization reaction of n-pentane. The results indicated that the desired core-shell composite molecular sieves were obtained when the crystallization conditions were 36 hours, 100 °C and secondary crystallization. The aromatization results showed that core-shell composite molecular sieves had better selectivity for producing high application value xylenes compared to mixed-crystal composite molecular sieves. PMID:27029526

Molecular simulations for adsorption and separation of natural gas in IRMOF-1 and Cu-BTC metal-organic frameworks.

PubMed

Martín-Calvo, Ana; García-Pérez, Elena; Manuel Castillo, Juan; Calero, Sofia

2008-12-21

We use Monte Carlo simulations to study the adsorption and separation of the natural gas components in IRMOF-1 and Cu-BTC metal-organic frameworks. We computed the adsorption isotherms of pure components, binary, and five-component mixtures analyzing the siting of the molecules in the structure for the different loadings. The bulk compositions studied for the mixtures were 50 : 50 and 90 : 10 for CH4-CO2, 90 : 10 for N2-CO2, and 95 : 2.0 : 1.5 : 1.0 : 0.5 for the CH4-C2H6-N2-CO2-C3H8 mixture. We choose this composition because it is similar to an average sample of natural gas. Our simulations show that CO2 is preferentially adsorbed over propane, ethane, methane and N2 in the complete pressure range under study. Longer alkanes are favored over shorter alkanes and the lowest adsorption corresponds to N2. Though IRMOF-1 has a significantly higher adsorption capacity than Cu-BTC, the adsorption selectivity of CO2 over CH4 and N2 is found to be higher in the latter, proving that the separation efficiency is largely affected by the shape, the atomic composition and the type of linkers of the structure.
Fe-FeS2 adsorbent prepared with iron powder and pyrite by facile ball milling and its application for arsenic removal.

PubMed

Min, Xiaobo; Li, Yangwenjun; Ke, Yong; Shi, Meiqing; Chai, Liyuan; Xue, Ke

2017-07-01

Arsenic is one of the major pollutants and a worldwide concern because of its toxicity and chronic effects on human health. An adsorbent of Fe-FeS 2 mixture for effective arsenic removal was successfully prepared by mechanical ball milling. The products before and after arsenic adsorption were characterized with scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent shows high arsenic removal efficiency when molar ratio of iron to pyrite is 5:5. The experimental data of As(III) adsorption are fitted well with the Langmuir isotherm model with a maximal adsorption capacity of 101.123 mg/g. And As(V) data were described perfectly by the Freundlich model with a maximal adsorption capacity of 58.341 L/mg. As(III) is partial oxidized to As(V) during the adsorption process. High arsenic uptake capability and cost-effectiveness of waste make it potentially attractive for arsenic removal.
Synergic Effect between Adsorption and Photocatalysis of Metal-Free g-C3N4 Derived from Different Precursors

PubMed Central

Xu, Huan-Yan; Wu, Li-Cheng; Zhao, Hang; Jin, Li-Guo; Qi, Shu-Yan

2015-01-01

Graphitic carbon nitride (g-C3N4) used in this work was obtained by heating dicyandiamide and melamine, respectively, at different temperatures. The differences of g-C3N4 derived from different precursors in phase composition, functional group, surface morphology, microstructure, surface property, band gap and specific surface area were investigated by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, UV-visible diffuse reflection spectroscopy and BET surface area analyzer, respectively. The photocatalytic discoloration of an active cationic dye, Methylene Blue (MB) under visible-light irradiation indicated that g-C3N4 derived from melamine at 500°C (CN-M500) had higher adsorption capacity and better photocatalytic activity than that from dicyandiamide at 500°C (CN-D500), which was attributed to the larger surface area of CN-M500. MB discoloration ratio over CN-M500 was affected by initial MB concentration and photocatalyst dosage. After 120 min reaction time, the blue color of MB solution disappeared completely. Subsequently, based on the measurement of the surface Zeta potentials of CN-M500 at different pHs, an active anionic dye, Methyl Orange (MO) was selected as the contrastive target pollutant with MB to reveal the synergic effect between adsorption and photocatalysis. Finally, the photocatalytic mechanism was discussed. PMID:26565712
Highly Permeable AlPO-18 Membranes for N 2 /CH 4 Separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zong, Zhaowang; Elsaidi, Sameh K.; Thallapally, Praveen K.

Herein we demonstrate that AlPO-18 membranes can separate N2/CH4 gas mixtures at unprecedented N2 permeances. The best membranes separated N2/CH4 mixtures with N2 permeances as high as 3076 GPU and separation selectivities as high as 4.6. Gas mixture separation data, N2 and CH4 adsorption isotherms, ideal adsorbed solution theory (IAST), and breakthrough experiments were collected to understand the separation mechanisms. Competitive adsorption and differences in diffusivities were identified as the prevailing separation mechanisms. Differences in diffusivity played a more dominant role than the competitive adsorption, and led to nitrogen selective membranes.
Low frequency sonochemical synthesis of nanoporous amorphous manganese dioxide (MnO{sub 2}) and adsorption of remazol reactive dye

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hasan, Siti Zubaidah; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali, E-mail: rozali@ukm.edu.my

2015-09-25

Nanoporous amorphous-MnO{sub 2} was synthesized by sonochemical process (sonication) on the solid manganese (II) acetate tetrahydrate (Mn(CH{sub 3}COO){sub 2}.4H{sub 2}O) in 0.1 M KMnO{sub 4}. The product was characterized by X-ray diffraction (XRD), morphology of the material was scanned by Field Emission Scanning Electron Microscopy (FE-SEM) and absorptions of MnO{sub 2} bonding was characterized by Fourier Transform Infra-Red Spectrometer (FT-IR). Remazol reactive dye or Red 3BS, was used in the adsorption study using nanoporous amorphous-MnO{sub 2}. In batch experiment, 10 ppm of Remazol reactive dye was used and experiment was carried out at room temperature. Adsorption of Remazol dye onmore » 0.2g synthesized nanoporous amorphous-MnO{sub 2} showed 99 – 100% decolorization.« less
Kinetics and thermodynamics studies on the BMP-2 adsorption onto hydroxyapatite surface with different multi-morphological features.

PubMed

Lu, Zhiwei; Huangfu, Changxin; Wang, Yanying; Ge, Hongwei; Yao, Yao; Zou, Ping; Wang, Guangtu; He, Hua; Rao, Hanbing

2015-01-01

The effect of the surface topography on protein adsorption process is of great significance for designing hydroxyapatite (HA) ceramic material surfaces. In this work, three different topographies of HA materials HA-sheet, HA-rod, and HA-whisker were synthesized and testified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Brunauer-Emmett-Teller (BET) and a field emission scanning electron microscopy (FE-SEM). We have systematically investigated the adsorption kinetics and thermodynamics of bone morphogenetic proteins (BMP-2) on the three different topography surfaces of HA, respectively. The results showed that the maximum adsorption capacities of HA-sheet, HA-rod and HA-whisker were (219.96 ± 10.18), (247.13 ± 12.35), and (354.67 ± 17.73) μg · g(-1), respectively. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated as well as discussed. It demonstrated that the adsorption of BMP-2 onto HA could be described by the pseudo second-order equation. Adsorption of BMP-2 onto HA followed the Langmuir isotherm. It confirmed that compared with other samples HA-whisker had more adsorption sites for its high specific surface area which could provide more opportunities for protein molecules. The adsorption processes were endothermic (ΔH > 0), spontaneous (ΔG < 0) and entropy increasing (ΔS > 0). A possible adsorption mechanism has been proposed. In addition, the BMP-2 could be adsorbed to the surface which existed slight conformational changes by FT-IR. Copyright © 2015 Elsevier B.V. All rights reserved.
Gas sorption and transition-metal cation separation with a thienothiophene based zirconium metal–organic framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

SK, Mostakim; Grzywa, Maciej; Volkmer, Dirk

2015-12-15

The modulated synthesis of the thienothiophene based zirconium metal–organic framework (MOF) material having formula [Zr{sub 6}O{sub 4}(OH){sub 4}(DMTDC){sub 6}]·4.8DMF·10H{sub 2}O (1) (H{sub 2}DMTDC=3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid; DMF=N,N'-dimethylformamide) was carried out by heating a mixture of ZrCl{sub 4}, H{sub 2}DMTDC linker and benzoic acid (used as a modulator) with a molar ratio of 1:1:30 in DMF at 150 °C for 24 h. Systematic investigations have been performed in order to realize the effect of ZrCl{sub 4}/benzoic acid molar ratio on the crystallinity of the material. The activation (i.e., the removal of the guest solvent molecules from the pores) of as-synthesized compound was achievedmore » by stirring it with methanol and subsequently heating under vacuum. A combination of X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric (TG) and elemental analysis was used to examine the phase purity of the as-synthesized and thermally activated 1. The material displays high thermal stability up to 310 °C in an air atmosphere. As revealed from the XRD measurements, the compound retains its crystallinity when treated with water, acetic acid and 1 M HCl solutions. The N{sub 2} and CO{sub 2} sorption analyses suggest that the material possesses remarkably high microporosity (S{sub BET}=1236 m{sup 2} g{sup −1}; CO{sub 2} uptake=3.5 mmol g{sup −1} at 1 bar and 0 °C). The compound also shows selective adsorption behavior for Cu{sup 2+} over Co{sup 2+} and Ni{sup 2+} ions. - Graphical abstract: Selective transition-metal cation adsorption by a thienothiophene based zirconium metal–organic framework material. - Highlights: • The modulated synthesis of a thienothiophene based Zr(IV) MOF has been described. • Effect of metal salt/modulator ratio on the crystallinity was thoroughly studied. • The compound showed high thermal and physiochemical stability. • N{sub 2} and CO{sub 2} sorption experiments revealed significantly high microporosity. • The material showed high adsorption selectivity for Cu{sup 2+} over Co{sup 2+} and Ni{sup 2+} ions.« less
Ordered hexagonal mesoporous aluminosilicates with low Si/Al ratio: synthesis, characterization, and catalytic application.

PubMed

Liu, Aifeng; Che, Hongwei; Liu, Chuanzhi; Fu, Quanrong; Jiang, Ruijiao; Wang, Cheng; Wang, Liang

2014-06-01

Ordered hexagonal mesoporous aluminosilicates with lower Si/Al ratio below 5 have been successfully synthesized via the co-assembly of preformed aluminosilicate precursors with Gemini surfactant [C12H25N+(CH3)2(CH2)6N+(CH3)2C12H25] x 2Br(-) as the template. Powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, N2 adsorption-desorption isotherm measurements, Fourier transform infrared spectroscopy, 27Al nuclear magnetic resonance, thermogravimetric analysis, and temperature-programmed desorption of cyclohexylamine are employed to characterize the resulting samples. The phenol alkylation reaction is carried out to evaluate their catalytic performances. These studies indicate that the sample with a low Si/Al ratio of 3 still retains a highly ordered hexagonal mesoporous structure. And it also possesses the highest acidity of 0.96 mmol among the samples with lower Si/Al ratios below 5 due to its higher specific surface area together with more content of tetrahedrally coordinated Al in the framework. The catalytic tests confirm that the acidity of the samples plays a key role in determining their catalytic performances.
Micro-structural analysis of NiFe2O4 nanoparticles synthesized by thermal plasma route and its suitability for BSA adsorption.

PubMed

Bhosale, Shivaji V; Kanhe, Nilesh S; Bhoraskar, Sudha V; Bhat, Suresh K; Bulakhe, Ravindra N; Shim, Jae-Jin; Mathe, Vikas L

2015-08-01

The paper presents the experimental studies pertaining to the adsorption of bovine serum albumin (BSA) on the nanoparticles of nickel ferrite (NiFe2O4) with a view of correlating the adsorption properties to their microstructure and zeta potentials. Physical properties of two kinds of nickel ferrites, one synthesized by thermal plasma route and the other by chemical co-precipitation method, are compared. Maximum adsorption (231.57 μg/mg) of BSA onto nickel ferrite nanoparticles, at body temperature (37 °C) was observed at pH-value of 5.58 for the thermal plasma synthesized particles showing its higher adsorption capacity than those synthesized by wet chemical means (178.71 μg/mg). Under the same physical conditions the value of zeta potential, obtained for the former, was higher than that of the latter over a wide range of pH values (3.64-9.66). This is attributed to the differences in the specific surface energies of the two kinds of nanoparticles arising from the degree of crystallinity. The paper presents the experimental evidence for the single crystalline nature of the individual nanoparticles, with mean size of 32 nm, for the thermal plasma synthesized particles as evidenced from the high resolution transmission electron microscopy and electron diffraction analysis. The measurements also reveal the poor crystalline morphology in the chemically prepared particles (mean size of 28 nm) although the X-ray diffraction patterns are not much different. The atomic force microscopy images confirm that the surfaces of plasma synthesized nanoparticles possesses higher surface roughness than that of chemically synthesized one. Presence of adsorbed protein was confirmed by vibrational spectroscopy. The Langmuir adsorption model is found to fit into the experimental data better than the Freundlich adsorption model.
Temporal changes in nitrogen adsorption properties of single-walled carbon nanotubes

USGS Publications Warehouse

Agnihotri, S.; Rostam-Abadi, M.; Rood, M.J.

2004-01-01

Temporal evolution of N2 adsorption (77 K) properties of as-produced and purified single-walled nanotubes (SWNTs) samples is described here. The N2 adsorption isotherms are used to characterize the samples' surface areas and porosities. The as-produced samples demonstrate a temporal increase in surface area and pore volumes for up to 16 months. The purified samples, however, reached their stable values of surface area and pore volumes within four to seven months. N2 adsorption capacity of the purified SWNTs also increased when the fresh samples were subjected to thermal pre-processing, with diminishing changes in adsorption capacity with increased age. These observations indicate that the freshly prepared SWNTs, both as-produced and purified, were in an unstable state with their porosity changing with increasing sample age and thermal treatments. It is hypothesized that SWNTs undergo slow but progressive changes in their surface chemistry which causes their N2 adsorption properties to change over several months. ?? 2004 Elsevier Ltd. All rights reserved.
Fluorine atom abstraction by Si(100). I. Experimental

NASA Astrophysics Data System (ADS)

Tate, M. R.; Gosalvez-Blanco, D.; Pullman, D. P.; Tsekouras, A. A.; Li, Y. L.; Yang, J. J.; Laughlin, K. B.; Eckman, S. C.; Bertino, M. F.; Ceyer, S. T.

1999-08-01

In the interaction of low energy F2 with Si(100) at 250 K, a dissociative chemisorption mechanism called atom abstraction is identified in which only one of the F atoms is adsorbed while the other F atom is scattered into the gas phase. The dynamics of atom abstraction are characterized via time-of-flight measurements of the scattered F atoms. The F atoms are translationally hyperthermal but only carry a small fraction (˜3%) of the tremendous exothermicity of the reaction. The angular distribution of F atoms is unusually broad for the product of an exothermic reaction. These results suggest an "attractive" interaction potential between F2 and the Si dangling bond with a transition state that is not constrained geometrically. These results are in disagreement with the results of theoretical investigations implying that the available potential energy surfaces are inadequate to describe the dynamics of this gas-surface interaction. In addition to single atom abstraction, two atom adsorption, a mechanism analogous to classic dissociative chemisorption in which both F atoms are adsorbed onto the surface, is also observed. The absolute probability of the three scattering channels (single atom abstraction, two atom adsorption, and unreactive scattering) for an incident F2 are determined as a function of F2 exposure. The fluorine coverage is determined by integrating the reaction probabilities over F2 exposure, and the reaction probabilities are recast as a function of fluorine coverage. Two atom adsorption is the dominant channel [P2=0.83±0.03(95%, N=9)] in the limit of zero coverage and decays monotonically to zero. Single atom abstraction is the minor channel (P1=0.13±0.03) at low coverage but increases to a maximum (P1=0.35±0.08) at about 0.5 monolayer (ML) coverage before decaying to zero. The reaction ceases at 0.94±0.11(95%, N=9) ML. Thermal desorption and helium diffraction confirm that the dangling bonds are the abstraction and adsorption sites. No Si lattice bonds are broken, in contrast to speculation by other investigators that the reaction exothermicity causes lattice disorder.
Facile synthesis N-doped hollow carbon spheres from spherical solid silica.

PubMed

Wenelska, K; Ottmann, A; Moszyński, D; Schneider, P; Klingeler, R; Mijowska, E

2018-02-01

Nitrogen-doped core/shell carbon nanospheres (NHCS are prepared and their capability as an anode material in lithium-ion batteries is investigated. The synthesis methodology is based on a fast template route. The resulting molecular nanostructures are characterized by X-ray diffraction, transmission electron microscopy, thermal analysis, and nitrogen adsorption/desorption measurement as well as by cyclic voltammetry and galvanostatic cycling. The core/shell structure provides a rapid lithium transport pathway and boasts a highly reversible capacity. For undoped HCS the BET specific surface area is 623m 2 /g which increases up to 1000m 2 /g upon N-doping. While there is no significant effect of N-doping on the electrochemical performance at small scan rates, the doped NHCS shows better specific capacities than the pristine HCS at elevated rates. For instance, the discharge capacities in the 40th cycle, obtained at 1000mA/g, amount to 170mAh/g and 138mAh/g for NHCS and HCS, respectively. Copyright © 2017 Elsevier Inc. All rights reserved.
Evaluation of the impact of H2O, O2, and SO2 on postcombustion CO2 capture in metal-organic frameworks.

PubMed

Yu, Jiamei; Ma, Yuguang; Balbuena, Perla B

2012-05-29

Molecular modeling methods are used to estimate the influence of impurity species: water, O(2), and SO(2) in flue gas mixtures present in postcombustion CO(2) capture using a metal organic framework, HKUST-1, as a model sorbent material. Coordinated and uncoordinated water effects on CO(2) capture are analyzed. Increase of CO(2) adsorption is observed for both cases, which can be attributed to the enhanced binding energy between CO(2) and HKUST-1 due to the introduction of a small amount of water. Density functional theory calculations indicate that the binding energy between CO(2) and HKUST-1 with coordinated water is ~1 kcal/mol higher than that without coordinated water. It is found that the improvement of CO(2)/N(2) selectivity induced by coordinated water may mainly be attributed to the increased CO(2) adsorption on the hydrated HKUST-1. On the other hand, the enhanced selectivity induced by uncoordinated water in the flue gas mixture can be explained on the basis of the competition of adsorption sites between water and CO(2) (N(2)). At low pressures, a significant CO(2)/N(2) selectivity increase is due to the increase of CO(2) adsorption and decrease of N(2) adsorption as a consequence of competition of adsorption sites between water and N(2). However, with more water molecules adsorbed at higher pressures, the competition between water and CO(2) leads to the decrease of CO(2) adsorption capacity. Therefore, high pressure operation should be avoided in HKUST-1 sorbents for CO(2) capture. In addition, the effects of O(2) and SO(2) on CO(2) capture in HKUST-1 are investigated: The CO(2)/N(2) selectivity does not change much even with relatively high concentrations of O(2) in the flue gas (up to 8%). A slightly lower CO(2)/N(2) selectivity of a CO(2)/N(2)/H(2)O/SO(2) mixture is observed compared with that in a CO(2)/N(2)/H(2)O mixture, especially at high pressures, due to the strong SO(2) binding with HKUST-1.
Simultaneous determination of epinephrene and paracetamol at copper-cobalt oxide spinel decorated nanocrystalline zeolite modified electrodes.

PubMed

Samanta, Subhajyoti; Srivastava, Rajendra

2016-08-01

In this study, CuCo2O4 and CuCo2O4 decorated nanocrystalline ZSM-5 materials were prepared. For comparative study, a series of MCo2O4 spinels were also prepared. Materials were characterized by the complementary combination of X-ray diffraction, N2-adsorption, UV-visible, and electron microscopic techniques. A simple and rapid method for the simultaneous determination of paracetamol and epinephrine at MCo2O4 spinels modified electrodes is presented in this manuscript. Among the materials investigated in this study, CuCo2O4 decorated nanocrystalline ZSM-5 exhibited the highest electrocatalytic activity with excellent stability, sensitivity, and selectivity. Analytical performance of the sensor was demonstrated in the determination of epinephrine and paracetamol in the commercial pharmaceutical samples. Copyright © 2016 Elsevier Inc. All rights reserved.
Adsorption of Cu(II) on Oxidized Multi-Walled Carbon Nanotubes in the Presence of Hydroxylated and Carboxylated Fullerenes

PubMed Central

Wang, Jing; Li, Zhan; Li, Shicheng; Qi, Wei; Liu, Peng; Liu, Fuqiang; Ye, Yuanlv; Wu, Liansheng; Wang, Lei; Wu, Wangsuo

2013-01-01

The adsorption of Cu(II) on oxidized multi-walled carbon nanotubes (oMWCNTs) as a function of contact time, pH, ionic strength, temperature, and hydroxylated fullerene (C60(OH)n) and carboxylated fullerene (C60(C(COOH)2)n) were studied under ambient conditions using batch techniques. The results showed that the adsorption of Cu(II) had rapidly reached equilibrium and the kinetic process was well described by a pseudo-second-order rate model. Cu(II) adsorption on oMWCNTs was dependent on pH but independent of ionic strength. Compared with the Freundlich model, the Langmuir model was more suitable for analyzing the adsorption isotherms. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that Cu(II) adsorption on oMWCNTs was spontaneous and endothermic. The effect of C60(OH)n on Cu(II) adsorption of oMWCNTs was not significant at low C60(OH)n concentration, whereas a negative effect was observed at higher concentration. The adsorption of Cu(II) on oMWCNTs was enhanced with increasing pH values at pH < 5, but decreased at pH ≥ 5. The presence of C60(C(COOH)2)n inhibited the adsorption of Cu(II) onto oMWCNTs at pH 4–6. The double sorption site model was applied to simulate the adsorption isotherms of Cu(II) in the presence of C60(OH)n and fitted the experimental data well. PMID:24009683
On the Structure-Property Relationships of Cation-Exchanged ZK-5 Zeolites for CO 2 Adsorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pham, Trong D.; Hudson, Matthew R.; Brown, Craig M.

2017-02-16

The CO 2 adsorption properties of cation-exchanged Li-, Na-, K-, and Mg-ZK-5 zeolites were correlated to the molecular structures determined by Rietveld refinements of synchrotron powder X-ray diffraction patterns. Li-, K-, and Na-ZK-5 all exhibited high isosteric heats of adsorption (Qst) at low CO 2 coverage, with Na-ZK-5 having the highest Qst (ca. 49 kJ mol -1). Mg2+ was located at the center of the zeolite hexagonal prism with the cation inaccessible to CO 2, leading to a much lower Qst (ca. 30 kJ mol-1) and lower overall uptake capacity. Multiple CO 2 adsorption sites were identified at a givenmore » CO 2 loading amount for all four cation-exchanged ZK-5 adsorbents. Site A at the flat eight-membered ring windows and site B/B* in the γ-cages were the primary adsorption sites in Li - and Na-ZK-5 zeolites. Relatively strong dual-cation adsorption sites contributed significantly to an enhanced electrostatic interaction for CO 2 in all ZK-5 samples. This interaction gives rise to a migration of Li + and Mg 2+ cations from their original locations at the center of the hexagonal prisms toward the α-cages, in which they interact more strongly with the adsorbed CO 2.« less
Adsorption, Desorption, and Diffusion of Nitrogen in a Model Nanoporous Material: II. Diffusion Limited Kinetics in Amorphous Solid Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zubkov, Tykhon; Smith, R. Scott; Engstrom, Todd R.

2007-11-14

Tykhon Zubkov, R. Scott Smith, Todd R. Engstrom, and Bruce D. Kay The adsorption, desorption, and diffusion kinetics of N2 on thick (up to ~9 mm) porous films of amorphous solid water (ASW) films were studied using molecular beam techniques and temperature programmed desorption (TPD). Porous ASW films were grown on Pt(111) at low temperature (<30 K) from a collimated H2O beam at glancing incident angles. In thin films (<1 mm), the desorption kinetics are well described by a model that assumes rapid and uniform N2 distribution throughout the film. In thicker films, (>1 mm), N2 adsorption at 27 Kmore » results in a non-uniform distribution where most of N2 is trapped in the outer region of the film. Redistribution of N2 can be induced by thermal annealing. The apparent activation energy for this process is ~7 kJ/mol, which is approximately half of the desorption activation energy at the corresponding coverage. Blocking adsorption sites near the film surface facilitates transport into the film. Despite the onset of limited diffusion, the adsorption kinetics are efficient, precursor-mediated and independent of film thickness. An adsorption mechanism is proposed, in which a high-coverage N2 front propagates into a pore by the rapid transport of physisorbed 2nd layer N2 species on top of the 1st layer chemisorbed layer.« less
Adsorption and photocatalysis efficiency of magnetite quantum dots anchored tin dioxide nanofibers for removal of mutagenic compound: Toxicity evaluation and antibacterial activity.

PubMed

Fakhri, Ali; Naji, Mahsa; Nejad, Pedram Afshar

2017-08-01

The Magnetite Fe 3 O 4 quantum dots anchored SnO 2 nanofibers (Fe 3 O 4 QDs/SnO 2 NFs) have been synthesized using the facile one step hydrothermal method. The characteristic structure of synthesized Fe 3 O 4 QDs/SnO 2 NFs was analyzed using X-ray diffraction, Transmission electron Microscopy, Scanning electron microscopy, UV-vis diffuse reflectance, photoluminescence spectroscopy, and N 2 adsorption-desorption instrumental techniques. The crystallites size of Fe 3 O 4 QDs/SnO 2 NFs was 7.0nm. The average diameters of Fe 3 O 4 QDs/SnO 2 NFs were 7.25nm. BET surface area of Fe 3 O 4 QDs/SnO 2 NFs has been found 53.064m 2 /g. The activity of Fe 3 O 4 QDs/SnO 2 NFs samples were compared towards adsorption and degradation of mutagenic compound such as Ethyl methanesulfonate (EMS). The Fe 3 O 4 QDs/SnO 2 NFs demonstrates 93.85% and 56.85% photo degradation and adsorption activity towards 10ppm EMS solution in 30 and 40min, respectively. Fe 3 O 4 QDs/SnO 2 NFs shows maximum removal of EMS at pH5. Additionally, cytotoxicity test showed that the newly developed catalyst has low cytotoxic effects on three kinds of human cells. The antibacterial activity evaluation against two bacterials, including Staphylococcus aureus (ATCC 43300), and Pseudomonas aeruginosa (ATCC 27853) was considered. It was found that the MIC values for the antibacterial assay in the presence of Fe 3 O 4 QDs/SnO 2 NFs were around 0.38mM with 83.4, and 85.5% inhibition for the S. aureus, and P. aeruginosa bacterial strains, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.
Facile synthesis of hollow Co3O4 microspheres and its use as a rapid responsive CL sensor of combustible gases.

PubMed

Teng, Fei; Yao, Wenqing; Zheng, Youfei; Ma, Yutao; Xu, Tongguang; Gao, Guizhi; Liang, Shuhui; Teng, Yang; Zhu, Yongfa

2008-09-15

The hollow Co(3)O(4) microspheres (HCMs) were prepared by the carbonaceous templates, which did not need the surface pretreatment. The chemiluminescence (CL) and catalytic properties for CO oxidation over these hollow samples were evaluated. The samples were characterized by scanning electron microscopy (SEM), energy disperse spectra (EDS), transmission electron microscopy (TEM), selected area electron diffraction (ED), X-ray diffraction (XRD), temperature-programmed desorption (TPD) and N(2) adsorption. The influences of filter' band length, flow rate of gas, test temperature, and particle structure on CL intensities were mainly investigated. It was found that compared with the solid Co(3)O(4) particles (SCPs), HCMs had a stronger CL intensity, which was ascribed to its hollow structure; and that CL properties of the catalysts were well correlated with their reaction activities. Moreover, HCMs were used to fabricate a highly sensitive gas detector, which is a rapid and effective method for the selection of catalysts or the detection of environmental deleterious gases.
Adsorption mechanism of 2,4-dichlorophenoxyacetic acid onto nitric-acid-modified activated carbon fiber.

PubMed

Li, Qun; Sun, Jie; Ren, Tianhao; Guo, Lin; Yang, Zhilin; Yang, Qi; Chen, Hai

2018-04-01

Adsorption by carbon materials is one of the relatively fast methods in present research, which is widely used in emergency events. Activated carbon fiber (ACF) modified by nitric acid (N-ACF) was studied in this research to determine the adsorption performance for 2,4-dichlorophenoxyacetic acid (2,4-D). Subsequently, influence factors, adsorption isotherm models, kinetics and thermodynamic were investigated in a batch system to realize this adsorption. Experimental results showed that ACF modified by 0.1M nitric acid had a better removal ability than 2,4-D. Removal rate of 2,4-D by N-ACF was greatly influenced by pH with the optimum pH at 2. The superiority of the Langmuir isotherm model in describing the adsorption equilibrium was revealed by correlation coefficients R2 (R 2 ≥ 0.997). Furthermore, adsorption kinetics was well described by pseudo-second-order model. The results of thermodynamic showed that adsorption was a spontaneous, endothermic process with randomness increasing. Additionally, surface structure properties of adsorbent were characterized by Scanning electron microscopy, Fourier transform infrared spectroscopy, Specific surface area analysis of Brunauer, Emmett and Teller and Boehm's titration. It turned out that the micropore structure and functional groups on N-ACF all can contribute to the removal of 2,4-D.

NaA zeolite derived from blast furnace slag: its application for ammonium removal.

PubMed

Guo, Hongwei; Tang, Lizhen; Yan, Bingji; Wan, Kang; Li, Peng

2017-09-01

In this paper, high value added NaA zeolite material was prepared from blast furnace (BF) slag by hydrothermal method and its adsorption behavior on the removal of ammonium ion was investigated. It was found out that the synthetic NaA cubic zeolite with smaller crystal size obtained at nSiO 2 /nAl 2 O 3 = 2 and nH 2 O/nNaOH = 20 showed better adsorption performance. The kinetics of the adsorption of ammonium ion by synthesized NaA zeolite was fitted by the pseudo-second-order kinetic model. The intra-particle diffusion modeling reveals that two mixed rate-controlling mechanisms were involved in the adsorption process. The relatively high value of activation energy of 92.3 kJ·mol -1 indicates a high impact of temperature on the adsorption rate, and the nature of ammonium adsorption is chemical reaction rather than physisorption. Based on the thermodynamics calculations, the adsorption of ammonium was found to be an endothermic, spontaneous process. The adsorption isothermal analysis showed that the Langmuir model could be well fitted and a maximum adsorption capacity of 83.3 mg·g -1 of NH 4 + was obtained. Thus, it was demonstrated that by forming low cost NaA zeolite and using it for environmental remediation, the synchronous minimization of BF slag and ammonia nitrogen contamination could be achieved.
Adsorption of Toluene and Paraxylene from Aqueous Solution Using Pure and Iron Oxide Impregnated Carbon Nanotubes: Kinetics and Isotherms Study

PubMed Central

Abbas, Aamir; Ihsanullah; Al-Baghli, Nadhir A. H.

2017-01-01

Multiwall carbon nanotubes (CNTs) and iron oxide impregnated carbon nanotubes (CNTs-iron oxide) were investigated for the adsorption of hazardous toluene and paraxylene (p-xylene) from aqueous solution. Pure CNTs were impregnated with iron oxides nanoparticles using wet impregnation technique. Various characterization techniques including thermogravimetric analysis, scanning electron microscopy, elemental dispersion spectroscopy, X-ray diffraction, and nitrogen adsorption analysis were used to study the thermal degradation, surface morphology, purity, and surface area of the materials. Batch adsorption experiments show that iron oxide impregnated CNTs have higher degree of removal of p-xylene (i.e., 90%) compared with toluene (i.e., 70%), for soaking time 2 h, with pollutant initial concentration 100 ppm, at pH 6 and shaking speed of 200 rpm at 25°C. Pseudo-second-order model provides better fitting for the toluene and p-xylene adsorption. Langmuir and Freundlich isotherm models demonstrate good fitting for the adsorption data of toluene and p-xylene. PMID:28386208
Quantifying adsorption-induced deformation of nanoporous materials on different length scales

PubMed Central

Morak, Roland; Braxmeier, Stephan; Ludescher, Lukas; Hüsing, Nicola; Reichenauer, Gudrung

2017-01-01

A new in situ setup combining small-angle neutron scattering (SANS) and dilatometry was used to measure water-adsorption-induced deformation of a monolithic silica sample with hierarchical porosity. The sample exhibits a disordered framework consisting of macropores and struts containing two-dimensional hexagonally ordered cylindrical mesopores. The use of an H2O/D2O water mixture with zero scattering length density as an adsorptive allows a quantitative determination of the pore lattice strain from the shift of the corresponding diffraction peak. This radial strut deformation is compared with the simultaneously measured macroscopic length change of the sample with dilatometry, and differences between the two quantities are discussed on the basis of the deformation mechanisms effective at the different length scales. It is demonstrated that the SANS data also provide a facile way to quantitatively determine the adsorption isotherm of the material by evaluating the incoherent scattering contribution of H2O at large scattering vectors. PMID:29021735
Incorporation of precious metal nanoparticles into various aerogels by different supercritical deposition methods

NASA Astrophysics Data System (ADS)

Saquing, Carl D.

2005-11-01

One major hurdle in nanoparticle fabrication is the difficulty in controlling size, distribution and concentration. Conventional methods in nanoparticle formation require high temperatures which lead to particle agglomeration and size broadening, or involve substantial amount of organic solvents. A clean route to supported-nanoparticles fabrication was investigated using various supercritical (SC) based deposition methods. The SC deposition involves the organometallic precursor (OP) (dimethyl(1,5-cyclooctadiene)platinum(II)[CODPtMe 2] or bis(2,2,6,6-tetramethyl-3,5-heptanedionato) (1,5-cyclooctadiene) ruthenium(II)) dissolution in SC fluid and contacting this solution with a substrate. The OP is adsorbed and subsequent reduction of the OP-impregnated substrate produces metal/substrate composites. The various methods were: (1) thermal reduction at atmospheric pressure in an inert atmosphere; (2) thermal reduction in SC carbon dioxide (scCO2); (3) chemical reduction in scCO2 with H2; and (4) chemical reduction at atmospheric pressure with H2. The synthesis of resorcinol-formaldehyde aerogels (RFAs) and carbon aerogels (CAs) was also studied and used as substrates (along with commercial silica aerogels (SAs)) in the SC deposition. The surface area, pore properties, and density of these aerogels were evaluated and the effects of reactant concentration, pyrolysis and SC deposition on these properties were determined. Using a static method, the adsorption isotherms of CODPtMe2 in scCO2 on two CAs with different pore sizes were measured at 28 MPa and 80°C to determine the maximum metal loading and the effect of pore properties on adsorption and to examine the interactions between the three components. The isotherms could be represented by the Langmuir model and the adsorption data indicated a strong CODPtMe2-CA interaction and that almost all the preexistent micropore area was covered with CODPtMe 2 molecules even at adsorption lower than the maximum capacity. The observed strong precursor-substrate interaction was corroborated by thermo-gravimetric analyses and N2 physisorption. Transmission electron microscopy, x-ray diffraction, H2 and CO chemisorption and N2 physisorption were employed to demonstrate the homogeneity of particle dispersion, to determine the morphology, range and variation in particle size within the solid matrices and to fully identify the resultant particles as Pt and Ru metals. (Abstract shortened by UMI.)
A microporous MOF with a polar pore surface exhibiting excellent selective adsorption of CO2 from CO2-N2 and CO2-CH4 gas mixtures with high CO2 loading.

PubMed

Pal, Arun; Chand, Santanu; Elahi, Syed Meheboob; Das, Madhab C

2017-11-14

A microporous MOF {[Zn(SDB)(L) 0.5 ]·S} n (IITKGP-5) with a polar pore surface has been constructed by the combination of a V-shaped -SO 2 functionalized organic linker (H 2 SDB = 4,4'-sulfonyldibenzoic acid) with an N-rich spacer (L = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene), forming a network with sql(2,6L1) topology. IITKGP-5 is characterized by TGA, PXRD and single crystal X-ray diffraction. The framework exhibits lozenge-shaped channels of an approximate size of 4.2 × 5.6 Å 2 along the crystallographic b axis with a potential solvent accessible volume of 26%. The activated IITKGP-5a revealed a CO 2 uptake capacity of 56.4 and 49 cm 3 g -1 at 273 K/1 atm and 295 K/1 atm, respectively. On the contrary, it takes up a much smaller amount of CH 4 (17 cm 3 g -1 at 273 K and 13.6 cm 3 g -1 at 295 K) and N 2 (5.5 cm 3 g -1 at 273 K; 4 cm 3 g -1 at 295 K) under 1 atm pressure exhibiting its potential for a highly selective adsorption of CO 2 from flue gas as well as a landfill gas mixture. Based on the ideal adsorbed solution theory (IAST), a CO 2 /N 2 selectivity of 435.5 and a CO 2 /CH 4 selectivity of 151.6 have been realized at 273 K/100 kPa. The values at 295 K are 147.8 for CO 2 /N 2 and 23.8 for CO 2 /CH 4 gas mixtures under 100 kPa. In addition, this MOF nearly approaches the target values proposed for PSA and TSA processes for practical utility exhibiting its prospect for flue gas separation with a CO 2 loading capacity of 2.04 mmol g -1 .
Understanding the breathing phenomena in nano-ZIF-7 upon gas adsorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cuadrado-Collados, Carlos; Fernández-Català, Javier; Fauth, François

For this research, synchrotron X-ray diffraction and inelastic neutron scattering measurements have been applied to evaluate the breathing phenomena in small nanocrystals of ZIF-7 upon gas adsorption. The experimental results show that an extended solvent exchange process with methanol is crucial to get a solvent-free narrow pore structure. Under these conditions, nano-ZIF-7 is indeed able to adsorb N 2 with a total BET surface area of around 380 m 2 g -1, in close agreement with theoretical predictions. The breathing phenomenon upon nitrogen adsorption is accompanied by a phase-to-phase transition, from a narrow-pore (phase II) to a large-pore (phase I)more » structure and a suppression of the cooperative deformation of the framework involving mainly the flapping motion of the benzimidazolate (bIm) ligand with the 4- and 6-membered rings. Whereas nitrogen requires temperature and pressure conditions close to condensation (close to 1 bar and 77 K) to induce the breathing in ZIF-7, CO 2 can do it under milder conditions (at room temperature and low relative pressures). These results reflect that the nature of the adsorptive probe and the gas–framework interactions, rather than the molecular diameter and/or shape, play a crucial role in defining the pressure and temperature conditions required to induce the breathing. Lastly, the presence of two different cavities in ZIF-7 as suggested by theoretical predictions, one with a window diameter of below 0.4 nm (cavity A) and the other with a pore size of around 0.6 nm (cavity B), has been confirmed experimentally using immersion calorimetry.« less
Understanding the breathing phenomena in nano-ZIF-7 upon gas adsorption

DOE PAGES

Cuadrado-Collados, Carlos; Fernández-Català, Javier; Fauth, François; ...

2017-09-11

For this research, synchrotron X-ray diffraction and inelastic neutron scattering measurements have been applied to evaluate the breathing phenomena in small nanocrystals of ZIF-7 upon gas adsorption. The experimental results show that an extended solvent exchange process with methanol is crucial to get a solvent-free narrow pore structure. Under these conditions, nano-ZIF-7 is indeed able to adsorb N 2 with a total BET surface area of around 380 m 2 g -1, in close agreement with theoretical predictions. The breathing phenomenon upon nitrogen adsorption is accompanied by a phase-to-phase transition, from a narrow-pore (phase II) to a large-pore (phase I)more » structure and a suppression of the cooperative deformation of the framework involving mainly the flapping motion of the benzimidazolate (bIm) ligand with the 4- and 6-membered rings. Whereas nitrogen requires temperature and pressure conditions close to condensation (close to 1 bar and 77 K) to induce the breathing in ZIF-7, CO 2 can do it under milder conditions (at room temperature and low relative pressures). These results reflect that the nature of the adsorptive probe and the gas–framework interactions, rather than the molecular diameter and/or shape, play a crucial role in defining the pressure and temperature conditions required to induce the breathing. Lastly, the presence of two different cavities in ZIF-7 as suggested by theoretical predictions, one with a window diameter of below 0.4 nm (cavity A) and the other with a pore size of around 0.6 nm (cavity B), has been confirmed experimentally using immersion calorimetry.« less
Label-free surface plasmon resonance biosensing with titanium nitride thin film.

PubMed

Qiu, Guangyu; Ng, Siu Pang; Wu, Chi-Man Lawrence

2018-05-30

In this report, titanium nitride thin film synthesized with reactive magneto-sputtering technique is proposed as an alternative surface plasmon resonance sensing material. The physical and chemical natures were initially studied by atomic force microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. In virtue of white-light common-path sensing system, the wavelength modulated TiN films achieved tunable evanescent plasmonic field from 573 nm to 627 nm. The optimized TiN film with 29.8 nm thickness exhibited good differential phase sensitivity (i.e. 1.932 × 10 -7 RIU) to refractive index alteration, which is comparable to the performance of gold film. We have also attained direct measurement of biotin adsorption on the TiN and monitored sub-sequential biotin-streptavidin conjugation. It was found that TiN films have significantly higher binding affinity toward biotin than that of gold in experiments, so we are able to detect biotin directly to 0.22 µg/ml (0.90 µM) in label-free manner. The adsorption mechanism of biotin on TiN(200) are also explored with periodic density functional theory (DFT) via computer simulation and it was found that the exceptional biotin-TiN affinity may be due to the stacking formation of both N-Ti and O-Ti bonds. Also, the adsorption energy of biotin-TiN was found to be - 1.85 eV, which was two times higher than that of biotin-gold. Both experimental and computational results indicate, for the first time, that the TiN film can be directly functionalized with biotin molecules, thus it serves as an alternative plasmonic material to existing gold-based SPR biosensors. Copyright © 2018 Elsevier B.V. All rights reserved.
Tannin-immobilized mesoporous silica bead (BT-SiO2) as an effective adsorbent of Cr(III) in aqueous solutions.

PubMed

Huang, Xin; Liao, Xuepin; Shi, Bi

2010-01-15

This study describes a new approach for the preparation of tannin-immobilized adsorbent by using mesoporous silica bead as the supporting matrix. Bayberry tannin-immobilized mesoporous silica bead (BT-SiO2) was characterized by powder X-ray diffraction to verify the crystallinity, field-emission scanning electron microscopy to observe the surface morphology, and surface area and porosity analyzer to measure the mesoporous porous structure. Subsequently, the adsorption experiments to Cr(III) were applied to evaluate the adsorption performances of BT-SiO2. It was found that the adsorption of Cr(III) onto BT-SiO2 was pH-dependent, and the maximum adsorption capacity was obtained in the pH range of 5.0-5.5. The adsorption capacity was 1.30 mmol g(-1) at 303 K and pH 5.5 when the initial concentration of Cr(III) was 2.0 mmol L(-1). Based on proton nuclear magnetic resonance (HNMR) analyses, the adsorption mechanism of Cr(III) on BT-SiO2 was proved to be a chelating interaction. The adsorption kinetic data can be well described using pseudo-first-order model and the equilibrium data can be well fitted by the Langmuir isothermal model. Importantly, no bayberry tannin was leached out during the adsorption process and BT-SiO2 can simultaneously remove coexisting metal ions from aqueous solutions. In conclusion, this study provides a new strategy for the preparation of tannin-immobilized adsorbents that are highly effective in removal of heavy metals from aqueous solutions.
Effect of degree of deacetylation of chitosan on adsorption capacity and reusability of chitosan/polyvinyl alcohol/TiO2 nano composite.

PubMed

Habiba, Umma; Joo, Tan Chin; Siddique, Tawsif A; Salleh, Areisman; Ang, Bee Chin; Afifi, Amalina M

2017-11-01

The chitosan/polyvinyl alcohol/TiO 2 composite was synthesized. Two different degrees of deacetylation of chitosan were prepared by hydrolysis to compare the effectiveness of them. The composite was analyzed via field emission scanning electron microscopy, Fourier transform infrared, X-ray diffraction, thermal gravimetric analysis, weight loss test and adsorption study. The FTIR and XRD results proved the interaction among chitosan, PVA and TiO 2 without any chemical reaction. It was found that, chitosan with higher degree of deacetylation has better stability. Furthermore, it also showed that higher DD of chitosan required less time to reach equilibrium for methyl orange. The adsorption followed the pseudo-second-order kinetic model. The Langmuir and Freundlich isotherm models were fitted well for isotherm study. Adsorption capacity was higher for the composite containing chitosan with higher DD. The dye removal rate was independent of the dye's initial concentration. The adsorption capacity was increased with temperature and it was found from reusability test that the composite containing chitosan with higher DD is more reusable. It was notable that adsorption capacity was even after 15 runs. Therefore, chitosan/PVA/TiO 2 composite can be a very useful material for dye removal. Copyright © 2017 Elsevier B.V. All rights reserved.
Removal of cadmium(II) ions from aqueous solution using Ni (15 wt.%)-doped α-Fe2O3 nanocrystals: equilibrium, thermodynamic, and kinetic studies.

PubMed

OuldM'hamed, Mohamed; Khezami, L; Alshammari, Abdulrahman G; Ould-Mame, S M; Ghiloufi, I; Lemine, O M

2015-01-01

The present publication investigates the performance of nanocrystalline Ni (15 wt.%)-doped α-Fe2O3 as an effective nanomaterial for the removal of Cd(II) ions from aqueous solutions. The nanocrystalline Ni-doped α-Fe2O3 powders were prepared by mechanical alloying, and characterized by X-ray diffraction and a vibrating sample magnetometer. Batch-mode experiments were realized to determine the adsorption equilibrium, kinetics, and thermodynamic parameters of toxic heavy metal ions by Ni (15 wt.%)-doped α-Fe2O3. The adsorption isotherms data were found to be in good agreement with the Langmuir model. The adsorption capacity of Cd(II) ion reached a maximum value of about 90.91 mg g(-1) at 328 K and pH 7. The adsorption process kinetics was found to comply with pseudo-second-order rate law. Thermodynamic parameters related to the adsorption reaction, free energy change, enthalpy change and entropy change, were evaluated. The found values of free energy and enthalpy revealed a spontaneous endothermic adsorption-process. Moreover, the positive entropy suggests an increase of randomness during the process of heavy metal removal at the adsorbent-solution interface.
Dye adsorption mechanisms in TiO2 films, and their effects on the photodynamic and photovoltaic properties in dye-sensitized solar cells.

PubMed

Hwang, Kyung-Jun; Shim, Wang-Geun; Kim, Youngjin; Kim, Gunwoo; Choi, Chulmin; Kang, Sang Ook; Cho, Dae Won

2015-09-14

The adsorption mechanism for the N719 dye on a TiO2 electrode was examined by the kinetic and diffusion models (pseudo-first order, pseudo-second order, and intra-particle diffusion models). Among these methods, the observed adsorption kinetics are well-described using the pseudo-second order model. Moreover, the film diffusion process was the main controlling step of adsorption, which was analysed using a diffusion-based model. The photodynamic properties in dye-sensitized solar cells (DSSCs) were investigated using time-resolved transient absorption techniques. The photodynamics of the oxidized N719 species were shown to be dependent on the adsorption time, and also the adsorbed concentration of N719. The photovoltaic parameters (Jsc, Voc, FF and η) of this DSSC were determined in terms of the dye adsorption amounts. The solar cell performance correlates significantly with charge recombination and dye regeneration dynamics, which are also affected by the dye adsorption amounts. Therefore, the photovoltaic performance of this DSSC can be interpreted in terms of the adsorption kinetics and the photodynamics of oxidized N719.
Highly Efficient Iodine Capture by Layered Double Hydroxides Intercalated with Polysulfides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Shulan; Islam, Saiful M.; Shim, Yurina

2014-12-23

We demonstrate strong iodine (I-2) vapor adsorption using Mg/Al layered double hydroxide (MgAl-LDH) nanocomposites intercalated with polysulfide (S-x(2-)) groups (S-x-LDH, x = 2, 4, 6). The as-prepared LDH/polysulfide hybrid materials display highly efficient iodine capture resulting from the reducing property of the intercalated polysulfides. During adsorption, the I-2 molecules are reduced to I-3(-) anions by the intercalated [S-x](2-) groups that simultaneously are oxidized to form S8. In addition to the chemical adsorption, additional molecular I-2 is physically captured by the LDH composites. As a result of these parallel processes, and despite their very low BET surface areas, the iodine capturemore » capacities of S-2-LDH, S-4-LDH, and S-6-LDH are similar to 1.32, 1.52, and 1.43 g/g, respectively, with a maximum adsorption of 152% (wt %). Thermogravimetric and differential thermal analysis (TG-DTA), energy dispersive X-ray spectroscopy (EDS), and temperature-variable powder X-ray diffraction (XRD) measurements show the resulting I-3(-) ions that intercalated into the LDH gallery have high thermal stability (>= 350 degrees C). The excellent iodine adsorption performance combined with the facile preparation points to the S-x-LDH systems as potential superior materials for adsorption of radioactive iodine, a waste product of the nuclear power industry.« less
Magnesium Oxide Embedded Nitrogen Self-Doped Biochar Composites: Fast and High-Efficiency Adsorption of Heavy Metals in an Aqueous Solution.

PubMed

Ling, Li-Li; Liu, Wu-Jun; Zhang, Shun; Jiang, Hong

2017-09-05

Lead (Pb) pollution in natural water bodies is an environmental concern due to toxic effects on aquatic ecosystems and human health, while adsorption is an effective approach to remove Pb from the water. Surface interactions between adsorbents and adsorbates play a dominant role in the adsorption process, and properly engineering a material's surface property is critical to the improvement of adsorption performance. In this study, the magnesium oxide (MgO) nanoparticles stabilized on the N-doped biochar (MgO@N-biochar) were synthesized by one-pot fast pyrolysis of an MgCl 2 -loaded N-enriched hydrophyte biomass as a way to increase the exchangeable ions and N-containing functional groups and facilitate the adsorption of Pb 2+ . The as-synthesized MgO@N-biochar has a high performance with Pb in an aqueous solution with a large adsorption capacity (893 mg/g), a very short equilibrium time (<10 min), and a large throughput (∼4450 BV). Results show that this excellent adsorption performance can be maintained with various environmentally relevant interferences including pH, natural organic matter, and other metal ions, suggesting that the material may be suitable for the treatment of wastewater, natural bodies of water, and even drinking water. In addition, MgO@N-biochar quickly and efficiently removed Cd 2+ and tetracycline. Multiple characterizations and comparative tests have been performed to demonstrate the surface adsorption and ion exchange contributed to partial Pb adsorption, and it can be inferred from these results that the high performance of MgO@N-biochar is mainly due to the surface coordination of Pb 2+ and C═O or O═C-O, pyridinic, pyridonic, and pyrrolic N. This work suggests that engineering surface functional groups of biochar may be crucial for the development of high performance heavy metal adsorbents.
DFT study on stability and H2 adsorption activity of bimetallic Au79-nPdn (n = 1-55) clusters

NASA Astrophysics Data System (ADS)

Liu, Xuejing; Tian, Dongxu; Meng, Changgong

2013-03-01

The stability and H2 adsorption activity of bimetallic Au79-nPdn (n = 1-55) clusters were studied by density functional theory with GGA-PW91 functional. The stability order for four Pd substitution types is face > mid-edge > corner > edge, and the stability is improved with increasing Pd content. In contrast with the stability order, H2 adsorption activity is corner ≈ edge > mid-edge > face. The Au36Pd43 (3) with Au:Pd ≈ 1:1 ratio and twenty-four Pd substitutions at (1 1 1) facets and nineteen Pd substitutions at subshell sites shows high stability and H2 non-activated dissociation activity. The partial density of d-states and d band center revealed that the electronic properties are closely associated with the geometric characteristic and adsorption activity. Correlating the d band center ɛd and the adsorption energies, the ɛd order agrees with the adsorption activity that the Pd substitution at edge and corner sites are more active than at face and mid-edge sites.
N2O reduction over a fullerene-like boron nitride nanocage: A DFT study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.

2017-07-01

We study, for the first time, the adsorption and catalytic decomposition of N2O molecule over a fullerene-like boron nitride nanocage (B12N12) using density functional theory calculations. It is found that the electron donating property of the cage plays an important role in the adsorption and activation of N2O. By the incorporation of a carbon atom into B12N12 cluster, our results indicate that the adsorption of N2O over B11N12C or B12N11C is more stronger than over pristine B12N12. The decomposition of N2O into N2 and O species over the C-doped clusters is energetically more favorable than that on B12N12. Moreover, the C-doping plays an important role in reducing the activation barrier for the CO + O* reaction over B12N12 surface.
A novel process for comprehensive utilization of vanadium slag

NASA Astrophysics Data System (ADS)

Liu, Li-ying; Du, Tao; Tan, Wen-jun; Zhang, Xin-pu; Yang, Fan

2016-02-01

Traditional processes for treating vanadium slag generate a huge volume of solid residue and a large amount of harmful gas, which cause serious environmental problems. In this study, a new process for the comprehensive utilization of vanadium slag was proposed, wherein zeolite A and a V2O5/TiO2 system were synthesized. The structural properties of the as-synthesized zeolite A and the V2O5/TiO2 system were characterized using various experimental techniques, including X-ray diffraction, X-ray fluorescence, scanning electron microscopy, and infrared spectroscopy. The results reveal that zeolite A and the V2O5/TiO2 system are successfully obtained with high purity. The results of gas adsorption measurements indicate that the prepared zeolite A exhibits high selectivity for CO2 over N2 and is a candidate material for CO2 capture from flue-gas streams.
Adsorption Behavior of Ferromagnetic Carbon Nanotubes for Methyl Orange from Aqueous Solution.

PubMed

Wang, Liping; Zhang, Mingyu; Zhao, Chenxi; Yang, Shan

2016-03-01

The ferromagnetic carbon nanotubes which can be easily separated from aqueous solution were prepared and characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). Batch experiments were carried out to investigate the adsorption behavior of ferromagnetic carbon nanotubes for removing methyl orange (MO). The results showed that these ferromagnetic carbon nanotubes were richer in surface function groups than the carbon nanotubes did, furthermore, both γ-Fe2O3 and Fe with ferromagnetism were found on the surface of carbon nanotubes. The results also demonstrated that ferromagnetic carbon nanotubes possessed stronger adsorption ability for MO than carbon nanotubes did. The adsorption isotherms followed Langmuir isotherm equation and the adsorption kinetics could be well described with the pseudo second-order kinetic model. The adsorption process involved an intraparticle diffusion, while it was not the only rate-controlling step. The values of AG were negative and the value of ΔH is -12.37 kJ/mol, proving that the adsorption of MO onto ferromagnetic carbon nanotubes was a spontaneous and exothermic process.
Comparison of nitrogen adsorption and transmission electron microscopy analyses for structural characterization of carbon nanotubes

NASA Astrophysics Data System (ADS)

Abbaslou, Reza Malek; Vosoughi, Vahid; Dalai, Ajay K.

2017-10-01

Carbon nanotubes (CNTs) are different from other porous substrates such as activated carbon due to their high external surfaces. This structural feature can lead in some uncertainties in the results of nitrogen adsorption analysis for characterization of CNTs. In this paper, the results of microscopic analyses and nitrogen adsorption method for characterization of carbon nanotubes were compared. Five different types of CNTs with different structures were either synthesized or purchased. The CNT samples were characterized by high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM) and N2 adsorption analysis. The comparisons between the results from the microscopic analyses and N2 adsorption showed that the total pore volume and BET surface measurements include the internal and external porosity of CNTs. Therefore, the interpretation of N2 adsorption data required accurate TEM analysis. In addition, the evaluation of pore size distribution curves from all CNT samples in this study and several instances in the literature revealed the presence of a common peak in the range of 2-5 nm. This peak does not explain the inner pore size distribution. The presence of this common peak can be attributed to the strong adsorption of N2 on the junction of touched and crossed nanotubes.
Properties and reactivity of Fe-organic matter associations formed by coprecipitation versus adsorption: Clues from arsenate batch adsorption

NASA Astrophysics Data System (ADS)

Mikutta, Robert; Lorenz, Dennis; Guggenberger, Georg; Haumaier, Ludwig; Freund, Anja

2014-11-01

Ferric oxyhydroxides play an important role in controlling the bioavailability of oxyanions such as arsenate and phosphate in soil. Despite this, little is known about the properties and reactivity of Fe(III)-organic matter phases derived from adsorption (reaction of organic matter (OM) to post-synthesis Fe oxide) versus coprecipitation (formation of Fe oxides in presence of OM). Coprecipitates and adsorption complexes were synthesized at pH 4 using two natural organic matter (NOM) types extracted from forest floor layers (Oi and Oa horizon) of a Haplic Podzol. Iron(III) coprecipitates were formed at initial molar metal-to-carbon (M/C) ratios of 1.0 and 0.1 and an aluminum (Al)-to-Fe(III) ratio of 0.2. Sample properties were studied by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), N2 gas adsorption, dynamic light scattering, and electrophoretic mobility measurements. Arsenic [As(V)] adsorption to Fe-OM phases was studied in batch experiments (168 h, pH 4, 100 μM As). The organic carbon (OC) contents of the coprecipitates (82-339 mg g-1) were higher than those of adsorption complexes (31 and 36 mg g-1), leading to pronounced variations in specific surface area (9-300 m2 g-1), average pore radii (1-9 nm), and total pore volumes (11-374 mm3 g-1) but being independent of the NOM type or the presence of Al. The occlusion of Fe solids by OM (XPS surface concentrations: 60-82 atom% C) caused comparable pHPZC (1.5-2) of adsorption complexes and coprecipitates. The synthesis conditions resulted in different Fe-OM association modes: Fe oxide particles in 'M/C 0.1' coprecipitates covered to a larger extent the outermost aggregate surfaces, for some 'M/C 1.0' coprecipitates OM effectively enveloped the Fe oxides, while OM in the adsorption complexes primarily covered the outer aggregate surfaces. Despite of their larger OC contents, adsorption of As(V) was fastest to coprecipitates formed at low Fe availability (M/C 0.1) and facilitated by desorption of weakly bonded OC and disaggregation. In contrast, 'M/C 1.0' coprecipitates showed a comparable rate of As uptake as the adsorption complexes. While small mesopores (2-10 nm) promoted the fast As uptake particularly to 'M/C 0.1' coprecipitates, the presence of micropores (<2 nm) appeared to impair As desorption. This study shows that the environmental reactivity of poorly crystalline Fe(III) oxides in terrestrial and aquatic systems can largely vary depending on the formation conditions. Carbon-rich Fe phases precipitated at low M/C ratios may play a more important role in oxyanion immobilization and Fe and C cycling than phases formed at higher M/C ratios or respective adsorption complexes.

Programming MOFs for water sorption: amino-functionalized MIL-125 and UiO-66 for heat transformation and heat storage applications.

PubMed

Jeremias, Felix; Lozan, Vasile; Henninger, Stefan K; Janiak, Christoph

2013-12-07

Sorption-based heat transformation and storage appliances are very promising for utilizing solar heat and waste heat in cooling or heating applications. The economic and ecological efficiency of sorption-based heat transformation depends on the availability of suitable hydrophilic and hydrothermally stable sorption materials. We investigated the feasibility of using the metal-organic frameworks UiO-66(Zr), UiO-67(Zr), H2N-UiO-66(Zr) and H2N-MIL-125(Ti) as sorption materials in heat transformations by means of volumetric water adsorption measurements, determination of the heat of adsorption and a 40-cycle ad/desorption stress test. The amino-modified compounds H2N-UiO-66 and H2N-MIL-125 feature high heat of adsorption (89.5 and 56.0 kJ mol(-1), respectively) and a very promising H2O adsorption isotherm due to their enhanced hydrophilicity. For H2N-MIL-125 the very steep rise of the H2O adsorption isotherm in the 0.1 < p/p0 < 0.2 region is especially beneficial for the intended heat pump application.
TiO2-BASED Composite Films for the Photodegradation of Oxytetracycline

NASA Astrophysics Data System (ADS)

Li, Hui; Guan, Ling-Xiao; Feng, Ji-Jun; Li, Fang; Yao, Ming-Ming

2015-02-01

The spread of the antibiotic oxytetracycline (OTC) has been thought as a threat to the safety of drinking water. In this paper, the photocatalytic activity of the nanocrystalline Fe/Ca co-doped TiO2-SiO2 composite film for the degradation of OTC was studied. The films were characterized by field emission scanning electron microscopy (FE-SEM) equipped with energy-dispersive spectroscopy (EDS), N2 adsorption/desorption isotherms, photoluminescence (PL) spectra, and UV-Vis diffraction reflectance absorption spectra (DRS). The FE-SEM results indicated that the Fe/Ca co-doped TiO2-SiO2 film was composed of smaller nanoparticles compared to pure TiO2 or TiO2-SiO2 film. The BET surface area results showed that the specific surface area of the pure TiO2, TiO2-SiO2 and Ca2+/Fe3+ co-doped TiO2-SiO2 is 118.3 m2g-1, 294.3 m2g-1 and 393.7 m2g-1, respectively. The DRS and PL spectra revealed that the Fe/Ca co-doped TiO2-SiO2 film had strong visible light adsorption and diminished electrons/holes recombination. Experimental results showed that the Fe/Ca co-doped TiO2-SiO2 film is effective in the degradation of OTC under both UV and visible light irradiation.
Silica Aerogel-supported Hydrozincite and Carbonate-intercalated Hydrotalcite for High-efficiency Removal of Pb(II) Ions by Precipitation Transformation Reactions

NASA Astrophysics Data System (ADS)

Wang, Lijun; Wang, Xiaoxia; Li, Jianfa; Feng, Xiaolan; Wang, Yusen

2017-09-01

In this work, hydrozincite and Zn/Al-CO3 2- hydrotalcite supported on silica aerogel were prepared via a simple and economical process and used as adsorbents for Pb(II) removal. The supported hydrozincite and Zn/Al-CO3 2- hydrotalcite possess ultra-thin thickness, high surface area, and weak crystallinity. In the batch Pb(II) adsorption experiments, the adsorbents with higher Zn(II) contents showed higher Pb(II) adsorption capacities, and the adsorption data fitted well with the Langmuir isotherm model and pseudo-second-order kinetic model, indicating a mechanism of surface chemisorption. The adsorption capacities calculated based Langmuir isotherm model are 684.9 mg/g and 555.6 mg/g for the supported hydrozincite and Zn/Al-CO3 2- hydrotalcite, respectively, higher than the adsorption capacities of other hydrotalcite-based adsorbents and most of other inorganic adsorbents reported previously. The XRD diffraction peaks of hydrozincite and Zn/Al-CO3 2- hydrotalcite disappeared after the adsorption, and the Pb(II) species were uniformly dispersed in the adsorbents in form of Pb3(CO3)2(OH)2 proven by TEM, EDS mapping and XRD analysis, demonstrating the nature of the adsorption is the precipitation conversion of hydrozincite or Zn/Al-CO3 2- hydrotalcite into Pb3(CO3)2(OH)2. These results demonstrate the synergic Pb(II) removal effect of the CO3 2- and OH- derived from hydrozincite and Zn/Al-CO3 2- hydrotalcite together with their ultra-thin thickness and high surface area contribute the excellent properties of the adsorbents.
Porous nano-cerium oxide wood chip biochar composites for aqueous levofloxacin removal and sorption mechanism insights.

PubMed

Yi, Shengze; Sun, Yuanyuan; Hu, Xin; Xu, Hongxia; Gao, Bin; Wu, Jichun

2017-01-14

The adsorption removal of levofloxacin (LEV), a widely used fluoroquinolone antibiotic, by using the biochars derived from the pyrolysis of pine wood chip pretreated with cerium trichloride was investigated through batch sorption experiments and multiple characterization techniques. The differences in the basic physicochemical properties between Ce-impregnated biochars and the pristine biochars were confirmed by the analysis of elemental compositions, specific surface areas, energy dispersive spectrometry, X-ray diffraction, and thermo-gravimetry. FT-IR spectra of the pre- and post-sorption biochars confirmed the chemical adsorption for LEV sorption onto the biochars. Large shifts in the binding energy of Ce 3d , O 1s , C 1s , and N 1s regions on the pre- and post-sorption biochars indicated the surface complexation of LEV molecule onto the biochars. The binding species of Ce 4+ and Ce 3+ identified by X-ray photoelectron spectroscopy reflect the role of Ce oxides during sorption. Batch adsorption showed the significant enhancement of adsorption capacity for LEV after the Ce modification. Batch adsorption kinetic data fitted well with the pseudo-second-order model. Both the Langmuir and the Freundlich models reproduced the isotherm data well. Findings from this work indicated that Ce-impregnated biochars can be effective for the removal of aqueous LEV.
Cobalt Oxide on N-Doped Carbon for 1-Butene Oligomerization to Produce Linear Octenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Dongting; Xu, Zhuoran; Chada, Joseph P.

Cobalt oxide supported on N-doped carbon catalysts were investigated for 1-butene oligomerization. The materials were synthesized by treating activated carbon with nitric acid and subsequently with NH3 at 200, 400, 600, and 800 °C, followed by impregnation with cobalt. The 1-butene oligomerization selectivity increased with ammonia treatment temperature of the carbon support. The oligomerization selectivity of cobalt oxide on N-doped carbon synthesized at 800 °C (800A-CoOx/N-C) is 2.6 times higher than previously reported cobalt oxide on N-doped carbon synthesized with NH4OH (2A-CoOx/N-C). Over 70% of the butene dimers were linear C8 olefins for all catalysts. The oligomerization selectivity increased withmore » 1-butene conversion. The catalysts were characterized by elemental analysis, N2 adsorption, X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). The nitrogen content of the catalysts increases with ammonia treatment temperature as confirmed by elemental analysis. The surface content of pyridinic nitrogen with a binding energy of 398.4 ± 0.1 eV increased with ammonia treatment temperature as evidenced by deconvolution of N 1s XPS spectra.« less
Removal of Crystal Violet by Using Reduced-Graphene-Oxide-Supported Bimetallic Fe/Ni Nanoparticles (rGO/Fe/Ni): Application of Artificial Intelligence Modeling for the Optimization Process

PubMed Central

Ruan, Wenqian; Qi, Jimei; Hou, Yu; Cao, Rensheng; Wei, Xionghui

2018-01-01

Reduced-graphene-oxide-supported bimetallic Fe/Ni nanoparticles were synthesized in this study for the removal of crystal violet (CV) dye from aqueous solutions. This material was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS), Raman spectroscopy, N2-sorption, and X-ray photoelectron spectroscopy (XPS). The influence of independent parameters (namely, initial dye concentration, initial pH, contact time, and temperature) on the removal efficiency were investigated via Box–Behnken design (BBD). Artificial intelligence (i.e., artificial neural network, genetic algorithm, and particle swarm optimization) was used to optimize and predict the optimum conditions and obtain the maximum removal efficiency. The zero point of charge (pHZPC) of rGO/Fe/Ni composites was determined by using the salt addition method. The experimental equilibrium data were fitted well to the Freundlich model for the evaluation of the actual behavior of CV adsorption, and the maximum adsorption capacity was estimated as 2000.00 mg/g. The kinetic study discloses that the adsorption processes can be satisfactorily described by the pseudo-second-order model. The values of Gibbs free energy change (ΔG0), entropy change (ΔS0), and enthalpy change (ΔH0) demonstrate the spontaneous and endothermic nature of the adsorption of CV onto rGO/Fe/Ni composites. PMID:29789483
a Novel Catalyst for Reductive Dechlorination of Chlorobenzene in Subcritical Water:. Bifunctional Fe/ZrO2

NASA Astrophysics Data System (ADS)

Wei, Guang-Tao; Wei, Chao-Hai; He, Feng-Mei; Wu, Chao-Fei

Bifunctional Fe/ZrO2 was prepared by mechanical mixing method, and its bifunctional effect on reductive dechlorination of chlorobenzene in subcritical water was studied. Dechlorination efficiency increased with increasing iron content in catalyst and catalyst amount. Dechlorination efficiency slowed when the iron content in catalyst reached 30%; bifunctional catalyst of Fe/ZrO2 was more efficient in dechlorination of chlorobenzene than Fe alone. Catalyst of Fe (30%)/ZrO2 was characterized by means of X-ray diffraction (XRD), H2 temperature programmed desorption (H2-TPD), and N2 adsorption. The possible mechanism of dechlorination in subcritical water by this bifunctional catalyst was proposed. H+ produced in the water dissociation formed the highly reactive spillover hydrogen on the surface of catalyst, and then reacted with chlorobenzene adsorbed on the catalyst surface by ZrO2 to form benzene and chloride ions.
Study of 2,4-dichlorophenoxyacetic acid (2,4-D) removal by Cu-Fe-layered double hydroxide from aqueous solution

NASA Astrophysics Data System (ADS)

Nejati, Kamellia; Davary, Soheila; Saati, Marziye

2013-09-01

The hydrotalcite-like compound of Cu-Fe-layered double hydroxide was studied as a potential adsorbent of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). The nanoparticles of Cu-Fe layered double hydroxide were prepared by Cu/Fe molar ratio of 2:1 using a coprecipitation method at pH 8.5 and characterized by the X-ray powder diffraction (XRD), the Fourier transform infrared spectroscopy (FT-IR), the thermal gravimetric analysis (TGA) and the elemental analysis. The size and morphology of nanoparticles were examined by the transmission electron microscopy (TEM). The adsorption experiments on LDH, on the other hand, were conducted in three different procedures, namely, time-dependent, pH-dependent and temperature-dependent. Characterization of the adsorption products by the XRD method indicates that the intercalation of 2,4-D between the LDH layers has not occurred and the surface adsorption had taken place. The adsorption kinetic was tested for pseudo-first-order, pseudo-second-order, Elovich and Intra-particle diffusion kinetic models and the rate constants were calculated. The equilibrium adsorption data were described by Langmuir and Freundlich equations. It was observed that, the Langmuir isotherm slightly better fitted to the experimental data rather than that of Freundlich. In the adsorption experiments, the Gibbs free energy values, ΔG°, the enthalpy, ΔH°, and the entropy, ΔS° were also determined.
Molecular adsorption of hydrogen peroxide on N- and Fe-doped titania nanoclusters

NASA Astrophysics Data System (ADS)

Mohajeri, Afshan; Dashti, Nasimeh Lari

2017-06-01

Titanium dioxide (titania) nanoparticles have been extensively investigated for photocatalytic applications such as the decomposition and adsorption of pollutant and undesirable compound in air and waste water. In this context, the present article reports the molecular adsorption of hydrogen peroxide on the surface of doped titania clusters. Density functional theory calculations were performed to investigate the structures and electronic properties of two nanoscale (TiO2)n clusters (n = 5,6) modified by nitrogen and iron dopants. The relative stability of all possible N-doped and Fe-doped isomers has been compared with each other and with the parent cluster. It was found that the Fe-doped clusters are in general more stable than the N-doped counterparts. Moreover, after N/Fe doping an enhanced in the magnetization of the clusters is observed. In the second part, we have investigated different modes of H2O2 adsorption on the lowest-energy isomers of doped clusters. In almost all the cases, the adsorptions on the doped clusters are found to be less exothermic than on the corresponding undoped parent cluster. Our results highlight the essential role of charge transfer into the interaction between H2O2 and doped (TiO2)n clusters, especially for Fe-doped clusters.
In situ vibrational spectroscopy of adsorbed nitrogen in porous carbon materials.

PubMed

Ray, Paramita; Xu, Enshi; Crespi, Vincent H; Badding, John V; Lueking, Angela D

2018-05-25

This study uses in situ vibrational spectroscopy to probe nitrogen adsorption to porous carbon materials, including single-wall carbon nanotubes and Maxsorb super-activated carbon, demonstrating how the nitrogen Raman stretch mode is perturbed by adsorption. In all porous carbon samples upon N2 physisorption in the mesopore filling regime, the N2 Raman mode downshifts by ∼2 cm-1, a downshift comparable to liquid N2. The relative intensity of this mode increases as pressure is increased to saturation, and trends in the relative intensity parallel the volumetric gas adsorption isotherm. This mode with ∼2 cm-1 downshift is thus attributed to perturbations arising due to N2-N2 interactions in a condensed film. The mode is also observed for the activated carbon at 298 K, and the relative intensity once again parallels the gas adsorption isotherm. For select samples, a mode with a stronger downshift (>4 cm-1) is observed, and the stronger downshift is attributed to stronger N2-carbon surface interactions. Simulations for a N2 surface film support peak assignments. These results suggest that N2 vibrational spectroscopy could provide an indication of the presence or absence of porosity for very small quantities of samples.
Research on the Treatment of Wastewater by Waste Ceramic Adsorption

NASA Astrophysics Data System (ADS)

He, Lingfeng; Zhang, Yongli; Shi, Liang

2018-03-01

The process of preparing porous ceramic with waste porcelain powder as aggregate was researched. The affect of assimilate time on cuprum removal efficiency in wastewater containing copper was investigated. The results show the water copper removal rate increased along with the augment of assimilate time, and the assimilate time is suitable for 35 min; XRD characterizations show the porous ceramic catalyst before and after calcination in active components of X ray diffraction peak position almost had no changes, and the diffraction intensity slightly changed with calcination and absorption, and diffraction peaks became sharper, and its crystallinity was improved. Baking leads to the growth of crystal particles, and the performance of porous ceramics is stable before and after adsorption.
New functionalized IRMOF-10 with strong affinity for methanol: A simulation study

NASA Astrophysics Data System (ADS)

Liu, Zewei; Zhang, Kai; Wu, Ying; Xi, Hongxia

2018-05-01

Grand Canonical Monte Carlo (GCMC) method simulation combined with density functional theory (DFT) calculation were used to investigate the methanol adsorption in IRMOF-10, with nitrogen and metal-doping functionalizations in order to understand the underlying performance of MOFs in methanol adsorption. New doped IRMOF-10s (M-2N-IRMOF-10, M = Be, Mg, Ca, Sr, Ba) were theoretically constructed by binding nitrogen atoms of organic linkers in N-doping IRMOF-10 (2N-IRMOF-10) with various metal atoms. 2N-IRMOF-10 shows only a little higher methanol capacity in the measured pressure range. However, M-2N-IRMOF-10s (especially Be-2N-IRMOF-10) demonstrate much higher methanol capacity due to the stronger interaction between the induced Be atoms and methanol molecules. Furthermore, the obtained results can be attributed to the new adsorption sites created by metal-doping, as revealed by the more exothermic binding energies (BEs) on Be-sites (-160.8 kJ/mol) than Zn-sites (-19.4 kJ/mol). According to the simulation results, it can be concluded that functionalized IRMOF-10 are capable of enhancing the adsorption capacity of methanol at pressure from 0 to 12 kPa at 298 K. This study provides a new functionalized method to effectively enhance methanol adsorption capacity of MOFs, which might extend the application of MOFs on methanol adsorption in the near future.
Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

NASA Astrophysics Data System (ADS)

Kardanpour, Reihaneh; Tangestaninejad, Shahram; Mirkhani, Valiollah; Moghadam, Majid; Mohammadpoor-Baltork, Iraj; Zadehahmadi, Farnaz

2016-03-01

Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66-NH2 metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl2. The prepared catalyst was characterized by FT-IR, UV-vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66-NH2-TC-Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzene or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency.
Synthesis, characterization and adsorptive performance of MgFe2O4 nanospheres for SO2 removal.

PubMed

Zhao, Ling; Li, Xinyong; Zhao, Qidong; Qu, Zhenping; Yuan, Deling; Liu, Shaomin; Hu, Xijun; Chen, Guohua

2010-12-15

A type of uniform Mg ferrite nanospheres with excellent SO(2) adsorption capacity could be selectively synthesized via a facile solvothermal method. The size of the MgFe(2)O(4) nanospheres was controlled to be 300-400 nm in diameter. The structural, textural, and surface properties of the adsorbent have been fully characterized by a variety of techniques (Brunauer-Emmett-Teller, BET; X-ray diffraction analysis, XRD; scanning electron microscopy, SEM; and energy-dispersive X-ray spectroscopy, EDS). The valence states and the surface chemical compositions of MgFe(2)O(4) nanospheres were further identified by X-ray photoelectron spectroscopy (XPS). The behaviors of SO(2) oxidative adsorption on MgFe(2)O(4) nanospheres were studied using Fourier transform infrared spectroscopy (FTIR). Both the sulfite and sulfate species could be formed on the surface of MgFe(2)O(4). The adsorption equilibrium isotherm of SO(2) was analyzed using a volumetric method at 298 K and 473 K. The results indicate that MgFe(2)O(4) nanospheres possess a good potential as the solid-state SO(2) adsorbent for applications in hot fuel gas desulfurization. Copyright © 2010 Elsevier B.V. All rights reserved.
Amination of activated carbon for enhancing phenol adsorption: Effect of nitrogen-containing functional groups

NASA Astrophysics Data System (ADS)

Yang, Guo; Chen, Honglin; Qin, Hangdao; Feng, Yujun

2014-02-01

To study the contribution of different nitrogen-containing functional groups to enhancement of phenol adsorption, the aminated activated carbons (AC) were characterized by N2 adsorption/desorption, XPS, Boehm titration, and pH drift method and tested for adsorption behaviors of phenol. Adsorption isotherm fitting revealed that the Langmuir model was preferred for the aminated ACs. The adsorption capacity per unit surface area (qm/SSABET) was linearly correlated with the amount of pyridinic and pyrrolic N, which suggested that these two functional groups played a critical role in phenol adsorption. The enhancement of adsorption capacity was attributed to the strengthened π-π dispersion between phenol and basal plane of AC by pyridinic, pyrrolic N. The adsorption kinetics was found to follow the pseudo-second-order kinetic model, and intraparticle diffusion was one of the rate-controlling steps in the adsorption process.
Methylamine adsorption and decomposition on B12N12 nanocage: A density functional theory study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Nurazar, Roghaye

2014-08-01

Density functional theory calculations are performed to investigate the adsorption and decomposition of methylamine (CH3NH2) on the surface of a B12N12 fullerene-like nanocage. Two adsorption types and two reaction channels are identified. It is found that the electrical conductivity of the nanocage can be modified upon the adsorption of CH3NH2. The pathways of CH3NH2 decomposition via bond scission of the Csbnd N and Nsbnd H bonds are examined. The results indicate that Nsbnd H bond scission is the most favorable pathway on the B12N12 surface. The side reaction that generates CH3 and NH2 fragments is endothermic by 15.6 kcal/mol with an energy-barrier height of 81.5 kcal/mol. For the CH3NH2 decomposition on the B12N12 surface, the rate-determining step appears to be as the following reaction: CH3NH → CH3N + H.
[Lead adsorption and arsenite oxidation by cobalt doped birnessite].

PubMed

Yin, Hui; Feng, Xiong-Han; Qiu, Guo-Hong; Tan, Wen-Feng; Liu, Fan

2011-07-01

In order to study the effects of transition metal ions on the physic-chemical properties of manganese dioxides as environmental friendly materials, three-dimensional nano-microsphere cobalt-doped birnessite was synthesized by reduction of potassium permanganate by mixtures of concentrated hydrochloride and cobalt (II) chloride. Powder X-ray diffraction, chemical analysis, N2 physical adsorption, field emission scanning electron microscopy (FE-SEM) and X-ray photoelectron spectra (XPS) were used to characterize the crystal structure, chemical composition and micro-morphologies of products. In the range of molar ratios from 0.05 to 0.20, birnessite was fabricated exclusively. It was observed that cobalt incorporated into the layers of birnessite and had little effect on the crystal structure and micromorpholgy, but crystallinity decreased after cobalt doping. Both chemical analysis and XPS results showed that manganese average oxidation state decreased after cobalt doping, and the percentage of Mn3+ increased. Co(III) OOH existed mainly in the structure. With the increase of cobalt, hydroxide oxygen percentage in molar increased from 12.79% for undoped birnessite to 13.05%, 17.69% and 17.79% for doped samples respectively. Adsorption capacity for lead and oxidation of arsenite of birnessite were enhanced by cobalt doping. The maximum capacity of Pb2+ adsorption increased in the order HB (2 538 mmol/kg) < CoB5 (2798 mmol/kg) < CoB10 (2932 mmol/kg) < CoB20 (3 146 mmol/kg). Oxidation percentage of arsenite in simulated waste water by undoped birnessite was 76.5%, those of doped ones increased by 2.0%, 12.8% and 18.9% respectively. Partial of Co3+ substitution for Mn4+ results in the increase of negative charge of the layer and the content of hydroxyl group, which could account for the improved adsorption capacity of Pb2+. After substitution of manganese by cobalt, oxidation capacity of arsenite by birnessite increases likely due to the higher standard redox potential of Co3+/Co2+ than those of Mn4+/Mn3+/Mn2+. Therefore, Co-doped birnessite is more applicable for the remediation of water polluted with heavy metal ions, implying new methods of modification of manganese dioxides in practice.
Fabrication of magnetic microsphere-confined graphene for the preconcentration of some phthalate esters from environmental water and soybean milk samples followed by their determination by HPLC.

PubMed

Wang, Weina; Ma, Ruiyang; Wu, Qiuhua; Wang, Chun; Wang, Zhi

2013-05-15

In this study, a magnetic microsphere-confined graphene (Fe3O4@SiO2-G) was prepared as a novel adsorbent for the preconcentration of some phthalate esters in environmental water and soybean milk samples prior to high performance liquid chromatography analysis. The properties and morphology of the Fe3O4@SiO2-G were characterized by transmission electron microscopy and X-ray diffraction. This novel graphene-based magnetic nanocomposite showed great adsorptive ability toward the analytes. The method, which takes the advantages of both the high adsorption capacity of G and easy phase separation of the magnetic adsorbent from the sample solution, could avoid the time-consuming experimental procedures related to the traditional solid phase extraction. Various experimental parameters that could affect the extraction efficiencies, such as the amount of Fe3O4@SiO2-G, the extraction time, the pH of sample solution and the desorption conditions, were investigated. Under the optimum conditions, the limits of detection (S/N=3) of the method for the compounds were between 0.07 and 0.10 ng mL(-1) in water samples, and between 0.15 and 0.30 ng mL(-1) in soybean milk samples. The relative standard deviations (RSDs) varied from 2.7% to 6.1% (n=5). The recoveries of the method were in the range between 87.2% and 109.0% for environmental water and soybean milk samples. The method is suitable to determine the five phthalate esters (diallyl phthalate, di-n-propyl-phthalate, benzyl butyl phthalate, dicyclohexyl-phthalate and diethyl-hexyl-phthalate) in environmental water and soybean milk samples. Copyright © 2013 Elsevier B.V. All rights reserved.
A flexible metal–organic framework: Guest molecules controlled dynamic gas adsorption

DOE PAGES

Mahurin, Shannon Mark; Li, Man -Rong; Wang, Hailong; ...

2015-04-13

A flexible metal–organic framework (MOF) of [Zn 3(btca) 2(OH) 2]·(guest) n (H 2btca = 1,2,3-benzotriazole-5-carboxylic acid) that exhibits guest molecule-controlled dynamic gas adsorption is reported in which carbon dioxide molecules rather than N 2, He, and Ar induce a structural transition with a corresponding appearance of additional steps in the isotherms. Physical insights into the dynamic adsorption behaviors of flexible compound 1 were detected by gas adsorption at different temperatures and different pressures and confirmed by Fourier transform infrared spectroscopy and molecular simulations. Interestingly, by taking advantage of the flexible nature inherent to the framework, this MOF material enables highlymore » selective adsorption of CO 2/N 2, CO 2/Ar, and CO 2/He of 36.3, 32.6, and 35.9, respectively, at 298 K. Furthermore, this class of flexible MOFs has potential applications for controlled release, molecular sensing, noble gas separation, smart membranes, and nanotechnological devices.« less
Photocatalytic decomposition of Congo red under visible light irradiation using MgZnCr-TiO2 layered double hydroxide.

PubMed

Ma, Chi; Wang, Fenghua; Zhang, Chang; Yu, Zhigang; Wei, Jingjing; Yang, Zhongzhu; Li, Yongqiu; Li, Zihao; Zhu, Mengying; Shen, Liuqing; Zeng, Guangming

2017-02-01

The new nanophotocatalyst MgZnCr-TiO 2 was prepared by co-precipitation under different molar ratio of metals (Zn:Cr) and the loaded amount of TiO 2 . And it was characterized by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy et al. Langmuir model fitted well the adsorption isotherm with the value of R 2 0.9765, the maximum adsorption capacity was 526.32 mg g -1 , the adsorption followed pseudo second order kinetic by MgZnCr-TiO 2 (1:1:2-0.05). The photocatalytic oxidation of Congo red was used to determine the photocatalytic performance of MgZnCr-TiO 2 (1:1:2-0.05) under visible light irradiation, and the removal rate reached 98% after reaction for 40 min. The degradation mechanism of Congo red also was proposed, and the MgZnCr-TiO 2 (1:1:2-0.05) was stable after five cycles. Compared to the adsorption, Congo red was removed fundamentally by photocatalysis and it is expected to be an effective way to eliminate Congo red. Copyright © 2016 Elsevier Ltd. All rights reserved.

Graphene-a promising material for removal of perchlorate (ClO4-) from water.

PubMed

Lakshmi, Jothinathan; Vasudevan, Subramanyan

2013-08-01

A batch adsorption process was applied to investigate the removal of perchlorate (ClO4 (-)) from water by graphene. In doing so, the thermodynamic adsorption isotherm and kinetic studies were also carried out. Graphene was prepared by a facile liquid-phase exfoliation. Graphene was characterized by Raman spectroscopy, Fourier-transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscope, and zeta potential measurements. A systematic study of the adsorption process was performed by varying pH, ionic strength, and temperature. The adsorption efficiency of graphene was 99.2 %, suggesting that graphene is an excellent adsorbent for ClO4 (-) removal from water. The rate constants for all these kinetic models were calculated, and the results indicate that second-order kinetics model was well suitable to model the kinetic adsorption of ClO4 (-). Equilibrium data were well described by the typical Langmuir adsorption isotherm. The experimental results showed that graphene is an excellent perchlorate adsorbent with an adsorbent capacity of up to 0.024 mg/g at initial perchlorate concentration of 2 mg/L and temperature of 298 K. Thermodynamic studies revealed that the adsorption reaction was a spontaneous and endothermic process. Graphene removed the perchlorate present in the water and reduced it to a permissible level making it drinkable.
A scanning tunnelling microscopy study of C and N adsorption phases on the vicinal Ni(100) surfaces Ni(810) and Ni(911)

NASA Astrophysics Data System (ADS)

Driver, S. M.; Toomes, R. L.; Woodruff, D. P.

2016-04-01

The influence of N and C chemisorption on the morphology and local structure of nominal Ni(810) and Ni(911) surfaces, both vicinal to (100) but with [001] and [ 01 1 bar ] step directions, respectively, has been investigated using scanning tunnelling microscopy (STM) and low energy electron diffraction. Ni(911) undergoes substantial step bunching in the presence of both adsorbates, with the (911)/N surface showing (411) facets, whereas for Ni(810), multiple steps 2-4 layers high are more typical. STM atomic-scale images show the (2 × 2)pg 'clock' reconstruction on the (100) terraces of the (810) surfaces with both C and N, although a second c(2 × 2) structure, most readily reconciled with a 'rumpling' reconstruction, is also seen on Ni(810)/N. On Ni(911), the clock reconstruction is not seen on the (100) terraces with either adsorbate, and these images are typified by protrusions on a (1 × 1) mesh. This absence of clock reconstruction is attributed to the different constraints imposed on the lateral movements of the surface Ni atoms adjacent to the up-step edge of the terraces with a [ 01 1 bar ] step direction.
Different effects of surface heterogeneous atoms of porous and non-porous carbonaceous materials on adsorption of 1,1,2,2-tetrachloroethane in aqueous environment.

PubMed

Chen, Weifeng; Ni, Jinzhi

2017-05-01

The surface heterogeneous atoms of carbonaceous materials (CMs) play an important role in adsorption of organic pollutants. However, little is known about the surface heterogeneous atoms of CMs might generate different effect on adsorption of hydrophobic organic compounds by porous carbonaceous materials - activated carbons (ACs) and non-porous carbonaceous materials (NPCMs). In this study, we observed that the surface oxygen and nitrogen atoms could decrease the adsorption affinity of both ACs and NPCMs for 1,1,2,2-tetrachloroethane (TeCA), but the degree of decreasing effects were very different. The increasing content of surface oxygen and nitrogen ([O + N]) caused a sharper decrease in adsorption affinity of ACs (slope of lg (k d /SA) vs [O + N]: -0.098∼-0.16) than that of NPCMs (slope of lg (k d /SA) vs [O + N]: -0.025∼-0.059) for TeCA. It was due to the water cluster formed by the surface hydrophilic atoms that could block the micropores and generate massive invalid adsorption sites in the micropores of ACs, while the water cluster only occupied the surface adsorption sites of NPCMs. Furthermore, with the increasing concentration of dissolved TeCA, the effect of surface area on adsorption affinity of NPCMs for TeCA kept constant while the effect of [O + N] decreased due to the competitive adsorption between water molecule and TeCA on the surface of NPCMs, meanwhile, both the effects of micropore volume and [O + N] on adsorption affinity of ACs for TeCA were decreased due to the mechanism of micropore volume filling. These findings are valuable for providing a deep insight into the adsorption mechanisms of CMs for TeCA. Copyright © 2017 Elsevier Ltd. All rights reserved.
Synthesis and Absorption Properties of Hollow-spherical Dy2Cu2O5 via a Coordination Compound Method with [DyCu(3,4-pdc)2(OAc)(H2O)2]•10.5H2O Precursor.

PubMed

Liu, Xuanwen; You, Junhua; Wang, Renchao; Ni, Zhiyuan; Han, Fei; Jin, Lei; Ye, Zhiqi; Fang, Zhao; Guo, Rui

2017-10-12

Dy 2 Cu 2 O 5 nanoparticles with perovskite structures were synthesized via a simple solution method (SSM) and a coordination compound method (CCM) using [DyCu(3,4-pdc) 2 (OAc)(H 2 O) 2 ]•10.5H 2 O (pdc = 3,4-pyridinedicarboxylic acid) as precursor. The as-prepared samples were structurally characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), x-ray photoelectron spectroscopy (XPS) and standard Brunauer-Emmett-Teller (BET) methods. Compared to the aggregated hexahedral particles prepared by SSM, the Dy 2 Cu 2 O 5 of CCM showed hollow spherical morphology composed of nanoparticles with average diameters of 100-150 nm and a larger special surface area up to 36.5 m 2 /g. The maximum adsorption capacity (Q m ) of CCM for malachite green (MG) determined by the adsorption isotherms with different adsorbent dosages of 0.03-0.07 g, reached 5.54 g/g at room temperature. The thermodynamic parameters of adsorption process were estimated by the fittings of the isotherms at 298, 318, and 338 K, and the kinetic parameters were obtained from the time-dependent adsorption isotherms. The results revealed that the adsorption process followed a pseudo-second-order reaction. Finally, the adsorption mechanism was studied using a competitive ion (CI) experiments, and the highly efficient selective adsorption was achieved due to strong O-Cu and O-Dy coordination bonds between Dy 2 Cu 2 O 5 and MG.
Synthesis of g-C3N4/Fe3O4 nanocomposites and application as a new sorbent for solid phase extraction of polycyclic aromatic hydrocarbons in water samples.

PubMed

Wang, Man; Cui, Shihai; Yang, Xiaodi; Bi, Wentao

2015-01-01

An easy preparation of g-C3N4/Fe3O4 nanocomposites by chemical co-precipitation has been demonstrated. The as-prepared materials were characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. The high affinity of g-C3N4 toward polycyclic aromatic hydrocarbons and the magnetic behavior of Fe3O4 were combined to provide an efficient and simple magnetic solid phase extraction (MSPE). The adsorption and desorption of polycyclic aromatic hydrocarbons on g-C3N4/Fe3O4 were examined. Different factors affecting the magnetic solid phase extraction of polycyclic aromatic hydrocarbons were assessed in terms of adsorption, desorption, and recovery. Under the optimized conditions, the proposed method showed good limits of detection (LOD, S/N=3) in the range of 0.05-0.1 ng mL(-1) and precision in the range of 1.8-5.3% (RSDs, n=3). This method was also successfully applied to the analysis of real water samples; good spiked recoveries over the range of 80.0-99.8% were obtained. Copyright © 2014 Elsevier B.V. All rights reserved.
Synthesis and characterization of microporous titanosilicate ETS-10 obtained with different Ti sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Casado, Clara; Amghouz, Zakariae; Garcia, Jose R.

2009-06-03

Titanosilicate ETS-10 crystals were prepared by hydrothermal synthesis varying Ti source (TiCl{sub 3} and commercial TiO{sub 2}-anatase), time in autoclave and seeding with previously prepared ETS-10 crystals. The crystalline powders were characterized by X-ray diffraction, N{sub 2} adsorption, thermogravimetric analysis, and scanning and transmission electron microscopies. Control of the particle size of ETS-10 crystals ranging from 0.32 {mu}m x 0.41 {mu}m to 16.4 {mu}m x 32.5 {mu}m was successfully achieved varying the seeding and synthesis conditions. In particular, it was found that the use of TiO{sub 2}-anatase alone or together with TiCl{sub 3} promotes heterogeneous primary nucleation. Transmission electron microscopymore » demonstrated that the largest crystals obtained here were twinned.« less
Facet-dependent solar ammonia synthesis of BiOCl nanosheets via a proton-assisted electron transfer pathway

NASA Astrophysics Data System (ADS)

Li, Hao; Shang, Jian; Shi, Jingu; Zhao, Kun; Zhang, Lizhi

2016-01-01

Under the pressure of a fossil fuels shortage and global climate change, solar ammonia synthesis and the need to develop N2 fixation under mild conditions is becoming more urgent need; however, their intrinsic mechanisms still remain unclear. Herein, we demonstrate that the kinetic inertia of N2 can be overcome using oxygen vacancies (OVs) of BiOCl as the catalytic centers to create lower energy molecular steps, which are amendable for the solar light driven N-N triple bond cleavage via a proton-assisted electron transfer pathway. Moreover, the distinct structures of OVs on different BiOCl facets strongly determine the N2 fixation pathways by influencing both the adsorption structure and the activation level of N2. The fixation of terminal end-on bound N2 on the OVs of BiOCl {001} facets follows an asymmetric distal mode by selectively generating NH3, while the reduction of side-on bridging N2 on the OVs of BiOCl {010} facets is more energetically favorable in a symmetric alternating mode to produce N2H4 as the main intermediate.Under the pressure of a fossil fuels shortage and global climate change, solar ammonia synthesis and the need to develop N2 fixation under mild conditions is becoming more urgent need; however, their intrinsic mechanisms still remain unclear. Herein, we demonstrate that the kinetic inertia of N2 can be overcome using oxygen vacancies (OVs) of BiOCl as the catalytic centers to create lower energy molecular steps, which are amendable for the solar light driven N-N triple bond cleavage via a proton-assisted electron transfer pathway. Moreover, the distinct structures of OVs on different BiOCl facets strongly determine the N2 fixation pathways by influencing both the adsorption structure and the activation level of N2. The fixation of terminal end-on bound N2 on the OVs of BiOCl {001} facets follows an asymmetric distal mode by selectively generating NH3, while the reduction of side-on bridging N2 on the OVs of BiOCl {010} facets is more energetically favorable in a symmetric alternating mode to produce N2H4 as the main intermediate. Electronic supplementary information (ESI) available: Other experimental details, additional SEM and TEM images, X-ray diffraction patterns (XRD), UV-Vis diffuse reflectance spectra (DRS), and additional data. See DOI: 10.1039/c5nr07380d
Application of Brazilian kaolinite clay as adsorbent to removal of U(VI) from aqueous solution: Kinetic and thermodynamic of cation-basic interactions

NASA Astrophysics Data System (ADS)

Guerra, Denis L.; Leidens, Victor L.; Viana, Rúbia R.; Airoldi, Claudio

2010-05-01

The compound N 1-[3-(trimethoxysilyl)propyl]diethylenetriamine was anchored onto Amazon kaolinite surface by heterogeneous route. The modified and natural kaolinite samples were characterized by transmission electron microscopy, scanning electron microscopic, X-ray diffraction, and nuclear magnetic nuclei of 29Si and 13C. The well-defined peaks obtained in the 13C NMR spectrum in the 5.0-62.1 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The ability of these materials to remove U(VI) from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 4.0. The kinetic parameters analyzed by the Lagergren and Elovich models gave a good fit for a pseudo-second order reaction with k2 values 16.0 and 25.1 mmol g -1 min -1 ranges for natural and modified kaolinite clays, respectively. The energetic effects caused by metal ion adsorption were determined through calorimetric titrations.
Two-Solvent Method Synthesis of NiO/ZnO Nanoparticles Embedded in Mesoporous SBA-15: Photocatalytic Properties Study.

PubMed

Dai, Peng; Yan, Tao-Tao; Yu, Xin-Xin; Bai, Zhi-Man; Wu, Ming-Zai

2016-12-01

Different loadings of NiO/ZnO nanoparticles embedded in mesoporous silica (SBA-15) were prepared via a two-solvent method with the ordered hexagonal mesoporous structure of SBA-15 kept. X-ray diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, diffusive reflective UV-vis spectroscopy, and N2 adsorption porosimetry were employed to characterize the nanocomposites. The results indicate that the ordered hexagonal mesoporous structure of SBA-15 is kept and the absorption band edges of the nanocomposites shift into the ultraviolet light regime. The photocatalytic activity of our samples for degradation of methylene orange was investigated under UV light irradiation, and the results show that the nanocomposites have higher photodegradation ability toward methylene orange than commercial pure P-25. The photocatalytic activity of the nanocomposites was found to be dependent on both the adsorption ability of the SBA-15 and the photocatalytic activity of NiO-ZnO nanoparticles encapsulated in SBA-15. In addition, there is an optimal loading of NiO-ZnO nanoparticles. Too high or low loading will lower the photodegradation ability of the nanocomposites.
Preparation of Chitosan Coated Magnetic Hydroxyapatite Nanoparticles and Application for Adsorption of Reactive Blue 19 and Ni2+ Ions

PubMed Central

Nguyen, Van Cuong; Pho, Quoc Hue

2014-01-01

An adsorbent called chitosan coated magnetic hydroxyapatite nanoparticles (CS-MHAP) was prepared with the purpose of improvement for the removal of Ni2+ ions and textile dye by coprecipitation. Structure and properties of CS-MHAP were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and vibrating sample magnetometer (VSM). Weight percent of chitosan was investigated by thermal gravimetric analysis (TGA). The prepared CS-MHAP presents a significant improvement on the removal efficiency of Ni2+ ions and reactive blue 19 dye (RB19) in comparison with chitosan and magnetic hydroxyapatite nanoparticles. Moreover, the adsorption capacities were affected by several parameters such as contact time, initial concentration, adsorbent dosage, and initial pH. Interestingly, the prepared adsorbent could be easily recycled from an aqueous solution by an external magnet and reused for adsorption with high removal efficiency. PMID:24592158
DOE Office of Scientific and Technical Information (OSTI.GOV)

Hlaing, Nwe Ni, E-mail: nwenihlaing76@gmail.com; Department of International Development Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo; Department of Physics, University of Yangon, 11041 Kamayut, Yangon

Recent years, CaO-based synthetic materials have been attracted attention as potential adsorbents for CO{sub 2} capture mainly due to their high CO{sub 2} adsorption capacity. In this study, micro/nanostructured aragonite CaCO{sub 3} was synthesized by a simple hydrothermal method with using polyacrylamide (PAM). The structural, morphological and thermal properties of the synthesized sample were investigated by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and thermogravimetry analysis (TG-DTA). The XRD and FESEM results showed that the obtained sample was aragonite CaCO{sub 3} with aggregated nanorods and microspheres composed of nanorods. A TG-DTA apparatus with Thermoplus 2 software was used tomore » investigate the effect of carbonation temperature on the CO{sub 2} adsorption capacity of CaO derived from aragonite CaCO{sub 3} sample. At 300 °C, the sample reached the CO{sub 2} adsorption capacity of 0.098 g-CO{sub 2}/g-adsorbent, whereas the sample achieved the highest capacity of 0.682 g-CO{sub 2}/g-adsorbent at 700 °C. The results showed that the carbonation temperature significantly influenced on the CO{sub 2} adsorption capacity of the CaO derived from aragonite CaCO{sub 3}.« less
Synthesis of N-doped microporous carbon via chemical activation of polyindole-modified graphene oxide sheets for selective carbon dioxide adsorption.

PubMed

Saleh, Muhammad; Chandra, Vimlesh; Kemp, K Christian; Kim, Kwang S

2013-06-28

A polyindole-reduced graphene oxide (PIG) hybrid was synthesized by reducing graphene oxide sheets in the presence of polyindole. We have shown PIG as a material for capturing carbon dioxide (CO2). The PIG hybrid was chemically activated at temperatures of 400-800 °C, which resulted in nitrogen (N)-doped graphene sheets. The N-doped graphene sheets are microporous with an adsorption pore size of 0.6 nm for CO2 and show a maximum (Brunauer, Emmet and Teller) surface area of 936 m(2) g(-1). The hybrid activated at 600 °C (PIG6) possesses a surface area of 534 m(2) g(-1) and a micropore volume of 0.29 cm(3) g(-1). PIG6 shows a maximum CO2 adsorption capacity of 3.0 mmol g(-1) at 25 °C and 1 atm. This high CO2 uptake is due to the highly microporous character of the material and its N content. The material retains its original adsorption capacity on recycling even after 10 cycles (within experimental error). PIG6 also shows high adsorption selectivity ratios for CO2 over N2, CH4 and H2 of 23, 4 and 85 at 25 °C, respectively.
A pair of polymorphous metal-organic frameworks based on an angular diisophthalate linker: synthesis, characterization and gas adsorption properties.

PubMed

Chen, Fengli; Bai, Dongjie; Wang, Yao; He, Minghui; Gao, Xiaoxia; He, Yabing

2018-01-15

The combination of an angular diisophthalate ligand, 5,5'-(naphthyl-2,7-yl)diisophthalate (H 4 L), and copper ions under different solvothermal conditions afforded two polymorphous metal-organic frameworks (ZJNU-77 and ZJNU-78) with the same framework composition of [Cu 2 (L)(H 2 O) 2 ], providing a platform to investigate the relationship between MOF polymorphism and gas adsorption properties. As determined by single-crystal X-ray diffraction, ZJNU-77 and ZJNU-78 exhibited three-dimensional networks crystallizing in different space groups. Their structural differences were mainly manifested by the ligand's conformation, the level of framework interpenetration and the network's topology. Interestingly, gas adsorption studies showed that the two compounds after desolvation displayed comparable gas adsorption properties with respect to C 2 H 2 , CO 2 and CH 4 , despite their different surface areas and pore volumes. The C 2 H 2 , CO 2 , and CH 4 uptake capacities at 298 K and 1 atm are 120.2, 78.1, and 18.4 cm 3 (STP) g -1 for ZJNU-77, and 122.0, 82.0, and 18.9 cm 3 (STP) g -1 for ZJNU-78, respectively. The IAST adsorption selectivities for the equimolar C 2 H 2 /CH 4 and CO 2 /CH 4 mixtures are 28.6 and 5.7 for ZJNU-77, and 28.4 and 5.9 for ZJNU-78 at 298 K and 1 atm. These results indicate that besides the surface area, the pore size also plays a crucial role in gas adsorption. This work not only represents an intriguing example of MOF polymorphism achieved by controlling solvothermal conditions, but also provides an insight into the correlation between MOF polymorphism and gas adsorption properties.
Membrane solid phase microextraction with alumina hollow fiber on line coupled with ICP-OES for the determination of trace copper, manganese and nickel in environmental water samples.

PubMed

Cui, Chao; He, Man; Hu, Bin

2011-03-15

A novel alumina hollow fiber was synthesized by sol-gel template method and was characterized by scanning electron microscopy, N(2) adsorption technique and X-ray diffraction. With the use of prepared alumina hollow fiber as extraction membrane, a new method of flow injection (FI)-membrane solid phase microextraction (MSPME) on-line coupled to inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed for simultaneous determination of trace metals (Cu, Mn and Ni) in environmental water samples. The adsorption capacities of the alumina hollow fiber for Cu, Mn and Ni were found to be 6.6, 8.7 and 13.3 mg g(-1), respectively. With a preconcentration factor of 10, the limits of detection (LODs) for Cu, Mn and Ni were found to be 0.88, 0.61 and 0.38 ng mL(-1), respectively, and the relative standard deviations (RSDs) were ranging from 6.2 to 7.9% (n = 7, c = 10 ng mL(-1)). To validate the accuracy, the proposed method was applied to the analysis of certified reference material GSBZ50009-88 environmental water and the determined values are in good agreement with the certified values. The developed method was also employed for the analysis of Yangtze River water and East Lake water, and the recoveries for the spiked samples were in the range of 87.4-110.2%. Copyright © 2011 Elsevier B.V. All rights reserved.
Colloid electrostatic self-assembly synthesis of SnO2/graphene nanocomposite for supercapacitors

NASA Astrophysics Data System (ADS)

Wang, Yankun; Liu, Yushan; Zhang, Jianmin

2015-10-01

In this paper, a simple and fast colloid electrostatic self-assembly method was adopted to prepare the SnO2/graphene nanocomposite (SGNC). The crystal structure, chemical composition, and porous property of composite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman microscopy, X-ray photoelectron spectroscopy (XPS), and N2 adsorption-desorption experiments. The morphology analyses showed that the SnO2 nanoparticles about 5 nm were distributed homogenously on the reduced graphene oxide (rGO) sheets surface. The electrochemical performance measurements exhibited that SGNC possessed the specific capacitance of 347.3 F g-1 at a scan rate of 5 mV s-1 in 1 M Na2SO4 electrolyte solution. Furthermore, this material also showed excellent cycling stability, and the specific capacitance still retained 90 % after 3000 cycles. These results indicate that the SGNC is a promising electrode material for high-performance supercapacitors.
Preparation of Fe3O4/TiO2 magnetic mesoporous composites for photocatalytic degradation of organic pollutants.

PubMed

Zhang, Hongfeng; He, Xiu; Zhao, Weiwei; Peng, Yu; Sun, Donglan; Li, Hao; Wang, Xiaocong

2017-04-01

Fe 3 O 4 /TiO 2 magnetic mesoporous composites were synthesized through a sol-gel method with tetra-n-butyl titanate as precursor and surfactant P123 as template. The as-prepared Fe 3 O 4 /TiO 2 composites were characterized by X-ray diffraction, diffuse reflectance spectroscopy, nitrogen adsorption-desorption isotherm and pore size distribution. The as-synthesized products were applied as photocatalysis for the degradation of Acid Black ATT and tannery wastewater under UV lamp irradiation. Fe 3 O 4 /TiO 2 -8 composites containing Fe 3 O 4 of 8 wt% were selected as model catalysts. The optimal catalyst dosage was 3 g/L in this photocalytic system. The magnetic Fe 3 O 4 /TiO 2 composites possessed good photocatalytic stability and durability. This approach may provide a platform to prepare a magnetic composite to optimize the catalytic ability.
Crystal growth, differential gas adsorption, high thermal stability, and reversible coordination of two new barium-organic frameworks, Ba(SBA)(DMF){sub 4} and Ba{sub 2}(BTEC)(H{sub 2}O)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halake, Shobha; Ok, Kang Min, E-mail: kmok@cau.ac.kr

2015-11-15

Single crystals of two barium-organic framework materials, Ba(SBA)(DMF){sub 4} (CAUMOF-15) and Ba{sub 2}(BTEC)(H{sub 2}O) (CAUMOF-16), have been grown through solvothermal reactions (H{sub 2}SBA=4,4′-sulfonyldibenzoic acid and H{sub 4}BTEC=1,2,4,5-benzenetetracarboxylic acid). The crystal structures of the reported frameworks have been determined by single-crystal X-ray diffraction. The materials have been fully characterized by powder X-ray diffraction (PXRD), elemental analyses, Infrared (IR) spectroscopy, and thermogravimetric analyses (TGA). CAUMOF-15 reveals a three-dimensional open-framework that comprises of an inorganic motif with one-dimensional chains and the SBA linkers. CAUMOF-16 shows another three-dimensional backbone consisting of layers of edge-shared BaO{sub 9} and BaO{sub 10} polyhedra, and BTEC pillars. Bothmore » of the 3D frameworks exhibit relatively high thermal stabilities. The PXRD and IR spectral data confirm that CAUMOF-15 and CAUMOF-16 reveal reversible coordinations of the respective solvent molecules, DMF and H{sub 2}O. Gas adsorption properties towards nitrogen, hydrogen, and carbon dioxide have been also investigated. - Graphical abstract: Crystals of two new barium-organic frameworks, Ba(SBA)(DMF){sub 4} and Ba{sub 2}(BTEC)(H{sub 2}O), exhibiting a differential gas adsorption, a high thermal stability, and a reversible coordination of solvent molecules have been grown. - Highlights: • Crystals of two new 3D Ba-MOFs are grown. • The two Ba-MOFs reveal very high thermal stabilities up to ca. 400 °C. • Ba(SBA)(DMF){sub 4} exhibits differential gas adsorption properties. • The two Ba-MOFs show reversible coordination of the solvent molecules.« less
Attached β-cyclodextrin/γ-(2,3-epoxypropoxy) propyl trimethoxysilane to graphene oxide and its application in copper removal.

PubMed

Yu, Zongxue; Chen, Qi; Lv, Liang; Pan, Yang; Zeng, Guangyong; He, Yi

2017-05-01

The environmental applications of graphene oxide and β-cyclodextrin (β-CD) have attracted great attention since their first discovery. Novel nanocomposites were successfully prepared by using an esterification reaction between β-cyclodextrin/γ-(2,3-epoxypropoxy) propyl trimethoxysilane grafted graphene oxide (β-CD/GPTMS/GO). The β-CD/GPTMS/GO nanocomposites were used to remove the Cu 2+ from aqueous solutions. The characteristics of β-CD/GPTMS/GO were detected by scanning electron microscopy (SEM), Fourier transform infrared, X-ray diffraction (XRD), thermogravimetric analysis (TG) and energy dispersive X-ray (EDX). The dispersibility of graphene oxide was excellent due to the addition of β-CD. The adsorption isotherms data obtained at the optimum pH 7 were fitted by Langmuir isotherm model. The excellent adsorption properties of β-CD/GPTMS/GO for Cu 2+ ions could be attributed to the apolar cavity structure of β-CD, the high surface area and abundant functional groups on the surface of GO. The adsorption patterns of β-CD/GPTMS/GO were electrostatic attraction, formation of host-guest inclusion complexes and the ion exchange adsorption. The efficient adsorption of β-CD/GPTMS/GO for Cu 2+ ions suggested that these novel nanocomposites may be ideal candidates for removing other cation pollutants from waste water.
Graphene-Supported Spinel CuFe2O4 Composites: Novel Adsorbents for Arsenic Removal in Aqueous Media

PubMed Central

La, Duong Duc; Nguyen, Tuan Anh; Jones, Lathe A.; Bhosale, Sheshanath V.

2017-01-01

A graphene nanoplate-supported spinel CuFe2O4 composite (GNPs/CuFe2O4) was successfully synthesized by using a facile thermal decomposition route. Scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), Electron Dispersive Spectroscopy (EDS), X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) were employed to characterize the prepared composite. The arsenic adsorption behavior of the GNPs/CuFe2O4 composite was investigated by carrying out batch experiments. Both the Langmuir and Freundlich models were employed to describe the adsorption isotherm, where the sorption kinetics of arsenic adsorption by the composite were found to be pseudo-second order. The selectivity of the adsorbent toward arsenic over common metal ions in water was also demonstrated. Furthermore, the reusability and regeneration of the adsorbent were investigated by an assembled column filter test. The GNPs/CuFe2O4 composite exhibited significant, fast adsorption of arsenic over a wide range of solution pHs with exceptional durability, selectivity, and recyclability, which could make this composite a very promising candidate for effective removal of arsenic from aqueous solution. The highly sensitive adsorption of the material toward arsenic could be potentially employed for arsenic sensing. PMID:28587257
Microporous metal organic framework [M2(hfipbb)2(ted)] (M=Zn, Co; H2hfipbb=4,4-(hexafluoroisopropylidene)-bis(benzoic acid); ted=triethylenediamine): Synthesis, structure analysis, pore characterization, small gas adsorption and CO2/N2 separation properties

NASA Astrophysics Data System (ADS)

Xu, William W.; Pramanik, Sanhita; Zhang, Zhijuan; Emge, Thomas J.; Li, Jing

2013-04-01

Carbon dioxide is a greenhouse gas that is a major contributor to global warming. Developing methods that can effectively capture CO2 is the key to reduce its emission to the atmosphere. Recent research shows that microporous metal organic frameworks (MOFs) are emerging as a promising family of adsorbents that may be promising for use in adsorption based capture and separation of CO2 from power plant waste gases. In this work we report the synthesis, crystal structure analysis and pore characterization of two microporous MOF structures, [M2(hfipbb)2(ted)] (M=Zn (1), Co (2); H2hfipbb=4,4-(hexafluoroisopropylidene)-bis(benzoic acid); ted=triethylenediamine). The CO2 and N2 adsorption experiments and IAST calculations are carried out on [Zn2(hfipbb)2(ted)] under conditions that mimic post-combustion flue gas mixtures emitted from power plants. The results show that the framework interacts with CO2 strongly, giving rise to relatively high isosteric heats of adsorption (up to 28 kJ/mol), and high adsorption selectivity for CO2 over N2, making it promising for capturing and separating CO2 from CO2/N2 mixtures.

Investigation of the adsorption of ozone molecules on TiO2/WSe2 nanocomposites by DFT computations: Applications to gas sensor devices

NASA Astrophysics Data System (ADS)

Abbasi, Amirali; Sardroodi, Jaber Jahanbin

2018-04-01

The adsorption of O3 molecule on the undoped and N-doped TiO2/WSe2 nanocomposites was studied using first principles density functional theory calculations. O3 interaction with TiO2/WSe2 nanocomposites is considered so as to investigate WSe2 effects on the adsorption process. WSe2 favors the adsorption of O3 on TiO2 particles. In other words, WSe2 is conducive to the interaction of O3 molecule with fivefold coordinated titanium sites of TiO2. The effects of vdW interactions were taken into account in order to obtain equilibrium geometries of O3 molecules at TiO2/WSe2 interfaces. For all adsorption configurations, the binding site was positioned on the fivefold coordinated titanium atoms. The results show that the interactions between O3 and TiO2 in TiO2/WSe2 nanocomposites are stronger than those between O3 and bare TiO2, suggesting that WSe2 helps to strengthen the interaction of ozone molecule with TiO2 particles. The results also indicate that the adsorption of the O3 molecule on the N-doped TiO2/WSe2 nanocomposite is more energetically favorable than the adsorption of O3 on the pristine one, representing that the N-doped nanocomposites are more sensitive than the undoped ones. Our DFT results clearly show that the N-doped TiO2/WSe2 nanocomposite would be a promising O3 gas sensor. The electronic structure of the adsorption system was also investigated, including analysis of the total and projected density of states, and charge density differences of the TiO2/WSe2 with adsorbed O3 molecules. The charge density difference calculations indicate that the charges were accumulated over the adsorbed O3 molecule. Besides, the N-doped nanocomposites have better sensing response than the pristine ones. This work was devoted to provide the theory basis for the design and development of novel and advanced O3 sensors based on modified TiO2/WSe2 nanocomposites.
Assessment of the role of micropore size and N-doping in CO2 capture by porous carbons.

PubMed

Sevilla, Marta; Parra, Jose B; Fuertes, Antonio B

2013-07-10

The role of micropore size and N-doping in CO2 capture by microporous carbons has been investigated by analyzing the CO2 adsorption properties of two types of activated carbons with analogous textural properties: (a) N-free carbon microspheres and (b) N-doped carbon microspheres. Both materials exhibit a porosity made up exclusively of micropores ranging in size between <0.6 nm in the case of the pristine materials and up to 1.6 nm for the highly activated carbons (47% burnoff). The N-doped carbons possess ~3 wt % of N heteroatoms that are incorporated into several types of functional groups (i.e., pyrrole/pyridone, pyridine, quaternary, and pyridine-N-oxide). Under conventional operation conditions (i.e., T ~ 0-25 °C and P(CO2) ~ 0-1 bar), CO2 adsorption proceeds via a volume-filling mechanism, the size limit for volume-filling being ~0.7-0.8 nm. Under these circumstances, the adsorption of CO2 by nonfunctionalized porous carbons is mainly determined by the volume of the micropores with a size below 0.8 nm. It was also observed that the CO2 capture capacities of undoped and N-doped carbons are analogous which shows that the nitrogen functionalities present in these N-doped samples do not influence CO2 adsorption. Taking into account the temperature invariance of the characteristic curve postulated by the Dubinin theory, we show that CO2 uptakes can be accurately predicted by using the adsorption data measured at just one temperature.
Enhancement of electrochemical performance of LiFePO4 nanoparticles by direct nanocoating with conductive carbon layers

NASA Astrophysics Data System (ADS)

Świder, Joanna; Molenda, Marcin; Kulka, Andrzej; Molenda, Janina

2016-07-01

The results of simple and environmental-friendly method of the carbon nanocoatings on low-conductive cathode material have been shown in this work. The carbon nanocoatings were prepared during wet impregnation process of precursor derived from hydrophilic polymer based on poly(N-vinylformamide) modified by pyromellitic acid. The crystal structures and morphology of all composites were characterized by X-ray powder diffraction (XRD), low temperature nitrogen adsorption/desorption measurements (N2-BET) and transmission electronic microscopy (TEM). The electrical properties of the obtained composites were examined by EC studies. The electrochemical performance was carried out in galvanostatic mode with stable charge-discharge current and performed in Li/Li+/(CCL/LiFePO4) type cells. The process of formation CCL/LiFePO4 nanocomposite significantly enhances the electrical conductivity of the material and improves its capacity retention and electrochemical performance.
Removal of Rhodamine B from aqueous solution using magnetic NiFe nanoparticles.

PubMed

Liu, Yan; Liu, Kaige; Zhang, Lin; Zhang, Zhaowen

2015-01-01

Surface-modified magnetic nano alloy particles Ni2.33Fe were prepared using a hydrothermal method and they were utilized for removing Rhodamine B (RhB) from aqueous solution. The magnetic nanoparticles were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis and Fourier transform infrared spectroscopy, which confirmed that the surface of the magnetic product with a face-centered cubic-type structure was successfully modified by sodium citrate. Kinetics studies were conducted. The pseudo-second-order kinetic model was used for fitting the kinetic data successfully. The Freundlich and Langmuir adsorption models were employed for the mathematical description of adsorption equilibrium. It was found that the adsorption isotherm can be very satisfactorily fitted by the Freundlich model.
Simultaneous adsorption and degradation of Zn(2+) and Cu (2+) from wastewaters using nanoscale zero-valent iron impregnated with clays.

PubMed

Shi, Li-Na; Zhou, Yan; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravi

2013-06-01

Clays such as kaolin, bentonite and zeolite were evaluated as support material for nanoscale zero-valent iron (nZVI) to simultaneously remove Cu(2+) and Zn(2+) from aqueous solution. Of the three supported nZVIs, bentonite-supported nZVI (B-nZVI) was most effective in the simultaneous removal of Cu(2+) and Zn(2+) from a aqueous solution containing a 100 mg/l of Cu(2+) and Zn(2+), where 92.9 % Cu(2+) and 58.3 % Zn(2+) were removed. Scanning electronic microscope (SEM) revealed that the aggregation of nZVI decreased as the proportion of bentonite increased due to the good dispersion of nZVI, while energy dispersive spectroscopy (EDS) demonstrated the deposition of copper and zinc on B-nZVI after B-nZVI reacted with Cu(2+) and Zn(2+). A kinetics study indicated that removing Cu(2+) and Zn(2+) with B-nZVI accorded with the pseudo first-order model. These suggest that simultaneous adsorption of Cu(2+)and Zn(2+) on bentonite and the degradation of Cu(2+)and Zn(2+) by nZVI on the bentonite. However, Cu(2+) removal by B-nZVI was reduced rather than adsorption, while Zn(2+) removal was main adsorption. Finally, Cu(2+), Zn(2+), Ni(2+), Pb(2+) and total Cr from various wastewaters were removed by B-nZVI, and reusability of B-nZVI with different treatment was tested, which demonstrates that B-nZVI is a potential material for the removal of heavy metals from wastewaters.
Efficient dehydrogenation of formic acid using Al12N12 nanocage: A DFT study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Nurazar, Roghaye

2014-11-01

We have studied the adsorption and decomposition of formic acid (HCOOH) on the surface of Al12N12 fullerene-like nanocage using density functional theory. Different adsorption modes were found for HCOOH on the Al12N12, i.e. molecular and dissociative monodentate or bidentate adsorption. Three reaction pathways were proposed to understand gas-phase HCOOH decomposition on the Al12N12 nanocage. Our results reveal that for the decomposition of HCOOH into CO2 and H2, the most favorable pathway should be the Csbnd H bond activation reaction. The reaction energies and the activation barriers obtained here suggest that for the dissociative adsorption configuration on the Al12N12 surface, the rate-determining step is the Csbnd H bond breaking.
Highly ordered mesoporous cobalt oxide nanostructures: synthesis, characterisation, magnetic properties, and applications for electrochemical energy devices.

PubMed

Wang, Guoxiu; Liu, Hao; Horvat, Josip; Wang, Bei; Qiao, Shizhang; Park, Jinsoo; Ahn, Hyojun

2010-09-24

Highly ordered mesoporous Co(3)O(4) nanostructures were prepared using KIT-6 and SBA-15 silica as hard templates. The structures were confirmed by small angle X-ray diffraction, high resolution transmission electron microscopy, and N(2) adsorption-desorption isotherm analysis. Both KIT-6 cubic and SBA-15 hexagonal mesoporous Co(3)O(4) samples exhibited a low Néel temperature and bulk antiferromagnetic coupling due to geometric confinement of antiferromagnetic order within the nanoparticles. Mesoporous Co(3)O(4) electrode materials have demonstrated the high lithium storage capacity of more than 1200 mAh g(-1) with an excellent cycle life. They also exhibited a high specific capacitance of 370 F g(-1) as electrodes in supercapacitors.
Synthesis and structural characterization of ZnO and CuO nanoparticles supported mesoporous silica SBA-15

NASA Astrophysics Data System (ADS)

El-Nahhal, Issa M.; Salem, Jamil K.; Selmane, Mohamed; Kodeh, Fawzi S.; Ebtihan, Heba A.

2017-01-01

Zinc oxide (ZnO) and copper oxide (CuO) nanoparticles were loaded into mesoporous silica SBA-15 by post-synthesis and direct methods. The structural properties were characterized using wide and small angle X-ray diffraction (WXRD & SXRD), X-ray photoelectron spectroscopy (XPS) and N2-adsorption desorption (BET). The WXRD showed that, the loaded zinc and copper oxides were present in crystalline forms (impregnation). The mesoporosity properties of SBA-15 silica were well maintained even after the introduction of metal oxide nanoparticles. BET analysis indicate that the impregnated and condensed ZnO and CuO supported SBA-15 nanocomposites have a lower surface area than that of its parent SBA-15.
Ambient Carbon Dioxide Capture Using Boron-Rich Porous Boron Nitride: A Theoretical Study.

PubMed

Li, Lanlan; Liu, Yan; Yang, Xiaojing; Yu, Xiaofei; Fang, Yi; Li, Qiaoling; Jin, Peng; Tang, Chengchun

2017-05-10

The development of highly efficient sorbent materials for CO 2 capture under ambient conditions is of great importance for reducing the impact of CO 2 on the environment and climate change. In this account, strong CO 2 adsorption on a boron antisite (B N ) in boron-rich porous boron nitrides (p-BN) was developed and studied. The results indicated that the material achieved larger adsorption energies of 2.09 eV (201.66 kJ/mol, PBE-D). The electronic structure calculations suggested that the introduction of B N in p-BN induced defect electronic states in the energy gap region, which strongly impacted the adsorption properties of the material. The bonding between the B N defect and the CO 2 molecule was clarified, and it was found that the electron donation first occurred from CO 2 to the B N double-acceptor state then, followed by electron back-donation from B N to CO 2 accompanied by the formation of a B N -C bond. The thermodynamic properties indicated that the adsorption of CO 2 on the B N defect to form anionic CO 2 δ- species was spontaneous at temperatures below 350 K. Both the large adsorption energies and the thermodynamic properties ensured that p-BN with a B N defect could effectively capture CO 2 under ambient conditions. Finally, to evaluate the energetic stability, the defect formation energies were estimated. The formation energy of the B N defects was found to strongly depend on the chemical environment, and the selection of different reactants (B or N sources) would achieve the goal of reducing the formation energy. These findings provided a useful guidance for the design and fabrication of a porous BN sorbent for CO 2 capture.
Effects of N precursor on the agglomeration and visible light photocatalytic activity of N-doped TiO2 nanocrystalline powder.

PubMed

Hu, Yulong; Liu, Hongfang; Rao, Qiuhua; Kong, Xiaodong; Sun, Wei; Guo, Xingpeng

2011-04-01

N-doped TiO2 nanocrystalline powders were prepared by the sol-gel method using various N precursors, including triethylamine, hydrazine hydrate, ethylenediamine, ammonium hydroxide, and urea. The samples were characterized by X-ray diffraction, N2 adsorption isotherms, transmission electron microscopy, ultraviolet-visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The photocatalytic activities of as-prepared samples under irradiation of visible light (lambda > 405 nm) were evaluated by photodecomposition of methyl orange. The alkalinity of N precursor was found to play a key role in the gel process. The N precursor with moderate alkalinity causes TiO2 nanoparticles to be sol-transformed into a loosely agglomerated gel. This transformation facilitates the preparation of an N-doped TiO2 powder with small nanocrystal size, large specific surface area, and high N doping level and results in high visible light photocatalytic activity. The N in TiO2 with N is binding energy at 399-400 eV may be assigned to the N-H species located in interstitial sites of TiO2 lattice which is the active N species responsible for the visible light photocatalytic activity. The N species of N 1s peak at 402 and 405 eV are ineffective to the visible light photocatalytic activity and may inhibit the photocatalytic activity. Moreover, a TiO2 nanoparticle powder with large specific area can be achieved by using urea as a template and then by using ammonium hydroxide to transform the sol into gel.
Enhanced adsorption of Eu(III) on mesoporous Al2O3/expanded graphite composites investigated by macroscopic and microscopic techniques.

PubMed

Sun, Yubing; Chen, Changlun; Tan, Xiaoli; Shao, Dadong; Li, Jiaxing; Zhao, Guixia; Yang, Shubin; Wang, Qi; Wang, Xiangke

2012-11-21

Mesoporous Al(2)O(3) was intercalated into an expanded graphite (EG) interlayer to prepare mesoporous Al(2)O(3)/EG composites. The basal spacing of mesoporous Al(2)O(3)/EG composites was enlarged as compared to raw graphite from the X-ray diffraction analysis. The massive surface functional groups and wedge-shaped pores were observed in terms of potentiometric acid-base titration analysis and scanning electron microscope, respectively. The pH-dependent adsorption of Eu(III) on mesoporous Al(2)O(3)/EG composites was evidently independent of ionic strength. The maximum adsorption capacity of Eu(III) on mesoporous Al(2)O(3)/EG composites at pH 6.0 and T = 293 K was calculated to be 5.14 mg g(-1). Desorption kinetics and cyclic operation results showed that mesoporous Al(2)O(3)/EG composites presented high hydrothermal stability in aqueous solution. The thermodynamic parameters suggested that Eu(III) adsorption on mesoporous Al(2)O(3)/EG composites is an endothermic and a spontaneous process. The decrease of Eu-O bond distance with the increasing pH demonstrated that the adsorption mechanism between Eu(III) and mesoporous Al(2)O(3)/EG composites would shift from outer-sphere surface complexation to inner-sphere surface complexation in terms of extended X-ray absorption fine structure spectroscopy analysis.
Silica Aerogel-supported Hydrozincite and Carbonate-intercalated Hydrotalcite for High-efficiency Removal of Pb(II) Ions by Precipitation Transformation Reactions.

PubMed

Wang, Lijun; Wang, Xiaoxia; Li, Jianfa; Feng, Xiaolan; Wang, Yusen

2017-09-25

In this work, hydrozincite and Zn/Al-CO 3 2- hydrotalcite supported on silica aerogel were prepared via a simple and economical process and used as adsorbents for Pb(II) removal. The supported hydrozincite and Zn/Al-CO 3 2- hydrotalcite possess ultra-thin thickness, high surface area, and weak crystallinity. In the batch Pb(II) adsorption experiments, the adsorbents with higher Zn(II) contents showed higher Pb(II) adsorption capacities, and the adsorption data fitted well with the Langmuir isotherm model and pseudo-second-order kinetic model, indicating a mechanism of surface chemisorption. The adsorption capacities calculated based Langmuir isotherm model are 684.9 mg/g and 555.6 mg/g for the supported hydrozincite and Zn/Al-CO 3 2- hydrotalcite, respectively, higher than the adsorption capacities of other hydrotalcite-based adsorbents and most of other inorganic adsorbents reported previously. The XRD diffraction peaks of hydrozincite and Zn/Al-CO 3 2- hydrotalcite disappeared after the adsorption, and the Pb(II) species were uniformly dispersed in the adsorbents in form of Pb 3 (CO 3 ) 2 (OH) 2 proven by TEM, EDS mapping and XRD analysis, demonstrating the nature of the adsorption is the precipitation conversion of hydrozincite or Zn/Al-CO 3 2- hydrotalcite into Pb 3 (CO 3 ) 2 (OH) 2 . These results demonstrate the synergic Pb(II) removal effect of the CO 3 2- and OH - derived from hydrozincite and Zn/Al-CO 3 2- hydrotalcite together with their ultra-thin thickness and high surface area contribute the excellent properties of the adsorbents.
Highly Efficient Performance and Conversion Pathway of Photocatalytic CH3SH Oxidation on Self-Stabilized Indirect Z-Scheme g-C3N4/I3--BiOI.

PubMed

Hu, Lingling; He, Huanjunwa; Xia, Dehua; Huang, Yajing; Xu, Jiarong; Li, Haoyue; He, Chun; Yang, Wenjing; Shu, Dong; Wong, Po Keung

2018-06-06

A self-stabilized Z-scheme porous g-C 3 N 4 /I 3- -containing BiOI ultrathin nanosheets (g-C 3 N 4 /I 3- -BiOI) heterojunction photocatalyst with I 3 - /I - redox mediator was successfully synthesized by a facile solvothermal method coupling with light illumination. The structure and optical properties of g-C 3 N 4 /I 3- -BiOI composites were systematically characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, X-ray photoelectron spectroscopy, N 2 adsorption/desorption, UV-vis diffuse reflectance spectrum, and photoluminescence. The g-C 3 N 4 /I 3- -BiOI composites, with a heterojunction between porous g-C 3 N 4 and BiOI ultrathin nanosheets, were first applied for the photocatalytic elimination of ppm-leveled CH 3 SH under light-emitting diode visible light illumination. The g-C 3 N 4 /I 3- -BiOI heterojunction with 10% g-C 3 N 4 showed a dramatically enhanced photocatalytic activity in the removal of CH 3 SH compared with pure BiOI and g-C 3 N 4 due to its effective interfacial charge transfer and separation. The adsorption and photocatalytic oxidation of CH 3 SH over g-C 3 N 4 /I 3- -BiOI were deeply explored by in situ diffuse reflectance infrared Fourier transform spectroscopy, and the intermediates and conversion pathways were elucidated and compared. Furthermore, on the basis of reactive species trapping, electron spin resonance and Mott-Schottky experiments, it was revealed that the responsible reactive species for catalytic CH 3 SH composition were h + , • O 2 - , and 1 O 2 ; thus, the g-C 3 N 4 /I 3- -BiOI heterojunction followed an indirect all-solid state Z-scheme charge-transfer mode with self-stabilized I 3 - /I - pairs as redox mediator, which could accelerate the separation of photogenerated charge and enhance the redox reaction power of charged carriers simultaneously.
The fabrication of porous N-doped carbon from widely available urea formaldehyde resin for carbon dioxide adsorption.

PubMed

Liu, Zhen; Du, Zhenyu; Song, Hao; Wang, Chuangye; Subhan, Fazle; Xing, Wei; Yan, Zifeng

2014-02-15

N-doped carbon material constitutes abundant of micropores and basic nitrogen species that have potential implementation for CO2 capture. In this paper, porous carbon material with high nitrogen content was simply fabricated by carbonizing low cost and widely available urea formaldehyde resin, and then followed by KOH activation. CO2 capture experiment showed high adsorption capacity of 3.21 mmol g(-1) at 25 °C under 1 atm for UFCA-2-600. XRD, SEM, XPS and FT-IR analysis confirmed that a graphitic-like structure was retained even after high temperature carbonization and strong base activation. Textural property analysis revealed that narrow micropores, especially below 0.8 nm, were effective for CO2 adsorption by physical adsorption mechanism. Chemical evolved investigation revealed that graphitic-like embedded basic nitrogen groups are generated from bridged and terminal amines of urea formaldehyde resin from thermal carbonization and KOH activation treatment, which is responsible for the enrichment of CO2 capacity by chemical adsorption mechanism. The relationship between CO2 adsorption capacity and pore size or basic N species was also studied, which turned out that both of them played crucial role by physical and chemical adsorption mechanism, respectively. Copyright © 2013 Elsevier Inc. All rights reserved.
Arsenate adsorption mechanisms at the allophane - Water interface

USGS Publications Warehouse

Arai, Y.; Sparks, D.L.; Davis, J.A.

2005-01-01

We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As(V)]0 from 50 to 1000 ??M (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0-10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline AI-As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane-water interface are attributable to ligand exchange reactions between As(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H2PO42- and H2AsO42-) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The innersphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments. ?? 2005 American Chemical Society.
Highly Selective and Efficient Removal of Heavy Metals by Layered Double Hydroxide Intercalated with the MoS4(2-) Ion.

PubMed

Ma, Lijiao; Wang, Qing; Islam, Saiful M; Liu, Yingchun; Ma, Shulan; Kanatzidis, Mercouri G

2016-03-02

The MoS4(2-) ion was intercalated into magnesium-aluminum layered double hydroxide (MgAl-NO3-LDH) to produce a single phase material of Mg0.66Al0.34(OH)2(MoS4)0.17·nH2O (MgAl-MoS4-LDH), which demonstrates highly selective binding and extremely efficient removal of heavy metal ions such as Cu(2+), Pb(2+), Ag(+), and Hg(2+). The MoS4-LDH displays a selectivity order of Co(2+), Ni(2+), Zn(2+) < Cd(2+) ≪ Pb(2+) < Cu(2+) < Hg(2+) < Ag(+) for the metal ions. The enormous capacities for Hg(2+) (∼500 mg/g) and Ag(+) (450 mg/g) and very high distribution coefficients (Kd) of ∼10(7) mL/g place the MoS4-LDH at the top of materials known for such removal. Sorption isotherm for Ag(+) agrees with the Langmuir model suggesting a monolayer adsorption. It can rapidly lower the concentrations of Cu(2+), Pb(2+), Hg(2+), and Ag(+) from ppm levels to trace levels of ≤1 ppb. For the highly toxic Hg(2+) (at ∼30 ppm concentration), the adsorption is exceptionally rapid and highly selective, showing a 97.3% removal within 5 min, 99.7% removal within 30 min, and ∼100% removal within 1 h. The sorption kinetics for Cu(2+), Ag(+), Pb(2+), and Hg(2+) follows a pseudo-second-order model suggesting a chemisorption with the adsorption mechanism via M-S bonding. X-ray diffraction patterns of the samples after adsorption demonstrate the coordination and intercalation structures depending on the metal ions and their concentration. After the capture of heavy metals, the crystallites of the MoS4-LDH material retain the original hexagonal prismatic shape and are stable at pH ≈ 2-10. The MoS4-LDH material is thus promising for the remediation of heavy metal polluted water.
Alkali layered compounds interfaces for energy conversion and energy storage

NASA Technical Reports Server (NTRS)

Papageorgopoulos, Chris A.

1996-01-01

During year one a new ultra-high vacuum, an Ar(+) ion sputterer, a low energy electron diffraction (LEED) system, an Auger electron spectrometer (AES), a work function measurement device with a Kelvin probe, and related accessories were used. The study found a focus in the adsorption of chalcogenides on Si and III-V compound semiconductors. In the second year, a scanning tunneling microscope was obtained along with a quadrapole mass spectrometer, power supplies, a computer, a chart recorder, etc. We started the systematic study on the adsorption of chalcogenides on the compound semiconductor surfaces. The third year saw the mounting of the scanning tunneling microscope (STM) on the existing UHV system. The investigation continued with the adsorption of Cs (alkali) on S-covered Si(100)2x1 surfaces. Then the adsorption of S on Cs-covered Si(100) surfaces was studied.
Selective adsorption of Pb (II) over the zinc-based MOFs in aqueous solution-kinetics, isotherms, and the ion exchange mechanism.

PubMed

Wang, Lei; Zhao, Xinhua; Zhang, Jinmiao; Xiong, Zhenhu

2017-06-01

Two series of metal-organic frameworks (MOFs) with similar formula units but different central metal ions (M) or organic linkers (L), M-BDC (BDC = terephthalate, M = Zn, Zr, Cr, or Fe), or Zn-L (L = imidazolate-2-methyl, BDC, BDC-NH 2 ), were prepared and employed as the receptors for adsorption lead ions. It was found that the Zn-BDC exhibited a much higher adsorption capacity than the other M-BDC series with various metal ions which have very closely low capacities at same conditions. Furthermore, the Zn-L (L = imidazolate-2-methyl, BDC, BDC-NH 2 ) still have highly efficient adsorption capacity of lead ions, although the adsorption capacity varies with different ligand, as well as the adsorption rate and the equilibrium pH of the solution. This significant high adsorption over Zn-L, different from other M-BDC series with various metal ions (Zr, Cr, or Fe), can be explained by ion exchange between the central metal ions of Zn-L and lead ion in solution. Based on the analysis of FT-IR, X-ray diffraction pattern, the nitrogen adsorption isotherms, the zeta potentials, and the results, a plausible adsorption mechanism is proposed. When equivalent Zn-L were added to equal volume of aqueous solution with different concentration of lead ion, the content of zinc ion in the solution increases with the increase of the initial concentration of lead ions. The new findings could provide a potential way to fabricate new metal organic frameworks with high and selective capacities of the heavy metal ions.
Utilization of Natural Zeolite from Ponorogo and Purworejo for Naphthol Substance Adsorption

NASA Astrophysics Data System (ADS)

Imandiani, Sundus; Indira, Christine; Johan, Anthony; Budiyono

2018-02-01

Indonesia has many zeolite producing areas yet untapped. Researchers developed the utilization of natural zeolites useful for the adsorption of naphthol dyes commonly found in batik waste. In this study researchers used natural zeolites from Purworejo and Ponorogo that are activated using hydrochloric acid that is used for adsorption. The purpose of this research is to know the effect of natural zeolite activation from Ponorogo and Purworejo on the effectiveness of adsorption of naphthol dyes widely used in batik industry. Natural zeolite was activated using HCl concentration of 1.3N; 1.8N; 3.2N; and 3.9N for 60 minutes. The methods are preparation of natural zeolite from Purworejo and Ponorogo, dealumination using hydrochloric acid, adsorption process of naphthol dyes using activated zeolite, and test of adsorption result with uv-vis spectrophotometry. The test results showed that the higher HCl concentration will increase adsorption capacity. This can be known from the concentration of naphthol dye which decreased both using natural zeolite Ponorogo and Purworejo. While the effectiveness of adsorption shows natural zeolite Purworejo has a greater adsorption capacity than Ponorogo with optimum conditions of dealumination using concentration HCl 3,9N.
Investigation of heterogeneous asymmetric dihydroxylation over OsO{sub 4}-(QN){sub 2}PHAL catalysts of functionalized bimodal mesoporous silica with ionic liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiu, Shenjie; Sun, Jihong, E-mail: jhsun@bjut.edu.cn; Li, Yuzhen

2011-08-15

Highlights: {yields} Functionalized bimodal mesoporous silica with MTMSPIm{sup +}Cl{sup -}. {yields} Mesoporous catalyst immobilized with OsO{sub 4}-(QN){sub 2}PHAL. {yields} Catalysts for asymmetric dihydroxylation reaction with high yield and enatioselectivity. {yields} Recyclable catalysts. -- Abstract: A novel synthesis of the functionalized bimodal mesoporous silica with ionic liquid (FBMMs) was performed. After grafting 1-methyl-3-(trimethoxysilyl)propylimidazolium chloride onto the surface of bimodal mesoporous silicas, 1,4-bis(9-O-quininyl)phthalazine ((QN){sub 2}-PHAL) and K{sub 2}Os(OH){sub 4}.2H{sub 2}O were immobilized onto the modified FBMMs by adsorption or ionic exchange methods, and then, the asymmetric dihydroxylation reaction was carried out by using solid catalysts. Techniques such as X-ray diffraction, Fourier Transformmore » Infrared spectroscopy, N{sub 2} adsorption and desorption were employed to characterize their structure and properties. The results showed that the mesoporous ordering degree of bimodal mesoporous silica decreased after functionalization and immobilization of OsO{sub 4}-(QN){sub 2}PHAL. Being very effective in asymmetric dihydroxylation with high yield and enantioselectivity, the prepared heterogeneous solid catalyst could be recycled for five times with little loss of enantioselectivity, with comparison of those results obtained in homophase system. Moreover, the effect of Osmium catalyst on asymmetric dihydroxylation was investigated.« less

Stability of hepatoprotecting agent IFC-305 encapsulated into sol-gel titania nanoparticles and drug release evaluation: water and drug concentration effect.

PubMed

Albarran, L; López, T; Quintana, P; Chagoya, V

2012-03-01

IFC-305 was encapsulated into nanostructured titania and functionalized with OH groups by the sol-gel process using titanium n-butoxide, to be used in a drug delivery system for the treatment of liver cancer. Synthesis was carried out at different molar hydrolysis ratios: 4, 8, 16 and 24 mol of water; and drug concentration of 10, 20 and 30%. Characterization of IFC-titania reservoirs was carried out by Fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermal analysis (DTA-TGA), scanning electron microscopy (SEM), and N2 adsorption-desorption isotherms (BET), confirms that IFC-305 is entrapped and stabilized in the TiO2-OH matrix. Drug liberation in vitro was determined by UV spectrometry over a period of 1000 h. This study demonstrated that the higher water content and the higher amount of loaded IFC, favored hydrogen bonding between titania-OH surface and IFC-NH groups, increasing the rate of drug release.
Effect of carbonization temperature on the physical and electrochemical properties of supercapacitor electrode from fibers of oil palm empty fruit bunches

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ishak, M. M.; Deraman, M., E-mail: madra@ukm.my; Talib, I. A.

Self-adhesive carbon grains (SACG) was prepared from fibers of oil palm empty fruit bunches. The SACG green monoliths were carbonized in N{sub 2} environment at 400, 500, 600 and 700°C to produce carbon monoliths labeled as CM1, CM2, CM3 and CM4 respectively. The CMs were activated in CO{sub 2} surrounding at 800°C for 1 hour to produce activated carbon monolith electrodes (ACM1, ACM2, ACM3 and ACM4). The physical properties of the CMs and ACMs were investigated using X-ray diffraction, field emission scanning electron microscopy (FESEM) and N{sub 2} adsorption-desorption isotherm techniques. ACMs were used as electrode to fabricate symmetry supercapacitormore » cells and the cells’ performances were investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) standard techniques. In this paper we report the physical and electrochemical properties of the ACM electrodes by analyzing the influence of the carbonization temperature on these properties.« less
Carbon dioxide adsorption on micro-mesoporous composite materials of ZSM-12/MCM-48 type: The role of the contents of zeolite and functionalized amine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santos, S.C.G.; Pedrosa, A.M.Garrido; Souza, M.J.B., E-mail: mjbsufs@gmail.com

2015-10-15

Highlights: • Synthesis of the micro-mesoporous composite materials of ZSM-12/MCM-48 type. • Application of these adsorbents in the carbon dioxide adsorption. • Effects of the contents of zeolite and amino group in the material surface on the CO{sub 2} capture efficiency. - Abstract: In this study ZSM-12/MCM-48 adsorbents have been synthesized at three ZSM-12 content, and also were functionalizated with amine groups by grafting. All the adsorbents synthesized were evaluated for CO{sub 2} capture. The X-ray diffraction analysis of the ZSM-12/MCM-48 composite showed the main characteristic peaks of ZSM-12 and MCM-48, and after the functionalization, the structure of MCM-48 onmore » the composite impregnated was affected due amine presence. For the composites without amine, the ZSM-12 content was the factor determining in the adsorption capacity of CO{sub 2} and for the composites with amine the amount of amine was that influenced in the adsorption capacity.« less
Investigating the Heavy Metal Adsorption of Mesoporous Silica Materials Prepared by Microwave Synthesis

NASA Astrophysics Data System (ADS)

Zhu, Wenjie; Wang, Jingxuan; Wu, Di; Li, Xitong; Luo, Yongming; Han, Caiyun; Ma, Wenhui; He, Sufang

2017-05-01

Mesoporous silica materials (MSMs) of the MCM-41 type were rapidly synthesized by microwave heating using silica fume as silica source and evaluated as adsorbents for the removal of Cu2+, Pb2+, and Cd2+ from aqueous solutions. The effects of microwave heating times on the pore structure of the resulting MSMs were investigated as well as the effects of different acids which were employed to adjust the solution pH during the synthesis. The obtained MCM-41 samples were characterized by nitrogen adsorption-desorption analyses, X-ray powder diffraction, and transmission electron microscopy. The results indicated that microwave heating method can significantly reduce the synthesis time of MCM-41 to 40 min. The MCM-41 prepared using citric acid (c-MCM-41(40)) possessed more ordered hexagonal mesostructure, higher pore volume, and pore diameter. We also explored the ability of c-MCM-41(40) for removing heavy metal ions (Cu2+, Pb2+, and Cd2+) from aqueous solution and evaluated the influence of pH on its adsorption capacity. In addition, the adsorption isotherms were fitted by Langmuir and Freundlich models, and the adsorption kinetics were assessed using pseudo-first-order and pseudo-second-order models. The intraparticle diffusion model was studied to understand the adsorption process and mechanism. The results confirmed that the as-synthesized adsorbent could efficiently remove the heavy metal ions from aqueous solution at pH range of 5-7. The adsorption isotherms obeyed the Langmuir model, and the maximum adsorption capacities of the adsorbent for Cu2+, Pb2+, and Cd2+ were 36.3, 58.5, and 32.3 mg/g, respectively. The kinetic data were well fitted to the pseudo-second-order model, and the results of intraparticle diffusion model showed complex chemical reaction might be involved during adsorption process.
Graphene supported heterogeneous catalysts for Li-O2 batteries

NASA Astrophysics Data System (ADS)

Alaf, M.; Tocoglu, U.; Kartal, M.; Akbulut, H.

2016-09-01

In this study production and characterization of free-standing and flexible (i) graphene, (ii) α-MnO2/graphene, (iii) Pt/graphene (iv) α-MnO2/Pt/graphene composite cathodes for Li-air batteries were reported. Graphene supported heterogeneous catalysts were produced by a facile method. In order to prevent aggregation of graphene sheets and increase not only interlayer distance but also surface area, a trace amount multi-wall carbon nano tube (MWCNT) was introduced to the composite structure. The obtained composite catalysts were characterized by SEM, X-ray diffraction, N2 adsorption-desorption analyze and Raman spectroscopy. The electrochemical characterization tests including galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS) measurement of catalyst were carried out by using an ECC-Air test cell. These highly active graphene supported heterogeneous composite catalysts provide competitive properties relative to other catalyst materials for Li-air batteries.
Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction.

PubMed

Li, Li; Yan, Zi F; Lu, Gao Q; Zhu, Zhong H

2006-01-12

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)3.9H2O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time.
Probing adsorption sites of carbon dioxide in metal organic framework of [Zn(bdc)(dpds)]n: A molecular simulation study

NASA Astrophysics Data System (ADS)

Lu, Shih-I.; Liao, Jian-Min; Huang, Xiao-Zhuang; Lin, Chia-Hsun; Ke, Szu-Yu; Wang, Chih-Chieh

2017-11-01

We used force-field based grand-canonical Monte Carlo simulation method and density functional theory to study adsorption characteristics of carbon dioxide (CO2) molecules in a metal-organic framework (MOF) compound, [Zn(bdc)(dpds)]n. The studied MOF include a metal ion (Zn(II)), an anion organic linker (dianion of benzene dicarboxylicacid, bdc2-) and a neutral organic linker (4,4‧-dipyridyldisulfide, dpds). Results from calculated adsorption isotherms and enthalpies of adsorption agree with the experimental data. The interactions between the adsorbed CO2 and the organic linkers were examined in simulations. Calculated results show available absorption sites are surrounded by two dpds ligands in which an S-S bond as an N-N‧ spacer connect two pyridines. In contrast, the bdc2- ligand does not give a significant contribution to the substantial adsorption amount even though it contains the carboxylate group that provides available bonding site to CO2.
Adsorption of selected volatile organic vapors on multiwall carbon nanotubes.

PubMed

Shih, Yang-hsin; Li, Mei-syue

2008-06-15

Carbon nanotubes are expected to play an important role in sensing, pollution treatment and separation techniques. This study examines the adsorption behaviors of volatile organic compounds (VOCs), n-hexane, benzene, trichloroethylene and acetone on two multiwall carbon nanotubes (MWCNTs), CNT1 and CNT2. Among these VOCs, acetone exhibits the highest adsorption capacity. The highest adsorption enthalpies and desorption energies of acetone were also observed. The strong chemical interactions between acetone and both MWCNTs may be the result from chemisorption on the topological defects. The adsorption heats of trichloroethylene, benzene, and n-hexane are indicative of physisorption on the surfaces of both MWCNTs. CNT2 presents a higher adsorption capacity than CNT1 due to the existence of an exterior amorphous carbon layer on CNT2. The amorphous carbon enhances the adsorption capacity of organic chemicals on carbon nanotubes. The morphological and structure order of carbon nanotubes are the primary affects on the adsorption process of organic chemicals.
The separation of uranium ions by natural and modified diatomite from aqueous solution.

PubMed

Sprynskyy, Myroslav; Kovalchuk, Iryna; Buszewski, Bogusław

2010-09-15

In this work the natural and the surfactant modified diatomite has been tested for ability to remove uranium ions from aqueous solutions. Such controlling factors of the adsorption process as initial uranium concentration, pH, contact time and ionic strength have been investigated. Effect of ionic strength of solution has been examined using the solutions of NaCl, Na(2)CO(3) and K(2)SO(4). The pseudo-first order and the pseudo-second order models have been used to analyze the adsorption kinetic results, whereas the Langmuir and the Freundlich isotherms have been used to the equilibrium adsorption data. The effects of the adsorbent modification as well as uranium adsorption on the diatomite surface have been studied using X-ray powder diffraction, scanning electron microscopy and FTIR spectroscopy. The maximum adsorption capacities of the natural and the modified diatomite towards uranium were 25.63 micromol/g and 667.40 micromol/g, respectively. The desorptive solutions of HCl, NaOH, Na(2)CO(3), K(2)SO(4), CaCO(3), humic acid, cool and hot water have been tested to recover uranium from the adsorbent. The highest values of uranium desorption (86%) have been reached using 0.1M HCl. Copyright 2010 Elsevier B.V. All rights reserved.
Impact of natural organic matter coatings on the microbial reduction of iron oxides

NASA Astrophysics Data System (ADS)

Poggenburg, Christine; Mikutta, Robert; Schippers, Axel; Dohrmann, Reiner; Guggenberger, Georg

2018-03-01

Iron (Fe) oxyhydroxides are important constituents of the soil mineral phase known to stabilize organic matter (OM) under oxic conditions. In an anoxic milieu, however, these Fe-organic associations are exposed to microbial reduction, releasing OM into soil solution. At present, only few studies have addressed the influence of adsorbed natural OM (NOM) on the reductive dissolution of Fe oxyhydroxides. This study therefore examined the impact of both the composition and concentration of adsorbed NOM on microbial Fe reduction with regard to (i) electron shuttling, (ii) complexation of Fe(II,III), (iii) surface site coverage and/or pore blockage, and (iv) aggregation. Adsorption complexes with varying carbon loadings were synthesized using different Fe oxyhydroxides (ferrihydrite, lepidocrocite, goethite, hematite, magnetite) and NOM of different origin (extracellular polymeric substances from Bacillus subtilis, OM extracted from soil Oi and Oa horizons). The adsorption complexes were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), N2 gas adsorption, electrophoretic mobility and particle size measurements, and OM desorption. Incubation experiments under anaerobic conditions were conducted for 16 days comparing two different strains of dissimilatory Fe(III)-reducing bacteria (Shewanella putrefaciens, Geobacter metallireducens). Mineral transformation during reduction was assessed via XRD and FTIR. Microbial reduction of the pure Fe oxyhydroxides was controlled by the specific surface area (SSA) and solubility of the minerals. For Shewanella putrefaciens, the Fe reduction of adsorption complexes strongly correlated with the concentration of potentially usable electron-shuttling molecules for NOM concentrations <2 mg C L-1, whereas for Geobacter metallireducens, Fe reduction depended on the particle size and thus aggregation of the adsorption complexes. These diverging results suggest that the influence of NOM on the stability of Fe-organic associations in soils cannot easily be assessed without considering the composition of the microbial soil community.
Sorption kinetics and isotherm modelling of imidacloprid on bentonite and organobentonites.

PubMed

Jain, Shailesh K; Shakil, Najam A; Dutta, Anirban; Kumar, Jitendra; Saini, Mukesh K

2017-05-04

Bentonite was modified by quaternary ammonium cations viz. cetytrimethylammonium (CTA), cetylpyridinium (CP), rioctylmethylammonium (TOM) and pcholine (PTC) at 100% cation exchange capacity of bentonite and was characterized by X-ray diffraction, CHNS elemental analyser and Fourier transform infrared spectroscopy. The sorption of imidacloprid on organobentonites/bentonite was studied by batch method. Normal bentonite could adsorb imidacloprid only upto 19.31-22.18% while all organobentonites except PTC bentonite (PTCB), enhanced its adsorption by three to four times. Highest adsorption was observed in case of TOM bentonite (TOMB) (76.94-83.16%). Adsorption kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models. For normal bentonite data were best fitted to pseudo-first-order kinetic, while for organobentonites fitted to pseudo-second-order kinetics. Sorption data were analysed using Freundlich, Langmuir, Temkin and Dubinin-Radushkevich isotherm models. Data were well fitted to Freundlich adsorption isotherm. Product of Freundlich adsorption constant and heterogeneity parameter (K f .1/n) was in following order: TOMB (301.87) > CTA bentonite (CTAB) (152.12) > CP bentonite (CPB) (92.58) > bentonite (27.25). Desorption study confirmed hysteresis and concentration dependence. The present study showed that the organobentonite could be a good sorbent for removal of imidacloprid from natural water sample also. Percentage adsorption and Distribution coefficient (mL g -1 ) value of different adsorbent was in following order: TOMB (74.85% and 297.54) > CTAB (55.78% and 126.15) > CPB (45.81% and 84.55) > bentonite (10.65% and 11.92).
Computational study of hydrocarbon adsorption in metal-organic framework Ni2(dhtp)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Xiuquan; Wick, Collin D.; Thallapally, Praveen K.

Molecular dynamic simulations were carried out to study the sorption, structural properties, and diffusivities of n-hexane and cyclohexane adsorbed in Ni2(dhtp). The results indicated strong interactions between the alkanes and the host material. The free energy perturbation method was employed to investigate the adsorption free energies of methane, ethane, n-butane, n-hexane and cyclohexane. For linear alkanes, the free energy lowered as the length of the carbon chain increased. Also, the adsorption of n-hexane was preferred over cyclohexane, due to its ability to rearrange its structure to maximize contacts with the host. Furthermore, due to the large pore size of Ni2(dhtp),more » higher loadings of alkanes did not significantly affect the alkane structure, and enhanced the free energy of adsorption for subsequent alkanes being loaded. According to our studies, Ni2(dhtp) has a very promising potential for adsorption and storage of alkanes. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less
Adsorption of acetanilide herbicides on soil and its components. II. Adsorption and catalytic hydrolysis of diethatyl-ethyl on saturated Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite.

PubMed

Liu, W P; Fang, Z; Liu, H J; Yang, W C

2001-04-01

Adsorption and catalytic hydrolysis of the herbicide diethatyl-ethyl [N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester] on homoionic Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite clays were investigated in water solution. The Freundlich adsorption coefficient, Ki, got from isotherms on clay followed the order of Na+ approximately K+ > Mg2+ approximately Ca2+. Analysis of FT-IR spectra of diethatyl-ethyl adsorbed on clay suggests probable bonding at the carboxyl and amide carbonyl groups of the herbicide. The rate of herbicide hydrolysis in homoionic clay suspensions followed the same order as that for adsorption, indicating that adsorption may have preceded and thus caused hydrolysis. Preliminary product identification showed that hydrolysis occurred via nucleophilic substitution at the carboxyl carbon, causing the cleavage of the ester bond and formation of diethatyl and its dechlorinated derivative, and at the amide carbon, yielding an ethyl ester derivative and its acid. These pathways also suggest that hydrolysis of diethatyl-ethyl was catalyzed by adsorption on the clay surface.
Rapid removal of bisphenol A on highly ordered mesoporous carbon.

PubMed

Sui, Qian; Huang, Jun; Liu, Yousong; Chang, Xiaofeng; Ji, Guangbin; Deng, Shubo; Xie, Tao; Yu, Gang

2011-01-01

Bisphenol A (BPA) is of global concern due to its disruption of endocrine systems and ubiquity in the aquatic environment. It is important, therefore, that efforts are made to remove it from the aqueous phase. A novel adsorbent, mesoporous carbon CMK-3, prepared from hexagonal SBA-15 mesoporous silica was studied for BPA removal from aqueous phase, and compared with conventional powdered activated carbon (PAC). Characterization of CMK-3 by transmission electron microscopy (TEM), X-ray diffraction, and nitrogen adsorption indicated that prepared CMK-3 had an ordered mesoporous structure with a high specific surface area of 920 m2/g and a pore-size of about 4.9 nm. The adsorption of BPA on CMK-3 followed a pseudo second-order kinetic model. The kinetic constant was 0.00049 g/(mg x min), much higher than the adsorption of BPA on PAC. The adsorption isotherm fitted slightly better with the Freundlich model than the Langmuir model, and adsorption capacity decreased as temperature increased from 10 to 40 degrees C. No significant influence of pH on adsorption was observed at pH 3 to 9; however, adsorption capacity decreased dramatically from pH 9 to 13.
Adsorption behavior and mechanism of Cd(II) on loess soil from China.

PubMed

Wang, Yan; Tang, Xiaowu; Chen, Yunmin; Zhan, Liangtong; Li, Zhenze; Tang, Qiang

2009-12-15

Cadmium is a toxic heavy metal that has caused serious public health problems. It is necessary to find a cost effective method to deal with wastewater containing Cd(II). Loess soils in China have proven to be a potential adsorbent for Cd(II) removal from wastewater. The adsorption capacity of loess towards Cd(II) has been determined to be about 9.37 mg g(-1). Slurry concentration, initial solution pH, reaction time and temperature have also been found to significantly influence the efficiency of Cd(II) removal. The adsorption isotherms and kinetics of loess soil from China can be best-fit with the Langmuir model and pseudo-second order kinetics model, respectively. The thermodynamic analysis revealed that the adsorption process was spontaneous, endothermic and the system disorder increased with duration. The natural organic matter in loess soil is mainly responsible for Cd(II) removal at pH < 4.2, while clay minerals contribute to a further gradual adsorption process. Chemical precipitation dominates the adsorption stage at pH > 8.97. Further studies using X-ray diffraction, Fourier transform infrared spectra of Cd(II) laden loess soil and Cd(II) species distribution have confirmed the adsorption mechanism.
Adsorption of ferrous ions onto montmorillonites

NASA Astrophysics Data System (ADS)

Qin, Dawei; Niu, Xia; Qiao, Min; Liu, Gang; Li, Hongxin; Meng, Zhenxiao

2015-04-01

The adsorption of Fe (II) onto montmorillonites was investigated through initial concentration, contact time, pH and temperature. During the whole adsorption process, the ascorbic acid (Vitamin C) was added as a kind of antioxidant, at the same time, deionized water (after boiling) and nitrogen protection were also used to avoid oxidation. The Fe2+/Fetotal ratio of the iron exists in the Fe-montmorillonites was found more than 95%. Two kinetic models, including pseudo-first-order and pseudo-second-order model, were used to analyze the adsorption process of Fe (II) on montmorillonites. The results of our study showed that adsorption process fitted with pseudo-second-order well. Adsorption isotherms showed that Langmuir model was better than Freundlich model. The thermodynamic parameters ΔG0 and ΔH0 were 3.696 kJ/mol and 6.689 kJ/mol (we just gave the values at 298 K), respectively. The positive values at different temperatures showed that the adsorption process was non-spontaneous and endothermic. The characteristics of materials were determined by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Surface area and porosity analyzer, Thermogravimetric analysis (TGA), Differential scanning calorimeter (DSC) and Zeta potential distribution.
Synthesis and CO{sub 2} adsorption study of modified MOF-5 with multi-wall carbon nanotubes and expandable graphite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ullah, Sami, E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Bustam, M. A., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Shariff, A. M., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com

2014-10-24

MOF-5 was synthesized by solvothermal method and its reactivation under anhydrous conditions. This research is conducted to investigate the effect of MOF-5 and MOF-5 modified with multi-wall carbon nanotubes (MWCNTs) and expandable graphite (EG) on the performance of CO{sub 2} adsorption. The synthesized MOFs were characterized using Field emission scanning electron microscopy (FESEM) for surface morphology, Thermogravimetric analysis (TGA) for thermal stability, X-ray diffraction (XRD) for crystals plane, Brunauer-Emmet-Teller (BET) for surface area and CO{sub 2} adsorption. The result had showed that the modified MOF-5 enhanced the CO{sub 2} adsorption compared to the pure MOF-5. The increment in the CO{submore » 2} uptake capacities of MOF materials was attributed to the decrease in the pore size and enhancement of micropore volume of MOF-5 by multi-walled carbon nanotube and EG incorporation. The BET surface area of the synthesized MOF-5@MWCNTs is more than MOF-5. The CO{sub 2} sorption capacities of MOF-5 and MOF-5@MWCNTs were observed to increase from 0.00008 to 0.00048 mol g-1 at 298 K and 1 bar. The modified MOF-5@MWCNTs resulted in the highest CO{sub 2} adsorption followed by the modified MOF-5@ EG and lastly, MOF-5.« less
A supramolecular Tröger's base derived coordination zinc polymer for fluorescent sensing of phenolic-nitroaromatic explosives in water.

PubMed

Shanmugaraju, Sankarasekaran; Dabadie, Charlyne; Byrne, Kevin; Savyasachi, Aramballi J; Umadevi, Deivasigamani; Schmitt, Wolfgang; Kitchen, Jonathan A; Gunnlaugsson, Thorfinnur

2017-02-01

A V-Shaped 4-amino-1,8-napthalimide derived tetracarboxylic acid linker ( L ; bis-[ N -(1,3-benzenedicarboxylic acid)]-9,18-methano-1,8-naphthalimide-[ b , f ][1,5]diazocine) comprising the Tröger's base (TB) structural motif was rationally designed and synthesised to access a nitrogen-rich fluorescent supramolecular coordination polymer. By adopting the straight forward precipitation method, a new luminescent nanoscale Zn(ii) coordination polymer ( TB-Zn-CP ) was synthesized in quantitative yield using Zn(OAc) 2 ·2H 2 O and tetraacid linker L (1 : 0.5) in DMF at room temperature. The phase-purity of as-synthesised TB-Zn-CP was confirmed by X-ray powder diffraction analysis, infra-red spectroscopy, and elemental analysis. Thermogravimetric analysis suggests that TB-Zn-CP is thermally stable up to 330 °C and the morphological features of TB-Zn-CP was analysed by SEM and AFM techniques. The N 2 adsorption isotherm of thermally activated TB-Zn-CP at 77 K revealed a type-II reversible adsorption isotherm and the calculated Brunauer-Emmett-Teller (BET) surface area was found to be 72 m 2 g -1 . Furthermore, TB-Zn-CP displayed an excellent CO 2 uptake capacity of 76 mg g -1 at 273 K and good adsorption selectivity for CO 2 over N 2 and H 2 . The aqueous suspension of as-synthesized TB-Zn-CP showed strong green fluorescence ( λ max = 520 nm) characteristics due to the internal-charge transfer (ICT) transition and was used as a fluorescent sensor for the discriminative sensing of nitroaromatic explosives. The aqueous suspension of TB-Zn-CP showed the largest quenching responses with high selectivity for phenolic-nitroaromatics (4-NP, 2,4-DNP and PA) even in the concurrent presence of other potentially competing nitroaromatic analytes. The fluorescence titration studies also provide evidence that TB-Zn-CP detects picric acid as low as the parts per billion (26.3 ppb) range. Furthermore, the observed fluorescence quenching responses of TB-Zn-CP towards picric acid were highly reversible. The highly selective fluorescence quenching responses including the reversible detection efficiency make the nanoscale coordination polymer TB-Zn-CP a potential material for the discriminative fluorescent sensing of nitroaromatic explosives.
Supported polytertiary amines: highly efficient and selective SO2 adsorbents.

PubMed

Tailor, Ritesh; Abboud, Mohamed; Sayari, Abdelhamid

2014-01-01

Tertiary amine containing poly(propyleneimine) second (G2) and third (G3) generation dendrimers as well as polyethyleneimine (PEI) were developed for the selective removal of SO2. N-Alkylation of primary and secondary amines into tertiary amines was confirmed by FTIR and NMR analysis. Such modified polyamines were impregnated on two nanoporous supports, namely, SBA-15PL silica with platelet morphology and ethanol-extracted pore-expanded MCM-41 (PME) composite. In the presence of 0.1% SO2/N2 at 23 °C, the uptake of modified PEI, G2, and G3 supported on SBA-15PL was 2.07, 2.35, and 1.71 mmol/g, respectively; corresponding to SO2/N ratios of 0.22, 0.4, and 0.3. Under the same conditions, the SO2 adsorption capacity of PME-supported modified PEI and G3 was significantly higher, reaching 4.68 and 4.34 mmol/g, corresponding to SO2/N ratios of 0.41 and 0.82, respectively. The working SO2 adsorption capacity decreased with increasing temperature, reflecting the exothermic nature of the process. The adsorption capacity of these materials was enhanced dramatically in the presence of humidity in the gas mixture. FTIR data before SO2 adsorption and after adsorption and regeneration did not indicate any change in the materials. Nonetheless, the SO2 working capacity decreased in consecutive adsorption/regeneration cycles due to evaporation of impregnated polyamines, rather than actual deactivation. FTIR and (13)C and (15)N CP-MAS NMR of fresh and SO2 adsorbed modified G3 on PME confirmed the formation of a complexation adduct.
Dispersion of Co/CNTs via strong electrostatic adsorption method: Thermal treatment effect

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akbarzadeh, Omid, E-mail: omid.akbarzadeh63@gmail.com; Abdullah, Bawadi, E-mail: bawadi-abdullah@petronas.com.my; Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my

The effect of different thermal treatment temperature on the structure of multi-walled carbon nanotubes (MWCNTs) and Co particle dispersion on CNTs support is studied using Strong electrostatic adsorption (SEA) method. The samples tested by N{sub 2}-adsorption, field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). N{sub 2}-adsorption results showed BET surface area increased using thermal treatment and TEM images showed that increasing the thermal treatment temperature lead to flaky CNTs and defects introduced on the outer surface and Co particle dispersion increased.

Black TiO2 nanobelts/g-C3N4 nanosheets Laminated Heterojunctions with Efficient Visible-Light-Driven Photocatalytic Performance

PubMed Central

Shen, Liyan; Xing, Zipeng; Zou, Jinlong; Li, Zhenzi; Wu, Xiaoyan; Zhang, Yuchi; Zhu, Qi; Yang, Shilin; Zhou, Wei

2017-01-01

Black TiO2 nanobelts/g-C3N4 nanosheets laminated heterojunctions (b-TiO2/g-C3N4) as visible-light-driven photocatalysts are fabricated through a simple hydrothermal-calcination process and an in-situ solid-state chemical reduction approach, followed by the mild thermal treatment (350 °C) in argon atmosphere. The prepared samples are evidently investigated by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, N2 adsorption, and UV-visible diffuse reflectance spectroscopy, respectively. The results show that special laminated heterojunctions are formed between black TiO2 nanobelts and g-C3N4 nanosheets, which favor the separation of photogenerated electron-hole pairs. Furthermore, the presence of Ti3+ and g-C3N4 greatly enhance the absorption of visible light. The resultant b-TiO2/g-C3N4 materials exhibit higher photocatalytic activity than that of g-C3N4, TiO2, b-TiO2 and TiO2/g-C3N4 for degradation of methyl orange (95%) and hydrogen evolution (555.8 μmol h−1 g−1) under visible light irradiation. The apparent reaction rate constant (k) of b-TiO2/g-C3N4 is ~9 times higher than that of pristine TiO2. Therefore, the high-efficient laminated heterojunction composites will have potential applications in fields of environment and energy. PMID:28165021
Effect of Different Activated Carbon as Carrier on the Photocatalytic Activity of Ag-N-ZnO Photocatalyst for Methyl Orange Degradation under Visible Light Irradiation.

PubMed

Chen, Xiaoqing; Wu, Zhansheng; Gao, Zhenzhen; Ye, Bang-Ce

2017-09-05

In order to enhance the photodegradation of methyl orange (MO) by ZnO under visible light irradiation, ZnO nanoparticles co-doped with Ag and N and supported on activated carbon (AC) with different properties were synthesized through the sol-gel method. The prepared photocatalysts were characterized in terms of the structure and properties through X-ray diffraction, N₂ adsorption-desorption, ultraviolet-visible (UV-vis), diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, photoluminescence, and electron spin resonance. The photocatalytic activities of these photocatalysts followed the order: Ag-N-ZnO/ACs > Ag-N-ZnO > N, or Ag single-doped ZnO > commercial ZnO. This result was attributed to the small particle size, large surface area, narrow band gap, and high charge separation of Ag-N-ZnO/ACs. The Ag-N-ZnO/coconut husk activated carbon (Ag-N-ZnO/CHAC) exhibited the highest degradation efficiency of 98.82% for MO under visible light irradiation. This outcome was due to the abundant pore structure of Ag-N-ZnO/CHAC, resulting in stronger adsorption than that of other Ag-N-ZnO/ACs. Moreover, the degradation of MO on photocatalysis followed first order kinetics. The reactive species ·OH and ·O₂ - played more important roles in the photocatalytic degradation of MO over composite photocatalyst. Ag-N-ZnO/CHAC photocatalyst exhibited higher photocatalytic activity than unsupported Ag-N-ZnO after five recycling runs.
CO adsorption on small Au{sub n} (n = 1–4) structures supported on hematite. I. Adsorption on iron terminated α-Fe{sub 2}O{sub 3} (0001) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pabisiak, Tomasz; Kiejna, Adam, E-mail: kiejna@ifd.uni.wroc.pl; Winiarski, Maciej J.

2016-01-28

This is the first of two papers dealing with the adsorption of Au and formation of Au{sub n} nanostructures (n = 1–4) on hematite (0001) surface and adsorption of CO thereon. The stoichiometric Fe-terminated (0001) surface of hematite was investigated using density functional theory in the generalized gradient approximation of Perdew-Burke-Ernzerhof (PBE) form with Hubbard correction U, accounting for strong electron correlations (PBE+U). The structural, energetic, and electronic properties of the systems studied were examined for vertical and flattened configurations of Au{sub n} nanostructures adsorbed on the hematite surfaces. The flattened ones, which can be viewed as bilayer-like structures, weremore » found energetically more favored than vertical ones. For both classes of structures the adsorption binding energy increases with the number of Au atoms in a structure. The adsorption of Au{sub n} induces charge rearrangement at the Au{sub n}/oxide contact which is reflected in work function changes. In most considered cases Au{sub n} adsorption increases the work function. A detailed analysis of the bonding electron charge is presented and the corresponding electron charge rearrangements at the contacts were quantified by a Bader charge analyses. The interaction of a CO molecule with the Au{sub n} nanostructures supported on α-Fe{sub 2}O{sub 3} (0001) and the oxide support was studied. It is found that the CO adsorption binding to the hematite supported Au{sub n} structures is more than twice as strong as to the bare hematite surface. Analysis of the Bader charges on the atoms showed that in each case CO binds to the most positively charged (cationic) atom of the Au{sub n} structure. Changes in the electronic structure of the Au{sub n} species and of the oxide support, and their consequences for the interactions with CO, are discussed.« less
The role of electric field in enhancing separation of gas molecules (H2S, CO2, H2O) on VIB modified g-C3N4 (0 0 1)

NASA Astrophysics Data System (ADS)

Wang, Fang; Li, Penghui; Wei, Shiqian; Guo, Jiaxing; Dan, Meng; Zhou, Ying

2018-07-01

In this study, the first-principles calculations were performed to investigate the adsorption behaviors of gas molecules H2S, CO2 and H2O on Cr, Mo and W modified g-C3N4 (0 0 1) surface. The results show that H2S, CO2 and H2O are physically adsorbed on the pristine g-C3N4, while the adsorption becomes chemisorbed due to the introduction of transition metals which significantly improve the interfacial electron transfer and narrow the band gap of g-C3N4 (0 0 1). Furthermore, it is found that the adsorption behaviors can be greatly influenced by the applied electric field. The adsorption energy is generally arranged in the order of Eads(H2S) > Eads(H2O) > Eads(CO2), and W/g-C3N4 (0 0 1) exhibits the best separation capability. The study could provide a versatile approach to selectively capture and separate the mixed gases in the catalytic reactions by controlling the applied intensity of electric field.
Optimizing the Removal of Rhodamine B in Aqueous Solutions by Reduced Graphene Oxide-Supported Nanoscale Zerovalent Iron (nZVI/rGO) Using an Artificial Neural Network-Genetic Algorithm (ANN-GA)

PubMed Central

Shi, Xuedan; Ruan, Wenqian; Hu, Jiwei; Fan, Mingyi; Cao, Rensheng; Wei, Xionghui

2017-01-01

Rhodamine B (Rh B) is a toxic dye that is harmful to the environment, humans, and animals, and thus the discharge of Rh B wastewater has become a critical concern. In the present study, reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) was used to treat Rh B aqueous solutions. The nZVI/rGO composites were synthesized with the chemical deposition method and were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, N2-sorption, and X-ray photoelectron spectroscopy (XPS) analysis. The effects of several important parameters (initial pH, initial concentration, temperature, and contact time) on the removal of Rh B by nZVI/rGO were optimized by response surface methodology (RSM) and artificial neural network hybridized with genetic algorithm (ANN-GA). The results suggest that the ANN-GA model was more accurate than the RSM model. The predicted optimum value of Rh B removal efficiency (90.0%) was determined using the ANN-GA model, which was compatible with the experimental value (86.4%). Moreover, the Langmuir, Freundlich, and Temkin isotherm equations were applied to fit the adsorption equilibrium data, and the Freundlich isotherm was the most suitable model for describing the process for sorption of Rh B onto the nZVI/rGO composites. The maximum adsorption capacity based on the Langmuir isotherm was 87.72 mg/g. The removal process of Rh B could be completed within 20 min, which was well described by the pseudo-second order kinetic model. PMID:28587196
Lateral ordering of PTCDA on the clean and the oxygen pre-covered Cu(100) surface investigated by scanning tunneling microscopy and low energy electron diffraction.

PubMed

Gärtner, Stefan; Fiedler, Benjamin; Bauer, Oliver; Marele, Antonela; Sokolowski, Moritz M

2014-01-01

We have investigated the adsorption of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) on the clean and on the oxygen pre-covered Cu(100) surface [referred to as (√2 × 2√2)R45° - 2O/Cu(100)] by scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). Our results confirm the (4√2 × 5√2)R45° superstructure of PTCDA/Cu(100) reported by A. Schmidt et al. [J. Phys. Chem. 1995, 99,11770-11779]. However, contrary to Schmidt et al., we have no indication for a dissociation of the PTCDA upon adsorption, and we propose a detailed structure model with two intact PTCDA molecules within the unit cell. Domains of high lateral order are obtained, if the deposition is performed at 400 K. For deposition at room temperature, a significant density of nucleation defects is found pointing to a strong interaction of PTCDA with Cu(100). Quite differently, after preadsorption of oxygen and formation of the (√2 × 2√2)R45° - 2O/Cu(100) superstructure on Cu(100), PTCDA forms an incommensurate monolayer with a structure that corresponds well to that of PTCDA bulk lattice planes.
Investigating water adsorption onto natural mineral dust particles: Linking DRIFTS experiments and BET theory

NASA Astrophysics Data System (ADS)

Joshi, Nitesh; Romanias, Manolis N.; Riffault, Veronique; Thevenet, Frederic

2017-08-01

The adsorption of water molecules on natural mineral dusts was investigated employing in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The natural dust samples originated from North and West Africa, Saudi Arabia and Gobi desert regions. Furthermore, the hygroscopicity of commercially available Arizona Test Dusts (ATDs) and Icelandic volcanic ash were examined. N2 sorption measurements, X-ray fluorescence and diffraction (XRF and XRD), as well as Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analyses were performed to determine the physicochemical properties of the particles. The water adsorption experiments were conducted in an optical cell, at room temperature under the relative humidity (RH) range of 1.9-95%. Results were simulated using a modified three-parameter Brunauer-Emmett-Teller (BET) equation. Water monolayer (ML) was formed in the RH range of 15-25%, while additional water layers were formed at higher RH. Besides, the standard adsorption enthalpies of water onto natural mineral dust samples were determined. A thorough comparison of two commercially available ATD samples indicated that size distribution and/or porosity should play a key role in particle hygroscopicity. Regarding the natural mineral particles, Ca/Si ratios, and to a lesser extent Al/Si, Na/Si, Mg/Si ratios, were found to impact the minimum RH level required for water monolayer formation. These results suggest that the hygroscopic properties of investigated African dusts are quite similar over the whole investigated RH range. Furthermore, one of the major conclusions is that under most atmospheric relative humidity conditions, natural mineral samples are always covered with at least one layer of adsorbed water.
A first-principles study on the interaction of biogas with noble metal (Rh, Pt, Pd) decorated nitrogen doped graphene as a gas sensor: A DFT study

NASA Astrophysics Data System (ADS)

Zhao, Chunjiang; Wu, Huarui

2018-03-01

Density functional theory calculations are carried out to investigate the adsorption characteristics of methane (CH4), carbon dioxide (CO2), hydrogen (H2), hydrogen sulfide (H2S), nitrogen (N2), and oxygen (O2) on the surface of pyridine-like nitrogen doped graphene (PNG) as well as noble metal (Rh, Pt, Pd) decorated PNG to elaborate their potentials as gas sensors. The adsorption intensities of biogas on noble metal (Rh, Pt, Pd) decorated PNG are in the order of O2> H2S> N2> CH4> CO2> H2, which are corresponded to the order of their sensitivity on surface. Compared with biogas adsorption on pristine PNG, there exist higher adsorption ability, higher charge transfer and higher orbital hybridization upon adsorption on noble metal (Rh, Pt, Pd) decorated PNG. Consequently, the noble metal (Rh, Pt, Pd) decorated PNG can transform the existence of CH4, CO2, H2, H2S, N2, and O2 molecules into electrical signal and they could potentially be used as ideal sensors for detection of biogas in ambient situation.
SAPO-34 Membranes for N-2/CH4 separation: Preparation, characterization, separation performance and economic evaluation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, SG; Zong, ZW; Zhou, SJ

2015-08-01

SAPO-34 membranes were synthesized by several routes towards N-2/CH4 separation. Membrane synthesis parameters including water content in the gel, crystallization time, support pore size, and aluminum source were investigated. High performance N-2-selective membranes were obtained on 100-nm-pore alumina tubes by using Al(i-C3H7O)(3) as aluminum source with a crystallization time of 6 h. These membranes separated N-2 from CH, with N-2 permeance as high as 500 GPU with separation selectivity of 8 at 24 degrees C. for a 50/50 N-2/CH4 mixture. Nitrogen and CH, adsorption isotherms were measured on SAPO-34 crystals. The N-2 and CH, heats of adsorption were 11 andmore » 15 kJ/mol, respectively, which lead to a preferential adsorption of CE-H-4 over N-2 in the N-2/CH4 mixture. Despite this, the SAPO-34 membranes were selective for N-2 over CH4 in the mixture because N-2 diffuses much faster than CH4 and differences in diffusivity played a more critical role than the competitive adsorption. Preliminary economic evaluation indicates that the required N-2/CH4 selectivity would be 15 in order to maintain a CH4 loss below 10%. For small nitrogen-contaminated gas wells, our current SAPO-34 membranes have potential to compete with the benchmark technology cryogenic distillation for N-2 rejection. (C) 2015 Elsevier B.V. All rights reserved,« less
Synthesis and characterization of a new microporous cesium silicotitanate (SNL-B) molecular sieve

DOE Office of Scientific and Technical Information (OSTI.GOV)

NYMAN,MAY D.; GU,B.X.; WANG,L.M.

2000-03-20

Ongoing hydrothermal Cs-Ti-Si-O-H{sub 2}O phase investigations has produced several new ternary phases including a novel microporous Cs-silicotitanate molecular sieve, SNL-B with the approximate formula of Cs{sub 3}TiSi{sub 3}O{sub 9.5}{center_dot}3H{sub 2}O. SNL-B is only the second molecular sieve Cs-silicotitanate phase reported to have been synthesized by hydrothermal methods. Crystallites are very small (0.1 x 2 microns) with a blade-like morphology. SNL-B is confirmed to be a 3-dimensional molecular sieve by a variety of characterization techniques (N{sub 2} adsorption, ion exchange, water adsorption/desorption, solid state CP-MAS NMR). SNL-B is able to desorb and adsorb water from its pores while retaining its crystalmore » structure and exchanges Cs cations readily. Additional techniques were used to describe fundamental properties (powder X-ray diffraction, FTIR, {sup 29}Si and {sup 133}/Cs MAS NMR, DTA, SEM/EDS, ion selectivity, and radiation stability). The phase relationships of metastable SNL-B to other hydrothermally synthesized Cs-Ti-Si-O-H{sub 2}O phases are discussed, particularly its relationship to a Cs-silicotitanate analogue of pharmacosiderite, and a novel condensed phase, a polymorph of Cs{sub 2}TiSi{sub 6}O{sub 15}(SNL-A).« less
Kinetic and isotherm studies of bisphenol A adsorption onto orange albedo(Citrus sinensis): Sorption mechanisms based on the main albedo components vitamin C, flavones glycosides and carotenoids.

PubMed

Kamgaing, Theophile; Doungmo, Giscard; Melataguia Tchieno, Francis Merlin; Gouoko Kouonang, Jimmy Julio; Mbadcam, Ketcha Joseph

2017-07-03

Orange albedo and its adsorption capacity towards bisphenol A (BPA) were studied. Adsorption experiments were conducted in batch mode at 25-55°C. Scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and Fourier transform infrared (FTIR) spectroscopy were used to characterise the biosorbent. The effects of various parameters including adsorption time, equilibrium pH, adsorbent dosage and initial adsorbate concentration were investigated. The optimum contact time and pH for the removal of BPA were 60 min and 2, respectively. It was found that the adsorption isotherms best matched the Freundlich model, the adsorption of BPA being multilayer and that of the albedo surface heterogeneous. From the kinetic studies, it was found that the removal of BPA best matched the pseudo-second order kinetic model. An adsorption mechanism based on the albedo surface molecules is proposed and gives a good account of π-π interactions and hydrogen bonding. Orange albedo, with a maximum BPA loading capacity of 82.36 mg g -1 (significantly higher than that of most agricultural residues), is a good candidate for BPA adsorption in aqueous media.
Adsorption kinetics of magnetic biochar derived from peanut hull on removal of Cr (VI) from aqueous solution: Effects of production conditions and particle size.

PubMed

Han, Yitong; Cao, Xi; Ouyang, Xin; Sohi, Saran P; Chen, Jiawei

2016-02-01

Magnetic biochar was made from peanut hull biomass using iron chloride in a simplified aqueous phase approach and pyrolysis at alternative peak temperatures (450-650 °C). Magnetic biochar showed an extreme capacity for adsorption of hexavalent chromium Cr (VI) from aqueous solution, which was 1-2 orders of magnitude higher compared to standard (non-magnetic) biochar from the same feedstock. Adsorption increased with pyrolysis temperature peaking at 77,542 mg kg(-1) in the sample pyrolysed at 650 °C. In contrast to magnetic biochar, the low adsorption capacity of standard biochar decreased with increasing pyrolysis temperature. The fine particle size of magnetic biochar and low aqueous pH were also important for adsorption. Surfaces of products from batch adsorption experiments were characterized by scanning electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction, X-ray photoelectron spectroscopy and vibrating sample magnetometer. This revealed that γ-Fe2O3 was crucial to the properties (adsorbance and magnetism) of magnetic biochar. The removal mechanism was the Cr (VI) electrostatic attracted on protonated -OH on γ-Fe2O3 surface and it could be desorbed by alkaline solution. Findings suggest that pyrolysis has potential to create effective, magnetically recoverable adsorbents relevant to environmental application. Copyright © 2015 Elsevier Ltd. All rights reserved.
Perfluoropentacene adsorption on Cu(110)

NASA Astrophysics Data System (ADS)

Gall, J.; Zhang, L.; Fu, X.; Zeppenfeld, P.; Sun, L. D.

2017-09-01

The adsorption of perfluoropentacene (PFP) on the Cu(110) surface has been investigated using reflectance difference spectroscopy (RDS), low-energy electron diffraction, and low-temperature scanning tunneling microscopy. The PFP molecules within the first monolayer align their long molecular axis exclusively oriented along the [001] azimuthal direction of the Cu substrate. In comparison with the adsorption behavior of pentacene on the same surface, a strong effect of the fluorination regarding the molecular orientation and the intermolecular and molecule-substrate interactions was identified. Furthermore, a two-dimensional gas-solid phase transition accompanied by a reversible azimuthal rotation of the PFP molecules was observed at the beginning of the second monolayer growth. The change of the optical anisotropy associated with this reorientation was used to explore the two-dimensional (2D) condensation as a function of coverage and temperature by RDS, and the 2D heat of condensation in the PFP bilayer on Cu(110) was determined to be 105 meV.
First-principles calculation of adsorption of shale gas on CaCO3 (100) surfaces.

PubMed

Luo, Qiang; Pan, Yikun; Guo, Ping; Wang, Zhouhua; Wei, Na; Sun, Pengfei; Liu, Yuxiao

2017-06-16

To demonstrate the adsorption strength of shale gas to calcium carbonate in shale matrix, the adsorption of shale gas on CaCO3 (100) surfaces was studied using the first-principles method, which is based on the density functional theory (DFT). The structures and electronic properties of CH4, C2H6, CO2 and N2 molecules were calculated by the generalized gradient approximation (GGA), for a coverage of 1 monolayer (ML). Under the same conditions, the density of states (DOS) of CaCO3 (100) surfaces before and after the adsorption of shale gas molecules at high-symmetry adsorption sites were compared. The results showed that the adsorption energies of CH4, C2H6, CO2 and N2 on CaCO3 (100) surfaces were between 0.2683 eV and -0.7388 eV. When a CH4 molecule was adsorbed at a hollow site and its 2 hydrogen atoms were parallel to the long diagonal (H3) on the CaCO3 (100) surface, it had the most stable adsorption, and the adsorption energy was only -0.4160 eV. The change of adsorption energy of CH4 was no more than 0.0535 eV. Compared with the DOS distribution of CH4 before adsorption, it shifted to the left overall after adsorption. At the same time, the partial density of states (PDOS) curves of CaCO3 (100) surfaces before and after adsorption basically overlapped. This work showed that the adsorption effect of shale gas on calcium carbonate is very weak, and the adsorption is physisorption at the molecular level.
Sono-assisted adsorption of a textile dye on milk vetch-derived charcoal supported by silica nanopowder.

PubMed

Jorfi, Sahand; Darvishi Cheshmeh Soltani, Reza; Ahmadi, Mehdi; Khataee, Alireza; Safari, Mahdi

2017-02-01

This study was performed to assess the efficiency of silica nanopowder (SNP)/milk vetch-derived charcoal (MVDC) nanocomposite coupled with the ultrasonic irradiation named sono-adsorption process for treating water-contained Basic Red 46 (BR46) dye. Field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and Fourier transform infrared spectroscopy (FT-IR) were performed for the characterization of as-prepared adsorbent. The sono-assisted adsorption process was optimized using response surface optimization on the basis of central composite design by the application of quadratic model. Accordingly, the color removal can be retained more than 93% by an initial BR46 concentration of 8 mg/L, sonication time of 31 min, adsorbent dosage of 1.2 g/L and initial pH of 9. The pseudo-second order kinetic model described the sono-assisted adsorption of BR46 reasonably well (R 2 > 0.99). The intra-particular diffusion kinetic model pointed out that the sono-assisted adsorption of BR46 onto SNP/MVDC nanocomposite was diffusion controlled as well as that ultrasonication enhanced the diffusion rate. Copyright © 2016 Elsevier Ltd. All rights reserved.
Cu-BTC/aminated graphite oxide composites as high-efficiency CO2 capture media.

PubMed

Policicchio, Alfonso; Zhao, Yunxia; Zhong, Qin; Agostino, Raffaele G; Bandosz, Teresa J

2014-01-08

CO2 adsorption isotherms on Cu-BTC/aminated graphite oxide composites were measured in the pressure range up to 1.5 MPa at three different temperatures close to ambient. Adsorption capacity, isosteric heat of adsorption, and regenerability were investigated. They are considered as significant factors determining the practical application of materials for CO2 capture. The results indicate a significant improvement in the performance of the composites as CO2 adsorbents in comparison with the parent Cu-BTC MOF. Among all samples analyzed, the composite of Cu-BTC and modified graphite oxide with the highest N content (MOF/GO-U3) is the best performing sample. On its surface 13.41 mmol/g CO2 was adsorbed at room temperature and 1.5 MPa. A high selectivity for CO2 adsorption over that of CH4 was found. The selectivities for CO2 adsorption over N2 are governed by the properties of the MOF phase. A relatively low heat of CO2 adsorption and the high degree of surface homogeneity cause that the composites can be fully regenerated and used in multicycle adsorption with the minimum energy demand.
Permeable reactive barrier of coarse sand-supported zero valent iron for the removal of 2,4-dichlorophenol in groundwater.

PubMed

Gao, Weichun; Zhang, Yongxiang; Zhang, Xiaoye; Duan, Zhilong; Wang, Youhao; Qin, Can; Hu, Xiao; Wang, Hao; Chang, Shan

2015-11-01

In this study, coarse sand-supported zero valent iron (ZVI) composite was synthesized by adding sodium alginate to immobilize. Composite was detected by scanning electron microscope (SEM), X-ray diffraction (XRD), and X-ray fluorescence (XRF). SEM results showed that composite had core-shell structure and a wide porous distribution pattern. The synthesized composite was used for degradation of 2,4-dichlorophenol (2,4-DCP) contamination in groundwater. Experimental results demonstrated that degradation mechanism of 2,4-DCP using coarse sand-supported ZVI included adsorption, desorption, and dechlorination. 2,4-DCP adsorption was described as pseudo-second-order kinetic model. It was concluded that dechlorination was the key reaction pathway, ZVI and hydrogen are prime reductants in dechlorination of 2,4-DCP using ZVI.
ZnS nanostructured thin-films deposited by successive ionic layer adsorption and reaction

NASA Astrophysics Data System (ADS)

Deshmukh, S. G.; Jariwala, Akshay; Agarwal, Anubha; Patel, Chetna; Panchal, A. K.; Kheraj, Vipul

2016-04-01

ZnS thin films were grown on glass substrate using successive ionic layer adsorption and reaction (SILAR) technique at room temperature. Aqueous solutions of ZnCl2 and Na2S were used as precursors. The X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Raman spectroscopy and optical absorption measurements were applied to study the structural, surface morphology and optical properties of as-deposited ZnS thin films. The X-ray diffraction profiles revealed that ZnS thin films consist of crystalline grains with cubic phase. Spherical nano grains of random size and well covered on the glass substrate were observed from FESEM. The average grain size were found to be 77 nm, 100 nm and 124 nm for 20 cycles, 40 cycles and 60 cycles samples respectively. For 60 cycle sample, Raman spectra show two prominent peaks at 554 cm-1 and 1094 cm-1. The optical band gap values were found to be 3.76 eV, 3.72 eV and 3.67 eV for 20 cycle, 40 cycle and 60 cycle samples respectively.
Calcinated tea and cellulose composite films and its dielectric and lead adsorption properties.

PubMed

Jayaramudu, Tippabattini; Varaprasad, Kokkarachedu; Kim, Hyun Chan; Kafy, Abdullahil; Kim, Jung Woong; Kim, Jaehwan

2017-09-01

In this paper, calcinated tea and cellulose composite (CTCC) films were fabricated via solution casting method. Chemical structure, morphology, crystallinity and thermal stability of the fabricated films were characterized by using Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction and thermogravimetric analysis. The effect of calcinated tea loading on the properties of the prepared CTCC films was studied. The results suggest that the prepared CTCC films show higher mechanical properties, thermal stability and dielectric constant than the neat cellulose film. In addition, the CTCC films adsorb Pb 2+ ions and its adsorption performance depends on the calcinated tea content and pH level. The CTCC films are useful for sensors, flexible capacitor as well as lead adsorption applications. Copyright © 2017 Elsevier Ltd. All rights reserved.
Near-Ideal Xylene Selectivity in Adaptive Molecular Pillar[ n]arene Crystals.

PubMed

Jie, Kecheng; Liu, Ming; Zhou, Yujuan; Little, Marc A; Pulido, Angeles; Chong, Samantha Y; Stephenson, Andrew; Hughes, Ashlea R; Sakakibara, Fumiyasu; Ogoshi, Tomoki; Blanc, Frédéric; Day, Graeme M; Huang, Feihe; Cooper, Andrew I

2018-06-06

The energy-efficient separation of alkylaromatic compounds is a major industrial sustainability challenge. The use of selectively porous extended frameworks, such as zeolites or metal-organic frameworks, is one solution to this problem. Here, we studied a flexible molecular material, perethylated pillar[ n]arene crystals ( n = 5, 6), which can be used to separate C8 alkylaromatic compounds. Pillar[6]arene is shown to separate para-xylene from its structural isomers, meta-xylene and ortho-xylene, with 90% specificity in the solid state. Selectivity is an intrinsic property of the pillar[6]arene host, with the flexible pillar[6]arene cavities adapting during adsorption thus enabling preferential adsorption of para-xylene in the solid state. The flexibility of pillar[6]arene as a solid sorbent is rationalized using molecular conformer searches and crystal structure prediction (CSP) combined with comprehensive characterization by X-ray diffraction and 13 C solid-state NMR spectroscopy. The CSP study, which takes into account the structural variability of pillar[6]arene, breaks new ground in its own right and showcases the feasibility of applying CSP methods to understand and ultimately to predict the behavior of soft, adaptive molecular crystals.

Predicting CH4 adsorption capacity of microporous carbon using N2 isotherm and a new analytical model

USGS Publications Warehouse

Sun, Jielun; Chen, S.; Rostam-Abadi, M.; Rood, M.J.

1998-01-01

A new analytical pore size distribution (PSD) model was developed to predict CH4 adsorption (storage) capacity of microporous adsorbent carbon. The model is based on a 3-D adsorption isotherm equation, derived from statistical mechanical principles. Least squares error minimization is used to solve the PSD without any pre-assumed distribution function. In comparison with several well-accepted analytical methods from the literature, this 3-D model offers relatively realistic PSD description for select reference materials, including activated carbon fibers. N2 and CH4 adsorption data were correlated using the 3-D model for commercial carbons BPL and AX-21. Predicted CH4 adsorption isotherms, based on N2 adsorption at 77 K, were in reasonable agreement with the experimental CH4 isotherms. Modeling results indicate that not all the pores contribute the same percentage Vm/Vs for CH4 storage due to different adsorbed CH4 densities. Pores near 8-9 A?? shows higher Vm/Vs on the equivalent volume basis than does larger pores.
A grand canonical Monte Carlo study of SO2 capture using functionalized bilayer graphene nanoribbons.

PubMed

Maurya, Manish; Singh, Jayant K

2017-01-28

Grand canonical Monte Carlo (GCMC) simulation is used to study the adsorption of pure SO 2 using a functionalized bilayer graphene nanoribbon (GNR) at 303 K. The functional groups considered in this work are OH, COOH, NH 2 , NO 2 , and CH 3 . The mole percent of functionalization considered in this work is in the range of 3.125%-6.25%. GCMC simulation is further used to study the selective adsorption of SO 2 from binary and ternary mixtures of SO 2 , CO 2 , and N 2 , of variable composition using the functionalized bilayer graphene nanoribbon at 303 K. This study shows that the adsorption and selectivity of SO 2 increase after the functionalization of the nanoribbon compared to the hydrogen terminated nanoribbon. The order of adsorption capacity and selectivity of the functionalized nanoribbon is found to follow the order COOH > NO 2 > NH 2 > CH 3 > OH > H. The selectivity of SO 2 is found to be maximum at a pressure less than 0.2 bar. Furthermore, SO 2 selectivity and adsorption capacity decrease with increase in the molar ratio of SO 2 /N 2 mixture from 1:1 to 1:9. In the case of ternary mixture of SO 2 , CO 2 , N 2 , having compositions of 0.05, 0.15, 0.8, the selectivity of SO 2 over N 2 is higher than that of CO 2 over N 2 . The maximum selectivity of SO 2 over CO 2 is observed for the COOH functionalized GNR followed by NO 2 and other functionalized GNRs.
Research of CO2 and N2 Adsorption Behavior in K-Illite Slit Pores by GCMC Method

PubMed Central

Chen, Guohui; Lu, Shuangfang; Zhang, Junfang; Xue, Qingzhong; Han, Tongcheng; Xue, Haitao; Tian, Shansi; Li, Jinbu; Xu, Chenxi; Pervukhina, Marina; Clennell, Ben

2016-01-01

Understanding the adsorption mechanisms of CO2 and N2 in illite, one of the main components of clay in shale, is important to improve the precision of the shale gas exploration and development. We investigated the adsorption mechanisms of CO2 and N2 in K-illite with varying pore sizes at the temperature of 333, 363 and 393 K over a broad range of pressures up to 30 MPa using the grand canonical Monte Carlo (GCMC) simulation method. The simulation system is proved to be reasonable and suitable through the discussion of the impact of cation dynamics and pore wall thickness. The simulation results of the excess adsorption amount, expressed per unit surface area of illite, is in general consistency with published experimental results. It is found that the sorption potential overlaps in micropores, leading to a decreasing excess adsorption amount with the increase of pore size at low pressure, and a reverse trend at high pressure. The excess adsorption amount increases with increasing pressure to a maximum and then decreases with further increase in the pressure, and the decreasing amount is found to increase with the increasing pore size. For pores with size greater larger than 2 nm, the overlap effect disappears. PMID:27897232
Zero-valent iron particles embedded on the mesoporous silica-carbon for chromium (VI) removal from aqueous solution

NASA Astrophysics Data System (ADS)

Xiong, Kun; Gao, Yuan; Zhou, Lin; Zhang, Xianming

2016-09-01

Nanoscale zero-valent iron (nZVI) particles were embedded on the walls of mesoporous silica-carbon (MSC) under the conditions of high-temperature carbonization and reduction and used to remove chromium (VI) from aqueous solution. The structure and textural properties of nZVI-MSC were characterized by the powder X-ray diffraction, transmission electron microscopy and N2 adsorption and desorption. The results show that nZVI-MSC has highly ordered mesoporous structure and large surface area, indistinguishable with that of MSC. Compared with the support MSC and iron particles supported on the activated carbon (nZVI/AC), nZVI-MSC exhibited much higher Cr(VI) removal efficiency with about 98 %. The removal process obeys a pseudo first-order model. Such excellent performance of nZVI-MSC could be ascribed to the large surface and iron particles embedded on the walls of the MSC, forming an intimate contact with the MSC. It is proposed that this feature might create certain micro-electrode on the interface of iron particles and MSC, which prevented the formation of metal oxide on the surface and provided fresh Fe surface for Cr(VI) removal.
Tuning the Formations of Metal-Organic Frameworks by Modification of Ratio of Reactant, Acidity of Reaction System, and Use of a Secondary Ligand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Q; Xie, YB; Li, JR

2012-01-01

Four porous coordination networks (PCNs), {[Zn3O(H2O)(3)(adc)(3)]center dot 2(C2H6NH2)center dot 2(DMF)center dot 3(H2O)}(n) (PCN-131), Zn-2(DMA)(2)(adc)(2)]center dot 2(DMA)}(n) (PCN-132), {[Zn3O(DMF)(adc)(3)(4,4'-bpy)]center dot 2(C2H6NH2)center dot S}(n) (PCN-131'), and {[Zn(adc)(4,4'-bpy)(0.5)]center dot S}(n) (PCN-132'), have been synthesized by the assembly of anthrancene-9,10-dicarboxylic acid (H(2)adc) with Zn(II) under different reaction conditions, including modifications of reactant ratio, acidity variations, and the use of a secondary ligand. Single-crystal X-ray diffraction studies reveal that PCN-131, obtained from the dimethylformamide (DMF) solution under acid condition, has a three-dimentional (3D) framework structure with one-dimensional (1D) honeycomb channels. PCN-132 isolated from dimethylacetamide (DMA) solution without adding acid in synthesis is a two-dimensional (2D)more » layer compound. By employing 4,4'-bipyridyl (4,4'-bpy) as a secondary ligand, PCN-131' and PCN-132' were synchronously synthesized as a mixture outcome with more PCN-131' than PCN-132'. In PCN-131', 4,4'-bpy acting as a secondary ligand is arranged inside the honeycomb channel of the 3D PCN-131, resulting in an effective improvement of thermal stability of the network, while in PCN-132', 4,4'-bpy ligands link 2D layers of PCN-132 to form a pillared-layer 3D framework Gas adsorption has been performed for selected materials. The results show that the framework of PCN-131 is thermally unstable after removing the solvent molecules coordinated to their metal sites. While PCN-131' is stable for gas uptake, with an evaluated Langmuir surface area of 199.04 m(2) g(-1), it shows a selective adsorption of CO2 over CH4.« less
Molecular simulation of CH4/CO2/H2O competitive adsorption on low rank coal vitrinite.

PubMed

Yu, Song; Bo, Jiang; Wu, Li

2017-07-21

The competitive adsorptions of CH 4 /CO 2 /H 2 O on coal vitrinite (DV-8, C 214 H 180 O 24 N 2 ) were computed based on density function theory (DFT) and grand canonical Monte Carlo (GCMC). The adsorption process reaches the saturation state after adsorbing 17 CH 4 s, 22 CO 2 s, and 35 H 2 Os per C 214 H 180 O 24 N 2 respectively. The optimal configurations of CH 4 -vitrinite, CO 2 -vitrinite, and H 2 O-vitrinite respectively manifest as aromatic 1 /T 2 /rT 3 (1 adsorption location, 2 adsorption sites and T here represents sites above the carbon atom and the heteroatom, 3 adsorption orientation and rT here means the orientations of three hydrogen atoms pointing to vitrinite), aromatic/T/v (v represents the orientations perpendicular to the plane of vitrinite), and aromatic/rV/T (rV represents an oxygen atom pointing to the vitrinite surface). The GCMC results show that high temperature is not conducive to the vitrinite's adsorption of adsorbates and the adsorption capacity order is H 2 O > CO 2 > CH 4 (263-363 K) in the one-component, binary, and ternary adsorbate systems. The optimal configurations of vitrinite are similar to graphite/graphene, while ΔE is significantly lower than graphite/graphene. Simulation data are in good agreement with the experimental results.
Magnetic hydroxyapatite nanoparticles: an efficient adsorbent for the separation and removal of nitrate and nitrite ions from environmental samples.

PubMed

Ghasemi, Ensieh; Sillanpää, Mika

2015-01-01

A novel type of magnetic nanosorbent, hydroxyapatite-coated Fe2O3 nanoparticles was synthesized and used for the adsorption and removal of nitrite and nitrate ions from environmental samples. The properties of synthesized magnetic nanoparticles were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray powder diffraction. After the adsorption process, the separation of γ-Fe2O3@hydroxyapatite nanoparticles from the aqueous solution was simply achieved by applying an external magnetic field. The effects of different variables on the adsorption efficiency were studied simultaneously using an experimental design. The variables of interest were amount of magnetic hydroxyapatite nanoparticles, sample volume, pH, stirring rate, adsorption time, and temperature. The experimental parameters were optimized using a Box-Behnken design and response surface methodology after a Plackett-Burman screening design. Under the optimum conditions, the adsorption efficiencies of magnetic hydroxyapatite nanoparticles adsorbents toward NO3(-) and NO2(-) ions (100 mg/L) were in the range of 93-101%. The results revealed that the magnetic hydroxyapatite nanoparticles adsorbent could be used as a simple, efficient, and cost-effective material for the removal of nitrate and nitrite ions from environmental water and soil samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Adsorption of selected endocrine disrupting compounds and pharmaceuticals on activated biochars.

PubMed

Jung, Chanil; Park, Junyeong; Lim, Kwang Hun; Park, Sunkyu; Heo, Jiyong; Her, Namguk; Oh, Jeill; Yun, Soyoung; Yoon, Yeomin

2013-12-15

Chemically activated biochar produced under oxygenated (O-biochar) and oxygen-free (N-biochar) conditions were characterized and the adsorption of endocrine disrupting compounds (EDCs): bisphenol A (BPA), atrazine (ATR), 17 α-ethinylestradiol (EE2), and pharmaceutical active compounds (PhACs); sulfamethoxazole (SMX), carbamazepine (CBM), diclofenac (DCF), ibuprofen (IBP) on both biochars and commercialized powdered activated carbon (PAC) were investigated. Characteristic analysis of adsorbents by solid-state nuclear magnetic resonance (NMR) was conducted to determine better understanding about the EDCs/PhACs adsorption. N-biochar consisted of higher polarity moieties with more alkyl (0-45 ppm), methoxyl (45-63 ppm), O-alkyl (63-108 ppm), and carboxyl carbon (165-187 ppm) content than other adsorbents, while aromaticity of O-biochar was higher than that of N-biochar. O-biochar was composed mostly of aromatic moieties, with low H/C and O/C ratios compared to the highly polarized N-biochar that contained diverse polar functional groups. The higher surface area and pore volume of N-biochar resulted in higher adsorption capacity toward EDCs/PhACs along with atomic-level molecular structural property than O-biochar and PAC. N-biochar had a highest adsorption capacity of all chemicals, suggesting that N-biochar derived from loblolly pine chip is a promising sorbent for agricultural and environmental applications. The adsorption of pH-sensitive dissociable SMX, DCF, IBP, and BPA varied and the order of adsorption capacity was correlated with the hydrophobicity (Kow) of adsorbates throughout the all adsorbents, whereas adsorption of non-ionizable CBM, ATR, and EE2 in varied pH allowed adsorbents to interact with hydrophobic property of adsorbates steadily throughout the study. Copyright © 2013 Elsevier B.V. All rights reserved.
Lithium and sodium adsorption properties of two-dimensional aluminum nitride

NASA Astrophysics Data System (ADS)

Sengupta, Amretashis

2018-09-01

In this work the lithiation and sodiation properties of 2-dimensional (2D) AlN sheets are studied from density functional theory (DFT) simulations. 2D AlN showed theoretical specific capacity of 500.8 and 385.3 mA h g-1, maximum open circuit voltage of 1.49 and 1.86 V and diffusion barriers 0.40 and 0.15 eV, for Li and Na adsorption respectively. The calculations show 2D AlN as a possible alternative as anode material in Li-ion and Na-ion batteries. Further the high specific capacity and small diffusion barriers for Na atoms can make 2D AlN useful in supercapacitors. The change in carrier transport properties due to Li/Na adsorption on monolayer AlN can also be useful in chemical/bio-sensors and nanoelectronics devices.
Tailoring pore properties of MCM-48 silica for selective adsorption of CO2.

PubMed

Kim, Sangil; Ida, Junichi; Guliants, Vadim V; Lin, Jerry Y S

2005-04-07

Four different types of amine-attached MCM-48 silicas were prepared and investigated for CO(2) separation from N(2). Monomeric and polymeric hindered and unhindered amines were attached to the pore surface of the MCM-48 silica and characterized with respect to their CO(2) sorption properties. The pore structures and amino group content in these modified silicas were investigated by XRD, FT-IR, TGA, N(2) adsorption/desorption at 77 K and CHN/Si analysis, which confirmed that in all cases the amino groups were attached to the pore surface of MCM-48 at 1.5-5.2 mmol/g. The N(2) adsorption/desorption analysis showed a considerable decrease of the pore volume and surface area for the MCM-48 silica containing a polymeric amine (e.g., polyethyleneimine). The CO(2) adsorption rates and capacities of the amine-attached MCM-48 samples were studied employing a sorption microbalance. The results obtained indicated that in addition to the concentration of surface-attached amino groups, specific interactions between CO(2) and the surface amino groups, and the resultant pore structure after amine group attachment have a significant impact on CO(2) adsorption properties of these promising adsorbent materials.
A Multifaceted Study of Methane Adsorption in Metal-Organic Frameworks by Using Three Complementary Techniques.

PubMed

Zhang, Yue; Lucier, Bryan E G; Fischer, Michael; Gan, Zhehong; Boyle, Paul D; Desveaux, Bligh; Huang, Yining

2018-03-25

Methane is a promising clean and inexpensive energy alternative to traditional fossil fuels, however, its low volumetric energy density at ambient conditions has made devising viable, efficient methane storage systems very challenging. Metal-organic frameworks (MOFs) are promising candidates for methane storage. In order to improve the methane storage capacity of MOFs, a better understanding of the methane adsorption, mobility, and host-guest interactions within MOFs must be realized. In this study, methane adsorption within α-Mg 3 (HCO 2 ) 6 , α-Zn 3 (HCO 2 ) 6 , SIFSIX-3-Zn, and M-MOF-74 (M=Mg, Zn, Ni, Co) has been comprehensively examined. Single-crystal X-ray diffraction (SCXRD) experiments and DFT calculations of the methane adsorption locations were performed for α-Mg 3 (HCO 2 ) 6 , α-Zn 3 (HCO 2 ) 6 , and SIFSIX-3-Zn. The SCXRD thermal ellipsoids indicate that methane possesses significant mobility at the adsorption sites in each system. 2 H solid-state NMR (SSNMR) experiments targeting deuterated CH 3 D guests in α-Mg 3 (HCO 2 ) 6 , α-Zn 3 (HCO 2 ) 6 , SIFSIX-3-Zn, and MOF-74 yield an interesting finding: the 2 H SSNMR spectra of methane adsorbed in these MOFs are significantly influenced by the chemical shielding anisotropy in addition to the quadrupolar interaction. The chemical shielding anisotropy contribution is likely due mainly to the nuclear independent chemical shift effect on the MOF surfaces. In addition, the 2 H SSNMR results and DFT calculations strongly indicate that the methane adsorption strength is linked to the MOF pore size and that dispersive forces are responsible for the methane adsorption in these systems. This work lays a very promising foundation for future studies of methane adsorption locations and dynamics within adsorbent MOF materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Preparation of RHA-silica/graphene oxide nanocomposite for removal of nickel ions from water

NASA Astrophysics Data System (ADS)

Tien, Tran Thi Thuy; Tu, Tran Hoang; Thao, Huynh Nguyen Phuong; Hieu, Nguyen Huu

2017-09-01

In this study, silica was synthesized from rice husk ash (RHA-SiO2) by precipitation method. Graphene oxide (GO) was prepared by modified Hummers method. RHA-SiO2/GO nanocomposite was fabricated by in-situ one-step method using 3-Aminopropyltriethoxysilane (APS) as a coupling agent. The nanocomposite was characterized by using X-ray Fluorescence, X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and Brunauer-Emmett-Teller (BET) specific surface area. The adsorption of RHA-SiO2/GO for Ni2+ ions from water was investigated and compared with the precursors. Ultraviolet-visible (UV-Vis) spectroscopy was used to quantify the amount of the initial and the residual Ni2+ concentration. The maximum adsorption capacity of the nanocomposite for Ni2+ calculated from Langmuir isotherm model, which was 256.4 mg/g. In addition, the adsorption data were well-fitted to the pseudo-second-order kinetic equation. Accordingly, this study demonstrated that RHA-SiO2/GO could be used as a highly efficient adsorbent for removal Ni2+ ions from aqueous solution.
Chemical surface modification of polycrystalline platinum thin-films to promote preferential chemisorption of n-hexane, piperidine, and cyclohexane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas, V.; Schwank, J.; Gland, J.

In this study, hard/soft Lewis acid-base (HSAB) principles are used to modify a thin-polycrystalline platinum film to promote preferential chemisorption of molecules such as piperidine, n-hexane, and cyclohexane. Specifically, the particle size and electron density distribution of the platinum surface is modified using thermal treatment and co-adsorption of electro-positive and negative species. These studies are conducted in an ultra-high vacuum chamber. The platinum surface is characterized, before and after modification protocols, using a variety of in-situ and ex-situ techniques. These include temperature programmed desorption (TPD), both resistance change and work function measurements, and both X-ray photoelectron spectroscopy and diffraction.
Surface interaction of H2S, SO2, and SO3 on fullerene-like gallium nitride (GaN) nanostructure semiconductor

NASA Astrophysics Data System (ADS)

Salimifard, M.; Rad, A. Shokuhi; Mahanpoor, K.

2017-10-01

Density functional theory (DFT) using MPW1PW91 and B3LYP hybrid functionals was utilized for quantum-based investigations of three major sulfur compounds (H2S, SO2, and SO3) adsorption onto fullerene-like Ga12N12 nanocluster. All chemicals showed high chemisorption with the order of SO3>SO2>>H2S. Results of charge analysis showed that during adsorption, transfer of charge is from H2S to nanocluster while reverse direction of charge transfer is found for SO2 and SO3 molecules. Partial dissociation is found for adsorbates especially for SO2 and SO3 molecules. Results of thermochemistry analysis show negative values for enthalpy and Gibbs free energy of adsorption, confirming exothermic spontaneous process. Analysis of frontier molecular orbital (FMO) showed important role of orbital hybridizing towards formation of new bonds upon adsorption. As a result, we introduce Ga12N12 nanocluster as a strong adsorbent for sulfur compounds.
Importance of Micropore-Mesopore Interfaces in Carbon Dioxide Capture by Carbon-Based Materials.

PubMed

Durá, Gema; Budarin, Vitaliy L; Castro-Osma, José A; Shuttleworth, Peter S; Quek, Sophie C Z; Clark, James H; North, Michael

2016-08-01

Mesoporous carbonaceous materials (Starbons®) derived from low-value/waste bio-resources separate CO2 from CO2 /N2 mixtures. Compared to Norit activated charcoal (AC), Starbons® have much lower microporosities (8-32 % versus 73 %) yet adsorb up to 65 % more CO2 . The presence of interconnected micropores and mesopores is responsible for the enhanced CO2 adsorption. The Starbons® also showed three-four times higher selectivity for CO2 adsorption rather than N2 adsorption compared to AC. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
A Diaminopropane-Appended Metal–Organic Framework Enabling Efficient CO 2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milner, Phillip J.; Siegelman, Rebecca L.; Forse, Alexander C.

A new diamine-functionalized metal–organic framework comprised of 2,2-dimethyl-1,3-diaminopropane (dmpn) appended to the Mg 2+ sites lining the channels of Mg 2(dobpdc) (dobpdc4– = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) is characterized for the removal of CO 2 from the flue gas emissions of coal-fired power plants. Unique to members of this promising class of adsorbents, dmpn–Mg2(dobpdc) displays facile step-shaped adsorption of CO 2 from coal flue gas at 40 °C and near complete CO 2 desorption upon heating to 100 °C, enabling a high CO 2 working capacity (2.42 mmol/g, 9.1 wt %) with a modest 60 °C temperature swing. Evaluation of the thermodynamic parametersmore » of adsorption for dmpn–Mg 2(dobpdc) suggests that the narrow temperature swing of its CO 2 adsorption steps is due to the high magnitude of its differential enthalpy of adsorption (Δhads = -73 ± 1 kJ/mol), with a larger than expected entropic penalty for CO 2 adsorption (Δsads = -204 ± 4 J/mol·K) positioning the step in the optimal range for carbon capture from coal flue gas. In addition, thermogravimetric analysis and breakthrough experiments indicate that, in contrast to many adsorbents, dmpn–Mg 2(dobpdc) captures CO 2 effectively in the presence of water and can be subjected to 1000 humid adsorption/desorption cycles with minimal degradation. Solid-state 13C NMR spectra and single-crystal X-ray diffraction structures of the Zn analogue reveal that this material adsorbs CO 2 via formation of both ammonium carbamates and carbamic acid pairs, the latter of which are crystallographically verified for the first time in a porous material. Taken together, these properties render dmpn–Mg 2(dobpdc) one of the most promising adsorbents for carbon capture applications.« less
A Diaminopropane-Appended Metal-Organic Framework Enabling Efficient CO2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism.

PubMed

Milner, Phillip J; Siegelman, Rebecca L; Forse, Alexander C; Gonzalez, Miguel I; Runčevski, Tomče; Martell, Jeffrey D; Reimer, Jeffrey A; Long, Jeffrey R

2017-09-27

A new diamine-functionalized metal-organic framework comprised of 2,2-dimethyl-1,3-diaminopropane (dmpn) appended to the Mg 2+ sites lining the channels of Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) is characterized for the removal of CO 2 from the flue gas emissions of coal-fired power plants. Unique to members of this promising class of adsorbents, dmpn-Mg 2 (dobpdc) displays facile step-shaped adsorption of CO 2 from coal flue gas at 40 °C and near complete CO 2 desorption upon heating to 100 °C, enabling a high CO 2 working capacity (2.42 mmol/g, 9.1 wt %) with a modest 60 °C temperature swing. Evaluation of the thermodynamic parameters of adsorption for dmpn-Mg 2 (dobpdc) suggests that the narrow temperature swing of its CO 2 adsorption steps is due to the high magnitude of its differential enthalpy of adsorption (Δh ads = -73 ± 1 kJ/mol), with a larger than expected entropic penalty for CO 2 adsorption (Δs ads = -204 ± 4 J/mol·K) positioning the step in the optimal range for carbon capture from coal flue gas. In addition, thermogravimetric analysis and breakthrough experiments indicate that, in contrast to many adsorbents, dmpn-Mg 2 (dobpdc) captures CO 2 effectively in the presence of water and can be subjected to 1000 humid adsorption/desorption cycles with minimal degradation. Solid-state 13 C NMR spectra and single-crystal X-ray diffraction structures of the Zn analogue reveal that this material adsorbs CO 2 via formation of both ammonium carbamates and carbamic acid pairs, the latter of which are crystallographically verified for the first time in a porous material. Taken together, these properties render dmpn-Mg 2 (dobpdc) one of the most promising adsorbents for carbon capture applications.
Synthesis, Structural, and Adsorption Properties and Thermal Stability of Nanohydroxyapatite/Polysaccharide Composites.

PubMed

Skwarek, Ewa; Goncharuk, Olena; Sternik, Dariusz; Janusz, Wladyslaw; Gdula, Karolina; Gun'ko, Vladimir M

2017-12-01

A series of composites based on nanohydroxyapatite (nHAp) and natural polysaccharides (PS) (nHAp/agar, nHAp/chitosan, nHAp/pectin FB300, nHAp/pectin APA103, nHAp/sodium alginate) was synthesized by liquid-phase two-step method and characterized using nitrogen adsorption-desorption, DSC, TG, FTIR spectroscopy, and SEM. The analysis of nitrogen adsorption-desorption data shows that composites with a nHAp: PS ratio of 4:1 exhibit a sufficiently high specific surface area from 49 to 82 m 2 /g. The incremental pore size distributions indicate mainly mesoporosity. The composites with the component ratio 1:1 preferably form a film-like structure, and the value of S BET varies from 0.3 to 43 m 2 /g depending on the nature of a polysaccharide. Adsorption of Sr(II) on the composites from the aqueous solutions has been studied. The thermal properties of polysaccharides alone and in nHAp/PS show the influence of nHAp, since there is a shift of characteristic DSC and DTG peaks. FTIR spectroscopy data confirm the presence of functional groups typical for nHAp as well as polysaccharides in composites. Structure and morphological characteristics of the composites are strongly dependent on the ratio of components, since nHAp/PS at 4:1 have relatively large S BET values and a good ability to adsorb metal ions. The comparison of the adsorption capacity with respect to Sr(II) of nHAp, polysaccharides, and composites shows that it of the latter is higher than that of nHAp (per 1 m 2 of surface).
Enhanced reactive adsorption of hydrogen sulfide on the composites of graphene/graphite oxide with copper (hydr)oxychlorides.

PubMed

Mabayoje, Oluwaniyi; Seredych, Mykola; Bandosz, Teresa J

2012-06-27

Composites of copper (hydr)oxychlorides with graphite oxide or graphene were synthesized and used as adsorbents of hydrogen sulfide at dynamic conditions at ambient temperatures. The materials were extensively characterized before and after adsorption in order to link their performance to the surface features. X-ray diffraction, FTIR, thermal analysis, TEM, SEM/EDX, and adsorption of nitrogen were used. It was found that the composite with graphene has the most favorable surface features enhancing reactive adsorption of hydrogen sulfide. The presence of moisture in the H2S stream has a positive effect on the removal process owing to the dissociation process. H2S is retained on the surface via a direct replacement of OH groups and via acid-base reactions with the copper (hydr)oxide. Highly dispersed reduced copper species on the surface of the composite with graphene enhance activation of oxygen and cause formation of sulfites and sulfates. Higher conductivity of the graphene phase than that of graphite oxide helps in electron transfer in redox reactions.
Statistical mechanical models for dissociative adsorption of O2 on metal(100) surfaces with blocking, steering, and funneling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Evans, James W.; Liu, Da-Jiang

We develop statistical mechanical models amenable to analytic treatment for the dissociative adsorption of O2 at hollow sites on fcc(100) metal surfaces. The models incorporate exclusion of nearest-neighbor pairs of adsorbed O. However, corresponding simple site-blocking models, where adsorption requires a large ensemble of available sites, exhibit an anomalously fast initial decrease in sticking. Thus, in addition to blocking, our models also incorporate more facile adsorption via orientational steering and funneling dynamics (features supported by ab initio Molecular Dynamics studies). Behavior for equilibrated adlayers is distinct from those with finite adspecies mobility. We focus on the low-temperature limited-mobility regime wheremore » analysis of the associated master equations readily produces exact results for both short- and long-time behavior. Kinetic Monte Carlo simulation is also utilized to provide a more complete picture of behavior. These models capture both the initial decrease and the saturation of the experimentally observed sticking versus coverage, as well as features of non-equilibrium adlayer ordering as assessed by surface-sensitive diffraction.« less

Statistical mechanical models for dissociative adsorption of O{sub 2} on metal(100) surfaces with blocking, steering, and funneling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Evans, James W.; Department of Physics and Astronomy, Iowa State University, Ames, Iowa 50011; Liu, Da-Jiang

We develop statistical mechanical models amenable to analytic treatment for the dissociative adsorption of O{sub 2} at hollow sites on fcc(100) metal surfaces. The models incorporate exclusion of nearest-neighbor pairs of adsorbed O. However, corresponding simple site-blocking models, where adsorption requires a large ensemble of available sites, exhibit an anomalously fast initial decrease in sticking. Thus, in addition to blocking, our models also incorporate more facile adsorption via orientational steering and funneling dynamics (features supported by ab initio Molecular Dynamics studies). Behavior for equilibrated adlayers is distinct from those with finite adspecies mobility. We focus on the low-temperature limited-mobility regimemore » where analysis of the associated master equations readily produces exact results for both short- and long-time behavior. Kinetic Monte Carlo simulation is also utilized to provide a more complete picture of behavior. These models capture both the initial decrease and the saturation of the experimentally observed sticking versus coverage, as well as features of non-equilibrium adlayer ordering as assessed by surface-sensitive diffraction.« less
A facile one-pot solvothermal method for synthesis of magnetically recoverable Pd-Fe3O4 hybrid nanocatalysts for the Mizoroki-Heck reaction

NASA Astrophysics Data System (ADS)

Zhen, Fangchen; Ran, Maofei; Chu, Wei; Jiang, Chengfa; Sun, Wenjing

2018-03-01

Pd-Fe3O4 hybrid nanostructures were prepared using a simple one-pot hydrothermal method. The prepared materials were characterized by Fourier transform-infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma, N2 adsorption-desorption, and vibrating sample magnetometry. This self-assembled nanosystem acted as an efficient magnetically recyclable noble metal-based multi-functional nanocatalyst. It showed excellent catalytic activity and stability for the Heck reaction of iodobenzene and styrene under mild conditions. The methods used to prepare the Pd-Fe3O4 catalysts were simple and low-cost, which will be useful for the large-scale development and application of a magnetically recoverable Pd catalyst.
Conversion of kraft lignin over hierarchical MFI zeolite.

PubMed

Kim, Seong-Soo; Lee, Hyung Won; Ryoo, Ryong; Kim, Wookdong; Park, Sung Hoon; Jeon, Jong-Ki; Park, Young-Kwon

2014-03-01

Catalytic pyrolysis of kraft lignin was carried out using pyrolysis gas chromatography/mass spectrometry. Hierarchical mesoporous MFI was used as the catalyst and another mesoporous material Al-SBA-15 was also used for comparison. The characteristics of mesoporous MFI were analyzed by X-ray diffraction patterns, N2 adsorption-desorption isotherms, and temperature programmed desorption of NH3. Two catalyst/lignin mass ratios were tested: 5/1 and 10/1. Aromatics and alkyl phenolics were the main products of the catalytic pyrolysis of lignin over mesoporous MFI. In particular, the yields of mono-aromatics such as benzene, toluene, ethylbenzene, and xylene were increased substantially by catalytic upgrading. Increase in the catalyst dose enhanced the production of aromatics further, which is attributed to decarboxylation, decarbonlyation, and aromatization reactions occurring over the acid sites of mesoporous MFI.
Self-organisation of adsorbed nitrogen on (100) and (410) copper faces: a SPA-LEED study

NASA Astrophysics Data System (ADS)

Sotto, M.; Croset, B.

2000-08-01

The self-organisation of nitrogen nanostructures at different coverages on a (100) copper surface is studied by spot profile analysing low energy electron diffraction (SPA-LEED). The existence of two surface states with a domain of coverage leading to coexistence of the two states as already observed by scanning tunneling microscopy (STM) [Leibsle and Robinson, Phys. Rev. B 47 (1993) 15 865; Leibsle et al., Surf. Sci. 317 (1994) 309; Leibsle, Surf. Sci. 440 (1999) L835] and low energy electron diffraction (LEED) [Sotto et al., Surf. Sci. 371 (1997) 36] is confirmed. In the first state, the surface is organised in square shape islands separated by bare copper <100> rows. This work shows that the surface periodicity depends on the preparation of the nitrogen overlayer. When nitrogen coverage is obtained by adsorption with a sample temperature near 320°C, the periodicity does not vary with coverage and is found to be equal to 55±2 Å. At coverages below 0.75±0.05 and if the nitrogen is deposited at room temperature followed by an anneal at 320°C, during long periods of time, the periodicity evolves to large values (˜97±3 Å). During thermal desorption, the long range order with decreasing coverage is maintained but the surface periodicity also evolves continuously to large values (˜100 Å). However, a surface periodicity of 55±2 Å seems to be a characteristic length of this system. The second surface state corresponds to large c(2×2)N domains separated by <110> trenches [Leibsle and Robinson, Phys. Rev. B 47 (1993) 15 865; Leibsle et al., Surf. Sci. 317 (1994) 309; Leibsle, Surf. Sci. 440 (1999) L835]. Nitrogen adsorption on a (410) stepped face induces a reconstruction into a (810) face with double step height. The complex behaviour of this film growth is discussed in the light of existing theories about the driving force leading to nanostructuration.
Application of Brazilian kaolinite clay as adsorbent to removal of U(VI) from aqueous solution: Kinetic and thermodynamic of cation-basic interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guerra, Denis L., E-mail: denis@cpd.ufmt.b; Leidens, Victor L.; Viana, Rubia R.

2010-05-15

The compound N{sup 1}-[3-(trimethoxysilyl)propyl]diethylenetriamine was anchored onto Amazon kaolinite surface by heterogeneous route. The modified and natural kaolinite samples were characterized by transmission electron microscopy, scanning electron microscopic, X-ray diffraction, and nuclear magnetic nuclei of {sup 29}Si and {sup 13}C. The well-defined peaks obtained in the {sup 13}C NMR spectrum in the 5.0-62.1 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The ability of these materials to remove U(VI) from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 4.0.more » The kinetic parameters analyzed by the Lagergren and Elovich models gave a good fit for a pseudo-second order reaction with k{sub 2} values 16.0 and 25.1 mmol g{sup -1} min{sup -1} ranges for natural and modified kaolinite clays, respectively. The energetic effects caused by metal ion adsorption were determined through calorimetric titrations. - Graphical abstract: This investigation reports the use of original and modified kaolinites as alternative absorbents. The compound N-[3-trimethoxysilyl)propyl]diethylenetriamine was anchored onto Amazon kaolinite surface by heterogeneous route.« less
The Effect of Pluronic 123 Surfactant concentration on The N2 Adsorption Capacity of Mesoporous Silica SBA-15: Dubinin-Astakhov Adsorption Isotherm Analysis

NASA Astrophysics Data System (ADS)

Dhaneswara, Donanta; Siti Agustina, A. A. A.; Dewantoro Adhy, P.; Delayori, Farhan; Fajar Fatriansyah, Jaka

2018-04-01

Mesoporous SBA-15 has been successfully synthesized at various concentration of Pluronic 123 surfactant (7mM, 50 mM, 54 mM, 60 mM and 66 mM) and the effect of these various concentrations on the N2 adsorption capacity has been investigated. The adsorption analysis was conducted using Dubinin-Astakhov isotherm model for multilayer adsorption phenomenon. It was found that etryat low concentration of Pluronic 123, the system exhibits type I adsorption isotherm while at high concentration, the system exhibits type IV adsorption with H1 hysteresis curve which indicates the existence of pores with cylindrical geometry, relatively uniform pore size and possibility of pore network effects. It also was found that, by using D-A isotherm model fitting, at 60 mM concentration of Pluronic 123, SBA-15 has the highest adsorption capacity which stands at 421 cm3/gram.
Synthesis of Cr3+-doped TiO2 nanoparticles: characterization and evaluation of their visible photocatalytic performance and stability.

PubMed

Mendiola-Alvarez, Sandra Yadira; Guzmán-Mar, Jorge Luis; Turnes-Palomino, Gemma; Maya-Alejandro, Fernando; Caballero-Quintero, Adolfo; Hernández-Ramírez, Aracely; Hinojosa-Reyes, Laura

2017-09-28

Cr 3+ -doped TiO 2 nanoparticles (Ti-Cr) were synthesized by microwave-assisted sol-gel method. The Ti-Cr catalyst was characterized by X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, N 2 adsorption-desorption analysis, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy (XPS) and zetametry. The anatase mesoporous Ti-Cr material exhibited a specific surface area of 54.5 m 2 /g. XPS analysis confirmed the proper substitution of Ti 4+ cations by Cr 3+ cations in the TiO 2 matrix. The particle size was of average size of 17 nm for the undoped TiO 2 but only 9.5 nm for Ti-Cr. The Cr atoms promoted the formation of hydroxyl radicals and modified the surface adsorptive properties of TiO 2 due to the increase in surface acidity of the material. The photocatalytic evaluation demonstrated that the Ti-Cr catalyst completely degraded (4-chloro-2-methylphenoxy) acetic acid under visible light irradiation, while undoped TiO 2 and P25 allowed 45.7% and 31.1%, respectively. The rate of degradation remained 52% after three cycles of catalyst reuse. The higher visible light photocatalytic activity of Ti-Cr was attributed to the beneficial effect of Cr 3+ ions on the TiO 2 surface creating defects within the TiO 2 crystal lattice, which can act as charge-trapping sites, reducing the electron-hole recombination process.
Hierarchical Na-doped cubic ZrO2 synthesis by a simple hydrothermal route and its application in biodiesel production

NASA Astrophysics Data System (ADS)

Lara-García, Hugo A.; Romero-Ibarra, Issis C.; Pfeiffer, Heriberto

2014-10-01

Hierarchical growth of cubic ZrO2 phase was successfully synthesized via a simple hydrothermal process in the presence of different surfactants (cationic, non-ionic and anionic) and sodium hydroxide. The structural and microstructural characterizations of different ZrO2 powders were performed using various techniques, such as X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption, scanning electron microscopy and infrared. Results indicated that sodium addition stabilized the cubic ZrO2 phase by a Na-doping process, independently of the surfactant used. In contrast, microstructural characteristics varied as a function of the surfactant and sodium presence. In addition, water vapor (H2O) and carbon dioxide (CO2) sorption properties were evaluated on ZrO2 samples. Results evidenced that sample surface reactivity changed as a function of the sodium content. Finally, this surface reactivity was evaluated on the biodiesel transesterification reaction using the different synthesized samples, obtaining yields of 93%.
Experimental and Theoretical Studies of Gas Adsorption in Cu3(BTC)2: An Effective Activation Procedure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, J.; Culp, J.T.; Natesakhawat, Sittichai

2007-07-05

We have improved the activation process for CuBTC [Cu3(BTC)2, BTC ) 1,3,5-benzenetricarboxylate] by extracting the N,N-dimethylformamide-solvated crystals with methanol; we identify material activated in this way as CuBTC-MeOH. This improvement allowed the activation to be performed at a much lower temperature, thus greatly mitigating the danger of reducing the copper ions. A review of the literature for H2 adsorption in CuBTC shows that the preparation and activation process has a significant impact on the adsorption capacity, surface area, and pore volume. CuBTC-MeOH exhibits a larger pore volume and H2 adsorption amount than any previously reported results for CuBTC. We havemore » performed atomically detailed modeling to complement experimentally measured isotherms. Quantum effects for hydrogen adsorption in CuBTC were found to be important at 77 K. Simulations that include quantum effects are in good agreement with the experimentally measured capacity for H2 at 77 K and high pressure. However, simulations underpredict the amount adsorbed at low pressures. We have compared the adsorption isotherms from simulations with experiments for H2 adsorption at 77, 87, 175, and 298 K; nitrogen adsorption at 253 and 298 K; and argon adsorption at 298 and 356 K. Reasonable agreement was obtained in all cases.« less
Synthesis of graphene aerogel for adsorption of bisphenol A

NASA Astrophysics Data System (ADS)

Trinh, Truong Thi Phuong Nguyet Xuan; Long, Nguyen Huynh Bach Son; Quang, Dong Thanh; Hieu, Nguyen Huu

2018-04-01

In this research, graphene aerogel (GA) was synthesized by chemical reduction method using ethylene diamine as a reducing agent. The morphology and properties of GA were characterized by calculating apparent density, Fourier transform infrared spectroscopy, X-ray diffraction, Raman spectroscopy, field emission scanning electron microscopy, and Brunauer-Emmett-Teller (BET) specific surface area. High-performance liquid chromatography (HPLC) was used to quantify the amount of the residual bisphenol A (BPA) concentration. The analysis results showed that GA exhibited low density ranging from 4-8 mg/cm3, hydrophobicity, high porosity, and specific surface area of 1883 m2/g according to BET. The obtained GA was used as an adsorbent for BPA. The effects of pH, contact time, and initial BPA concentration on the adsorption were investigated. The adsorption equilibrium time could be reached within 240 minutes. The adsorption data were well-fitted to pseudo-second-order kinetic equation and Langmuir isotherm model. The maximum adsorption capacity of GA for BPA calculated by the Langmuir model was 185.185 mg/g at pH 7. Accordingly, GA could be considered as promising adsorbents for BPA in water.
The effects of ageing time on the microstructure and properties of mesoporous silica-hydroxyapatite nanocomposite

NASA Astrophysics Data System (ADS)

Yousefpour, Mardali; Taherian, Zahra

2013-02-01

In this study, a mesoporous silica-hydroxyapatite nanocomposite (MCM-41/HA) was synthesized via sol-gel technique as a drug delivery system. The synthesis of MCM-41/hydroxyapatite nanocomposite was carried out at room temperature. The effect of various ageing time on the nanocomposite properties was studied during synthesis process. 0, 24, 36, and 48 h aging times were chosen. Textural properties and microstructure of the nanocomposites were characterized by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Energy Dispersive X-ray Spectroscopy (EDS), Electron Diffraction pattern (ED), and N2 adsorption-desorption. Results showed that ageing process led to HA crystals nucleation and growth on the surface of mesoporous silica. At 48 h of aging time, the surface area and total pore volume increased from 36.2 to 334 m2/g and 0.14-0.7 cm3/g, respectively. In contrast, the average pore diameter considerably decreased from 20.1 nm for (MCM-41/HA)24 to 8.39 nm for (MCM-41/HA)48. Furthermore, it was observed more homogeneous pore distribution with increasing the ageing time. In conclusion, the ageing time play an important role on textural properties of MCM-41/HA nanocomposite which could have a major effect on drug delivery properties such as molecular loading and release kinetics.
Synthesis of hierarchical Ni(OH)(2) and NiO nanosheets and their adsorption kinetics and isotherms to Congo red in water.

PubMed

Cheng, Bei; Le, Yao; Cai, Weiquan; Yu, Jiaguo

2011-01-30

Ni(OH)(2) and NiO nanosheets with hierarchical porous structures were synthesized by a simple chemical precipitation method using nickel chloride as precursors and urea as precipitating agent. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy and nitrogen adsorption-desorption isotherms. Adsorption of Congo red (CR) onto the as-prepared samples from aqueous solutions was investigated and discussed. The pore structure analyses indicate that Ni(OH)(2) and NiO nanosheets are composed of at least three levels of hierarchical porous organization: small mesopores (ca. 3-5 nm), large mesopores (ca. 10-50 nm) and macropores (100-500 nm). The equilibrium adsorption data of CR on the as-prepared samples were analyzed by Langmuir and Freundlich models, suggesting that the Langmuir model provides the better correlation of the experimental data. The adsorption capacities for removal of CR was determined using the Langmuir equation and found to be 82.9, 151.7 and 39.7 mg/g for Ni(OH)(2) nanosheets, NiO nanosheets and NiO nanoparticles, respectively. Adsorption data were modeled using the pseudo-first-order, pseudo-second-order and intra-particle diffusion kinetics equations. The results indicate that pseudo-second-order kinetic equation and intra-particle diffusion model can better describe the adsorption kinetics. The as-prepared Ni(OH)(2) and NiO nanosheets are found to be effective adsorbents for the removal of Congo red pollutant from wastewater as a result of their unique hierarchical porous structures and high specific surface areas. Copyright © 2010 Elsevier B.V. All rights reserved.
Dynamics of adsorption in micellar and non micellar solutions of derivatives of lysosomotropic substances.

PubMed

Dopierala, Katarzyna; Prochaska, Krystyna

2010-04-22

Dynamics of adsorption in micellar and non micellar solutions of derivatives of lysosomotropic substances was studied. The following compounds were considered in our research work: alkyl N,N-dimethyl-alaninates methobromides (DMALM-n), alkyl N,N-dimethylglycinates methobromides (DMGM-n), fatty acids N,N-dimethylaminoethylesters methobromides (DMM-n), fatty acids N,N-dimethylaminopropylesters methobromides (DMPM-n), fatty acids 1-dimethylamino-2-propyl methobromides (DMP(2)M-n), and derivatives of aminoesters with double alkyl chains (M(2)M-n). The examined compounds show interesting biological properties which can be useful, especially in medicine. The exact mechanism of interaction of such compounds with biological membrane is not fully known. However, it is supposed that the presence of micelles has an important role in biological systems. In this paper we show the results of dynamic surface tension measurements in solutions containing the investigated compounds at concentrations above and below cmc. Moreover, we analyzed the influence of the chemical structure of molecules on the diameters of the micelles formed in the solutions. It was found that adsorption dynamics for the studied compounds is strongly affected by the chemical structure of the considered derivatives, especially by the presence of the ester bond, linearity of the molecule, as well as its hydrophobicity. The obtained results show that the structure of the bromide M(2)M-n with two short hydrocarbon chains favors a faster and more efficient adsorption of the molecules at the air/water interface, compared with compounds having one long alkyl chain. Moreover, the double chained derivatives of the M(2)M-n type do not form typical spherical micelles but bilayer structures probably exist in these solutions. The micelles present in the solutions influence the dynamics of adsorption drastically. Moreover, the obtained results indicated that the compounds with especially high biological activity form rather small aggregates. Copyright 2010 Elsevier B.V. All rights reserved.
Missing dimer defects investigated by adsorption of nitric oxide (NO) on silicon (100) 2 × 1

NASA Astrophysics Data System (ADS)

Sasse, A. G. B. M.; Kleinherenbrink, P. M.; Van Silfhout, A.

This paper describes a study concerning the interaction of nitric oxide (NO) with the clean Si(100)2×1 surface in ultra-high vacuum at room temperature. Differential reflectometry (DR) in the photon energy range of 2.4-4.4 eV. Auger electron spectroscopy (AES) and low energy electron diffraction (LEED) have been used to investigate the chemisorption of NO on Si(100)2×1. With this combination of techniques it is possible to make an analysis of the geometric and electronic structure and chemical composition of the surface layer. The aim of the present study was to explain the experimental results of the adsorption of NO on the clean Si(100)2×1 at 300 K. Analysing the electronic and geometric structure of a simplified stepped 2×1 reconstructed Si(100) surface and of the NO molecule in combination with the use of Woodward-Hoffmann rules (WHR) we were able to model a surface defect specific adsorption mechanism. Surface defects such as missing dimer defects seem to play an important role in the adsorption mechanism of NO on the silicon surface. The experimental results are consistent with this developed model. We also suggest a relation between the missing dimer defects and the number of steps on the silicon surface.
Cs/NF3 adsorption on [001]-oriented GaN nanowire surface: A first principle calculation

NASA Astrophysics Data System (ADS)

Diao, Yu; Liu, Lei; Xia, Sihao; Kong, Yike

2017-11-01

In this study, the adsorption mechanism of Cs/NF3 on the [001]-oriented GaN nanowire surface is investigated by using the density function theory based on first-principles. In the Cs/NF3 co-activation process, the system is inclined to form NF3-in structure. Through the calculation results of adsorption energy, NF3 molecule adsorption tends to take an orientation with F atoms on top and the most favorable adsorption site is BGa-N. The NF3 activation process can further cut down the work function of the Cs-covered nanowire surface only when Cs coverage is 0.75 ML and 1 ML, which can be explained by the double dipole moment theory. With increasing Cs coverage, the valence band and conduction band both shift to lower energy side, contributing to the appearance of a downward band bending region and promoting the escape of surface photoelectrons. After NF3 molecule adsorption, the peak of total density of states near Fermi level increase due to the orbital hybridization between NF3-2s, Cs-5s states and N-2p states, which strengthen the conductivity of the nanowire surface and leads to the metallic properties. All these calculations may direct the Cs/NF3 activation process of GaN nanowire optoelectronic devices.
Mechanism of tyramine adsorption on Ca-montmorillonite.

PubMed

Chang, Po-Hsiang; Jiang, Wei-Teh; Li, Zhaohui

2018-06-10

Tyramine (TY) adsorption on a Ca-montmorillonite (SAz-2) was investigated with batch experiments and complementary analyses utilizing ultra-high performance liquid chromatography, ion chromatography, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetry (TG). The adsorption reached equilibrium in 8 h, complying with the pseudo-second-order rate equation, and came to an adsorption capacity of 682 mmol kg -1 at pH 6-8.1, utilizing the Langmuir isotherm model. The adsorption of TY and desorption of exchangeable cations exhibited a linear relationship with a slope of 0.9, implying that the adsorption was largely influenced by a cation exchange mechanism. The effective adsorption was further verified by the characteristic TY bands in the FTIR spectra and the signals of mass loss due to TY decomposition in the TG measurements of the clay after adsorption experiments. Intercalation of hydrated TY into the clay interlayer was confirmed by XRD and TG analyses of the heated samples loaded with TY. The adsorption reached only 0.57 cation exchange capacity of the clay which was probably limited by the low charge density of TY as compared to the negative charge density of the clay surface and by the steric effects arising from the hydration of TY that increased its molecular size. Adsorption of TY on montmorillonite can make TY more resistant to thermal decomposition and possibly better preserved in aquatic and soil environments. Copyright © 2018 Elsevier B.V. All rights reserved.
CO adsorption on small Au{sub n} (n = 1–4) structures supported on hematite. II. Adsorption on the O-rich termination of α-Fe{sub 2}O{sub 3}(0001) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pabisiak, Tomasz; Kiejna, Adam, E-mail: kiejna@ifd.uni.wroc.pl; Winiarski, Maciej J.

2016-01-28

The adsorption of small Au{sub n} (n = 1–4) nanostructures on oxygen terminated α-Fe{sub 2}O{sub 3}(0001) surface was investigated using density functional theory in the generalized gradient approximation of Perdew-Burke-Ernzerhof (PBE) form with Hubbard correction U, accounting for strong electron correlations (PBE+U). The structural, energetic, and electronic properties were examined for two classes of the adsorbed Au{sub n} nanostructures with vertical and flattened configurations. Similarly to the Fe-terminated α-Fe{sub 2}O{sub 3}(0001) surface considered in Part I, the flattened configurations were found energetically more favored than vertical ones. The binding of Au{sub n} to the O-terminated surface is much stronger thanmore » to the Fe-termination. The adsorption bonding energy of Au{sub n} and the work function of the Au{sub n}/α-Fe{sub 2}O{sub 3}(0001) systems decrease with the increased number of Au atoms in a structure. All of the adsorbed Au{sub n} structures are positively charged. The bonding of CO molecules to the Au{sub n} structures is distinctly stronger than on the Fe-terminated surface; however, it is weaker than the binding to the bare O-terminated surface. The CO molecule binds to the Au{sub n}/α-Fe{sub 2}O{sub 3}(0001) system through a peripheral Au atom partly detached from the Au{sub n} structure. The results of this work indicate that the most energetically favored sites for adsorption of a CO molecule on the Au{sub n}/α-Fe{sub 2}O{sub 3}(0001) systems are atoms in the Au{sup 0.5+} oxidation state.« less
First-principles investigation of CO adsorption on pristine, C-doped and N-vacancy defected hexagonal AlN nanosheets

NASA Astrophysics Data System (ADS)

Ouyang, Tianhong; Qian, Zhao; Ahuja, Rajeev; Liu, Xiangfa

2018-05-01

The optimized atomic structures, energetics and electronic structures of toxic gas CO adsorption systems on pristine, C-doped and N-vacancy defected h-AlN nanosheets respectively have been investigated using Density functional theory (DFT-D2 method) to explore their potential gas detection or sensing capabilities. It is found that both the C-doping and the N-vacancy defect improve the CO adsorption energies of AlN nanosheet (from pure -3.847 eV to -5.192 eV and -4.959 eV). The absolute value of the system band gap change induced by adsorption of CO can be scaled up to 2.558 eV or 1.296 eV after C-doping or N-vacancy design respectively, which is evidently larger than the value of 0.350 eV for pristine material and will benefit the robustness of electronic signals in potential gas detection. Charge transfer mechanisms between CO and the AlN nanosheet have been presented by the Bader charge and differential charge density analysis to explore the deep origin of the underlying electronic structure changes. This theoretical study is proposed to predict and understand the CO adsorption properties of the pristine and defected h-AlN nanosheets and would help to guide experimentalists to develop better AlN-based two-dimensional materials for efficient gas detection or sensing applications in the future.
Production of carbon molecular sieves from Illinois coal

USGS Publications Warehouse

Lizzio, A.A.; Rostam-Abadi, M.

1993-01-01

Carbon molecular sieves (CMS) have become an increasingly important class of adsorbents for application in the separation of gas molecules that vary in size and shape. A study is in progress at the Illinois State Geological Survey to determine whether Illinois basin coals are suitable feedstocks for the production of CMS and to evaluate their potential application in gas separation processes of commercial importance. Chars were prepared from Illinois coal in a fixed-bed reactor under a wide range of heat treatment and activation conditions. The effects of various coal/char pretreatments, including coal demineralization, preoxidation, char activation, and carbon deposition, on the molecular sieve properties of the chars were also investigated. Chars with commercially significant BET surface areas of 1500 m2/g were produced by chemical activation using potassium hydroxide as the activant. These high-surface-area (HSA) chars had more than twice the adsorption capacity of commercial carbon and zeolite molecular sieves. The kinetics of adsorption of various gases, e.g., N2, O2, CO2, CH4, CO and H2, on these chars at 25??C was measured. The O2/N2 molecular sieve properties of one char prepared without chemical activation were similar to those of a commercial CMS. On the other hand, the O2/N2 selectivity of the HSA char was comparable to that of a commercial activated carbon, i.e., essentially unity. Carbon deposition, using methane as the cracking gas, increased the O2/N2 selectivity of the HSA char, but significantly decreased its adsorption capacity. Several chars showed good potential for efficient CO2/CH4 separation; both a relatively high CO2 adsorption capacity and CO2/CH4 selectivity were achieved. The micropore size distribution of selected chars was estimated by equilibrium adsorption of carbon dioxide, n-butane and iso-butane at O??C. The extent of adsorption of each gas corresponded to the effective surface area contained in pores with diameters greater than 3.3, 4.3 and 5.0 A??, respectively. Kinetic and equilibrium adsorption data provided complementary information on the molecular sieving capabilities and microstructure of the prepared chars. ?? 1993.
Adsorption of phenol and hydrazine upon pristine and X-decorated (X = Sc, Ti, Cr and Mn) MoS2 monolayer

NASA Astrophysics Data System (ADS)

Wang, Meiyan; Wang, Wei; Ji, Min; Cheng, Xinlu

2018-05-01

Using density functional theory (DFT), we present a theoretical investigation of phenol (C6H5OH) and hydrazine (N2H4) on pristine and decorated MoS2 monolayer. In our work, we first focus on the interactions between several metal atoms and MoS2 monolayer and then choose the MoS2 nanosheet decorated by Sc, Ti, Cr and Mn to be the substrate. Furthermore, the properties of phenol and N2H4 on pure and X-doped (X = Sc, Ti, Cr and Mn) MoS2 base materials are discussed in terms of adsorption energy, adsorption distance, charge transfer, charge density difference, HOMO and LUMO molecular orbitals and density of states (DOS). The results predict that the adsorption of phenol and hydrazine upon X-decorated MoS2 monolayers are more favorable than the adsorption on isolated ones, which demonstrating that Sc, Ti, Cr and Mn doping help to improve the adsorption abilities. Calculations also show shorter adsorption distance and more charge transfer for Sc-, Ti-, Cr- and Mn-doped systems than the pristine one. The results confirm that X-doped MoS2 monolayer can be used as effective and potential adsorbents for toxic phenol and hydrazine.

Interaction of hydrogen chloride with alumina. [influence of outgas and temperature conditions on adsorption

NASA Technical Reports Server (NTRS)

Bailey, R. R.; Wightman, J. P.

1975-01-01

The influence of outgas conditions and temperature on the adsorptive properties of two aluminas Alon-c and Al6sG were studied using adsorption isotherm measurements. Alon-C and Al6SG were characterized using X-ray powder diffraction, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and BET nitrogen surface areas. Some of these techniques were applied to two other aluminas but no isotherm data was obtained. Isotherm data and techniques applied to each alumina are summarized in tabular form.
Debye ring diffraction elucidation of 2D photonic crystal self-assembly and ordering at the air-water interface.

PubMed

Smith, N L; Coukouma, A; Dubnik, S; Asher, S A

2017-12-06

We fabricate 2D photonic crystals (2DPC) by spreading a dispersion of charged colloidal particles (diameters = 409, 570, and 915 nm) onto the surface of electrolyte solutions using a needle tip flow method. When the interparticle electrostatic interaction potential is large, particles self-assemble into highly ordered hexagonal close packed (hcp) monolayers. Ordered 2DPC efficiently forward diffract monochromatic light to produce a Debye ring on a screen parallel to the 2DPC. The diameter of the Debye ring is inversely proportional to the 2DPC particle spacing, while the Debye ring brightness and thickness depends on the 2DPC ordering. The Debye ring thickness increases as the 2DPC order decreases. The Debye ring ordering measurements of 2DPC attached to glass slides track measurements of the 2D pair correlation function order parameter calculated from SEM micrographs. The Debye ring method was used to investigate the 2DPC particle spacing, and ordering at the air-solution interface of NaCl solutions, and for 2DPC arrays attached to glass slides. Surprisingly, the 2DPC ordering does not monotonically decrease as the salt concentration increases. This is because of chloride ion adsorption onto the anionic particle surfaces. This adsorption increases the particle surface charge and compensates for the decreased Debye length of the electric double layer when the NaCl concentration is below a critical value.
The temperature dependence of atomic incorporation characteristics in growing GaInNAs films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jingling; Gao, Fangliang; Wen, Lei

We have systematically studied the temperature dependence of incorporation characteristics of nitrogen (N) and indium (In) in growing GaInNAs films. With the implementation of Monte-Carlo simulation, the low N adsorption energy (−0.10 eV) is demonstrated. To understand the atomic incorporation mechanism, temperature dependence of interactions between Group-III and V elements are subsequently discussed. We find that the In incorporation behaviors rather than that of N are more sensitive to the T{sub g}, which can be experimentally verified by exploring the compositional modulation and structural changes of the GaInNAs films by means of high-resolution X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope,more » and secondary ion mass spectroscopy.« less
CARBON NANOTUBES AND NANO-Ce-Zr OXIDES SUPPORTED H3PW12O40 FOR EFFECTIVE ADSORPTION-DECOMPOSITION OF NOx

NASA Astrophysics Data System (ADS)

Cheng, Lin; Wang, Rui

2012-01-01

Surface-modified carbon nanotubes (CNTs) and nano-Ce-Zr mixed oxides (CZO) were prepared and employed initially as supports of H3PW12O40 (HPW) for NOx adsorption-decomposition. Both CNTs and nano-CZO are favorable supports for HPW. After loading with HPW, the NOx adsorption efficiency increases, especially for HPW/CZO in which the highest adsorption efficiency can achieve 98% at the HPW loading of 70%, much higher than that of single HPW. NOx adsorption efficiency can be influenced considerably by catalyst preparing conditions, in particularly, ethyl alcohol is superior to water as solvent for HPW loading onto CNTs; the -OH containing CNTs shows better promotion effect on the adsorption of NOx than that containing -COOH when using absolute ethyl alcohol as solvent; mechanical grinding method is superior to incipient impregnation method in loading HPW onto the support of CZO. For both catalysts of HPW/CNTs and HPW/CZO, with the increase of HPW loading, the NOx adsorption efficiency tends to reach a peak value before dropping down. Heated from 150°C to 450°C at a rate of 50°C/min, the adsorbed NO was found to decompose into N2, O2 and N2O, and yields of N2 being 21.8% and 27.3%, respectively for HPW/CNTs and HPW/CZO were obtained.
Use of micrometric latex beads to improve the porosity of hydroxyapatite obtained by chemical coprecipitation method

NASA Astrophysics Data System (ADS)

Webler, G. D.; Rodrigues, W. C.; Silva, A. E. S.; Silva, A. O. S.; Fonseca, E. J. S.; Degenhardt, M. F. S.; Oliveira, C. L. P.; Otubo, L.; Barros Filho, D. A.

2018-04-01

Hydroxyapatite is one of the most important biomaterials whose application mainly extends to implants and drug delivery. This work will discuss the changes in the pore size distribution of hydroxyapatite when there are latex beads present during the synthesis. These changes were monitored using different techniques: small angle X-ray scattering, X-ray diffraction, thermal gravimetrical analysis, N2 adsorption, scanning and transmission electron microscopy. Latex beads and hydroxyapatite form a single nanocomposite with well-distinguished inorganic and organic phases. Latex bead removal in the temperature range of 300-600 °C did not modify the original crystalline structure of hydroxyapatite. However, the latex beads favored an increase in the adsorption capacity of mesopores at temperatures higher than their glassy transition (Tg). The main result of this research work consists on the increase of surface area and pore size distribution obtained after the removal of latex beads template. Latex beads have been used in a different approach changing the porosity of hydroxyapatite scaffolds not only introducing new routes for cell integration but also broadening the pore size distribution which can result in a more high efficiency for drug release in living cells.
Adsorptive separation of isobutene and isobutane on Cu3(BTC)2.

PubMed

Hartmann, Martin; Kunz, Sebastian; Himsl, Dieter; Tangermann, Oliver; Ernst, Stefan; Wagener, Alex

2008-08-19

The metal organic framework material Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate) has been synthesized using different routes: under solvothermal conditions in an autoclave, under atmospheric pressure and reflux, and by electrochemical reaction. Although the compounds display similar structural properties as evident from the powder X-ray diffraction (XRD) patterns, they differ largely in specific surface area and total pore volume. Thermogravimetric and chemical analysis support the assumption that pore blocking due to trimesic acid and/or methyltributylammoniummethylsulfate (MTBS) which has been captured in the pore system during reaction is a major problem for the electrochemically synthesized samples. Isobutane and isobutene adsorption has been studied for all samples at different temperatures in order to check the potential of Cu3(BTC)2 for the separation of small hydrocarbons. While the isobutene adsorption isotherms are of type I according to the IUPAC classification, the shape of the isobutane isotherm is markedly different and closer to type V. Adsorption experiments at different temperatures show that a somewhat higher amount of isobutene is adsorbed as compared to isobutane. Nevertheless, the differential enthalpies of adsorption are only different by about 5 kJ/mol, indicating that a strong interaction between the copper centers and isobutene does not drive the observed differences in adsorption capacity. The calculated breakthrough curves of isobutene and isobutane reveal that a low pressure separation is preferred due to the peculiar shape of the isobutane adsorption isotherms. This has been confirmed by preliminary breakthrough experiments using an equimolar mixture of isobutane and isobutene.
Controlling Cooperative CO2 Adsorption in Diamine-Appended Mg2(dobpdc) Metal-Organic Frameworks.

PubMed

Siegelman, Rebecca L; McDonald, Thomas M; Gonzalez, Miguel I; Martell, Jeffrey D; Milner, Phillip J; Mason, Jarad A; Berger, Adam H; Bhown, Abhoyjit S; Long, Jeffrey R

2017-08-02

In the transition to a clean-energy future, CO 2 separations will play a critical role in mitigating current greenhouse gas emissions and facilitating conversion to cleaner-burning and renewable fuels. New materials with high selectivities for CO 2 adsorption, large CO 2 removal capacities, and low regeneration energies are needed to achieve these separations efficiently at scale. Here, we present a detailed investigation of nine diamine-appended variants of the metal-organic framework Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) that feature step-shaped CO 2 adsorption isotherms resulting from cooperative and reversible insertion of CO 2 into metal-amine bonds to form ammonium carbamate chains. Small modifications to the diamine structure are found to shift the threshold pressure for cooperative CO 2 adsorption by over 4 orders of magnitude at a given temperature, and the observed trends are rationalized on the basis of crystal structures of the isostructural zinc frameworks obtained from in situ single-crystal X-ray diffraction experiments. The structure-activity relationships derived from these results can be leveraged to tailor adsorbents to the conditions of a given CO 2 separation process. The unparalleled versatility of these materials, coupled with their high CO 2 capacities and low projected energy costs, highlights their potential as next-generation adsorbents for a wide array of CO 2 separations.
Adsorption of NH4+-N on Chinese loess: Non-equilibrium and equilibrium investigations.

PubMed

Xie, Haijian; Wang, Shaoyi; Qiu, Zhanhong; Jiang, Jianqun

2017-11-01

NH 4 + -N is a crucial pollutant in landfill leachate and can be in high concentrations for a long period of time due to anaerobic condition of landfills. The adsorption properties of NH 4 + -N on the Chinese loess were investigated using Batch test. The influences of ammonium concentration, temperature, reaction time, slurry concentration, and pH on the adsorption process are evaluated. Adsorption kinetics and isotherm behaviors were studied by applying different models to the test data to determine the adsorption parameters. The equilibrating duration was shown to be less than 60 min. The data on adsorption kinetics can be well fitted by the pseudo-second-order kinetics model. According to the Langmuir isotherm model, the adsorption capacity of Chinese loess about NH 4 + -N was predicted to be 72.30 mg g -1 . The uptake of NH 4 + -N by Chinese loess was considered to be the type of physical adsorption on the basis of D-R isotherm analysis. The optimal pH and slurry concentration are 4 and 2 g/50 ml, respectively. According to the calculated values of free energy, enthalpy and entropy change, the adsorption process is determined to be exothermic. The disorder of the system appeared lowest at temperature of 308.15 K. The predicted Gibb's free energies also indicate the adsorption process is endothermic and spontaneous. The FTIR spectrum and EDX analysis showed the adsorption process of NH 4 + involves cation exchange and dissolution of calcite. Copyright © 2017 Elsevier Ltd. All rights reserved.
Microphysical, microchemical and adhesive properties of lunar material. 3: Gas interaction with lunar material

NASA Technical Reports Server (NTRS)

Grossman, J. J.; Mukherjee, N. R.; Ryan, J. A.

1972-01-01

Knowledge of the reactivity of lunar material surfaces is important for understanding the effects of the lunar or space environment upon this material, particularly its nature, behavior and exposure history in comparison to terrestrial materials. Adsorptive properties are one of the important techniques for such studies. Gas adsorption measurements were made on an Apollo 12 ultrahigh vacuum-stored sample and Apollo 14 and 15 N2-stored samples. Surface area measurements were made on the latter two. Adsorbate gases used were N2, A, O2 and H2O. Krypton was used for the surface area determinations. Runs were made at room and liquid nitrogen temperature in volumetric and gravimetric systems. It was found that the adsorptive/desorptive behavior was in general significantly different from that of terrestrial materials of similar type and form. Specifically (1) the UHV-stored sample exhibited very high initial adsorption indicative of high surface reactivity, and (2) the N2-stored samples at room and liquid nitrogen temperatures showed that more gas was desorbed than introduced during adsorption, indicative of gas release from the samples. The high reactivity is a scribed cosmic ray track and solar wind damage.
Microwave-Assisted Synthesis of Goethite Nanoparticles Used for Removal of Cr(VI) from Aqueous Solution

PubMed Central

Kynicky, Jindrich; Adam, Vojtech

2017-01-01

The microwave-assisted synthesis of goethite nanoparticles has been studied. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential thermal analysis (DTA) and Brunauer–Emmett–Teller (BET) method. Goethite rod-like nanoparticles have been successfully synthesized in 10 min of microwave treating at 100 °C. Particle size is in the range from 30 to 60 nm in width and from 200 to 350 nm in length. BET analysis indicated that the surface area of the product is 158.31 m2g−1. The feasibility of Cr(VI) removal fromaqueous solution depends on the pH of the solution and contact time. The maximum adsorptionis reached at pH 4.0 and 540 min of contact time. The adsorption kinetics was analyzedby the pseudo-first- and second-order models and the results reveal that the adsorption process obeys the pseudo-second-order model. The adsorption data were fitted well with the Langmuir adsorption isotherm. PMID:28773142
Facile hydrothermal synthesis of mesoporous In2O3 nanoparticles with superior formaldehyde-sensing properties

NASA Astrophysics Data System (ADS)

Zhang, Su; Song, Peng; Yang, Zhongxi; Wang, Qi

2018-03-01

Mesoporous In2O3 nanoparticles were successfully synthesized via a facile, template free, and low-cost hydrothermal method. Their morphology and structure were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential thermal and thermogravimetry analysis (DSC-TG), and N2 adsorption-desorption analyses. The results reveal that mesoporous In2O3 nanoparticles with a size range of 40-60 nm, possess plenty of pores, and average pore size is about 5 nm. Importantly, the mesoporous structure, large specific surface area, and small size endow the mesoporous In2O3 nanoparticles with highly sensing performance for formaldehyde detection. The response value to 10 ppm HCHO is 20 at an operating temperature of 280 °C, and the response and recovery time are 4 and 8 s, respectively. It is expected that the mesoporous In2O3 nanoparticles with large specific surface area and excellent sensing properties will become a promising functional material in monitoring and detecting formaldehyde.
Effect of Fe doping on the electrochemical capacitor behavior of MnO2 nanocrystals

NASA Astrophysics Data System (ADS)

Poonguzhali, R.; Shanmugam, N.; Gobi, R.; Senthilkumar, A.; Viruthagiri, G.; Kannadasan, N.

2015-10-01

In this work, the influence of Fe doping on the capacitance behavior of MnO2 nanoparticles synthesized by chemical precipitation was investigated. During the doping process the concentration of Fe was increased from 0.025 M to 0.125 M in steps of 0.025 M. The products obtained were characterized by X-ray diffraction, Fourier infrared spectroscopy, scanning electron microscopy and N2 adsorption-desorption isotherms. To demonstrate the suitability of Fe-doped MnO2 for capacitor applications, cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance were recorded. Among the different levels of doping, the specific capacitance of 912 F/g was delivered by 0.075 M of Fe-doped MnO2 at a scan rate of 10 mV/s, which is almost more than fourfold that of the bare MnO2 electrode (210 F/g). Moreover, for the same concentration the charge, discharge studies revealed the highest specific capacitance of 1084 F/g at a current density of 10 A/g.
Correlating N2 and CH4 adsorption on microporous carbon using a new analytical model

USGS Publications Warehouse

Sun, Jielun; Chen, S.; Rood, M.J.; Rostam-Abadi, M.

1998-01-01

A new pore size distribution (PSD) model is developed to readily describe PSDs of microporous materials with an analytical expression. Results from this model can be used to calculate the corresponding adsorption isotherm to compare the calculated isotherm to the experimental isotherm. This aspect of the model provides another check on the validity of the model's results. The model is developed on the basis of a 3-D adsorption isotherm equation that is derived from statistical mechanical principles. Least-squares error minimization is used to solve the PSD without any preassumed distribution function. In comparison with several well-accepted analytical methods from the literature, this 3-D model offers a relatively realistic PSD description for select reference materials, including activated-carbon fibers. N2 and CH4 adsorption is correlated using the 3-D model for commercial carbons BPL and AX-21. Predicted CH4 adsorption isotherms at 296 K based on N2 adsorption at 77 K are in reasonable agreement with experimental CH4 isotherms. Use of the model is also described for characterizing PSDs of tire-derived activated carbons and coal-derived activated carbons for air-quality control applications.
Adsorption in a Fixed-Bed Column and Stability of the Antibiotic Oxytetracycline Supported on Zn(II)-[2-Methylimidazolate] Frameworks in Aqueous Media

PubMed Central

Anceski Bataglion, Giovana; Nogueira Eberlin, Marcos; Machado Ronconi, Célia

2015-01-01

A metal-organic framework, Zn-[2-methylimidazolate] frameworks (ZIF-8), was used as adsorbent material to remove different concentrations of oxytetracycline (OTC) antibiotic in a fixed-bed column. The OTC was studied at concentrations of 10, 25 and 40 mg L-1. At 40 mg L-1, the breakthrough point was reached after approximately 10 minutes, while at 10 and 25 mg L-1 this point was reached in about 30 minutes. The highest removal rate of 60% for the 10 mg L-1 concentration was reached after 200 minutes. The highest adsorption capacity (28.3 mg g-1) was attained for 25 mg L-1 of OTC. After the adsorption process, a band shift was observed in the UV-Vis spectrum of the eluate. Additional studies were carried out to determine the cause of this band shift, involving a mass spectrometry (MS) analysis of the supernatant liquid during the process. This investigation revealed that the main route of adsorption consisted of the coordination of OTC with the metallic zinc centers of ZIF-8. The materials were characterized by thermal analysis (TA), scanning electron microscopy (SEM), powder X-ray diffraction (XRD), and infrared spectroscopy (IR) before and after adsorption, confirming the presence of OTC in the ZIF-8 and the latter’s structural stability after the adsorption process. PMID:26057121
Novel band gap-tunable K-Na co-doped graphitic carbon nitride prepared by molten salt method

NASA Astrophysics Data System (ADS)

Zhao, Jiannan; Ma, Lin; Wang, Haoying; Zhao, Yanfeng; Zhang, Jian; Hu, Shaozheng

2015-03-01

Novel band gap-tunable K-Na co-doped graphitic carbon nitride was prepared by molten salt method using melamine, KCl, and NaCl as precursor. X-ray diffraction (XRD), N2 adsorption, Scanning electron microscope (SEM), UV-vis spectroscopy, Photoluminescence (PL), and X-ray photoelectron spectroscopy (XPS) were used to characterize the prepared catalysts. The CB and VB potentials of graphitic carbon nitride could be tuned from -1.09 and +1.55 eV to -0.29 and +2.25 eV by controlling the weight ratio of eutectic salts to melamine. Besides, ions doping inhibited the crystal growth of graphitic carbon nitride, enhanced the surface area, and increased the separation rate of photogenerated electrons and holes. The visible-light-driven Rhodamine B (RhB) photodegradation and mineralization performances were significantly improved after K-Na co-doping.
Construction of a novel pH-sensitive drug release system from mesoporous silica tablets coated with Eudragit

NASA Astrophysics Data System (ADS)

Xu, Yingpu; Qu, Fengyu; Wang, Yu; Lin, Huiming; Wu, Xiang; Jin, Yingxue

2011-03-01

A novel pH-sensitive drug release system has been established by coating Eudragit (Eud) on drug-loaded mesoporous silica (MS) tablets. The release rate of ibuprofen (IBU) from the MS was retarded by coating with Eudragit S-100, and the higher retardation was due to the increase of coating concentration and the coating layers. The target position of the release depended on the pH of the release medium, which was confirmed by the drug release from IBU/MS/Eud increasing rapidly with the change of medium pH from 1.2 to 7.4. This drug delivery system could prohibit irritant drug from leaking in the stomach and make it only release in the intestine. The loaded and unloaded drug samples were characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR), N 2 adsorption/desorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM).
Biomolecule-controlled hydrothermal synthesis of C-N-S-tridoped TiO2 nanocrystalline photocatalysts for NO removal under simulated solar light irradiation.

PubMed

Wang, Yawen; Huang, Yu; Ho, Wingkei; Zhang, Lizhi; Zou, Zhigang; Lee, Shuncheng

2009-09-30

In this study, C-N-S-tridoped titanium dioxide (TiO(2)) nanocrystals were synthesized by using a facile hydrothermal method in the presence of a biomolecule l-cysteine. This biomolecule could not only serve as the common source for the carbon, sulfur and nitrogen tridoping, but also could control the final crystal phases and morphology. The resulting materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and UV-vis diffuse reflectance spectroscopy. XPS analysis revealed that S was incorporated into the lattice of TiO(2) through substituting oxygen atoms, N might coexist in the forms of N-Ti-O and Ti-O-N in tridoped TiO(2) and most C could form a mixed layer of carbonate species deposited on the surface of TiO(2) nanoparticles. The photocatalytic activities of the samples were tested on the removal of NO at typical indoor air level in a flow system under simulated solar light irradiation. The tridoped TiO(2) samples showed much higher removal efficiency than commercial P25 and the undoped counterpart photocatalyst. The enhanced visible light photocatalytic activity of C-N-S-tridoped TiO(2) nanocrystals was explained on the basis of characterizations. The possible formation process of the monodispersed C-N-S-tridoped anatase TiO(2) nanocrystals was also proposed. This study provides a new method to prepare visible light active TiO(2) photocatalyst.
Prediction of Adsorption Equilibrium of VOCs onto Hyper-Cross-Linked Polymeric Resin at Environmentally Relevant Temperatures and Concentrations Using Inverse Gas Chromatography.

PubMed

Jia, Lijuan; Ma, Jiakai; Shi, Qiuyi; Long, Chao

2017-01-03

Hyper-cross-linked polymeric resin (HPR) represents a class of predominantly microporous adsorbents and has good adsorption performance toward VOCs. However, adsorption equilibrium of VOCs onto HPR are limited. In this research, a novel method for predicting adsorption capacities of VOCs on HPR at environmentally relevant temperatures and concentrations using inverse gas chromatography data was proposed. Adsorption equilibrium of six VOCs (n-pentane, n-hexane, dichloromethane, acetone, benzene, 1, 2-dichloroethane) onto HPR in the temperature range of 403-443 K were measured by inverse gas chromatography (IGC). Adsorption capacities at environmentally relevant temperatures (293-328 K) and concentrations (P/P s = 0.1-0.7) were predicted using Dubinin-Radushkevich (DR) equation based on Polany's theory. Taking consideration of the swelling properties of HPR, the volume swelling ratio (r) was introduced and r·V micro was used instead of V micro determined by N 2 adsorption data at 77 K as the parameter q 0 (limiting micropore volume) of the DR equation. The results showed that the adsorption capacities of VOCs at environmentally relevant temperatures and concentrations can be predicted effectively using IGC data, the root-mean-square errors between the predicted and experimental data was below 9.63%. The results are meaningful because they allow accurate prediction of adsorption capacities of adsorbents more quickly and conveniently using IGC data.
Effect of solvents on the extraction of natural pigments and adsorption onto TiO2 for dye-sensitized solar cell applications

NASA Astrophysics Data System (ADS)

Al-Alwani, Mahmoud A. M.; Mohamad, Abu Bakar; Kadhum, Abd. Amir H.; Ludin, Norasikin A.

2015-03-01

Nine solvents, namely, n-hexane, ethanol, acetonitrile, chloroform, ethyl-ether, ethyl-acetate, petroleum ether, n-butyl alcohol, and methanol were used to extract natural dyes from Cordyline fruticosa, Pandannus amaryllifolius and Hylocereus polyrhizus. To improve the adsorption of dyes onto the TiO2 particles, betalain and chlorophyll dyes were mixed with methanol or ethanol and water at various ratios. The adsorption of the dyes mixed with titanium dioxide (TiO2) was also observed. The highest adsorption of the C.fruticosa dye mixed with TiO2 was achieved at ratio 3:1 of methanol: water. The highest adsorption of P.amaryllifolius dye mixed with TiO2 was observed at 2:1 of ethanol: water. H.polyrhizus dye extracted by water and mixed with TiO2 demonstrated the highest adsorption among the solvents. All extracted dye was adsorbed onto the surface of TiO2 based on Fourier Transform Infrared Spectroscopy (FTIR) analysis. The inhibition of crystallinity of TiO2 was likewise investigated by X-ray analysis. The morphological properties and composition of dyes were analyzed via SEM and EDX.
Ab initio molecular dynamics determination of competitive O 2 vs. N 2 adsorption at open metal sites of M 2 (dobdc)

DOE PAGES

Parkes, Marie V.; Greathouse, Jeffery A.; Hart, David B.; ...

2016-04-04

The separation of oxygen from nitrogen using metal–organic frameworks (MOFs) is of great interest for potential pressure-swing adsorption processes for the generation of purified O 2 on industrial scales. This study uses ab initio molecular dynamics (AIMD) simulations to examine for the first time the pure-gas and competitive gas adsorption of O 2 and N 2 in the M 2(dobdc) (M = Cr, Mn, Fe) MOF series with coordinatively unsaturated metal centers. Effects of metal, temperature, and gas composition are explored. Lastly, this unique application of AIMD allows us to study in detail the adsorption/desorption processes and to visualize themore » process of multiple guests competitively binding to coordinatively unsaturated metal sites of a MOF.« less

Adsorption of carbon monoxide on smaller gold-cluster anions in an atmospheric-pressure flow-reactor: temperature and humidity dependence.

PubMed

Wallace, William T; Wyrwas, Richard B; Leavitt, Andrew J; Whetten, Robert L

2005-03-07

In the absence of moisture and at room temperature, the activity and saturation of CO on gold cluster anions, Au(N)-, are known to be highly dependent on the size of the cluster. Small Au(N)- clusters (N = 2,3) showed no adsorption activity, and the saturation CO adsorption values did not increase proportionately to cluster size or area. Here, we report on the effects of water vapor and temperature on the ability of Au(N)- clusters to adsorb CO in a high-pressure, fast-flow reactor. In contrast to all earlier reports, our results using this method show that smaller gold-cluster anions bind single and multiple CO groups at ambient temperature and above. In particular, species previously unseen at room temperature, corresponding to Au2(CO)-, Au3(CO) and Au4(CO)2, have been observed. Apparently, the presence of water vapor facilitates the adsorption of CO on the smaller clusters, possibly by aiding in the release of adsorption energy. As the number of studies concerning gold catalysis has continually increased over the past decade, these results provide important new information on the possible role of moisture in gold catalysis.
Activated carbon-supported CuO nanoparticles: a hybrid material for carbon dioxide adsorption

NASA Astrophysics Data System (ADS)

Boruban, Cansu; Esenturk, Emren Nalbant

2018-03-01

Activated carbon-supported copper(II) oxide (CuO) nanoparticles were synthesized by simple impregnation method to improve carbon dioxide (CO2) adsorption capacity of the support. The structural and chemical properties of the hybrid material were characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX), X-ray diffraction (https://www.google.com.tr/url?sa=t&rct=j&q=&esrc=s&source=web&cd=3&cad=rja&uact=8&ved=0CCsQFjAC&url=http%3A%2F%2Fwww.intertek.com%2Fanalytical-laboratories%2Fxrd%2F&ei=-5WZVYSCHISz7Aatqq-IAw&usg=AFQjCNFBlk-9wqy49foh8tskmbD-GGbG9g&sig2=eKrhYjO75rl_Id2sLGpq4w&bvm=bv.96952980,d.bGg) (XRD), X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS), and Brunauer-Emmett-Teller (BET) analyses. The analyses showed that CuO nanoparticles are well-distributed on the activated carbon surface. The CO2 adsorption behavior of the activated carbon-supported CuO nanoparticles was observed by thermogravimetric analysis (TGA), temperature programmed desorption (TPD), Fourier transform infrared (FTIR), and BET analyses. The results showed that CuO nanoparticle loading on activated carbon led to about 70% increase in CO2 adsorption capacity of activated carbon under standard conditions (1 atm and 298 K). The main contributor to the observed increase is an improvement in chemical adsorption of CO2 due to the presence of CuO nanoparticles on activated carbon.
GIS-NaP1 zeolite microspheres as potential water adsorption material: Influence of initial silica concentration on adsorptive and physical/topological properties

PubMed Central

Sharma, Pankaj; Song, Ju-Sub; Han, Moon Hee; Cho, Churl-Hee

2016-01-01

GIS-NaP1 zeolite samples were synthesized using seven different Si/Al ratios (5–11) of the hydrothermal reaction mixtures having chemical composition Al2O3:xSiO2:14Na2O:840H2O to study the impact of Si/Al molar ratio on the water vapour adsorption potential, phase purity, morphology and crystal size of as-synthesized GIS-NaP1 zeolite crystals. The X-ray diffraction (XRD) observations reveal that Si/Al ratio does not affect the phase purity of GIS-NaP1 zeolite samples as high purity GIS-NaP1 zeolite crystals were obtained from all Si/Al ratios. Contrary, Si/Al ratios have remarkable effect on the morphology, crystal size and porosity of GIS-NaP1 zeolite microspheres. Transmission electron microscopy (TEM) evaluations of individual GIS-NaP1 zeolite microsphere demonstrate the characteristic changes in the packaging/arrangement, shape and size of primary nano crystallites. Textural characterisation using water vapour adsorption/desorption, and nitrogen adsorption/desorption data of as-synthesized GIS-NaP1 zeolite predicts the existence of mix-pores i.e., microporous as well as mesoporous character. High water storage capacity 1727.5 cm3 g−1 (138.9 wt.%) has been found for as-synthesized GIS-NaP1 zeolite microsphere samples during water vapour adsorption studies. Further, the total water adsorption capacity values for P6 (1299.4 mg g−1) and P7 (1388.8 mg g−1) samples reveal that these two particular samples can absorb even more water than their own weights. PMID:26964638
GIS-NaP1 zeolite microspheres as potential water adsorption material: Influence of initial silica concentration on adsorptive and physical/topological properties.

PubMed

Sharma, Pankaj; Song, Ju-Sub; Han, Moon Hee; Cho, Churl-Hee

2016-03-11

GIS-NaP1 zeolite samples were synthesized using seven different Si/Al ratios (5-11) of the hydrothermal reaction mixtures having chemical composition Al2O3:xSiO2:14Na2O:840H2O to study the impact of Si/Al molar ratio on the water vapour adsorption potential, phase purity, morphology and crystal size of as-synthesized GIS-NaP1 zeolite crystals. The X-ray diffraction (XRD) observations reveal that Si/Al ratio does not affect the phase purity of GIS-NaP1 zeolite samples as high purity GIS-NaP1 zeolite crystals were obtained from all Si/Al ratios. Contrary, Si/Al ratios have remarkable effect on the morphology, crystal size and porosity of GIS-NaP1 zeolite microspheres. Transmission electron microscopy (TEM) evaluations of individual GIS-NaP1 zeolite microsphere demonstrate the characteristic changes in the packaging/arrangement, shape and size of primary nano crystallites. Textural characterisation using water vapour adsorption/desorption, and nitrogen adsorption/desorption data of as-synthesized GIS-NaP1 zeolite predicts the existence of mix-pores i.e., microporous as well as mesoporous character. High water storage capacity 1727.5 cm(3) g(-1) (138.9 wt.%) has been found for as-synthesized GIS-NaP1 zeolite microsphere samples during water vapour adsorption studies. Further, the total water adsorption capacity values for P6 (1299.4 mg g(-1)) and P7 (1388.8 mg g(-1)) samples reveal that these two particular samples can absorb even more water than their own weights.
Predicting mixed-gas adsorption equilibria on activated carbon for precombustion CO2 capture.

PubMed

García, S; Pis, J J; Rubiera, F; Pevida, C

2013-05-21

We present experimentally measured adsorption isotherms of CO2, H2, and N2 on a phenol-formaldehyde resin-based activated carbon, which had been previously synthesized for the separation of CO2 in a precombustion capture process. The single component adsorption isotherms were measured in a magnetic suspension balance at three different temperatures (298, 318, and 338 K) and over a large range of pressures (from 0 to 3000-4000 kPa). These values cover the temperature and pressure conditions likely to be found in a precombustion capture scenario, where CO2 needs to be separated from a CO2/H2/N2 gas stream at high pressure (~1000-1500 kPa) and with a high CO2 concentration (~20-40 vol %). Data on the pure component isotherms were correlated using the Langmuir, Sips, and dual-site Langmuir (DSL) models, i.e., a two-, three-, and four-parameter model, respectively. By using the pure component isotherm fitting parameters, adsorption equilibrium was then predicted for multicomponent gas mixtures by the extended models. The DSL model was formulated considering the energetic site-matching concept, recently addressed in the literature. Experimental gas-mixture adsorption equilibrium data were calculated from breakthrough experiments conducted in a lab-scale fixed-bed reactor and compared with the predictions from the models. Breakthrough experiments were carried out at a temperature of 318 K and five different pressures (300, 500, 1000, 1500, and 2000 kPa) where two different CO2/H2/N2 gas mixtures were used as the feed gas in the adsorption step. The DSL model was found to be the one that most accurately predicted the CO2 adsorption equilibrium in the multicomponent mixture. The results presented in this work highlight the importance of performing experimental measurements of mixture adsorption equilibria, as they are of utmost importance to discriminate between models and to correctly select the one that most closely reflects the actual process.
New physicochemical interpretations for the adsorption of food dyes on chitosan films using statistical physics treatment.

PubMed

Dotto, G L; Pinto, L A A; Hachicha, M A; Knani, S

2015-03-15

In this work, statistical physics treatment was employed to study the adsorption of food dyes onto chitosan films, in order to obtain new physicochemical interpretations at molecular level. Experimental equilibrium curves were obtained for the adsorption of four dyes (FD&C red 2, FD&C yellow 5, FD&C blue 2, Acid Red 51) at different temperatures (298, 313 and 328 K). A statistical physics formula was used to interpret these curves, and the parameters such as, number of adsorbed dye molecules per site (n), anchorage number (n'), receptor sites density (NM), adsorbed quantity at saturation (N asat), steric hindrance (τ), concentration at half saturation (c1/2) and molar adsorption energy (ΔE(a)) were estimated. The relation of the above mentioned parameters with the chemical structure of the dyes and temperature was evaluated and interpreted. Copyright © 2014 Elsevier Ltd. All rights reserved.
Application of 1-(2-pyridylazo)-2-naphthol-modified nanoporous silica as a technique in simultaneous trace monitoring and removal of toxic heavy metals in food and water samples.

PubMed

Abolhasani, Jafar; Behbahani, Mohammad

2015-01-01

Solid-phase extraction is one the most useful and efficient techniques for sample preparation, purification, cleanup, preconcentration, and determination of heavy metals at trace levels. In this paper, functionalized MCM-48 nanoporous silica with 1-(2-pyridylazo)-2-naphthol was applied for trace determination of copper, lead, cadmium, and nickel in water and seafood samples. The experimental conditions such as pH, sample and eluent flow rate, type, concentration and volume of the eluent, breakthrough volume, and effect of coexisting ions were optimized for efficient solid-phase extraction of trace heavy metals in different water and seafood samples. The content of solutions containing the mentioned heavy metals was determined by flame atomic absorption spectrometry (FAAS), and the limits of detection were 0.3, 0.4, 0.6, and 0.9 ng mL(-1) for cadmium, copper, nickel, and lead, respectively. Recoveries and precisions were >98.0 and <4%, respectively. The adsorption capacity of the modified nanoporous silica was 178 mg g(-1) for cadmium, 110 mg g(-1) for copper, 98 mg g(-1) for nickel, and 210 mg g(-1) for lead, respectively. The functionalized MCM-48 nanoporous silica with 1-(2-pyridylazo)-2-naphthol was characterized by thermogravimetry analysis (TGA), differential thermal analysis (DTA), transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FT-IR), X-ray diffraction (XRD), elemental analysis (CHN), and N2 adsorption surface area measurement.
Fabrication of a novel NiFe2O4/Zn-Al layered double hydroxide intercalated with EDTA composite and its adsorption behavior for Cr(VI) from aqueous solution

NASA Astrophysics Data System (ADS)

Deng, Lin; Shi, Zhou; Wang, Li; Zhou, Shiqing

2017-05-01

A novel magnetic NiFe2O4/Zn-Al layered double hydroxide intercalated with EDTA composite (NiFe2O4/ZnAl-EDTA LDH) was prepared through modified coprecipitation method and employed for adsorptive removal of Cr(VI) from aqueous solution. The adsorbents were characterized using Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), vibrating sample magnetometer (VSM), and X-ray photoelectron spectroscopy (XPS). Factors affecting the Cr(VI) adsorption, such as initial solution pH, adsorbent dosage, contact time, initial Cr(VI) concentration, temperature and coexisting ions, were studied systematically. Experiments results show that the magnetic NiFe2O4/ZnAl-EDTA LDH exhibits high adsorption efficiency within a wide pH range of 3.0-7.0 (R>80% at Cr(VI) concentration 50 mg L-1, contact time 360 min, and adsorbent dosage 2 g/L) and quick separation property. The adsorption process is fitted well with the Langmuir isotherm and pseudo-second-order kinetic model. The maximum theoretical adsorption capacity is found to be 77.22 mg g-1 at pH 6.0 and 318 K. The positive ΔH value (2.907 kJ mol-1) and negative ΔG value (-4.722 kJ mol-1) at 298-318 K reveals that the adsorption process is feasible, spontaneous and endothermic. Coexisting anions (PO43-, SO42-, CO32-, HCO3-, Cl-, and NO3-) have no significant effect on Cr(VI) removal. The mechanism study indicates that the adsorption of Cr(VI) onto NiFe2O4/ZnAl-EDTA LDH mainly involves electrostatic attraction and ion exchange interaction. It is interesting to note that a proportion of Cr(VI) adsorbed on the adsorbent surface are reduced to Cr(III) during the adsorption process. Results from this study demonstrate the potential utility of the magnetic NiFe2O4/ZnAl-EDTA LDH that could be developed into a viable technology for efficient removal of Cr(VI) from aqueous solution.
A structural study of the K adsorption site on a Si(001)2 × 1 surface: Dimer, caves or both

NASA Astrophysics Data System (ADS)

Asensio, M. C.; Michel, E. G.; Alvarez, J.; Ocal, C.; Miranda, R.; Ferrer, S.

1989-04-01

The atomic structure of the clean Si(100) and K covered surfaces has been investigated by Auger electron diffraction (AED) monitoring the intensities along polar scans. This technique is sensitive to the asymmetric-dimer nature of the 2 × 1 reconstruction of the Si(001) surface. Data taken at room temperature for submonolayer coverages are consistent with adsorption of K on the troughs (cave position) existing between two consecutive dimer chains along the [110] direction. At 110 K both dimer and cave sites are occupied. A mild annealing to 300 K produces an overlayer redistribution in favor of the "cave" site further indicating that this site is energetically favoured as found in some recent calculations.
Removal of nickel from aqueous solution using supported zeolite-Y hollow fiber membranes.

PubMed

Muhamad, Norfazilah; Abdullah, Norfazliana; Rahman, Mukhlis A; Abas, Khairul Hamimah; Aziz, Azian Abd; Othman, Mohd Hafiz Dzarfan; Jaafar, Juhana; Ismail, Ahmad Fauzi

2018-05-02

This work describes the development of supported zeolite-Y membranes, prepared using the hydrothermal method, for the removal of nickel from an aqueous solution. Alumina hollow fibers prepared using the phase inversion and sintering technique were used as an inert support. The supported zeolite-Y membranes were characterized using the field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), and the water permeation and rejection test. The performance of the supported zeolite-Y membranes for heavy metal removal using batch adsorption and filtration test was studied using the atomic absorption spectroscopy (AAS). The adsorption study shows that the removal of nickel was pH-dependent but affected by the presence of α-alumina. The seeded zeolite-Y membrane gave the highest adsorption capacity which was 126.2 mg g -1 . This enabled the membrane to remove 63% of nickel ions from the aqueous solution within 180 min of contact time. The adsorption mechanism of nickel onto the zeolite-Y membrane was best fitted to the Freundlich isotherm. The kinetic study concluded that the adsorption was best fitted to pseudo-second-order model with higher correlation coefficient (R 2 = 0.9996). The filtration study proved that the zeolite-Y membrane enabled to reduce the concentration of heavy metal at parts per billion level.
Sequential pH-dependent adsorption of ionic amphiphilic diblock copolymer micelles and choline oxidase onto conductive substrates: toward the design of biosensors.

PubMed

Sigolaeva, Larisa V; Günther, Ulrike; Pergushov, Dmitry V; Gladyr, Snezhana Yu; Kurochkin, Ilya N; Schacher, Felix H

2014-07-01

This work examines the fabrication regime and the properties of polymer-enzyme thin-films adsorbed onto conductive substrates (graphite or gold). The films are formed via two-steps, sequential adsorption of poly(n-butylmethacrylate)-block-poly(N,N-dimethylaminoethyl methacrylate) (PnBMA-b-PDMAEMA) diblock copolymer micelles (1st step of adsorption), followed by the enzyme choline oxidase (ChO) (2nd step of adsorption). The solution properties of both adsorbed components are studied and the pH-dependent step-by-step fabrication of polymer-enzyme biosensor coatings reveals rather drastic differences in their enzymatic activities in dependence on the pH of both adsorption steps. The resulting hybrid thin-films represent highly active biosensors for choline with a low detection limit of 30 nM and a good linearity in a range between 30 nM and 100 μM. The sensitivity is found to be 175 μA mM(-1) cm(-2) and the operational stability of the polymer-enzyme thin-films can be additionally improved via enzyme-to-enzyme crosslinking with glutaraldehyde. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Highly efficient and recyclable basic mesoporous zeolite catalyzed condensation, hydroxylation, and cycloaddition reactions.

PubMed

Sarmah, Bhaskar; Satpati, Biswarup; Srivastava, Rajendra

2017-05-01

Crystalline mesoporous ZSM-5 zeolite was prepared in the presence of 1,4-diazabicyclo[2.2.2]octane derived multi-cationic structure directing agent. The calcined form of the mesoprous zeolite was treated with NH 4 OH to obtain basic mesoporous ZSM-5. Catalyst was characterized by the complementary combination of X-ray diffraction, N 2 -adsorption, electron microscopes, and temperature programme desorption techniques. Catalytic activity of the basic mesoporous ZSM-5 was systematically assessed using Knoevenagel condensation reaction for the synthesis a wide range of substituted styrene. Applications of the catalyst were investigated in the benzamide hydroxylation for the synthesis of carbinolamides and one-pot, multi-component condensation reaction for the synthesis of naphthopyrans. Finally, the catalyst was evaluated in the cycloaddition of CO 2 to epoxide for the synthesis of cyclic carbonates. Recycling study shows that no significant decrease in the catalytic activity was observed after five recycles. Copyright © 2017. Published by Elsevier Inc.
Synthesis of nanometer-sized sodalite without adding organic additives.

PubMed

Fan, Wei; Morozumi, Kazumasa; Kimura, Riichiro; Yokoi, Toshiyuki; Okubo, Tatsuya

2008-06-01

Aggregates (80 nm) of sodalite nanocrystals with crystallite sizes ranging from 20 to 40 nm have been synthesized from a sodium aluminosilicate solution at low temperature, without adding any organic additives, while paying attention to the key factors for the synthesis of nanosized zeolite crystals. The physical properties of nanosized sodalite crystals were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, 29Si solid-state magic-angle spinning (MAS) NMR, and N2 adsorption. As expected, the external surface area of nanosized sodalite crystals is significantly increased compared with that of microsized sodalite crystals. The size of synthesized sodalite crystals can be controlled from 20 nm to 10 microm. It is found that the preparation of a homogeneous aluminosilicate solution followed by the formation of an aluminosilicate hard gel by adjusting the initial composition, for example, SiO2/Al2O3 and Na2O/H2O ratios, is critical for synthesis.
Corrosion behavior of low alloy steels in a wet-dry acid humid environment

NASA Astrophysics Data System (ADS)

Zhao, Qing-he; Liu, Wei; Yang, Jian-wei; Zhu, Yi-chun; Zhang, Bin-li; Lu, Min-xu

2016-09-01

The corrosion behavior of corrosion resistant steel (CRS) in a simulated wet-dry acid humid environment was investigated and compared with carbon steel (CS) using corrosion loss, polarization curves, X-ray diffraction (XRD), scanning electron microscopy (SEM), electron probe micro-analysis (EPMA), N2 adsorption, and X-ray photoelectron spectroscopy (XPS). The results show that the corrosion kinetics of both steels were closely related to the composition and compactness of the rust, and the electrochemical properties of rusted steel. Small amounts of Cu, Cr, and Ni in CRS increased the amount of amorphous phases and decreased the content of γ-FeOOH in the rust, resulting in higher compactness and electrochemical stability of the CRS rust. The elements Cu, Cr, and Ni were uniformly distributed in the CRS rust and formed CuFeO2, Cu2O, CrOOH, NiFe2O4, and Ni2O3, which enhanced the corrosion resistance of CRS in the wet-dry acid humid environment.
Response surface modeling for optimization heterocatalytic Fenton oxidation of persistence organic pollution in high total dissolved solid containing wastewater.

PubMed

Sekaran, G; Karthikeyan, S; Boopathy, R; Maharaja, P; Gupta, V K; Anandan, C

2014-01-01

The rice-husk-based mesoporous activated carbon (MAC) used in this study was precarbonized and activated using phosphoric acid. N2 adsorption/desorption isotherm, X-ray powder diffraction, electron spin resonance, X-ray photoelectron spectroscopy and scanning electron microscopy, transmission electron microscopy, (29)Si-NMR spectroscopy, and diffuse reflectance spectroscopy were used to characterize the MAC. The tannery wastewater carrying high total dissolved solids (TDS) discharged from leather industry lacks biodegradability despite the presence of dissolved protein. This paper demonstrates the application of free electron-rich MAC as heterogeneous catalyst along with Fenton reagent for the oxidation of persistence organic compounds in high TDS wastewater. The heterogeneous Fenton oxidation of the pretreated wastewater at optimum pH (3.5), H2O2 (4 mmol/L), FeSO4[Symbol: see text]7H2O (0.2 mmol/L), and time (4 h) removed chemical oxygen demand, biochemical oxygen demand, total organic carbon and dissolved protein by 86, 91, 83, and 90%, respectively.
The adsorption of Run (n = 1-4) on γ-Al2O3 Surface: A DFT study

NASA Astrophysics Data System (ADS)

Liu, Zhe; Guo, Yafei; Chen, Yu; Shen, Rong

2018-05-01

The density functional theory (DFT) was adopted to study the adsorption and growth of Run (n = 1-4) clusters on γ-Al2O3 surface, which is of great significances for the design of many important catalysts, especially for carbon dioxide methanation. It is found that both the Rusbnd Ru bond length and adsorption energy Eads of Ru clusters with the surface increase with the Run clusters increasing. The growth ability of the supported Run cluster is weaker than the gas phase Run clusters through comparing their respective growth process, which ascribes to the stabilization of γ-Al2O3 support. An interesting discovery is that the basin structure was supposed to be the most favorable adsorption geometry for Run clusters. Additionally, the distances between Ru atoms in the adsorbed clusters are longer than that in their isolated counterparts. Bader charge analysis was conducted for the most stable configurations of Run (n = 1-4) clusters on γ-Al2O3 surface as well. And the results suggest that Run (n = 1-4) clusters serve as the electron donators. The result of projected density of states (PDOS) shows that strong adsorption of Ru atom on the γ-Al2O3 surface correlates with strong interaction between d orbital of Ru atom and p orbital of Al or O atom of the Al2O3 support.
Monitoring N3 dye adsorption and desorption on TiO2 surfaces: a combined QCM-D and XPS study.

PubMed

Wayment-Steele, Hannah K; Johnson, Lewis E; Tian, Fangyuan; Dixon, Matthew C; Benz, Lauren; Johal, Malkiat S

2014-06-25

Understanding the kinetics of dye adsorption and desorption on semiconductors is crucial for optimizing the performance of dye-sensitized solar cells (DSSCs). Quartz crystal microbalance with dissipation monitoring (QCM-D) measures adsorbed mass in real time, allowing determination of binding kinetics. In this work, we characterize adsorption of the common RuBipy dye N3 to the native oxide layer of a planar, sputter-coated titanium surface, simulating the TiO2 substrate of a DSSC. We report adsorption equilibrium constants consistent with prior optical measurements of N3 adsorption. Dye binding and surface integrity were also verified by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS). We further study desorption of the dye from the native oxide layer on the QCM sensors using tetrabutylammonium hydroxide (TBAOH), a commonly used industrial desorbant. We find that using TBAOH as a desorbant does not fully regenerate the surface, though little ruthenium or nitrogen is observed by XPS after desorption, suggesting that carboxyl moieties of N3 remain bound. We demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption and desorption and begin to investigate the mechanism of dye desorption in DSSCs, a system that requires further study.
Cd(II) removal on surface-modified activated carbon: equilibrium, kinetics and mechanism.

PubMed

Liang, Jianjun; Liu, Meiling; Zhang, Yufei

2016-10-01

Commercial pulverous activated carbon (AC-0) was modified through two steps: oxidize AC-0 acid firstly, impregnate it with iron using ferric chloride secondly. Orthogonal experiment was conducted then to prepare modified activated carbon with high Cd(II) adsorption capacity (ACNF). Batch adsorption experiments were undertaken to determine the adsorption characteristics of Cd(II) from aqueous solution onto AC-0 and ACNF and the effect of pH, contact time and initial Cd(II) concentration. The results indicate that: the adsorption behavior of Cd(II) on ACNF can be well fitted with Langmuir model, and the maximum adsorption capacity of ACNF was 2.3 times higher than that of AC-0, supporting a monolayer coverage of Cd(II) on the surface. The kinetics of the adsorption process can be described by pseudo-second-order rate equation very well, and the adsorption capacity increased from 0.810 mg/g to 0.960 mg/g after modification. Compared with AC-0, the kinetic parameters of ACNF showed a higher adsorption rate through the aqueous solution to the solid surface and a lower intraparticle diffusion rate. Surface modification resulted in a lower Brunauer-Emmett-Teller (BET) surface area and pore size because of the collapse and blockage of pores, according to the X-ray diffraction (XRD) analysis, while the total number of surface oxygen acid groups increased, and this was supposed to contribute to the enhanced adsorption capacity of modified activated carbon.
Application of Zero-Valent Iron Nanoparticles for the Removal of Aqueous Zinc Ions under Various Experimental Conditions

PubMed Central

Liang, Wen; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei

2014-01-01

Application of zero-valent iron nanoparticles (nZVI) for Zn2+ removal and its mechanism were discussed. It demonstrated that the uptake of Zn2+ by nZVI was efficient. With the solids concentration of 1 g/L nZVI, more than 85% of Zn2+ could be removed within 2 h. The pH value and dissolved oxygen (DO) were the important factors of Zn2+ removal by nZVI. The DO enhanced the removal efficiency of Zn2+. Under the oxygen-contained condition, oxygen corrosion gave the nZVI surface a shell of iron (oxy)hydroxide, which could show high adsorption affinity. The removal efficiency of Zn2+ increased with the increasing of the pH. Acidic condition reduced the removal efficiency of Zn2+ by nZVI because the existing H+ inhibited the formation of iron (oxy)hydroxide. Adsorption and co-precipitation were the most likely mechanism of Zn2+ removal by nZVI. The FeOOH-shell could enhance the adsorption efficiency of nZVI. The removal efficiency and selectivity of nZVI particles for Zn2+ were higher than Cd2+. Furthermore, a continuous flow reactor for engineering application of nZVI was designed and exhibited high removal efficiency for Zn2+. PMID:24416439
Cation-Exchanged Zeolitic Chalcogenides for CO2 Adsorption.

PubMed

Yang, Huajun; Luo, Min; Chen, Xitong; Zhao, Xiang; Lin, Jian; Hu, Dandan; Li, Dongsheng; Bu, Xianhui; Feng, Pingyun; Wu, Tao

2017-12-18

We report here the intrinsic advantages of a special family of porous chalcogenides for CO 2 adsorption in terms of high selectivity of CO 2 /N 2 , large uptake capacity, and robust structure due to their first-ever unique integration of the chalcogen-soft surface, high porosity, all-inorganic crystalline framework, and the tunable charge-to-volume ratio of exchangeable cations. Although tuning the CO 2 adsorption properties via the type of exchangeable cations has been well-studied in oxides and MOFs, little is known about the effects of inorganic exchangeable cations in porous chalcogenides, in part because ion exchange in chalcogenides can be very sluggish and incomplete due to their soft character. We have demonstrated that, through a methodological change to progressively tune the host-guest interactions, both facile and nearly complete ion exchange can be accomplished. Herein, a series of cation-exchanged zeolitic chalcogenides (denoted as M@RWY) were studied for the first time for CO 2 adsorption. Samples were prepared through a sequential ion-exchange strategy, and Cs + -, Rb + -, and K + -exchanged samples demonstrated excellent CO 2 adsorption performance. Particularly, K@RWY has the superior CO 2 /N 2 selectivity with the N 2 adsorption even undetected at either 298 or 273 K. It also has the large uptake of 6.3 mmol/g (141 cm 3 /g) at 273 K and 1 atm with an isosteric heat of 35-41 kJ mol -1 , the best among known porous chalcogenides. Moreover, it permits a facile regeneration and exhibits an excellent recyclability, as shown by the multicycling adsorption experiments. Notably, K@RWY also demonstrates a strong tolerance toward water.

Studying the loading effect of acidic type antioxidant on amorphous silica nanoparticle carriers

NASA Astrophysics Data System (ADS)

Ravinayagam, Vijaya; Rabindran Jermy, B.

2017-06-01

The study investigates the suitable nanosilica carriers to transport acidic type cargo molecules for potential targeted drug delivery application. Using phenolic acidic type antioxidant gallic acid (GA) as model compound, the present study investigates the loading effect of GA (0.3-15.9 mmol GA g-1 support) on textural characteristics of amorphous silica nanoparticles such as Q10 silica (1D), structured two-dimensional Si-MCM-41 (2D), and three-dimensional Si-SBA-16 (3D). The variation in the nature of textures after GA loading was analyzed using X-ray diffraction, N2 adsorption, FT-IR, scanning electron microscopy with energy dispersive X-ray spectroscopy, and high-resolution transmission electron microscopy. Among the nanocarriers, high adsorption of GA was found in the following order: Si-SBA-16 (3D)˜Si-KIT-6 (3D) > Si-MCM-41 (2D) > ultralarge pore FDU-12 (ULPFDU-12; 3D) > Q10 (1D)˜mesostructured cellular silica foam (MSU-F). 3D-type silicas Si-SBA-16 and KIT-6 were shown to maintain structural integrity at acidic condition (pH ˜3) and accommodate GA in non-crystalline form. In the case of ULPFDU-12 and MSU-F cellular foam, only crystalline deposition of GA occurs with a significant variation in the surface area and pore volume. [Figure not available: see fulltext.
Reflection high energy electron diffraction observation of surface mass transport at the two- to three-dimensional growth transition of InAs on GaAs(001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patella, F.; Arciprete, F.; Fanfoni, M.

2005-12-19

We have followed by reflection high-energy electron diffraction the nucleation of InAs quantum dots on GaAs(001), grown by molecular-beam epitaxy with growth interruptions. Surface mass transport gives rise, at the critical InAs thickness, to a huge nucleation of three-dimensional islands within 0.2 monolayers (ML). Such surface mass diffusion has been evidenced by observing the transition of the reflection high-energy electron diffraction pattern from two- to three-dimensional during the growth interruption after the deposition of 1.59 ML of InAs. It is suggested that the process is driven by the As{sub 2} adsorption-desorption process and by the lowering of the In bindingmore » energy due to compressive strain. The last condition is met first in the region surrounding dots at step edges where nucleation predominantly occurs.« less
Microwave-assisted activated carbon from cocoa shell as adsorbent for removal of sodium diclofenac and nimesulide from aqueous effluents.

PubMed

Saucier, Caroline; Adebayo, Matthew A; Lima, Eder C; Cataluña, Renato; Thue, Pascal S; Prola, Lizie D T; Puchana-Rosero, M J; Machado, Fernando M; Pavan, Flavio A; Dotto, G L

2015-05-30

Microwave-induced chemical activation process was used to prepare an activated carbon from cocoa shell for efficient removal of two anti-inflammatories, sodium diclofenac (DFC) and nimesulide (NM), from aqueous solutions. A paste was obtained from a mixture of cocoa shell and inorganic components; with a ratio of inorganic: organic of 1 (CSC-1.0). The mixture was pyrolyzed in a microwave oven in less than 10 min. The CSC-1.0 was acidified with a 6 mol L(-1) HCl under reflux to produce MWCS-1.0. The CSC-1.0 and MWCS-1.0 were characterized using FTIR, SEM, N2 adsorption/desorption curves, X-ray diffraction, and point of zero charge (pHpzc). Experimental variables such as initial pH of the adsorbate solutions and contact time were optimized for adsorptive characteristics of MWCS-1.0. The optimum pH for removal of anti-inflammatories ranged between 7.0 and 8.0. The kinetic of adsorption was investigated using general order, pseudo first-order and pseu do-second order kinetic models. The maximum amounts of DCF and NM adsorbed onto MWCS-1.0 at 25 °C are 63.47 and 74.81 mg g(-1), respectively. The adsorbent was tested on two simulated hospital effluents. MWCS-1.0 is capable of efficient removal of DCF and NM from a medium that contains high sugar and salt concentrations. Copyright © 2015 Elsevier B.V. All rights reserved.
Optimization of tetracycline hydrochloride adsorption on amino modified SBA-15 using response surface methodology.

PubMed

Hashemikia, Samaneh; Hemmatinejad, Nahid; Ahmadi, Ebrahim; Montazer, Majid

2015-04-01

Several researchers are focused on preparation of mesoporous silica as drug carriers with high loading efficiency to control or sustain the drug release. Carriers with highly loaded drug are utilized to minimize the time of drug intake. In this study, amino modified SBA-15 was synthesized through grafting with amino propyl triethoxy silane and then loaded with tetracycline hydrochloride. The drug loading was optimized by using the response surface method considering various factors including drug to silica ratio, operation time, and temperature. The drug to silica ratio indicated as the most influential factor on the drug loading yield. Further, a quadratic polynomial equation was developed to predict the loading percentage. The experimental results indicated reasonable agreement with the predicted values. The modified and drug loaded mesoporous particles were characterized by FT-IR, SEM, TEM, X-ray diffraction (XRD), elemental analysis and N2 adsorption-desorption. The release profiles of tetracycline-loaded particles were studied in different pH. Also, Higuchi equation was used to analyze the release profile of the drug and to evaluate the kinetic of drug release. The drug release rate followed the conventional Higuchi model that could be controlled by amino-functionalized SBA-15. Further, the drug delivery system based on amino modified SBA-15 exhibits novel features with an appropriate usage as an anti-bacterial drug delivery system with effective management of drug adsorption and release. Copyright © 2014 Elsevier Inc. All rights reserved.
A chemiluminescence biosensor based on the adsorption recognition function between Fe3O4@SiO2@GO polymers and DNA for ultrasensitive detection of DNA

NASA Astrophysics Data System (ADS)

Sun, Yuanling; Li, Jianbo; Wang, Yanhui; Ding, Chaofan; Lin, Yanna; Sun, Weiyan; Luo, Chuannan

2017-05-01

In this work, a chemiluminescence (CL) biosensor was prepared for ultrasensitive determination of deoxyribonucleic acid (DNA) based on the adsorption recognition function between core-shell Fe3O4@SiO2 - graphene oxide (Fe3O4@SiO2@GO) polymers and DNA. The Fe3O4@SiO2@GO polymers were composed by GO and magnetite nanoparticles. And the core-shell polymers were confirmed by Scanning Electron Microscope (SEM), X-Ray Powder Diffraction (XRD) and Fourier Transform Infrared (FTIR). Then Fe3O4@SiO2@GO was modified by DNA. Based on the principle of complementary base, Fe3O4@SiO2@GO-DNA was introduced to the CL system and the selectivity, sensitivity of DNA detection was significantly improved. The adsorption properties of Fe3O4@SiO2@GO to DNA were researched through the adsorption equilibrium, adsorption kinetic and thermodynamics. Under optimized CL conditions, DNA could be assayed with the linear concentration range of 5.0 × 10- 12-2.5 × 10- 11 mol/L. The detection limit was 1.7 × 10- 12 mol/L (3δ) and the relative standard deviation (RSD) was 3.1%. The biosensor was finally used for the determination of DNA in laboratory samples and recoveries ranged from 99% to 103%. The satisfactory results revealed the potential application of Fe3O4@SiO2@GO-DNA-CL biosensor in the diagnosis and the treatment of human genetic diseases.
Effect of heat treatment on CO2 adsorption of KOH-activated graphite nanofibers.

PubMed

Meng, Long-Yue; Park, Soo-Jin

2010-12-15

In this work, graphite nanofibers (GNFs) were successfully expanded intercalating KOH followed by heat treatment in the temperature range of 700-1000 °C. The aim was to improve the CO(2) adsorption capacity of the GNFs by increasing the porosity of GNFs. The effects of heat treatment on the pore structures of GNFs were investigated by N(2) full isotherms, XRD, SEM, and TEM. The CO(2) adsorption capacity was measured by CO(2) isothermal adsorption at 25 °C and 1 atm. From the results, it was found that the activation temperature had a major influence on CO(2) adsorption capacity and textural properties of GNFs. The specific surface area, total pore volume, and mesopore volume of the GNFs increased after heat treatment. The CO(2) adsorption isotherms showed that G-900 exhibited the best CO(2) adsorption capacity with 59.2 mg/g. Copyright © 2010 Elsevier Inc. All rights reserved.
Performance Characteristics of Waste Glass Powder Substituting Portland Cement in Mortar Mixtures

NASA Astrophysics Data System (ADS)

Kara, P.; Csetényi, L. J.; Borosnyói, A.

2016-04-01

In the present work, soda-lime glass cullet (flint, amber, green) and special glass cullet (soda-alkaline earth-silicate glass coming from low pressure mercury-discharge lamp cullet and incandescent light bulb borosilicate glass waste cullet) were ground into fine powders in a laboratory planetary ball mill for 30 minutes. CEM I 42.5N Portland cement was applied in mortar mixtures, substituted with waste glass powder at levels of 20% and 30%. Characterisation and testing of waste glass powders included fineness by laser diffraction particle size analysis, specific surface area by nitrogen adsorption technique, particle density by pycnometry and chemical analysis by X-ray fluorescence spectrophotometry. Compressive strength, early age shrinkage cracking and drying shrinkage tests, heat of hydration of mortars, temperature of hydration, X-ray diffraction analysis and volume stability tests were performed to observe the influence of waste glass powder substitution for Portland cement on physical and engineering properties of mortar mixtures.
CO{sub 2} adsorption-based separation by metal organic framework (Cu-BTC) versus zeolite (13X)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhijian Liang; Marc Marshall; Alan L. Chaffee

2009-05-15

The potential for the metal organic framework (MOF) Cu-BTC to selectively adsorb and separate CO{sub 2} is considered. Isotherms for CO{sub 2}, CH{sub 4}, and N{sub 2} were measured from 0 to 15 bar and at temperatures between 25 and 105{sup o}C. The isotherms suggest a much higher working capacity (x4) for CO{sub 2} adsorption on Cu-BTC relative to the benchmark zeolite 13X over the same pressure range. Higher CO{sub 2}/N{sub 2} and CO{sub 2}/CH{sub 4} selectivities in the higher pressure range (1-15 bar) and with lower heats of adsorption were also demonstrated. Cu-BTC was observed to be stable inmore » O{sub 2} at 25{sup o}C, but its crystallinity was reduced in humid environments. The CO{sub 2} adsorption capacity was progressively reduced upon cyclic exposure to water vapor at low relative humidity (<30%), but leveled out at 75% of its original value after several water adsorption/desorption cycles. 27 refs., 1 fig.« less
The sensing mechanism of N-doped SWCNTs toward SF6 decomposition products: A first-principle study

NASA Astrophysics Data System (ADS)

Gui, Yingang; Tang, Chao; Zhou, Qu; Xu, Lingna; Zhao, Zhongyong; Zhang, Xiaoxing

2018-05-01

In order to monitor the insulation status of SF6-insulated equipment on-line, SOF2 and SO2F2, two typical decomposition products of SF6 under electric discharge condition, are chosen as the target gases to evaluate the type and severity of discharge. In this work, single N atom doping method is adopted to improve the gas sensitivity of single wall carbon nanotubes to SOF2 and SO2F2. Single and double gas molecules adsorptions are considered to completely analyze the adsorption properties of N-doped single wall carbon nanotubes. Calculation results show that N atom doping enhances the surface activity of carbon nanotubes. When gas molecules physically adsorbed on N-doped single wall carbon nanotubes, the weak interaction between gas molecules and N-doped single wall carbon nanotubes nearly not changes the electrical property according to analysis of the density of states and molecular orbitals. While the chemisorption between gas molecules and N-doped single wall carbon nanotubes distinctly decreases the conductivity of adsorption system.
Assembly and property research on seven 0D–3D complexes derived from imidazole dicarboxylate and 1,2-bi(pyridin-4-yl)ethene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mu, Bao; Li, Qian; Lv, Lei

2015-03-15

The hydrothermal reaction of transition metals, 1H-imidazole-4,5-dicarboxylic acid (H{sub 3}ImDC) and 1,2-bi(pyridin-4-yl)ethene (bpe) affords a series of new complexes, namely, [Mn(HImDC)(bpe)(H{sub 2}O)] (1), [M(H{sub 2}ImDC){sub 2}(H{sub 2}O){sub 2}]·(bpe) (M=Fe(2), Co(3), Zn(4), Cd(6)), [Zn{sub 3}(ImDC){sub 2}(bpe)(H{sub 2}O)]·3H{sub 2}O (5) and [Cd(H{sub 2}ImDC)(bpe)] (7), which are characterized by elemental analyses, IR, TG, XRPD and single crystal X-ray diffraction. Complex 1 exhibits a one dimensional (1D) zigzag chain with two types of irregular rings, and the 1D chains are linked to form a three dimensional (3D) supramolecular framework by the hydrogen bonding interactions (O–H∙∙∙O and O–H∙∙∙N). Complexes 2–4 and 6 are isomorphous, andmore » they display the mononuclear structures. In these complexes, the O–H∙∙∙O and O–H∙∙∙N hydrogen bonds play an important role in sustaining the whole 3D supramolecular frameworks. Complex 5 shows a (3,3)-connected 3D framework with (10{sup 3}) topology, and the lattice water molecules as guest molecules exist in the 3D framework. Complex 7 is a wave-like two dimensional (2D) structure, in which the adjacent 1D chains point at the opposite directions. Moreover, the fluorescent properties of complexes 1–7 and the magnetic property of 1 have been investigated. The water vapor adsorption for complex 5 has been researched at 298 K. - Graphical abstract: Seven new complexes based on different structural characteristics have been hydrothermally synthesized by the mixed ligands. The fluorescent properties, the magnetic property and the water vapor adsorption have been investigated. - Highlights: • The semi-rigid ligand with C=C bonds and imidazole dicarboxylates with some advantages have been used. • A series of new complexes with different structural characteristics have been discussed in detail. • The fluorescent properties, the magnetic property and the water vapor adsorption have been investigated.« less
A floating macro/mesoporous crystalline anatase TiO2 ceramic with enhanced photocatalytic performance for recalcitrant wastewater degradation.

PubMed

Xing, Zipeng; Zhou, Wei; Du, Fan; Qu, Yang; Tian, Guohui; Pan, Kai; Tian, Chungui; Fu, Honggang

2014-01-14

A macro/mesoporous anatase TiO2 ceramic floating photocatalyst has been successfully synthesized using highly thermally stable mesoporous TiO2 powder as a precursor, followed by a camphene-based freeze-casting process and high-temperature calcinations. The ceramics are characterized in detail by X-ray diffraction, Raman spectra, scanning electron microscopy, transmission electron microscopy and N2 adsorption-desorption isotherms. The results indicate that the TiO2 ceramics present hierarchical macro/mesoporous structures, which maintain high porosity and high compressive strength at the optimal sintering temperature of 800 °C. The ordered mesoporous TiO2 network still possesses high thermal stability and inhibits the anatase-to-rutile phase transformation during calcinations. The obtained ceramics exhibit good adsorptive and photocatalytic activity for the degradation of octane and rhodamine B, and the total organic carbon removal ratio is up to 98.8% and 98.6% after photodegradation for 3 h, respectively. The roles of active species in the photocatalytic process are compared using different types of active species scavengers, and the degradation mechanism is also proposed. Furthermore, the ceramics are recyclable, and no clear changes are observed after ten cycles. In addition, the ceramics are also active in the photodegradation of phenol, thiobencarb, and atrazine. Therefore, these novel floating photocatalysts will have wide applications, including the removal of floating organic pollutants from the wastewater surfaces or the removal of soluble organic pollutants from wastewater.
Surface enhanced Raman spectroscopic studies on aspirin : An experimental and theoretical approach

NASA Astrophysics Data System (ADS)

Premkumar, R.; Premkumar, S.; Rekha, T. N.; Parameswari, A.; Mathavan, T.; Benial, A. Milton Franklin

2016-05-01

Surface enhanced Raman scattering (SERS) studies on aspirin molecule adsorbed on silver nanoparticles (AgNPs) were investigated by experimental and density functional theory approach. The AgNPs were synthesized by the solution-combustion method and characterized by the X-ray diffraction and high resolution-transmission electron microscopy techniques. The averaged particle size of synthesized AgNPs was calculated as ˜55 nm. The normal Raman spectrum (nRs) and SERS spectrum of the aspirin were recorded. The molecular structure of the aspirin and aspirin adsorbed on silver cluster were optimized by the DFT/ B3PW91 method with LanL2DZ basis set. The vibrational frequencies were calculated and assigned on the basis of potential energy distribution calculation. The calculated nRs and SERS frequencies were correlated well with the observed frequencies. The flat-on orientation was predicted from the nRs and SERS spectra, when the aspirin adsorbed on the AgNPs. Hence, the present studies lead to the understanding of adsorption process of aspirin on the AgNPs, which paves the way for biomedical applications.
Surface enhanced Raman spectroscopic studies on aspirin : An experimental and theoretical approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Premkumar, R.; Premkumar, S.; Parameswari, A.

Surface enhanced Raman scattering (SERS) studies on aspirin molecule adsorbed on silver nanoparticles (AgNPs) were investigated by experimental and density functional theory approach. The AgNPs were synthesized by the solution-combustion method and characterized by the X-ray diffraction and high resolution-transmission electron microscopy techniques. The averaged particle size of synthesized AgNPs was calculated as ∼55 nm. The normal Raman spectrum (nRs) and SERS spectrum of the aspirin were recorded. The molecular structure of the aspirin and aspirin adsorbed on silver cluster were optimized by the DFT/ B3PW91 method with LanL2DZ basis set. The vibrational frequencies were calculated and assigned on the basismore » of potential energy distribution calculation. The calculated nRs and SERS frequencies were correlated well with the observed frequencies. The flat-on orientation was predicted from the nRs and SERS spectra, when the aspirin adsorbed on the AgNPs. Hence, the present studies lead to the understanding of adsorption process of aspirin on the AgNPs, which paves the way for biomedical applications.« less
Highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste with amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent.

PubMed

Bao, Shuangyou; Tang, Lihong; Li, Kai; Ning, Ping; Peng, Jinhui; Guo, Huibin; Zhu, Tingting; Liu, Ye

2016-01-15

Amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent was used as a novel sorbent to highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste in the presence of Fe(II). These hot-dip galvanizing pickling waste mainly contain ZnCl2 and FeCl2 in aqueous HCl media. The properties of this magnetic adsorbent were examined by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), infrared spectrometer (FT-IR) and BET surface area measurements. Various factors influencing the adsorption of Zn(II) ion such as initial concentration of metal ions, the amount of adsorbent, pH value of the solutions, the concentration of coexisting iron ion were investigated by batch experiments. The results indicated that the adsorption equilibrium data obeyed the Freundlich model with maximum adsorption capacities for Zn(II) to 169.5mg/g. The maximum adsorption occurred at pH 5±0.1 and Fe(II) interferences had no obvious influence. This work provides a potential and unique technique for zinc ion removal from hot-dip galvanizing pickling waste. Copyright © 2015 Elsevier Inc. All rights reserved.
Photocatalytic and adsorption properties of TiO2-pillared montmorillonite obtained by hydrothermally activated intercalation of titanium polyhydroxo complexes

PubMed Central

Ovchinnikov, Nikolay L; Karasev, Nikita S; Kochkina, Nataliya E; Agafonov, Alexander V; Vinogradov, Alexandr V

2018-01-01

We report on a new approach for the synthesis of TiO2-pillared montmorillonite, where the pillars exhibit a high degree of crystallinity (nanocrystals) representing a mixture of anatase and rutile phases. The structures exhibit improved adsorption and photocatalytic activity as a result of hydrothermally activated intercalation of titanium polyhydroxo complexes (i.e., TiCl4 hydrolysis products) in a solution with a concentration close to the sol formation limit. The materials, produced at various annealing temperatures from the intercalated samples, were characterized by infrared spectroscopy, differential scanning calorimetry (DSC)/thermogravimetric analysis (TGA), X-ray diffraction, dynamic light scattering (DLS) measurements, and liquefied nitrogen adsorption/desorption. The photocatalytic activity of the TiO2-pillared materials was studied using the degradation of anionic (methyl orange, MO) and cationic (rhodamine B, RhB) dyes in water under UV irradiation. The combined effect of adsorption and photocatalysis resulted in removal of 100% MO and 97.5% RhB (with an initial concentration of 40 mg/L and a photocatalyst-sorbent concentration of 1 g/L) in about 100 minutes. The produced TiO2-pillared montmorillonite showed increased photocatalytic activity as compared to the commercially available photocatalyst Degussa P25. PMID:29515950
Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption.

PubMed

Wu, Hui; Chua, Yong Shen; Krungleviciute, Vaiva; Tyagi, Madhusudan; Chen, Ping; Yildirim, Taner; Zhou, Wei

2013-07-17

UiO-66 is a highly important prototypical zirconium metal-organic framework (MOF) compound because of its excellent stabilities not typically found in common porous MOFs. In its perfect crystal structure, each Zr metal center is fully coordinated by 12 organic linkers to form a highly connected framework. Using high-resolution neutron power diffraction technique, we found the first direct structural evidence showing that real UiO-66 material contains significant amount of missing-linker defects, an unusual phenomenon for MOFs. The concentration of the missing-linker defects is surprisingly high, ∼10% in our sample, effectively reducing the framework connection from 12 to ∼11. We show that by varying the concentration of the acetic acid modulator and the synthesis time, the linker vacancies can be tuned systematically, leading to dramatically enhanced porosity. We obtained samples with pore volumes ranging from 0.44 to 1.0 cm(3)/g and Brunauer-Emmett-Teller surface areas ranging from 1000 to 1600 m(2)/g, the largest values of which are ∼150% and ∼60% higher than the theoretical values of defect-free UiO-66 crystal, respectively. The linker vacancies also have profound effects on the gas adsorption behaviors of UiO-66, in particular CO2. Finally, comparing the gas adsorption of hydroxylated and dehydroxylated UiO-66, we found that the former performs systematically better than the latter (particularly for CO2) suggesting the beneficial effect of the -OH groups. This finding is of great importance because hydroxylated UiO-66 is the practically more relevant, non-air-sensitive form of this MOF. The preferred gas adsorption on the metal center was confirmed by neutron diffraction measurements, and the gas binding strength enhancement by the -OH group was further supported by our first-principles calculations.
A highly sensitive chemical gas detecting device based on N-doped ZnO as a modified nanostructure media: A DFT+NBO analysis

NASA Astrophysics Data System (ADS)

Abbasi, Amirali; Sardroodi, Jaber Jahanbin

2018-02-01

We presented a density functional theory study of the adsorption of O3 and NO2 molecules on ZnO nanoparticles. Various adsorption geometries of O3 and NO2 over the nanoparticles were considered. For both O3 and NO2 adsorption systems, it was found that the adsorption on the N-doped nanoparticle is more favorable in energy than that on the pristine one. Therefore, the N-doped ZnO has a better efficiency to be utilized as O3 and NO2 detection device. For all cases, the binding sites were located on the zinc atoms of the nanoparticle. The charge analysis based on natural bond orbital (NBO) analysis indicates that charge was transferred from the surface to the adsorbed molecule. The projected density of states of the interacting atoms represent the formation of chemical bonds at the interface region. Molecular orbitals of the adsorption systems indicate that the HOMOs were mainly localized on the adsorbed O3 and NO2 molecules, whereas the electronic densities in the LUMOs were dominant at the ZnO nanocrystal surface. By examining the distribution of spin densities, we found that the magnetization was mainly located over the adsorbed molecules. For NO2 adsorbate, we found that the symmetric and asymmetric stretches were shifted to a lower frequency. The bending stretch mode was shifted to the higher frequency. Our DFT results thus provide a theoretical basis for why the adsorption of O3 and NO2 molecules on the N-doped ZnO nanoparticles may increase, giving rise to design and development of innovative and highly efficient sensor devices for O3 and NO2 recognition.
Effect of cetyl trimethyl ammonium bromide concentration on structure, morphology and carbon dioxide adsorption capacity of calcium hydroxide based sorbents

NASA Astrophysics Data System (ADS)

Hlaing, Nwe Ni; Vignesh, K.; Sreekantan, Srimala; Pung, Swee-Yong; Hinode, Hirofumi; Kurniawan, Winarto; Othman, Radzali; Thant, Aye Aye; Mohamed, Abdul Rahman; Salim, Chris

2016-02-01

Calcium hydroxide (Ca(OH)2) has been proposed as an important material for industrial, architectural, and environmental applications. In this study, calcium acetate was used as a precursor and cetyl trimethyl ammonium bromide (CTAB) was used as a surfactant to synthesize Ca(OH)2 based adsorbents for carbon dioxide (CO2) capture. The effect of CTAB concentration (0.2-0.8 M) on the structure, morphology and CO2 adsorption performance of Ca(OH)2 was studied in detail. The synthesized samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), BET surfaced area and thermogravimetry-differential thermal analysis (TG-DTA) techniques. The phase purity, crystallite size, Brunauer-Emmett-Teller (BET) surface area and CO2 adsorption performance of Ca(OH)2 precursor adsorbents were significantly increased when the concentration of CTAB was increased. XRD results showed that pure Ca(OH)2 phase was obtained at the CTAB concentration of 0.8 M. TGA results exhibited that 0.8 M of CTAB-assisted Ca(OH)2 precursor adsorbent possessed a residual carbonation conversion of ∼56% after 10 cycles.
Effect of metal cation ratio on chemical properties of ZnFe2O4/AC composite and adsorption of organic contaminant

NASA Astrophysics Data System (ADS)

Meilia, Demara; Misbah Khunur, Mochamad; Setianingsih, Tutik

2018-01-01

Porous woody char is biochar prepared through pyrolisis. The biochar can be used as adsorbent. In this research, ZnFe2O4/AC composite was synthesized through imregnation of the woody biochar with ZnFe2O4 to study effect of mol ratio of Fe(III) and Zn(II) toward their physicochemistry and adsorption of drug wastewater. Paracetamol was used as adsorbate model. This research was conducted in several steps, including activation of the woody biochar using KOH activator at temperatur 500 °C for 15 min to produce the activated carbon, fungsionalization of the carbon using H2SO4 oxidator (6M) at temperature of 80 °C for 3 h, impregnation of the oxidized activated carbon with Zn-Fe-LDH (Layered Double Hydroxide) at various mol ratio of Fe(III) and Zn(III), including 1:2, 1:3 and 1:4 using NaOH solution (5M) for coprecipitation, and calcination of Zn-Fe-LDH/AC at 950 °C for 5 min to produce ZnFe2O4/AC. FTIR diffraction characterization indicated existence of M-O (M = Zn(II), Fe(III)) and OH functional groups. FTIR spectra showed increasing of bands connected to -OH by increasing of the ratio till the ratio was achieved at 1:4, then decreased again. The ratio mol showed effect on the adsorption of paracetamol. Profile of adsorption value was fit with changing of functional groups. The highest adsorption was achieved at the ratio of 1:4. After calcination it gave the adsorption value of 17,66 mg/g.
Insights into the Hydrothermal Stability of Triamine-Functionalized SBA-15 Silica for CO2 Adsorption.

PubMed

Jahandar Lashaki, Masoud; Ziaei-Azad, Hessam; Sayari, Abdelhamid

2017-10-23

The hydrothermal stability of triamine-grafted, large-pore SBA-15 CO 2 adsorbents was studied by using steam stripping. Following two 3 h cycles of steam regeneration, lower CO 2 uptakes, lower CO 2 /N ratios, and slower adsorption kinetics were observed relative to fresh samples, particularly at the lowest adsorption temperature (25 °C). CO 2 adsorption measurements for a selected sample exposed to 48 h of steam stripping depicted that after the initial loss during the first exposure to steam (3-6 h), the adsorptive properties stabilized. For higher adsorption temperatures (i.e., 50 and 75 °C), however, all adsorptive properties remained almost unchanged after steaming, indicating the significance of diffusional limitations. Thermogravimetric analysis and FTIR spectroscopy on grafted samples before and after steam stripping showed no amine leaching and no change in the chemical nature of the amine groups, respectively. Also, a six-cycle CO 2 adsorption/desorption experiment under dry conditions showed no thermal degradation. However, N 2 adsorption measurement at 77 K showed significant reductions in the BET surface area of the grafted samples following steaming. Based on the pore size distribution of calcined, grafted samples before and after steaming, it is proposed that exposure to steam restructured the grafted materials, causing mass transfer resistance. It is inferred that triamine-grafted, large-pore SBA-15 adsorbents are potential candidates for CO 2 capture at relatively high temperatures (50-75 °C; for example, flue gas) combined with steam regeneration. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene oxide/MnO2 nanocomposite as destructive adsorbent of nerve-agent simulants in aqueous media

NASA Astrophysics Data System (ADS)

Šťastný, Martin; Tolasz, Jakub; Štengl, Václav; Henych, Jiří; Žižka, David

2017-08-01

Graphene oxide/MnO2 nanocomposite was prepared by thermal hydrolysis of potassium permanganate (KMnO4) and 2-chloroacetamide aqueous solutions with graphene oxide (GO) suspension. The synthesized samples were characterized by specific surface area (BET) and porosity determination (BJH), X-ray Diffraction (XRD) and high-resolution electron microscopes (HRSEM, HRTEM). These nanocomposites were used in an experimental evaluation of their adsorption activity with nerve agent simulants dimethyl methyl phosphonate (DMMP) and triethyl phosphate (TEP) in aqueous media. The nanocomposites exhibited enhanced adsorptive degradation ability compared to pure manganese oxide (MnO2) and GO. The GO amount in the nanocomposites affected their degradation activity substantially. The best adsorption efficiency was observed for samples with moderate GO amount. Three methods were used to observe the mechanism of the nerve-agent simulants deactivation: Gas chromatography with mass spectrometry (GC-MS), High-Performance Liquid Chromatography (HPLC) and in situ Infrared spectroscopy (FTIR). It was shown that the hydrolysis on the surface of prepared nanocomposites yields volatile primary alcohols (methanol and ethanol) as the main hydrolysis products.
Comparative study on ultrasonic assisted adsorption of dyes from single system onto Fe3O4 magnetite nanoparticles loaded on activated carbon: Experimental design methodology.

PubMed

Bagheri, Ahmad Reza; Ghaedi, Mehrorang; Asfaram, Arash; Bazrafshan, Ali Akbar; Jannesar, Ramin

2017-01-01

The present study the ultrasound assisted adsorption of dyes in single system onto Fe 3 O 4 magnetite nanoparticles loaded on activated carbon (Fe 3 O 4 -MNPs-AC) was described following characterization and identification of this adsorbent by conventional techniques likes field emission scanning electron microscopy, transmission electron microscopy, particle-size distribution, X-ray diffraction and Fourier transform infrared spectroscopy. A central composite design in conjunction with a response surface methodology according to f-test and t-test for recognition and judgment about significant term led to construction of quadratic model which represent relation among responses and effective terms. This model has unique ability to predict adsorption data behavior over a large space around central and optimum point. Accordingly Optimum conditions for well and quantitative removal of present dyes was obtained best operation and conditions: initial SY, MB and EB dyes concentration of 15, 15 and 25mgL -1 , 4.0, 6.0 and 5.0 of pH, 360, 360 and 240s sonication time and 0.04, 0.03 and 0.032g of Fe 3 O 4 -MNPs-AC. Replication of similar experiment (N=5) guide that average removal percentage of SY, MB and EB were found to be 96.63±2.86%, 98.12±1.67% and 99.65±1.21% respectively. Good agreement and closeness of Predicted and experimental result and high adsorption capacity of dyes in short time strongly confirm high suitability of present method for waste water treatment, while easy separation of present nanoparticle and its good regeneration all support good applicability of Fe 3 O 4 -MNPs-AC for waste water treatment. The kinetic study can be represented by combination of pseudo second-order and intraparticle diffusion. The obtained maximum adsorption capacities correspond to Langmuir as best model for representation of experimental data correspond to dyes adsorption onto Fe 3 O 4 -MNPs-AC were 76.37, 78.76 and 102.00mgg -1 for SY, MB and EB, respectively. In addition, the performance comparison of ultrasound-assisted, magnetic stirrer assisted and vortex assisted adsorption methods demonstrates that ultrasound is an effective and good choice for facilitation of adsorption process via. Compromise of simple and facile diffusion. Copyright © 2016 Elsevier B.V. All rights reserved.
Hydrothermal stability of SAPO-34 for refrigeration and air conditioning applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Haijun; Cui, Qun, E-mail: cuiqun@njtech.edu.cn; Wu, Juan

Graphical abstract: The SAPO-34 was synthesized by a hydrothermal method using diethylamine as a template. Water adsorption strength on SAPO-34 is between that on 13X and A type silica gel. During 100–400 Pa, the water uptake on SAPO-34 increases sensitively to pressure, and equilibrium water uptake reaches 0.35 kg/kg, 25% higher than 13X. SAPO-34 shows no significant reduced cyclic water uptake over 60 cycles. Most of the initial SAPO-34 phase is restored, while the regular cubic-like morphology is well maintained, and the specific surface area only decreases by 8.6%. - Highlights: • Water adsorption strength on SAPO-34 is between thatmore » on 13X and A type silica gel. During 100–400 Pa, the water uptake on SAPO-34 increases sensitively to pressure, and equilibrium water uptake reaches 0.35 kg/kg, 25% higher than 13X. • SAPO-34 with diethylamine as the template shows no significant reduced cyclic water uptake over 60 cycles, and most of the initial SAPO-34 phase is well maintained. • SAPO-34 has an excellent adsorption performance and a good hydrothermal stability, thus is promising for application in adsorption refrigeration. - Abstract: Hydrothermal stability is one of the crucial factors in applying SAPO-34 molecular sieve to adsorption refrigration. The SAPO-34 was synthesized by a hydrothermal method using diethylamine as a template. Both a vacuum gravimetric method and an intelligent gravimetric analyzer were applied to analyze the water adsorption performance of SAPO-34. Cyclic hydrothermal performance was determined on the modified simulation adsorption refrigeration test rig. Crystal phase, morphology, and porosity of SAPO-34 were characterized by X-ray diffraction, scanning electron microscopy, and N{sub 2} sorption, respectively. The results show that, water adsorption strength on SAPO-34 is between that on 13X and A type silica gel. During 100–400 Pa, the water uptake on SAPO-34 increases sensitively to pressure, and equilibrium water uptake reaches 0.35 kg/kg, 25% higher than 13X. SAPO-34 shows no significant reduced cyclic water uptake over 60 cycles. Most of the initial SAPO-34 phase is restored, while the regular cubic-like morphology is well maintained, and the specific surface area only decreases by 8.6%.« less
Facile preparation of nitrogen and sulfur co-doped graphene-based aerogel for simultaneous removal of Cd2+ and organic dyes.

PubMed

Kong, Qiaoping; Wei, Chaohai; Preis, Sergei; Hu, Yun; Wang, Feng

2018-05-17

The need in simultaneous removal of heavy metals and organic compounds dictates the development of synthetic adsorbents with tailor-made properties. A nitrogen (N) and sulfur (S) co-doped graphene-based aerogel (GBA) modified with 2,5-dithiobisurea was synthesized hydrothermally for simultaneous adsorption of Cd 2+ and organic dyes-safranin-O (SO), crystal violet (CV), and methylene blue (MB). 2,5-Dithiobisurea was used as nitrogen and sulfur sources to introduce N and S-containing functional group onto graphene oxide. The adsorption mechanism of GBA towards Cd 2+ and organic dyes was studied by Dumwald-Wagner models and the results showed that surface and intraparticle diffusion was the key factor in controlling the rate of adsorption. The maximum adsorption capacities of GBA towards Cd 2+ , SO, CV, and MB comprised 1.755, 0.949, 0.538, and 0.389 mmol/g in monocomponent system, respectively. Adsorption synergism was observed with respect to Cd 2+ in presence of the dyes. The performance of GBA with respect to Cd 2+ removal from binary solutions, Cd 2+ -SO, Cd 2+ -CV, and Cd 2+ -MB, was enhanced by the presence of the dyes significantly, while the adsorption capacities towards the dyes were not affected by the presence of Cd 2+ .
Chitosan-rectorite nanospheres immobilized on polystyrene fibrous mats via alternate electrospinning/electrospraying techniques for copper ions adsorption

NASA Astrophysics Data System (ADS)

Tu, Hu; Huang, Mengtian; Yi, Yang; Li, Zhenshun; Zhan, Yingfei; Chen, Jiajia; Wu, Yang; Shi, Xiaowen; Deng, Hongbing; Du, Yumin

2017-12-01

Chitosan (CS), as a kind of well characterized biopolymer, has been used for heavy metal adsorption due to its low cost and high efficacy. However, when used directly, chitosan particles had small surface area and weak mechanical strength which is unfavorable to metal adsorption and reused. Besides, it cannot be easily recycled that may cause a secondary pollution. In this paper, CS and layered silicate rectorite (REC) were fully mixed and the mixtures were subsequently electrosprayed nano-sized spheres, which were immobilized on the surface of electrospun polystyrene (PS) mats for metal adsorption. The morphology analysis taken from SEM confirmed that CS-REC nanospheres were loaded on the surface of PS fibrous mats. Small Angle X-ray diffraction patterns showed that the interlayer distance of REC in composite mats was enlarged by the intercalation of CS chains; such structure meant bigger surface area which was helpful for metal adsorption. The data of contact angle implied that PS mats coated with CS-REC nanospheres exhibited better hydrophilicity than PS mats, which was conductive to adsorption rate. Besides, the copper ions adsorption of composite mats was tested at different conditions including the adsorption time, the initial pH and the initial concentration of copper ion. The results demonstrated that PS mats coated with CS-REC nanospheres had the adsorption capacity up to 134 mg/g. In addition, the addition of REC containing Ca2+ could also improve the metal adsorption because of cation exchange. The desorption assay indicated that PS mats immobilized with CS and CS-REC still kept high adsorption ability which retained 74% and 78% after three adsorption-desorption cycles.
Cation Movements during Dehydration and NO2 Desorption in a Ba-Y,FAU zeolite: an in situ Time-resolved X-ray Diffraction Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xianqin; Hanson, Jonathan C.; Kwak, Ja Hun

2013-02-28

Synchrotron-based in situ time-resolved X-ray diffraction and Rietveld analysis were used to probe the interactions between BaY, FAU zeolite frameworks and H2O or NO2 molecules. These results provided information about the migration of the Ba2+ cations in the zeolite framework during dehydration and during NO2 adsorption/desorption processes in a water free zeolite. In the hydrated structure water molecules form four double rings of hexagonal ice-like clusters [(H2O)6] in the 12-ring openings of the super-cage. These water rings interacted with the cations and the zeolite framework through four cation/water clusters centered over the four 6-membered rings of the super-cage (site II).more » Interpenetrating tetrahedral water clusters [(H2O)4] and tetrahedral Ba+2 cation clusters were observed in the sodalite cage. Consistent with the reported FT-IR results, three different ionic NOx species (NO+, NO+-NO2, and NO3-) were observed following NO2 adsorption by the dehydrated Ba-Y,FAU zeolite. The structure of the water and the NOx species were correlated with the interactions between the adsorbates, the cations, and the framework. The population of Ba2+ ions at different cationic positions strongly depended on the amount of bound water or NOx species. Both dehydration and NO2 adsorption/desorption resulted in facile migration of Ba2+ ions among the different cationic positions. Data obtained in this work have provided direct evidence for the Ba2+ cation migration to accommodate the binding of gas molecules. This important feature may play a pivotal role in the strong binding of NO2 to Ba-Y,FAU zeolite, a prerequisite for high catalytic activity in lean NOx reduction catalysis.« less
Characterization and adsorption properties of diatomaceous earth modified by hydrofluoric acid etching.

PubMed

Tsai, Wen-Tien; Lai, Chi-Wei; Hsien, Kuo-Jong

2006-05-15

This work was a study of the chemical modification of diatomaceous earth (DE) using hydrofluoric acid (HF) solution. Under the experimental conditions investigated, it was found that HF under controlled conditions significantly etched inward into the interior of the existing pore structure in the clay mineral due to its high content of silica, leaving a framework possessing a larger BET surface area (ca. 10 m2 g(-1)) in comparison with that (ca. 4 m2 g(-1)) of its precursor (i.e., DE). Further, the results indicated that the HF concentration is a more determining factor in creating more open pores than other process parameters (temperature, holding time, and solid/liquid ratio). This observation was also in close agreement with the examinations by the silicon analysis, scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The adsorption kinetics and the adsorption isotherm of methylene blue onto the resulting clay adsorbent can be well described by a pseudo-second-order reaction model and the Freundlich model, respectively.
The synthesis of novel hybrid thiol-functionalized nano-structured SBA-15

NASA Astrophysics Data System (ADS)

Hoang, Van Duc; Phuong Dang, Tuyet; Khieu Dinh, Quang; Phu Nguyen, Huu; Vu, Anh Tuan

2010-09-01

Mesoporous thiol-functionalized SBA-15 has been directly synthesized by co-condensation of tetraethyl orthosilicate (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) with triblock copolymer P123 as-structure-directing agent under hydrothermal conditions. Surfactant removal was performed by Soxhlet ethanol extraction. These materials have been characterized by powder x-ray diffraction (XRD), nitrogen adsorption/desorption (BET model), transmission electron microscopy (TEM), thermal analysis, infrared spectroscopy (IR) and energy-dispersive x-ray spectroscopy (EDX). The main parameters, such as the initial molar ratio of MPTMS to TEOS, the time of adding MPTMS to synthesized gel and the Soxhlet ethanol extraction on the thiol functionalized SBA-15 with high thiol content and highly ordered hexagonal mesostructure, were investigated and evaluated. The adsorption capacity of the thiol-functionalized and non-functionalized SBA-15 materials for Pb2+ ion from aqueous solution was tested. It was found that the Pb2+ adsorption capacity of the thiol functionalized SBA-15 is three times higher than that of non-functionalized SBA-15.
ZnS nanostructured thin-films deposited by successive ionic layer adsorption and reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deshmukh, S. G., E-mail: deshmukhpradyumn@gmail.com; Jariwala, Akshay; Agarwal, Anubha

ZnS thin films were grown on glass substrate using successive ionic layer adsorption and reaction (SILAR) technique at room temperature. Aqueous solutions of ZnCl{sub 2} and Na{sub 2}S were used as precursors. The X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Raman spectroscopy and optical absorption measurements were applied to study the structural, surface morphology and optical properties of as-deposited ZnS thin films. The X-ray diffraction profiles revealed that ZnS thin films consist of crystalline grains with cubic phase. Spherical nano grains of random size and well covered on the glass substrate were observed from FESEM. The average grainmore » size were found to be 77 nm, 100 nm and 124 nm for 20 cycles, 40 cycles and 60 cycles samples respectively. For 60 cycle sample, Raman spectra show two prominent peaks at 554 cm{sup −1} and 1094 cm{sup −1}. The optical band gap values were found to be 3.76 eV, 3.72 eV and 3.67 eV for 20 cycle, 40 cycle and 60 cycle samples respectively.« less
Adsorption of methyl orange by synthesized and functionalized-CNTs with 3-aminopropyltriethoxysilane loaded TiO2 nanocomposites.

PubMed

Ahmad, Amirah; Razali, Mohd Hasmizam; Mamat, Mazidah; Mehamod, Faizatul Shimal Binti; Anuar Mat Amin, Khairul

2017-02-01

This study aims to develop a highly efficient adsorbent material. CNTs are prepared using a chemical vapor deposition method with acetylene and synthesized mesoporous Ni-MCM41 as the carbon source and catalyst, respectively, and are then functionalized using 3-aminopropyltriethoxysilane (APTES) through the co-condensation method and loaded with commercial TiO 2 . Results of X-ray powder diffraction (XRD), Raman spectra, and Fourier transform infrared spectroscopy (FTIR) confirm that the synthesized CNTs grown are multi-walled carbon nanotubes (MWNTs). Transmission electron microscopy shows good dispersion of TiO 2 nanoparticles onto functionalized-CNTs loaded TiO 2 , with the diameter of a hair-like structure measuring between 3 and 8 nm. The functionalized-CNTs loaded TiO 2 are tested as an adsorbent for removal of methyl orange (MO) in aqueous solution, and results show that 94% of MO is removed after 10 min of reaction, and 100% after 30 min. The adsorption kinetic model of functionalized-CNTs loaded TiO 2 follows a pseudo-second order with a maximum adsorption capacity of 42.85 mg/g. This study shows that functionalized-CNTs loaded TiO 2 has considerable potential as an adsorbent material due to the short adsorption time required to achieve equilibrium. Copyright © 2016 Elsevier Ltd. All rights reserved.
Adsorption of dodecylamine hydrochloride on graphene oxide in water

NASA Astrophysics Data System (ADS)

Chen, Peng; Li, Hongqiang; Song, Shaoxian; Weng, Xiaoqing; He, Dongsheng; Zhao, Yunliang

Cationic surfactants in water are difficult to be degraded, leading to serious water pollution. In this work, graphene oxide (GO) was used as an adsorbent for removing Dodecylamine Hydrochloride (DACl), a representative cationic surfactant. X-ray diffraction (XRD), FT-IR spectroscopy and atomic force microscope (AFM) were used to characterize the prepared GO. The adsorption of DACl on GO have been investigated through measurements of adsorption capacity, zeta potential, FTIR, and X-ray photoelectron spectroscopy (XPS). The experimental results have shown that the adsorption kinetics could be described as a rate-limiting pseudo second-order process, and the adsorption isotherm agreed well with the Freundlich model. GO was a good adsorbent for DACl removal, compared with coal fly ash and powdered activated carbon. The adsorption process was endothermic, and could be attributed to electrostatic interaction and hydrogen bonding between DACl and GO.
DFT study of gases adsorption on sharp tip nano-catalysts surface for green fertilizer synthesis

NASA Astrophysics Data System (ADS)

Yahya, Noorhana; Irfan, Muhammad; Shafie, Afza; Soleimani, Hassan; Alqasem, Bilal; Rehman, Zia Ur; Qureshi, Saima

2016-11-01

The energy minimization and spin modifications of sorbates with sorbents in magnetic induction method (MIM) play a vital role in yield of fertilizer. Hence, in this article the focus of study is the interaction of sorbates/reactants (H2, N2 and CO2) in term of average total adsorption energies, average isosteric heats of adsorption energies, magnetic moments, band gaps energies and spin modifications over identical cone tips nanocatalyst (sorbents) of Fe2O3, Fe3O4 (magnetic), CuO and Al2O3 (non-magnetic) for green nano-fertilizer synthesis. Study of adsorption energy, band structures and density of states of reactants with sorbents are purely classical and quantum mechanical based concepts that are vividly illustrated and supported by ADSORPTION LOCATOR and Cambridge Seriel Total Energy Package (CASTEP) modules following classical and first principle DFT simulation study respectively. Maximum values of total average energies, total average adsorption energies and average adsorption energies of H2, N2 and CO2 molecules are reported as -14.688 kcal/mol, -13.444 kcal/mol, -3.130 kcal/mol, - kcal/mol and -6.348 kcal/mol over Al2O3 cone tips respectively and minimum over magnetic cone tips. Whereas, the maximum and average minimum values of average isosteric heats of adsorption energies of H2, N2 and CO2 molecules are figured out to be 3.081 kcal/mol, 4.842 kcal/mol and 6.848 kcal/mol, 0.988 kcal/mol, 1.554 kcal/mol and 2.236 kcal/mol over aluminum oxide and Fe3O4 cone tips respectively. In addition to the adsorption of reactants over identical cone sorbents the maximum and minimum values of net spin, electrons and number of bands for magnetite and aluminum oxide cone structures are attributed to 82 and zero, 260 and 196, 206 and 118 for Fe3O4 and Al2O3 cones respectively. Maximum and least observed values of band gap energies are figured out to be 0.188 eV and 0.018 eV with Al2O3 and Fe3O4 cone structures respectively. Ultimately, with the adsorption of reactants an identical increment of 14 electrons each in up and down spins is resulted.
Nitrogen-doped porous carbon derived from biomass waste for high-performance supercapacitor.

PubMed

Ma, Guofu; Yang, Qian; Sun, Kanjun; Peng, Hui; Ran, Feitian; Zhao, Xiaolong; Lei, Ziqiang

2015-12-01

High capacitance property and low cost are the pivotal requirements for practical application of supercapacitor. In this paper, a low cost and high capacitance property nitrogen-doped porous carbon with high specific capacitance is prepared. The as-prepared nitrogen-doped porous carbon employing potato waste residue (PWR) as the carbon source, zinc chloride (ZnCl2) as the activating agent and melamine as nitrogen doping agent. The morphology and structure of the carbon materials are studied by scanning electron microscopy (SEM), N2 adsorption/desorption, X-ray diffraction (XRD) and Raman spectra. The surface area of the nitrogen-doped carbon which prepared under 700°C is found to be 1052m(2)/g, and the specific capacitance as high as 255Fg(-1) in 2M KOH electrolyte is obtained utilize the carbon as electrode materials. The electrode materials also show excellent cyclability with 93.7% coulombic efficiency at 5Ag(-1) current density of for 5000cycles. Copyright © 2015 Elsevier Ltd. All rights reserved.
Adsorption of sugar surfactants at the air/water interface.

PubMed

Varga, Imre; Mészáros, Róbert; Stubenrauch, Cosima; Gilányi, Tibor

2012-08-01

The adsorption isotherms of n-decyl-β-D-glucoside (β-C(10)G(1)) as well as various n-alkyl-β-D-maltosides (β-C(n)G(2)) with n=8, 10, 12 and 14 were determined from surface tension measurements. Based on the analysis of the adsorption isotherms, the total free energy change of adsorption was determined and a novel method was proposed to determine the maximum adsorbed amount of surfactant. It can be concluded that the driving force for adsorption first increases with increasing adsorbed amount of the sugar surfactants and then levels off in a plateau. This peculiar behaviour is interpreted as formation of a thin liquid-like alkane film of overlapping alkyl chains at the air/water interface once a certain adsorbed amount is exceeded. The driving force of adsorption depends on the alkyl chain length only and is not affected by the type of the head group. The hydrophobic contribution to the standard free energy change of adsorption was compared with the values of sodium alkylsulfate and alkyltrimethylammonium bromide surfactants. This comparison reveals that the hydrophobic driving force of adsorption is the largest for the sodium alkylsulfates, whereas it is the same for the sugar surfactants and the alkyltrimethylammonium bromides. Copyright © 2012 Elsevier Inc. All rights reserved.
Chemical splitting of multiwalled carbon nanotubes to enhance electrochemical capacitance for supercapacitors

NASA Astrophysics Data System (ADS)

Li, Xinlu; Li, Tongtao; Zhang, Xinlin; Zhong, Qineng; Li, Hongyi; Huang, Jiamu

2014-06-01

Multiwalled carbon nanotubes (MWCNTs) were chemically split and self-assembled to a flexible porous paper made of graphene oxide nanoribbons (GONRs). The morphology and microstructure of the pristine MWCNTs and GONRs were analyzed by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Raman spectroscopy and Fourier transform infrared spectroscopy. And the specific surface area and porosity structure were measured by N2 adsorption-desorption. The longitudinally split MWCNTs show an enhancement in specific capacitance from 21 F g-1 to 156 F g-1 compared with the pristine counterpart at 0.1 A g-1 in a 6 M KOH aqueous electrolytes. The electrochemical experiments prove that the chemical splitting of MWCNTs will make inner carbon layers opened and exposed to electrochemical double layers, which can effectively improve the electrochemical capacitance for supercapacitors.
The effect of the distance between acidic site and basic site immobilized on mesoporous solid on the activity in catalyzing aldol condensation

NASA Astrophysics Data System (ADS)

Yu, Xiaofang; Yu, Xiaobo; Wu, Shujie; Liu, Bo; Liu, Heng; Guan, Jingqi; Kan, Qiubin

2011-02-01

Acid-base bifunctional heterogeneous catalysts containing carboxylic and amine groups, which were immobilized at defined distance from one another on the mesoporous solid were synthesized by immobilizing lysine onto carboxyl-SBA-15. The obtained materials were characterized by X-ray diffraction (XRD), N 2 adsorption, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron micrographs (SEM), transmission electron micrographs (TEM), elemental analysis, and back titration. Proximal-C-A-SBA-15 with a proximal acid-base distance was more active than maximum-C-A-SBA-15 with a maximum acid-base distance in aldol condensation reaction between acetone and various aldehydes. It appears that the distance between acidic site and basic site immobilized on mesoporous solid should be an essential factor for catalysis optimization.
Immobilization of Chlorosulfonyl-Calix[4]arene onto the surface of silica gel through the directly estrification

NASA Astrophysics Data System (ADS)

Taghvaei-Ganjali, Saeed; Zadmard, Reza; Saber-Tehrani, Mandana

2012-06-01

For the first time Chlorosulfonyl-Calix[4]arene has been chemically bonded to silica gel through the directly estrification without silane coupling agent to prepare Chlorosulfonyl-Calix[4]arene-bonded silica gel. Sample characterization was performed by various techniques such as elemental analysis, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), powder X-ray diffraction (XRD), N2 adsorption-desorption, thermal gravimetric analysis (TGA), 29Si CP/MAS spectroscopy and acid-base titration. All data approve the successful incorporation of organic group via covalent bond. From the comparison between sulfur content determined by elemental analysis and the number of H+ determined by acid-base titration, it was shown that two ester units took place onto the new synthesized sample and two acidic sites exist on the surface.
Influence of vacancy defect on surface feature and adsorption of Cs on GaN(0001) surface.

PubMed

Ji, Yanjun; Du, Yujie; Wang, Meishan

2014-01-01

The effects of Ga and N vacancy defect on the change in surface feature, work function, and characteristic of Cs adsorption on a (2 × 2) GaN(0001) surface have been investigated using density functional theory with a plane-wave ultrasoft pseudopotential method based on first-principles calculations. The covalent bonds gain strength for Ga vacancy defect, whereas they grow weak for N vacancy defect. The lower work function is achieved for Ga and N vacancy defect surfaces than intact surface. The most stable position of Cs adatom on Ga vacancy defect surface is at T1 site, whereas it is at B(Ga) site on N vacancy defect surface. The E(ads) of Cs on GaN(0001) vacancy defect surface increases compared with that of intact surface; this illustrates that the adsorption of Cs on intact surface is more stable.
Influence of Vacancy Defect on Surface Feature and Adsorption of Cs on GaN(0001) Surface

PubMed Central

Ji, Yanjun; Du, Yujie; Wang, Meishan

2014-01-01

The effects of Ga and N vacancy defect on the change in surface feature, work function, and characteristic of Cs adsorption on a (2 × 2) GaN(0001) surface have been investigated using density functional theory with a plane-wave ultrasoft pseudopotential method based on first-principles calculations. The covalent bonds gain strength for Ga vacancy defect, whereas they grow weak for N vacancy defect. The lower work function is achieved for Ga and N vacancy defect surfaces than intact surface. The most stable position of Cs adatom on Ga vacancy defect surface is at T1 site, whereas it is at BGa site on N vacancy defect surface. The E ads of Cs on GaN(0001) vacancy defect surface increases compared with that of intact surface; this illustrates that the adsorption of Cs on intact surface is more stable. PMID:25126599
Growth of hydroxyapatite in a biocompatible mesoporous ordered silica.

PubMed

Díaz, A; López, T; Manjarrez, J; Basaldella, E; Martínez-Blanes, J M; Odriozola, J A

2006-03-01

A novel biomaterial (HA-SBA-15) has been developed based on the growth of calcium phosphate hydroxyapatite (HA) nanoparticles within an organized silica structure (SBA-15). Characterization of the material was carried out using a combination of X-ray diffraction, X-ray fluorescence, transmission electron microscopy, N2 adsorption-desorption isotherms and nuclear magnetic resonance. Transmission electron microscopy observations and N2 porosimetry revealed the crystallization of hydroxyapatite nanoparticles inside the mesopore cavities of the silica structure. Specific surface areas of 760 m2 g(-1) and 260 m2 g(-1) were measured for the SBA-15 and the HA-SBA-15 material, respectively. The hydroxyl groups present in the silica nanostructure surface have brought about cationic defects in the silicium sites, mainly with those of tetrahedral symmetry, and promoted the formation of siloxanes. 29Si MAS-NMR analysis shows a significant reduction of the silanol groups concentration with HA growing within the base (SBA-15) material. Studies and brain tissue biocompatibility tests were carried out. Histopathological studies on the SBA-15 implant material showed no changes to the tissue nearby. The results confirmed the synthesis of a silica-based composite containing HA nanoparticles with the potential for biomedical applications.

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