Dynamic laser speckle technique as an alternative tool to determine hygroscopic capacity and specific surface area of microporous zeolites

NASA Astrophysics Data System (ADS)

Mojica-Sepulveda, Ruth Dary; Mendoza-Herrera, Luís Joaquín; Grumel, Eduardo; Soria, Delia Beatriz; Cabello, Carmen Inés; Trivi, Marcelo

2018-07-01

Adsorption phenomena have several technological applications such as desiccants, catalysts, and separation of gases. Their uses depend on the textural properties of the solid adsorbent and the type of the adsorbed liquid or gas. Therefore, it is important to determine these properties. The most common measurement methods are physicochemical based on adsorption of N2 to determine the surface area and the distribution of pores size. However these techniques present certain limitations for microporous materials. In this paper we propose the use of the Dynamic Laser Speckle (DLS) technique to measure the hygroscopic capacity of a microporous natural zeolite and their modified forms. This new approach based on the adsorption of water by solids allows determine their specific surface area (S). To test the DLS results, we compared the obtained S values to those calculated by different conventional isotherms using the N2 adsorption-desorption method.

Application of activated carbon modified by acetic acid in adsorption and separation of CO2 and CH4

NASA Astrophysics Data System (ADS)

Song, Xue; Wang, Li'ao; Zeng, Yunmin; Zhan, Xinyuan; Gong, Jian; Li, Tong

2018-03-01

Compared with the methods to modify the activated carbons by alkalis for gas adsorption, fewer studies of that by organic acids have been reported. The acid modified activated carbons are usually utilized to treat wastewater, whereas the application in the separation of CO2/CH4 has less been studied. In this study, acetic acid was used to modify activated carbon. N2 adsorption/desorption isotherms and FT-IR were adopted to describe the properties of the samples. According to the adsorption data of pure gas component at 298 K, the gas adsorbed amount and the selectivity on the modified samples were larger than that on the raw sample. Besides, the adsorbed amount of CO2 and the selectivity on 15H-AC in the adsorption breakthrough experiments showed better performance. The results confirm that the method to modify the activated carbons with acetic acid is feasible to improve the adsorption capacity and the separation effect of CO2/CH4.

Adsorptive Behavior and Voltammetric Determination of Hydralazine Hydrochloride at A Glassy Carbon Electrode Modified with Multiwalled Carbon Nanotubes

PubMed Central

Khodadadian, Mehdi; Jalili, Ronak; Bahrami, Mohammad Taher; Bahrami, Gholamreza

2017-01-01

An electroanalytical method has been introduced for highly sensitive determination of hydralazine hydrochloride (Hy-HCl) based on its oxidation at a glassy carbon electrode modified with multiwalled carbon nanotubes (MWCNT/GCE). Studies showed that the electrochemical oxidation of Hy-HCl was accompanied by adsorption and highly sensitive responses could be achieved by adsorptive stripping voltammetry. The electrooxidation of Hy-HCl at MWCNT/GCE occurred at ~32 mV which was lower than that observed at bare GCE (~52 mV). The optimum working conditions for determination of the drug using differential-pulse adsorptive stripping voltammetry (DPAdSV) were established. The method exhibited linear responses to Hy-HCl in the concentration range 10-220 nM with a detection limit of 2.7 nM. The proposed method was successfully applied to the determination of this compound in pharmaceutical dosage forms. PMID:29552043

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

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.

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.

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.

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.

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.

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).

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.

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.

Density function theory study of the adsorption and dissociation of carbon monoxide on tungsten nanoparticles.

PubMed

Weng, Meng-Hsiung; Ju, Shin-Pon; Chen, Hsin-Tsung; Chen, Hui-Lung; Lu, Jian-Ming; Lin, Ken-Huang; Lin, Jenn-Sen; Hsieh, Jin-Yuan; Yang, Hsi-Wen

2013-02-01

The adsorption and dissociation properties of carbon monoxide (CO) molecule on tungsten W(n) (n = 10-15) nanoparticles have been investigated by density-functional theory (DFT) calculations. The lowest-energy structures for W(n) (n = 10-15) nanoparticles are found by the basin-hopping method and big-bang method with the modified tight-binding many-body potential. We calculated the corresponding adsorption energies, C-O bond lengths and dissociation barriers for adsorption of CO on nanoparticles. The electronic properties of CO on nanoparticles are studied by the analysis of density of state and charge density. The characteristic of CO on W(n) nanoparticles are also compared with that of W bulk.

Activated carbon with excellent chromium(VI) adsorption performance prepared by acid-base surface modification.

PubMed

Liu, S X; Chen, X; Chen, X Y; Liu, Z F; Wang, H L

2007-03-06

In the present work, activated carbon (AC) with excellent Cr(VI) adsorption performance especially at low concentrations was prepared by an acid-base surface modification method. Raw activated carbon (AC(0)) was first oxidized in boiling HNO(3) (AC(1)), then treated with a mixture of NaOH and NaCl (AC(2)). Batch equilibrium and continuous column adsorption were conducted to evaluate the adsorption performance. Boehm titration, elemental analysis, and N(2)/77K adsorption isotherm methods were used to characterize the surface properties and pore structure of modified ACs. The results revealed that the modified AC exhibited excellent Cr(VI) adsorption performance in terms of adsorption capacity and adsorption rate: AC(2)>AC(1)>AC(0). Modification caused S(BET) to decrease and the total number of surface oxygen acidic groups to increase. HNO(3) oxidization produced positive acid groups, and subsequently NaOH treatment replaced H(+) of surface acid groups by Na(+), and the acidity of AC decreased. The main cause of higher Cr(VI) adsorption capacity and rate for AC(2) was the presence of more oxygen surface acidic groups and suitable surface acidity. HNO(3)-NaOH modification shows potential for the preparation of high quality AC for the effective removal of low concentrations of Cr(VI).

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.

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.

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

Li-adsorption on doped Mo2C monolayer: A novel electrode material for Li-ion batteries

NASA Astrophysics Data System (ADS)

Mehta, Veenu; Tankeshwar, K.; Saini, Hardev S.

2018-04-01

A first principle calculation has been used to study the electronic and magnetic properties of pristine and N/Mn-doped Mo2C with and without Li-adsorption. The pseudopotential method implemented in SIESTA code based on density functional theory with generalized gradient approximation (GGA) as exchange-correlation (XC) potential has been employed. Our calculated results revealed that the Li gets favorably adsorbed on the hexagonal centre in pristine Mo2C and at the top of C-atom in case of N/Mn-doped Mo2C. The doping of Mn and N atom increases the adsorption of Li in Mo2C monolayer which may results in enhancement of storage capacity in Li-ion batteries. The metallic nature of Li-adsorbed pristine and N/Mn-doped Mo2C monolayer implies a good electronic conduction which is crucial for anode materials for its applications in rechargeable batteries. Also, the open circuit voltage for single Li-adsorption in doped Mo2C monolayer comes in the range of 0.4-1.0 eV which is the optimal range for any material to be used as an anode material. Our result emphasized the enhanced performance of doped Mo2C as an anode material in Li-ion batteries.

Effect of TiO2, ZrO2, and TiO2-ZrO2 on the performance of CuO-ZnO catalyst for CO2 hydrogenation to methanol

NASA Astrophysics Data System (ADS)

Xiao, Jie; Mao, Dongsen; Guo, Xiaoming; Yu, Jun

2015-05-01

The influence of TiO2, ZrO2, and TiO2-ZrO2 mixed oxide on the catalytic performance of CuO-ZnO catalyst in the methanol synthesis from CO2 hydrogenation was studied. The catalysts were prepared by oxalate co-precipitation method and characterized by TGA, N2 adsorption, XRD, reactive N2O adsorption, XPS, H2-TPR, H2-TPD, and CO2-TPD techniques. Characterization results reveal that all the additives improve the CuO dispersion in the catalyst body and increase the Cu surface area and adsorption capacities of CO2 and H2. The results of catalytic test reveal that the additives increase both the CO2 conversion and methanol selectivity, and TiO2-ZrO2 mixed oxide is more effective than single components of TiO2 or ZrO2. Moreover, the activity of methanol synthesis is correlated directly with CO2 adsorption capacity over the catalysts.

Adsorption mechanism of SF6 decomposed species on pyridine-like PtN3 embedded CNT: A DFT study

NASA Astrophysics Data System (ADS)

Cui, Hao; Zhang, Xiaoxing; Chen, Dachang; Tang, Ju

2018-07-01

Metal-Nx embedded CNT have aroused considerable attention in the field of gas interaction due to their strong catalytic behavior, which provides prospective scopes for gas adsorption and sensing. Detecting SF6 decomposed species in certain devices is essential to guarantee their safe operation. In this work, we performed DFT method and simulated the adsorption of three SF6 decomposed gases (SO2, SOF2 and SO2F2) onto the PtN3 embedded CNT surface, in order to shed light on its adsorption ability and sensing mechanism. Results suggest that the CNT embedded with PtN3 center has strong interaction with these gas molecules, leading to high hybridization between Pt dopant and active atoms inner gas molecules. These interactions are assumed to be chemisorption due to the remarkable Ead and QT, thus resulting in dramatic deformations in electronic structure of PtN3-CNT near the Fermi level. Furthermore, the electronic redistribution cause the conductivity increase of proposed material in three systems, based on frontier molecular orbital theory. Our calculations attempt to suggest novel sensing material that are potentially employed in detection of SF6 decomposed components.

Investigation on Adsorption and the Corrosion Inhibition Effect of Some Novel Hydrazide Derivatives for Mild Steel in HCl Solution

NASA Astrophysics Data System (ADS)

Singh, Dharmendra Kumar; Behera, Debasis; Singh, Mantu Kumar; Udayabhanu, G.; John, Rohith P.

2017-10-01

Two hydrazide derivatives, namely, N'-(thiophene-2-ylmethylene)nicotinic hydrazone (TNH) and N'-(pyrrol-2-ylmethylene)nicotinic hydrazone (PNH), have been synthesized and investigated as corrosion inhibitors for mild steel in 1 M HCl solution by electrochemical, weight loss, field emission-scanning electron microscope (FE-SEM), atomic force microscope (AFM), and quantum chemical calculation methods. The experimental results show that both the compounds are good inhibitors for mild steel in 1 M HCl. They act as mixed type inhibitors with predominating cathodic character. The adsorption of inhibitors obeys the Langmuir adsorption isotherm. Correlation between quantum chemical parameters and experimental results is discussed.

[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.

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.

Investigation of protein adsorption performance of Ni2+-attached diatomite particles embedded in composite monolithic cryogels.

PubMed

Ünlü, Nuri; Ceylan, Şeyda; Erzengin, Mahmut; Odabaşı, Mehmet

2011-08-01

As a low-cost natural adsorbent, diatomite (DA) (2 μm) has several advantages including high surface area, chemical reactivity, hydrophilicity and lack of toxicity. In this study, the protein adsorption performance of supermacroporous composite cryogels embedded with Ni(2+)-attached DA particles (Ni(2+)-ADAPs) was investigated. Supermacroporous poly(2-hydroxyethyl methacrylate) (PHEMA)-based monolithic composite cryogel column embedded with Ni(2+)-ADAPs was prepared by radical cryo-copolymerization of 2-hydroxyethyl methacrylate (HEMA) with N,N'-methylene-bis-acrylamide (MBAAm) as cross-linker directly in a plastic syringe for affinity purification of human serum albumin (HSA) both from aqueous solutions and human serum. The chemical composition and surface area of DA was determined by XRF and BET method, respectively. The characterization of composite cryogel was investigated by SEM. The effect of pH, and embedded Ni(2+)-ADAPs amount, initial HSA concentration, temperature and flow rate on adsorption were studied. The maximum amount of HSA adsorption from aqueous solution at pH 8.0 phosphate buffer was very high (485.15 mg/g DA). It was observed that HSA could be repeatedly adsorbed and desorbed to the embedded Ni(2+)-ADAPs in poly(2-hydroxyethyl methacrylate) composite cryogel without significant loss of adsorption capacity. The efficiency of albumin adsorption from human serum before and after albumin adsorption was also investigated with SDS-PAGE analyses. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of the amount of gas adsorption on SiO2/Si(100) surfaces to realize precise mass measurement

NASA Astrophysics Data System (ADS)

Mizushima, S.

2004-06-01

The adsorption isotherms on SiO2/Si(100) surfaces were measured using a vacuum mass comparator. Samples with a surface area difference of 816.6 cm2 were used for the measurement, and a substitution weighing method was adopted to reduce the uncertainty due to the drift and non-linearity of the indication of the mass comparator. We measured adsorption isotherms of water vapour on the SiO2/Si(100) surfaces outgassed at a temperature of 500 °C and found that dissociative adsorption caused an irreversible increase of 0.028 µg cm-2 with an uncertainty of 0.004 µg cm-2 (k = 1). We also found that the physical adsorption of water molecules on hydroxylated surfaces had a monolayer capacity of 0.004 µg cm-2 with an uncertainty of 0.002 µg cm-2 (k = 1). In addition, the adsorption isotherms for ethanol vapour and n-octane vapour, which were different from water vapour in adsorption properties, were measured and analysed.

Iron-based magnetic molecular imprinted polymers and their application in removal and determination of di-n-pentyl phthalate in aqueous media

PubMed Central

Zhou, Qingxiang; Yuan, Yongyong; Wu, Yalin

2017-01-01

Iron-based magnetic molecular imprinted polymers (Fe@SiO2@MIP) were synthesized for highly selective removal and recognition of di-n-pentyl phthalate (DnPP) from water. Well-defined core-shell Fe@SiO2 nanoparticles (less than 70 nm) were decorated on MIPs reticular layers to endow DnPP-MIPs with magnetic property for the first time. Five other phthalic acid esters including dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate and di-iso-octyl phthalate were used to investigate the adsorptive selectivity to DnPP. The designed experiments were carried out to explore the adsorption kinetics, isotherms and thermodynamics and the results demonstrated that the adsorption was a spontaneous, exothermal and physical adsorption process. The materials were proved to be excellent adsorbents in removal of DnPP with an adsorption capacity as high as 194.15 mg g−1 in optimal condition. Furthermore, a magnetic solid phase extraction with Fe@SiO2@MIP coupled to high-performance liquid chromatography method was successfully developed for the determination of DnPP, and the proposed method achieved a good linear range of 0.5–250 µg l−1 with a correlation coefficient (R2) of 0.999 and low limit of detection (LOD) of 0.31 µg l−1. These materials exhibited excellent capacity in removal and highly sensitive identification of DnPP from aqueous environment samples, and opened a valuable direction for developing new adsorbents for the removal and enrichment of important pollutants. PMID:28879009

Iron-based magnetic molecular imprinted polymers and their application in removal and determination of di-n-pentyl phthalate in aqueous media.

PubMed

Li, Jing; Zhou, Qingxiang; Yuan, Yongyong; Wu, Yalin

2017-08-01

Iron-based magnetic molecular imprinted polymers (Fe@SiO 2 @MIP) were synthesized for highly selective removal and recognition of di- n -pentyl phthalate (DnPP) from water. Well-defined core-shell Fe@SiO 2 nanoparticles (less than 70 nm) were decorated on MIPs reticular layers to endow DnPP-MIPs with magnetic property for the first time. Five other phthalic acid esters including dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di- n -butyl phthalate and di-iso-octyl phthalate were used to investigate the adsorptive selectivity to DnPP. The designed experiments were carried out to explore the adsorption kinetics, isotherms and thermodynamics and the results demonstrated that the adsorption was a spontaneous, exothermal and physical adsorption process. The materials were proved to be excellent adsorbents in removal of DnPP with an adsorption capacity as high as 194.15 mg g -1 in optimal condition. Furthermore, a magnetic solid phase extraction with Fe@SiO 2 @MIP coupled to high-performance liquid chromatography method was successfully developed for the determination of DnPP, and the proposed method achieved a good linear range of 0.5-250 µg l -1 with a correlation coefficient ( R 2 ) of 0.999 and low limit of detection (LOD) of 0.31 µg l -1 . These materials exhibited excellent capacity in removal and highly sensitive identification of DnPP from aqueous environment samples, and opened a valuable direction for developing new adsorbents for the removal and enrichment of important pollutants.

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.

Adsorption Kinetics of Manganese (II) in wastewater of Chemical laboratory with Column Method using Sugarcane Bagasse as Adsorbent

NASA Astrophysics Data System (ADS)

Zaini, H.; Abubakar, S.; Saifuddin

2018-01-01

The purpose of this research is to separate manganese (II) metal in the wastewater using sugarcane bagasse as an adsorbent. Experimental design, the independent variables are contact time (0; 30; 60; 90; 120; 150; 180; 210; 240 minutes, respectively) and activation treatment (without activation, physical activation, activation by H2SO4 0.5 N and activation by NaOH 0.5 N. Fixed variables consist of adsorbent mass (50 g), adsorbent particle size (30 mesh), flow rate (7 L/min) and volume of adsorbent (10 L). The dependent variable is the concentration of manganese. The results showed that the separation process of manganese by adsorption method was influenced by contact time and activation type. The kinetic studies show that the adsorption mechanism satisfies the pseudo-second-order kinetics model. Maximum adsorption capacity (qm) for adsorbents without treatment is 0.971 mg/g, physical treatment is 0.889 mg/g, chemical treatment by H2SO4 is 0.858 mg/g and chemical treatment by NaOH is 1.016 mg/g.

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

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.

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.

Mesoporous g-C₃N₄ Nanosheets: Synthesis, Superior Adsorption Capacity and Photocatalytic Activity.

PubMed

Li, Dong-Feng; Huang, Wei-Qing; Zou, Lan-Rong; Pan, Anlian; Huang, Gui-Fang

2018-08-01

Elimination of pollutants from water is one of the greatest challenges in resolving global environmental issues. Herein, we report a high-surface-area mesoporous g-C3N4 nanosheet with remarkable high adsorption capacity and photocatalytic performance, which is prepared through directly polycondensation of urea followed by a consecutive one-step thermal exfoliation strategy. This one-pot method to prepare mesoporous g-C3N4 nanosheet is facile and rapid in comparison with others. The superior adsorption capacity of the fabricated mesoporous g-C3N4 nanostructures is demonstrated by a model organic pollutant-methylene blue (MB), which is up to 72.2 mg/g, about 6 times as that of the largest value of various g-C3N4 adsorbents reported so far. Moreover, this kind of porous g-C3N4 nanosheet exhibits high photocatalytic activity to MB and phenol degradation. Particularly, the regenerated samples show excellent performance of pollutant removal after consecutive adsorption/degradation cycles. Therefore, this mesoporous g-C3N4 nanosheet may be an attractive robust metal-free material with great promise for organic pollutant elimination.

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.

Study of CO2 adsorption capacity of mesoporous carbon and activated carbon modified by triethylenetetramine (TETA)

NASA Astrophysics Data System (ADS)

Sulistianti, I.; Krisnandi, Y. K.; Moenandar, I.

2017-04-01

Mesoporous carbon was synthesized by soft template method using phloroglucinol and formaldehyde as a carbon source; and Pluronic F-127 as a mesoporous template. The synthesized mesoporous carbon and commercial activated carbon were modified with triethylenetetramine (TETA) to increase CO2 adsorption capacity. Based on FTIR characterization, the synthesized mesoporous carbon and the activated carbon without modification process has similarity pattern. After the modification, both of them showed absorption peaks in the area around 1580 to 1650 cm-1 which is known as N-H bending vibration and absorption peaks in the area around 3150 to 3380 cm-1 which is known as N-H stretching vibration. The XRD results showed two peaks at 2θ = 24.21° and 2θ = 43.85°, according to JCPDS index No. 75-1621 those peak are the typical peaks for hexagonal graphite carbon. In BET analysis, the synthesized mesoporous carbon and activated carbon modified TETA have surface area, pore volume and pore diameter lower than without modification process. In carbon dioxide adsorption testing, the synthesized mesoporous carbon showed better performance than the commercial activated carbon for CO2 adsorption both without modification and by modification. The synthesized mesoporous carbon obtained CO2 adsorption of 9.916 mmol/g and the activated carbon of 3.84 mmol/g for on 3.5 hours of adsorption. It is three times better than activated carbon for adsorption of carbon dioxide. The modified mesoporous carbon has the best performance for adsorption of gas CO2 if compared by unmodified.

Monodispersed ZIF-8 particles with enhanced performance for CO2 adsorption and heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Guan, Yebin; Shi, Juanjuan; Xia, Ming; Zhang, Jun; Pang, Zhenfeng; Marchetti, Alessandro; Wang, Xiaohong; Cai, Jingsong; Kong, Xueqian

2017-11-01

Monodispersed zeolitic imidazolate frameworks (ZIFs) were prepared with a simple method using dimethylsulfoxide (DMSO) as solvent. This method yields ZIF-8 nanoparticles with a narrow particle size distribution of 90-110 nm and the dispersion is highly stable against agglomeration. These particles have larger nanosized porosity and enhanced CO2 adsorption capability compared to ZIF-8 prepared with different solvents such as methanol or N, N-dimethyl formamide. Their uniform size and surface chemistry also lead to superior performance in the Knoevenagel condensation reactions. The ZIF-8 nanoparticles possess high thermal stability up to 550 °C and the preparation steps are easy for scaling up which are favorable for industrial applications.

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.

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.

Revisiting the adsorption of copper-phthalocyanine on Au(111) including van der Waals corrections.

PubMed

Lüder, Johann; Eriksson, Olle; Sanyal, Biplab; Brena, Barbara

2014-03-28

We have studied the adsorption of copper-phthalocyanine on Au(111) by means of van der Waals corrected density functional theory using the Tkatchenko-Scheffler method. We have compared the element and site resolved adsorption distances to recent experimental normal-incident X-ray standing wave measurements. The measured adsorption distances could be reproduced within a deviation of 1% for the Cu atom, 1% for the C atoms, and 2% for the N atoms. The molecule was found to have a magnetic moment of 1 μB distributed over the Cu and the N atoms of the pyrrole ring. Simulated scanning tunnel microscopy images based on the total and on the spin-resolved differential charge densities are provided for bias voltages of -1.45 and 1.45 eV.

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.

Synthesis, characterization and metal adsorption properties of the new ion exchanger polymer 3-n-propyl(4-methylpyridinium) silsesquioxane chloride.

PubMed

Magosso, H A; Panteleimonov, A V; Kholin, Y V; Gushikem, Y

2006-11-01

The preparation and anion exchange properties of 3-n-propyl(4-methylpyridinium) silsesquioxane chloride polymer are described. This new polymer was prepared by the sol-gel processing method and is designated as SiPic+Cl-. It is insoluble in water and showed an anion exchange capacity of 1.46x10(-3) mol g-1. The adsorption isotherms of ZnCl2, CdCl2 and HgCl2 were determined from aqueous solutions and the adsorption equilibria simulations fit the model of fixed bidentate centers with the absence of lateral interactions and energetic heterogeneity between them. The metal ions diffuse into the solid solution interface and are dominantly present as MCl2-(4) species for Zn(II), MCl(2-)4 and MCl-3 species for Cd(II) and MCl-3 species for Hg(II).

Synergic mechanism of adsorption and metal-free catalysis for phenol degradation by N-doped graphene aerogel.

PubMed

Ren, Xiaohua; Guo, Huanhuan; Feng, Jinkui; Si, Pengchao; Zhang, Lin; Ci, Lijie

2018-01-01

3D porous N-doped reduced graphene oxide (N-rGO) aerogels were synthesized by a hydrothermal reduction of graphene oxide (GO) with urea and following freeze-drying process. N-rGO aerogels have a high BET surface of 499.70 m 2 /g and a high N doping content (5.93-7.46 at%) including three kinds of N (graphitic, pyridinic and pyrrolic). Their high catalytic performance for phenol oxidation in aqueous solution was investigated by catalytic activation of persulfate (PS). We have demonstrated that N-rGO aerogels are promising metal-free catalysts for phenol removal. Kinetics studies indicate that phenol degradation follows first-order reaction kinetics with the reaction rate constant of 0.16799 min -1 for N-rGO-A(1:30). Interestingly, the comparison of direct catalytic oxidation with adsorption-catalytic oxidation experiments indicates that adsorption plays an important role in the catalytic oxidation of phenol by decreasing the phenol degradation time. Spin density and adsorption modeling demonstrates that graphitic N in N-rGO plays the most important role for the catalytic performance by inducing high positive charge densities to adjacent carbon atoms and facilitating phenol adsorption on these carbon sites. Furthermore, the activation mechanism of persulfate (PS) on N-rGO was first investigated by DFT method and PS can be activated to generate strongly oxidative radical (SO 4 · - ) by transferring electrons to N-rGO. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reflectometric measurement of n-hexane adsorption on ZnO2 nanohybrid film modified by hydrophobic gold nanoparticles

NASA Astrophysics Data System (ADS)

Sebők, Dániel; Csapó, Edit; Ábrahám, Nóra; Dékány, Imre

2015-04-01

Zinc-peroxide/poly(styrenesulfonate) nanohybrid thin films (containing 20 bilayers: [ZnO2/PSS]20, d ∼ 500 nm) were prepared using layer-by-layer (LbL) method. The thin film surface was functionalized by different surface modifying agents (silanes, alkylthiols and hydrophobized nanoparticles). Based on the experimental results of quartz crystal microbalance (QCM) and contact angle measurements (as prequalifications) the octanethiol covered gold nanoparticles (OT-AuNPs) were selected for further vapour adsorption studies. Reflectometric interference spectroscopy (RIfS) was used to measure n-hexane vapour adsorption on the original and modified nanohybrid films in a gas flow platform. The thin film provides only the principle of the measurement (by interference phenomenon), the selectivity and hydrophobicity is controlled and enhanced by surface functionalization (by dispersion interaction between the alkyl chains). The interference pattern shift (Δλ) caused by the increase of the optical thickness of the thin film due to vapour adsorption was investigated. It was found that due to the surface functionalization by hydrophobic nanoparticles the effect of water vapour adsorption decreased significantly, while for n-hexane opposite tendency was observed (the effective refractive index and thus the interference pattern shift increased drastically). The correlation between QCM technique and optical method (RIfS) was specified: linear specific adsorbed amount vs. wavelength shift calibration curves were determined in the pr = 0-0.4 relative vapour pressure range. The thin film is suitable for sensorial application (e.g. volatile organic compound/VOC sensor).

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.

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.

Ab Initio Prediction of Adsorption Isotherms for Small Molecules in Metal-Organic Frameworks.

PubMed

Kundu, Arpan; Piccini, GiovanniMaria; Sillar, Kaido; Sauer, Joachim

2016-10-26

For CO and N 2 on Mg 2+ sites of the metal-organic framework CPO-27-Mg (Mg-MOF-74), ab initio calculations of Gibbs free energies of adsorption have been performed. Combined with the Bragg-Williams/Langmuir model and taking into account the experimental site availability (76.5%), we obtained adsorption isotherms in close agreement with those in experiment. The remaining deviations in the Gibbs free energy (about 1 kJ/mol) are significantly smaller than the "chemical accuracy" limit of about 4 kJ/mol. The presented approach uses (i) a DFT dispersion method (PBE+D2) to optimize the structure and to calculate anharmonic frequencies for vibrational partition functions and (ii) a "hybrid MP2:(PBE+D2)+ΔCCSD(T)" method to determine electronic energies. With the achieved accuracy (estimated uncertainty ±1.4 kJ/mol), the ab initio energies become useful benchmarks for assessing different DFT + dispersion methods (PBE+D2, B3LYP+D*, and vdW-D2), whereas the ab initio heats, entropies, and Gibbs free energies of adsorption are used to assess the reliability of experimental values derived from fitting isotherms or from variable-temperature IR studies.

Evaluation of phosphorus adsorption capacity of sesame straw biochar on aqueous solution: influence of activation methods and pyrolysis temperatures.

PubMed

Park, J H; Ok, Y S; Kim, S H; Cho, J S; Heo, J S; Delaune, R D; Seo, D C

2015-12-01

The phosphorus (P) adsorption characteristic of sesame straw biochar prepared with different activation agents and pyrolysis temperatures was evaluated. Between 0.109 and 0.300 mg L(-1) in the form of inorganic phosphate was released from raw sesame straw biochar in the first 1 h. The release of phosphate was significantly enhanced from 62.6 to 168.2 mg g(-1) as the pyrolysis temperature increased. Therefore, sesame straw biochar cannot be used as an adsorbent for P removal without change in the physicochemical characteristics. To increase the P adsorption of biochar in aqueous solution, various activation agents and pyrolysis temperatures were applied. The amount of P adsorbed from aqueous solution by biochar activated using different activation agents appeared in the order ZnCl2 (9.675 mg g(-1)) > MgO (8.669 mg g(-1)) ⋙ 0.1N-HCl > 0.1N-H2SO4 > K2SO4 ≥ KOH ≥ 0.1N-H3PO4, showing ZnCl2 to be the optimum activation agent. Higher P was adsorbed by the biochar activated using ZnCl2 under different pyrolysis temperatures in the order 600 °C > 500 °C > 400 °C > 300 °C. Finally, the amount of adsorbed P by activated biochar at different ratios of biochar to ZnCl2 appeared in the order 1:3 ≒ 1:1 > 3:1. As a result, the optimum ratio of biochar to ZnCl2 and pyrolysis temperature were found to be 1:1 and 600 °C for P adsorption, respectively. The maximum P adsorption capacity by activated biochar using ZnCl2 (15,460 mg kg(-1)) was higher than that of typical biochar, as determined by the Langmuir adsorption isotherm. Therefore, the ZnCl2 activation of sesame straw biochar was suitable for the preparation of activated biochar for P adsorption.

Physicochemical and adsorptive characteristics of activated carbons from waste polyester textiles utilizing MgO template method.

PubMed

Xu, Zhihua; Zhang, Daofang; Yuan, Zhihang; Chen, Weifang; Zhang, Tianqi; Tian, Danqi; Deng, Haixuan

2017-10-01

Activated carbons with high specific surface areas were produced, utilizing waste polyester textiles as carbon precursor by magnesium oxide (MgO) template method. Magnesium chloride (MgCl 2 ), magnesium citrate (MgCi), and MgO were employed as MgO precursors to prepare activated carbons (AC-MgCl 2 , AC-MgCi, and AC-MgO). Thermogravimetry-differential scanning calorimetry was conducted to investigate the pore-forming mechanism, and N 2 adsorption/desorption isotherms, XRD, SEM-EDS, TEM, FTIR and pH pzc were achieved to analyze physicochemical characteristics of the samples. The specific surface areas of AC-MgCl 2 (1173 m 2 /g) and AC-MgCi (1336 m 2 /g) were much higher than that of AC-MgO (450 m 2 /g), and the pores sizes of which were micro-mesoporous, mesoporous, and macropores, respectively, due to the formation of MgO crystal with different sizes. All activated carbons had abundant acidic oxygen groups. In addition, batch adsorption experiments were carried out to investigate the adsorptive characteristics of the prepared activated carbons toward Cr(VI). The adsorption kinetics fitted well with the pseudo-second order, and the adsorptive capacity of AC-MgCl 2 (42.55 mg/g) was higher than those of AC-MgCi (40.93 mg/g) and AC-MgO (35.87 mg/g).

Adsorption behavior of Cr(VI) on modified natural zeolite by a new bolaform N,N,N,N',N',N'-hexamethyl-1,9-nonanediammonium dibromide reagent.

PubMed

Noroozifar, M; Khorasani-Motlagh, M; Gorgij, M N; Naderpour, H R

2008-07-15

The demand for effective adsorbents is to increase in response to the widespread recognition of the deleterious health effects of Cr(VI)-oxyanions exposure through drinking water. In this study, Cr(VI)-oxyanions uptake from aqueous solutions by a new bolaform N,N,N,N',N',N'-hexamethyl-1,9-nonanediammonium dibromide reagent-modified natural zeolitic materials from Zahedan, Iran, was investigated using batch technique. Spectrophotometry method was used for Cr determination. The Cr(VI)-solution concentration varied between 2 and 104 mg L(-1). It was shown that the Cr(VI) uptake strongly depended on pH. The maximum removal of Cr(VI) occurred in acidic media at pH<1.5. The amounts of Cr(VI) adsorbed increased with increase in dose of both adsorbents and their contact time. Based on results an adsorption mechanism has been suggested. The adsorption data for modified zeolite using the amine was consistent with Langmuir isotherm equation and the equilibrium data was analyzed using the Langmuir isotherm.

p-Chlorophenol adsorption on activated carbons with basic surface properties

NASA Astrophysics Data System (ADS)

Lorenc-Grabowska, Ewa; Gryglewicz, Grażyna; Machnikowski, Jacek

2010-05-01

The adsorption of p-chlorophenol (PCP) from aqueous solution on activated carbons (ACs) with basic surface properties has been studied. The ACs were prepared by two methods. The first method was based on the modification of a commercial CWZ AC by high temperature treatment in an atmosphere of ammonia, nitrogen and hydrogen. The second approach comprised the carbonization followed by activation of N-enriched polymers and coal tar pitch using CO 2 and steam as activation agent. The resultant ACs were characterized in terms of porous structure, elemental composition and surface chemistry (pH PZC, acid/base titration, XPS). The adsorption of PCP was carried out from an aqueous solution in static conditions. Equilibrium adsorption isotherm was of L2 type for polymer-based ACs, whereas L3-type isotherm was observed for CWZ ACs series. The Langmuir monolayer adsorption capacity was related to the porous structure and the amount of basic sites. A good correlation was found between the adsorption capacity and the volume of micropores with a width < 1.4 nm for polymer-based ACs. Higher nitrogen content, including that in basic form, did not correspond to the enhanced adsorption of PCP from aqueous solution. The competitive effect of water molecule adsorption on the PCP uptake is discussed.

Adsorption performance of titanium dioxide (TiO2) coated air filters for volatile organic compounds.

PubMed

Zhong, Lexuan; Lee, Chang-Seo; Haghighat, Fariborz

2012-12-01

The photocatalytic oxidation (PCO) technology as an alternative method for air purification has been studied for decades and a variety of PCO models indicate that the adsorption of reactants on the catalyst surface is one of the major physical and chemical processes occurring at a heterogeneous photocatalytic reaction. However, limited study explored the adsorption effect of a photocatalyst. This study carried out a systematic evaluation of adsorption performance of titanium dioxide (TiO(2)) coated fiberglass fibers (FGFs), TiO(2) coated carbon cloth fibers (CCFs), and original CCFs air filters at various relative humidity conditions for nine volatile organic compounds. TiO(2)/FGFs, TiO(2)/CCFs, and CCFs were characterized by SEM for morphology and N(2) adsorption isotherm for BET surface area and pore structure. A bench-scale adsorption test setup was constructed and adsorption tests were performed at various relative humidity conditions and four different injected concentrations for each compound. The isothermal adsorption curves at low concentration levels were obtained and they were well described by Langmuir isotherm model. It was noticed that there were significant differences between the adsorption behaviors and photocatalytic activities of TiO(2)/FGFs and TiO(2)/CCFs. It was concluded that adsorption performance is closely related to the characteristics of substrates and therefore, the development of a substrate with high adsorption ability is a promising trend for improving the performance of the UV-PCO technology. Copyright © 2012 Elsevier B.V. All rights reserved.

Revisiting the adsorption of copper-phthalocyanine on Au(111) including van der Waals corrections

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

Lüder, Johann; Eriksson, Olle; Sanyal, Biplab

2014-03-28

We have studied the adsorption of copper-phthalocyanine on Au(111) by means of van der Waals corrected density functional theory using the Tkatchenko-Scheffler method. We have compared the element and site resolved adsorption distances to recent experimental normal-incident X-ray standing wave measurements. The measured adsorption distances could be reproduced within a deviation of 1% for the Cu atom, 1% for the C atoms, and 2% for the N atoms. The molecule was found to have a magnetic moment of 1 μ{sub B} distributed over the Cu and the N atoms of the pyrrole ring. Simulated scanning tunnel microscopy images based onmore » the total and on the spin-resolved differential charge densities are provided for bias voltages of −1.45 and 1.45 eV.« less

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.

Enhancement of p-nitrophenol adsorption capacity through N2-thermal-based treatment of activated carbons

NASA Astrophysics Data System (ADS)

Álvarez-Torrellas, S.; Martin-Martinez, M.; Gomes, H. T.; Ovejero, G.; García, J.

2017-08-01

In this work several activated carbons showing different textural and chemical properties were obtained by chemical and physical activation methods, using a lignocellulosic material (peach stones) as precursor. The activated carbon resulting from the chemical activation, namely as CAC, revealed the best textural properties (SBET = 1521 m2 g-1, pore volume = 0.90 cm3 g-1) and an acidic character. It was found that the activated carbon obtained at 300 °C (under air atmosphere, PAC_air), and those synthesized at 750 °C in presence of N2 flow with bubbling of water/12 M H3PO4 solution (PAC_N2(H2O)/PAC_N2(H3PO4)), respectively, revealed worse textural properties, compared to CAC. Two functionalization treatments, by using sulphuric acid at boiling temperature (PACS) and nitric acid-urea-N2 heating at 800 °C (PAC-NUT), were applied to PAC_air, in order to enhance the adsorption ability of the carbon material. Several techniques were carried out to characterize the physical and chemical properties of the obtained carbon materials. The modification treatments had influence on the carbon surface properties, since the nitric acid-urea-N2 heating treatment led to a carbon material with highly-improved properties (SBET = 679 m2 g-1, pHIEP = 5.3). Accordingly, the original and modified-carbon materials were tested as adsorbents to remove 4-nitrophenol (4-NP), assessing batch and fixed-bed column adsorption tests. PAC-NUT carbon offered the best adsorption behavior (qe = 234 mg g-1), showing a high ability for the removal of 4-NP from water.

Functionalization of silica-gel with polyamidoamine and 2-mercaptobenzothiazole and its adsorption property for lead

NASA Astrophysics Data System (ADS)

Wu, X. Z.; Liu, Y.; Luo, L. L.; Chen, Z. Y.

2018-01-01

Adsorbents PAMAM-n.0MBTSG (n=1-4) have been prepared by immobilizing polyamidoamine (PAMAM) and 2-mercaptobenzothiazole (MBT) on silica-gel. Characterized with FTIR, SEM, TGA, the preconcentration of Pb2+ with PAMAM-n.0MBTSG(n=1-4) has been investigated by graphite furnace atomic absorption spectroscopy (GFAAS). SEM showed that the surface morphology of adsorbent changed with the generation increase of PAMAM. Adsorption capacity of PAMAM-n.0MBTSG for Pb2+ (n=1-4) reached 16.22, 19.84, 22.92 and 27.56 mg g-1 respectively. Pb2+ (1.0 ng mL-1) in 2000 mL solution could be quantitatively absorbed with PAMAM-4.0MBTSG and eluted to obtain a preconcentration factor (PF) of 200. GFAAS method for analysis of Pb2+ with PAMAM-4.0MBTSG as adsorbent was proposed and successfully applied to analysis of Pb2+ of standard reference material, sea water and squid sample.

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.

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.

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.

A high precision gas flow cell for performing in situ neutron studies of local atomic structure in catalytic materials

DOE PAGES

Olds, Daniel; Page, Katharine; Paecklar, Arnold A.; ...

2017-03-17

Gas-solid interfaces enable a multitude of industrial processes, including heterogeneous catalysis; however, there are few methods available for studying the structure of this interface under operating conditions. Here, we present a new sample environment for interrogating materials under gas-flow conditions using time-of-flight neutron scattering under both constant and pulse probe gas flow. Outlined are descriptions of the gas flow cell and a commissioning example using the adsorption of N 2 by Ca-exchanged zeolite-X (Na 78–2xCa xAl 78Si 144O 384,x ≈ 38). We demonstrate sensitivities to lattice contraction and N 2 adsorption sites in the structure, with both static gas loadingmore » and gas flow. A steady-state isotope transient kinetic analysis of N 2 adsorption measured simultaneously with mass spectrometry is also demonstrated. In the experiment, the gas flow through a plugged-flow gas-solid contactor is switched between 15N 2 and 14N 2 isotopes at a temperature of 300 K and a constant pressure of 1 atm; the gas flow and mass spectrum are correlated with the structure factor determined from event-based neutron total scattering. As a result, available flow conditions, sample considerations, and future applications are discussed.« less

Investigation of Dynamic Oxygen Adsorption in Molten Solder Jetting Technology

NASA Technical Reports Server (NTRS)

Megaridis, Constantine M.; Bellizia, Giulio; McNallan, Michael; Wallace, David B.

2003-01-01

Surface tension forces play a critical role in fluid dynamic phenomena that are important in materials processing. The surface tension of liquid metals has been shown to be very susceptible to small amounts of adsorbed oxygen. Consequently, the kinetics of oxygen adsorption can influence the capillary breakup of liquid-metal jets targeted for use in electronics assembly applications, where low-melting-point metals (such as tin-containing solders) are utilized as an attachment material for mounting of electronic components to substrates. By interpreting values of surface tension measured at various surface ages, adsorption and diffusion rates of oxygen on the surface of the melt can be estimated. This research program investigates the adsorption kinetics of oxygen on the surface of an atomizing molten-metal jet. A novel oscillating capillary jet method has been developed for the measurement of dynamic surface tension of liquids, and in particular, metal melts which are susceptible to rapid surface degradation caused by oxygen adsorption. The experimental technique captures the evolution of jet swells and necks continuously along the jet propagation axis and is used in conjunction with an existing linear, axisymmetric, constant-property model to determine the variation of the instability growth rate, and, in turn, surface tension of the liquid as a function of surface age measured from the exit orifice. The conditions investigated so far focus on a time window of 2-4ms from the jet orifice. The surface properties of the eutectic 63%Sn-37%Pb solder alloy have been investigated in terms of their variation due to O2 adsorption from a N2 atmosphere containing controlled amounts of oxygen (from 8 ppm to 1000 ppm). The method performed well for situations where the oxygen adsorption was low in that time window. The value of surface tension for the 63Sn-37Pb solder in pure nitrogen was found to be 0.49 N/m, in good agreement with previously published work. A characteristic time of O(1ms) or less was determined for the molten-metal surface to be saturated by oxygen at 1000 ppm concentration in N2.

Micropore Formation of [Zn2(Oxac) (Taz)2]·(H2O)2.5 via CO2 Adsorption.

PubMed

Zubir, Moondra; Hamasaki, Atom; Iiyama, Taku; Ohta, Akira; Ohki, Hiroshi; Ozeki, Sumio

2017-01-24

As-synthesized [Zn 2 (Oxac) (Taz) 2 ]·(H 2 O) 2.5 , referred to as ZOTW 2.5 , was prepared from aqueous methanol solutions of Zn 5 (CO 3 ) 2 (OH) 6 and two kinds of ligands of 1,2,4-triazole (Taz) and oxalic acid (Oxac) at 453 K for 12 h. The crystal structure was determined by the Rietveld method. As-synthesized ZOTW 2.5 was pretreated at 383 K and 1 mPa for t pt h, ZOTW x (t pt h). ZOTW x (≥3h) showed a type I adsorption isotherm for N 2 at 77 K having a saturation amount (V s ) of 180 mg/g, but that pretreated shortly showed only 1/10 in V s . CO 2 was adsorbed at 303 K in sigmoid on nonporous ZOTW x (≤2h) and in Langmuir-type on ZOTW x (≥3h) to reach the adsorption amount of 120 mg/g at 700 Torr. N 2 adsorption on ZOTW x (≤2h)deCO 2 , degassed after CO 2 adsorption on ZOTW x (≤2h), was promoted 5-fold from 180 mg/g on ZOTW x (t pt h) and ZOTW x (≥3h)deCO 2 up to ca. 1000 mg/g. The interaction of CO 2 and H 2 O molecules in micropores may lead to a new route for micropore formation.

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.

Adsorption and separation of binary and ternary mixtures of SO2, CO2 and N2 by ordered carbon nanotube arrays: grand-canonical Monte Carlo simulations.

PubMed

Rahimi, Mahshid; Singh, Jayant K; Müller-Plathe, Florian

2016-02-07

The adsorption and separation behavior of SO2-CO2, SO2-N2 and CO2-N2 binary mixtures in bundles of aligned double-walled carbon nanotubes is investigated using the grand-canonical Monte Carlo (GCMC) method and ideal adsorbed solution theory. Simulations were performed at 303 K with nanotubes of 3 nm inner diameter and various intertube distances. The results showed that the packing with an intertube distance d = 0 has the highest selectivity for SO2-N2 and CO2-N2 binary mixtures. For the SO2-CO2 case, the optimum intertube distance for having the maximum selectivity depends on the applied pressure, so that at p < 0.8 bar d = 0 shows the highest selectivity and at 0.8 bar < p < 2.5 bar, the highest selectivity belongs to d = 0.5 nm. Ideal adsorbed solution theory cannot predict the adsorption of the binary systems containing SO2, especially when d = 0. As the intertube distance is increased, the ideal adsorbed solution theory based predictions become closer to those of GCMC simulations. Only in the case of CO2-N2, ideal adsorbed solution theory is everywhere in good agreement with simulations. In a ternary mixture of all three gases, the behavior of SO2 and CO2 remains similar to that in a SO2-CO2 binary mixture because of the weak interaction between N2 molecules and CNTs.

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.

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.

Time distribution of adsorption entropy of gases on heterogeneous surfaces by reversed-flow gas chromatography.

PubMed

Katsanos, Nicholas A; Kapolos, John; Gavril, Dimitrios; Bakaoukas, Nicholas; Loukopoulos, Vassilios; Koliadima, Athanasia; Karaiskakis, George

2006-09-15

The reversed-flow gas chromatography (RF-GC) technique has been applied to measure the adsorption entropy over time, when gaseous pentane is adsorbed on the surface of two solids (gamma-alumina and a silica supported rhodium catalyst) at 393.15 and 413.15K, respectively. Utilizing experimental chromatographic data, this novel methodology also permits the simultaneous measurement of the local adsorption energy, epsilon, local equilibrium adsorbed concentration, c(s)(*), and local adsorption isotherm, theta(p, T, epsilon) in a time resolved way. In contrast with other inverse gas chromatographic methods, which determine the standard entropy at zero surface coverage, the present method operates over a wide range of surface coverage taking into account not only the adsorbate-adsorbent interaction, but also the adsorbate-adsorbate interaction. One of the most interesting observations of the present work is the fact that the interaction of n-pentane is spontaneous on the Rh/SiO(2) catalyst for a very short time interval compared to that on gamma-Al(2)O(3). This can explain the different kinetic behavior of each particular gas-solid system, and it can be attributed to the fact that large amounts of n-C(5)H(12) are present on the active sites of the Rh/SiO(2) catalyst compared to those on gamma-Al(2)O(3), as the local equilibrium adsorbed concentration values, c(s)(*), indicate.

Mesoporous Nb2O5/SiO2 material obtained by sol-gel method and applied as adsorbent of crystal violet dye.

PubMed

Umpierres, Cibele S; Prola, Lizie D T; Adebayo, Matthew A; Lima, Eder C; Dos Reis, Glaydson S; Kunzler, Diego D F; Dotto, G L; Arenas, Leliz T; Benvenutti, Edilson V

2017-03-01

In this work, SiO 2 /Nb 2 O 5 (SiNb) material was prepared using sol-gel method and employed as adsorbent for removal of crystal violet dye (CV). The material was characterized using nitrogen adsorption-desorption isotherms, FTIR spectroscopy, pH pzc , and SEM-EDS. The analysis of N 2 isotherms revealed the presence of micro- and mesopores in the SiNb sample with specific surface area as high as 747 m 2  g -1 . For the CV adsorption process, variations of several parameters such as of pH, temperature, contact time, and concentration of dye of the process were evaluated. The optimum initial pH of the CV dye solution was 7.0. The adsorption kinetic and equilibrium data for CV adsorption were suitably represented by the general-order and Liu models, respectively. The maximum adsorption capacity of the CV dye by SiNb was achieved at 303 K, which attained 116 mg g -1 at this temperaure. Dye effluents were simulated and used to check the applicability of the SiNb material for treatment of effluents - the material showed very good efficiency for decolorization of dye effluents.

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.

Surface Condensation of CO2 onto Kaolinite

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

Schaef, Herbert T.; Glezakou, Vassiliki Alexandra; Owen, Antionette T.

2014-02-11

The fundamental adsorption behavior of gaseous and supercritical carbon dioxide (CO2) onto poorly crystalline kaolinite (KGa-2) at conditions relevant to geologic sequestration has been investigated using a quartz crystal microbalance (QCM) and density functional theory (DFT) methods. The QCM data indicated linear adsorption of CO2 (0-0.3 mmol CO2/g KGa-2) onto the kaolinite surface up through the gaseous state (0.186 g/cm3). However in the supercritical region, CO2 adsorption increases dramatically, reaching a peak (0.9-1.0 mmol CO2/g KGa-2) near 0.43 g/cm3, before declining rapidly to surface adsorption values equivalent or below gaseous CO2. This adsorption profile was not observed with He ormore » N2. Comparative density functional studies of CO2 interactions with kaolinite surface models rule out CO2 intercalation and confirm that surface adsorption is favored up to approximately 0.35 g/cm3 of CO2, showing distorted T-shaped CO2-CO2 clustering, typical of supercritical CO2 aggregation over the surface as the density increases. Beyond this point, the adsorption energy gain for any additional CO2 becomes less than the CO2 interaction energy (~0.2 eV) in the supercritical medium resulting in overall desorption of CO2 from the kaolinite surface.« less

Preparation of new nano magnetic material Fe3O4@g-C3N4 and good adsorption performance on uranium ion

NASA Astrophysics Data System (ADS)

Long, Wei; Liu, Huijun; Yan, Xueming; Fu, Li

2018-03-01

A new nano magnetic material Fe3O4@g-C3N4 was prepared by deposition reduction method, which performed good adsorption performance to uranium ion. Characterization results showed that the g-C3N4 particles were wrapped around the nano magnetic Fe3O4 particles, and the textural properties of this material was improved, so the adsorption performance to uranium ion was good. Adsorption experiments of this material demonstrated that the optimum pH value was 10, the optimum mass of adsorbent was 6.5 mg and the optimum adsorption time was 150 min in the initial concentration of 140 mg/L uranium ion solution system, and the maximum adsorption capacity was up to 352.1 mg/g and the maximum adsorption rate was more than 90%.

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.

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

Sorption of DNA by diatomite-Zn(II) embedded supermacroporous monolithic p(HEMA) cryogels.

PubMed

Tozak, Kabil Özcan; Erzengin, Mahmut; Sargin, Idris; Ünlü, Nuri

2013-01-01

In this study, the DNA sorption performance of diatomite-Zn(II) embedded supermacroporous monolithic p(HEMA) cryogels were investigated for the purpose of designing a novel adsorbent that can be utilized for DNA purification, separation and immunoadsorption studies such as removal of anti-dsDNA antibodies from systemic lupus erythematosus (SLE) patient plasma. Poly(2-hydroxyethyl methacrylate) [p(HEMA)]-based monolithic cryogel column embedded with Zn(2+)-diatomite particles was prepared by free radical cryo-copolymerization of 2-hydroxyethyl methacrylate (HEMA) with N,N'-methylene-bis-acrylamide (MBAAm). The polymerization reaction was initiated by N,N,N',N'-tetramethylene diamine (TEMED) and ammonium persulfate (APS) pair in an ice bath. After thawing, the monolithic composite cryogels were used for affinity sorption and then subsequent desorption of DNA molecules from aqueous solutions. Diatomite (DA) particles were characterized by XRF and BET method. The characterization of composite cryogel was done through SEM imaging. The effects of pH of the solution, initial DNA concentration, ionic strength, temperature and flow rates on adsorption were investigated to determine the optimum conditions for adsorption/desorption experiments. The particle embedding procedure was shown to yield significantly enhanced adsorption of DNA on the adsorbent. Furthermore, considering its excellent bio-compatibility, p(HEMA) cryogels are promising a candidate for further DNA sorption studies.

Sorption of DNA by diatomite-Zn(II) embedded supermacroporous monolithic p(HEMA) cryogels

PubMed Central

Tozak, Kabil Özcan; Erzengin, Mahmut; Sargin, Idris; Ünlü, Nuri

2013-01-01

In this study, the DNA sorption performance of diatomite-Zn(II) embedded supermacroporous monolithic p(HEMA) cryogels were investigated for the purpose of designing a novel adsorbent that can be utilized for DNA purification, separation and immunoadsorption studies such as removal of anti-dsDNA antibodies from systemic lupus erythematosus (SLE) patient plasma. Poly(2-hydroxyethyl methacrylate) [p(HEMA)]-based monolithic cryogel column embedded with Zn2+-diatomite particles was prepared by free radical cryo-copolymerization of 2-hydroxyethyl methacrylate (HEMA) with N,N'-methylene-bis-acrylamide (MBAAm). The polymerization reaction was initiated by N,N,N',N'-tetramethylene diamine (TEMED) and ammonium persulfate (APS) pair in an ice bath. After thawing, the monolithic composite cryogels were used for affinity sorption and then subsequent desorption of DNA molecules from aqueous solutions. Diatomite (DA) particles were characterized by XRF and BET method. The characterization of composite cryogel was done through SEM imaging. The effects of pH of the solution, initial DNA concentration, ionic strength, temperature and flow rates on adsorption were investigated to determine the optimum conditions for adsorption/desorption experiments. The particle embedding procedure was shown to yield significantly enhanced adsorption of DNA on the adsorbent. Furthermore, considering its excellent bio-compatibility, p(HEMA) cryogels are promising a candidate for further DNA sorption studies. PMID:26600734

Ti, Al and N adatom adsorption and diffusion on rocksalt cubic AlN (001) and (011) surfaces: Ab initio calculations

NASA Astrophysics Data System (ADS)

Mastail, C.; David, M.; Nita, F.; Michel, A.; Abadias, G.

2017-11-01

We use ab initio calculations to determine the preferred nucleation sites and migration pathways of Ti, Al and N adatoms on cubic NaCl-structure (B1) AlN surfaces, primary inputs towards a further thin film growth modelling of the TiAlN alloy system. The potential energy landscape is mapped out for both metallic species and nitrogen adatoms for two different AlN surface orientations, (001) and (110), using density functional theory. For all species, the adsorption energies on AlN(011) surface are larger than on AlN(001) surface. Ti and Al adatom adsorption energy landscapes determined at 0 K by ab initio show similar features, with stable binding sites being located in, or near, epitaxial surface positions, with Ti showing a stronger binding compared to Al. In direct contrast, N adatoms (Nad) adsorb preferentially close to N surface atoms (Nsurf), thus forming strong N2-molecule-like bonds on both AlN(001) and (011). Similar to N2 desorption mechanisms reported for other cubic transition metal nitride surfaces, in the present work we investigate Nad/Nsurf desorption on AlN(011) using a drag calculation method. We show that this process leaves a Nsurf vacancy accompanied with a spontaneous surface reconstruction, highlighting faceting formation during growth.

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

Functionalized SBA-15 materials for bilirubin adsorption

NASA Astrophysics Data System (ADS)

Tang, Tao; Zhao, Yanling; Xu, Yao; Wu, Dong; Xu, Jun; Deng, Feng

2011-05-01

To investigate the driving force for bilirubin adsorption on mesoporous materials, a comparative study was carried out between pure siliceous SBA-15 and three functionalized SBA-15 mesoporous materials: CH 3-SBA-15 (MS), NH 2-SBA-15 (AS), and CH 3/NH 2-SBA-15 (AMS) that were synthesized by one-pot method. The obtained materials exhibited large surface areas (553-810 m 2/g) and pore size (6.6-7.1 nm) demonstrated by XRD and N 2-ad/desorption analysis. The SEM images showed that the materials had similar fiberlike morphology. The functionalization extent was calculated according to 29Si MAS NMR spectra and it was close to the designed value (10%). The synthesized mesoporous materials were used as bilirubin adsorbents and showed higher bilirubin adsorption capacities than the commercial active carbon. The adsorption capacities of amine functionalized samples AMS and AS were larger than those of pure siliceous SBA-15 and MS, indicating that electrostatic interaction was the dominant driving force for bilirubin adsorption on mesoporous materials. Increasing the ionic strength of bilirubin solution by adding NaCl would decrease the bilirubin adsorption capacity of mesoporous material, which further demonstrated that the electrostatic interaction was the dominant driving force for bilirubin adsorption. In addition, the hydrophobic interaction provided by methyl groups could promote the bilirubin adsorption.

Study of the voltammetric behaviour of the ethalfluralin and methalpropalin and its determination in environmental matrices at hanging mercury drop electrode.

PubMed

Thriveni, T; Kumar, J Rajesh; Lee, Jin Young; Sreedhar, N Y

2009-04-01

An electroanalytical method has been developed for the determination of the herbicides ethalfluralin[N-ethyl-N-(2-methyl-2-propenyl)-2,6-dinitro-4-(trifluoromethyl) bezenamine] and methalpropalin [N-(2-methyl-2-propenyl)-2, 6-dinitro-N-propyl-4 (trifluoromethyl) benzenamine] by differential pulse adsorptive stripping voltammetry (DP-AdSV) on a hanging mercury drop electrode (HMDE) with universal buffer as supporting electrolyte. The optimum adsorption conditions were found to be pH 6.0, an accumulation potential of -0.6 V (HMDE vs SCE), an accumulation time of 80 s. and scan rate 45 mVs(-1). Calibration curve is linear in the range 1.30 x 10(-9) to 1.32 x 10(-5) M of ethalfluralin and 1.13 x 10(-5) to 2.0 x 10(-8) M of methalpropalin with detection limits of 1.08 x 10(-9) and 1.87 x 10(-8) M, respectively. The relative SD and correlation coefficients were found to be 1.24%, 0.998 and 1.34%, 0.995, respectively for ten replicates. The method is applied to the determination of the ethalfluralin and methalpropalin in formulations and environmental matrices.

FTIR spectroscopy and thermodynamics of hydrogen adsorbed in a cross-linked polymer.

PubMed

Spoto, Giuseppe; Vitillo, Jenny G; Cocina, Donato; Damin, Alessandro; Bonino, Francesca; Zecchina, Adriano

2007-09-28

The adsorption of H(2) in a cross-linked poly(styrene-co-divinylbenzene) (St-DVB) microporous polymer (BET surface area 920 m(2) g(-1)) is studied by volumetric and gravimetric methods, FTIR spectroscopy at variable temperature (300-14 K) and ab initio calculations. At 77 K the polymer reversibly stores up to 1.3 mass% H(2) at a pressure of 1 bar and 1.8 mass% at 10 bar. The adsorption process involves the specific interaction of H(2) with the structural phenyl rings through weak dispersive forces. The interacting molecules become IR active and give rise to vibrational and rotational-vibrational manifestations which are affected by the temperature, the contact time and the H(2) equilibrium pressure. The spectra of the H(2)/St-DVB system reported here represent the first IR evidence of the adsorption of hydrogen on unsaturated molecules. The adsorption enthalpy is evaluated by the VTIR (variable temperature IR spectroscopy) method (C. Otero Areán et al., Phys. Chem. Chem. Phys., 2007, DOI: 10.1039/b615535a) and compared with the results of ab initio calculations for the H(2)/benzene interaction and with literature data.

Evaluating metal-organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption

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

Mason, JA; Sumida, K; Herm, ZR

Two representative metal-organic frameworks, Zn4O(BTB)(2)(BTB3- = 1,3,5-benzenetribenzoate; MOF-177) and Mg-2(dobdc) (dobdc(4-) = 1,4-dioxido-2,5-benzenedicarboxylate; Mg-MOF-74, CPO-27-Mg), are evaluated in detail for their potential use in post-combustion CO2 capture via temperature swing adsorption (TSA). Low-pressure single-component CO2 and N-2 adsorption isotherms were measured every 10 degrees C from 20 to 200 degrees C, allowing the performance of each material to be analyzed precisely. In order to gain a more complete understanding of the separation phenomena and the thermodynamics of CO2 adsorption, the isotherms were analyzed using a variety of methods. With regard to the isosteric heat of CO2 adsorption, Mg-2(dobdc) exhibits anmore » abrupt drop at loadings approaching the saturation of the Mg2+ sites, which has significant implications for regeneration in different industrial applications. The CO2/N-2 selectivities were calculated using ideal adsorbed solution theory (IAST) for MOF-177, Mg-2(dobdc), and zeolite NaX, and working capacities were estimated using a simplified TSA model. Significantly, MOF-177 fails to exhibit a positive working capacity even at regeneration temperatures as high as 200 degrees C, while Mg-2(dobdc) reaches a working capacity of 17.6 wt% at this temperature. Breakthrough simulations were also performed for the three materials, demonstrating the superior performance of Mg-2(dobdc) over MOF-177 and zeolite NaX. These results show that the presence of strong CO2 adsorption sites is essential for a metal-organic framework to be of utility in post-combustion CO2 capture via a TSA process, and present a methodology for the evaluation of new metal-organic frameworks via analysis of single-component gas adsorption isotherms.« less

Experimental aspects of buoyancy correction in measuring reliable high-pressure excess adsorption isotherms using the gravimetric method

NASA Astrophysics Data System (ADS)

Nguyen, Huong Giang T.; Horn, Jarod C.; Thommes, Matthias; van Zee, Roger D.; Espinal, Laura

2017-12-01

Addressing reproducibility issues in adsorption measurements is critical to accelerating the path to discovery of new industrial adsorbents and to understanding adsorption processes. A National Institute of Standards and Technology Reference Material, RM 8852 (ammonium ZSM-5 zeolite), and two gravimetric instruments with asymmetric two-beam balances were used to measure high-pressure adsorption isotherms. This work demonstrates how common approaches to buoyancy correction, a key factor in obtaining the mass change due to surface excess gas uptake from the apparent mass change, can impact the adsorption isotherm data. Three different approaches to buoyancy correction were investigated and applied to the subcritical CO2 and supercritical N2 adsorption isotherms at 293 K. It was observed that measuring a collective volume for all balance components for the buoyancy correction (helium method) introduces an inherent bias in temperature partition when there is a temperature gradient (i.e. analysis temperature is not equal to instrument air bath temperature). We demonstrate that a blank subtraction is effective in mitigating the biases associated with temperature partitioning, instrument calibration, and the determined volumes of the balance components. In general, the manual and subtraction methods allow for better treatment of the temperature gradient during buoyancy correction. From the study, best practices specific to asymmetric two-beam balances and more general recommendations for measuring isotherms far from critical temperatures using gravimetric instruments are offered.

Experimental aspects of buoyancy correction in measuring reliable highpressure excess adsorption isotherms using the gravimetric method.

PubMed

Nguyen, Huong Giang T; Horn, Jarod C; Thommes, Matthias; van Zee, Roger D; Espinal, Laura

2017-12-01

Addressing reproducibility issues in adsorption measurements is critical to accelerating the path to discovery of new industrial adsorbents and to understanding adsorption processes. A National Institute of Standards and Technology Reference Material, RM 8852 (ammonium ZSM-5 zeolite), and two gravimetric instruments with asymmetric two-beam balances were used to measure high-pressure adsorption isotherms. This work demonstrates how common approaches to buoyancy correction, a key factor in obtaining the mass change due to surface excess gas uptake from the apparent mass change, can impact the adsorption isotherm data. Three different approaches to buoyancy correction were investigated and applied to the subcritical CO 2 and supercritical N 2 adsorption isotherms at 293 K. It was observed that measuring a collective volume for all balance components for the buoyancy correction (helium method) introduces an inherent bias in temperature partition when there is a temperature gradient (i.e. analysis temperature is not equal to instrument air bath temperature). We demonstrate that a blank subtraction is effective in mitigating the biases associated with temperature partitioning, instrument calibration, and the determined volumes of the balance components. In general, the manual and subtraction methods allow for better treatment of the temperature gradient during buoyancy correction. From the study, best practices specific to asymmetric two-beam balances and more general recommendations for measuring isotherms far from critical temperatures using gravimetric instruments are offered.

Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes.

PubMed

Liu, Kexi; Lei, Yinkai; Wang, Guofeng

2013-11-28

Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O2 adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N4 chelation, as well as the molecular and electronic structures for the O2 adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O2 on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d(z(2)), d(xy), d(xz), and d(yz)) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O2 adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

Vibrational and thermodynamic properties of Ar, N2, O2, H2 and CO adsorbed and condensed into (H,Na)-Y zeolite cages as studied by variable temperature IR spectroscopy.

PubMed

Gribov, Evgueni N; Cocina, Donato; Spoto, Giuseppe; Bordiga, Silvia; Ricchiardi, Gabriele; Zecchina, Adriano

2006-03-14

The adsorption of Ar, H2, O2, N2 and CO on (H,Na)-Y zeolite (Si/Al = 2.9, H+/Na+ approximately 5) has been studied at variable-temperature (90-20 K) and sub-atmospheric pressure (0-40 mbar) by FTIR spectroscopy. Unprecedented filling conditions of the zeolite cavities were attained, which allowed the investigation of very weakly adsorbed species and of condensed, liquid-like or solid-like, phases. Two pressure regimes were singled out, characterized by: (i) specific interaction at low pressure of the probe molecules (P) with the internal Brønsted and Lewis sites, and (ii) multilayer adsorption at higher pressure. In the case of CO the perturbation of the protonic sites located inside the sodalite cages was also observed. As the molecule is too large to penetrate the sodalite cage, the perturbation is thought to involve a proton jump tunneling mechanism. The adsorption energy for the (HF)OH...P (P = Ar, H2, O2, N2 and CO) specific interaction involving the high frequency Brønsted acid sites exposed in the supercages was derived following the VTIR (variable temperature infrared spectroscopy) method described by E. Garrone and C. Otero Areán (Chem. Soc. Rev., 2005, 34, 846).

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.

Zinc Oxide Coating Effect for the Dye Removal and Photocatalytic Mechanisms of Flower-Like MoS2 Nanoparticles

NASA Astrophysics Data System (ADS)

Tian, Qingyong; Wu, Wei; Yang, Shuanglei; Liu, Jun; Yao, Weijing; Ren, Feng; Jiang, Changzhong

2017-03-01

Flower-like MoS2 nanoparticles (NPs) consist of ultra-thin MoS2 nanosheets are synthesized via a facile one-pot hydrothermal method. The MoS2/ZnO p-n heterostructure is formed by coating n-type ZnO on the surface of flower-like MoS2 NPs through the seed-mediate route and post-annealing treatment. The effects for the dye removal and photocatalytic performances after ZnO coating are systematically investigated. The results demonstrated that the coating of ZnO nanoparticles has a positive promotion to the photodegrading properties while negative effect on the adsorption capacity of the MoS2/ZnO heterostructures. The related mechanisms on the relationship of adsorption capacity and photocatalysis are discussed in detail.

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.

Benzimidazole ligands in the corrosion inhibition for carbon steel in acid medium: DFT study of its interaction on Fe30 surface

NASA Astrophysics Data System (ADS)

Garcia-Ochoa, E.; Guzmán-Jiménez, S. J.; Hernández, J. Guadalupe; Pandiyan, Thangarasu; Vásquez-Pérez, José M.; Cruz-Borbolla, Julián

2016-09-01

The corrosion inhibition of N,N‧-bis(benzimidazole-2-yl-methyl)amine (L1) and N, N‧-bis(benzimidazole-2-yl-methyl)hydroxyethylamine (L2) was analyzed by electrochemical and theoretical methods. The data show that ligands form an adsorption layer over an iron surface, obeying the Langmuir isotherm (Δ Gads° of -32.96 kJ mol-1); the value are higher than -20 kJ mol-1 but less than -40 kJ mol-1, belonging to a conversion stage of physical adsorption to chemical adsorption or a comprehensive adsorption. This is consistent with fractal dimension of the electrode surface, estimated by an impedance depression angle of a semicircle that the surface is homogeneously covered by the formation of an inhibitor film. Furthermore, the electronic parameters of the ligands were analyzed by DFT, showing that L1 and L2 possesses corrosion inhibition properties that give up its p orbital electron density through its HOMO orbital to the metal LUMO to form an adsorption layer, and this has been proved theoretically by the interaction of ligands with Fe30. In addition, we have collected corrosion inhibition data for around 70 organic compounds reported in the literature, and the inhibition data plotted against different inhibitors, showing that amine ligands are good corrosion inhibitors.

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.

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

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.

Effects of resident water and non-equilibrium adsorption on the primary and enhanced coalbed methane gas recovery

NASA Astrophysics Data System (ADS)

Jahediesfanjani, Hossein

The major part of the gas in coalbed methane and shale gas reservoirs is stored as the adsorbed gas in the coal and organic materials of the black shale internal surfaces. The sorption sites in both reservoirs are composed of several macropores that contain very small pore sizes. Therefore, the adsorption/desorption is very slow process and follows a non-equilibrium trend. The time-dependency of the sorption process is further affected by the reservoir resident water. Water can diffuse into the matrix and adsorption sites, plug the pores and affect the reservoir gas production. This study presents an experimental and theoretical procedure to investigate the effects of the resident water and time-dependency of the sorption process on coalbed and shale gas primary and enhanced recovery by simultaneous CO 2/N2 injection. Series of the experiments are conducted to construct both equilibrium and non-equilibrium single and multi-component isotherms with the presence of water. A novel and rapid data interpretation technique is developed based on the nonequilibrium adsorption/desorption thermodynamics, mass conservation law, and volume filling adsorption theory. The developed technique is implemented to construct both equilibrium and non-equilibrium multi-component multi-phase isotherms from the early time experimental measurements. The non-equilibrium isotherms are incorporated in the coalbed methane/shale gas reservoir simulations to account for the time-dependency of the sorption process. The experimental results indicate that the presence of water in the sorption system reduces both carbon dioxide and nitrogen adsorption rates. Reduction in the adsorption rate for carbon dioxide is more than nitrogen. The results also indicate that the resident water reduces the adsorption ability of low rank coals more than high rank ones. The results of the multi-component sorption tests indicate that increasing the initial mole fraction of the nitrogen gas in the injected CO2/N2 mixture will increase the net carbon dioxide sequestration rate on coals in the presence of water. The optimum CO2/N2 ratio that can result in the maximum carbon dioxide sequestration rate can be obtained by conducting the experiments for various CO2/N2 ratios. The results of applying the developed non-equilibrium interpretation technique for several literature and in-house data indicate that both the equilibrium and non-equilibrium isotherms can be constructed in shorter time period (around 70 times less than the time required with the equilibrium techniques) and with higher accuracy using this method. (Abstract shortened by UMI.)

Structure and adsorption properties of a porous cooper hexacyanoferrate polymorph

NASA Astrophysics Data System (ADS)

Roque-Malherbe, R.; Carballo, E.; Polanco, R.; Lugo, F.; Lozano, C.

2015-11-01

The key questions addressed here were: the structure elucidation and the investigation of the adsorption space and framework expansion effect of a Cu(II) hexacyanoferrate (III) polymorph (labeled Cu-PBA-I). The structural analysis was performed with a broad set of characterization methods. Additionally, a low and high pressure carbon dioxide adsorption investigation was performed, assuming, to comprehend the adsorption experiments, that the adsorbent plus the adsorbed phase were a solid solution. We concluded: that the Cu-PBA-I presented the following composition, K1/4 Cu (II)[ Fe (III)(CN)6 ] 3 / 4⋄1/4 nH2 O , exhibited an antiferromagnetic behavior and displayed a thermally stable I 4 bar m 2 space group lattice in the degassed state. Moreover, the low pressure adsorption study allowed the calculation of the micropore volume, W=0.09 cm3/g and the isosteric heat of adsorption, qiso=19 kJ/mol; further, the high pressure adsorption data revealed an extremely high adsorption capacity owing to a framework expansion effect. Finally, the DRIFTS spectrum of adsorbed CO2 displayed peaks corresponding to carbon dioxide physically adsorbed and interacting with electron accepting Lewis acid sites. Hence, was produced an excellent adsorbent which combine porosity and anti-ferromagnetism, antagonist properties rarely found together.

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.

Graphene oxide/alginate beads as adsorbents: Influence of the load and the drying method on their physicochemical-mechanical properties and adsorptive performance.

PubMed

Platero, Emiliano; Fernandez, Maria Emilia; Bonelli, Pablo Ricardo; Cukierman, Ana Lea

2017-04-01

Graphene oxide/alginate beads were prepared from lab-synthesized graphene oxide, varying its content within the beads (0.05, 0.125, and 0.25wt.%). Ethanol-drying and lyophilization were compared as drying methods to obtain suitable adsorbents which were later tested to the removal of a model organic molecule (methylene blue). The morphological and textural properties of all the beads were characterized by scanning electron microscopy and N 2 adsorption/desorption isotherms at -196°C, respectively. Limited porosity was obtained for all cases (S BET <60m 2 /g). Uniaxial compression tests were performed to assess the mechanical properties of the beads. Ethanol-dried ones exhibited higher Young's elasticity modulus (E=192kPa) than the lyophilized samples (twice at 0.25wt.% graphene oxide loading), which disclosed breakage points at lower deformation percentages. Adsorption experiments were conducted and dye adsorption isotherms were obtained for the beads with the best removal performance. The experimental data were better fitted by the Langmuir model. The highest maximum adsorption capacity (4.25mmol/g) was obtained for the lyophilized beads with the highest graphene oxide content. Mechanical properties were found to be affected also by the dye adsorption. Copyright © 2016 Elsevier Inc. All rights reserved.

Dynamic adsorption of CO2/N2 on cation-exchanged chabazite SSZ-13: A breakthrough analysis

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

Bower, Jamey K.; Barpaga, Dushyant; Prodinger, Sebastian

2018-04-17

Alkali exchanged SSZ-13 adsorbents were investigated for their applicability in separating N2 from CO2 in flue gas streams using a dynamic breakthrough method. In contrast to IAST calculations based on equilibrium isotherms, K+ exchanged SSZ-13 was found to yield the best N2 productivity under dynamic conditions where diffusion properties play a significant role. This was attributed to the selective, partial blockage of access to the CHA cavities enhancing the separation potential in a 15/85 CO2/N2 binary gas mixture.

Dynamic Adsorption of CO 2 /N 2 on Cation-Exchanged Chabazite SSZ-13: A Breakthrough Analysis

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

Bower, Jamey K.; Barpaga, Dushyant; Prodinger, Sebastian

2018-03-30

Alkali exchanged SSZ-13 adsorbents were investigated for their applicability in separating N2 from CO 2 in flue gas streams using a dynamic breakthrough method. In contrast to IAST calculations based on equilibrium isotherms, K+ exchanged SSZ-13 was found to yield the best N2 productivity under dynamic conditions where diffusion properties play a significant role. This was attributed to the selective, partial blockage of access to the CHA cavities enhancing the separation potential in a 15/85 CO2/N2 binary gas mixture.

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.

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

Promoted Fixation of Molecular Nitrogen with Surface Oxygen Vacancies on Plasmon-Enhanced TiO2 Photoelectrodes.

PubMed

Li, Chengcheng; Wang, Tuo; Zhao, Zhi-Jian; Yang, Weimin; Li, Jian-Feng; Li, Ang; Yang, Zhilin; Ozin, Geoffrey A; Gong, Jinlong

2018-05-04

A hundred years on, the energy-intensive Haber-Bosch process continues to turn the N 2 in air into fertilizer, nourishing billions of people while causing pollution and greenhouse gas emissions. The urgency of mitigating climate change motivates society to progress toward a more sustainable method for fixing N 2 that is based on clean energy. Surface oxygen vacancies (surface O vac ) hold great potential for N 2 adsorption and activation, but introducing O vac on the very surface without affecting bulk properties remains a great challenge. Fine tuning of the surface O vac by atomic layer deposition is described, forming a thin amorphous TiO 2 layer on plasmon-enhanced rutile TiO 2 /Au nanorods. Surface O vac in the outer amorphous TiO 2 thin layer promote the adsorption and activation of N 2 , which facilitates N 2 reduction to ammonia by excited electrons from ultraviolet-light-driven TiO 2 and visible-light-driven Au surface plasmons. The findings offer a new approach to N 2 photofixation under ambient conditions (that is, room temperature and atmospheric pressure). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of the PIXEL method to investigate gas adsorption in metal–organic frameworks† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ce00555a Click here for additional data file. Click here for additional data file. Click here for additional data file.

PubMed Central

Maloney, Andrew G. P.; Wood, Peter A.

2016-01-01

PIXEL has been used to perform calculations of adsorbate-adsorbent interaction energies between a range of metal–organic frameworks (MOFs) and simple guest molecules. Interactions have been calculated for adsorption between MOF-5 and Ar, H2, and N2; Zn2(BDC)2(TED) (BDC = 1,4-benzenedicarboxylic acid, TED = triethylenediamine) and H2; and HKUST-1 and CO2. The locations of the adsorption sites and the calculated energies, which show differences in the Coulombic or dispersion characteristic of the interaction, compare favourably to experimental data and literature energy values calculated using density functional theory. PMID:28496380

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.

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.

Magnetic N-doped mesoporous carbon as an adsorbent for the magnetic solid-phase extraction of phthalate esters from soft drinks.

PubMed

Li, Menghua; Jiao, Caina; Yang, Xiumin; Wang, Chun; Wu, Qiuhua; Wang, Zhi

2017-04-01

A new kind of magnetic N-doped mesoporous carbon was prepared by the one-step carbonization of a hybrid precursor (glucose, melamine, and iron chloride) in a N 2 atmosphere with a eutectic salt (KCl/ZnCl 2 ) as the porogen. The obtained magnetic N-doped mesoporous carbon showed excellent characteristics, such as strong magnetic response, high surface area, large pore volume, and abundant π-electron system, which endow it with a great potential as a magnetic solid-phase extraction adsorbent. To evaluate its adsorption performance, the magnetic N-doped mesoporous carbon was used for the extraction of three phthalate esters from soft drink samples followed by high-performance liquid chromatographic analysis. Under the optimum conditions, the developed method showed a good linearity (1.0-120.0 ng/mL), low limit of detection (0.1-0.3 ng/mL, S/N = 3), and good recoveries (83.2-119.0%) in soft drink samples. The results indicated that the magnetic N-doped mesoporous carbon has an excellent adsorption capacity for phthalate esters and the present method is simple, accurate, and highly efficient for the extraction and determination of phthalate esters in complex matrix samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Recovery in Tight Gas Reservoirs using Maxwell-Stefan Equations

NASA Astrophysics Data System (ADS)

Santiago, C. J. S.; Kantzas, A.

2017-12-01

Due to the steep production decline in unconventional gas reservoirs, enhanced recovery (ER) methods are receiving great attention from the industry. Wet gas or liquid rich reservoirs are the preferred ER candidates due to higher added value from natural gas liquids (NGL) production. ER in these reservoirs has the potential to add reserves by improving desorption and displacement of hydrocarbons through the medium. Nevertheless, analysis of gas transport at length scales of tight reservoirs is complicated because concomitant mechanisms are in place as pressure declines. In addition to viscous and Knudsen diffusion, multicomponent gas modeling includes competitive adsorption and molecular diffusion effects. Most models developed to address these mechanisms involve single component or binary mixtures. In this study, ER by gas injection is investigated in multicomponent (C1, C2, C3 and C4+, CO2 and N2) wet gas reservoirs. The competing effects of Knudsen and molecular diffusion are incorporated by using Maxwell-Stefan equations and the Dusty-Gas approach. This model was selected due to its superior properties on representing the physics of multicomponent gas flow, as demonstrated during the presented model validation. Sensitivity studies to evaluate adsorption, reservoir permeability and gas type effects are performed. The importance of competitive adsorption on production and displacement times is demonstrated. In the absence of adsorption, chromatographic separation is negligible. Production is merely dictated by competing effects between molecular and Knudsen diffusion. Displacement fronts travel rapidly across the medium. When adsorption effects are included, molecules with lower affinity to the adsorption sites will be produced faster. If the injected gas is inert (N2), an increase in heavier fraction composition occurs in the medium. During injection of adsorbing gases (CH4 and CO2), competitive adsorption effects will contribute to improved recovery of heavier fractions. In this case, displacement fronts will be delayed due to molecular interaction with pore walls. Therefore, a balance between competitive adsorption versus faster displacement will ultimately define which gas is more efficient for hydrocarbon recovery.

Structural characteristics of biochar-graphene nanosheet composites and their adsorption performance for phthalic acid esters

NASA Astrophysics Data System (ADS)

Ghaffar, Abdul; Zhu, Xiaoying; Chen, Baoliang

2017-04-01

The nonuniform and unhomogenous structure of biochar including defects could affect the adsorption performance of biochars. Biochar and graphene nanosheet (GNS) composites (BG) were prepared by simple dip coating method following thermal route of bamboo wood biomass at three different temperatures (300, 500, 700°C), in addition to biochars. The morphology and structural composition of biochars and BG composites were examined by scanning electron microscopy, transmission electron microscopy, Brunauer-Emmet-Teller surface area with N2 and CO2, Raman spectroscopy, Fourier Transformed Infrared spectroscopy, X-ray Photoelectron spectroscopy, Thermogravimetric analysis and CHN elemental analysis. It was found that GNS ( 1µm, 0.1% mass) provided higher thermal stability, porous structure, and relatively higher surface area (N2 and CO2), to BG composites. BG composites portrayed the existence of GNS bearing cavities and evidently increased the graphitic structure. The adsorption capabilities of biochars and BG composites towards dimethyl phthalate (DMP), diethyl phthalate (DEP), and dibutyl phthalate (DBP) as model phthalic acid esters (PAEs) were examined by batch sorption technique. The BG composites exhibited the increased adsorption capacity comparatively to biochars. The aromatic sheets of biochars and GNS on biochars dominated the π-π EDA (electron donor-acceptor) interaction for ring structure of DMP molecule in addition to pore-diffusion mechanism, whereas adsorption of DBP was attributed to hydrophobicity. Our results suggest that surface composition and morphology of biochars can be regulated with GNS and may enhance their adsorption capacity, thus could be considered for effective environmental remediation of various organic contaminants.

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.

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.

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.

ZIRCONIUM PHOSPHATE ADSORPTION METHOD

DOEpatents

Russell, E.R.; Adamson, A.S.; Schubert, J.; Boyd, G.E.

1958-11-01

A method is presented for separating plutonium values from fission product values in aqueous acidic solution. This is accomplished by flowing the solutlon containing such values through a bed of zirconium orthophosphate. Any fission products adsorbed can subsequently be eluted by washing the column with a solution of 2N HNO/sub 3/ and O.lN H/sub 3/PO/sub 4/. Plutonium values may subsequently be desorbed by contacting the column with a solution of 7N HNO/sub 3/ .

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.

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.

Research and Development of Methods for Estimating Physicochemical Properties of Organic Compounds of Environmental Concern

DTIC Science & Technology

1979-02-01

coefficient (at equilibrium) when hysteresis is apparent. 6. Coefficient n in Freundlich equation for 1/n soil or sediment adsorption isotherms ýX - KC . 7...Biodegradation Chemical structures cal clasaes (e.g., Diffusion Correlations phenols). General Diffusion coefficients Equations terms for organic...OF THE FATE AND TRANSPORT OF ORGANIC CHEMICALS Adsorption coefficients: K, n* from Freundlich equation + Desorption coefficients: K’*, n’* from

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.

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.

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.

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 .

Enhanced adsorption of congo red from aqueous solutions by chitosan hydrogel beads impregnated with cetyl trimethyl ammonium bromide.

PubMed

Chatterjee, Sudipta; Lee, Dae S; Lee, Min W; Woo, Seung H

2009-06-01

The adsorption of congo red (CR) onto chitosan (CS) beads impregnated by a cationic surfactant (CTAB, cetyl trimethyl ammonium bromide) was investigated. Chitosan beads impregnated at a ratio of 1/20 of CTAB to CS (0.05% of CTAB and 1% of CS) increased the CR adsorption capacity by 2.2 times from 162.3 mg/g (0% CTAB) to 352.5 mg/g (0.05% CTAB). The CR adsorption decreased with an increase in pH of the CR solution from 4.0 to 9.0. The Sips isotherm model showed a good fit with the equilibrium experimental data and the values of the heterogeneity factor (n) indicated heterogeneous adsorption of CR onto CS/CTAB beads, as well as CS beads. The kinetic data showed better fit to the pseudo second-order rate model than to the pseudo first-order rate model. The impregnation of CS beads by cationic surfactants showed the highest adsorption capacities of CR compared to any other adsorbents and would be a good method to increase adsorption efficiency for the removal of anionic dyes in a wastewater treatment process.

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.

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.

In situ IR studies of Co and Ce doped Mn/TiO2 catalyst for low-temperature selective catalytic reduction of NO with NH3

NASA Astrophysics Data System (ADS)

Qiu, Lu; Pang, Dandan; Zhang, Changliang; Meng, Jiaojiao; Zhu, Rongshu; Ouyang, Feng

2015-12-01

The Mn-Co-Ce/TiO2 catalyst was prepared by wet co-impregnation method for selective catalytic reduction of NO by NH3 in the presence of oxygen. The adsorption and co-adsorption of NH3, NO and O2 on catalysts were investigated by in situ FTIR spectroscopy. The results suggested that addition of cobalt and cerium oxides increased the numbers of acid and redox sites. Especially, the cobalt oxide produced lots of Brønsted acid sites, which favor to the adsorption of coordinated NH3 through NH3 migration. Ce addition improved amide ions formation to reach best NO reduction selectivity. A mechanistic pathway over Mn-Co-Ce/TiO2 was proposed. At low-temperature SCR reaction, coordinated NH3 reacted with NO2-, and amide reacted with NO (ad) or NO (g) to form N2. NO2 was related to the formation of nitrite on Co-contained catalysts and the generation of sbnd NH2- on Ce-contained catalysts. At high temperature, the other branch reaction also occurred between the coordinated NH3 and nitrate species, resulting in N2O yield increase.

Adsorptive Stripping Voltammetric Determination of Amaranth and Tartrazine in Drinks and Gelatins Using a Screen-Printed Carbon Electrode

PubMed Central

Perdomo, Yeny; Arancibia, Verónica; Nagles, Edgar

2017-01-01

A fast, sensitive, and selective method for the simultaneous determination of one pair of synthetic colorants commonly found mixed in food products, Amaranth (AM) and Tartrazine (TZ), based on their adsorption and oxidation on a screen-printed electrode (SPE) is presented. The variation of peak current with pH, supporting electrolyte, adsorption time, and adsorption potential were optimized using square wave adsorptive voltammetry. The optimal conditions were found to be: pH 3.2 (PBS), Eads 0.00 V, and tads 30 s. Under these conditions, the AM and TZ signals were observed at 0.56 and 0.74 V, respectively. A linear response were found over the 0.15 to 1.20 µmol L−1 and 0.15 to 0.80 µmol L−1 concentrations, with detection limits (3σ/slope) of 26 and 70 nmol L−1 for AM and TZ, respectively. Reproducibility for 17.7 µmol L–1 AM and TZ solutions were 2.5 and 3.0% (n = 7), respectively, using three different electrodes. The method was validated by determining AM and TZ in spiked tap water and unflavored gelatin spiked with AM and TZ. Because a beverage containing both AM and TZ was not found, the method was applied to the determination of AM in a kola soft drink and TZ in an orange jelly and a soft drink powder. PMID:29156561

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.

Simulated moving bed system for CO.sub.2 separation, and method of same

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

Elliott, Jeannine Elizabeth; Copeland, Robert James; Lind, Jeff

A system and method for separating and/or purification of CO.sub.2 gas from a CO.sub.2 feed stream is described. The system and method include a plurality of fixed sorbent beds, adsorption zones and desorption zones, where the sorbent beds are connected via valve and lines to create a simulated moving bed system, where the sorbent beds move from one adsorption position to another adsorption position, and then into one regeneration position to another regeneration position, and optionally back to an adsorption position. The system and method operate by concentration swing adsorption/desorption and by adsorptive/desorptive displacement.

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.

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.

Selective adsorption of flavor-active components on hydrophobic resins.

PubMed

Saffarionpour, Shima; Sevillano, David Mendez; Van der Wielen, Luuk A M; Noordman, T Reinoud; Brouwer, Eric; Ottens, Marcel

2016-12-09

This work aims to propose an optimum resin that can be used in industrial adsorption process for tuning flavor-active components or removal of ethanol for producing an alcohol-free beer. A procedure is reported for selective adsorption of volatile aroma components from water/ethanol mixtures on synthetic hydrophobic resins. High throughput 96-well microtiter-plates batch uptake experimentation is applied for screening resins for adsorption of esters (i.e. isoamyl acetate, and ethyl acetate), higher alcohols (i.e. isoamyl alcohol and isobutyl alcohol), a diketone (diacetyl) and ethanol. The miniaturized batch uptake method is adapted for adsorption of volatile components, and validated with column breakthrough analysis. The results of single-component adsorption tests on Sepabeads SP20-SS are expressed in single-component Langmuir, Freundlich, and Sips isotherm models and multi-component versions of Langmuir and Sips models are applied for expressing multi-component adsorption results obtained on several tested resins. The adsorption parameters are regressed and the selectivity over ethanol is calculated for each tested component and tested resin. Resin scores for four different scenarios of selective adsorption of esters, higher alcohols, diacetyl, and ethanol are obtained. The optimal resin for adsorption of esters is Sepabeads SP20-SS with resin score of 87% and for selective removal of higher alcohols, XAD16N, and XAD4 from Amberlite resin series are proposed with scores of 80 and 74% respectively. For adsorption of diacetyl, XAD16N and XAD4 resins with score of 86% are the optimum choice and Sepabeads SP2MGS and XAD761 resins showed the highest affinity towards ethanol. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Surface rheology of saponin adsorption layers.

PubMed

Stanimirova, R; Marinova, K; Tcholakova, S; Denkov, N D; Stoyanov, S; Pelan, E

2011-10-18

Extracts of the Quillaja saponaria tree contain natural surfactant molecules called saponins that very efficiently stabilize foams and emulsions. Therefore, such extracts are widely used in several technologies. In addition, saponins have demonstrated nontrivial bioactivity and are currently used as essential ingredients in vaccines, food supplements, and other health products. Previous preliminary studies showed that saponins have some peculiar surface properties, such as a very high surface modulus, that may have an important impact on the mechanisms of foam and emulsion stabilization. Here we present a detailed characterization of the main surface properties of highly purified aqueous extracts of Quillaja saponins. Surface tension isotherms showed that the purified Quillaja saponins behave as nonionic surfactants with a relatively high cmc (0.025 wt %). The saponin adsorption isotherm is described well by the Volmer equation, with an area per molecule of close to 1 nm(2). By comparing this area to the molecular dimensions, we deduce that the hydrophobic triterpenoid rings of the saponin molecules lie parallel to the air-water interface, with the hydrophilic glucoside tails protruding into the aqueous phase. Upon small deformation, the saponin adsorption layers exhibit a very high surface dilatational elasticity (280 ± 30 mN/m), a much lower shear elasticity (26 ± 15 mN/m), and a negligible true dilatational surface viscosity. The measured dilatational elasticity is in very good agreement with the theoretical predictions of the Volmer adsorption model (260 mN/m). The measured characteristic adsorption time of the saponin molecules is 4 to 5 orders of magnitude longer than that predicted theoretically for diffusion-controlled adsorption, which means that the saponin adsorption is barrier-controlled around and above the cmc. The perturbed saponin layers relax toward equilibrium in a complex manner, with several relaxation times, the longest of them being around 3 min. Molecular interpretations of the observed trends are proposed when possible. Surprisingly, in the course of our study we found experimentally that the drop shape analysis method (DSA method) shows a systematically lower surface elasticity, in comparison with the other two methods used: Langmuir trough and capillary pressure tensiometry with spherical drops. The possible reasons for the observed discrepancy are discussed, and the final conclusion is that the DSA method has specific problems and may give incorrect results when applied to study the dynamic properties of systems with high surface elasticity, such as adsorption layers of saponins, lipids, fatty acids, solid particles, and some proteins. The last conclusion is particularly important because the DSA method recently became the preferred method for the characterization of fluid interfaces because of its convenience. © 2011 American Chemical Society

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.

Biosensor-assisted selection of optimal parameters for designing molecularly imprinted polymers selective to phosmet insecticide.

PubMed

Aftim, Nadin; Istamboulié, Georges; Piletska, Elena; Piletsky, Sergey; Calas-Blanchard, Carole; Noguer, Thierry

2017-11-01

Molecularly imprinted polymers (MIPs) for phosmet insecticide were synthesized by batch polymerization. The affinity of functional monomers to phosmet was tested using an original method involving an electrochemical biosensor based on acetylcholinesterase inhibition. It was demonstrated that association of phosmet with appropriate functional monomers resulted in a decrease of enzyme inhibition. Using this method, it was shown that N,N-methylenebis(acrylamide) displayed the highest interactions with phosmet using DMSO as solvent. These results were in good accordance with those obtained by conventional computational modeling. Molecularly imprinted polymers (MIPs) and non-imprinted polymers (NIPs) were synthesized and adsorption isotherms were studied to describe their interaction with phosmet. Freundlich isotherm was able to fit phosmet adsorption on MIPs with good agreement (R 2 = 0.9). The pre-exponential factor K F determined for MIPs was 1.439mg (1-N) g -1 L N , more that 10 times higher than for NIPs (0.125mg (1-N) g -1 . L N ), indicating an increase of binding sites number and average affinity. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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

Sensing mechanism of SnO2/ZnO nanofibers for CH3OH sensors: heterojunction effects

NASA Astrophysics Data System (ADS)

Tang, Wei

2017-11-01

SnO2/ZnO composite nanofibers were synthesized by a simple electrospinning method. The prepared SnO2/ZnO gas sensors exhibited good linear and high response to methanol. The enhanced sensing behavior of SnO2/ZnO might be associated with the homotypic heterojunction effects formed in n-SnO2/n-ZnO nanograins boundaries. In addition, the possible sensing mechanisms of methanol on SnO2/ZnO surface were investigated by density functional theory in order to make the methanol adsorption and desorption process clear. Zn doped SnO2 model was adopted to approximate the SnO2/ZnO structure because of the calculation power limitations. Calculation results showed that when exposed to methanol, the methanol would react with bridge oxygen O2c , planar O3c and pre adsorbed oxygen vacancy on the lattice surface. The -CH3 and -OH of methanol molecule would both lose one H atom. The lost H atoms bonded with oxygen at the adsorption sites. The final products were HCHO and H2O. Electrons were transferred from methanol to the lattice surface to reduce the resistance of semiconductor gas sensitive materials, which is in agreement with the experimental phenomena. More adsorption models of other interfering gases, such as ethanol, formaldehyde and acetone will be built and calculated to explain the selectivity issue from the perspective of adsorption energy, transferred charge and density of states in the future work.

Carbon Dioxide (CO2) Adsorption by Activated Carbon Functionalized with Deep Eutectic Solvent (DES)

NASA Astrophysics Data System (ADS)

Zulkurnai, N. Z.; Ali, U. F. Md.; Ibrahim, N.; Manan, N. S. Abdul

2017-06-01

In recent years, carbon dioxide (CO2) emission has become a major concern as the amount of the emitted gas significantly increases annually. Consequently, this phenomenon contributes to global warming. Several CO2 capture methods, including chemical adsorption by activated carbon, have been proposed. In this study, activated carbon was prepared from sea mango (Cerbera odollam), which was functionalized with deep eutectic solvent (DES) composed of choline chloride and glycerol to increase the efficiency of CO2 capture. The samples underwent pre-carbonization and carbonization processes at 200 °C and 500 °C, respectively, with nitrogen gas and flowing several gases, namely, CO2 and steam, and then followed by impregnation with 50 phosphoric acid (H3PO4) at 1:2 precursor-to-activant ratio. The prepared activated carbon was impregnated with DES at 1:2 precursor-to-activant ratio. The optimum CO2 adsorption capacity of the activated carbon was obtained by using CO2 gas treatment method (9.851 mgCO2/gsol), followed by the absence of gases (9.685 mgCO2/gsol), steam (9.636 mgCO2/gsol), and N2 (9.536 mgCO2/gsol).

Preparation and characterization of activated carbon from acorn shell by physical activation with H2O-CO2 in two-step pretreatment.

PubMed

Şahin, Ömer; Saka, Cafer

2013-05-01

Activated carbons have been prepared by physical activation with H2O-CO2 in two-step pre-treatment including ZnCl2-HCl from acorn shell at 850 °C. The active carbons were characterized by N2 adsorption at 77 K. Adsorption capacity was demonstrated by the iodine numbers. The surface chemical characteristics of activated carbons were determined by FTIR spectroscopic method. The microstructure of the activated carbons prepared was examined by scanning electron microscopy. The maximum BET surface area of the obtained activated carbon was found to be around 1779 m(2)/g. Copyright © 2013 Elsevier Ltd. All rights reserved.

Method of Synthesizing a Novel Absorbent Titanosilicate Material (UPRM-5)

NASA Technical Reports Server (NTRS)

Hernandez-Maldonado, Arturo (Inventor); Primera-Pedrozo, Jose N (Inventor)

2013-01-01

A titanium silicate variant named UPRM-5 was prepared using tetraethylammonium hydroxide as a structure-directing agent (SDA). Successful detemplation was achieved via ion exchange with NH4Cl. Effective functionalization was obtained after ion exchanging the detemplated material using SrCl2 and BaCl2. Adsorption of CO2 at 25 deg C in Sr(-) and Ba-UPRM-5 materials activated at different temperatures. For low partial pressures, the observed CO2 adsorption capacities increased as follows: NH4-UPRM-5 less than Sr-UPRM-5 less than Ba-UPRM-5. Both the Sr(-) and Ba-UPRM-5 materials exhibited outstanding selectivity for CO2 over CH4, N2 and O2.

Pore size distribution calculation from 1H NMR signal and N2 adsorption-desorption techniques

NASA Astrophysics Data System (ADS)

Hassan, Jamal

2012-09-01

The pore size distribution (PSD) of nano-material MCM-41 is determined using two different approaches: N2 adsorption-desorption and 1H NMR signal of water confined in silica nano-pores of MCM-41. The first approach is based on the recently modified Kelvin equation [J.V. Rocha, D. Barrera, K. Sapag, Top. Catal. 54(2011) 121-134] which deals with the known underestimation in pore size distribution for the mesoporous materials such as MCM-41 by introducing a correction factor to the classical Kelvin equation. The second method employs the Gibbs-Thompson equation, using NMR, for melting point depression of liquid in confined geometries. The result shows that both approaches give similar pore size distribution to some extent, and also the NMR technique can be considered as an alternative direct method to obtain quantitative results especially for mesoporous materials. The pore diameter estimated for the nano-material used in this study was about 35 and 38 Å for the modified Kelvin and NMR methods respectively. A comparison between these methods and the classical Kelvin equation is also presented.

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.

Removal of DDE by exploiting the alcoho-phobic interactions.

PubMed

Köse, Kazım; Köse, Dursun Ali

2017-04-01

DDE (1,1-bis-(4-chlorophenyl)-2,2-dichloroethene), which is a commonly used pesticides in agriculture, has harmful effects on human health. Therefore, the removal of this substance from the drinking water and the soil is essential. Since DDT (1,1″-(2,2,2-Trichloroethane-1,1-diyl) bis(4-chlorobenzene)) is derivation of DDE, the presence of DDT can be monitored by the detection of DDE present in the environment. Herein, we report on the development of aspartic acid-incorporated poly(2-hydroxyethyl methacrylate-L-aspartic acid) [poly(HEMA-MAsp)] cryogel for the removal of DDE from aqueous solutions for the first time in the literature. The synthesized cryogels were characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), an N 2 adsorption method, elemental analysis, and swelling test. The separation experiments were carried out via a batch system to get the optimum adsorption conditions including pH, interaction time, initial DDE concentration, and temperature. The desorption and the reusability results revealed that there was no significant decrease in the DDE adsorption capacity of the cryogels after five adsorption-desorption cycles. The maximum DDE adsorption capacity of poly(HEMA-MAsp) cryogels was found to be 31.51 mg DDE/g polymer for 50 mg DDE/L solution.

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 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.

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.

The adsorption of 1,3-butadiene on Pd/Ni multilayers: The interplay between spin polarization and chemisorption strength

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

Gomez, Guillermina; Belelli, Patricia G., E-mail: pbelelli@plapiqui.edu.a; Cabeza, Gabriela F.

2010-12-15

The adsorption of 1,3-butadiene (BD) on the Pd/Ni(1 1 1) multilayers has been studied using the VASP method in the framework of the density functional theory (DFT). The adsorption on two different configurations of the Pd{sub n}/Ni{sub m}(1 1 1) systems were considered. The most stable adsorption sites are dependent on the substrate composition and on the inclusion or not of spin polarization. On Pd{sub 1}Ni{sub 3}(1 1 1) surface, di-{pi}-cis and 1,2,3,4-tetra-{sigma} adsorption structures are the most stable for non-spin polarized (NSP) and spin polarized (SP) levels of calculation, respectively. Conversely, on Pd{sub 3}Ni{sub 1}(1 1 1) surface, themore » 1,2,3,4-tetra-{sigma} adsorption structure is the most stable for both NSP and SP levels, respectively. The magnetization of the Pd atoms strongly modifies the adsorption energy of BD and its most stable adsorption mode. On the other hand, as a consequence of BD adsorption, the Pd magnetization decreases. The smaller adsorption energies of BD and 1-butene on the Pd{sub 1}Ni{sub 3}(1 1 1) surface than on Pd(1 1 1) can be associated to the strained Pd overlayer deposited on Ni(1 1 1). -- Graphical Abstract: The adsorption of 1,3-butadiene on Pd/Ni(1 1 1) multilayers was theoretically studied. The most stable adsorption site depends on the substrate composition and on the inclusion of spin polarization. Display Omitted« less

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

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.

Band structure of graphene modulated by Ti or N dopants and applications in gas sensoring.

PubMed

Zhang, Hong-Ping; Luo, Xue-Gang; Lin, Xiao-Yan; Zhang, Ya-Ping; Tang, Ping-Ping; Lu, Xiong; Tang, Youhong

2015-09-01

The exploration of novel sensors for NO2 detection is particularly important in material and environmental sciences. In this work, the HOMO-LUMO gap of graphene, Ti- or N-doped graphene is investigated by DFT methods. The adsorption of NO2, NO, and O2 on Ti- or N-doped graphene of different sizes is also explored. Results reveal that the interactions between gases (NO2, NO, and O2) and Ti- or N-doped graphenes is not affected by the size of graphene. The doped Ti greatly improves the interactions between gases and graphene whereas the doped N has no effect on those interactions. The HOMO- LUMO gap of Ti-doped graphene can be modulated by adsorption of the gases. The cross effect of the NO and O2 is also investigated, and it is demonstrated that Ti-doped graphene has specific interactions with NO2. Thus, Ti-doped graphene can be a candidate for NO2 sensor materials. Furthermore, doping the graphene with Ti or N improves the sensitivity of the sheets toward NO2, which can be trapped and detected by the intrinsic graphene. Efficient sensors are rationally designed to diversify their applications in environmental science and engineering. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

Theoretical study of the accuracy of the pulse method, frontal analysis, and frontal analysis by characteristic points for the determination of single component adsorption isotherms.

PubMed

Andrzejewska, Anna; Kaczmarski, Krzysztof; Guiochon, Georges

2009-02-13

The adsorption isotherms of selected compounds are our main source of information on the mechanisms of adsorption processes. Thus, the selection of the methods used to determine adsorption isotherm data and to evaluate the errors made is critical. Three chromatographic methods were evaluated, frontal analysis (FA), frontal analysis by characteristic point (FACP), and the pulse or perturbation method (PM), and their accuracies were compared. Using the equilibrium-dispersive (ED) model of chromatography, breakthrough curves of single components were generated corresponding to three different adsorption isotherm models: the Langmuir, the bi-Langmuir, and the Moreau isotherms. For each breakthrough curve, the best conventional procedures of each method (FA, FACP, PM) were used to calculate the corresponding data point, using typical values of the parameters of each isotherm model, for four different values of the column efficiency (N=500, 1000, 2000, and 10,000). Then, the data points were fitted to each isotherm model and the corresponding isotherm parameters were compared to those of the initial isotherm model. When isotherm data are derived with a chromatographic method, they may suffer from two types of errors: (1) the errors made in deriving the experimental data points from the chromatographic records; (2) the errors made in selecting an incorrect isotherm model and fitting to it the experimental data. Both errors decrease significantly with increasing column efficiency with FA and FACP, but not with PM.

Theoretical and experimental studies on the corrosion inhibition potentials of some purines for aluminum in 0.1 M HCl

PubMed Central

Eddy, Nnabuk O.; Momoh-Yahaya, H.; Oguzie, Emeka E.

2014-01-01

Experimental aspect of the corrosion inhibition potential of adenine (AD), guanine (GU) and, hypoxanthine (HYP) was carried out using weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) methods while the theoretical aspect of the work was carried out by calculations of semi-empirical parameters (for AM1, MNDO, CNDO, PM3 and RM1 Hamiltonians), Fukui functions and inhibitor–metal interaction energies. Results obtained from the experimental studies were in good agreement and indicated that adenine (AD), guanine (GU) and hypoxanthine (HYP) are good adsorption inhibitors for the corrosion of aluminum in solutions of HCl. Data obtained from electrochemical experiment revealed that the studied purines functioned by adsorption on the aluminum/HCl interface and inhibited the cathodic half reaction to a greater extent and anodic half reaction to a lesser extent. The adsorption of the purines on the metal surface was found to be exothermic and spontaneous. Deviation of the adsorption characteristics of the studied purines from the Langmuir adsorption model was compensated by the fitness of Flory Huggins and El Awardy et al. adsorption models. Quantum chemical studies revealed that the experimental inhibition efficiencies of the studied purines are functions of some quantum chemical parameters including total energy of the molecules (TE), energy gap (EL–H), electronic energy of the molecule (EE), dipole moment and core–core repulsion energy (CCR). Fukui functions analysis through DFT and MP2 theories indicated slight complications and unphysical results. However, results obtained from calculated Huckel charges, molecular orbital and interaction energies, the adsorption of the inhibitors proceeded through the imine nitrogen (N5) in GU, emanine nitrogen (N7) in AD and the pyridine nitrogen (N5) in HPY. PMID:25750754

Theoretical and experimental studies on the corrosion inhibition potentials of some purines for aluminum in 0.1 M HCl.

PubMed

Eddy, Nnabuk O; Momoh-Yahaya, H; Oguzie, Emeka E

2015-03-01

Experimental aspect of the corrosion inhibition potential of adenine (AD), guanine (GU) and, hypoxanthine (HYP) was carried out using weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) methods while the theoretical aspect of the work was carried out by calculations of semi-empirical parameters (for AM1, MNDO, CNDO, PM3 and RM1 Hamiltonians), Fukui functions and inhibitor-metal interaction energies. Results obtained from the experimental studies were in good agreement and indicated that adenine (AD), guanine (GU) and hypoxanthine (HYP) are good adsorption inhibitors for the corrosion of aluminum in solutions of HCl. Data obtained from electrochemical experiment revealed that the studied purines functioned by adsorption on the aluminum/HCl interface and inhibited the cathodic half reaction to a greater extent and anodic half reaction to a lesser extent. The adsorption of the purines on the metal surface was found to be exothermic and spontaneous. Deviation of the adsorption characteristics of the studied purines from the Langmuir adsorption model was compensated by the fitness of Flory Huggins and El Awardy et al. adsorption models. Quantum chemical studies revealed that the experimental inhibition efficiencies of the studied purines are functions of some quantum chemical parameters including total energy of the molecules (TE), energy gap (E L-H), electronic energy of the molecule (EE), dipole moment and core-core repulsion energy (CCR). Fukui functions analysis through DFT and MP2 theories indicated slight complications and unphysical results. However, results obtained from calculated Huckel charges, molecular orbital and interaction energies, the adsorption of the inhibitors proceeded through the imine nitrogen (N5) in GU, emanine nitrogen (N7) in AD and the pyridine nitrogen (N5) in HPY.

Thermodynamical and structural insights of orange II adsorption by Mg{sub R}AlNO{sub 3} layered double hydroxides

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

Mustapha Bouhent, Mohamed; Laboratoire des Materiaux Inorganiques, UMR CNRS 6002, Universite Blaise Pascal, F-63177 Aubiere Cedex; Derriche, Zoubir, E-mail: derriche_zoubir@yahoo.co

2011-05-15

[Mg{sub 1-x} Al{sub x}(OH){sub 2}][(NO{sub 3}){sub x}, nH{sub 2}O] Layered Double Hydroxide (LDH) sorbents with variable Mg/Al molar (R=(1-x)/x) ratios were investigated for adsorption of azo dye, orange II (OII) at various pH and temperature conditions. Mg{sub 2}AlNO{sub 3} displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg{sub 2}AlNO{sub 3} at 40 {sup o}C. Adsorption isotherms have been fitted using the Langmuir model and free energy of adsorption ({Delta}G{sup o}), enthalpy ({Delta}H{sup o}) and entropy ({Delta}S{sup o}) were calculated. The experimental values for {Delta}G{sup o} in temperature range between 10 and 40 {sup o}C weremore » found to be negative indicating that a spontaneous process occurred. Positive calculated enthalpy values, characteristic of an endothermic process were found. Characterization of solids (PXRD, FTIR, UV-vis, TGA/DTA, adsorption isotherm BET analysis, SEM and Zetametry) before and after adsorption showed that adsorption proceeds in two steps. First, adsorption occurs at the LDH surface, followed by intercalation via anion exchange. -- Graphical Abstract: Structural and thermodynamical insight of adsorption/Intercalation of OII in Mg{sub R}Al LDH Display Omitted Highlights: {yields} The nitrate containing hydrotalcite-like compounds (Mg{sub R}AlNO{sub 3} LDH) were prepared by the coprecipitation method. {yields} Adsorption of anionic orange dye(OII) is studied on LDHs at different temperatures. {yields} The adsorption process is well described by the Langmuir isotherm model. {yields} Mg{sub 2}AlNO{sub 3} displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg{sub 2}AlNO{sub 3} at 40 {sup o}C. {yields} Adsorption process does not occur on the surface of the LDH only but an intercalation process is also occurring concomitantly according to the thermodynamical values.« less

Adsorption of methyl green dye onto multi-walled carbon nanotubes decorated with Ni nanoferrite

NASA Astrophysics Data System (ADS)

Bahgat, Mohamed; Farghali, Ahmed Ali; El Rouby, Waleed; Khedr, Mohamed; Mohassab-Ahmed, Mohassab Y.

2013-06-01

This research was carried out to evaluate the capability of multi-walled carbon nanotubes (CNTs) and NiFe2O4-decorated multi-walled carbon nanotubes (NiFe2O4-CNTs) toward waste water treatment relevant to organic dyes. CNTs were prepared via chemical vapor deposition method. NiFe2O4-CNTs were prepared by in-situ chemical precipitation of metal hydroxides followed by hydrothermal processing. The samples were characterized using XRD and TEM. The adsorption efficiency of CNTs and NiFe2O4-CNTs of methyl green dye at various temperatures was examined. The adsorbed amount increased with the CNTs and NiFe2O4-CNTs dosage. The linear correlation coefficients and standard deviations of Langmuir and Freundlich isotherms were determined. It was found that Langmuir isotherm fitted the experimental results well in both adsorption cases n of methyl green onto CNTs and NiFe2O4-CNTs. Kinetics analyses were conducted using pseudo first-order, second-order and the intraparticle diffusion models. The results showed that the adsorption kinetics was controlled by a pseudo second-order model for adsorption of methyl green onto CNTs and best controlled by pseudo first-order in case of NiFe2O4-CNTs. Changes in the free energy of adsorption (Δ G°), enthalpy (Δ H°), entropy (Δ S°), and the activation energy ( E a) were determined. The Δ H°, Δ G° and E a values indicated that the adsorption of methyl green onto MWCNTs and NiFe2O4-MWCNTs was physisorption.

Highly efficient removal of ammonia nitrogen from wastewater by dielectrophoresis-enhanced adsorption.

PubMed

Liu, Dongyang; Cui, Chenyang; Wu, Yanhong; Chen, Huiying; Geng, Junfeng; Xia, Jianxin

2018-01-01

A new approach, based on dielectrophoresis (DEP), was developed in this work to enhance traditional adsorption for the removal of ammonia nitrogen (NH 3 -N) from wastewater. The factors that affected the removal efficiency were systematically investigated, which allowed us to determine optimal operation parameters. With this new method we found that the removal efficiency was significantly improved from 66.7% by adsorption only to 95% by adsorption-DEP using titanium metal mesh as electrodes of the DEP and zeolite as the absorbent material. In addition, the dosage of the absorbent/zeolite and the processing time needed for the removal were greatly reduced after the introduction of DEP into the process. In addition, a very low discharge concentration (C, 1.5 mg/L) of NH 3 -N was achieved by the new method, which well met the discharge criterion of C < 8 mg/L (the emission standard of pollutants for rare earth industry in China).

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.

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.

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.

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.

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

Oleksiak, Matthew D.; Ghorbanpour, Arian; Conato, Marlon T.

Designing zeolites with tunable physicochemical properties can substantially impact their performance in commercial applications such as adsorption, separations, catalysis, and drug delivery. Zeolite synthesis typically requires an organic structure-directing agent to obtain crystals with specific pore topology. Attempts to remove organics from syntheses to achieve commercially-viable methods of preparing zeolites often lead to the formation of impurities. Here, we present organic-free syntheses of two polymorphs of the small-pore zeolite P (GIS), P1 and P2. Using a combination of adsorption measurements and density functional theory calculations, we show that GIS polymorphs are selective adsorbents for H2O relative to other light gasesmore » (e.g., H2, N2, CO2).« less

Adsorptive removal of bisphenol A using synthesized magnetite nanoparticles

NASA Astrophysics Data System (ADS)

Orimolade, B. O.; Adekola, F. A.; Adebayo, G. B.

2018-03-01

Bisphenol A (BPA) is an organic compound which is often used as plasticizer and has been reported to be hazardous to man. In this research the efficiency of removal of BPA from water by magnetite through adsorption process was studied. The magnetite was synthesized using reverse co-precipitation method and fully characterized. Various physicochemical parameters affecting the adsorption of BPA using magnetite were studied as well. The optimum time for the adsorption process was found to be 60 min at pH of 6, adsorbent dose of 0.2 g and 50 ppm of BPA. The adsorption data were fitted by the Langmuir adsorption isotherm best with a regression value of 0.957. The R L value was 0.179 which revealed that the process is favorable. The Freundlich constant n which was 1.901 also revealed that the adsorption is normal and favorable. The data were in agreement with the pseudo-second-order kinetics with regression value of 0.98. From the thermodynamic studies, the process was found to be exothermic and the Gibb's free energy value which was negative showed that the adsorption was spontaneous. The synthesized magnetite therefore offers great potential for the remediation of bisphenol A-contaminated media.

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.

Macroporous monoliths for trace metal extraction from seawater

DOE PAGES

Yue, Yanfeng; Mayes, Richard T.; Gill, Gary; ...

2015-05-29

The viability of seawater-based uranium recovery depends on the uranium adsorption rate and capacity, since the concentration of uranium in the oceans is relatively low (3.3 gL -1). An important consideration for a fast adsorption is to maximize the adsorption properties of adsorbents such as surface areas and pore structures, which can greatly improve the kinetics of uranium extraction and the adsorption capacity simultaneously. Following this consideration, macroporous monolith adsorbents were prepared from the copolymerization of acrylonitrile (AN) and N,N -methylenebis(acrylamide) (MBAAm) based on a cryogel method using both hydrophobic and hydrophilic monomers. The monolithic sorbents were tested with simulatedmore » seawater containing a high uranyl concentration (–6 ppm) and the uranium adsorption results showed that the adsorption capacities are strongly influenced by the ratio of monomer to the crosslinker, i.e., the density of the amidoxime groups. Furthermore, the preliminary seawater testing indicates the high salinity content of seawater does not hinder the adsorption of uranium.« less

Role of size, composition and substrate in controlling the reactivity of α(0001)-Al2O3 supported AgnAum (n + m = 2 - 4) alloy clusters for CO-oxidation: A comprehensive density functional study

NASA Astrophysics Data System (ADS)

Singh, Akansha; Majumder, Chiranjib; Sen, Prasenjit

2018-03-01

Catalytic efficiency of gas phase and alumina-supported bimetallic AgnAum (n + m = 2 - 4) alloy clusters is studied using density functional methods As a pre-requite, adsorption of O2 and CO molecules, and co-adsorption of both molecules on these clusters are studied in detail. O2 and CO are co-adsorbed on nearby sites on the gas phase tetramer clusters Ag2Au2 and Ag3Au. But their catalytic efficiency is hindered by large barriers (1.55 eV and 1.44 eV, respectively) to the breaking of Osbnd O bond. Among the deposited clusters, Ag2Au and AgAu2 have O2 and CO co-adsorbed on nearby locations. Of these two, Ag2Au has a lower kinetic barrier for subsequent CO2 formation. Thus Ag2Au looks the most promising candidate.

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

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.

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.

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.

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

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.

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.

Nanoclay-Based Solid-Amine Adsorbents for Carbon Dioxide Capture

NASA Astrophysics Data System (ADS)

Roth, Elliot A.

The objective of this research was to develop an efficient, low cost, recyclable solid sorbent for carbon dioxide adsorption from large point sources, such as coal-fired power plants. The current commercial way to adsorb CO 2 is to use a liquid amine or ammonia process. These processes are used in industry in the "sweetening" of natural gas, but liquid based technologies are not economically viable in the adsorption of CO2 from power plants due to the extremely large volume of CO2 and the inherent high regeneration costs of cycling the sorbent. Therefore, one of the main objectives of this research was to develop a novel sorbent that can be cycled and uses very little energy for regeneration. The sorbent developed here is composed of a nanoclay (montmorillonite), commonly used in the production of polymer nanocomposites, grafted with commercially available amines. (3-aminopropyl) trimethoxysilane (APTMS) was chemically grafted to the edge hydroxyl groups of the clay. While another amine, polyethylenimine (PEI), was attached to the surface of the clay by electrostatic interactions. To confirm the attachment of amines to the clay, the samples were characterized using FTIR and the corresponding peaks for amines were observed. The amount of amine loaded onto the support was determined by TGA techniques. The treated clay was initially analyzed for CO2 adsorption in a pure CO 2 stream. The adsorption temperatures that had the highest adsorption capacity were determined to be between 75°C and 100°C for all of the samples tested at atmospheric pressure. The maximum CO2 adsorption capacity observed was with nanoclay treated with both APTMS and PEI at 85°C. In a more realistic flue gas of 10% CO2 and 90% N2, the adsorbents had essentially the same overall CO2 adsorption capacity indicating that the presence of nitrogen did not hinder the adsorption of CO2. Adsorption studies in pure CO2 at room temperature under pressure from 40-300 PSI were also conducted. The average adsorption capacity for the adsorbents did not change significantly over the range of pressures studied, indicating that the uptake of CO2 was due mainly to chemical reaction and not to the physical absorption of CO2. The average CO2 adsorption capacity at 300 psi and room temperature for clay treated with APTMS alone was 7.6 wt% CO2. The combination of APTMS and PEI treatment increased the average adsorption capacity to 11.4 wt% CO2. The regeneration method for the majority of the adsorption tests employed pure N2 at 100°C as a sweep gas, and it was successful in regenerating the adsorbent. The regeneration of the adsorbent was also studied with pure and humid CO2 at 155°C. Using CO2 as a sweep gas for regeneration is more commercially relevant and was able to regenerate the sorbents. Vacuum regeneration and the stability of the adsorbents to water vapor were also studied. Our studies showed that the developed adsorbents were able to adsorb CO2 at atmospheric conditions using pure CO 2 as well as 10% CO2 and 90% nitrogen. Additionally, the adsorbents developed have the potential to be cycled using commercially applicable regeneration schemes. While these results are comparable to results of other emerging CO2 adsorption technologies, our adsorbent has the benefit of a very cheap support, and it could provide a commercially useful CO 2 adsorbent.

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.

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.

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.

Combining the Physical Adsorption Approach and the Covalent Attachment Method to Prepare a Bifunctional Bioreactor

PubMed Central

Dong, Mengxing; Wu, Zhuofu; Lu, Ming; Wang, Zhi; Li, Zhengqiang

2012-01-01

Aminopropyl-functionalized SBA-15 mesoporous silica was used as a support to adsorb myoglobin. Then, in order to avoid the leakage of adsorbed myoglobin, lysozyme was covalently tethered to the internal and external surface of the mesoporous silica with glutaraldehyde as the coupling agent. The property of amino-functionalized mesoporous silica was characterized by N2 adsorption-desorption and thermogravimetric (TG) analysis. The feature of the silica-based matrix before and after myoglobin adsorption was identified by fourier transform infrared (FTIR) and UV/VIS measurement. With o-dianisidine and H2O2 as the substrate, the peroxidase activity of adsorbed myoglobin was determined. With Micrococus lysodeilicus as the substrate, the antibacterial activity of covalently tethered lysozyme was measured. Results demonstrated that the final product not only presented peroxidase activity of the myoglobin but yielded antibacterial activity of the lysozyme. PMID:23109864

Fast and efficient adsorption of methylene green 5 on activated carbon prepared from new chemical activation method.

PubMed

Tran, Hai Nguyen; You, Sheng-Jie; Chao, Huan-Ping

2017-03-01

Activated carbon (AC) was synthesized from golden shower (GS) through a new chemical activation process. The three-stage process comprised (1) hydrothermal carbonization of GS to produce hydrochar, (2) pyrolysis of hydrochar to produce biochar, and (3) subsequent chemical activation of biochar with K 2 CO 3 to obtain GSHBAC. The traditional synthesis processes (i.e., one-stage and two-stage) were also examined for comparison. In the one-stage process, GS that was impregnated with K 2 CO 3 was directly pyrolyzed (GSAC), and the two-stage process consisted of (1) pyrolytic or hydrothermal carbonization to produce biochar or hydrochar and (2) subsequent chemical activation was defined as GSBAC and GSHAC, respectively. The synthesized ACs were characterized by scanning electron microscope, Brunauer-Emmett-Teller (BET) surface area analysis, Fourier transform infrared spectrometry, point zero charge, and Boehm titration. The adsorption results demonstrated that the MG5 adsorption process was not remarkably affected by neither the solution pH (2.0-10) nor ionic strength (0-0.5 M NaCl). Kinetic studies showed that the adsorption equilibrium was quickly established, with a low activation energy required for adsorption (Ea; 3.30-27.8 kJ/mol), and the ACs removed 50-73% of the MG5 concentration from solution within 01 min. Desorption studies confirmed the adsorption was irreversible. Thermodynamic experiments suggested that the MG5 adsorption was spontaneous (-ΔG°) and endothermic (+ΔH°), and increased the randomness (+ΔS°) in the system. Although the specific surface areas of the ACs followed the order GSAC (1,413) > GSHAC (1,238) > GSHBAC (903) > GSBAC (812 m 2 /g), the maximum adsorption capacities determined from the Langmuir model (Q o max ) at 30 °C exhibited the following order: GSHBAC (531) > GSAC (344) > GSHAC (332) > GSBAC (253 mg/g). Oxygenation of the ACs' surface through a hydrothermal process with acrylic acid resulted in a decrease in MG5 adsorption and identified the importance of π-π interactions to the adsorption process. The primary interactions in MG5 adsorption were π-π interactions and pore filling, while hydrogen bonding and n-π interactions were minor contributors. The three-stage process can be regarded as the effective preparation method of AC with a high adsorption capacity toward the cationic dye. Copyright © 2016 Elsevier Ltd. All rights reserved.

Determination of Pb2+ metal ion level in liquid waste from adsorption process by combination adsorbent of rice husk and water hyacinth charcoal using solid-phase spectrophotometry (sps)

NASA Astrophysics Data System (ADS)

Saputro, S.; Masykuri, M.; Mahardiani, L.; Hidayah, AN

2018-03-01

This research are to find out the influence of adsorbent composition between rice husk and water hyacinth in decreasing of Pb2+ ion in simulation liquid waste; the optimumcomposition of combination adsorbent of rice husk and water hyacinth charcoal on Pb2+ ion adsorption; and theeffectivenessof SPS as a method to determine the decreasing level of Pb2+ ion in simulation liquid waste by combination adsorbent of rice husk and water hyacinth charcoal in µg/L level. Rice husk and water hyacinth carbonization using muffle furnace at 350°C for 1 hour. Rice husk charcoal activation in a 2 N NaOH solution and water hyacinth charcoal activated in a 5 M HCl solution. Contacting the combination adsorbent of rice husk and water hyacinth charcoal with a Pb2+ solution with variation of mass composition, 1:0 ; 0:1 ; 1:1 ; 1:2 and 2:1. Analysis of the Pb2+ ion level using SPS method. Characterization of rice husk and water hyacinth charcoal using the FTIR. The results showed that the combination adsorbent composition of rice husk and water hyacinth charcoal have an impact on decreasing Pb2+ ion level. The optimum composition of combination adsorbent of rice husk and water hyacinth charcoal on the adsorption Pb2+ ion is 1:2. SPS is an effective method to determine the decreasing Pb2+ ion in simulation liquid waste from the adsorption process by combination adsorbent of rice husk and water hyacinth in µg/L, with Limit of Detection (LOD) was 0,06 µg/L.

Enrichment process of biogas using simultaneous Absorption - Adsorption methods

NASA Astrophysics Data System (ADS)

Kusrini, Eny; Lukita, Maya; Gozan, Misri; Susanto, Bambang Heru; Nasution, Dedy Alharis; Rahman, Arif; Gunawan, Cindy

2017-03-01

Removal of CO2 in biogas is an essential methods to the purification and upgrading of biogas. Natural Clinoptilolite zeolites were evaluated as sorbents for purification of biogas that produced from palm oil mill effluent (POME) by anerobic-digestion method. The absorption and adsorption experiments were conducted in a fixed-bed two column adsorption unit by simultaneous absorption-adsorption method. The Ca(OH)2 solution with concentration of 0.062 M was used as absorption method. Sorbent for removal of CO2 in biogas have been prepared by modifying of Clinoptilolite zeolites with an acid (HCl, 2M) and alkaline (NaOH, 2M), calcined at 450°C and then coated using chitosan (0.5 w/v%) in order to increase their adsorption capacity. The removal of CO2 in biogas was achieved about ˜83% using 2.5 g of sorbent zeolite (2M)/chitosan dosage for each column, breakthrough time of 30 min, and flow rate of 100 mL/min. Clinoptilolite zeolites with modifications of an acid-alkaline and chitosan (zeolite (2M)/chitosan) are promising sorbents due to the amine groups from chitosan and high surface-volume ratio are one of important factors in a simultaneous absorption-adsorption method.

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.

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.

Environmentally Friendly Method: Development and Application to Carbon Aerogel as Sorbent for Solid-Phase Extraction.

PubMed

Dong, Sheying; Huang, Guiqi; Su, Meiling; Huang, Tinglin

2015-10-14

We developed two simple, fast, and environmentally friendly methods using carbon aerogel (CA) and magnetic CA (mCA) materials as sorbents for micro-solid-phase extraction (μ-SPE) and magnetic solid-phase extraction (MSPE) techniques. The material performances such as adsorption isotherm, adsorption kinetics, and specific surface area were discussed by N2 adsorption-desorption isotherm measurements, ultraviolet and visible (UV-vis) spectrophotometry, scanning electron microscopy (SEM), and high resolution transmission electron microscopy (HR-TEM). The experimental results proved that the heterogeneities of CA and mCA were well modeled with the Freundlich isotherm model, and the sorption process well followed the pseudo-second-order rate equation. Moreover, plant growth regulators (PGRs) such as kinetin (6-KT), 6-benzylaminopurine (6-BA), 2,4-dichlorophenoxyacetic acid (2,4-D), and uniconazole (UN) in a reservoir raw water sample were selected as the evaluation of applicability for the proposed μ-SPE and MSPE techniques using high performance liquid chromatography (HPLC). The experimental conditions of two methods such as the amount of sorbent, extraction time, pH, salt concentration, and desorption conditions were studied. Under the optimized conditions, two extraction methods provided high recoveries (89-103%), low the limits of detection (LODs) (0.01-0.2 μg L(-1)), and satisfactory analytical features in terms of precision (relative standard deviation, RSD, 1.7-5.1%, n=3). This work demonstrates the feasibility and the potential of CA and mCA materials as sorbents for μ-SPE and MSPE techniques. Besides, it also could serve as a basis for future development of other functional CAs in pretreatment technology and make them valuable for analysis of pollutants in environmental applications.

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

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.

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.

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.

Scavenging performance and antioxidant activity of γ-alumina nanoparticles towards DPPH free radical: Spectroscopic and DFT-D studies.

PubMed

Zamani, Mehdi; Moradi Delfani, Ali; Jabbari, Morteza

2018-05-03

The radical scavenging performance and antioxidant activity of γ-alumina nanoparticles towards 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical were investigated by spectroscopic and computational methods. The radical scavenging ability of γ-alumina nanoparticles in the media with different polarity (i.e. i-propanol and n-hexane) was evaluated by measuring the DPPH absorbance in UV-Vis absorption spectra. The structure and morphology of γ-alumina nanoparticles before and after adsorption of DPPH were studied using XRD, FT-IR and UV-Vis spectroscopic techniques. The adsorption of DPPH free radical on the clean and hydrated γ-alumina (1 1 0) surface was examined by dispersion corrected density functional theory (DFT-D) and natural bond orbital (NBO) calculations. Also, time-dependent density functional theory (TD-DFT) was used to predict the absorption spectra. The adsorption was occurred through the interaction of radical nitrogen N and NO 2 groups of DPPH with the acidic and basic sites of γ-alumina surface. The high potential for the adsorption of DPPH radical on γ-alumina nanoparticles was investigated. Interaction of DPPH with Brønsted and Lewis acidic sites of γ-alumina was more favored than Brønsted basic sites. The following order for the adsorption of DPPH over the different active sites of γ-alumina was predicted: Brønsted base < Lewis acid < Brønsted acid. These results are of great significance for the environmental application of γ-alumina nanoparticles in order to remove free radicals. Copyright © 2018. Published by Elsevier B.V.

Modification process optimization, characterization and adsorption property of granular fir-based activated carbon

NASA Astrophysics Data System (ADS)

Chen, Congjin; Li, Xin; Tong, Zhangfa; Li, Yue; Li, Mingfei

2014-10-01

Granular fir-based activated carbon (GFAC) was modified with H2O2, and orthogonal array experimental design method was used to optimize the process. The properties of the original and modified GFAC were characterized by N2 adsorption-desorption isotherms, Brunauer-Emmett-Teller (BET) equation, Barett-Joyner-Halenda (BJH) equation, field emission scanning electron microscopy (FESEM), and Fourier transform infrared spectroscopy (FT-IR) analysis, etc. When 10.00 g of GFAC with particle size of 0.25-0.85 mm was modified by 150.0 ml of aqueous H2O2 solution, the optimized conditions were found to be as follows: aqueous H2O2 solution concentration 1.0 mol·l-1, modification temperature 30.0 °C, modification time 4.0 h. Modified under the optimized conditions, decolonization of caramel, methylene blue adsorption, phenol adsorption and iodine number of the modified GFAC increased by 500.0%, 59.7%, 32.5%, and 15.1%, respectively. The original and optimally modified GFAC exhibited adsorption isotherms of hybrid Type I-IV isotherms with H4 hysteresis. BET surface area, micropore area, total pore volume, micropore volume, and microporosity of the modified GFAC increased by 7.33%, 11.25%, 3.89%, 14.23%, 9.91%, respectively. Whereas the average pore width decreased by 3.16%. In addition, the amount of surface oxygen groups (such as carbonyl or carboxyl) increased in the modified GFAC.

Effects of impurity adsorption on topological surface states of Bi2Te3

NASA Astrophysics Data System (ADS)

Shati, Khaqan; Arshad Farhan, M.; Selva Chandrasekaran, S.; Shim, Ji Hoon; Lee, Geunsik

2017-08-01

Electronic structures of Bi2Te3 with adsorption of Rb, In, Ga and Au atoms are studied by using the first-principle method, focusing on the effect of non-magnetic impurities on the topologically protected surface states. Upon monolayer formation, the bulk conduction band is moved down to the Fermi level with a significant Rashba splitting due to n-doping behavior with band modification details depending on the adatom chemistry. Our study shows the robustness of the intrinsic spin-momentum coupled surface band and emergence of a new similar one, which could provide helpful insight for developing novel spintronic devices.

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.

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.

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.

Computational evaluation of metal-organic frameworks for carbon dioxide capture

NASA Astrophysics Data System (ADS)

Yu, Jiamei

Metal-organic frameworks (MOFs), a new class of porous solids comprised of metal-containing nodes linked by organic ligands, have become promising materials for gas separations. In particular, their flexible chemistry makes them attractive for CO2 capture from flue gas streams in post-combustion plants. Although numerous efforts have been exerted on the investigation of MOFs for CO2 capture, the exploration of the effects from coexisting components present in very dilute proportions in flue gases is limited because of the experimental difficulty to determine the coadsorption of CO2 with trace components. In this regard, molecular simulations show superiority. In this study, molecular simulations are used to estimate the influence of impurities: water, O2, and SO2 on post-combustion CO2 capture in MOFs. Firstly, two MOFs with coordinatively unsaturated metal sites (CUMs), HKUST-1 and Mg-MOF-74 are explored. Increase of CO 2 adsorption is observed for hydrated HKUST-1; on the contrary, the opposite water adsorption behavior is observed in hydrated Mg-MOF-74, leading to decrease of CO2 adsorption. Further, water effects on CO 2 capture in M-HKUST1 (M = Mg, Zn, Co, Ni) are evaluated to test whether comparing the binding energy could be a general method to evaluate water effects in MOFs with CUMs. It is found that the method works well for Zn-, Co-, and Ni-HKUST1 but partially for Mg-HKUST1. In addition, the effects of O2 and SO2 on CO2 capture in MOFs are also investigated for the first time, showing that the effects of O2 may be negligible but SO2 has negative effects in the CO 2 capture process in HKUST-1 systems. Secondly, the influences of water on CO2 capture in three UiO-66 MOFs with functional groups, --NH2, --OH and --Br are explored, respectively. For UiO-66-NH2 and -OH, the presence of water lowers CO2 adsorption significantly; in contrast, water shows much smaller effects in UiO-66-Br. Moreover, the presence of SO 2 decreases water adsorption but enhances CO2 uptakes slightly in both UiO-66-NH2 and -Br. Finally, the effects of impurities on CO2 capture in a MOF with suitable pore size (PCN-200) are analyzed. The adsorption of both CO 2 and N2 decrease substantially even with 1% water present in the mixture. In addition, the presence of low SO2 does not show obvious effect in PCN-200. However, a lower CO2 adsorption is observed for a mixture with a high SO2 content. In collaboration with experimental groups, the performances of three new MOFs in CO2 capture are evaluated using molecular simulations. The computational results demonstrate the feasibility of precisely designing single-molecule traps (SMT) for CO2 capture. Also, a multi-functional MOF with micro-porosity, open Cu2+ sites and amine groups has also proved computationally the selective adsorption of CO2 over CH4 and N2. Last, we demonstrate that charge separation is an effective strategy for improving CO2 capture in MOFs.

Theoretical Calculation of the Gas-Sensing Properties of Pt-Decorated Carbon Nanotubes

PubMed Central

Zhang, Xiaoxing; Dai, Ziqiang; Wei, Li; Liang, Naifeng; Wu, Xiaoqing

2013-01-01

The gas-sensing properties of Pt-decorated carbon nanotubes (CNTs), which provide a foundation for the fabrication of sensors, have been evaluated. In this study, we calculated the gas adsorption of Pt-decorated (8,0) single-wall CNTs (Pt-SWCNTs) with SO2, H2S, and CO using GGA/PW91 method based on density functional theory. The adsorption energies and the changes in geometric and electronic structures after absorption were comprehensively analyzed to estimate the responses of Pt-SWCNTs. Results indicated that Pt-SWCNTs can respond to the three gases. The electrical characteristics of Pt-SWCNTs show different changes after adsorption. Pt-SWCNTs donate electrons and increase the number of hole carriers after adsorbing SO2, thereby enhancing its conductivity. When H2S is adsorbed on CNTs, electrons are transferred from H2S to Pt-SWCNTs, converting Pt-SWCNTs from p-type to n-type sensors with improved conductivity. However, Pt-SWCNTs obtain electrons and show decreased conductivity when reacted with CO gas. PMID:24201317

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.

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

Ultralow temperature synthesis and improved adsorption performance of graphene oxide nanosheets

NASA Astrophysics Data System (ADS)

Tao, Xiaojun; Wang, Xiaodong; Li, Zhiwei; Zhou, Shaomin

2015-01-01

In this article, we first report an ultralow temperature (-60 °C) synthesis of graphene oxide nanosheets (GONs), which is achieved via the reduction reaction of tetrachloroethylene (C2Cl4) and potassium in liquid ammonia solution at atmospheric pressure. The as-obtained multilayer GONs with a high quality exhibit a low C/O atomic ratio of approximately 2:1, indicating that GONs are rich in the oxygen-containing functional groups. In order to improve their adsorption property, GONs are reduced at 500 °C for 2 h in flowing N2, which results in the successful preparation of graphene nanosheets (GNs) with a high C/O atomic ratio of approximately 32:1. GNs show high specific surface area (508 m2/g), high adsorption capacity (Qe = 148.36 mg/g, Co = 180 mg/L), and rapid adsorption rate (>96%, 10 min) of organic dye rhodamine B (RhB) from water, suggesting that GNs have potential environmental applications as alternatives to commercial materials in wastewater treatment for the removal of organic dye. Compared with the reported methods to prepare GONs, our techniques have attractive advantages, such as low reaction temperature and being friendly to environment.

Highly selective and stable carbon dioxide uptake in polyindole-derived microporous carbon materials.

PubMed

Saleh, Muhammad; Tiwari, Jitendra N; Kemp, K Christain; Yousuf, Muhammad; Kim, Kwang S

2013-05-21

Adsorption with solid sorbents is considered to be one of the most promising methods for the capture of carbon dioxide (CO₂) from power plant flue gases. In this study, microporous carbon materials used for CO₂ capture were synthesized by the chemical activation of polyindole nanofibers (PIF) at temperatures from 500 to 800 °C using KOH, which resulted in nitrogen (N)-doped carbon materials. The N-doped carbon materials were found to be microporous with an optimal adsorption pore size for CO₂ of 0.6 nm and a maximum (Brunauer-Emmett-Teller) BET surface area of 1185 m(2) g(-1). The PIF activated at 600 °C (PIF6) has a surface area of 527 m(2) g(-1) and a maximum CO₂ storage capacity of 3.2 mmol g(-1) at 25 °C and 1 bar. This high CO₂ uptake is attributed to its highly microporous character and optimum N content. Additionally, PIF6 material displays a high CO₂ uptake at low pressure (1.81 mmol g(-1) at 0.2 bar and 25 °C), which is the best low pressure CO₂ uptake reported for carbon-based materials. The adsorption capacity of this material remained remarkably stable even after 10 cycles. The isosteric heat of adsorption was calculated to be in the range of 42.7-24.1 kJ mol(-1). Besides the excellent CO₂ uptake and stability, PIF6 also exhibits high selectivity values for CO₂ over N₂, CH₄, and H₂ of 58.9, 12.3, and 101.1 at 25 °C, respectively, and these values are significantly higher than reported values.

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.

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.

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.

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.

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

Recyclable graphene oxide grafted with poly(N-isopropylacrylamide) and its enhanced selective adsorption for phenols

NASA Astrophysics Data System (ADS)

Gong, Zailin; Li, Shujin; Han, Weifang; Wang, Jiaping; Ma, Jun; Zhang, Xiangdong

2016-01-01

The graphene oxide (GO) was synthesized with Brodie's method and grafted with poly (N-isopropylacrylamide) (NIPAM) in aqueous solution at ambient temperature. Compared with the initial GO, the PNIPAM graft GO (GO-PNIPAM) has larger surface area, pore volume and self-flocculation effect with rapid response to temperature. Moreover, the GO-PNIPAM also has selective adsorptions with different phenol pollutants because of the different interactions of hydrogen bonds and the molecule structure of the adsorbates. Compared with phenol and bisphenol A, hydroquinone has better adsorption on GO-PNIPAM because of the ample phenolic hydroxyl group and the appropriate molecule structure. The adsorption performance of hydroquinone on GO-PNIPAM is also temperature sensitive because of the thermoresponsive transition of the hydrogen bond. The thermoresponsive adsorption and self-flocculation will make the GO-PNIPAM recyclable in the potential water remediation.

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+ .

Optical regulation of protein adsorption and cell adhesion by photoresponsive GaN nanowires.

PubMed

Li, Jingying; Han, Qiusen; Zhang, Ying; Zhang, Wei; Dong, Mingdong; Besenbacher, Flemming; Yang, Rong; Wang, Chen

2013-10-09

Interfacing nanowires with living cells is attracting more and more interest due to the potential applications, such as cell culture engineering and drug delivery. We report on the feasibility of using photoresponsive semiconductor gallium nitride (GaN) nanowires (NWs) for regulating the behaviors of biomolecules and cells at the nano/biointerface. The GaN NWs have been fabricated by a facile chemical vapor deposition method. The superhydrophobicity to superhydrophilicity transition of the NWs is achieved by UV illumination. Bovine serum albumin adsorption could be modulated by photoresponsive GaN NWs. Tunable cell detachment and adhesion are also observed. The mechanism of the NW surface responsible for modulating both of protein adsorption and cell adhesion is discussed. These observations of the modulation effects on protein adsorption and cell adhesion by GaN NWs could provide a novel approach toward the regulation of the behaviors of biomolecules and cells at the nano/biointerface, which may be of considerable importance in the development of high-performance semiconductor nanowire-based biomedical devices for cell culture engineering, bioseparation, and diagnostics.

Development of a field-deployable method for simultaneous, real-time measurements of the four most abundant N2O isotopocules.

PubMed

Ibraim, Erkan; Harris, Eliza; Eyer, Simon; Tuzson, Béla; Emmenegger, Lukas; Six, Johan; Mohn, Joachim

2018-03-01

Understanding and quantifying the biogeochemical cycle of N 2 O is essential to develop effective N 2 O emission mitigation strategies. This study presents a novel, fully automated measurement technique that allows simultaneous, high-precision quantification of the four main N 2 O isotopocules ( 14 N 14 N 16 O, 14 N 15 N 16 O, 15 N 14 N 16 O and 14 N 14 N 18 O) in ambient air. The instrumentation consists of a trace gas extractor (TREX) coupled to a quantum cascade laser absorption spectrometer, designed for autonomous operation at remote measurement sites. The main advantages this system has over its predecessors are a compact spectrometer design with improved temperature control and a more compact and powerful TREX device. The adopted TREX device enhances the flexibility of the preconcentration technique for higher adsorption volumes to target rare isotope species and lower adsorption temperatures for highly volatile substances. All system components have been integrated into a standardized instrument rack to improve portability and accessibility for maintenance. With an average sampling frequency of approximately 1 h -1 , this instrumentation achieves a repeatability of 0.09, 0.13, 0.17 and 0.12 ‰ for δ 15 N α , δ 15 N β , δ 18 O and site preference of N 2 O, respectively, for pressurized ambient air. The repeatability for N 2 O mole fraction measurements is better than 1 ppb (parts per billion, 10 -9 moles per mole of dry air).

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.

An accurate empirical method to predict the adsorption strength for π-orbital contained molecules on two dimensional materials.

PubMed

Li, Hongping; Wang, Changwei; Xun, Suhang; He, Jing; Jiang, Wei; Zhang, Ming; Zhu, Wenshuai; Li, Huaming

2018-06-01

To obtain the adsorption strength is the key point for materials design and parameters optimization in chemical engineering. Here we report a simple but accuracy method to estimate the adsorptive energies by counting the number of π-orbital involved atoms based on theoretical computations for hexagonal boron nitride (h-BN) and graphene. Computational results by density function theory (DFT) as well as spin-component scaled second-order Møller-Plesset perturbation theory (SCS-MP2) both confirm that the adsorptive energies correlate well with the number of π-orbital involved atoms for π-orbital contained molecules. The selected molecules (adsorbates) are commonly used in chemical industry, which contains C, N, S, O atoms. The predicted results for the proposed formulas agree well with the current and previous DFT calculated values both on h-BN and graphene surfaces. Further, it can be also used to predict the adsorptive energies for small π-orbital contained molecules on BN and carbon nanotubes. The interaction type for these adsorptions is typical π-π interaction. Further investigations show that the physical origin of these interactions source from the polar interactions between the adsorbents and adsorbates. Hence, for separation or removal of aromatic molecules, how to modify the aromaticity and polarity of both adsorbents and adsorbates will be the key points for experiments. Copyright © 2018 Elsevier Inc. All rights reserved.

Adsorption and wetting characterization of hydrophobic SBA-15 silicas.

PubMed

Bernardoni, Frank; Fadeev, Alexander Y

2011-04-15

This work describes adsorption and wetting characterization of hydrophobic ordered mesoporous silicas (OMSs) with the SBA-15 motif. Three synthetic approaches to prepare hydrophobic SBA-15 silicas were explored: grafting with (1) covalently-attached monolayers (CAMs) of C(n)H(2)(n+1)Si(CH(3))(2)N(CH(3))(2), (2) self-assembled monolayers (SAMs) of C(n)H(2)(n+1)Si(OEt)(3), and (3) direct ("one-pot") co-condensation of TEOS with C(n)H(2)(n+1)Si(OEt)(3) in presence of P123 (n=1-18). The materials prepared were characterized by nitrogen adsorption, TEM, and chemical analysis. The surface properties of the materials were assessed by water contact angles (CAs) and by BET C constants. The results showed that, while loadings of the alkyl groups (%C) were comparable, the surface properties and pore ordering of the materials prepared through different methods were quite different. The best quality hydrophobic surfaces were prepared for SBA-15 grafted with CAMs of alkylsilanes. For these materials, the water CAs were above ∼120°/100° (adv/rec) and BET C constants were in the range of ∼15-25, indicating uniform low-energy surfaces of closely packed alkyl groups on external and internal surfaces of the pores respectively. Moreover, surfaces grafted with the long-chained (C(12)-C(18)) silanes showed super-hydrophobic behavior (CAs∼150-180°) and extremely low adhesion for water. The pore uniformity of parental SBA-15 was largely preserved and the pore volume and pore diameter were consistent with the formation of a single layer of alkylsilyl groups inside the pores. Post-synthesis grafting of SBA-15 with SAMs worked not as well as CAMs: the surfaces prepared demonstrated lower water CAs and higher BET C constants, thereby indicating a small amount of accessible polar groups (Si-OH) related to packing constrains for SAMs supported on highly curved surfaces of mesopores. The co-condensation method produced substantially more disordered materials and less hydrophobic surfaces than any of the grafting methods. The surfaces of these materials showed low water CAs and high BET C constants (∼100-200) thereby demonstrating a non-uniform surface coverage and presence of unmodified silica. It is concluded that CAMs chemistry is the most efficient approach in preparation of the functionalized OMS materials with uniform surfaces and pores. Copyright © 2011 Elsevier Inc. All rights reserved.

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

Kaczmarski, Krzysztof; Guiochon, Georges A

The adsorption isotherms of selected compounds are our main source of information on the mechanisms of adsorption processes. Thus, the selection of the methods used to determine adsorption isotherm data and to evaluate the errors made is critical. Three chromatographic methods were evaluated, frontal analysis (FA), frontal analysis by characteristic point (FACP), and the pulse or perturbation method (PM), and their accuracies were compared. Using the equilibrium-dispersive (ED) model of chromatography, breakthrough curves of single components were generated corresponding to three different adsorption isotherm models: the Langmuir, the bi-Langmuir, and the Moreau isotherms. For each breakthrough curve, the best conventionalmore » procedures of each method (FA, FACP, PM) were used to calculate the corresponding data point, using typical values of the parameters of each isotherm model, for four different values of the column efficiency (N = 500, 1000, 2000, and 10,000). Then, the data points were fitted to each isotherm model and the corresponding isotherm parameters were compared to those of the initial isotherm model. When isotherm data are derived with a chromatographic method, they may suffer from two types of errors: (1) the errors made in deriving the experimental data points from the chromatographic records; (2) the errors made in selecting an incorrect isotherm model and fitting to it the experimental data. Both errors decrease significantly with increasing column efficiency with FA and FACP, but not with PM.« less

The adsorption of NO, NH3, N2 on carbon surface: a density functional theory study.

PubMed

Wang, Jiayong; Yang, Mo; Deng, Debing; Qiu, Shuxia

2017-08-11

To explore the adsorption mechanism of NO, NH 3 , N 2 on a carbon surface, and the effect of basic and acidic functional groups, density functional theory was employed to investigate the interactions between these molecules and carbon surfaces. Molecular electrostatic potential, Mulliken population analyses, reduced density gradient, and Mayer bond order analyses were used to clarify the adsorption mechanism. The results indicate that van der Waals interactions are responsible for N 2 physisorption, and N 2 is the least likely to adsorb on a carbon surface. Modification of carbon materials to decorate basic or acidic functional groups could enhance the NH 3 physisorption because of hydrogen bonding or electrostatic interactions, however, NO physisorption on a carbon surface is poor. Zig-zag sites are more reactive than armchair sites when these gas molecules absorb on the edge sites of carbon surface. Graphical abstract NH 3 , N 2 , NO adsortion on carbon surface.

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.

Carbon dioxide capture using covalent organic frameworks (COFs) type material-a theoretical investigation.

PubMed

Dash, Bibek

2018-04-26

The present work deals with a density functional theory (DFT) study of porous organic framework materials containing - groups for CO 2 capture. In this study, first principle calculations were performed for CO 2 adsorption using N-containing covalent organic framework (COFs) models. Ab initio and DFT-based methods were used to characterize the N-containing porous model system based on their interaction energies upon complexing with CO 2 and nitrogen gas. Binding energies (BEs) of CO 2 and N 2 molecules with the polymer framework were calculated with DFT methods. Hybrid B3LYP and second order MP2 methods combined with of Pople 6-31G(d,p) and correlation consistent basis sets cc-pVDZ, cc-pVTZ and aug-ccVDZ were used to calculate BEs. The effect of linker groups in the designed covalent organic framework model system on the CO 2 and N 2 interactions was studied using quantum calculations.

Adsorptive separation of CO 2 in sulfur-doped nanoporous carbons: Selectivity and breakthrough simulation

DOE PAGES

Saha, Dipendu; Orkoulas, Gerassimos; Chen, Jihua; ...

2017-03-01

In this research, we have synthesized two sulfur functionalized nanoporous carbons by post-synthesis modifications with sulfur bearing activating agents that simultaneously enhanced the surface area and introduced sulfur functionalities on the carbon surface. The Brunauer–Emmett–Teller (BET) surface areas of these materials were 2865 and 837 m 2/g with total sulfur contents of 8.2 and 12.9 %, respectively. The sulfur-functionalized carbons were characterized with pore textural properties, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and electron microscopy (SEM and TEM). In both the carbons, CO 2 adsorption isotherms and kinetics were measured in three different temperatures of 298, 288 and 278more » K and pressures up to 760 torr. The gravimetric CO 2 uptake followed the trend with BET surface area but the surface area-based uptake was reversed and it followed the trend of sulfur content. The heat of adsorption of CO 2 in low uptake was 60-65 kJ/mol, which is the highest for CO 2 adsorption in porous carbons. In order to investigate the adsorptive separation of CO 2, N 2 and CH 4 adsorption isotherms were also measured at 298 K and 760 torr. The selectivity of separation for CO 2/N 2 and CO 2/CH 4 was calculated based on the Ideal Adsorbed Solution Theory (IAST) and all the results demonstrated the high CO 2 selectivity for the carbon with higher sulfur content. The adsorption isotherms were combined with mass balances to calculate the breakthrough behavior of the binary mixtures of CO 2/N 2 and CO 2/CH 4. The simulation results demonstrated that the dimensionless breakthrough time is a decreasing function of the mole fraction of CO 2 in the feed stream. The overall results suggest that the sulfurfunctionalized carbons can be employed as potential adsorbents for CO 2 separation.« less

Magnetically separable Prussian blue analogue Mn₃[Co(CN)₆]₂·nH₂O porous nanocubes as excellent absorbents for heavy metal ions.

PubMed

Hu, Lin; Mei, Ji-Yang; Chen, Qian-Wang; Zhang, Ping; Yan, Nan

2011-10-05

The application of Prussian blue analogue (PBA) Mn(3)[Co(CN)(6)](2)·nH(2)O porous nanocubes as absorbents for heavy metal ions has been demonstrated. The result indicates that Mn(3)[Co(CN)(6)](2)·nH(2)O porous nanocubes with average diameter of 240 nm possess excellent adsorption efficiency for Pb(2+) ions (94.21% at initial Pb(2+) concentration of 10 mg L(-1)). Moreover, Mn(3)[Co(CN)(6)](2)·nH(2)O porous nanocubes can also show high adsorption efficiency on heavy metal ions even in a strong acidic solution due to its chemical stability. Notably, an external magnet could be used to accelerate the separation of Mn(3)[Co(CN)(6)](2)·nH(2)O from the treated solution. It is suggested that the high adsorption efficiency may derive from the large surface area, M(3)(II)[M(III)(CN)(6)](2)·nH(2)O porous framework structure and affinity between polarizable π-electron clouds of the cyanide bridges and heavy metals ions.

Rapid and efficient removal of Pb(II) from aqueous solutions using biomass-derived activated carbon with humic acid in-situ modification.

PubMed

Guo, Zizhang; Zhang, Jian; Kang, Yan; Liu, Hai

2017-11-01

This study developed an humic acid (HA) in-situ modified activated carbon adsorbent (AC-HA) for the rapid and efficient removal of Pb(II) from aqueous media, and adsorption mechanisms are discussed. The physicochemical characteristics of activated carbons (AC) were investigated via N 2 adsorption/desorption, scanning electron microscopy (SEM), Boehm's titration method and Fourier transform infrared spectroscopy (FTIR). AC-HA exhibited richer oxygen-containing functional groups than the original AC. In addition, the removal performance of AC-HA (250.0mg/g) toward Pb(II) was greatly improved compared with the original AC (166.7mg/g). The batch adsorption study results revealed that the Pb(II) adsorption data were best fit by the pseudo-second-order model of kinetics and Langmuir isotherm of isothermals, and therefore, the effect of the solution pH was studied. The superior performance of AC-HA was attributed to the HA modification, which contains numbers of groups and has a strong π-π interaction binding energy with AC and Pb(II) species. The adsorption mechanisms were confirmed via the XPS study. More importantly, the modified method is simple and has a low cost of production. Copyright © 2017 Elsevier Inc. All rights reserved.

Monolayer Cu2Si as a potential gas sensor for NOx and COx (x = 1, 2): A first-principles study

NASA Astrophysics Data System (ADS)

Zhu, Hao-Hao; Ye, Xiao-Juan; Liu, Chun-Sheng; Yan, Xiao-Hong

2018-02-01

Although the metal-decoration can enhance the sensing properties of two-dimensional (2D) materials, the cyclic utilization of materials is hindered by the clustering tendency of metal atoms. Furthermore, there exists a risk of explosion of combustible gases with the electrical measure. Based on first-principles calculations, we investigate the adsorption of various gas molecules (O2, NO, NO2, NH3, N2, CO, CH4 and CO2) on the 2D Cu-Si extended system (Cu2Si). The NOx molecules are chemisorbed on the Cu2Si monolayer, while other gas molecules (except CH4 and N2) are held by an interaction intermediating between the physisorbed and chemisorbed states. The strong hybridizations between N 2p and Si 3p (Cu 4p) orbitals lead to the large adsorption energies. Interestingly, the adsorption of NOx (1 μB) and CO2 (2 μB) can induce magnetic moments on the intrinsically nonmagnetic Cu2Si monolayer. The magnetic moment of NO-Cu2Si mainly arises from the molecule, while the magnetic moments for the NO2 and CO2 adsorption almost origin from the monolayer. In addition, an antiferromagnetic coupling is found in CO-Cu2Si. The changes in magnetization upon the gas adsorption may be detected sensitively and safely, suggesting the Cu2Si monolayer is potential for gas sensing.

Comparative study of carbon nanotubes and granular activated carbon: Physicochemical properties and adsorption capacities.

PubMed

Gangupomu, Roja Haritha; Sattler, Melanie L; Ramirez, David

2016-01-25

The overall goal was to determine an optimum pre-treatment condition for carbon nanotubes (CNTs) to facilitate air pollutant adsorption. Various combinations of heat and chemical pre-treatment were explored, and toluene was tested as an example hazardous air pollutant adsorbate. Specific objectives were (1) to characterize raw and pre-treated single-wall (SW) and multi-wall (MW) CNTs and compare their physical/chemical properties to commercially available granular activated carbon (GAC), (2) to determine the adsorption capacities for toluene onto pre-treated CNTs vs. GAC. CNTs were purified via heat-treatment at 400 °C in steam, followed by nitric acid treatment (3N, 5N, 11N, 16N) for 3-12 h to create openings to facilitate adsorption onto interior CNT sites. For SWNT, Raman spectroscopy showed that acid treatment removed impurities up to a point, but amorphous carbon reformed with 10h-6N acid treatment. Surface area of SWNTs with 3 h-3N acid treatment (1347 m(2)/g) was higher than the raw sample (1136 m(2)/g), and their toluene maximum adsorption capacity was comparable to GAC. When bed effluent reached 10% of inlet concentration (breakthrough indicating time for bed cleaning), SWNTs had adsorbed 240 mg/g of toluene, compared to 150 mg/g for GAC. Physical/chemical analyses showed no substantial difference for pre-treated vs. raw MWNTs. Copyright © 2015 Elsevier B.V. All rights reserved.

Adsorption of plasma proteins on uncoated PLGA nanoparticles.

PubMed

Sempf, Karim; Arrey, Tabiwang; Gelperina, Svetlana; Schorge, Tobias; Meyer, Björn; Karas, Michael; Kreuter, Jörg

2013-09-01

The biodistribution of nanoparticles is significantly influenced by their interaction with plasma proteins. In order to optimize and possibly monitor the delivery of drugs bound to nanoparticles across the blood-brain barrier (BBB), the protein adsorption pattern of uncoated poly(lactic-co-glycolic acid) (PLGA) nanoparticles after their incubation in human plasma was studied by mass spectrometry. After washing of the particles with water, the proteins were directly digested on the nanoparticle surface using trypsin and then analyzed by nLC MALDI-TOF/TOF. Up to now, the standard method for investigation into the plasma protein adsorption to the particles was 2D gel electrophoresis (2D-PAGE), in certain cases followed by mass spectrometry. The non-gel-based method proposed in the present study provides novel insights into the protein corona surrounding the nanoparticles. The proteins adsorbed on the PLGA nanoparticles after incubation that gave the best signal in terms of quality (high MASCOT score) in human plasma were apolipoprotein E, vitronectin, histidine-rich glycoprotein and kininogen-1. These proteins also are constituents of HDL. Copyright © 2013 Elsevier B.V. All rights reserved.

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 © 2011 Elsevier B.V. All rights reserved.

Adsorption properties of Silochrom chemically modified with nickel acetylacetonate

NASA Astrophysics Data System (ADS)

Pakhnutova, Evgeniya; Slizhov, Yuriy

2017-11-01

One of the areas of development of gas chromatography is the creation of new chromatographic materials that have improved sorption and analytical characteristics. In this work, for the first time, a new sorbent based on Silochrom C-120 modified with nickel acetylacetonate was studied using a complex of physico-chemical methods. It has been established that due to chemical modification of silica gel surface with nickel acetylacetonate the surface area of the specific surface decreases from 112 to 98 m2/g and surface acidity diminishes by 1.2 pH units. Using the thermogravimetric analysis it has been revealed that the obtained sorbent can be used in gas chromatography up to 290°C. Gas chromatography method was used to investigate the adsorption properties of the modified materials. According to the retention data of adsorbates: n-alkanes (C6-C9), benzene, ethanol, nitropropane and butanone-2 the differential molar adsorption energy q¯dif, 1, Henry adsorption constants K1,C, the differential molar entropy ΔS¯S1 and Δ q¯dif, 1 (special) of adsorbates in dispersion and specific interactions were calculated. The influence of the modifying additive on the changings in the thermodynamic retention characteristics of all sorbates because of the manifestation of specific sorbate-sorbent interactions has been shown. The highest values of the thermodynamic parameters were indicative for sorbates forming hydrogen bonds and capable of donor-acceptor interaction.

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.

Magnetic N-doped carbon nanotubes: A versatile and efficient material for the determination of polycyclic aromatic hydrocarbons in environmental water samples.

PubMed

Menezes, Helvécio Costa; de Barcelos, Stella Maris Resende; Macedo, Damiana Freire Dias; Purceno, Aluir Dias; Machado, Bruno Fernades; Teixeira, Ana Paula Carvalho; Lago, Rochel Monteiro; Serp, Philippe; Cardeal, Zenilda Lourdes

2015-05-11

This paper describes a new, efficient and versatile method for the sampling and preconcentration of PAH in environmental water matrices using special hybrid magnetic carbon nanotubes. These N-doped amphiphilic CNT can be easily dispersed in any aqueous matrix due to the N containing hydrophilic part and at the same time show high efficiency for the adsorption of different PAH contaminants due to the very hydrophobic surface. After adsorption, the CNT can be easily removed from the medium by a simple magnetic separation. GC/MS analyses showed that the CNT method is more efficient than the use of polydimethylsiloxane (PDMS) with much lower solvent consumption, technical simplicity and time, showing good linearity (range 0.18-80.00 μg L(-1)) and determination coefficient (R(2) > 0.9810). The limit of detection ranged from 0.05 to 0.42 μg L(-1) with limit of quantification from 0.18 to 1.40 μg L(-1). Recovery (n=9) ranged from 80.50 ± 10 to 105.40 ± 12%. Intraday precision (RSD, n=9) ranged from 1.91 to 9.01%, whereas inter day precision (RSD, n=9) ranged from 7.02 to 17.94%. The method was applied to the analyses of PAH in four lake water samples collected in Belo Horizonte City, Brazil. Copyright © 2015 Elsevier B.V. All rights reserved.

Carbon dioxide capture by activated methyl diethanol amine impregnated mesoporous carbon

NASA Astrophysics Data System (ADS)

Ardhyarini, N.; Krisnandi, Y. K.

2017-07-01

Activated Methyl Diethanol Amine (aMDEA) were impregnated onto the surface of the mesoporous carbon to increase carbon dioxide (CO2) adsorption capacity. The mesoporous carbon was synthesized through soft template method with phloroglucinol as carbon precursor and triblock copolymer (Pluronic F127) as structure directing agent. These activated MDEA impregnated mesoporous carbon (aMDEA-MC) were characterized using various solid characterization techniques. CO2 adsorption was investigated using autoclaved-reactor in the batch system. The FTIR spectrum of aMDEA-MC had absorption peaks at 3395 cm-1 and 1031 cm-1 which are characteristic for O-H stretch and amine C-N stretch in MDEA. The elemental analyzer showed that nitrogen content on the mesoporous carbon increased after impregnation by 23 wt.%. The BET surface area and total pore volume of mesoporous carbon decreased after impregnation, 43 wt.% and 50 wt.%, respectively. The maximum CO2 adsorption capacity of aMDEA43-MC was 2.63 mmol/g (298 K, 5 psi and pure CO2). This is 64 % and 35 % higher compared to the CO2 adsorption capacity of the starting MC and also commercially available activated carbon with higher surface area. All the results suggest that MDEA-MC is a promising adsorbent for CO2 capture.

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.

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.

Surface modification of pitch-based spherical activated carbon by CVD of NH 3 to improve its adsorption to uric acid

NASA Astrophysics Data System (ADS)

Liu, Chaojun; Liang, Xiaoyi; Liu, Xiaojun; Wang, Qin; Zhan, Liang; Zhang, Rui; Qiao, Wenming; Ling, Licheng

2008-08-01

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH 3 (NH 3-CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N 2 adsorption, pH PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH 3-CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH 3-CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH PZC, surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature.

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

Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

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

Alyoshina, Nonna A.; Parfenyuk, Elena V., E-mail: evp@iscras.ru

2013-09-15

A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N{sub 2} adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption processmore » of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica.« less

Study on adsorption properties and mechanism of Pb2+ with different carbon based adsorbents.

PubMed

Song, Min; Wei, Yuexing; Cai, Shipan; Yu, Lei; Zhong, Zhaoping; Jin, Baosheng

2018-03-15

Different activated carbon materials are prepared from a series of solid wastes (sawdust, acrylic fabric, tire powder and rice husk) by combination of the KOH activation method and steam activation method. The influences of several parameters such as pH, contact time, adsorbent dosage and temperature on adsorption performance of Pb 2+ with those different carbon adsorbents are investigated. The results demonstrate that C rice husk performance well in the adsorption process. In the following, the C rice husk is used to explain the adsorption mechanism of Pb 2+ by SEM-EDS, FT-IR and XPS. The results illustrate that the surface oxygen-containing functional groups such as carboxyl, lactone group, phenolic hydroxyl and other alkaline metal ions like Na + and K + have significant effect on the adsorption process. A reasonable mechanism of Pb 2+ adsorption is proposed that the ion exchange play key roles in the adsorption process. In addition, the effects of Cu 2+ , Zn 2+ on the Pb 2+ adsorption capacity with the four carbon adsorbents are also studied and the results demonstrate that other heavy metals play positive effects on the adsorption of Pb 2+ . Copyright © 2017 Elsevier B.V. All rights reserved.

[Method for Simultaneous Determination of 11 Veterinary Antibiotics in Piggery Wastewater and Sludge and Its Application in Biological Treatment].

PubMed

Ding, Jia-li; Liu, Rui; Zheng, Wei; Yu, Wei-juan; Ye, Zhao-xia; Chen, Lu-jun; Zhang, Yong-ming

2015-10-01

In order to determine eleven commonly used veterinary antibiotics (including four tetracyclines, two sulfonamides, three quinolones and two macrolides) in piggery wastewater and activated sludge in the Yangtze River Delta region, the conditions of solid phase extraction and high performance liquid chromatography-tandem mass spectrometry were optimized. The recovery rate and relative standard deviations of the method were confirmed as 73% - 105.2%, 3.1% - 10.2% for piggery wastewater (n = 3) and 57.4% - 104.6%, 1.9% - 10.9% (n = 3) respectively for the activated sludge. Removal of antibiotics was then studied in a membrane bioreactor. The results showed that antibiotics of both tetracycline and sulfonamide species took a large portion in the wastewater, while tetracycline species were the dominant in the sludge. Tetracycline species in the wastewater were removed by 85.2%, mainly through biodegradation (51.9%) and secondly by sludge adsorption (33.2%). By comparison, sulfonamide species was removed by 95.8%, almost all through biodegradation while little by sludge adsorption. Flask tests suggested that the accumulated antibiotics in the sludge give no significant influence on the microbial removal of organics and ammonium.

Utilization of a by-product produced from oxidative desulfurization process over Cs-mesoporous silica catalysts.

PubMed

Kim, Hyeonjoo; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Kim, Do Heui; Jeon, Jong-Ki

2011-02-01

We investigated the use of Cs-mesoporous silica catalysts to upgrade a by-product of oxidative desulfurization (ODS). Cs-mesoporous silica catalysts were characterized through N2 adsorption, XRD, CO2-temperature-programmed desorption, and XRF. Cs-mesoporous silica prepared by the direct incorporation method showed higher catalytic performance than a Cs/MCM-41 catalyst by impregnation method for the catalytic decomposition of sulfone compounds produced from ODS process.

Magnetic sulfur-doped porous carbon for preconcentration of trace mercury in environmental water prior to ICP-MS detection.

PubMed

Peng, Chuyu; He, Man; Chen, Beibei; Huang, Lijin; Hu, Bin

2017-11-20

A novel magnetic sulfur-doped porous carbon (MSPC) was fabricated via a simple one-step carbonization of a mixture of sucrose, basic magnesium sulfate whiskers and Fe 3 O 4 @SiO 2 nanoparticles. Due to the high S content, the prepared MSPC possessed high adsorption capacity for Hg 2+ (343 mg g -1 ) with good selectivity. Based on this, a method coupling magnetic solid phase extraction (MSPE) with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace Hg 2+ in environmental water samples. Various parameters such as pH, desorption solvent and its concentration, desorption volume and time, sample volume, and adsorption time that affect the determination have been optimized. Under the optimal conditions, a high enrichment factor of 100-fold was obtained, the limit of detection (LOD) was found to be 0.52 pg mL -1 with a relative standard deviation (c = 10 pg mL -1 , n = 7) of 7.1%, and a good linearity was obtained within the concentration range of 2-5000 pg mL -1 for Hg 2+ . Besides, the proposed method has very fast adsorption/desorption kinetics, target Hg 2+ could be rapidly adsorbed on the prepared MSPC in 2 min and desorbed from the MSPC in 2 min with the assistance of a permanent magnet. Therefore, the proposed method of MSPE-ICP-MS exhibits good application potential in the determination of trace Hg 2+ in environmental water samples.

Melamine derivatives as effective corrosion inhibitors for mild steel in acidic solution: Chemical, electrochemical, surface and DFT studies

NASA Astrophysics Data System (ADS)

Verma, Chandrabhan; Haque, J.; Ebenso, Eno E.; Quraishi, M. A.

2018-06-01

In present study two condensation products of melamine (triazine) and glyoxal namely, 2,2-bis(4,6-diamino-1,3,5-triazin-2-ylamino)acetaldehyde (ME-1) and (N2,N2‧E,N2,N2‧E)-N2,N2‧-(ethane-1,2-diylidene)-bis-(1,3,5-triazine-2,4,6-triamine) (ME-2) are tested as mild steel corrosion inhibitors in acidic solution (1M HCl). The inhibition efficiency of ME-1 and ME-2 increases with increase in their concentrations and maximum values of 91.47% and 94.88% were derived, respectively at 100 mgL-1 (34.20 × 10-5 M) concentration. Adsorption of ME-1 and ME-2 on the surface of metal obeyed the Langmuir adsorption isotherm. Polarization investigation revealed that ME-1 and ME-2 act as mixed type inhibitors with minor cathodic prevalence. The chemical and electrochemical analyses also supported by surface characterization methods where significant smoothness in the surface morphologies was observed in the images of SEM and AFM spectra. Several DFT indices such as EHOMO and ELUMO, ΔE, η, σ, χ, μ and ΔN were derived for both ME-1 and ME-2 molecules and correlated with experimental results. The DFT studies have also been carried out for protonated or cationic form of the inhibitor molecules by considering that in acidic medium the heteroatoms of organic inhibitors easily undergo protonation. The experimental and density functional theory (DFT) studies (neutral and protonated) were in good agreement.

Adsorption of small hydrocarbons on rutile TiO2(110)

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

Chen, Long; Smith, R. Scott; Kay, Bruce D.

2016-08-01

Temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes with 1 - 4 carbon atoms of C1-C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of an additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar tomore » previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2-C4 hydrocarbons are found nearly independent of the chain length with values of ~1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.« less

Adsorption of small hydrocarbons on rutile TiO 2(110)

DOE PAGES

Chen, Long; Smith, R. Scott; Kay, Bruce D.; ...

2015-11-21

Here, temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C 1–C 4) on rutile TiO 2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti 5c sites. Similar to previous studiesmore » on the adsorption of n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti 5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti 5c sites were also determined. The saturation coverage of CH 4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C 2–C 4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.« less

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

Kim, S.; Sorescu, D.C.; Yates, J.T., Jr.

The adsorption and vibrational properties of chemisorbed HCN on Lewis acid sites, Lewis base sites, and Brønsted Al-OH acid sites on a partially hydroxylated [gamma]-Al2O3 surface have been obtained by a combination of FTIR and density functional theory studies. The vibrational modes from the molecular and dissociative adsorption of HCN were assigned by using deuterium and 13C-labeled D13CN molecules at 170 K. In addition, [eta]2(C, N)-HCN bonding is also found from the [nu](CdN) vibrational spectra. Good correlation of the calculated vibrational frequencies for the adsorbed species with experimental data is found. The effect of triethylenediamine (TEDA) (also called 1, 4-diazabicyclomore » [2.2.2]octane, DABCO) on the adsorption of hydrogen cyanide (HCN) on the high area [gamma]-Al2O3 surface has been investigated using transmission FTIR spectroscopy. During HCN adsorption on TEDA-functionalized surfaces, there is no spectral change or emerging feature in either the TEDA or HCN spectral regions, indicating that no direct interaction occurs between these two molecules. Instead, we found that TEDA competes with HCN for the active sites on [gamma]-Al2O3. The observed [nu](C [identical with] N) mode on a TEDA-precovered surface is due to the HCN adsorption on Lewis base sites (Al-O-Al) which are less affected by TEDA preadsorption.« less

Titania/CnTAB Nanoskeleton as adsorbent and photocatalyst for removal of alkylphenols dissolved in water.

PubMed

Sakai, Toshio; Da Loves, Albar; Okada, Tomohiko; Mishima, Shozi

2013-03-15

We report here on the removal of alkylphenols (phenol, 4-n-propylphenol, 4-n-heptylphenol and 4-nonylphenol) dissolved in water using the composite particles of nanocrystalline titania and alkyltrimethylammonium bromide (CnH2n+1N(CH3)3Br, CnTAB; n=12, 14, 16 and 18) (named as TiO2/CnTAB Nanoskeleton) as adsorbents and photocatalysts. In particular, the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton in water was investigated in terms of hydrophobic interaction between alkylphenols and CnTAB, surface area, pore structure and crystal size of TiO2/CnTAB Nanoskeleton. We revealed that CnTAB incorporated in the TiO2/CnTAB Nanoskeleton promotes the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton due to the hydrophobic interaction between alkylphenols and CnTAB. On the other hand, the surface area, pore structure and crystal size of TiO2/CnTAB Nanoskeleton did not affect the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton. We also found that the alkylphenols dissolved in water were completely removed by the combination of adsorption and photocatalytic degradation by the TiO2/CnTAB Nanoskeleton under UV irradiation. These results prove that the TiO2/CnTAB Nanoskeleton acts as in tandem an adsorbent and a photocatalyst for removal of alkylphenols dissolved in water. Copyright © 2013 Elsevier B.V. All rights reserved.

The adsorption properties of titanium dioxide

NASA Astrophysics Data System (ADS)

Lanin, S. N.; Vlasenko, E. V.; Kovaleva, N. V.; Zung, Fam Tien

2008-12-01

The adsorption properties of titanium dioxide were studied by gas chromatography. We used organic compounds from different classes, namely, n-alkanes, n-alkenes (C6-C8), and polar compounds (electron donors and acceptors) as test adsorbates. The differential heats of adsorption and the contributions of dispersion and specific intermolecular interaction energies were determined for the systems from the experimental retention data. The electron-donor and electron-acceptor characteristics of the ultimately hydroxylated surface of TiO2 were evaluated.

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.

Gallium(III) adsorption on carbonates and oxides: X-ray absorption fine structure spectroscopy study and surface complexation modeling.

PubMed

Pokrovsky, O S; Pokrovski, G S; Schott, J

2004-11-15

Adsorption of Ga on calcite, magnesite, amorphous silica, and manganese oxide as a function of pH and gallium concentration in solution was studied using a batch adsorption technique. Adsorbed complexes of Ga on calcite, magnesite, and delta-MnO2 were further characterized using XAFS spectroscopy. At high surface loadings from supersaturated solutions, Ga is likely to form a polymeric network at the surface (edge- and corner-sharing octahedra). At low surface loadings, Ga presents as isolated octahedra, probably attached to the Me-O sites on the surface, and coordinated by water molecules and hydroxide groups at 1.90-1.94 A. At pH>6, Ga therefore changes its coordination from 4 to 6 when adsorbing from solution (Ga(OH)(-)4(aq)) onto metal surface sites (MeOGa(OH)n(H2O)2-n(5-n), Me = Ca, Mg, or Mn, and n=1 and 2 for carbonate minerals and MnO2, respectively). Because the EXAFS is not capable of seeing hydrogen atoms, the protonation of surface complexes was determined by fitting the experimental pH-dependent Ga adsorption edge. A surface complexation model which assumes the constant capacitance of the electric double layer (CCM) and postulates the formation of positively charged, neutral and negatively charged surface complexes for carbonates, manganese oxide and silica, respectively, was used to describe the dependence of adsorption equilibria on aqueous solution composition in a wide range of pH and Ga concentration.

Magnetically separable polymer (Mag-MIP) for selective analysis of biotin in food samples.

PubMed

Uzuriaga-Sánchez, Rosario Josefina; Khan, Sabir; Wong, Ademar; Picasso, Gino; Pividori, Maria Isabel; Sotomayor, Maria Del Pilar Taboada

2016-01-01

This work presents an efficient method for the preparation of magnetic nanoparticles modified with molecularly imprinted polymers (Mag-MIP) through core-shell method for the determination of biotin in milk food samples. The functional monomer acrylic acid was selected from molecular modeling, EGDMA was used as cross-linking monomer and AIBN as radical initiator. The Mag-MIP and Mag-NIP were characterized by FTIR, magnetic hysteresis, XRD, SEM and N2-sorption measurements. The capacity of Mag-MIP for biotin adsorption, its kinetics and selectivity were studied in detail. The adsorption data was well described by Freundlich isotherm model with adsorption equilibrium constant (KF) of 1.46 mL g(-1). The selectivity experiments revealed that prepared Mag-MIP had higher selectivity toward biotin compared to other molecules with different chemical structure. The material was successfully applied for the determination of biotin in diverse milk samples using HPLC for quantification of the analyte, obtaining the mean value of 87.4% recovery. Copyright © 2015 Elsevier Ltd. All rights reserved.

Microphysical, microchemical, and adhesive properties of lunar material. III - Gas interaction with lunar material.

NASA Technical Reports Server (NTRS)

Grossman, J. J.; Mukherjee, N. R.; Ryan, J. A.

1972-01-01

Gas adsorption measurements on an Apollo 12 ultrahigh vacuum-stored sample and Apollo 14 and 15 N2-stored samples, show that the cosmic ray track and solar wind damaged surface of lunar soil is very reactive. Room temperature monolayer adsorption of N2 by the Apollo 12 sample at 0.0001 atm was observed. Gas evolution of Apollo 14 lunar soil at liquid nitrogen temperature during adsorption/desorption cycling is probably due to cosmic ray track stored energy release accompanied by solar gas release from depths of 100-200 nm.

Overcoming double-step CO2 adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg2(dobpdc).

PubMed

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

2018-01-07

Alkyldiamine-functionalized variants of the metal-organic framework Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising for CO 2 capture applications owing to their unique step-shaped CO 2 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 CO 2 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 CO 2 adsorption/desorption profiles. This two-step behavior likely results from steric interactions between ammonium carbamate chains induced by the asymmetrical hexagonal pores of Mg 2 (dobpdc) and leads to decreased CO 2 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 Mg 2 (dotpdc) (dotpdc 4- = 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 Mg 2 (pc-dobpdc) (pc-dobpdc 4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate, pc = para -carboxylate), which, in contrast to Mg 2 (dobpdc), possesses uniformally hexagonal pores. By minimizing the steric interactions between ammonium carbamate chains, these frameworks enable a single CO 2 adsorption/desorption step in all cases, as well as decreased water co-adsorption and increased stability to diamine loss. Functionalization of Mg 2 (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.

Overcoming double-step CO 2 adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg 2(dobpdc)

DOE PAGES

Milner, Phillip J.; Martell, Jeffrey D.; Siegelman, Rebecca L.; ...

2017-10-26

Alkyldiamine-functionalized variants of the metal–organic framework Mg 2(dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising for CO 2 capture applications owing to their unique step-shaped CO 2 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 CO 2 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 CO 2 adsorption/desorption profiles. This two-step behaviormore » likely results from steric interactions between ammonium carbamate chains induced by the asymmetrical hexagonal pores of Mg 2(dobpdc) and leads to decreased CO 2 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 Mg 2(dotpdc) (dotpdc 4- = 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 Mg 2(pc-dobpdc) (pc-dobpdc 4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate, pc = para-carboxylate), which, in contrast to Mg 2(dobpdc), possesses uniformally hexagonal pores. By minimizing the steric interactions between ammonium carbamate chains, these frameworks enable a single CO 2 adsorption/desorption step in all cases, as well as decreased water co-adsorption and increased stability to diamine loss. Functionalization of Mg 2(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.« less

Enhancement of the dissolution rate and bioavailability of fenofibrate by a melt-adsorption method using supercritical carbon dioxide

PubMed Central

Cha, Kwang-Ho; Cho, Kyung-Jin; Kim, Min-Soo; Kim, Jeong-Soo; Park, Hee Jun; Park, Junsung; Cho, Wonkyung; Park, Jeong-Sook; Hwang, Sung-Joo

2012-01-01

Background: The aim of this study was to enhance the bioavailability of fenofibrate, a poorly water-soluble drug, using a melt-adsorption method with supercritical CO2. Methods: Fenofibrate was loaded onto Neusilin® UFL2 at different weight ratios of fenofibrate to Neusilin UFL2 by melt-adsorption using supercritical CO2. For comparison, fenofibrate-loaded Neusilin UFL2 was prepared by solvent evaporation and hot melt-adsorption methods. The fenofibrate formulations prepared were characterized by differential scanning calorimetry, powder x-ray diffractometry, specific surface area, pore size distribution, scanning electron microscopy, and energy-dispersive x-ray spectrometry. In vitro dissolution and in vivo bioavailability were also investigated. Results: Fenofibrate was distributed into the pores of Neusilin UFL2 and showed reduced crystal formation following adsorption. Supercritical CO2 facilitated the introduction of fenofibrate into the pores of Neusilin UFL2. Compared with raw fenofibrate, fenofibrate from the prepared powders showed a significantly increased dissolution rate and better bioavailability. In particular, the area under the drug concentration-time curve and maximal serum concentration of the powders prepared using supercritical CO2 were 4.62-fold and 4.52-fold greater than the corresponding values for raw fenofibrate. Conclusion: The results of this study highlight the usefulness of the melt-adsorption method using supercritical CO2 for improving the bioavailability of fenofibrate. PMID:23118538

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

The Preparation of Porous Sol-Gel Silica with Metal Organic Framework MIL-101(Cr) by Microwave-Assisted Hydrothermal Method for Adsorption Chillers

PubMed Central

Uma, Kasimayan; Pan, Guan-Ting; Yang, Thomas C.-K.

2017-01-01

Metal organic framework (MOF) of MIL-101(Cr)-Silica (SiO2) composites with highly mesoporous and uniform dispersions were synthesized by a microwave-assisted hydrothermal method followed by the sol-gel technique. Water vapor adsorption experiments were conducted on the MIL-101(Cr)-SiO2 composites for industrial adsorption chiller applications. The effects of MIL-101(Cr)-SiO2 mixing ratios (ranging from 0% to 52%), the surface area and amount of Lewis and Brønsted sites were comprehensively determined through water vapor adsorption experiments and the adsorption mechanism is also explained. The BET and Langmuir results indicate that the adsorption isotherms associated with the various MIL-101(Cr)-SiO2 ratios demonstrated Type I and IV adsorption behavior, due to the mesoporous structure of the MIL-101(Cr)-SiO2. It was observed that the increase in the amount of Lewis and Brønsted sites on the MIL-101(Cr)-SiO2 composites significantly improves the water vapor adsorption efficiency, for greater stability during the water vapor adsorption experiments. PMID:28772969

Methylene blue biosorption by pericarp of corn, alfalfa, and agave bagasse wastes.

PubMed

Rosas-Castor, José M; Garza-González, María T; García-Reyes, Refugio B; Soto-Regalado, Eduardo; Cerino-Córdova, Felipe J; García-González, Alcione; Loredo-Medrano, José A

2014-01-01

The presence of dyes in effluent is a matter of concern due to their toxicologic and aesthetical effects. In this research, locally available agro-industrial wastes (Zea mays pericarp, ZMP; Agave tequilana bagasse, ATB; and Medicago sativa waste, MSW) were used as alternative low-cost adsorbents for the removal of methylene blue (MB) from aqueous solutions. The adsorbents were characterized physically and chemically by Fourier transform infrared, scanning electron microscopy, potentiometric titrations, and N2 physisorption. MB adsorption experiments were carried out in batch systems and experimental data were used to calculate the adsorption isotherm model parameters (Langmuir, Freundlich, and Temkin) and the adsorption kinetic model parameters (pseudo-first- and pseudo-second-order models). MB-loaded biosorbents were desorbed with deionized water, ethanol (10% and 50% v/v), hydrochloric acid (0.01 and 0.05 N), and sodium hydroxide (0.1 N) at room temperature, and the best eluent was used in various adsorption-desorption cycles. The selected agricultural wastes can be considered as promising adsorbents for dye uptake from water since they exhibit considerable MB adsorption capacity (MSW 202.6 mg g(-1), ATB 156.2mg g(-1), and ZMP 110.9mg g(-1)), but it is lower than that reported for activated carbon; however, the biosorbents show higher adsorption rate than powdered activated carbon. Furthermore, the adsorbents can be economically regenerated with HCl solutions and reused for seven adsorption-desorption cycles.

Supported Intrinsically Porous Oligomers as Hybrid Materials for Separations, Storage, and Sensing

NASA Astrophysics Data System (ADS)

Thompson, Anthony Boone

Adsorption-desorption phenomena are often difficult to study at the molecular level because the surfaces on which they occur can be heterogeneous, giving a wide distribution of adsorption sites and associated energies. Considering that these phenomena underlie an incredibly wide variety of industrially important processes, a better understanding could aid in the development of more efficient methods. In this work, we describe an approach to designing materials with well-defined adsorption sites by covalently attaching intrinsically porous molecules to solid surfaces by a rigid multidentate linker. These cup-shaped molecules are intended to act as adsorption sites on the material, whereas the rigid attachment to the solid support serves to prevent movement and conformational changes of the sites, leading to better understanding of adsorption phenomena. As a proof-of-concept application, materials were used for adsorption of n-butanol biofuel and related compounds from dilute aqueous solution. The materials were thermally and hydrolytically stable, and adsorption phenomena were reversible. Adsorption sites containing more hydrophobic molecular area led to stronger adsorption, suggesting that it is driven by weak van der Waals forces. Likewise, adsorption sites that were strongly polarized performed poorly, possibly reflecting a greater energy penalty of removing water molecules from the cavity. Upon placing a Lewis acidic metal at the bottom of the cavity, an enhancement was seen only with the most acidic metal, which may indicate weak guest coordination. Observing that hydrophobic interactions dominate adsorption on these materials, efforts were made to develop hybrid materials with large hydrophobic area for adsorption. Glaser coupling of diethynylbenzene was used to grow oligo(phenylene butadiynylene)s from the surface of silica, resulting in materials that were more than 25% organic by weight. In addition to their potential use as adsorbents, these materials may be promising for hydrogen storage via spillover. Finally, to demonstrate other potential uses of supported intrinsically porous oligomers, a TiO2-supported calixarene material was synthesized and used as a simple molecular sensor, opening up the possibility of using these materials for sensing. Overall, the methods used here result in robust hybrid materials with narrow adsorption site distributions and therefore are of potential use in many future applications.

Oxidative degradation of silica-supported polyethylenimine for CO2 adsorption: insights into the nature of deactivated species.

PubMed

Ahmadalinezhad, Asieh; Sayari, Abdelhamid

2014-01-28

The oxidative degradation of polyethylenimine-impregnated mesoporous SBA-15 silica for CO2 capture was investigated at the molecular level. The adsorbents were exposed to flowing air at different temperatures, and their degree of deactivation was evaluated through the measurement of CO2 adsorption capacity prior and subsequent to air exposure. A solvent-extraction method was employed to isolate the deactivated species from the silica support. The extracted species were investigated by a variety of 1D and 2D NMR techniques such as (13)C, (1)H, (1)H-(15)N HMBC, (1)H-(13)C HMQC, and (1)H-(13)C HMBC. This in-depth investigation showed that they contain predominantly fragments involving imine and carbonyl groups. Several structural units were conclusively established.

Novel adsorbent for DNA adsorption: Fe(3+)-attached sporopollenin particles embedded composite cryogels.

PubMed

Ceylan, Şeyda; Odabaşı, Mehmet

2013-12-01

The aim of this study is to prepare supermacroporous cryogels embedded with Fe(3+)-attached sporopollenin particles (Fe(3++)-ASPs) having large surface area for high DNA adsorption capacity. Supermacroporous poly(2-hydroxyethyl methacrylate) (PHEMA)-based monolithic cryogel column embedded with Fe3+(+)-ASPs was prepared by radical cryo-copolymerization of 2-hydroxyethyl methacrylate (HEMA) with N,N´-methylene- bis-acrylamide (MBAAm) as cross-linker directly in a plastic syringe for DNA adsorption studies. Firstly, Fe3+(+) ions were attached to the sporopollenin particles (SPs), then the supermacroporous PHEMA cryogel with embedded Fe(3++)-ASPs was produced by free radical polymerization using N,N,N´, N´-Tetramethylethylenediamine (TEMED) and ammonium persulfate (APS) as initiator/activator pair in an ice bath. Optimum conditions of adsorption experiments were performed at pH 6.0 (0.02 M Tris buffer containing 0.2 M NaCl), with flow rate of 0.5 mL/min, and at 5°C. The maximum amount of DNA adsorption from aqueous solution was very high (109 mg/g SPs) with initial concentration of 3 mg/mL. It was observed that DNA could be repeatedly adsorbed and desorbed with this composite cryogel without significant loss of adsorption capacity. As a result, higher amounts of DNA adsorbed these composite cryogels are expected to be good candidate for achieving higher removal of anti-DNA antibodies from systemic lupus erythematosus (SLE) patients plasma.

Co-modified MCM-41 as an effective adsorbent for levofloxacin removal from aqueous solution: optimization of process parameters, isotherm, and thermodynamic studies.

PubMed

Jin, Ting; Yuan, Wenhua; Xue, Yujie; Wei, Hong; Zhang, Chaoying; Li, Kebin

2017-02-01

Antibiotics are emerging contaminants due to their potential risks to human health and ecosystems. Poor biodegradability makes it necessary to develop effective physical-chemical methods to eliminate these contaminants from water. The cobalt-modified MCM-41 was prepared by a one-pot hydrothermal method and characterized by SAXRD, N 2 adsorption-desorption, SEM, UV-Vis DR, and FTIR spectroscopy. The results revealed that the prepared 3% Co-MCM-41 possessed mesoporous structure with BET surface areas at around 898.5 m 2 g -1 . The adsorption performance of 3% Co-MCM-41 toward levofloxacin (LVF) was investigated by batch experiments. The adsorption of LVF on 3% Co-MCM-41 was very fast and reached equilibrium within 2 h. The adsorption kinetics followed the pseudo-second-order kinetic model with the second-order rate constants in the range of 0.00198-0.00391 g mg -1  min -1 . The adsorption isotherms could be well represented by the Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherm equations. Nevertheless, D-R isotherm provided the best fit based on the coefficient of determination and average relative error values. The mean free energy of adsorption (E) calculated from D-R model was about 11 kJ mol -1 , indicating that the adsorption was mainly governed by a chemisorption process. Moreover, the adsorption capacity was investigated as a function of pH, adsorbent dosage, LVF concentration, and temperature with help of respond surface methodology (RSM). A quadratic model was established, and an optimal condition was obtained as follows: pH 8.5, adsorbent dosage of 1 g L -1 , initial LVF concentration of 119.8 mg L -1 , and temperature of 31.6 °C. Under the optimal condition, the adsorption capacity of 3% Co-MCM-41 to LVF could reach about 108.1 mg g -1 . The solution pH, adsorbent dosage, LVF concentration, and a combination of adsorbent dose and LVF concentration were significant factors affecting the adsorption process. The adsorption thermodynamic functions were also determined. The negative ΔH 0 (-33.50 kJ mol -1 ) and ΔS 0 (-43.57 J mol -1  K -1 ) suggested that the adsorption was an exothermic process accompanied by decreasing disorder. This study may indicate that 3% Co-MCM-41 is a promising adsorbent for removing emerging pollutants of LVF from water.

Application of a High-Throughput Analyzer in Evaluating Solid Adsorbents for Post-Combustion Carbon Capture via Multicomponent Adsorption of CO2, N-2, and H2O

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

Mason, JA; McDonald, TM; Bae, TH

Despite the large number of metal-organic frameworks that have been studied in the context of post-combustion carbon capture, adsorption equilibria of gas mixtures including CO2, N-2, and H2O, which are the three biggest components of the flue gas emanating from a coal- or natural gas-fired power plant, have never been reported. Here, we disclose the design and validation of a high-throughput multicomponent adsorption instrument that can measure equilibrium adsorption isotherms for mixtures of gases at conditions that are representative of an actual flue gas from a power plant. This instrument is used to study 15 different metal-organic frameworks, zeolites, mesoporousmore » silicas, and activated carbons representative of the broad range of solid adsorbents that have received attention for CO2 capture. While the multicomponent results presented in this work provide many interesting fundamental insights, only adsorbents functionalized with alkylamines are shown to have any significant CO2 capacity in the presence of N-2 and H2O at equilibrium partial pressures similar to those expected in a carbon capture process. Most significantly, the amine-appended metal organic framework mmen-Mg-2(dobpdc) (mmen = N,N'-dimethylethylenediamine, dobpdc (4-) = 4,4'-dioxido-3,3'-biphenyldicarboxylate) exhibits a record CO2 capacity of 4.2 +/- 0.2 mmol/g (16 wt %) at 0.1 bar and 40 degrees C in the presence of a high partial pressure of H2O.« less

Application of a high-throughput analyzer in evaluating solid adsorbents for post-combustion carbon capture via multicomponent adsorption of CO2, N2, and H2O.

PubMed

Mason, Jarad A; McDonald, Thomas M; Bae, Tae-Hyun; Bachman, Jonathan E; Sumida, Kenji; Dutton, Justin J; Kaye, Steven S; Long, Jeffrey R

2015-04-15

Despite the large number of metal-organic frameworks that have been studied in the context of post-combustion carbon capture, adsorption equilibria of gas mixtures including CO2, N2, and H2O, which are the three biggest components of the flue gas emanating from a coal- or natural gas-fired power plant, have never been reported. Here, we disclose the design and validation of a high-throughput multicomponent adsorption instrument that can measure equilibrium adsorption isotherms for mixtures of gases at conditions that are representative of an actual flue gas from a power plant. This instrument is used to study 15 different metal-organic frameworks, zeolites, mesoporous silicas, and activated carbons representative of the broad range of solid adsorbents that have received attention for CO2 capture. While the multicomponent results presented in this work provide many interesting fundamental insights, only adsorbents functionalized with alkylamines are shown to have any significant CO2 capacity in the presence of N2 and H2O at equilibrium partial pressures similar to those expected in a carbon capture process. Most significantly, the amine-appended metal organic framework mmen-Mg2(dobpdc) (mmen = N,N'-dimethylethylenediamine, dobpdc (4-) = 4,4'-dioxido-3,3'-biphenyldicarboxylate) exhibits a record CO2 capacity of 4.2 ± 0.2 mmol/g (16 wt %) at 0.1 bar and 40 °C in the presence of a high partial pressure of H2O.

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

Protein Adsorption to Titanium and Zirconia Using a Quartz Crystal Microbalance Method

PubMed Central

Kusakawa, You

2017-01-01

Protein adsorption onto titanium (Ti) or zirconia (ZrO2) was evaluated using a 27 MHz quartz crystal microbalance (QCM). As proteins, fibronectin (Fn), a cell adhesive protein, and albumin (Alb), a cell adhesion-inhibiting protein, were evaluated. The Ti and ZrO2 sensors for QCM were characterized by atomic force microscopy and electron probe microanalysis observation, measurement of contact angle against water, and surface roughness. The amounts of Fn and Alb adsorbed onto the Ti and ZrO2 sensors and apparent reaction rate were obtained using QCM measurements. Ti sensor showed greater adsorption of Fn and Alb than the ZrO2 sensor. In addition, amount of Fn adsorbed onto the Ti or ZrO2 sensors was higher than that of Alb. The surface roughness and hydrophilicity of Ti or ZrO2 may influence the adsorption of Fn or Alb. With regard to the adsorption rate, Alb adsorbed more rapidly than Fn onto Ti. Comparing Ti and ZrO2, Alb adsorption rate to Ti was faster than that to ZrO2. Fn adsorption will be effective for cell activities, but Alb adsorption will not. QCM method could simulate in vivo Fn and Alb adsorption to Ti or ZrO2. PMID:28246591

Tungsten substituted molybdophosphoric acid loaded on various types of mesoporous silica SBA-15 for application of thorium ion adsorption

NASA Astrophysics Data System (ADS)

Aghayan, H.; Khanchi, A. R.; Yousefi, T.; Ghasemi, H.

2017-12-01

In this research, three type of mesoporous silica with different morphologies, namely fibers, spheres and platelets were synthesized and used as a support for immobilization of [H3PMo6W6O40].nH2O. The samples were then applied as an inorganic composite ion-exchanger for sorption of thorium from aqueous solution. Various techniques including ICP, XRD, BET, SEM and FT-IR methods were used to characterize of the products. The experiment results showed that the [H3PMo6W6O40].nH2O supported on the platelet mesoporous silica exhibited both the highest sorption capacity and fastest kinetics when compared with the fibers and spheres adsorbents. Our results show that the morphology of the mesoporous support, which can produce different channel lengths, pore size and surface area, has a serious effect on the sorption properties and influences: (1) the amount of loading of heteropoly acid in the support (2) the kinetic of the sorption process and (3) the maximum of adsorption capacity. The platelet morphology showed the shortest equilibrium time, the highest loading amount and the highest adsorption capacity therefore delivering the best performance among the three morphologies.

Simplified adsorption method for detection of antibodies to Candida albicans germ tubes.

PubMed Central

Ponton, J; Quindos, G; Arilla, M C; Mackenzie, D W

1994-01-01

Two modifications that simplify and shorten a method for adsorption of the antibodies against the antigens expressed on both blastospore and germ tube cell wall surfaces (methods 2 and 3) were compared with the original method of adsorption (method 1) to detect anti-Candida albicans germ tube antibodies in 154 serum specimens. Adsorption of the sera by both modified methods resulted in titers very similar to those obtained by the original method. Only 5.2% of serum specimens tested by method 2 and 5.8% of serum specimens tested by method 3 presented greater than one dilution discrepancies in the titers with respect to the titer observed by method 1. When a test based on method 2 was evaluated with sera from patients with invasive candidiasis, the best discriminatory results (sensitivity, 84.6%; specificity, 87.9%; positive predictive value, 75.9%; negative predictive value, 92.7%; efficiency, 86.9%) were obtained when a titer of > or = 1:160 was considered positive. PMID:8126184

Adsorption and photocatalytic degradation of methylene blue using high surface area titanate nanotubes (TNT) synthesized via hydrothermal method

NASA Astrophysics Data System (ADS)

Subramaniam, M. N.; Goh, P. S.; Abdullah, N.; Lau, W. J.; Ng, B. C.; Ismail, A. F.

2017-06-01

Removal of methylene blue (MB) via adsorption and photocatalysis using titanate nanotubes (TNTs) with different surface areas were investigated and compared to commercial titanium dioxide (TiO2) P25 Degussa nanoparticles. The TNTs with surface area ranging from 20 m2/g to 200 m2/g were synthesized via hydrothermal method with different reaction times. TEM imaging confirmed the tubular structure of TNT while XRD spectra indicated all TNTs exhibited anatase crystallinity. Batch adsorption rate showed linearity with surface properties of TNTs, where materials with higher surface area showed higher adsorption rate. The highest MB adsorption (70%) was achieved by TNT24 in 60 min whereas commercial TiO2 exhibited the lowest adsorption of only 10% after 240 min. Adsorption isotherm studies indicated that adsorption using TNT is better fitted into Langmuir adsorption isotherm than Freundlich isotherm model. Furthermore, TNT24 was able to perform up to 90% removal of MB within 120 min, demonstrating performance that is 2-fold better compared to commercial TiO2. The high surface area and surface Bronsted acidity are the main reasons for the improvement in MB removal performance exhibited by TNT24. The improvement in surface acidity enhanced the adsorption properties of all the nanotubes prepared in this study.

Adsorption of cadmium by sulphur dioxide treated activated carbon.

PubMed

Macías-García, A; Gómez-Serrano, V; Alexandre-Franco, M F; Valenzuela-Calahorro, C

2003-10-01

Merck carbon (1.5 mm) was treated in three ways: heating from ambient temperature to 900 degrees C in SO(2); treatment at ambient temperature in SO(2); or successive treatments in SO(2) and H(2)S at ambient temperature. All samples were then characterised and tested as adsorbents of Cd(2+) from aqueous solution. The characterisation was in terms of composition by effecting ultimate and proximate analyses and also of textural properties by N(2) adsorption at -196 degrees C. Kinetics and extent of the adsorption process of Cd(2+) were studied at 25 and 45 degrees C at pH of the Cd(2+) solution (i.e., 6.2) and at 25 degrees C also at pH 2.0. The various treatments of the starting carbon had no significant effect on the kinetics of the adsorption of Cd(2+), but increased its adsorption capacity. The most effective treatment was heating to 900 degrees C, the adsorption in this case being 70.3% more than that of the starting carbon. The adsorption increased at 45 degrees C but decreased at pH 2.0 when compared to adsorption at 25 degrees C and pH 6.2, respectively.

Polyethyleneimine Incorporated Metal-Organic Frameworks Adsorbent for Highly Selective CO2 Capture

PubMed Central

Lin, Yichao; Yan, Qiuju; Kong, Chunlong; Chen, Liang

2013-01-01

A series of polyethyleneimine (PEI) incorporated MIL-101 adsorbents with different PEI loadings were reported for the first time in the present work. Although the surface area and pore volume of MIL-101 decreased significantly after loading PEI, all the resulting composites exhibited dramatically enhanced CO2 adsorption capacity at low pressures. At 100 wt% PEI loading, the CO2 adsorption capacity at 0.15 bar reached a very competitive value of 4.2 mmol g−1 at 25°C, and 3.4 mmol g−1 at 50°C. More importantly, the resulting adsorbents displayed rapid adsorption kinetics and ultrahigh selectivity for CO2 over N2 in the designed flue gas with 0.15 bar CO2 and 0.75 bar N2. The CO2 over N2 selectivity was up to 770 at 25°C, and 1200 at 50°C. We believe that the PEI based metal-organic frameworks is an attractive adsorbent for CO2 capture. PMID:23681218

NH3 molecule adsorption on spinel-type ZnFe2O4 surface: A DFT and experimental comparison study

NASA Astrophysics Data System (ADS)

Zou, Cong-yang; Ji, Wenchao; Shen, Zhemin; Tang, Qingli; Fan, Maohong

2018-06-01

Ammonia (NH3) is a caustic environment pollutant which contributes to haze formation and water pollution. Zinc ferrite (ZnFe2O4) exhibits good catalytic activity in NH3 removal. The density functional theory (DFT) was applied to explore the interaction mechanism of NH3 molecule adsorption on spinel-type ZnFe2O4 (1 1 0) surface with GGA-PW91 method in atomic and electronic level. The results indicated that NH3 molecule preferred to adsorb on surface Zn atom with the formation of H3Nsbnd Zn coordinate bond over ZnFe2O4 (1 1 0) surface. The H3Nsbnd Zn state was exothermic process with adsorption energy of -203.125 kJ/mol. About 0.157e were transferred from NH3 molecule to the surface which resulted in strong interaction. Higher activation degree occurred in H3Nsbnd Zn configuration with two Nsbnd H bonds elongated and NH3 structure became more flat on the surface. The PDOS change of NH3 molecule was consistent with the result of adsorption energy. It was concluded that s orbital of NH3 (N) and s, p orbitals of Zn atom overlapped at -0.619 Ha. The p orbital of NH3 (N) has interaction with d orbital of Zn atom suggesting the hybridization between them. Based on NH3 removal experimental and XPS spectra results, NH3sbnd ZnFe2O4 interaction was mainly depended on the coordination between Zn atom and NH3 molecule. The DFT calculations have deepened our understanding on NH3sbnd ZnFe2O4 interaction system.

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

Uptake of pharmaceuticals by sorbent-amended struvite fertilisers recovered from human urine and their bioaccumulation in tomato fruit.

PubMed

de Boer, Marissa A; Hammerton, Michelle; Slootweg, J Chris

2018-04-15

Struvite precipitation is a well-documented method for recovering up to 98% of phosphorus from urine, which is one of the main nutrients in fertilizers besides nitrogen and potassium. Shortcomings of this process, however, are the low nitrogen recovery ratio and the possible uptake of pharmaceuticals from urine. In this work, the NH 4 + adsorbent materials biochar and zeolite are coupled with struvite precipitation to increase the N-recovery of struvite from 5.7% to 9.8%. Since nitrogen is one of the main nutrients in fertilisers, this increase is of significance for its potential commercial use. In addition, urine is spiked with pharmaceuticals to measure the consequential uptake in struvite-based fertilisers and crops afterwards. Five fertilisers are prepared by nutrient recovery from spiked urine using: (1) struvite crystallisation, (2) struvite crystallisation combined with N adsorption on zeolite, (3) struvite crystallisation combined with N adsorption on biochar, (4) N adsorption on zeolite without struvite crystallisation, and (5) N adsorption on biochar without struvite crystallisation. The fertiliser with the highest purity product and the lowest uptake of pharmaceuticals was struvite combined with zeolite. Next, the contaminated struvite-sorbent fertilisers are tested in a crop trial in which the bioaccumulation of pharmaceuticals in edible plant tissue (tomatoes) is measured. This bioaccumulation in tomato fruit biomass from each of the spiked fertilisers in the crop trial was found to be lower than 0.0003% in all cases, far below the acceptable daily intake (ADI) levels (750 kg of dry tomatoes should be consumed per day to reach the ADI limit). Consequently, the subsequent risk to human health from tomato fruit grown using urine derived struvite-sorbent fertilisers is found to be insignificant. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Enhanced photocatalytic degradation of 2-propanol over macroporous GaN/ZnO solid solution prepared by a novel sol-gel method

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

Wang, Lizhong; Ouyang, Shuxin; Ren, Bofan

2015-10-01

Macroporous GaN/ZnO solid solution photocatalyst is synthesized through a novel sol-gel method under mild conditions. The performance of as-synthesized solid solution photocatalyst is evaluated for decomposition of gaseous 2-propanol (IPA). It is found that due to enhancement in both the adsorption to gaseous IPA and the absorbance to visible light, the porous GaN/ZnO solid solution exhibits a good photocatalytic performance for IPA decomposition. Moreover, the mechanism for photocatalytic degradation IPA over porous GaN/ZnO solid solution is also investigated in comparison with those for the two end materials ZnO and GaN. The trapping effects with different scavengers prove that both themore » photoexcited electrons and holes affect the IPA photodegradation process, simultaneously.« less

Adsorption of SO2 on bituminous coal char and activated carbon fiber

USGS Publications Warehouse

DeBarr, Joseph A.; Lizzio, Anthony A.; Daley, Michael A.

1997-01-01

The SO2 adsorption behaviors of activated carbons produced from Illinois coal and of commercially prepared activated carbon fibers (ACFs) were compared. There was no relation between surface area of coal-based carbons and SO2 adsorption, whereas adsorption of SO2 on the series of ACFs was inversely proportional to N2 BET surface area. Higher surface area ACFs had wider pores and adsorbed less SO2; thus, pore size distribution is thought to play a significant role in SO2 adsorption for these materials. Oxidation with HNO3 and/or H2SO4, followed by heat treatment at 700−925°C to remove carbon−oxygen complexes, resulted in increased SO2 adsorption for both coal chars and ACFs. This behavior was explained by an increase in the available number of free sites, previously occupied by oxygen and now available for SO2 adsorption. The use of nitrogen-containing functional groups on ACFs of proper pore size shows promise for further increasing SO2 adsorption capacities. Knowledge of the relationship among the number of free sites, pore size, and surface chemistry on corresponding SO2 adsorption should lead to the development of more efficient adsorbents prepared from either coal or ACFs.

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

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.

Adsorption properties of congo red from aqueous solution onto N,O-carboxymethyl-chitosan.

PubMed

Wang, Li; Wang, Aiqin

2008-03-01

N,O-carboxymethyl-chitosans (N,O-CMC) with different degree of substitution (DS) were synthesized under heterogeneous conditions by controlling the reaction temperature. The factors influencing adsorption capacity of N,O-CMC such as the DS of N,O-CMC, initial pH value of the dye solution and adsorption temperature for anionic dye congo red (CR) were investigated. Compared with chitosan (78.90 mg/g), N,O-CMC with the DS of 0.35 exhibited much higher adsorption capacity (330.62 mg/g) for CR at the same adsorption conditions. The adsorption kinetics and isotherms showed that the sorption processes were better fitted by pseudo-second-order equation and the Langmuir equation, respectively. The adsorption mechanism of N,O-CMC was also discussed by means of IR and XPS spectra. The results in this study indicated that N,O-CMC was an attractive candidate for removing CR from the dye wastewater.

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

DFT study on the adsorption behavior and electronic response of AlN nanotube and nanocage toward toxic halothane gas

NASA Astrophysics Data System (ADS)

Mohammadi, R.; Hosseinian, A.; Khosroshahi, E. Saedi; Edjlali, L.; Vessally, E.

2018-04-01

We have investigated the adsorption of a halothane molecule on the AlN nanotube, and nanocage using density functional theory calculations. We predicted that the halothane molecule tends to be physically adsorbed on the surface of AlN nanotube with adsorption energy (Ead) of -4.2 kcal/mol. The electronic properties of AlN nanotube are not affected by the halothane, and it is not a sensor. But the AlN nanocage is more reactive than the AlN nanotube because of its higher curvature. The halothane tends to be adsorbed on a hexagonal ring, an Alsbnd N bond, and a tetragonal ring of the AlN nanocage. The adsorption ability order is as follows: tetragonal ring (Ead = -14.7 kcal/mol) > Alsbnd N bond (Ead = -12.3 kcal/mol) > hexagonal ring (Ead = -10.1 kcal/mol). When a halothane molecule is adsorbed on the AlN nanocage, its electrical conductivity is increased, demonstrating that it can yield an electronic signal at the presence of this molecule, and can be employed in chemical sensors. The AlN nanocage benefits from a short recovery time of about 58 ms at room temperature.

Removal of As(V) and Sb(V) in aqueous solution by Mg/Al-layered double hydroxide-incorporated polyethersulfone polymer beads (PES-LDH).

PubMed

Lee, Sang-Ho; Choi, Heechul; Kim, Kyoung-Woong

2018-03-13

To develop a novel granular adsorbent to remove arsenic and antimony from water, calcined Mg/Al-layered double-hydroxide (CLDH)-incorporated polyethersulfone (PES) granular adsorbents (PES-LDH) were prepared using a core-shell method having 25% PES in an N,N-dimethylformamide solution. The PES-LDH displayed a spherical hollow shape having a rough surface and the average particle size of 1-2 mm. On the PES-LDH surface, nanosized CLDH (100-150 nm) was successfully immobilized by consolidation between PES and CLDH. The adsorption of Sb(V) by PES-LDH was found to be more favorable than for As(V), with the maximum adsorption capacity of As(V) and Sb(V) being 7.44 and 22.8 mg/g, respectively. The regeneration results indicated that a 0.5 M NaOH and 5 M NaCl mixed solution achieved an 80% regeneration efficiency in As(V) adsorption and desorption. However, the regeneration efficiency of Sb(V) gradually decreased due to its strong binding affinity, even though the PES-LDH showed much higher Sb(V) adsorption efficiency than As(V). This study suggested that PES-LDH could be a promising granular adsorbent for the remediation of As(V) and Sb(V) contained in wastewater.

Superior Adsorption and Regenerable Dye Adsorbent Based on Flower-Like Molybdenum Disulfide Nanostructure

NASA Astrophysics Data System (ADS)

Han, Sancan; Liu, Kerui; Hu, Linfeng; Teng, Feng; Yu, Pingping; Zhu, Yufang

2017-03-01

Herein we report superior dye-adsorption performance for flower-like nanostructure composed of two dimensional (2D) MoS2 nanosheets by a facile hydrothermal method, more prominent adsorption of cationic dye compared with anodic dye indicates the dye adsorption performance strongly depends on surface charge of MoS2 nanosheets. The adsorption mechanism of dye is analyzed, the kinetic data of dye adsorption fit well with the pseudo-second-order model, meanwhile adsorption capability at different equilibrium concentrations follows Langmuir model, indicating the favorability and feasibility of dye adsorption. The regenerable property for MoS2 with full adsorption of dye molecules by using alkaline solution were demonstrated, showing the feasibility of reuse for the MoS2, which is promising in its practical water treatment application.

Green preparation of a novel red mud@carbon composite and its application for adsorption of 2,4-dichlorophenoxyacetic acid from aqueous solution.

PubMed

Kazak, Omer; Eker, Yasin Ramazan; Akin, Ilker; Bingol, Haluk; Tor, Ali

2017-10-01

This study reports the eco-friendly preparation of a novel composite material consisting of red mud and carbon spheres, denoted as red mud@C composite, and its application for the removal of 2,4-dichlorophenoxyacetic acid herbicide (2,4-D) from aqueous solution. The preparation route has a green approach because it follows the low-energy consuming one-step hydrothermal process by using starch as a renewable carbon precursor and red mud as a waste from aluminum production industry. Characterization of the red mud@C composite was performed by FT-IR, TGA, SEM, TEM, BET, XRD, and Raman microscopy analyses. The batch adsorption studies revealed that the red mud@C composite has higher 2,4-D adsorption efficiency than those of the red mud and the naked carbon spheres. The maximum removal at initial pH of 3.0 is explained by considering the pKa of 2,4-D and pH of point of zero charge (pH pzc ) of the composite material. The adsorption equilibrium time was 60 min, which followed the pseudo-second-order kinetic model together with intra-particle diffusion model. The isotherm analysis indicated that Freundlich isotherm model better represented the adsorption data, with isotherm parameters of k [15.849 (mg/g) (mg/L) -1/n ] and n (2.985). The prepared composite is reusable at least 5 cycles of adsorption-desorption with no significant decrease in the adsorption capacity.

Selective adsorption of sulfur dioxide in a robust metal-organic framework material

DOE PAGES

Savage, Mathew; Cheng, Yongqiang; Easun, Timothy L.; ...

2016-08-16

Here, selective adsorption of SO 2 is realized in a porous metal–organic framework material, and in-depth structural and spectroscopic investigations using X-rays, infrared, and neutrons define the underlying interactions that cause SO 2 to bind more strongly than CO 2 and N 2.

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

Unraveling the multi-functional behavior in a series of Metal Organic Frameworks

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

Sanda, Suresh; Biswas, Soumava; Parshamoni, Srinivasulu

2015-09-15

Three new 2D/3D Metal-Organic Frameworks (MOFs), ([Zn(2,6-ndc)(aldrithiol)]·3(H{sub 2}O)){sub n} (1), ([Co(2,6-ndc)(aldrithiol)(H{sub 2}O){sub 2}]·2(H{sub 2}O)){sub n} (2), ([Cd{sub 2}(2,6-ndc){sub 2}(aldrithiol){sub 2}(H{sub 2}O){sub 2}]·(aldrithiol)·(EtOH)·3(H{sub 2}O)){sub n} (3), (2,6-ndc = 2,6-naphthalene dicarboxylic acid; aldrithiol = 4,4'-dipyridyl disulphide) have been synthesized and structurally characterized. Compounds 1 and 2 have 2D layered architectures with similar framework topology whereas 3 is a 2-fold interwoven three dimensional framework. Sorption studies reveal that compounds 1-3 selectively adsorbs CO{sub 2} over other gases and H{sub 2}O over other solvents. Proton conductivity study of compounds 1 and 2 show highest values of 6.73 x 10{sup -7} S.cm{sup -1}, 1.96 xmore » 10{sup -5} S.cm{sup -1} at 318 K and 95% RH and these values are humidity dependent. Photoluminescent properties of compounds 1 and 3 show metal perturbed (π*–π and π*-n) intra ligand charge transfer transitions. Additionally, Compound 3 also displays reversible adsorption of molecular iodine. - Graphical abstarct: Three new 2D/3D interpenetrated MOFs are synthesized and their multifunctional material properties such as adsorption, proton conduction, iodine adsorption as well as luminscence have been explored. - Highlights: • We report multifunctional material properties in a series MOFs (Compounds 1-3) • All the compounds show selective adsorption of CO{sub 2} over other gases and H{sub 2}O over other solvents. • The proton conduction property studies of all the compounds reveal the humidity dependent conductivity. • Compound 2 shows reversible adsorption of molecular iodine in the framework. • Photoluminescent properties of compounds 1 and 2 show metal perturbed intra ligand charge transfer transitions.« less

Molecular mechanism of hydrocarbons binding to the metal–organic framework

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

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

The adsorption and diffusivity of methane, ethane, n-butane, n-hexane and cyclohexane in a metal organic framework (MOF) with the organic linker tetrakis[4-(carboxyphenyl)oxamethyl]methane, the metal salt, Zn2+, and organic pillar, 4,4’-bipyridin was studied using molecular dynamics simulations. For the n-alkanes, the longer the chain, the lower the free energy of adsorption, which was attributed to a greater number of contacts between the alkane and MOF. Cyclohexane had a slightly higher adsorption free energy than n-hexane. Furthermore, for cyclo- and n-hexane, there were no significant differences in adsorption free energies between systems with low to moderate loadings. The diffusivity of the n-alkanesmore » was found to strongly depend on chain length with slower diffusion for longer chains. Cyclohexane had no effective diffusion, suggesting that the selectivity the MOF has towards n-hexane over cyclohexane is the result of kinetics instead of energetics. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.« less

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.

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.

Analyzing adsorption characteristics of CO2, N2 and H2O in MCM-41 silica by molecular simulation

NASA Astrophysics Data System (ADS)

Chang, Shing-Cheng; Chien, Shih-Yao; Chen, Chieh-Li; Chen, Cha'o.-Kuang

2015-03-01

The adsorption characteristics of carbon dioxide, nitrogen and water molecules in MCM-41 mesoporous molecular sieve have been investigated by the molecular simulation. We evaluate the pressure-adsorption isotherms and adsorption density profiles under variant gas pressure, operating temperature and mesopore radius of MCM-41 by the grand canonical Monte Carlo simulation. According to the calculated adsorption energy distributions, the adsorption mechanisms of gas in MCM-41 are mainly divided into three types, namely "surface adsorption" on the pore wall, "multilayer adsorption" on the adsorbed gas molecules and "molecular self-aggregation" near the pore center. In addition, the adsorption characteristics of water molecules in MCM-41 are found to be quite different from those of carbon dioxide and nitrogen due to the hydrogen bonds effect. The results indicate that the MCM-41 is practicable in engineering application for the capture, storage, and re-use of water molecules, since it is temperature-sensitive and can achieve significant adsorption loadings within a small range of pressure values via the capillary condensation phenomena.

Experimental study on removals of SO2 and NO(x) using adsorption of activated carbon/microwave desorption.

PubMed

Ma, Shuang-Chen; Yao, Juan-Juan; Gao, Li; Ma, Xiao-Ying; Zhao, Yi

2012-09-01

Experimental studies on desulfurization and denitrification were carried out using activated carbon irradiated by microwave. The influences of the concentrations of nitric oxide (NO) and sulfur dioxide (SO2), the flue gas coexisting compositions, on adsorption properties of activated carbon and efficiencies of desulfurization and denitrification were investigated. The results show that adsorption capacity and removal efficiency of NO decrease with the increasing of SO2 concentrations in flue gas; adsorption capacity of NO increases slightly first and drops to 12.79 mg/g, and desulfurization efficiency descends with the increasing SO2 concentrations. Adsorption capacity of SO2 declines with the increasing of O2 content in flue gas, but adsorption capacity of NO increases, and removal efficiencies of NO and SO2 could be larger than 99%. Adsorption capacity of NO declines with the increase of moisture in the flue gas, but adsorption capacity of SO2 increases and removal efficiencies of NO and SO2 would be relatively stable. Adsorption capacities of both NO and SO2 decrease with the increasing of CO2 content; efficiencies of desulfurization and denitrification augment at the beginning stage, then start to fall when CO2 content exceeds 12.4%. The mechanisms of this process are also discussed. The prominent SO2 and NOx treatment techniques in power plants are wet flue gas desulfurization (FGD) and the catalytic decomposition method like selective catalytic reduction (SCR) or nonselective catalytic reduction (NSCR). However, these processes would have some difficulties in commercial application due to their high investment, requirement of expensive catalysts and large-scale equipment, and so on. A simple SO2 and NOx reduction utilizing decomposition by microwave energy method can be used. The pollutants control of flue gas in the power plants by the method of microwave-induced decomposition using adsorption of activated carbon/microwave desorption can meet the requirements of environmental protection, which will be stricter in the future.

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.

Design theory and performance of cryogenic molecular adsorption refrigeration systems

NASA Technical Reports Server (NTRS)

Hartwig, W. H.; Woltman, A. W.; Masson, J. P.

1978-01-01

Closed-cycle operation of molecular adsorption refrigeration systems (MARS) has been demonstrated by using thermally cycled zeolites to adsorb and desorb various gases under pressures of 20-60 atm. This paper develops three aspects of the design theory: the physical theory of molecular adsorption of small molecules such as A, N2, N2O and NH3, the design relations for closed-cycle flow for three or more compressors, and the coefficient of performance. This work is intended to demonstrate nonmechanical gas compression for various cryogenic gases than can compete with mechanical systems with a different mix of advantages and disadvantages.

Comparison of Fenton process and adsorption method for treatment of industrial container and drum cleaning industry wastewater.

PubMed

Güneş, Elçin; Çifçi, Deniz İzlen; Çelik, Suna Özden

2018-04-01

The present study aims to explore the characterization of industrial container and drum cleaning (ICDC) industry wastewater and treatment alternatives of this wastewater using Fenton and adsorption processes. Wastewater derived from ICDC industry is usually treated by chemical coagulation and biological treatment in Turkey and then discharged in a centralized wastewater treatment facility. It is required that the wastewater COD is below 1500 mg/L to treat in a centralized wastewater treatment facility. The wastewater samples were characterized for parameters of pH, conductivity, COD, BOD 5 , TSS, NH 3 -N, TN, TOC, TP, Cd, Cr, Cu, Fe, Ni, Pb, Zn, and Hg. Initial COD values were in the range of 11,300-14,200 mg/L. The optimum conditions for Fenton treatment were 35-40 g/L for H 2 O 2 , 2-5 g/L for Fe 2+ , and 13-36 for H 2 O 2 /Fe 2+ molar ratio. The optimum conditions of PAC doses and contact times in adsorption studies were 20-30 g/L and 5-12 h, respectively. Removal efficiencies of characterized parameters for the three samples were compared for both Fenton and adsorption processes under optimum conditions. The results suggest that these wastewaters are suitable for discharge to a centralized wastewater treatment plant.

Theoretical study on adsorption and dissociation of NO2 molecules on BNNT surface

NASA Astrophysics Data System (ADS)

Singla, Preeti; Singhal, Sonal; Goel, Neetu

2013-10-01

The adsorption of NO2 molecules on (8,0) zigzag single-walled boron nitride nanotube surface is investigated using density functional theory calculations. Two interaction modes, nitro (interacting atom is N) and nitrite (O interacts with BNNT) have been studied with increase in number of NO2 molecules. The adsorption of single NO2 molecule in both configurations is observed to be exothermic and physical in nature. However, in nitrite configuration, NO2 molecules are chemisorbed on the surface leading to the dissociation of NO2 molecules into NO and O. The density of states, natural bond orbital analysis and frontier orbital pictures provide rational understanding of the charge transfer involved in the process and predict significant enhancement in the conductivity of the BNNT after NO2 adsorption. The DFT calculations show that NO2 adsorption introduces new impurity states in the band gap of bare BNNT and expand their applications as NO2 molecule gas sensor and catalytic surface for Nsbnd O dissociation depending upon the mode of adsorption.

Continuous Processing With Mars Gases

NASA Technical Reports Server (NTRS)

Parrish, Clyde; Jennings, Paul

2000-01-01

Current Martian missions call for the production of oxygen for breathing, and fuel and oxygen for propulsion to be produced from atmospheric carbon dioxide (CO2). Adsorption and freezing are the two methods considered for capturing CO2 from the atmosphere. However, the nitrogen (N2) and argon (Ar), which make up less than 5 percent of the atmosphere, cause difficulties with both of these processes by blocking the CO2. This results in the capture process rapidly changing from a pressure driven process to a diffusion controlled process. To increase the CO2 capture rates, some type of mechanical pump is usually proposed to remove the N2 and Ar. The N2 and Ar are useful and have been proposed for blanketing and pressurizing fuel tanks and as buffer gas for breathing air for manned missions. Separation of the Martian gases with the required purity can be accomplished with a combination of membranes. These membrane systems do not require a high feed pressure and provide suitable separation. Therefore, by use of the appropriate membrane combination with the Martian atmosphere supplied by a compressor a continuous Supply Of CO2 for fuel and oxygen production can be supplied. This phase of our program has focused on the selection of the membrane system. Since permeation data for membranes did not exist for Martian atmospheric pressures and temperatures, this information had to be compiled. The general trend as the temperature was lowered was for the membranes to become more selective. In addition, the relative permeation rates between the three gases changed with temperature. The end result was to provide design parameters that could be used to separate CO2 from N2 and Ar. This paper will present the membrane data, provide the design requirements for a compressor, and compare the results with adsorption and freezer methods.

Adsorption of CO2 from flue gas streams by a highly efficient and stable aminosilica adsorbent.

PubMed

Liu, Shou-Heng; Lin, Yuan-Chung; Chien, Yi-Chi; Hyu, Han-Ren

2011-02-01

Three ordered mesoporous silicas (OMSs) with different pore sizes and pore architectures were prepared and modified with amine functional groups by a postgrafting method. The carbon dioxide (CO2) adsorption on these amine-modified OMSs was measured by using microbalances at 348 K, and their adsorption capacities were found to be 0.2-1.4 mmol g(-1) under ambient pressure using dry 15% CO2. It was found experimentally that the CO2 adsorption capacity and adsorption rate were attributed to the density of amine groups and pore volume, respectively. A simple method is described for the production of densely anchored amine groups on a solid adsorbent invoking direct incorporation of tetraethylenepentamine onto the as-synthesized OMSs. Unlike conventional amine-modified OMSs, which typically show CO2 adsorption capacity less than 2 mmol g(-1), such organic template occluded amine-OMS composites possessed remarkably high CO2 uptake of approximately 4.6 mmol g(-1) at 348 K and 1 atm for a dry 15% CO2/nitrogen feed mixture. The enhancement of 8% in CO2 adsorption capacity was also observed in the presence of 10.6% water vapor. Durability tests done by cyclic adsorption-desorption revealed that these adsorbents also possess excellent stability.

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 phosphate from seawater on calcined MgMn-layered double hydroxides.

PubMed

Chitrakar, Ramesh; Tezuka, Satoko; Sonoda, Akinari; Sakane, Kohji; Ooi, Kenta; Hirotsu, Takahiro

2005-10-01

Adsorptive properties of MgMn-3-300 (MgMn-type layered double hydroxide with Mg/Mn mole ratio of 3, calcined at 300 degrees C) for phosphate were investigated in phosphate-enriched seawater with a concentration of 0.30 mg-P/dm3. It showed the highest phosphate uptake from the seawater among the inorganic adsorbents studied (hydrotalcite, calcined hydrotalcite, activated magnesia, hydrous aluminum oxide, manganese oxide (delta-MnO2)). The phosphate uptake by MgMn-3-300 reached 7.3 mg-P/g at an adsorbent/solution ratio of 0.05 g/2 dm3. The analyses of the uptakes of other constituents (Na+, K+, Ca(+, Cl-, and SO(2-)4) of seawater showed that the adsorbent had a markedly high selectivity for the adsorption of phosphate ions. Effects of initial phosphate concentration, temperature, pH, and salinity on phosphate uptake were investigated in detail by a batch method. The phosphate uptake increased slightly with an increase in the adsorption temperature. The adsorption isotherm followed Freundlich's equation with constants of logK(F)=1.25 and 1/n=0.65, indicating that it could effectively remove phosphate even from a solution of markedly low phosphate concentration as well as with large numbers of coexisting ions. The pH dependence showed a maximum phosphate uptake around pH 8.5. The pH dependence curve suggested that selective phosphate adsorption progresses mainly by the ion exchange of HPO(2-)4. The study on the effect of salinity suggested the presence of two kinds of adsorption sites in the adsorbent: one nonspecific site with weak interaction and one specific site with strong interaction. The effective desorption of phosphate could be achieved using a mixed solution of 5 M NaCl + 0.1 M NaOH (1 M = 1 mol/dm3), with negligible dissolution of adsorbent. The adsorbent had high chemical stability against the adsorption/desorption cycle; it kept a good phosphate uptake even after the repetition of the seventh cycle.

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.

CO 2 induced phase transitions in diamine-appended metal–organic frameworks

DOE PAGES

Vlaisavljevich, Bess; Odoh, Samuel O.; Schnell, Sondre K.; ...

2015-06-17

Using a combination of density functional theory and lattice models, we study the effect of CO 2 adsorption in an amine functionalized metal–organic framework. These materials exhibit a step in the adsorption isotherm indicative of a phase change. The pressure at which this step occurs is not only temperature dependent but is also metal center dependent. Likewise, the heats of adsorption vary depending on the metal center. Herein we demonstrate via quantum chemical calculations that the amines should not be considered firmly anchored to the framework and we explore the mechanism for CO 2 adsorption. An ammonium carbamate species ismore » formed via the insertion of CO 2 into the M–N amine bonds. Furthermore, we translate the quantum chemical results into isotherms using a coarse grained Monte Carlo simulation technique and show that this adsorption mechanism can explain the characteristic step observed in the experimental isotherm while a previously proposed mechanism cannot. Furthermore, metal analogues have been explored and the CO 2 binding energies show a strong metal dependence corresponding to the M–N amine bond strength. We show that this difference can be exploited to tune the pressure at which the step in the isotherm occurs. Additionally, the mmen–Ni 2(dobpdc) framework shows Langmuir like behavior, and our simulations show how this can be explained by competitive adsorption between the new model and a previously proposed model.« less

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.

Surface complexation model for multisite adsorption of copper(II) onto kaolinite

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2005-08-01

We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 inner-sphere complexes on variable-charge ≡AlOH sites and as Cu 2+ on ion exchangeable ≡X-H + sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH) 6 polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH) 2Cu(OH) 20, tridentate (≡Al 3O(OH) 2)Cu 2(OH) 30 and ≡X-Cu 2+ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions

A first principle simulation of competitive adsorption of SF6 decomposition components on nitrogen-doped anatase TiO2 (101) surface

NASA Astrophysics Data System (ADS)

Dong, Xingchen; Zhang, Xiaoxing; Cui, Hao; Zhang, Jun

2017-11-01

Gas insulated switchgear has been widely used in modern electric systems due to its significantly excellent performances such as compact structure and low land occupation as well as the security stability. However, inside defects caused during manufacture process can lead to partial discharge which might develop into serious insulation failure. Online monitoring method on basis of gas sensors is considered a promising way of detecting partial discharge for alarm ahead of time. Research has found that TiO2 nanotubes sensors show good response to SO2, SOF2, SO2F2, the decomposition components as a result of partial discharge. In order to investigate the gas-sensing mechanism of nitrogen-doped TiO2 prepared via plasma treatment methods to SO2, SOF2, and SO2F2, the adsorption structures of both three gas molecules and anatase TiO2 (101) surface were built, and DFT calculations were then carried out for calculation and analysis of adsorption parameters. Adsorption property comparison of anatase TiO2 (101) surface after nitrogen doping with Au doping and without doping shows that nitrogen doping can obviously enhance the adsorption energy for SO2 and SOF2 adsorption and no charge transfer for SO2F2 adsorption, further explaining the adsorption mechanism and doping influence of different doping elements.

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

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.

Nanospines incorporation into the structure of the hydrophobic cryogels via novel cryogelation method: an alternative sorbent for plasmid DNA purification.

PubMed

Üzek, Recep; Uzun, Lokman; Şenel, Serap; Denizli, Adil

2013-02-01

In this study, it was aimed to prepare hydrophobic cryogels for plasmid DNA (pDNA) purification from Escherichia coli lysate. The hydrophobicity was achieved by incorporating a hydrophobic ligand, N-methacryloyl-(L)-phenylalanine (MAPA), into the cryogel backbone. In addition to the conventional cryogelation process, freeze-drying step was included to create nanospines. Three different cryogels {poly(2-hydoxyethyl methacrylate-N-methacryloyl-L-phenylalanine)-freeze dried, [P(HEMA-MAPA)-FD]; poly(2-hydoxyethyl methacrylate-N-methacryloyl-L-phenylalanine, [P(HEMA-MAPA)] and poly(2-hydoxyethyl methacrylate)-freeze dried, [P(HEMA)-FD]} were prepared, characterized, and used for DNA (salmon sperm DNA) adsorption studies from aqueous solution. The specific surface areas of cryogels were determined to be 21.4 m(2)/g for P(HEMA)-FD, 17.65 m(2)/g for P(HEMA-MAPA) and 36.0 m(2)/g for P(HEMA-MAPA)-FD. The parameters affecting adsorption such as temperature, initial DNA concentration, salt type and concentration were examined in continuous mode. The maximum adsorption capacities were observed as 45.31 mg DNA/g, 27.08 mg DNA/g and 1.81 mg DNA/g for P(HEMA-MAPA)-FD, P(HEMA-MAPA) and P(HEMA)-FD, respectively. Desorption process was performed using acetate buffer (pH 5.50) without salt. First, pDNA was isolated from E. coli lysate and the purity of pDNA was then determined by agarose gel electrophoresis. Finally, the chromatographic performance of P(HEMA-MAPA)-FD cryogel for pDNA purification was tested in FPLC. The resolution (R(s)) was 2.84, and the specific selectivity for pDNA was 237.5-folds greater than all impurities. Copyright © 2012 Elsevier B.V. All rights reserved.

A new perspective of particle adsorption: Dispersed oil and granular materials interactions in simulated coastal environment.

PubMed

Meng, Long; Bao, Mutai; Sun, Peiyan

2017-09-15

This study, adsorption behaviors of dispersed oil in seawaters by granular materials were explored in simulation environment. We quantitatively demonstrated the dispersed oil adsorbed by granular materials were both dissolved petroleum hydrocarbons (DPHs) and oil droplets. Furthermore, DPHs were accounted for 42.5%, 63.4%, and 85.2% (35.5% was emulsion adsorption) in the adsorption of dispersed oil by coastal rocks, sediments, and bacterial strain particles respectively. Effects of controlling parameters, such as temperature, particle size and concentration on adsorption of petroleum hydrocarbons were described in detail. Most strikingly, adsorption concentration was followed a decreasing order of bacterial strain (0.5-2μm)>sediments (0.005-0.625mm)>coastal rocks (0.2-1cm). With particle concentration or temperature increased, adsorption concentration increased for coastal rocks particle but decreased for sediments particle. Besides, particle adsorption rate of petroleum hydrocarbons (n-alkanes and PAHs) was different among granular materials during 60 days. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ultrasensitive detection of lead (II) based on fluorescent aptamer-functionalized carbon nanotubes.

PubMed

Taghdisi, Seyed Mohammad; Emrani, Somayeh Sarreshtehdar; Tabrizian, Kaveh; Ramezani, Mohammad; Abnous, Khalil; Emrani, Ahmad Sarreshtehdar

2014-05-01

Lead contamination is a serious environmental problem with toxic effects in human. Here, we developed a simple and sensitive sensing method employing ATTO 647N/aptamer-SWNT ensemble for detection of Pb(2+). This method is based on the super quenching capability of single-walled carbon nanotubes (SWNTs), high affinity of the aptamer toward Pb(2+) and different propensities of ATTO 647N-aptamer and ATTO 647N-aptamer/Pb(2+) complex for adsorption on SWNTs. In the absence of Pb(2+), the fluorescence of ATTO 647N-aptamer is efficiently quenched by SWNTs. Upon addition of Pb(2+), the aptamer binds to its target, leading to the formation of a G-quadruplex/Pb(2+) complex and does not interact with SWNTs and ATTO 647N-aptamer starts fluorescing. This sensor exhibited a high selectivity toward Pb(2+) and a limit of detection (LOD) as low as 0.42 nM was obtained. Also this sensor could be applied for detection of Pb(2+) ions in tap water and biological sample like serum with high sensitivity. Copyright © 2014 Elsevier B.V. All rights reserved.

Metal-porphyrin: a potential catalyst for direct decomposition of N(2)O by theoretical reaction mechanism investigation.

PubMed

Maitarad, Phornphimon; Namuangruk, Supawadee; Zhang, Dengsong; Shi, Liyi; Li, Hongrui; Huang, Lei; Boekfa, Bundet; Ehara, Masahiro

2014-06-17

The adsorption of nitrous oxide (N2O) on metal-porphyrins (metal: Ti, Cr, Fe, Co, Ni, Cu, or Zn) has been theoretically investigated using density functional theory with the M06L functional to explore their use as potential catalysts for the direct decomposition of N2O. Among these metal-porphyrins, Ti-porphyrin is the most active for N2O adsorption in the triplet ground state with the strongest adsorption energy (-13.32 kcal/mol). Ti-porphyrin was then assessed for the direct decomposition of N2O. For the overall reaction mechanism of three N2O molecules on Ti-porphyrin, two plausible catalytic cycles are proposed. Cycle 1 involves the consecutive decomposition of the first two N2O molecules, while cycle 2 is the decomposition of the third N2O molecule. For cycle 1, the activation energies of the first and second N2O decompositions are computed to be 3.77 and 49.99 kcal/mol, respectively. The activation energy for the third N2O decomposition in cycle 2 is 47.79 kcal/mol, which is slightly lower than that of the second activation energy of the first cycle. O2 molecules are released in cycles 1 and 2 as the products of the reaction, which requires endothermic energies of 102.96 and 3.63 kcal/mol, respectively. Therefore, the O2 desorption is mainly released in catalytic cycle 2 of a TiO3-porphyrin intermediate catalyst. In conclusion, regarding the O2 desorption step for the direct decomposition of N2O, the findings would be very useful to guide the search for potential N2O decomposition catalysts in new directions.

Preparation of calcium oxalate-bromopyrogallol red inclusion sorbent and application to treatment of cationic dye and heavy metal wastewaters.

PubMed

Wang, Hong-Yan; Gao, Hong-Wen

2009-05-01

Dye pollutants are a major class of environmental contaminants. Over 100,000 dyes have been synthesized worldwide and more than 700,000 tons are produced annually and over 5% are discharged into aquatic environments. The adsorption or sorption is one of the most efficient methods to remove dye and heavy metal pollutants from wastewater. However, most of the present sorbents often bear some disadvantages, e.g. low sorption capacity, difficult separation of spoil, complex reproduction, or secondary pollution. Development of novel sorbents that can overcome these limitations is desirable. On the basis of the chemical coprecipitation of calcium oxalate (CaC(2)O(4)), bromopyrogallol red (BPR) was embedded during the growing of CaC(2)O(4) particles. The ternary C(2)O(4) (2-)-BPR-Ca(2+) sorbent was yielded by the centrifugation. Its composition was determined by spectrophotometry and AAS, and its structure and morphology were characterized by powder X-ray diffraction (XRD), laser particle-size analysis, and scanning electron microscopy (SEM). The adsorption of ethyl violet (EV) and heavy metals, e.g. Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) were carried out and their removal rate determined by spectrophotometry and ICP-OES. The adsorption performance of the sorbent was compared with powder activated carbon. The Langmuir isothermal model was applied to fit the embedment of BPR and adsorption of EV. The saturation number of BPR binding to CaC(2)O(4) reached 0.0105 mol/mol and the adsorption constant of the complex was 4.70 x 10(5) M(-1). Over 80% of the sorbent particles are between 0.7 and 1.02 microm, formed by the aggregation of the global CaC(2)O(4)/BPR inclusion grains of 30-50 nm size. Such a material was found to adsorb cationic dyes selectively and sensitively. Ethyl violet (EV) was used to investigate the adsorption mechanism of the material. One BPR molecule may just bind with one EV molecule. The CaC(2)O(4)/BPR inclusion material adsorbed EV over two times more efficiently than the activated carbon. The adsorption of EV on the CaC(2)O(4)/BPR inclusion sorbent was complete in only 5 min and the sedimentation complete in 1 h. However, those of EV onto activated carbon took more than 1.5 and 5 h, respectively. The treatment of methylene blue and malachite green dye wastewaters indicated that only 0.4% of the sorbent adsorbed over 80% of color substances. Besides, the material can also adsorb heavy metals by complexation with BPR. Over 90% of Pb(2+), and approximately 50% of Cd(2+) and Cu(2+), were removed in a high Zn(2+)-electroplating wastewater when 3% of the material was added. Eighty-six percent of Cu(2+), and 60% of Ni(2+) and Cd(2+), were removed in a high Cd(2+)-electroplating wastewater. The embedment of BPR into CaC(2)O(4) particles responded to the Langmuir isothermal adsorption. As the affinity ligand of Ca(2+), BPR with sulfonic groups may be adsorbed into the temporary electric double layer during the growing of CaC(2)O(4) particles. Immediately, C(2)O(4) (2-) captured the Ca(2+) to form the CaC(2)O(4) outer enclosed sphere. Thus, BPR may be released and embedded as a sandwich between CaC(2)O(4) layers. The adsorption of EV on the sorbent obeyed the Langmuir isothermal equation and adsorption is mainly due to the ion-pair attraction between EV and BPR. Different from the inclusion sorbent, the activated carbon depended on the specific surface area to adsorb organic substances. Therefore, the adsorption capacity, equilibrium, and sedimentation time of the sorbent are much better than activated carbon. The interaction of heavy metals with the inclusion sorbent responded to their coordination. By characterizing the C(2)O(4) (2-)-BPR-Ca(2+) inclusion material using various modern instruments, the ternary in situ embedment particle, [(CaC(2)O(4))(95)(BPR)]( n ) (2n-), an electronegative, micron-sized adsorbent was synthesized. It is selective, rapid, and highly effective for adsorbing cationic dyes and heavy metals. Moreover, the adsorption is hardly subject to the impact of electrolytes. The present work provides a simple and valuable method for preparing the highly effective adsorbent. If a concentrated BPR wastewater was reused as the inclusion reactant, the sorbent will be low cost. By selecting the inclusion ligand with a special structure, we may prepare some particular functional materials to recover the valuable substances from seriously polluted wastewaters. The recommended method will play a significant role in development of advanced adsorption materials.

Advanced CO2 Removal Technology Development

NASA Technical Reports Server (NTRS)

Finn, John E.; Verma, Sunita; Forrest, Kindall; LeVan, M. Douglas

2001-01-01

The Advanced CO2 Removal Technical Task Agreement covers three active areas of research and development. These include a study of the economic viability of a hybrid membrane/adsorption CO2 removal system, sorbent materials development, and construction of a database of adsorption properties of important fixed gases on several adsorbent material that may be used in CO2 removal systems. The membrane/adsorption CO2 removal system was proposed as a possible way to reduce the energy consumption of the four-bed molecular sieve system now in use. Much of the energy used by the 4BMS is used to desorb water removed in the device s desiccant beds. These beds might be replaced by a desiccating membrane that moves the water from [he incoming stream directly into the outlet stream. The approach may allow the CO2 removal beds to operate at a lower temperature. A comparison between models of the 4BMS and hybrid systems is underway at Vanderbilt University. NASA Ames Research Center has been investigating a Ag-exchanged zeolites as a possible improvement over currently used Ca and Na zeolites for CO2 removal. Silver ions will complex with n:-bonds in hydrocarbons such as ethylene, giving remarkably improved selectivity for adsorption of those materials. Bonds with n: character are also present in carbon oxides. NASA Ames is also continuing to build a database for adsorption isotherms of CO2, N2, O2, CH4, and Ar on a variety of sorbents. This information is useful for analysis of existing hardware and design of new processes.

Hydrophilic crosslinked-polymeric surface capable of effective suppression of protein adsorption

NASA Astrophysics Data System (ADS)

Kamon, Yuri; Inoue, Naoko; Mihara, Erika; Kitayama, Yukiya; Ooya, Tooru; Takeuchi, Toshifumi

2016-08-01

We investigated the nonspecific adsorption of proteins towards three hydrophilic crosslinked-polymeric thin layers prepared by surface-initiated atom transfer radical polymerization using N,N‧-methylenebisacrylamide, 2-(methacryloyloxy)ethyl-[N-(2-methacryloyloxy)ethyl]phosphorylcholine (MMPC), or 6,6‧-diacryloyl-trehalose crosslinkers. Protein binding experiments were performed by surface plasmon resonance with six proteins of different pI values including α-lactalbumin, bovine serum albumin (BSA), myoglobin, ribonuclease A, cytochrome C, and lysozyme in buffer solution at pH 7.4. All of the obtained crosslinked-polymeric thin layers showed low nonspecific adsorption of negatively charged proteins at pH 7.4 such as α-lactalbumin, BSA, and myoglobin. Nonspecific adsorption of positively charged proteins including ribonuclease A, cytochrome C, and lysozyme was the lowest for poly(MMPC). These results suggest poly(MMPC) can effectively reduce nonspecific adsorption of a wide range of proteins that are negatively or positively charged at pH 7.4. MMPC is a promising crosslinker for a wide range of polymeric materials requiring low nonspecific protein binding.

Removal of tetracycline from aqueous solution by MCM-41-zeolite A loaded nano zero valent iron: Synthesis, characteristic, adsorption performance and mechanism.

PubMed

Guo, Yige; Huang, Wenli; Chen, Bin; Zhao, Ying; Liu, Dongfang; Sun, Yu; Gong, Bin

2017-10-05

In this study, nano zero valent iron (NZVI) modified MCM-41-zeolite A (Fe-MCM-41-A) composite as a novel adsorbent was prepared by precipitation method and applied for tetracycline (TC) removal from aqueous solution. The adsorbent was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and N 2 -BET analysis. Hysteresis loops indicated that the sample has a desirable magnetic property and can be separated quickly. Adsorption studies were carried out to evaluate its potential for TC removal. Results showed that the optimal Fe-MCM-41-A dosage, initial pH and reaction time at initial TC concentration of 100mgL -1 solution are 1gL -1 , pH=5, and 60 min respectively, at which the removal efficiency of TC was 98.7%. The TC adsorption results fitted the Langmuir isotherm model very well and the adsorption process could be described by a pseudo-second-order kinetic model. A maximum TC adsorption capacity of 526.32mgg -1 was achieved. This study demonstrates that Fe-MCM-41-A is a promising and efficient material for TC adsorption from aqueous solution. Copyright © 2017 Elsevier B.V. All rights reserved.

Controlled drug release on amine functionalized spherical MCM-41

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

Szegedi, Agnes, E-mail: szegedi@chemres.hu; Popova, Margarita; Goshev, Ivan

2012-10-15

MCM-41 silica with spherical morphology and small particle sizes (100 nm) was synthesized and modified by post-synthesis method with different amounts of 3-aminopropyltriethoxysilane (APTES). A comparative study of the adsorption and release of a model drug, ibuprofen, was carried out. The modified and drug loaded mesoporous materials were characterized by XRD, TEM, N{sub 2} physisorption, elemental analysis, thermal analysis and FT-IR spectroscopy. A new method was developed for the quantitative determination of amino groups in surface modified mesoporous materials by the ninhydrin reaction. Good correlation was found between the amino content of the MCM-41 materials determined by the ninhydrin methodmore » and their ibuprofen adsorption capacity. Amino modification resulted in high degree of ibuprofen loading and slow release rate in comparison to the parent non-modified MCM-41. - Graphical abstract: Determination of surface amino groups by ninhidrin method. Highlights: Black-Right-Pointing-Pointer Spherical MCM-41 modified by different amounts of APTES was studied. Black-Right-Pointing-Pointer Ibuprofen (IBU) adsorption and release characteristics was tested. Black-Right-Pointing-Pointer The ninhydrin reaction was used for the quantitative determination of amino groups. Black-Right-Pointing-Pointer Stoichiometric amount of APTES is enough for totally covering the surface with amino groups. Black-Right-Pointing-Pointer Good correlation was found between the amino content and IBU adsorption capacity.« less

Optical graphene quantum dots gas sensors: Theoretical study

NASA Astrophysics Data System (ADS)

Raeyani, D.; Shojaei, S.; Ahmadi-Kandjani, S.

2018-02-01

In this work, we theoretically studied the changes of graphene quantum dots (GQD) absorption spectra under the influence of different gases to indicate optical gas sensing features of GQDs. The adsorption of gas molecules such as CO2, N2 and Ar on GQDs have been theoretically investigated through time-dependent density functional theory (TDDFT) calculations. Our study revealed that UV-Vis absorption spectrum of GQDs in the presence of CO2 undergoes considerable changes than that of N2 and Ar. The shift of maximum absorption wavelength for adsorption of CO2, N2 and Ar in same distance from GQD in addition to density of state (DOS) and orbital analyses have been obtained. To verify our theoretical results, comparison with experimental study has been done and good agreement has been observed. Comparing with electrical property of GQD, optical properties showed an efficient tool to be implemented in gas adsorption and paves the way towards GQD optical gas sensors.

The role of counter ions in nano-hematite synthesis: Implications for surface area and selenium adsorption capacity.

PubMed

Lounsbury, Amanda W; Yamani, Jamila S; Johnston, Chad P; Larese-Casanova, Philip; Zimmerman, Julie B

2016-06-05

Nano metal oxides are of interest for aqueous selenium (Se) remediation, and as such, nano-hematite (nα-Fe2O3) was examined for use as a Se adsorbent. The effect of surface area on adsorption was also studied. nα-Fe2O3 particles were synthesized from Fe(NO3)3 and FeCl3 via forced hydrolysis. The resulting particles have similar sizes, morphologies, aggregate size, pore size, and PZC. The nα-Fe2O3 from FeCl3 (nα-Fe2O3-C) differs from the nα-Fe2O3 from Fe(NO3)3 (nα-Fe2O3-N) with a ∼25±2m(2)/g greater surface area. Selenite Se(IV) adsorption capacity on nα-Fe2O3 has a qmax ∼17mg/g for the freeze-dried and re-suspended nα-Fe2O3. The Δqmax for nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension was 4.6mg/g. For selenate Se(VI), the freeze-dried and re-suspended particles realize a Δqmax= 1.5mg/g for nα-Fe2O3 from Fe(NO3)3 and FeCl3. The nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension demonstrated Se(VI) Δqmax=5.4mg/g. In situ ATR-FTIR isotherm measurements completed for Se(VI) at a pH 6 suggest that Se(VI) forms primarily outer-sphere complexes with nα-Fe2O3 synthesized from both salts. Copyright © 2016 Elsevier B.V. All rights reserved.

Study on separation of platinum group metals from high level liquid waste using macroporous (MOTDGA-TOA)/SiO{sub 2}-P silica-based absorbent

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

Ito, Tatsuya; Japan Atomic Energy Agency, Tokai-mura Naka-gun, Ibarak319-1195; Kim, Seong-Yun

2013-07-01

The recovery of platinum group metals (PGMs) from high level liquid waste (HLLW) by macroporous silica-based adsorbent, (MOTDGA-TOA)/SiO{sub 2}-P has been developed by impregnating two extractants of N,N'-dimethyl-N,N'-di-n-octyl-thio-diglycolamide (MOTDGA) and tri-n-octylamine (TOA) into a silica/polymer composite support (SiO{sub 2}-P). The adsorption of Ru(III), Rh(III) and Pd(II) have been investigated in simulated HLLW by batch method. The adsorbent has shown good uptake property for Pd(II). In addition, the combined use of MOTDGA and TOA improved the adsorption of Ru(III) and Rh(III) better than the individual use of them. The usability of adsorbent in radiation fields was further confirmed by irradiation experiments.more » The adsorbent remained to have the uptake capability for PGMs over the absorbed dose of 100 kGy, corresponding with one really adsorbed by the adsorbent, and showed good retention capability for Pd(II) even at the absorbed dose of 800 kGy. The chromatographic separation of metal ions was demonstrated with the adsorbent packed column, there is no influence of Re(VII) (instead of Tc) on the excellent separation behavior of Pd(II). (authors)« less

Low Temperature Synthesized H2Ti3O7 Nanotubes with a High CO2 Adsorption Property by Amine Modification.

PubMed

Ota, Misaki; Hirota, Yuichiro; Uchida, Yoshiaki; Sakamoto, Yasuhiro; Nishiyama, Norikazu

2018-06-12

Carbon dioxide (CO 2 ) capture and storage (CCS) technologies have been attracting attention in terms of tackling with global warming. To date, various CO 2 capture technologies including solvents, membranes, cryogenics, and solid adsorbents have been proposed. Currently, a liquid adsorption method for CO 2 using amine solution (monoethanolamine) has been practically used. However, this liquid phase CO 2 adsorption process requires heat regeneration, and it can cause many problems such as corrosion of equipment and degradation of the solution. Meanwhile, solid adsorption methods using porous materials are more advantageous over the liquid method at these points. In this context, we here evaluated if hydrogen titanate (H 2 Ti 3 O 7 ) nanotubes and the surface modification effectively capture CO 2 . For this aim, we first developed a facile synthesis method of H 2 Ti 3 O 7 nanotubes different from any conventional methods. Briefly, they were converted from the precursors-amorphous TiO 2 nanoparticles at room temperature (25 °C). We then determined the outer and the inner diameters of the H 2 Ti 3 O 7 nanotubes as 3.0 and 0.7 nm, respectively. It revealed that both values were much smaller than the reported ones; thus the specific surface area showed the highest value (735 m 2 /g). Next, the outer surface of H 2 Ti 3 O 7 nanotubes was modified using ethylenediamine to examine if CO 2 adsorption capacity increases. The ethylendiamine-modified H 2 Ti 3 O 7 nanotubes showed a higher CO 2 adsorption capacity (50 cm 3 /g at 0 °C, 100 kPa). We finally concluded that the higher CO 2 adsorption capacity could be explained, not only by the high specific surface area of the nanotubes but also by tripartite hydrogen bonding interactions among amines, CO 2 , and OH groups on the surface of H 2 Ti 3 O 7 .

Post-combustion CO2 capture with activated carbons using fixed bed adsorption

NASA Astrophysics Data System (ADS)

Al Mesfer, Mohammed K.; Danish, Mohd; Fahmy, Yasser M.; Rashid, Md. Mamoon

2018-03-01

In the current work, the capturing of carbon dioxide from flue gases of post combustion emission using fixed bed adsorption has been carried out. Two grades of commercial activated carbon (sorbent-1 and sorbent-2) were used as adsorbent. Feed consisting of CO2 and N2 mixture was used for carrying out the adsorption. The influence of bed temperature, feed rate, equilibrium partial pressure and initial % CO2 in feed were considered for analyzing adsorption-desorption process. It was found that the total adsorption-desorption cycle time decreases with increased column temperature and feed rates. The time required to achieve the condition of bed saturation decreases with increased bed temperature and feed rates. The amount of CO2 adsorbed/Kg of the adsorbent declines with increased bed temperature with in studied range for sorbent-1 and sorbent-2. It was suggested that the adsorption capacity of the both the sorbents increases with increased partial pressure of the gas.

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

Continuous Processing with Mars Gases

NASA Technical Reports Server (NTRS)

Parrish, Clyde; Jennings, Paul; Delgado, Hugo (Technical Monitor)

2001-01-01

Current Martian missions call for the production of oxygen for breathing, and fuel and oxygen for propulsion to be produced from atmospheric carbon dioxide (CO2). Adsorption and freezing are the two methods considered for capturing CO, from the atmosphere. However, the nitrogen (N2) and argon (Ar), which make up less than 5 percent of the atmosphere, cause difficulties with both of these processes by blocking the CO2, This results in the capture process rapidly changing from a pressure driven process to a diffusion controlled process. To increase the CO, capture rates, some type of mechanical pump is usually proposed to remove the N2 and Ar. The N2 and Ar are useful and have been proposed for blanketing and pressurizing fuel tanks and as buffer gas for breathing air for manned missions. Separation of the Martian gases with the required purity can be accomplished with a combination of membranes. These membrane systems do not require a high feed pressure and provide suitable separation. Therefore, by use of the appropriate membrane combination with the Martian atmosphere supplied by a compressor a continuous supply of CO2 for fuel and oxygen production can be supplied. This phase of our program has focused on the selection of the membrane system. Since permeation data for membranes did not exist for Martian atmospheric pressures and temperatures, this information had to be compiled. The general trend as the temperature was lowered was for the membranes to become more selective. In addition, the relative permeation rates between the three gases changed with temperature. The end result was to provide design parameters that could be used to separate CO2 from N2 and Ar. This paper will present the membrane data, provide the design requirements for a compressor, and compare the results with adsorption and freezer methods.

Physicochemical factors affecting ethanol adsorption by activated carbon.

PubMed

Bradley, K J; Hamdy, M K; Toledo, R T

1987-03-01

Powder and granular activated charcoal were evaluated for ethanol adsorptivity from aqueous mixtures using an adsorption isotherm. Ethanol adsorption capacity was more pronounced at 25 degrees C as compared to 5, 15, and 40 degrees C. When pH of the ethanol-buffer mixture (0.09 ionic strength) was changed from acidic (2.3) to neutral and then to alkaline (11.2), ethanol adsorption was decreased. Increasing ionic strength of the ethanol-buffer mixtures from 0.05 to 0.09 enhanced ethanol adsorption but a further increase to 0.14 showed no significant effect. Ethanol adsorption was more efficient from an aqueous ethanol mixture as compared to semidefined and nondefined fermentation worts, respectively. Heating granular charcoal to 400 degrees C for 1 h and 600 degrees C for 3 h in N(2) increased ethanol adsorptivity and heating to 1000 degrees C (1 h) in CO(2) decreased it when ethanol was removed from dilute solutions by simple pass adsorption in a carbon packed column. Granular charcoal was superior to powdered charcoal and an inverse relationship was noted between the weight of the granular carbon bed in the column and ethanol adsorbed/g carbon. Decreasing the column feed flow rate from 7.5 to 2.0 L aqueous ethanol/min increased the adsorption rate.

Dissociative adsorption of a multifunctional compound on a semiconductor surface: a theoretical study of the adsorption of hydroxylamine on Ge(100).

PubMed

Park, Hyunkyung; Kim, Do Hwan

2018-06-06

The adsorption behavior of hydroxylamine on a Ge(100) surface was investigated using density functional theory (DFT) calculations. These calculations predicted that hydroxylamine, a multifunctional compound consisting of a hydroxyl group and an amine group, would initially become adsorbed through N-dative bonding, or alternatively through the hydroxyl group via O-H dissociative adsorption. An N-O dissociative reaction may also occur, mainly via N-dative molecular adsorption, and the N-O dissociative product was calculated to be the most stable of all the possible adsorption structures. The calculations furthermore indicated the formation of the N-O dissociative product from the N-dative structure to be nearly barrierless and the dissociated hydroxyl and amine groups to be bonded to two Ge atoms of adjacent Ge dimers. Simulated STM images suggested the change in electron density that would occur upon adsorption of hydroxylamine in various adsorption configurations, and specifically indicated the N-O dissociative product to have greater electron density around the amine groups, and the hydroxyl groups to mainly contribute electron density to the unoccupied electronic states.

The effect of alkali metal on the surface properties of potassium doped Au-Beta zeolites

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

Sobczak, Izabela, E-mail: sobiza@amu.edu.pl; Rydz, Michal; Ziolek, Maria

2013-02-15

Graphical abstract: Display Omitted Highlights: ► Interaction of gold with K leads to the change of electronic state and redox properties of gold. ► The amount of potassium incorporated into Au-zeolites determines the size of gold particles. ► K(0.2 wt.%)/Au-Beta exhibits the best performance in decomposition of N{sub 2}O and removal of Bu{sub 2}S. -- Abstract: Beta zeolite was applied as support for gold introduced by gold-precipitation method and potassium added by impregnation or adsorption. The effect of zeolite composition and the amount of potassium introduced on the surface properties of the final materials was considered. Moreover, the interaction ofmore » gold and potassium species was found to be related to the adsorptive and catalytic behaviour of zeolites in NO reduction with propene and deodorization. K/Au-Beta(Impregnated) exhibits the best performance in the above mentioned processes because of the small gold particles (between 2 and 5 nm) and interaction of gold with potassium species leading to the change of electronic properties of the surface (the appearance of cationic gold species). Potassium added as a promoter improves the catalytic properties of Au-zeolite in N{sub 2}O decomposition and also in deodorization (increase of the ability to dibutyl sulphide oxidation). The catalysts prepared were characterized by XRD, XPS, UV–vis, TEM, pyridine adsorption combined with FTIR and test reaction (2-propanol transformation).« less

Effects of ammonium hydroxide on the structure and gas adsorption of nanosized Zr-MOFs (UiO-66).

PubMed

Abid, Hussein Rasool; Ang, Ha Ming; Wang, Shaobin

2012-05-21

Several zirconium-based metal-organic frameworks (Zr-MOFs) have been synthesized using ammonium hydroxide as an additive in the synthesis process. Their physicochemical properties have been characterized by N(2) adsorption/desorption, XRD, SEM, FTIR, and TGA, and their application in CO(2) adsorption was evaluated. It was found that addition of ammonium hydroxide produced some effects on the structure and adsorption behavior of Zr-MOFs. The pore size and pore volume of Zr-MOFs were enhanced with the additive, however, specific surface area of Zr-MOFs was reduced. Using an ammonium hydroxide additive, the crystal size of Zr-MOF was reduced with increasing amount of the additive. All the samples presented strong thermal stability. Adsorption tests showed that capacity of CO(2) adsorption on the Zr-MOFs under standard conditions was reduced due to decreased micropore fractions. However, modified Zr-MOFs had significantly lower adsorption heat. The adsorption capacity of carbon dioxide was increased at high pressure, reaching 8.63 mmol g(-1) at 987 kPa for Zr-MOF-NH(4)-2.

Adsorption of ammonia at GaN(0001) surface in the mixed ammonia/hydrogen ambient - a summary of ab initio data

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

Kempisty, Paweł; Krukowski, Stanisław; Interdisciplinary Centre for Materials Modelling, Warsaw University, Pawińskiego 5a, 02-106 Warsaw

Adsorption of ammonia at NH{sub 3}/NH{sub 2}/H-covered GaN(0001) surface was analyzed using results of ab initio calculations. The whole configuration space of partially NH{sub 3}/NH{sub 2}/H-covered GaN(0001) surface was divided into zones of differently pinned Fermi level: at the Ga broken bond state for dominantly bare surface (region I), at the valence band maximum (VBM) for NH{sub 2} and H-covered surface (region II), and at the conduction band minimum (CBM) for NH{sub 3}-covered surface (region III). The electron counting rule (ECR) extension was formulated for the case of adsorbed molecules. The extensive ab intio calculations show the validity of themore » ECR in case of all mixed H-NH{sub 2}-NH{sub 3} coverages for the determination of the borders between the three regions. The adsorption was analyzed using the recently identified dependence of the adsorption energy on the charge transfer at the surface. For region I ammonia adsorbs dissociatively, disintegrating into a H adatom and a HN{sub 2} radical for a large fraction of vacant sites, while for region II adsorption of ammonia is molecular. The dissociative adsorption energy strongly depends on the Fermi level at the surface (pinned) and in the bulk (unpinned) while the molecular adsorption energy is determined by bonding to surface only, in accordance to the recently published theory. Adsorption of Ammonia in region III (Fermi level pinned at CBM) leads to an unstable configuration both molecular and dissociative, which is explained by the fact that broken Ga-bonds are doubly occupied by electrons. The adsorbing ammonia brings 8 electrons to the surface, necessitating the transfer of these two electrons from the Ga broken bond state to the Fermi level. This is an energetically costly process. Adsorption of ammonia at H-covered site leads to the creation of a NH{sub 2} radical at the surface and escape of H{sub 2} molecule. The process energy is close to 0.12 eV, thus not large, but the direct inverse process is not possible due to the escape of the hydrogen molecule.« less

A study in the adsorption of Fe(2+) and NO(3)(-) on pine needles based hydrogels.

PubMed

Chauhan, Ghanshyam S; Chauhan, Sandeep; Kumar, Sunil; Kumari, Anita

2008-09-01

Novel supports for use as cation and anion adsorbents were prepared from lignocellulosics using pine needles and their carboxymethylated forms by network/hydrogel formation with acrylamide and N,N-methylene bisacrylamide. The hydrogels thus prepared were further functionalized by partial alkaline hydrolysis with 0.5 N NaOH and were characterized by FTIR, SEM and nitrogen analysis. Adsorption of Fe(2+) on these hydrogels was carried as a function of time, temperature, pH and ionic strength. The hydrogel having the maximum adsorption capacity was loaded with Fe(2+) at the conditions those afforded maximum uptake and was used as novel anionic adsorbent for NO(3)(-). The water uptake capacities and biodegradability of the hydrogels before and after the ion loading was studied to evaluate the possible end-uses of these hydrogels as alternate materials in the removal of ionic species from water.

Transformations of lead 1,3-propylenediaminetetraacetate to its MOF products for the selective adsorption of methanol

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

Dai, Jun-Wei; Li, Xing; Zheng, Jian-Mei

2016-05-15

Water soluble coordination polymer of potassium lead 1,3-propylenediaminetetraacetate {K_4[Pb_2(1,3-pdta)_2]·6H_2O}{sub n} (1) and its insoluble products {[Pb(1,3-H_2pdta)(H_2O)]·2H_2O}{sub n} (2), {[Pb_2(1,3-pdta)(H_2O)_4]·4H_2O}{sub n} (3) and [Pb{sub 2}(1,3-pdta)(H{sub 2}O){sub 2}]{sub n} (4) were obtained from the direct reactions of lead nitrate with 1,3-propylenediaminetetraacetic acid in different conditions (1,3-H{sub 4}pdta=1,3-propylenediaminetetraacetic acid). The former 1 could be converted to the insoluble products of {[Pb_2(1,3-pdta)(H_2O)_4]·4H_2O}{sub n} (3) and [Pb{sub 2}(1,3-pdta)(H{sub 2}O){sub 2}]{sub n} (4) in weak acidic solution. The complexes have been full characterized by EA, FT-IR, solution and solid state {sup 13}C NMR spectra, thermogravimetric and structural analyses. Interestingly, 3 contains a unique (H{sub 2}O){sub 26}more » cluster and a 5.2 Å pore after eliminating the guest water molecules, which exhibits reversible adsorption for methanol. This is confirmed by PXRD and solid state {sup 13}C NMR analyses. Nano-confined methanol in microporous structure has been observed based on the large downfield shift of {sup 13}C NMR signal (Δδ 9.72 ppm), attributing to the methyl group in methanol. - Graphical abstract: Water soluble coordination polymer K{sub 4n}[Pb{sub 2}(1,3-pdta){sub 2}]{sub n}·6nH{sub 2}O (1) is converted to its insoluble product [Pb{sub 2}(1,3-pdta)(H{sub 2}O){sub 4}]{sub n}·4nH{sub 2}O (3), which contains a unique (H{sub 2}O){sub 26} cluster and exhibits reversible adsorption for methanol. - Highlights: • Water-soluble coordination polymer was constructed by lead propylenediaminetetraacetate. • Its MOF product has a unique (H{sub 2}O){sub 26} cluster. • The product exhibits reversible adsorption for methanol.« less

Determination of Phenols Isomers in Water by Novel Nanosilica/Polydimethylsiloxane-Coated Stirring Bar Combined with High Performance Liquid Chromatography-Fourier Transform Infrared Spectroscopy.

PubMed

Zheng, Bei; Li, Wentao; Liu, Lin; Wang, Xin; Chen, Chen; Yu, Zhiyong; Li, Hongyan

2017-08-18

A novel nanosilica/polydimethylsiloxane (SiO 2 /PDMS) coated stirring bar was adopted in the sorption extraction (SBSE) of phenols in water, and the high performance liquid chromatography-fourier transform infrared spectroscopy (HPLC-FTIR) was subsequently used to determination of phenol concentration. The SiO 2 /PDMS coating was prepared by sol-gel method and characterized with respect to morphology and specific surface area. The results of field-emission scanning electron microscope (FE-SEM) and N 2 adsorption-desorption as well as phenol adsorption experiments denoted that SiO 2 /PDMS has larger surface area and better adsorption capacity than commercial PDMS. The extraction efficiency of phenol with SiO 2 /PDMS coated stirring bar was optimized in terms of ion strength, flow rate of phenol-involved influent, type of desorption solvent and desorption time. More than 75% of phenol desorption efficiency could be kept even after 50 cycles of extraction, indicating the high stability of the SiO 2 /PDMS coated stirring bar. Approximately 0.16 mg/L 2, 5-dimethylphenol (2, 5-DMP), which was 34-fold more toxic than phenol, was detected in water through HPLC-FTIR. However, 2, 5-DMP could be oxidized to 5-methy-2-hydroxy benzaldehyde after disinfection in drinking water treatment process. Therefore, the proposed method of SiO 2 /PDMS-SBSE-HPLC-FTIR is successfully applied in the analysis of phenols isomers in aqueous environment.

Chitosan/nanohydroxyapatite composite based scallop shells as an efficient adsorbent for mercuric ions: Static and dynamic adsorption studies.

PubMed

Hassan, Asaad F; Hrdina, Radim

2018-04-01

Chitosan/nanohydroxyapatite composites based on scallop shells (CP12, CP14 and CP21) were prepared with different chitosan: nanohydroxyapatite ratios (1:2, 1:4 and 2:1, respectively). Nanohydroxyapatite (P), chitosan(C) and their composites were characterized by means of TGA, XRD, N 2 adsorption/desorption analysis, SEM, Zeta potential and FTIR. The BET surface area ranged between 189 and 512 m 2 /g. Static adsorption of Hg +2 was tested for the effect of adsorbent dosage, pH, time and initial Hg +2 concentrations indicating that maximum static adsorption capacity was confirmed by CP12 (111.6 mg/g). Static adsorption well fitted with Langmuir adsorption isotherm and Pseudo-second order kinetic models. CP12 was selected for dynamic adsorption of Hg +2 considering the effect of bed height, flow rate and the effect of Hg +2 concentrations. Maximum dynamic adsorption capacity was confirmed at bed height of 3 cm, 2.0 mL/min flow rate and 300 mg/L as Hg +2 concentration with breakthrough time (t b ) and exhaustion time (t e ) of 9 and 21 h. Yoon-Nelson and Thomas models best described the experimental Hg +2 breakthrough curve model. After static adsorption, EDTA solution confirmed the maximum desorption efficiency. The validity of CP12 was tested through three cycles of column dynamic adsorption-desorption. Copyright © 2017 Elsevier B.V. All rights reserved.

Template-free hydrothermal synthesis of MgO-TiO2 microcubes toward high potential removal of toxic water pollutants

NASA Astrophysics Data System (ADS)

Chowdhury, Ipsita Hazra; Kundu, Sukanya; Naskar, Milan Kanti

2018-01-01

MgO-TiO2 microcubes were synthesized by a facile template-free hydrothermal method followed by calcination. Different analytical tools such as XRD, DTA/TG, FTIR, N2 adsorption-desorption study, FESEM, TEM and UV-DRS were used to characterize the sample. The FESEM images exhibited cube shaped particles of size 2-4 μm. The MgO-TiO2 microcubes exhibit a high potential removal of toxic Pb (II) ions and photocatalytic degradation of organic dye methyl orange from water. The absorption capacity was determined by changing different experimental conditions. The spontaneity of the reaction was confirmed by thermodynamic study. The prepared MgO-TiO2 microcubes showed superior adsorption capacity up to 2900 mg g-1 for Pb (II) ions, and about 95% of photodegradation of methyl orange (MO), the water pollutants.

Role of the concentration and nature of grafted groups in the adsorption of hydrocarbon vapors on silica modified by monofunctional polyfluoroalkylsilanes

NASA Astrophysics Data System (ADS)

Roshchina, T. M.; Shoniya, N. K.; Tayakina, O. Ya.; Tkachenko, O. P.; Kustov, L. M.; Bernardoni, F.; Fadeev, A. Y.

2012-03-01

The role of the grafting density of monofunctional polyfluoroalkylsilanes of the C n F2 n - 1(CH2) m Si(CH3)2Cl general formula (where n = 3, 4, and 6; and m = 2 and 3) and their composition in intermolecular interactions of the molecules of saturated and aromatic hydrocarbons with a surface of chemically modified silica is studied by means of IR spectroscopy and adsorption-static and gas chromatography. It is shown that the higher the concentration and the shorter the length of the grafted chain, the greater (by a factor of 2 to 25) the drop in the adsorption values of hydrocarbons as a result of modifications, due to an increase in the degree of oleophobization of surface upon the formation of polyorganofluorine coatings. The high specificity of the surface with respect to benzene, which is due to the active participation of the polar fragment of a grafted chain in adsorption process, is related to the features of a relatively low-density sample with a concentration of grafted perfluorobutyl groups of 1.7 nm-2. It is shown that the thermodestruction of polyfluoroalkyl silica remains virtually unobserved upon heating to 523 K in an argon flow.

Changing the adsorption capacity of coal-based honeycomb monoliths for pollutant removal from liquid streams by controlling their porosity

NASA Astrophysics Data System (ADS)

Gatica, José M.; Harti, Sanae; Vidal, Hilario

2010-09-01

Coal-based honeycomb monoliths extruded using methods developed for ceramic materials have been used to retain methylene blue and p-nitrophenol from aqueous solutions. The influence of the filters' thermal treatment on their textural properties and performance as adsorbents was examined. Characterization by N 2 physisorption, mercury porosimetry and scanning electron microscopy along with adsorption tests under dynamic conditions suggest that, depending on the pollutant and its initial concentration, it can be more convenient to previously submit the monoliths to a simple carbonization or to an additional activation, with or without preoxidation, as a consequence of their different resulting pore structures. Infrared spectroscopy indicates that their different adsorption behaviour seems not to be related to differences in their surface chemical groups. In addition, axial crushing tests show that the monoliths have an acceptable mechanical resistance for the application investigated.

Precise identification and manipulation of adsorption geometry of donor-π-acceptor dye on nanocrystalline TiO₂ films for improved photovoltaics.

PubMed

Zhang, Fan; Ma, Wei; Jiao, Yang; Wang, Jingchuan; Shan, Xinyan; Li, Hui; Lu, Xinghua; Meng, Sheng

2014-12-24

Adsorption geometry of dye molecules on nanocrystalline TiO2 plays a central role in dye-sensitized solar cells, enabling effective sunlight absorption, fast electron injection, optimized interface band offsets, and stable photovoltaic performance. However, precise determination of dye binding geometry and proportion has been challenging due to complexity and sensitivity at interfaces. Here employing combined vibrational spectrometry and density functional calculations, we identify typical adsorption configurations of widely adopted cyanoacrylic donor-π bridge-acceptor dyes on nanocrystalline TiO2. Binding mode switching from bidentate bridging to hydrogen-bonded monodentate configuration with Ti-N bonding has been observed when dye-sensitizing solution becomes more basic. Raman and infrared spectroscopy measurements confirm this configuration switch and determine quantitatively the proportion of competing binding geometries, with vibration peaks assigned using density functional theory calculations. We further found that the proportion of dye-binding configurations can be manipulated by adjusting pH value of dye-sensitizing solutions. Controlling molecular adsorption density and configurations led to enhanced energy conversion efficiency from 2.4% to 6.1% for the fabricated dye-sensitized solar cells, providing a simple method to improve photovoltaic performance by suppressing unfavorable binding configurations in solar cell applications.

Preparation of Calcined Zirconia-Carbon Composite from Metal Organic Frameworks and Its Application to Adsorption of Crystal Violet and Salicylic Acid

PubMed Central

Hasan, Zubair; Cho, Dong-Wan; Nam, In-Hyun; Chon, Chul-Min; Song, Hocheol

2016-01-01

Zirconia-carbon (ZC) composites were prepared via calcination of Zr-based metal organic frameworks, UiO-66 and amino-functionalized UiO-66, under N2 atmosphere. The prepared composites were characterized using a series of instrumental analyses. The surface area of the ZC composites increased with the increase of calcination temperature, with the formation of a graphite oxide phase observed at 900 °C. The composites were used for adsorptive removal of a dye (crystal violet, CV) and a pharmaceutical and personal care product (salicylic acid, SA). The increase of the calcination temperature resulted in enhanced adsorption capability of the composites toward CV. The composite calcined at 900 °C exhibited a maximum uptake of 243 mg·g−1, which was much greater than that by a commercial activated carbon. The composite was also effective in SA adsorption (102 mg·g−1), and N-functionalization of the composite further enhanced its adsorption capability (109 mg·g−1). CV adsorption was weakly influenced by solution pH, but was more dependent on the surface area and pore volume of the ZC composite. Meanwhile, SA adsorption showed strong pH dependence, which implies an active role of electrostatic interactions in the adsorption process. Base-base repulsion and hydrogen bonding are also suggested to influence the adsorption of CV and SA, especially for the N-functionalized composite. PMID:28773387

Isotherm and kinetic studies on adsorption of oil sands process-affected water organic compounds using granular activated carbon.

PubMed

Islam, Md Shahinoor; McPhedran, Kerry N; Messele, Selamawit A; Liu, Yang; Gamal El-Din, Mohamed

2018-07-01

The production of oil from oil sands in northern Alberta has led to the generation of large volumes of oil sands process-affected water (OSPW) that was reported to be toxic to aquatic and other living organisms. The toxicity of OSPW has been attributed to the complex nature of OSPW matrix including the inorganic and organic compounds primarily naphthenic acids (NAs: C n H 2n+Z O x ). In the present study, granular activated carbon (GAC) adsorption was investigated for its potential use to treat raw and ozonated OSPW. The results indicated that NA species removal increased with carbon number (n) for a fixed Z number; however, the NA species removal decreased with Z number for a fixed carbon number. The maximum adsorption capacities obtained from Langmuir adsorption isotherm based on acid-extractable fraction (AEF) and NAs were 98.5 mg and 60.9 mg AEF/g GAC and 60 mg and 37 mg NA/g GAC for raw and ozonated OSPW, respectively. It was found that the Freundlich isotherm model best fits the AEF and NA equilibrium data (r 2  ≥ 0.88). The adsorption kinetics showed that the pseudo-second order and intraparticle diffusion models were both appropriate in modeling the adsorption kinetics of AEF and NAs to GAC (r 2  ≥ 0.97). Although pore diffusion was the rate limiting step, film diffusion was still significant for assessing the rate of diffusion of NAs. This study could be helpful to model, design and optimize the adsorption treatment technologies of OSPW and to assess the performance of other adsorbents. Copyright © 2018 Elsevier Ltd. All rights reserved.

Surface and adsorptive properties of Moringa oleifera bark for removal of V(V) from aqueous solutions.

PubMed

Mnisi, Robert Londi; Ndibewu, Peter Papoh

2017-11-04

The bark of Moringa oleifera, a cheap and readily available natural biopolymeric resource material, found to significantly reduce coliform load and turbidity in contaminated water is investigated in this paper. Its surface and adsorptive properties are investigated to explore its adsorptive potential in removing V(V) from aqueous solutions. Surface properties were investigated using FTIR, HRSEM/EDS, IC, and BET-N 2 adsorption techniques. Adsorptive properties were investigated by optimizing adsorption parameters such as pH, temperature, initial metal concentration, and adsorbent dosage, using V(V) as an adsorbate. The adsorption-desorption isotherms are typical of type II with a H3 hysteresis loop and is characteristic of a largely macroporous material. Bottle ink pores are observed, which can provide good accessibility of the active sites, even though the internal BET surface area is typically low (1.79 g/m 2 ). Solution pH significantly influences the adsorptive potential of the material. The low surface area negatively impacts on the adsorption capacity, but is compensated for by the exchangeable anions (Cl - , F - , PO 4 3- , NO 3 - , and SO 4 2- ) and cations (Ca 2+ , K + , Mg 2+ , and Al 3+ ) at the surface and the accessibility of the active sites. Adsorption isotherm modeling show that the surface is largely heterogeneous with complex multiple sites and adsorption is not limited to monolayer.

Effect of Carbon Type on Arsenic and Trichloroethylene Removal Capacity of Iron (Hydr)oxide Nanoparticle Impregnated Granulated Activated Carbon

NASA Astrophysics Data System (ADS)

Cooper, Anne Marie

This study investigates the effect of the virgin granular activated carbon (GAC) on the properties of synthesized iron (hydr)oxide nanoparticles impregnated GAC (Fe-GAC) media and its ability to remove arsenate and organic trichloroethylene (TCE) from water. Fe-GAC media were synthesized from bituminous and lignite-based virgin GAC via three variations of a permanganate/Fe(II) synthesis method. Data obtained from an array of characterization techniques indicated that differences in pore size distribution and surface chemistry of the virgin GAC favor different reaction paths for the iron (hydr)oxide nanoparticles formation. Batch equilibrium isotherm testing (120 microg-As/L; 6 mg-TCE/L, 10 mM NaHCO3 at pH = 7.2 +/- 0.1 and pH = 8.2 +/- 0.1) showed arsenic removal capability was increased as a result of iron (nanoparticles) impregnation, while TCE removal properties were decreased in Fe-GAC media. This tradeoff was displayed by both lignite and bituminous Fe-GAC but was most pronounced in lignite-based Fe-GAC having the highest Fe content (13.4% Fe) which showed the most favorable Freundlich adsorption and intensity parameters for arsenic of Ka = 72.6 (microg-As/g-FeGAC)(L/microg-As)1/n, 1/n = 0.6; and least favorable adsorption for TCE of Ka = 0.8 (mg-TCE/g-FeGAC)(L/mg-TCE)1/n, 1/n = 4.47. It was concluded that iron content was the main factor contributing to enhanced arsenic removal and that this was affected by base GAC properties such as pore size distribution and surface functional groups. However high Fe content can result in pore blockage; reduction in available adsorption sites for organic co-contaminants; and have a significant effect on the Fe-GACs overall adsorption capacity.

Th(IV) Adsorption onto Oxidized Multi-Walled Carbon Nanotubes in the Presence of Hydroxylated Fullerene and Carboxylated Fullerene.

PubMed

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

2013-09-17

The adsorption of Th(IV) onto the surface of oxidized multi-walled carbon nanotubes (oMWCNTs) in the absence and presence of hydroxylated fullerene (C 60 (OH) n ) and carboxylated fullerene (C 60 (C(COOH)₂) n ) has been investigated. C 60 (OH) n , C 60 (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 C 60 (OH) n or C 60 (C(COOH)₂) n , the study of a ternary system showed the inhibition effect of C 60 (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 C 60 (C(COOH)₂) n , even at its low concentration, on Th(IV) adsorption was observed in acid medium.

Experimental approach to the anion problem in DFT calculation of the partial charge transfer during adsorption at electrochemical interfaces

NASA Astrophysics Data System (ADS)

Marichev, V. A.

2005-08-01

In DFT calculation of the charge transfer (Δ N), anions pose a special problem since their electron affinities are unknown. There is no method for calculating reasonable values of the absolute electronegativity ( χA) and chemical hardness ( ηA) for ions from data of species themselves. We propose a new approach to the experimental measurement of χA at the condition: Δ N = 0 at which η values may be neglected and χA = χMe. Electrochemical parameters corresponding to this condition may be obtained by the contact electric resistance method during in situ investigation of anion adsorption in the particular system anion-metal.

Adsorption of four perfluorinated acids on non ion exchange polymer sorbents.

PubMed

Senevirathna, S T M L D; Tanaka, S; Fujii, S; Kunacheva, C; Harada, H; Shivakoti, B R; Dinh, H; Ariyadasa, T

2011-01-01

Perfluorinated compounds (PFCs) have attracted global concern due to their ubiquitous distribution and properties of persistence, bio accumulation and toxicity. The process of adsorption has been identified as an effective technique to remove PFCs in water. Different non ion-exchange polymeric adsorbents were tested with regard to their sorption kinetics and isotherms at low PFCs concentrations. Selected PFCs were perfluorobutanoic acid (PFBA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA) and perfluorodecanoic acid (PFDA) and the tested polymers were three types of Dowex optopores (V-493, V503, and L493), Amberlite XAD-4, and Filtrasorb 400 (Granular Activated Carbon-GAC). We observed the selective adsorption of PFCs on synthetic polymers. For PFDA, Amberlite XAD-4 gave the Freundlich adsorption constant of 2,965 (microg PFCs/g sorbent)(microg PFCs/L)(-n), which was higher than that of GAC (121.89 (microg PFCs/g sorbent) (microg PFCS/L)(-n)). In the case of PFBA, GAC showed better performance (13.36) (microg PFCs/g sorbent) microg PFCS/L)(-n) than synthetic polymers (0.62-5.23) (microg PFCs/g sorbent) (microg PFCS/L)(-n). Adsorption kinetics of all adsorbents were well described (R2 = 0.85-1) by pseudo-second order kinetic model. Sorption capacity was influenced by initial PFCs concentration for all adsorbents. GAC reached the equilibrium concentration within 4 hours, Amberlite XAD 4 reached it within 10 hours and other polymers took more than 70 hours.

CO₂ adsorption on amine-functionalized periodic mesoporous benzenesilicas.

PubMed

Sim, Kyohyun; Lee, Nakwon; Kim, Joonseok; Cho, Eun-Bum; Gunathilake, Chamila; Jaroniec, Mietek

2015-04-01

CO2 adsorption was investigated on amine-functionalized mesoporous silica (SBA-15) and periodic mesoporous organosilica (PMO) samples. Hexagonally (p6mm) ordered mesoporous SBA-15 and benzene-PMO (BPMO) samples were prepared in the presence of Pluronic P123 block copolymer template under acidic conditions. Three kinds of amine-containing organosilanes and polyethylenimine were used to functionalize SBA-15 and BPMO. Small-angle X-ray scattering and nitrogen adsorption isotherms showed that these samples featured ordered mesostructure, high surface area, and narrow pore size distributions. Solid-state (13)C- and (29)Si cross-polarization magic-angle spinning NMR spectra showed chemical linkage between amine-containing modifiers and the surface of mesoporous materials. The chemically linked amine-containing modifiers were found to be on both the inner and outer surfaces. N-[3-(trimethoxysilyl)propyl]ethylenediamine-modified BPMO (A2-BPMO) sample exhibited the highest CO2 uptake (i.e., ∼3.03 mmol/g measured on a volumetric adsorption analyzer) and the fastest adsorption rate (i.e., ∼13 min to attain 90% of the maximum amount) among all the samples studied. Selectivity and reproducibility measurements for the A2-BPMO sample showed quite good performance in flowing N2 gas at 40 mL/min and CO2 gas of 60 mL/min at 25 °C.

Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

EPA Science Inventory

Arsenate adsorption on amorphous (RuO₂•1.1H₂O) and crystalline (RuO₂) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

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.

Total N-nitrosamine Precursor Adsorption with Carbon Nanotubes: Elucidating Controlling Physiochemical Properties and Developing a Size-Resolved Precursor Surrogate

NASA Astrophysics Data System (ADS)

Needham, Erin Michelle

As drinking water sources become increasingly impaired with nutrients and wastewater treatment plant (WWTP) effluent, formation of disinfection byproducts (DBPs)--such as trihalomethanes (THMs), dihaloacetonitriles (DHANs), and N-nitrosamines--during water treatment may also increase. N-nitrosamines may comprise the bulk of the chronic toxicity in treated drinking waters despite forming at low ng/L levels. This research seeks to elucidate physicochemical properties of carbon nanotubes (CNTs) for removal of DBP precursors, with an emphasis on total N-nitrosamines (TONO). Batch experiments with CNTs were completed to assess adsorption of THM, DHAN, and TONO precursors; physiochemical properties of CNTs were quantified through gas adsorption isotherms and x-ray photoelectron spectroscopy. Numerical modeling was used to elucidate characteristics of CNTs controlling DBP precursor adsorption. Multivariate models developed with unmodified CNTs revealed that surface carboxyl groups and, for TONO precursors, cumulative pore volume (CPV), controlled DBP precursor adsorption. Models developed with modified CNTs revealed that specific surface area controlled adsorption of THM and DHAN precursors while CPV and surface oxygen content were significant for adsorption of TONO precursors. While surrogates of THM and DHAN precursors leverage metrics from UV absorbance and fluorescence spectroscopy, a TONO precursor surrogate has proved elusive. This is important as measurements of TONO formation potential (TONOFP) require large sample volumes and long processing times, which impairs development of treatment processes. TONO precursor surrogates were developed using samples that had undergone oxidative or sorption treatments. Precursors were analyzed with asymmetric flow field-flow fractionation (AF4) with inline fluorescence detection (FLD) and whole water fluorescence excitation-emission matrices (EEMs). TONO precursor surrogates were discovered, capable of predicting changes in TONOFP in WWTP samples that have undergone oxidation (R2 = 0.996) and sorption (R2 = 0.576). Importantly, both surrogates only require just 2 mL of sample volume to measure and take only 1 hour. Application of the sorption precursor surrogate revealed that DBP precursor adsorption was feasible with freeform CNT microstructures with various dimensions and surface chemistries, establishing a framework for development of this novel CNT application for drinking water treatment.

Study of Cs/NF3 adsorption on GaN (0 0 1) surface

NASA Astrophysics Data System (ADS)

Diao, Yu; Liu, Lei; Xia, Sihao; Kong, Yike

2017-03-01

To investigate the optoelectronics properties of Cs/NF3 adsorption on GaN (0 0 1) photocathode surface, different adsorption models of Cs-only, Cs/O, Cs/NF3 adsorption on GaN clean surface were established, respectively. Atomic structures, work function, adsorption energy, E-Mulliken charge distribution, density of states and optical properties of all these adsorption systems were calculated using first principles. Compared with Cs/O co-adsorption, Cs/NF3 co-adsorption show better stability and more decline of work function, which is more beneficial for photoemission efficiency. Besides, surface band structures of Cs/NF3 co-adsorption system exhibit metal properties, implying good conductivity. Meanwhile, near valence band minimum of Cs/NF3 co-adsorption system, more acceptor levels emerges to form a p-type emission surface, which is conductive to the escape of photoelectrons. In addition, imaginary part of dielectric function curve and absorption curve of Cs/NF3 co-adsorption system both move towards lower energy side. This work can direct the optimization of activation process of NEA GaN photocathode.

Determination of Adsorption Equations for Chloro Derivatives of Aniline on Halloysite Adsorbents Using Inverse Liquid Chromatography.

PubMed

Słomkiewicz, Piotr M; Szczepanik, Beata; Garnuszek, Magdalena; Rogala, Paweł; Witkiewicz, Zygfryd

2017-11-01

Chloro derivatives of aniline are commonly used in the production of dyes, pharmaceuticals, and agricultural agents. They are toxic compounds with a large accumulation ability and low natural biodegradability. Halloysite is known as an efficient adsorbent of toxic compounds, such as phenols or herbicides, from wastewater. Inverse LC was applied to measure the adsorption of aniline and 2-chloroaniline (2-CA), 3-chloroaniline (3-CA), and 4-chloroaniline (4-CA) on halloysite adsorbents. A peak division (PD) method was used to determine a Langmuir equation in accordance with the adsorption measurement results. The values of adsorption equilibrium constants and enthalpy were determined and compared by breakthrough curve and PD methods. The physical sense of the calculated adsorption enthalpy values was checked by applying Boudart's entropy criteria. Of note, adsorption enthalpy values for halloysite adsorbents decreased in the following order: aniline > 4-CA > 2-CA > 3-CA.

CO2 Separation and Capture Properties of Porous Carbonaceous Materials from Leather Residues

PubMed Central

Bermúdez, José M.; Dominguez, Pablo Haro; Arenillas, Ana; Cot, Jaume; Weber, Jens; Luque, Rafael

2013-01-01

Carbonaceous porous materials derived from leather skin residues have been found to have excellent CO2 adsorption properties, with interestingly high gas selectivities for CO2 (α > 200 at a gas composition of 15% CO2/85% N2, 273K, 1 bar) and capacities (>2 mmol·g−1 at 273 K). Both CO2 isotherms and the high heat of adsorption pointed to the presence of strong binding sites for CO2 which may be correlated with both: N content in the leather residues and ultrasmall pore sizes. PMID:28788352

Adsorptive Removal and Adsorption Kinetics of Fluoroquinolone by Nano-Hydroxyapatite

PubMed Central

Chen, Yajun; Lan, Tao; Duan, Lunchao; Wang, Fenghe; Zhao, Bin; Zhang, Shengtian; Wei, Wei

2015-01-01

Various kinds of antibiotics, especially fluoroquinolone antibiotics (FQs) have been widely used for the therapy of infectious diseases in human and livestock. For their poorly absorbed by living organisms, large-scale misuse or abuse of FQs will foster drug resistance among pathogenic bacteria, as well as a variety of environmental problems when they were released in the environment. In this work, the adsorption properties of two FQs, namely norfloxacin (NOR) and ciprofloxacin (CIP), by nano-hydroxyapatite (n-HAP) were studied by batch adsorption experiments. The adsorption curves of FQs by n-HAP were simulated by Langmuir and Freundlich isotherms. The results shown that NOR and CIP can be adsorbed effectively by the adsorbent of n-HAP, and the adsorption capacity of FQs increase with increasing dosage of n-HAP. The optimum dosage of n-HAP for FQs removal was 20 g·L-1, in which the removal efficiencies is 51.6% and 47.3%, and an adsorption equilibrium time is 20 min. The maximum removal efficiency occurred when pH is 6 for both FQs. The adsorption isotherm of FQs fits well for both Langmuir and Freundlich equations. The adsorption of both FQs by n-HAP follows second-order kinetics. PMID:26698573

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.

Ion bombardment and adsorption studies on ilmenite (FeTiO3) by X-ray photoelectron spectroscopy

NASA Technical Reports Server (NTRS)

Schulze, P. D.

1983-01-01

The effects of 5 KeV argon and oxygen ion bombardment on FeTiO3 (ilmenite) at low temperatures have been studied using X-ray photoelectron spectroscopy (XPS). Also, using this same technique, the adsorption of O2, NO, N2O, and CO at 300 K and the adsorption of O2 and D2O at 150K have been studied. Argon and oxygen ion bombardment of ilmenite have confirmed earlier studies on metal oxides that argon ions generally reduce the anion species while oxygen ions generally oxidize the anion species. The two iron states involved were Fe sup +2 and Fe sup O. The reduction of Ti sup +4 was not verified although a significant shift in the Ti(2p1,3) binding energies toward the metallic state was observed after oxygen ion bombardment at low temperatures. At temperatures above 150K, O2 adsorbs dissociatively on ilmenite while D2O adsorbs molecularly below 170K. Above 300 K No, N2O, and CO do not appear to adsorb dissociatively. Low temperature adsorption of D2O was found to be inhibited by predosing the ilmenite with O2.

Adsorption and recognition characteristics of surface molecularly imprinted polymethacrylic acid/silica toward genistein.

PubMed

Zhang, Yanyan; Gao, Baojiao; An, Fuqiang; Xu, Zeqing; Zhang, Tingting

2014-09-12

In this paper, on the basis of surface-initiated graft polymerization, a new surface molecular imprinting technique is established by molecular design. And molecularly imprinted polymer MIP-PMAA/SiO2 is successfully prepared with genistein as template. The adsorption and recognition characteristics of MIP-PMAA/SiO2 for genistein are studied in depth by using static method, dynamic method and competitive adsorption experiment. The experimental results show that MIP-PMAA/SiO2 possesses very strong adsorption affinity and specific recognition for genistein. The saturated adsorption capacity could reach to 0.36mmolg(-1). The selectivity coefficients relative to quercetin and rutin are 5.4 and 11.8, respectively. Besides, MIP-PMAA/SiO2 is regenerated easily and exhibits excellent reusability. Copyright © 2014 Elsevier B.V. All rights reserved.

Adsorption behavior of methacryloyloxydecyl dihydrogen phosphate on an apatite surface at neutral pH.

PubMed

Bista, Baba; Nakashima, Syozi; Nikaido, Toru; Sadr, Alireza; Takagaki, Tomohiro; Romero, Maria J R H; Sato, Takaaki; Tagami, Junji

2016-04-01

This study aimed to quantify the adsorption affinity of neutralized 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP-N) toward hydroxyapatite (HA) and dicalcium phosphate dihydrate (DCPD) at pH 7.0 by employing the Langmuir isotherm model. Furthermore, the effects of inorganic phosphate (Pi) and fluoride (F(-) ) ions on the adsorption of 10-MDP-N onto HA and DCPD were examined. Fixed amounts of HA and DCPD powders were suspended in different concentrations of 10-MDP-N solutions and were incubated for 18 h. Equilibrated concentrations of 10-MDP-N were measured by spectrophotometry and the adsorption affinity was estimated using the Langmuir model. Moreover, the adsorption was examined by zeta-potential analysis. The results indicated that significant Langmuir correlation was noted in both substrates, along with an increasing negative zeta-potential; however, in DCPD the correlation was less strong. The addition of 1.0 mM Pi slightly delayed the adsorption of 10-MDP-N onto both substrates, whereas 3.0 mM Pi drastically delayed adsorption onto HA but completely inhibited adsorption onto DCPD. Up to 50 ppm, F(-) enhanced the adsorption onto HA, and the adsorption plateaued at higher concentrations of F(-) , whereas no obvious influence of F(-) on the adsorption onto DCPD was noted. © 2016 Eur J Oral Sci.

Cyclic Nanostructures of Tungsten Oxide (WO3) n   (n = 2-6) as NO x Gas Sensor: A Theoretical Study.

PubMed

Izadyar, Mohammad; Jamsaz, Azam

2014-01-01

Today's WO3-based gas sensors have received a lot of attention, because of important role as a sensitive layer for detection of the small quantities of  NO x . In this research, a theoretical study has been done on the sensing properties of different cyclic nanoclusters of (WO3) n   (n = 2-6) for NO x   (x = 1,2) gases. Based on the calculated adsorption energies by B3LYP and X3LYP functionals, from the different orientations of  NO x molecule on the tungsten oxide clusters, O-N⋯W was preferred. Different sizes of the mentioned clusters have been analyzed and W2O6 cluster was chosen as the best candidate for NO x detection from the energy viewpoint. Using the concepts of the chemical hardness and electronic charge transfer, some correlations between the energy of adsorption and interaction energy have been established. These analyses confirmed that the adsorption energy will be boosted with charge transfer enhancement. However, the chemical hardness relationship is reversed. Finally, obtained results from the natural bond orbital and electronic density of states analysis confirmed the electronic charge transfer from the adsorbates to WO3 clusters and Fermi level shifting after adsorption, respectively. The last parameter confirms that the cyclic clusters of tungsten oxide can be used as NO x gas sensors.

"Explosive" synthesis of metal-formate frameworks for methane capture: an experimental and computational study.

PubMed

Liu, Xiao-Wei; Guo, Ya; Tao, Andi; Fischer, Michael; Sun, Tian-Jun; Moghadam, Peyman Z; Fairen-Jimenez, David; Wang, Shu-Dong

2017-10-17

In this work, we show a solvent-free "explosive" synthesis (SFES) method for the ultrafast and low-cost synthesis of metal-formate frameworks (MFFs). A combination of experiments and in-depth molecular modelling analysis - using grand canonical Monte Carlo (GCMC) simulations - of the adsorption performance of the synthesized nickel-formate framework (Ni-FA) revealed extremely high quality products with permanent porosity, prominent CH 4 /N 2 selectivity (ca. 6.0), and good CH 4 adsorption capacity (ca. 0.80 mmol g -1 or 33.97 cm 3 cm -3 ) at 1 bar and 298 K. This performance is superior to those of many other state-of-the-art porous materials.

Ordered mesoporous ternary mixed oxide materials as potential adsorbent of biomolecules

NASA Astrophysics Data System (ADS)

Pal, Nabanita; Bhaumik, Asim

2012-05-01

Designing a suitable mesoporous framework material for the selective adsorption or immobilization of biomolecules is a very challenging area of research. Mesoporous ternary Co-Si-Al oxide materials with large mesopore and their nanoscale ordering have been reported. The synthesis of these ternary oxides are accomplished through evaporation induced self-assembly (EISA) method using Pluronic non-ionic surfactant F127 under non-aqueous sol-gel route. N2 sorption study revealed high BET surface areas for these materials. These materials exhibited very efficient and selective adsorption for the essential biomolecules like vitamin C (ascorbic acid), vitamin B6 (pyridoxine) and vitamin B3 (nicotinic acid) from their respective aqueous solutions.

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.

Adsorptive Removal of Artificial Sweeteners from Water Using Metal-Organic Frameworks Functionalized with Urea or Melamine.

PubMed

Seo, Pill Won; Khan, Nazmul Abedin; Hasan, Zubair; Jhung, Sung Hwa

2016-11-02

A highly porous metal-organic framework (MOF), MIL-101, was modified to introduce urea or melamine via grafting on open metal sites of the MOF. Adsorptive removal of three artificial sweeteners (ASWs) was studied using the MOFs, with or without modifications (including nitration), and activated carbon (AC). The adsorbed quantities (based on the weight of the adsorbent) of saccharin (SAC) under various conditions decreased in the order urea-MIL-101 > melamine-MIL-101 > MIL-101 > AC > O 2 N-MIL-101; however, the quantities based on unit surface area are in the order melamine-MIL-101 > urea-MIL-101 > MIL-101 > O 2 N-MIL-101. Similar ASWs [acesulfame (ACE) and cyclamate (CYC)] showed the same tendency. The mechanism for very favorable adsorption of SAC, ACE, and CYC over urea- and melamine-MIL-101 could be explained by H-bonding on the basis of the contents of -NH 2 groups on the MOFs and the adsorption results under a wide range of pH values. Moreover, the direction of H-bonding could be clearly defined (H acceptor: ASWs; H donor: MOFs). Urea-MIL-101 and melamine-MIL-101 could be suggested as competitive adsorbents for organic contaminants (such as ASWs) with electronegative atoms, considering their high adsorption capacity (for example, urea-MIL-101 had 2.3 times the SAC adsorption of AC) and ready regeneration.

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.

Theoretical insights into the uranyl adsorption behavior on vanadium carbide MXene

NASA Astrophysics Data System (ADS)

Zhang, Yu-Juan; Zhou, Zhang-Jian; Lan, Jian-Hui; Ge, Chang-Chun; Chai, Zhi-Fang; Zhang, Peihong; Shi, Wei-Qun

2017-12-01

Remediation of the contamination by long-lived actinide wastes is extremely important but also challenging. Adsorption based techniques have attracted much research attention for their potential as low-cost and effective methods to reduce the radioactive waste from solution. In this work, we have investigated the adsorption behavior of uranyl species [with the general form UO2(L1)x(L2)y(L3)z, where L1, L2 and L3 stand for ligands H2O, OH and CO3, respectively] on hydroxylated vanadium carbide V2C(OH)2 MXene nanosheets using density functional theory based simulation methods We find that all studied uranyl species can stably bond to hydroxylated MXene with binding energies ranging from -3.3 to -4.6 eV, suggesting that MXenes could be effective adsorbers for uranyl ions. The strong adsorption is achieved by forming two Usbnd O bonds with the hydroxylated Mxene. In addition, the axial oxygen atoms from the uranyl ions form hydrogen bonds with the hydroxylated V2C, further strengthening the adsorption. We have also investigated the effects of F termination on the uranyl adsorption properties of V2C nanosheets. Usbnd F bonds are in general weaker than Usbnd O bonds on the adsorption site, suggesting that F terminated Mexne is less favorable for uranyl adsorption applications.

Adsorption Mechanisms of Dodecylbenzene Sulfonic Acid by Corn Straw and Poplar Leaf Biochars

PubMed Central

Zhao, Nan; Yang, Xixiang; Zhang, Jing; Zhu, Ling; Lv, Yizhong

2017-01-01

Biochar is an eco-friendly, renewable, and cost-effective material that can be used as an adsorbent for the remediation of contaminated environments. In this paper, two types of biochar were prepared through corn straw and poplar leaf pyrolysis at 300 °C and 700 °C (C300, C700, P300, P700). Brunaer–Emmett–Teller N2 surface area, scanning electron microscope, elemental analysis, and infrared spectra were used to characterize their structures. These biochars were then used as adsorbents for the adsorption of dodecylbenzene sulfonic acid (DBSA). The microscopic adsorption mechanisms were studied by using infrared spectra, 13C-nuclear magnetic resonance spectra, and electron spin resonance spectra. The surface area and pore volume of C700 (375.89 m2/g and 0.2302 cm3/g) were the highest among all samples. Elemental analysis results showed that corn straw biochars had a higher aromaticity and carbon to nitrogen (C/N) ratio than the poplar leaf biochars. High temperature caused the increase of carbon content and the decrease of oxygen content, which also gave the biochars a higher adsorption rate. Pseudo-second order kinetic provided a better fit with the experimental data. Adsorption isotherm experiments showed that the adsorption isotherm of C300 fit the linear model. For other biochars, the adsorption isotherms fitted Langmuir model. Biochars with high temperatures exhibited enhanced adsorption capacity compared with ones at low temperatures. The qmax values of biochars to DBSA followed the order of P700 > C700 > P300. The adsorption mechanisms were complex, including partition, anion exchange, the formation of H bonds, covalent bonds, and charge transfer. The adsorption by covalent bonding might be the key mechanism determining the adsorption capacity of P700. PMID:28937637

Adsorption of 4-n-Nonylphenol and Bisphenol-A on Magnetic Reduced Graphene Oxides: A Combined Experimental and Theoretical Studies.

PubMed

Jin, Zhongxiu; Wang, Xiangxue; Sun, Yubing; Ai, Yuejie; Wang, Xiangke

2015-08-04

Adsorption of 4-n-nonylphenol (4-n-NP) and bisphenol A (BPA) on magnetic reduced graphene oxides (rGOs) as a function of contact time, pH, ionic strength and humic acid were investigated by batch techniques. Adsorption of 4-n-NP and BPA were independent of pH at 3.0- 8.0, whereas the slightly decreased adsorption was observed at pH 8.0-11.0. Adsorption kinetics and isotherms of 4-n-NP and BPA on magnetic rGOs can be satisfactorily fitted by pseudo-second-order kinetic and Freundlich model, respectively. The maximum adsorption capacities of magnetic rGOs at pH 6.5 and 293 K were 63.96 and 48.74 mg/g for 4-n-NP and BPA, respectively, which were significantly higher than that of activated carbon. Based on theoretical calculations, the higher adsorption energy of rGOs + 4-n-NP was mainly due to π-π stacking and flexible long alkyl chain of 4-n-NP, whereas adsorption of BPA on rGOs was energetically favored by a lying-down configuration due to π-π stacking and dispersion forces, which was further demonstrated by FTIR analysis. These findings indicate that magnetic rGOs is a promising adsorbent for the efficient elimination of 4-n-NP/BPA from aqueous solutions due to its excellent adsorption performance and simple magnetic separation, which are of great significance for the remediation of endocrine-disrupting chemicals in environmental cleanup.

Activated Carbon Preparation and Modification for Adsorption

NASA Astrophysics Data System (ADS)

Cao, Yuhe

Butanol is considered a promising, infrastructure-compatible biofuel. Butanol has a higher energy content than ethanol and can be used in conventional gas engines without modifications. Unfortunately, the fermentation pathway for butanol production is restricted by its toxicity to the microbial strains used in the process. Butanol is toxic to the microbes, and this can slow fermentation rates and reduce butanol yields. Gas stripping technology can efficiently remove butanol from the fermentation broth as it is produced, thereby decreasing its inhibitory effects. Traditional butanol separation heavily depends on the energy intensive distillation method. One of the main issues in acetone-butanol-ethanol fermentation is that butanol concentrations in the fermentation broth are low, ranging from 1 to 1.2 percent in weight, because of its toxicity to the microorganisms. Therefore distillation of butanol is even worse than distillation of corn ethanol. Even new separation methods, such as solid- extraction methods involve adding substances, such as polymer resin and zeolite or activated carbon, to biobutanol fermentatioon broth did not achieve energy efficient separation of butanol due to low adsorption selectivity and fouling in broth. Gas-stripping - condensation is another new butanol recovery method, however, the butanol in gas-stripping stream is too low to be condensed without using expensive and energy intensive liquid nitrogen. Adsorption can then be used to recover butanol from the vapor phase. Activated carbon (AC) samples and zeolite were investigated for their butanol vapor adsorption capacities. Commercial activated carbon was modified via hydrothermal H2O2 treatment, and the specific surface area and oxygen-containing functional groups of activated carbon were tested before and after treatment. Hydrothermal H2O 2 modification increased the surface oxygen content, Brunauer-Emmett-Teller surface area, micropore volume, and total pore volume of active carbon. The adsorption capacities of these active carbon samples were almost three times that of zeolite. However, the un-modified active carbon had the highest adsorption capacity for butanol vapor (259.6 mg g-1), compared to 222.4 mg g-1 after 10% H2O2 hydrothermal treatment. Both modified and un-modified active carbon can be easily regenerated for repeatable adsorption by heating to 150 °C. Therefore, surface oxygen groups significantly reduced the adsorption capacity of active carbons for butanol vapor. In addition, original active carbon and AC samples modified by nitric acid hydrothermal modification were assessed for their ability to adsorb butanol vapor. The specific surface area and oxygen-containing functional groups of AC were tested before and after modification. The adsorption capacity of unmodified AC samples were the highest. Hydrothermal oxidation of AC with HNO3 increased the surface oxygen content, Brunauer-Emmett-Teller (BET) surface area, micropore, mesopore and total pore volume of AC. Although the pore structure and specific surface area were greatly improved after hydrothermal oxidization with 4 M HNO3, the increased oxygen on the surface of AC decreased the dynamic adsorption capacity. In order to get high adsorption capacity adsorbents, we used corn stalk as precursor to fabricate porous carbon. ACs were prepared through chemical activation of biochar from whole corn stalk (WCS) and corn stalk pith (CSP) at varying temperatures using potassium hydroxide as the activating agent. ACs were characterized via pore structural analysis and scanning electron microscopy (SEM). These adsorbents were then assessed for their adsorption capacity for butanol vapor. It was found that WCS activated at 900 °C for 1 h (WCS-900) had optimal butanol adsorption characteristics. The BET surface area and total pore volume of the WCS-900 were 2330 m2 g-1 and 1.29 cm3 g-1, respectively. The dynamic adsorption capacity of butanol vapor was 410.0 mg g-1, a 185.1 % increase compared to charcoal-based commercial AC (143.8 mg g -1). Based on the adsorption experiments of butanol vapor, we found the chemical properties of the AC surface play an important role in adsorbing molecules. The adsorption of creatinine on active carbons was also studied, which is a toxic compound generated by human. High levels of creatinine in the blood stream is normally caused by malfunction or failure of the kidneys. Activated carbons is taken by the patients orally to reduce creatinine level. In order to figure out whether chemical modification could increase the adsorption capacity of creatinine, AC samples modified by nitric acid hydrothermal modification were assessed for their ability to adsorb creatinine. The pore structure and surface properties of the AC samples were characterized by N 2 adsorption, temperature programmed desorption (TPD), Fourier Transform Infrared spectroscopy (FTIR), and X-ray photoelectron spectrometer (XPS). It indicated that 4M HNO3 hydrothermal modification with 180 °C was an efficient method in improvement of the creatinine adsorption. The improved adsorption capacity can be attributed mainly to an increase in the acidic oxygen-containing functional groups. The adsorption of creatinine over AC may involve an interaction with the acidic oxygen-containing groups on AC. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherm and isotherm constants. Equilibrium data fitted very well to the Freundlich model in the entire saturation range (3.58-59.08 mg L-1 ). The maximum adsorption capacities of AC modified with 180 °C is 62.5 mg g-1 according to the Langmuir model. Pseudo first-order and second-order kinetic models were used to describe the kinetic data and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model, which indicates that the chemical adsorption was the rate-limiting step, instead of mass transfer. (Abstract shortened by ProQuest.).

Photoassisted oxygen reduction reaction on mpg-C3N4: The effects of elements doping on the performance of ORR

NASA Astrophysics Data System (ADS)

He, Qiuchen; Zhou, Feng; Zhan, Su; Huang, Naibao; Tian, Yu

2018-02-01

The oxygen reduction reaction (ORR) is a crux step in the fuel cells, which is limited to the catalysts. Low-cost nonmetal inorganic catalysts were considered to be the best prospect that may replace platinum. Graphitic carbon nitride (g-C3N4), which has wide prospect in photocatalysis, was found with the activity of ORR. In calculation work, we used the elements of the VIA family (O, S, and Se) to dope g-C3N4 and investigated the electronic properties and the ability of O2 adsorption in details based on the first principle. The result suggested that the performance of ORR of g-C3N4 may be enhanced by O doping, which can uplift the Fermi level of g-C3N4 and weaken the OH- absorption ability to enhance the O2 adsorption ability. After that, we synthetised O/g-C3N4 and S/g-C3N4 to test their ORR performance. According to the result, O doping can significantly enhance the performance of ORR of g-C3N4 which correspond with the calculation result. Then, the photo-assistant method was used to further enhance the ORR of g-C3N4 which was caused by the transition of the photo-induced electrons of g-C3N4 from VB to CB.

Computational study of hydrocarbon adsorption in metal-organic framework Ni2(dhtp).

PubMed

Sun, Xiuquan; Wick, Collin D; Thallapally, Praveen K; McGrail, B Peter; Dang, Liem X

2011-03-31

Enhancing the efficiency of the Rankine cycle, which is utilized for multiple renewable energy sources, requires the use of a working fluid with a high latent heat of vaporization. To further enhance its latent heat, a working fluid can be placed in a metal organic heat carrier (MOHC) with a high heat of adsorption. One such material is Ni\\DOBDC, in which linear alkanes have a higher heat of adsorption than cyclic alkanes. We carried out molecular dynamics simulations to investigate the structural, diffusive, and adsorption properties of n-hexane and cyclohexane in Ni\\DOBDC. The strong binding for both n-hexane and cyclohexane with Ni\\DOBDC is attributed to the increase of the heat of adsorption observed in experiments. Our structural results indicate the organic linkers in Ni\\DOBDC are the primary binding sites for both n-hexane and cyclohexane molecules. However, at all temperatures and loadings examined in present work, n-hexane clearly showed stronger binding with Ni\\DOBDC than cyclohexane. This was found to be the result of the ability of n-hexane to reconfigure its structure to a greater degree than cyclohexane to gain more contacts between adsorbates and adsorbents. The geometry and flexibility of guest molecules were also related to their diffusivity in Ni\\DOBDC, with higher diffusion for flexible molecules. Because of the large pore sizes in Ni\\DOBDC, energetic effects were the dominant force for alkane adsorption and selectivity.

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.

Adsorption kinetics of malachite green onto activated carbon prepared from Tunçbilek lignite.

PubMed

Onal, Y; Akmil-Başar, C; Eren, Didem; Sarici-Ozdemir, Cigdem; Depci, Tolga

2006-02-06

Adsorbent (T3K618) has been prepared from Tunçbilek lignite by chemical activation with KOH. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by t-plot based on N2 adsorption isotherm. The N2 adsorption isotherm of malachite green on T3K618 is type I. The BET surface area of the adsorbent which was primarily contributed by micropores was determined 1000 m2/g. T3K618 was used to adsorb malachite green (MG) from an aqueous solution in a batch reactor. The effects of initial dye concentration, agitation time, initial pH and adsorption temperature have been studied. It was also found that the adsorption isotherm followed both Freundlich and Dubinin-Radushkevich models. However, the Freundlich gave a better fit to all adsorption isotherms than the Dubinin-Radushkevich. The kinetics of adsorption of MG has been tested using pseudo-first-order, pseudo-second-order and intraparticle diffusion models. Results show that the adsorption of MG from aqueous solution onto micropores T3K618 proceeds according to the pseudo-second-order model. The intraparticle diffusion of MG molecules within the carbon particles was identified to be the rate-limiting step. The adsorption of the MG was endothermic (DeltaH degrees = 6.55-62.37 kJ/mol) and was accompanied by an increase in entropy (DeltaS degrees = 74-223 J/mol K) and a decrease in mean value of Gibbs energy (DeltaG degrees = -6.48 to -10.32 kJ/mol) in the temperature range of 20-50 degrees C.

Ammonia Vapor Removal by Cu3(BTC)2 and Its Characterization by MAS NMR

DTIC Science & Technology

2009-01-01

Experimental Section Materials. Cu(acetate)2(H2O), Cu(L-tartrate)3(H2O)3, Cu( CO3 )- Cu(OH)2, 1,3,5-benzenetricarboxylic acid, NH4HCO3, and N,N...for 3 days. The crystals were activated under high vacuum at a temperature of 170 °C. Nitrogen Adsorption Equilibria. Nitrogen adsorption equi- libria...solid (NH4)3BTC. 13C CP-MAS NMR confirmed the identity and purity of the trisubstituted material. BTC-Cu( CO3 )Cu(OH)2-NH4HCO3 Reaction. BTC (100 mg, 480

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

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.

Density functional theory study on the interactions of l-cysteine with graphene: adsorption stability and magnetism

NASA Astrophysics Data System (ADS)

Luo, Huijuan; Li, Hejun; Fu, Qiangang; Chu, Yanhui; Cao, Xiaoyu; Sun, Can; Yuan, Xiaoyan; Liu, Lei

2013-12-01

Understanding the interactions between graphene and biomolecules is of fundamental relevance to the area of nanobiotechnology. Herein, we take l-cysteine as the probe biomolecule and investigate its adsorption on pristine graphene and B-, N-, Al-, Ni-, Ga-, Pd-doped graphene using density functional theory calculations. Three kinds of upright adsorption configurations, via unprotonated functional groups (-SH, -NH2, -COOH), are considered. The calculations reveal pristine graphene physically adsorbs l-cysteine. N-doped graphene shows physisorption towards the S-end and N-end l-cysteine, and chemisorption towards the O-end radical. Strong chemisorption, with site-specific preference, occurs on Al-, Ni-, Ga- and Pd-doped graphene, accompanied by severe structural changes. Spin polarization with an unusual mirror symmetry on Ni- and Pd-doped graphene is induced by chemisorption of unprotonated l-cysteine, except for O-end adsorption on Pd-doped graphene. The magnetization arises mainly from spin polarization of the C 2pz orbital, with a minor magnetism located on Ni or Pd. The influence of van der Waals forces is also evaluated. A thorough analysis of the adsorption stability and magnetism of these systems would be beneficial to facilitate applications in graphene-based biosensing, biomolecule immobilization, magnetic bio-separation and other fields in bionanotechnology.

Some Phthalocyanine and Naphthalocyanine Derivatives as Corrosion Inhibitors for Aluminium in Acidic Medium: Experimental, Quantum Chemical Calculations, QSAR Studies and Synergistic Effect of Iodide Ions.

PubMed

Dibetsoe, Masego; Olasunkanmi, Lukman O; Fayemi, Omolola E; Yesudass, Sasikumar; Ramaganthan, Baskar; Bahadur, Indra; Adekunle, Abolanle S; Kabanda, Mwadham M; Ebenso, Eno E

2015-08-28

The effects of seven macrocyclic compounds comprising four phthalocyanines (Pcs) namely 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (Pc1), 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine (Pc2), 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (Pc3) and 29H,31H-phthalocyanine (Pc4), and three naphthalocyanines namely 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine (nPc1), 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (nPc2) and 2,3-naphthalocyanine (nP3) were investigated on the corrosion of aluminium (Al) in 1 M HCl using a gravimetric method, potentiodynamic polarization technique, quantum chemical calculations and quantitative structure activity relationship (QSAR). Synergistic effects of KI on the corrosion inhibition properties of the compounds were also investigated. All the studied compounds showed appreciable inhibition efficiencies, which decrease with increasing temperature from 30 °C to 70 °C. At each concentration of the inhibitor, addition of 0.1% KI increased the inhibition efficiency compared to the absence of KI indicating the occurrence of synergistic interactions between the studied molecules and I(-) ions. From the potentiodynamic polarization studies, the studied Pcs and nPcs are mixed type corrosion inhibitors both without and with addition of KI. The adsorption of the studied molecules on Al surface obeys the Langmuir adsorption isotherm, while the thermodynamic and kinetic parameters revealed that the adsorption of the studied compounds on Al surface is spontaneous and involves competitive physisorption and chemisorption mechanisms. The experimental results revealed the aggregated interactions between the inhibitor molecules and the results further indicated that the peripheral groups on the compounds affect these interactions. The calculated quantum chemical parameters and the QSAR results revealed the possibility of strong interactions between the studied inhibitors and metal surface. QSAR analysis on the quantum chemical parameters obtained with B3LYP/6-31G (d,p) method show that a combination of two quantum chemical parameters to form a composite index provides the best correlation with the experimental data.

DFT Study of the Oxygen Reduction Reaction Activity on Fe−N4-Patched Carbon Nanotubes: The Influence of the Diameter and Length

PubMed Central

Chen, Xin; Hu, Rui; Bai, Fan

2017-01-01

The influences of diameter and length of the Fe−N4-patched carbon nanotubes (Fe−N4/CNTs) on oxygen reduction reaction (ORR) activity were investigated by density functional theory method using the BLYP/DZP basis set. The results indicate that the stability of the Fe−N4 catalytic site in Fe−N4/CNTs will be enhanced with a larger tube diameter, but reduced with shorter tube length. A tube with too small a diameter makes a Fe−N4 site unstable in acid medium since Fe−N and C−N bonds must be significantly bent at smaller diameters due to hoop strain. The adsorption energy of the ORR intermediates, especially of the OH group, becomes weaker with the increase of the tube diameter. The OH adsorption energy of Fe−N4/CNT with the largest tube diameter is close to that on Pt(111) surface, indicating that its catalytic property is similar to Pt. Electronic structure analysis shows that the OH adsorption energy is mainly controlled by the energy levels of Fe 3d orbital. The calculation results uncover that Fe−N4/CNTs with larger tube diameters and shorter lengths will exhibit better ORR activity and stability. PMID:28772903

An analysis of bipropellant neutralization for spacecraft refueling operations

NASA Technical Reports Server (NTRS)

Kauffman, David

1987-01-01

Refueling of satellites on orbit with storable propellants will involve venting part or all of the pressurant gas from the propellant tanks. This gas will be saturated with propellant vapor, and it may also have significant amounts of entrained fine droplets of propellant. The two most commonly used bipropellants, monomethyl hydrazine (MMH) and nitrogen tetroxide (N2O4), are highly reactive and toxic. Various possible ways of neutralizing the vented propellants are examined. The amount of propellant vented in a typical refueling operation is shown to be in the range of 0.2 to 5% of the tank capacity. Four potential neutralization schemes are examined: chemical decomposition, chemical reaction, condensation and adsorption. Chemical decomposition to essentially inert materials is thermodynamically feasible for both MMH and N2O4. It would be the simplest and easiest neutralization method to implement. Chemical decomposition would require more complex control. Condensation would require a refrigeration system and a very efficent phase separator. Adsorption is likely to be much heavier. A preliminary assessment of the four neutralization shemes is presented, along with suggested research and development plans.

Adsorption of fluoride to UiO-66-NH2 in water: Stability, kinetic, isotherm and thermodynamic studies.

PubMed

Lin, Kun-Yi Andrew; Liu, Yu-Ting; Chen, Shen-Yi

2016-01-01

To provide safe drinking water, fluoride in water must be removed and adsorption processes appear to be the most widely used method. Metal organic frameworks (MOFs) represent a new class of adsorbents that have been used in various adsorption applications. To study the adsorption mechanism of fluoride to MOFs in water and obtain related adsorption parameters, we synthesized a zirconium-based MOF with a primary amine group on its ligand, named UiO-66-NH2. The kinetics, adsorption isotherm and thermodynamics of fluoride adsorption to UiO-66-NH2 were investigated. The crystalline structure of UiO-66-NH2 remained intact and the local structure of zirconium in UiO-66-NH2 did not change significantly after being exposed to fluoride. The kinetics of the fluoride adsorption in UiO-66-NH2 could be well represented by the pseudo second order rate law. The enthalpy of the adsorption indicates that the F(-) adsorption to UiO-66-NH2 was classified as a physical adsorption. However, the comparison between the adsorption capacities of UiO-66-NH2 and UiO-66 suggests that the fluoride adsorption to UiO-66-NH2 might primarily involve a strong interaction between F(-) and the metal site. The fluoride adsorption capacity of UiO-66-NH2 was found to decrease when pH>7. While the presence of chloride/bromide ions did not noticeably change the adsorption capacity of UiO-66-NH2, the ionic surfactants slightly affected the adsorption capacity of UiO-66-NH2. These findings provide insights to further optimize the adsorption process for removal of fluoride using zirconium-based MOFs. Copyright © 2015 Elsevier Inc. All rights reserved.

Effective adsorption of phenolic compound from aqueous solutions on activated semi coke

NASA Astrophysics Data System (ADS)

Gao, Xiaoming; Dai, Yuan; Zhang, Yu; Fu, Feng

2017-03-01

Activated Semi coke was prepared by KOH activation and employed as adsorbent to study adsorption function of phenolic compound from aqueous solutions. The adsorption result showed that the adsorption capacity of the activated semi coke for phenolic compound increased with contact time and adsorbent dosage, and slightly affected by temperature. The surface structure property of the activated semi coke was characterized by N2 adsorption, indicating that the activated semi coke was essentially macroporous, and the BET surface area was 347.39 m2 g-1. Scanning electron microscopy indicated that the surface of the activated semi coke had a high developed pore. The adsorption kinetics were investigated according to pseudofirst order, pseudosecond order and intraparticle diffusion, and the kinetics data were fitted by pseudosecond order model, and intraparticle diffusion was not the only rate-controlling step. Adsorption isotherm was studied by Langmuir, Freundlich, Temkin, Redlich-Peterson, Sips and Toth models. The result indicated that adsorption isotherm data could fit well with Langmuir, Redlich-Peterson, Sips and Toth models.

Macroporous monoliths for trace metal extraction from seawater

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

Yue, Yanfeng; Mayes, Richard; Gill, Gary A.

2015-05-29

The viability of seawater-based uranium recovery depends on the uranium adsorption rate and capacity, since the concentration of uranium in the oceans is relatively low (3.3 μgL⁻¹). An important consideration for a fast adsorption is to maximize the adsorption properties of adsorbents such as surface areas and pore structures, which can greatly improve the kinetics of uranium extraction and the adsorption capacity simultaneously. Following this consideration, macroporous monolith adsorbents were prepared from the copolymerization of acrylonitrile (AN) and N, N’-methylenebis(acrylamide) (MBAAm) based on a cryogel method using both hydrophobic and hydrophilic monomers. The monolithic sorbents were tested with simulated seawatermore » containing a high uranyl concentration (–6 ppm) and the uranium adsorption results showed that the adsorption capacities are strongly influenced by the ratio of monomer to the crosslinker, i.e., the density of the amidoxime groups. The preliminary seawater testing indicates the high salinity content of seawater does not hinder the adsorption of uranium.« less

Adsorption and separation of n/iso-pentane on zeolites: A GCMC study.

PubMed

Fu, Hui; Qin, Hansong; Wang, Yajun; Liu, Yibin; Yang, Chaohe; Shan, Honghong

2018-03-01

Separation of branched chain hydrocarbons and straight chain hydrocarbons is very important in the isomerization process. Grand canonical ensemble Monte Carlo simulations were used to investigate the adsorption and separation of iso-pentane and n-pentane in four types of zeolites: MWW, BOG, MFI, and LTA. The computation of the pure components indicates that the adsorption capacity is affected by physical properties of zeolite, like pore size and structures, and isosteric heat. In BOG, MFI and LTA, the amount of adsorption of n-pentane is higher than iso-pentane, while the phenomenon is contrary in MWW. For a given zeolite, a stronger adsorption heat corresponds to a higher loading. In the binary mixture simulations, the separation capacity of n-and iso-pentane increases with the elevated pressure and the increasing iso-pentane composition. The adsorption mechanism and competition process have been examined. Preferential adsorption contributions prevail at low pressure, however, the size effect becomes important with the increasing pressure, and the relatively smaller n-pentane gradually competes successfully in binary adsorption. Among these zeolites, MFI has the best separation performance due to its high shape selectivity. This work helps to better understand the adsorption and separation performance of n- and iso-pentane in different zeolites and explain the relationship between zeolite structures and adsorption performance. Copyright © 2017 Elsevier Inc. All rights reserved.

Adsorption mechanism of different organic chemicals on fluorinated carbon nanotubes.

PubMed

Li, Hao; Zheng, Nan; Liang, Ni; Zhang, Di; Wu, Min; Pan, Bo

2016-07-01

Multi-walled carbon nanotubes (MC) were fluorinated by a solid-phase reaction method using polytetrafluoroethylene (PTFE). The surface alteration of carbon nanotubes after fluorination (MC-F) was confirmed based on surface elemental analysis, TEM and SEM. The incorporation of F on MC surface was discussed as F incorporation on carbon defects, replacement of carboxyl groups, as well as surface coating of PTFE. The adsorption performance and mechanisms of MC-F for five kinds of representative organic compounds: sulfamethoxazole (SMX), ofloxacin (OFL), norfloxacin (NOR), bisphenol a (BPA) and phenanthrene (PHE) were investigated. Although BET-N2 surface area of the investigated CNTs decreased after fluorination, the adsorption of all five chemicals increased. Because of the glassification of MC-F surface coating during BET-N2 surface area measurement, the accessible surface area of MC-F was underestimated. Desorption hysteresis was generally observed in all the sorption systems in this study, and the desorption hysteresis of MC-F were stronger than the pristine CNTs. The enhanced adsorption of MC-F may be attributed the pores generated on the coated PTFE and the dispersed CNT aggregates due to the increased electrostatic repulsion after fluorination. The rearrangement of the bundles or diffusion of the adsorbates in MC-F inner pores were the likely reason for the strong desorption hysteresis of MC-F. The butterfly structure of BPA resulted in its high sorption and strong desorption hysteresis. The exothermic sorption character of OFL on CNTs resulted in its strong desorption hysteresis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Contribution of tertiary amino groups to Re(VII) biosorption on modified corn stalk: competitiveness and regularity.

PubMed

Lou, Zhenning; Zhao, Ziyi; Li, Yexia; Shan, Weijun; Xiong, Ying; Fang, Dawei; Yue, Shuang; Zang, Shuliang

2013-04-01

The effects of basic strength and steric hindrance of gels modified by dimethylamine, diethylamine, di-n-octylamine and di-2-ethylhexylamine, respectively, on rhenium (Re(VII)) adsorption capacity and selectivity were discussed. By comparing with the adsorption of other coexisting metals, such as Mo(VI), Cu(II), Pb(II), Fe(III), Zn(II), Mn(VII) and Ni(II), the gel modified by di-n-octylamine (DNOA-OCS) showed a high affinity for Re(VII) at higher hydrochloric acid concentration (C(H)(+)≥1.0 mol L(-1)), and the maximum adsorption capacity was 98.69 mg g(-1). This article not only described the adsorption behavior but also suggested isotherms, kinetics and thermodynamics of Re(VII) onto the DNOA-OCS gel in an aqueous medium using several models. Further study on adsorption of rhenium in a fixed-bed column packed with the DNOA-OCS gel under continuous and recirculating modes could confirm that the corn stalk gel modified by di-n-octylamine could be used as the adsorbent of Re(VII) from Mo-containing wastewater. Copyright © 2013 Elsevier Ltd. All rights reserved.

Enhanced removal of humic acid from aqueous solution by novel stabilized nano-amorphous calcium phosphate: Behaviors and mechanisms

NASA Astrophysics Data System (ADS)

Jiang, Ling; Li, Yiming; Shao, Yi; Zhang, Yong; Han, Ruiming; Li, Shiyin; Wei, Wei

2018-01-01

Stabilized nano-amorphous calcium phosphate (nACP) was prepared using polyethylene glycol as stabilizer to obtain a nanosized amorphous adsorbent. The produced nACP was evaluated by using XRD, FTIR, SEM and X-ray photoelectron spectroscopy (XPS). The sedimentation test demonstrated that nACP exhibited better stability than crystallized hydroxyapatite. The adsorption efficiency of the nACP material for aqueous humic acid (HA) was evaluated from the point of view of medium pH, adsorption time, temperature, and ionic strength, as well as the presences of metal ions. The results of the study showed very good adsorption performance towards aqueous HA. The Sips modeling results revealed that the stabilized nACP adsorbent had a considerably high adsorption capacity (248.3 mg/g) for HA at 298 K. The adsorption data fitted well into pseudo-second order and Elovich kinetic models. XPS analyses indicated that HA retention on nACP material might be due to the surface complexation reaction between oxygen-containing group and calcium of HA and nACP, respectively. Moreover, the HA adsorption capacity of nACP could still keep more than 86% after four adsorption-desorption cycles. By taking into account all results it was concluded that the nACP adsorbent leveraged its stability in combination with its high uptake capacity to offer a great promise for HA adsorption from water.

Selective CO2 gas adsorption in the narrow crystalline cavities of flexible peptide metallo-macrocycles.

PubMed

Miyake, Ryosuke; Kuwata, Chika; Masumoto, Yui

2015-02-21

Crystalline peptide Ni(ii)-macrocycles (BF4(-) salt) exhibited moderate CO2 gas adsorption (ca. 6-7 CO2 molecules per macrocycle) into very narrow cavities (narrowest part <2 Å), accompanied by the expansion of the cavities. The BF4(-) salt demonstrated selective uptake of CO2 gas in preference to CH4 and N2 gases.

Enhanced role of Al or Ga-doped graphene on the adsorption and dissociation of N2O under electric field.

PubMed

Lv, Yong-an; Zhuang, Gui-lin; Wang, Jian-guo; Jia, Ya-bo; Xie, Qin

2011-07-21

To find an effective strategy for the capture and decomposition of nitrous oxide (N(2)O) is very important in order to protect the ozone layer and control the effects of global warming. Based on first-principles calculations, such a strategy is proposed by the systemic study of N(2)O interaction with pristine and Al (or Ga)-doped graphene, and N(2)O dissociation on the surface of Al (or Ga)-doped graphene in an applied electric field. The calculated adsorption energy value shows the N(2)O molecule more firmly adsorbs on the surface of Al (or Ga)-doped graphene than that of pristine graphene, deriving from a stronger covalent bond between the N(2)O molecule and the Al (or Ga) atom. Furthermore, our study suggests that N(2)O molecules can be easily decomposed to N(2) and O(2) with the appropriate electric field, which reveals that Al-doped graphene may be a new candidate for control of N(2)O. This journal is © the Owner Societies 2011

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.

Effect of Spin Multiplicity in O2 Adsorption and Dissociation on Small Bimetallic AuAg Clusters.

PubMed

García-Cruz, Raúl; Poulain, Enrique; Hernández-Pérez, Isaías; Reyes-Nava, Juan A; González-Torres, Julio C; Rubio-Ponce, A; Olvera-Neria, Oscar

2017-08-17

To dispose of atomic oxygen, it is necessary the O 2 activation; however, an energy barrier must be overcome to break the O-O bond. This work presents theoretical calculations of the O 2 adsorption and dissociation on small pure Au n and Ag m and bimetallic Au n Ag m (n + m ≤ 6) clusters using the density functional theory (DFT) and the zeroth-order regular approximation (ZORA) to explicitly include scalar relativistic effects. The most stable Au n Ag m clusters contain a higher concentration of Au with Ag atoms located in the center of the cluster. The O 2 adsorption energy on pure and bimetallic clusters and the ensuing geometries depend on the spin multiplicity of the system. For a doublet multiplicity, O 2 is adsorbed in a bridge configuration, whereas for a triplet only one O-metal bond is formed. The charge transfer from metal toward O 2 occupies the σ* O-O antibonding natural bond orbital, which weakens the oxygen bond. The Au 3 ( 2 A) cluster presents the lowest activation energy to dissociate O 2 , whereas the opposite applies to the AuAg ( 3 A) system. In the O 2 activation, bimetallic clusters are not as active as pure Au n clusters due to the charge donated by Ag atoms being shared between O 2 and Au atoms.

Ab initio molecular dynamics determination of competitive O₂ vs. N₂ adsorption at open metal sites of M₂(dobdc).

PubMed

Parkes, Marie V; Greathouse, Jeffery A; Hart, David B; Gallis, Dorina F Sava; Nenoff, Tina M

2016-04-28

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 O2 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 O2 and N2 in the M2(dobdc) (M = Cr, Mn, Fe) MOF series with coordinatively unsaturated metal centers. Effects of metal, temperature, and gas composition are explored. This unique application of AIMD allows us to study in detail the adsorption/desorption processes and to visualize the process of multiple guests competitively binding to coordinatively unsaturated metal sites of a MOF.

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

Milner, Phillip J.; Martell, Jeffrey D.; Siegelman, Rebecca L.

Alkyldiamine-functionalized variants of the metal–organic framework Mg 2(dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising for CO 2 capture applications owing to their unique step-shaped CO 2 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 CO 2 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 CO 2 adsorption/desorption profiles. This two-step behaviormore » likely results from steric interactions between ammonium carbamate chains induced by the asymmetrical hexagonal pores of Mg 2(dobpdc) and leads to decreased CO 2 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 Mg 2(dotpdc) (dotpdc 4- = 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 Mg 2(pc-dobpdc) (pc-dobpdc 4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate, pc = para-carboxylate), which, in contrast to Mg 2(dobpdc), possesses uniformally hexagonal pores. By minimizing the steric interactions between ammonium carbamate chains, these frameworks enable a single CO 2 adsorption/desorption step in all cases, as well as decreased water co-adsorption and increased stability to diamine loss. Functionalization of Mg 2(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.« less

Adsorption property of Br-PADAP-impregnated multiwall carbon nanotubes towards uranium and its performance in the selective separation and determination of uranium in different environmental samples.

PubMed

Khamirchi, Ramzanali; Hosseini-Bandegharaei, Ahmad; Alahabadi, Ahmad; Sivamani, Selvaraju; Rahmani-Sani, Abolfazl; Shahryari, Taher; Anastopoulos, Ioannis; Miri, Mohammad; Tran, Hai Nguyen

2018-04-15

A newer efficient U(VI) ion adsorbent was synthesized by impregnating Br-PADAP [2-(5-Bromo-2-pyridylazo)-5-(diethylamino)phenol] onto multiwall carbon nanotubes (MWCNTs). The effects of various operation conditions on uranium adsorption (i.e., pH contact time, temperature, and initial uranium concentration) were systematically evaluated using batch experiments. The results indicated that the uranium adsorption on modified MWNCTs (5.571 × 10 -3 g/mg × min) reached faster equilibrium than that on pristine MWNCTs (4.832 × 10 -3 g/mg × min), reflecting the involvement of appropriate functional groups of Br-PADAP on the chelating ion-exchange mechanism of U(VI) adsorption. Modified MWNCTs (83.4mg/g) exhibited significantly higher maximum Langmuir adsorption capacity than pristine MWNCTs (15.1mg/g). Approximately 99% of uranium adsorbed onto modified MWNCTs can be desorbed by 2.5mL of 1M HNO 3 solution. Therefore, Br-PADAP-modified MWNCTs can server as a promising adsorbent for efficient uranium adsorption applications in water treatment. Subsequently, the proposed solid-phase extraction (using a mini-column packed with Br-PADAP/MWCNT) was successfully utilized for analysing trace uranium levels by the ICP-AES method in different environmental samples with a pre-concentration factor of 300-fold. The coexistence of other ions demonstrated an insignificant interference on the separative pre-concentration of uranium. the detection limit was recognized as 0.14μg/L, and the relative standard deviation was approximately 3.3% (n = 7). Copyright © 2017 Elsevier Inc. All rights reserved.

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

Removal of uranium from aqueous solution by a low cost and high-efficient adsorbent

NASA Astrophysics Data System (ADS)

Liu, Yun-Hai; Wang, You-Qun; Zhang, Zhi-Bin; Cao, Xiao-Hong; Nie, Wen-Bin; Li, Qin; Hua, Rong

2013-05-01

In this study, a low-cost and high-efficient carbonaceous adsorbent (HTC-COOH) with carboxylic groups was developed for U(VI) removal from aqueous solution compared with the pristine hydrothermal carbon (HTC). The structure and chemical properties of resultant adsorbents were characterized by Scanning electron microscope (SEM), N2 adsorption-desorption, Fourier transform-infrared spectra (FT-IR) and acid-base titration. The key factors (solution pH, contact time, initial U(VI) concentrations and temperature) affected the adsorption of U(VI) on adsorbents were investigated using batch experiments. The adsorption of U(VI) on HTC and HTC-COOH was pH-dependent, and increased with temperature and initial ion concentration. The adsorption equilibrium of U(VI) on adsorbents was well defined by the Langmuir isothermal equation, and the monolayer adsorption capacity of HTC-COOH was found to be 205.8 mg/g. The kinetics of adsorption was very in accordance with the pseudo-second-order rate model. The adsorption processes of U(VI) on HTC and HTC-COOH were endothermic and spontaneous in nature according to the thermodynamics of adsorption. Furthermore, HTC-COOH could selectively adsorption of U(VI) in aqueous solution containing co-existing ions (Mg2+, Co2+, Ni2+, Zn2+ and Mn2+). From the results of the experiments, it is found that the HTC-COOH is a potential adsorbent for effective removal of U(VI) from polluted water.

Water Adsorption on Clean and Defective Anatase TiO2 (001) Nanotube Surfaces: A Surface Science Approach.

PubMed

Kenmoe, Stephane; Lisovski, Oleg; Piskunov, Sergei; Bocharov, Dmitry; Zhukovskii, Yuri F; Spohr, Eckhard

2018-05-31

We use ab initio molecular dynamics simulations to study the adsorption of thin water films with 1 and 2 ML coverage on anatase TiO 2 (001) nanotubes. The nanotubes are modeled as 2D slabs, which consist of partially constrained and partially relaxed structural motifs from nanotubes. The effect of anion doping on the adsorption is investigated by substituting O atoms with N and S impurities on the nanotube slab surface. Due to strain-induced curvature effects, water adsorbs molecularly on defect-free surfaces via weak bonds on Ti sites and H bonds to surface oxygens. While the introduction of an S atom weakens the interaction of the surface with water, which adsorbs molecularly, the presence of an N impurity renders the surface more reactive to water, with a proton transfer from the water film and the formation of an NH group at the N site. At 2 ML coverage, a further surface-assisted proton transfer takes place in the water film, resulting in the formation of an OH - group and an NH 2 + cationic site on the surface.

Identification of adsorption sites in Cu-BTC by experimentation and molecular simulation.

PubMed

García-Pérez, Elena; Gascón, Jorge; Morales-Flórez, Víctor; Castillo, Juan Manuel; Kapteijn, Freek; Calero, Sofía

2009-02-03

The adsorption of several quadrupolar and nonpolar gases on the Metal Organic Framework Cu-BTC has been studied by combining experimental measurements and Monte Carlo simulations. Four main adsorption sites for this structure have been identified: site I close to the copper atoms, site I' in the bigger cavities, site II located in the small octahedral cages, and site III at the windows of the four open faces of the octahedral cage. Our simulations identify the octahedral cages (sites II and III) and the big cages (site I') as the preferred positions for adsorption, while site I, near the copper atoms, remains empty over the entire range of pressures analyzed due to its reduced accessibility. The occupation of the different sites for ethane and propane in Cu-BTC proceeds similarly as for methane, and shows small differences for O2 and N2 that can be attributed to the quadrupole moment of these molecules. Site II is filled predominantly for methane (the nonpolar molecule), whereas for N2, the occupation of II and I' can be considered almost equivalent. The molecular sitting for O2 shows an intermediate behavior between those observed for methane and for N2. The differences between simulated and experimental data at elevated temperatures for propane are tentatively attributed to a reversible change in the lattice parameters of Cu-BTC by dehydration and by temperature, blocking the accessibility to site III and reducing that to site I'. Adsorption parameters of the investigated molecules have been determined from the simulations.

Microcalorimetric, {sup 13}C NMR spectroscopic, and reaction kinetic studies of silica- and L-zeolite-supported platinum catalysts for n-hexane conversion

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

Sharma, S.B.; Ouraipryvan, P.; Nair, H.A.

Reaction kinetics measurement of n-hexane conversion over 4% Pt/SiO{sub 2} and 1% Pt/SiO{sub 2} and 1% Pt/K(Ba)-L catalysts were made at a pressure of 3 atm and temperatures from 698 to 750 K. The rates of benzene and methylcyclopentane formation decrease with time during reaction over Pt/SiO{sub 2}, while 1% Pt/K(Ba)-L does not deactivate significantly. Microcalorimetric measurements at 353 K show that the heat of carbon monoxide adsorption is the same on freshly reduced Pt/SiO{sub 2} and Pt/K(Ba)-L catalysts; however, carbonaceous species that accumulate on Pt/SiO{sub 2} during n-hexane conversion decrease the total number of adsorption sites and the numbermore » of sites that adsorb carbon monoxide strongly. The 1% Pt/K(Ba)-L catalyst retains the adsorptive properties of the freshly reduced catalyst. Nuclear magnetic resonance studies of {sup 13}CO adsorption show that cluster-sized platinum particles are more resistant to deactivation by self-poisoning reactions than larger platinum particles. The greater catalyst stability and higher steady-state activity of L-zeolite-supported platinum catalysts may be attributed to the ability of L-zeolite to stabilize cluster-sized particles under reaction conditions. Differences in dehydrocyclization activity between catalysts may be related to differences in the number of strong adsorption sites that are present under reaction conditions. 31 refs., 7 figs., 4 tabs.« less

Adsorption behavior and mechanism of chloramphenicols, sulfonamides, and non-antibiotic pharmaceuticals on multi-walled carbon nanotubes.

PubMed

Zhao, Heng; Liu, Xue; Cao, Zhen; Zhan, Yi; Shi, Xiaodong; Yang, Yi; Zhou, Junliang; Xu, Jiang

2016-06-05

The adsorption behavior of different emerging contaminants (3 chloramphenicols, 7 sulfonamides, and 3 non-antibiotic pharmaceuticals) on five types of multi-walled carbon nanotubes (MWCNTs), and the underlying factors were studied. Adsorption equilibriums were reached within 12h for all compounds, and well fitted by the Freundlich isotherm model. The adsorption affinity of pharmaceuticals was positively related to the specific surface area of MWCNTs. The solution pH was an important parameter of pharmaceutical adsorption on MWCNTs, due to its impacts on the chemical speciation of pharmaceuticals and the surface electrical property of MWCNTs. The adsorption of ionizable pharmaceuticals decreased in varying degrees with the increased ionic strength. MWCNT-10 was found to be the strongest adsorbent in this study, and the Freundlich constant (KF) values were 353-2814mmol(1-n)L(n)/kg, 571-618mmol(1-n)L(n)/kg, and 317-1522mmol(1-n)L(n)/kg for sulfonamides, chloramphenicols, and non-antibiotic pharmaceuticals, respectively. The different adsorption affinity of sulfonamides might contribute to the different hydrophobic of heterocyclic substituents, while chloramphenicols adsorption was affected by the charge distribution in aromatic rings via substituent effects. Copyright © 2016 Elsevier B.V. All rights reserved.

A combination of computational-experimental study on metal-organic frameworks MIL-53(Al) as sorbent for simultaneous determination of estrogens and glucocorticoids in water and urine samples by dispersive micro-solid-phase extraction coupled to UPLC-MS/MS.

PubMed

Gao, Guihua; Li, Sijia; Li, Shuo; Wang, Yudan; Zhao, Pan; Zhang, Xiangyu; Hou, Xiaohong

2018-04-01

In this work, computational and experimental methods were used to study the adsorption of estrogens and glucocorticoids on metal-organic frameworks (MOFs). Computer-aided molecular simulation was applied to predict the adsorption of eight analytes on four MOFs (MIL-101(Cr), MIL-100(Fe), MIL-53(Al), and UiO-66(Zr)) by examining molecular interactions and calculating free binding energies. Subsequently, the four water-stable MOFs were synthesized and evaluated as adsorbents for the target hormones in aqueous solution. As the MOF exhibiting the highest adsorption capacity in both computations and experiments, MIL-53(Al) was chosen as a sorbent to develop a dispersive micro-solid-phase extraction procedure coupled to ultra-performance liquid chromatography tandem mass spectrometry for simultaneous determination of the target analytes in water and human urine samples. Experimental parameters affecting the extraction recoveries, including pH, ionic strength, MIL-53(Al) amount, extraction time, desorption time, and desorption solvent, were optimized. The optimized method provided a linear range of 0.005025-368.6μg/L with good correlation coefficients (0.9982 ≤ r 2 ≤ 0.9992), and limits of detection (S/N = 3) and quantification (S/N = 10) of 0.0015-1.0μg/L and 0.005-1.8μg/L, respectively. The analyte recoveries were in the range of 80.6-98.4% in water samples and 88.4-93.2% in urine samples. Furthermore, MIL-53(Al) showed good stability over 10 extraction cycles (RSD < 10.0%). Good agreement between experimental measurements and computational results showed the potential of this approach for elucidating adsorption mechanisms and predicating extraction efficiencies for MOFs and targets, providing new directions for the development and utilization of MOFs. Copyright © 2017 Elsevier B.V. All rights reserved.

Adsorption of a single polymer chain on a surface: Effects of the potential range

NASA Astrophysics Data System (ADS)

Klushin, Leonid I.; Polotsky, Alexey A.; Hsu, Hsiao-Ping; Markelov, Denis A.; Binder, Kurt; Skvortsov, Alexander M.

2013-02-01

We investigate the effects of the range of adsorption potential on the equilibrium behavior of a single polymer chain end-attached to a solid surface. The exact analytical theory for ideal lattice chains interacting with a planar surface via a box potential of depth U and width W is presented and compared to continuum model results and to Monte Carlo (MC) simulations using the pruned-enriched Rosenbluth method for self-avoiding chains on a simple cubic lattice. We show that the critical value Uc corresponding to the adsorption transition scales as W-1/ν, where the exponent ν=1/2 for ideal chains and ν≈3/5 for self-avoiding walks. Lattice corrections for finite W are incorporated in the analytical prediction of the ideal chain theory Uc≈((π2)/(24))(W+1/2)-2 and in the best-fit equation for the MC simulation data Uc=0.585(W+1/2)-5/3. Tail, loop, and train distributions at the critical point are evaluated by MC simulations for 1≤W≤10 and compared to analytical results for ideal chains and with scaling theory predictions. The behavior of a self-avoiding chain is remarkably close to that of an ideal chain in several aspects. We demonstrate that the bound fraction θ and the related properties of finite ideal and self-avoiding chains can be presented in a universal reduced form: θ(N,U,W)=θ(NUc,U/Uc). By utilizing precise estimations of the critical points we investigate the chain length dependence of the ratio of the normal and lateral components of the gyration radius. Contrary to common expectations this ratio attains a limiting universal value /=0.320±0.003 only at N˜5000. Finite-N corrections for this ratio turn out to be of the opposite sign for W=1 and for W≥2. We also study the N dependence of the apparent crossover exponent ϕeff(N). Strong corrections to scaling of order N-0.5 are observed, and the extrapolated value ϕ=0.483±0.003 is found for all values of W. The strong correction to scaling effects found here explain why for smaller values of N, as used in most previous work, misleadingly large values of ϕeff(N) were identified as the asymptotic value for the crossover exponent.

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.

Research on dye wastewater decoloration by pulse discharge plasma combined with charcoal derived from spent tea leaves.

PubMed

Wang, Tiecheng; Qu, Guangzhou; Pei, Shuzhao; Liang, Dongli; Hu, Shibin

2016-07-01

Pulsed discharge plasma (PDP) combined with charcoal (PDP-charcoal) was employed to treat dye wastewater, with methyl orange (MO) as the model pollutant. The charcoal was prepared using spent tea leaves and was characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, and Boehm titration to investigate the adsorption and catalytic characteristics before and after adsorption and PDP treatment. The prepared charcoal exhibited a high MO adsorption capacity, and the adsorption process followed the pseudo-second-order kinetic model and the Freundlich model. The MO decoloration efficiency reached 69.8 % within 7.5 min of treatment in the PDP-charcoal system, whereas values of 29.2 and 25.9 % were achieved in individual PDP and charcoal systems, respectively. The addition of n-butanol and H2PO4 (-) presented inhibitive effects on MO decoloration in the PDP system. However, these effects were much weaker in the PDP-charcoal system. In addition, the effects of charcoal on O3 and H2O2 formation were evaluated, and the results showed that both the O3 and H2O2 concentrations decreased in the presence of charcoal. The MO decomposition intermediates were analyzed using UV-Vis spectrometry and GC-MS. 1,4-Benzoquinone, 4-nitrophenol, 4-hydroxyaniline, and N,N'-dimethylaniline were detected. A possible pathway for MO decomposition in this system was proposed.

The Relationship Between DOC Partition Coefficient and Mineral Soil C:N Ratio

NASA Astrophysics Data System (ADS)

Aitkenhead-Peterson, J. A.; McDowell, W. H.

2001-12-01

Since our recent publication showing that soil C:N predicts DOC flux at local and global scales, an effort has been made to understand mechanisms controlling the relationship between the two variables. We have approached this at multiple scales, using soil batch experiments, soil column experiments, and long-term field manipulations. We present here the results from our batch adsorption experiment. Mineral soils from tropical (wet and moist) and temperate (coniferous and hardwood) forests were used to assess DOC adsorption by the initial mass isotherm approach. We found that the DOC partition co-efficient (m) which represents a soil's tendency to adsorb DOC is strongly and inversely related to mineral soil C:N ratio (R2 = 0.99 n = 10 p < 0.001). The intercept of the mass isotherm, or the desorption term, was positively related to mineral soil C:N ratio (R2 = 0.80 n = 10 p < 0.01), but we found that desorption of DOC was more closely correlated with equilibrium DOC concentration (R2 = 0.97 n = 10 p < 0.001) than with mineral soil C:N. The mass isotherm approach is also useful in calculating the reactive soil pool (RSP), the fraction of the soil pool of organic carbon that may be lost to leaching. The RSP was not significantly related to mineral soil C:N, but tropical soils tended to have a larger RSP than temperate soils. Although some of the tropical soils came from areas where the natural forest had been cleared, used for plantations and then abandoned, the relationship between DOC adsorption and mineral soil C:N was not compromised. Watershed soil C:N ratio is an excellent predictor of DOC export because soil C:N is related to physiochemical adsorption processes in mineral soils and biotic production of DOC in organic soil horizons. It appears that soil C:N is a relatively robust predictor of soil solution DOC concentration and surface water DOC export for ecosystems undergoing environmental stress.

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

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.

Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics.

PubMed

Kusaba, Akira; Li, Guanchen; von Spakovsky, Michael R; Kangawa, Yoshihiro; Kakimoto, Koichi

2017-08-15

Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and N ad -H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on N ad -H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches.

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.

A density functional theory study on the adsorption and decomposition of methanol on B12N12 fullerene-like nanocage

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Nurazar, Roghaye

2014-03-01

The adsorption and dissociative reaction of methanol on B12N12 fullerene-like nanocage is investigated by using density functional calculations. Equilibrium geometries, adsorption energies, and electronic properties of CH3OH adsorption on the surface of the B12N12 were identified. The calculated adsorption energies range from -1.3 to -34.9 kcal/mol. It is found that the electrical conductivity of the nanocage can be modified upon the adsorption of CH3OH. The mechanism of methanol decomposition via CO and OH bond scissions is also studied. The results indicate that OH bond scission is the most favorable pathway on the B12N12 surface.

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.

Adsorption of CO2 on KOH activated, N-enriched carbon derived from urea formaldehyde resin: kinetics, isotherm and thermodynamic studies

NASA Astrophysics Data System (ADS)

Tiwari, Deepak; Bhunia, Haripada; Bajpai, Pramod K.

2018-05-01

High surface area nitrogen enriched carbon adsorbents were prepared from a low cost and widely available urea-formaldehyde resin using a standard chemical activation with KOH and characterized using different characterization techniques for their porous structure and surface functional groups. Maximum surface area and total pore volume of 4547 m2 g-1 and 4.50 cm3 g-1 were found by controlling the activation conditions. Nitrogen content of this sample was found to be 5.62%. Adsorption of CO2 uptake for the prepared carbon adsorbents was studied using a dynamic fixed bed adsorption system at different adsorption temperatures (30-100 °C) and at different CO2 concentrations (5-12.5%), relevant from the flue gas point application. Maximum CO2 uptake of 1.40 mmol g-1 for UFA-3-700 at 30 °C under 12.5% CO2 flow was obtained. Complete regenerability of the adsorbents over multiple adsorption-desorption cycles was obtained. Fractional order kinetic model provided best description over all adsorption temperatures and CO2 concentrations. Heterogeneity of the adsorbent surface was confirmed from Temkin adsorption isotherm model fit and isosteric heat of adsorption values. Negative value of ΔG° and ΔH° confirms spontaneous, feasible nature and exothermic nature of adsorption process. Overall, very high surface area of carbon adsorbent makes this adsorbent a new promising carbon material for CO2 capture from power plant flue gas and for other relevant applications.

Interactions of SO{sub x} and NO{sub x} with soot

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

Smith, D.M.; Chughtai, A.R.; Konowalchuk, B.K.

1996-10-01

Studies of the adsorption of oxides of sulfur and nitrogen, and their coadsorption, on black carbon in the form of n-hexane soot have been carried out by microgravimetry, EPR and FTIR spectroscopy over a wide range of experimental conditions. The mechanisms of adsorption of O{sub 2} and NO{sub 2} are entirely different, as reflected by adsorption isotherms, the behavior of carbon`s unpaired electrons, the spectral features of surface species formed, mass changes during adsorption-desorption cycles, and an essential lack of competition for surface sites. Significant effects of temperature, water, SO{sub 2} and NO{sub 2} concentration, O{sub 2}, simulated solar radiation,more » and the presence of trace metals, have been observed and interpreted.« less

One-pot engineering TiO2/graphene interface for enhanced adsorption and photocatalytic degradation of multiple organics.

PubMed

Song, Jianhua; Ling, Yun; Xie, Yu; Liu, Lianjun; Zhu, Huihua

2018-06-13

It is challenging to design a multifunctional structure or composite for simultaneously adsorb and photocatalytic degrade organic pollutants in water. Towards this goal, this work innovatively engineered interfacial sites between TiO2 particles and reduced graphene oxide (RGO) sheets by employing in situ one-pot one-step solvothermal method. The interface was associated with the content of RGO, solvothermal time and solvent ratio of n-pentanol to n-hexane. It was found that when at a moderate amount of RGO (25%), TiO2 nanoparticles were well dispersed on the surface of RGO or wrapped by RGO, thus leading to a fully contact and strong interaction to form Ti - O - C interfacial structure. But when at a low content of RGO (6%), TiO2 aggregates were mixture of nanosheets, nanoparticles and nanorods. 25%RGO/TiO2 also had 175% higher surface area (146m2/g), 95% larger volume (0.339 cm3/g) and smaller band gap than 6%RGO/TiO2. More importantly, 25%RGO/TiO2 demonstrated higher adsorption efficiency (25%) and 4 times faster degradation rate than TiO2 (0%). It also exhibited good capability to eliminate multiple organics and stable long-term cycle performance (up to 93% retention after 30 cycles). Its superiority was attributed to the large surface area and unique interface between TiO2 and RGO, which not only provided more active sites to capture pollutants but also enhanced charge transfer (3 µA/cm2, 5 times higher than TiO2). This work offered a promising way to purify water through engineering new materials structure and integrating adsorption and photodegradation technologies. © 2018 IOP Publishing Ltd.

Ultrasonic assisted synthesis of Bikitaite zeolite: A potential material for hydrogen storage application.

PubMed

Roy, Priyanka; Das, Nandini

2017-05-01

Li containing Bikitaite zeolite has been synthesized by an ultrasound-assisted method and used as a potential material for hydrogen storage application. The Sonication energy was varied from 150W to 250W and irradiation time from 3h to 6h. The Bikitaite nanoparticles were characterized by X-ray diffraction (XRD), infrared (IR) spectral analysis, and field-emission scanning electron microscopy (FESEM) thermo-gravimetrical analysis and differential thermal analysis (TGA, DTA). XRD and IR results showed that phase pure, nano crystalline Bikitaite zeolites were started forming after 3h irradiation and 72h of aging with a sonication energy of 150W and nano crystalline Bikitaite zeolite with prominent peaks were obtained after 6h irradiation of 250W sonic energy. The Brunauer-Emmett-Teller (BET) surface area of the powder by N 2 adsorption-desorption measurements was found to be 209m 2 /g. The TEM micrograph and elemental analysis showed that desired atomic ratio of the zeolite was obtained after 6h irradiation. For comparison, sonochemical method, followed by the hydrothermal method, with same initial sol composition was studied. The effect of ultrasonic energy and irradiation time showed that with increasing sonication energy, and sonication time phase formation was almost completed. The FESEM images revealed that 50nm zeolite crystals were formed at room temperature. However, agglomerated particles having woollen ball like structure was obtained by sonochemical method followed by hydrothermal treatment at 100°C for 24h. The hydrogen adsorption capacity of Bikitaite zeolite with different Li content, has been investigated. Experimental results indicated that the hydrogen adsorption capacities were dominantly related to their surface areas as well as total pore volume of the zeolite. The hydrogen adsorption capacity of 143.2c.c/g was obtained at 77K and ambient pressure of (0.11MPa) for the Bikitaite zeolite with 100% Li, which was higher than the reported values for other zeolites. To the best of our knowledge, there is no report on the synthesis of a Bikitaite zeolite by sonochemical method for H 2 storage. Copyright © 2016. Published by Elsevier B.V.

Adsorption of the natural protein surfactant Rsn-2 onto liquid interfaces.

PubMed

Brandani, Giovanni B; Vance, Steven J; Schor, Marieke; Cooper, Alan; Kennedy, Malcolm W; Smith, Brian O; MacPhee, Cait E; Cheung, David L

2017-03-22

To stabilize foams, droplets and films at liquid interfaces a range of protein biosurfactants have evolved in nature. Compared to synthetic surfactants, these combine surface activity with biocompatibility and low solution aggregation. One recently studied example is Rsn-2, a component of the foam nest of the frog Engystomops pustulosus, which has been predicted to undergo a clamshell-like opening transition at the air-water interface. Using atomistic molecular dynamics simulations and surface tension measurements we study the adsorption of Rsn-2 onto air-water and cyclohexane-water interfaces. The protein adsorbs readily at both interfaces, with adsorption mediated by the hydrophobic N-terminus. At the cyclohexane-water interface the clamshell opens, due to the favourable interaction between hydrophobic residues and cyclohexane molecules and the penetration of cyclohexane molecules into the protein core. Simulations of deletion mutants showed that removal of the N-terminus inhibits interfacial adsorption, which is consistent with the surface tension measurements. Deletion of the hydrophilic C-terminus also affects adsorption, suggesting that this plays a role in orienting the protein at the interface. The characterisation of the interfacial behaviour gives insight into the factors that control the interfacial adsorption of proteins, which may inform new applications of this and similar proteins in areas including drug delivery and food technology and may also be used in the design of synthetic molecules showing similar changes in conformation at interfaces.

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.

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.

Enhanced Cr(VI) removal by polyethylenimine- and phosphorus-codoped hierarchical porous carbons.

PubMed

Chen, Shixia; Wang, Jun; Wu, Zeliang; Deng, Qiang; Tu, Wenfeng; Dai, Guiping; Zeng, Zheling; Deng, Shuguang

2018-08-01

The amino- and phosphorus-codoped (N,P-codoped) porous carbons derived from oil-tea shells were facilely fabricated through a combination of phosphoric acid (H 3 PO 4 ) activation and amino (polyethylenimine, PEI) modification method. The as-synthesized carbon adsorbents were systematically characterized and evaluated for Cr(VI) removal in aqueous solutions. The relationship between adsorbent properties and adsorption behaviors was illustrated. Moreover, the influences of contact time, initial Cr(VI) concentration, pH, coexisting anions and temperature were also investigated. The adsorption behavior of Cr(VI) could be perfectly described by the pseudo-second-order kinetic model and Sips adsorption model. The maximum adsorption capacity of Cr(VI) on the carbon adsorbents synthesized in this work was 355.0 mg/g, and this excellent Cr(VI) capacity could be sustained with other coexisting anions. In addition to high surface area and suitable pore size distribution, the high Cr(VI) removal capacity is induced by rich heteroatoms incorporation and the Cr(VI) removal mechanism was clearly illustrated. Furthermore, the continuous column breakthrough experiment on obtained N,P-codoped carbon was conducted and well fitted by the Thomas model. This work revealed that PEI modification and P-containing groups could significantly enhance Cr(VI) adsorption capacity and make these N,P-codoped biomass-derived carbons potent adsorbents in practical water treatment applications. Copyright © 2018 Elsevier Inc. 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.

Metallic MoN layer and its application as anode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Qiaoxuan; Ma, Jiachen; Lei, Ming; Quhe, Ruge

2018-04-01

Recently, two-dimensional (2D) metallic MoN was manufactured successfully in experiment. Its intrinsic properties remain to be explored theoretically, in depth. The intrinsic properties of a MoN monolayer are investigated by first-principles calculations. The distinct geometric properties of the outermost Mo and N surfaces are discovered. We predict an extremely high work function of 6.3 eV of the N surface, which indicates the great value of the 2D MoN for application in the semiconductor industry. We further explore the potential of 2D MoN as anode material for lithium-ion batteries. It is found that the adsorption energy of a single Li atom on an MoN surface can be as low as -4.04 eV. The small diffusion barriers (0.41 eV) and high theoretical maximum capacity (406 mAh · g-1 with the inclusion of multilayer adsorption) all imply an outstanding lithium-ion battery performance by 2D MoN.

Mechanisms of the oxygen reduction reaction on B- and/or N-doped carbon nanomaterials with curvature and edge effects.

PubMed

Zou, Xiaolong; Wang, Luqing; Yakobson, Boris I

2018-01-18

Despite recent increased research interest in hetero-atom (B and/or N) doping effects on the oxygen reduction reaction (ORR) performance of carbon nanomaterials, microscopic understanding of active catalytic sites and effects of B and/or N doping has not been conclusively reached. Here, through comparative first-principles simulations between BN codoping and isolated B or N doping in both graphene nanoribbons (GNRs) and carbon nanotubes (CNTs), we not only identify active sites in these doped carbon nanomaterials, but elucidate the underlying mechanism of ORR processes. While the distortion of C-C bonds in CNTs leads to strong binding of O 2 , spin density distribution along the edges plays a key role in enhancing the adsorption strength of O 2 on GNRs. The effective adsorption of O 2 facilitates the following elementary reduction reactions. Based on thermodynamic analyses, O 2 adsorption as well as the electron and proton transfer to O atom are identified as key rate-determining steps. For CNTs, a good linear scaling is found between the adsorption energies of key intermediate products and that of atomic O, and thus the latter serves as a good descriptor for ORR activities. Further, N-doped high-quality CNTs are shown to exhibit best performance. For GNRs, due to edge effects, the linear relationship is broken, which promotes the catalytic activities in the BN codoping case. These findings resolve the long-standing controversy on the synergetic effects of B and N codoping, which deepens our understanding of the reaction mechanism. This work might further facilitate the optimization of the doping strategies for high-efficiency carbon-based ORR catalysts.

The importance of surface functional groups in the adsorption of copper onto walnut shell derived activated carbon.

PubMed

Xie, Ruzhen; Jin, Yan; Chen, Yao; Jiang, Wenju

2017-12-01

In this study, activated carbon (AC) was prepared from walnut shell using chemical activation. The surface chemistry of the prepared AC was modified by introducing or blocking certain functional groups, and the role of the different functional groups involved in the copper uptake was investigated. The structural and chemical heterogeneity of the produced carbons are characterized by Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy, Boehm titration method and N 2 /77 K adsorption isotherm analysis. The equilibrium and the kinetics of copper adsorption onto AC were studied. The results demonstrated that the functional groups on AC played an important role in copper uptake. Among various surface functional groups, the oxygen-containing group was found to play a critical role in the copper uptake, and oxidation is the most effective way to improve Cu (II) adsorption onto AC. Ion-exchange was identified to be the dominant mechanism in the copper uptake by AC. Some other types of interactions, like complexation, were also proven to be involved in the adsorption process, while physical force was found to play a small role in the copper uptake. The regeneration of copper-loaded AC and the recovery of copper were also studied to evaluate the reusability of the oxidized AC.

The study of structures and properties of PdnHm(n=1-10, m=1,2) clusters by density functional theory

NASA Astrophysics Data System (ADS)

Wen, Jun-Qing; Chen, Guo-Xiang; Zhang, Jian-Min; Wu, Hua

2018-04-01

The geometrical evolution, local relative stability, magnetism and charge transfer characteristics of PdnHm(n = 1-10, m = 1,2) have been systematically calculated by using density functional theory. The studied results show that the most stable geometries of PdnH and PdnH2 (n = 1-10) can be got by doping one or two H atoms on the sides of Pdn clusters except Pd6H and Pd6H2. It is found that doping one or two H atoms on Pdn clusters cannot change the basic framework of Pdn. The analysis of stability shows that Pd2H, Pd4H, Pd7H, Pd2H2, Pd4H2 and Pd7H2 clusters have higher local relative stability than neighboring clusters. The analysis of magnetic properties demonstrates that absorption of hydrogen atoms decreases the average atomic magnetic moments compared with pure Pdn clusters. More charges transfer from H atoms to Pd atoms for Pd6H and Pd6H2 clusters, demonstrating the adsorption of hydrogen atoms change from side adsorption to surface adsorption.

Novel heavy-metal adsorption material: ion-recognition P(NIPAM-co-BCAm) hydrogels for removal of lead(II) ions.

PubMed

Ju, Xiao-Jie; Zhang, Shi-Bo; Zhou, Ming-Yu; Xie, Rui; Yang, Lihua; Chu, Liang-Yin

2009-08-15

A novel polymeric lead(II) adsorbent is prepared by incorporating benzo-18-crown-6-acrylamide (BCAm) as metal ion receptor into the thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) hydrogel. Both stimuli-sensitive properties and the Pb(2+)-adsorption capabilities of the prepared P(NIPAM-co-BCAm) hydrogels are investigated. The prepared P(NIPAM-co-BCAm) hydrogels exhibit good ion-recognition and Pb(2+)-adsorption characteristics. When crown ether units capture Pb(2+) and form BCAm/Pb(2+) host-guest complexes, the lower critical solution temperature (LCST) of the hydrogel shifts to a higher temperature due to both the repulsion among charged BCAm/Pb(2+) groups and the osmotic pressure within the hydrogel. The adsorption results at different temperatures show that P(NIPAM-co-BCAm) hydrogels adsorb Pb(2+) ions at temperature lower than the LCST, but undergo desorption at temperature higher than the LCST due to the "stretch-to-shrink" configuration change of copolymer networks which is triggered by the change in environmental temperature. This kind of ion-recognition hydrogel is promising as a novel adsorption material for adsorption and separation of Pb(2+) ions. The adsorption and desorption of Pb(2+) could be rationally achieved by simply changing the environmental temperature.

Bio-template-assisted synthesis of hierarchically hollow SiO2 microtubes and their enhanced formaldehyde adsorption performance

NASA Astrophysics Data System (ADS)

Le, Yao; Guo, Daipeng; Cheng, Bei; Yu, Jiaguo

2013-06-01

The indoor air quality is crucial for human health, taking into account that people often spend more than 80% of their time in houses, offices and cars. Formaldehyde (HCHO) is a major pollutant and long-term exposure to HCHO may cause health problems such as nasal tumors and skin irritation. In this work, for the first time, hierarchically hollow silica microtubes (HHSM) were synthesized by a simple sol-gel and calcination method using cetyltrimethyl ammonium bromide (CTAB) and bio-template poplar catkin (PC) as co-templates and the PC/SiO2 weight ratio R was varied from 0, 0.1, 0.3 and 1. The prepared samples were further modified with tetraethylenepentamine (TEPA) and characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), differential thermal analysis (DTA), thermal gravimetric analysis (TGA), and N2 physisorption techniques. This was followed by formaldehyde adsorption tests at ambient temperature. The results showed that all the prepared HHSM samples contained small mesopores with peak pore size at ca. 2.5 nm and large several tens of nanometer-sized pores on the tube wall. The R exhibited an obvious influence on specific surface areas and the sample prepared at R = 0.3 exhibited highest specific surface area (896 m2/g). All the TEPA-modified samples exhibited enhanced formaldehyde adsorption performance. The maximum HCHO adsorption capacity (20.65 mg/g adsorbent) was achieved on the sample prepared at R = 0.3 and modified by 50 wt.% TEPA. The present study will provide new insight for the utilization of bio-template used for the fabrication of inorganic hollow tubes with high HCHO adsorption performance for indoor air purification.

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.

Porous materials as high performance adsorbents for CO2 capture, gas separation and purification

NASA Astrophysics Data System (ADS)

Wang, Jun

Global warming resulted from greenhouse gases emission has received a widespread attention. Among the greenhouse gases, CO2 contributes more than 60% to global warming due to its huge emission amount. The flue gas contains about 15% CO2 with N2 as the balance. If CO2 can be separated from flue gas, the benefit is not only reducing the global warming effect, but also producing pure CO2 as a very useful industry raw material. Substantial progress is urgent to be achieved in an industrial process. Moreover, energy crisis is one of the biggest challenges for all countries due to the short life of fossil fuels, such as, petroleum will run out in 50 years and coal will run out in 150 years according to today's speed. Moreover, the severe pollution to the environment caused by burning fossil fuels requires us to explore sustainable, environment-friendly, and facile energy sources. Among several alternative energy sources, natural gas is one of the most promising alternative energy sources due to its huge productivity, abundant feed stock, and ease of generation. In order to realize a substantial adsorption process in industry, synthesis of new adsorbents or modification of existing adsorbent with improved properties has become the most critical issue. This dissertation reports systemic characterization and development of five serials of novel adsorbents with advanced adsorption properties. In chapter 2, nitrogen-doped Hypercross-linking Polymers (HCPs) have been synthesized successfully with non-carcinogenic chloromethyl methyl ether (CME) as the cross-linking agent within a single step. Texture properties, surface morphology, CO2/N2 selectivity, and adsorption heat have been presented and demonstrated properly. A comprehensive discussion on factors that affect the CO2 adsorption and CO2/N 2 separation has also been presented. It was found that high micropore proportion and N-content could effectively enhance CO2 uptake and CO2/N2 separation selectivity. In chapter 3, a new series of oxygen-doped ACs were synthesized from polyfuran. Different factors that affect the AC formation were investigated, and two kinds of porogens (ZnC12 and KOH) and two active temperatures (600 and 800 °C) were tested. At 298K and 1bar, an excellent selectivity for separating CO2/N2 (41.7) and CO2/CH 4(6.8) gas mixture pairs was obtained on the PF-600 KOH. A breakthrough simulation was also performed to demonstrate the potential of industrial applications. The PF-600 KOH sample showed the best separation result in the simulated adsorption breakthrough as well. In chapter 4, quinone and hydroquinone on the surface of PF-600 ZnC1 2 were integrated. Significantly pore size shrinkage, improved CO 2/N2 and CO2/CH4 IAST selectivity were observed, which is 58.7% and 28.4 % higher than pristine porous carbon at 298K and 1 atm, respectively. In addition, transient breakthrough simulations for CO2/CH4/N2 binary mixtures were conducted in order to demonstrate the good separation performance in fixed bed adsorbers. In chapter 5, a novel nitrogen doped polymer poly(2-phenyl-1,3,6,8tetraazacyclodecane) will be used as the precursor to produce microporous N-doped activated carbons. Three activation temperatures (600, 700, and 800 °C) has been investigated with KOH as the porogen. High nitrogen content has been remained in the resultant carbon materials. Improved CO2 adsorption capacity and selectivites for the separation of CO2/CH4/N2 binary gas mixtures were achieved by the carbon adsorbents due to their N-containing groups, narrow pore size distribution, and large specific surface area. In chapter 6, MOF-derived activated carbons are developed from MIL-100(Al) as hard-template. Direct carbonization of MIL-100, MIL-100(Al)/F-127 composite, and MIL-100(Al)/KOH mixture has been investigated. Pore structure and surface morphology have been demonstrated. CO2/CH4/N2 binary selectivity, adsorption heats, and kinetic selectivity have been calculated. Breakthrough simulation has been conducted to mimic industrial application. We found that resultant carbons showed better CO2 capture ability and selectivity than parental MIL-100(Al).

Metal complexes of the nanosized ligand N-benzoyl-N‧-(p-amino phenyl) thiourea: Synthesis, characterization, antimicrobial activity and the metal uptake capacity of its ligating resin

NASA Astrophysics Data System (ADS)

Elhusseiny, Amel F.; Eldissouky, Ali; Al-Hamza, Ahmed M.; Hassan, Hammed H. A. M.

2015-11-01

The new nanosized N-benzoyl-N‧-(p-amino phenyl) thiourea ligand H2L was synthesized by nanoprecipitation method. The [Cu (H2L)2 Cl]·2H2O, [Zn (H2L)2(OAc)2], [Cd (H2L)2Cl2] and [Hg (H2L)2Cl2] complexes were synthesized and characterized by various physicochemical methods. Results revealed that the ligand act as hypodentate and bonded to the metal ion via the sulfur atom forming mononuclear non-electrolyte diamagnetic complex. Magnetic moment results indicated a reduction of Cu (II) to Cu (I) during the coordination process. Thermal studies demonstrated variable stabilities of the complexes and [Zn (H2L)2(OAc)2] exhibited the highest thermal stability while [Hg (H2L)2Cl2] was volatile. The prepared compounds were screened against different pathogenic microorganisms. The ligand performed high antibacterial activity against certain bacterial strain compared to its complexes, and the standard bacteriocide in use. The ligand was successfully immobilized on modified Amberlite XAD-16 forming the hypodentate ligating resin PS-SO2-H2L. The new resin was characterized and the extent of metal adsorption reached maximum at pH 6.0 for Cu (II), Cd (II) and Ag (I), with an adsorption amount of 4.3, 4.0 and 3.7 mmol g-1 respectively. The nanosized H2L represents a new category of promising adsorbent that would have a practical impact on biological and water treatment applications.

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.

Spin switch in iron phthalocyanine on Au(111) surface by hydrogen adsorption

NASA Astrophysics Data System (ADS)

Wang, Yu; Li, Xiaoguang; Zheng, Xiao; Yang, Jinlong

2017-10-01

The manipulation of spin states at the molecular scale is of fundamental importance for the development of molecular spintronic devices. One of the feasible approaches for the modification of a molecular spin state is through the adsorption of certain specific atoms or molecules including H, NO, CO, NH3, and O2. In this paper, we demonstrate that the local spin state of an individual iron phthalocyanine (FePc) molecule adsorbed on an Au(111) surface exhibits controllable switching by hydrogen adsorption, as evidenced by using first-principles calculations based on density functional theory. Our theoretical calculations indicate that different numbers of hydrogen adsorbed at the pyridinic N sites of the FePc molecule largely modify the structural and electronic properties of the FePc/Au(111) composite by forming extra N-H bonds. In particular, the adsorption of one or up to three hydrogen atoms induces a redistribution of charge (spin) density within the FePc molecule, and hence a switching to a low spin state (S = 1/2) from an intermediate spin state (S = 1) is achieved, while the adsorption of four hydrogen atoms distorts the molecular conformation by increasing Fe-N bond lengths in FePc and thus breaks the ligand field exerted on the Fe 3d orbitals via stronger hybridization with the substrate, leading to an opposite switching to a high-spin state (S = 2). These findings obtained from the theoretical simulations could be useful for experimental manipulation or design of single-molecule spintronic devices.

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

Influence of surface treatments on micropore structure and hydrogen adsorption behavior of nanoporous carbons.

PubMed

Kim, Byung-Joo; Park, Soo-Jin

2007-07-15

The scope of this work was to control the pore sizes of porous carbons by various surface treatments and to investigate the relation between pore structures and hydrogen adsorption capacity. The effects of various surface treatments (i.e., gas-phase ozone, anodic oxidation, fluorination, and oxygen plasma) on the micropore structures of porous carbons were investigated by N(2)/77 K isothermal adsorption. The hydrogen adsorption capacity was measured by H(2) isothermal adsorption at 77 K. In the result, the specific surface area and micropore volume of all of the treated samples were slightly decreased due to the micropore filling or pore collapsing behaviors. It was also found that in F(2)-treated carbons the center of the pore size distribution was shifted to left side, meaning that the average size of the micropores decreased. The F(2)- and plasma-treated samples showed higher hydrogen storage capacities than did the other samples, the F(2)-treated one being the best, indicating that the micropore size of the porous carbons played a key role in the hydrogen adsorption at 77 K.

Adsorption of Reactive Red M-2BE dye from water solutions by multi-walled carbon nanotubes and activated carbon.

PubMed

Machado, Fernando M; Bergmann, Carlos P; Fernandes, Thais H M; Lima, Eder C; Royer, Betina; Calvete, Tatiana; Fagan, Solange B

2011-09-15

Multi-walled carbon nanotubes and powdered activated carbon were used as adsorbents for the successful removal of Reactive Red M-2BE textile dye from aqueous solutions. The adsorbents were characterised by infrared spectroscopy, N(2) adsorption/desorption isotherms and scanning electron microscopy. The effects of pH, shaking time and temperature on adsorption capacity were studied. In the acidic pH region (pH 2.0), the adsorption of the dye was favourable using both adsorbents. The contact time to obtain equilibrium at 298K was fixed at 1h for both adsorbents. The activation energy of the adsorption process was evaluated from 298 to 323K for both adsorbents. The Avrami fractional-order kinetic model provided the best fit to the experimental data compared with pseudo-first-order or pseudo-second-order kinetic adsorption models. For Reactive Red M-2BE dye, the equilibrium data were best fitted to the Liu isotherm model. Simulated dyehouse effluents were used to check the applicability of the proposed adsorbents for effluent treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

Equilibrium and kinetics of adsorption of phosphate onto iron-doped activated carbon.

PubMed

Wang, Zhengfang; Nie, Er; Li, Jihua; Yang, Mo; Zhao, Yongjun; Luo, Xingzhang; Zheng, Zheng

2011-08-01

Two series of activated carbons modified by Fe (II) and Fe (III) (denoted as AC/N-Fe(II) and AC/N-Fe(III)), respectively, were used as adsorbents for the removal of phosphate in aqueous solutions. The synthesized adsorbent materials were investigated by different experimental analysis means. The adsorption of phosphate on activated carbons has been studied in kinetic and equilibrium conditions taking into account the adsorbate concentration, temperature, and solution pH as major influential factors. Maximum removals of phosphate are obtained in the pH range of 3.78-6.84 for both adsorbents. Langmuir isotherm adsorption equation well describes the experimental adsorption isotherms. Kinetic studies revealed that the adsorption process followed a pseudo-second order kinetic model. Results suggest that the main phase formed in AC/N-Fe(II) and AC/N-Fe(III) is goethite and akaganeite, respectively; the presence of iron oxides significantly affected the surface area and the pore structure of the activated carbon. Studies revealed that iron-doped activated carbons were effective in removing phosphate. AC/N-Fe(II) has a higher phosphate removal capacity than AC/N-Fe(III), which could be attributed to its better intra-particle diffusion and higher binding energy. The activation energy for adsorption was calculated to be 22.23 and 10.89 kJ mol(-1) for AC/N-Fe(II) and AC/N-Fe(III), respectively. The adsorption process was complex; both surface adsorption and intra-particle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism.

Adsorption kinetics of alkanethiol-capped gold nanoparticles at the hexane-water interface

NASA Astrophysics Data System (ADS)

Ferdous, Sultana; Ioannidis, Marios A.; Henneke, Dale

2011-12-01

The pendant drop technique was used to characterize the adsorption behavior of n-dodecane-1-thiol and n-hexane-1-thiol-capped gold nanoparticles at the hexane-water interface. The adsorption process was studied by analyzing the dynamic interfacial tension versus nanoparticle concentration, both at early times and at later stages (i.e., immediately after the interface between the fluids is made and once equilibrium has been established). A series of gold colloids were made using nanoparticles ranging in size from 1.60 to 2.85 nm dissolved in hexane for the interfacial tension analysis. Following free diffusion of nanoparticles from the bulk hexane phase, adsorption leads to ordering and rearrangement of the nanoparticles at the interface and formation of a dense monolayer. With increasing interfacial coverage, the diffusion-controlled adsorption for the nanoparticles at the interface was found to change to an interaction-controlled assembly and the presence of an adsorption barrier was experimentally verified. At the same bulk concentration, different sizes of n-dodecane-1-thiol nanoparticles showed different absorption behavior at the interface, in agreement with the findings of Kutuzov et al. (Phys Chem Chem Phys 9:6351-6358, 2007). The experiments additionally demonstrated the important role played by the capping agent. At the same concentration, gold nanoparticles stabilized by n-hexane-1-thiol exhibited greater surface activity than gold nanoparticles of the same size stabilized by n-dodecane-1-thiol. These findings contribute to the design of useful supra-colloidal structures by the self-assembly of alkane-thiol-capped gold nanoparticles at liquid-liquid interfaces.

Molecular adsorption properties of CO and H2O on Au-, Cu-, and AuxCuy-doped MoS2 monolayer

NASA Astrophysics Data System (ADS)

Kadioglu, Yelda; Gökoğlu, Gökhan; Üzengi Aktürk, Olcay

2017-12-01

In this study, we investigate the adsorption properties of Au, Cu, and AuxCuy nanoclusters on MoS2 sheet and the interactions of the adsorbed systems with CO and H2O molecules by using first principles calculations. Results indicate that Au, Cu, or AuxCuy strongly binds to MoS2 monolayer resulting in enhanced chemical activity and sensitivity toward CO and H2O molecules compared to bare MoS2 monolayer. Although both CO and H2O molecules bind weakly to pristine MoS2 monolayer, CO strongly binds to MoS2 sheet in the presence of Au, Cu atoms or AuxCuy clusters. Semiconductor MoS2 monolayer turns into metal upon Au or Cu adsorption. AuxCuy nanocluster adsorption decreases the band gap of MoS2 monolayer acting as a n-type dopant. AuxCuy-doped MoS2 systems have improved adsorption properties for CO and H2O molecules, so the conclusions provided in this study can be useful as a guide for next generation device modeling.

Graphene oxide-TiO2 composite solid phase extraction combined with graphite furnace atomic absorption spectrometry for the speciation of inorganic selenium in water samples.

PubMed

Zhang, Yanan; Chen, Beibei; Wu, Shaowei; He, Man; Hu, Bin

2016-07-01

In this paper, a method of graphene oxide (GO)-TiO2 composite solid phase extraction followed by graphite furnace atomic absorption spectrometry (GFAAS) detection was proposed for the speciation of inorganic selenium in environmental waters. The adsorption behavior of inorganic Se(IV) and Se(VI) on the GO-TiO2(1:1) composite was investigated. It was found that Se(IV) was quantitatively retained on the GO-TiO2 composites within a wide pH range of 0.5-10, while Se(VI) was quantitatively adsorbed on GO-TiO2(1:1) composite at pH 0.5-2, and no obvious adsorption of Se(VI) within the pH range of 4-10 was found. By selecting pH 6.0, Se(IV) could be easily determined. After reduction of Se(VI), total Se was determined by the proposed method, and Se(VI) was calculated as the difference between the total Se and Se(IV). The factors affecting the separation/preconcentration of Se(IV) and Se(VI) were studied. Under the optimum conditions, the isothermal adsorption of Se(IV) on the GO-TiO2(1:1) composite fitted Langmuir model; a linear range over 0.1-12ngmL(-1) was obtained. The limit of detection (LOD) and precision of the method for Se(IV) was 0.04ngmL(-1) and 9.4% (cSe(IV)=0.5ngmL(-1), n=7), respectively. In order to verify the accuracy of the method, a standard water sample (GSBZ50031-94) was analyzed, and the determined value was in a good agreement to the certified value. The established method was applied to inorganic Se speciation in environmental water samples and the recovery of 87.4-102% was obtained for the spiked samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Ching-Yuan Chang; Wen-Tien Tsai; Horng-Chia Lee

Such thermodynamic properties as enthalpy, free energy, and entropy of adsorption have been computed for N,N-dimethylformamide (DMF) vapor on two commercial adsorbents: coconut shell Type PCB of activated carbon and Type DAY of hydrophobic zeolite. The computation is based on the Langmuir adsorption isotherms obtained at 293, 303, and 313 K as reported by Tsai et al. The laden adsorbents were regenerated with hot inert nitrogen gas and studied by thermal gravimetric analysis at three different heating rates. The apparent activation energies (E{sub des}) of thermal desorption were determined by using the Friedman method. The zeolite DAY has an adsorptionmore » potential higher than that of activated carbon PCB as indicated by the more negative value of the adsorption enthalpy of DMF vapor. The average value of E{sub des} of zeolite DAY is larger than that of activated carbon PCB.« less

Modification of bamboo-based activated carbon using microwave radiation and its effects on the adsorption of methylene blue

NASA Astrophysics Data System (ADS)

Liu, Qing-Song; Zheng, Tong; Li, Nan; Wang, Peng; Abulikemu, Gulizhaer

2010-03-01

Modification of bamboo-based activated carbon was carried out in a microwave oven under N 2 atmosphere. The virgin and modified activated carbons were characterized by means of low temperature N 2 adsorption, acid-base titration, point of zero charge (pH pzc) measurement, FTIR and XPS spectra. A gradual decrease in the surface acidic groups was observed during the modification, while the surface basicity was enhanced to some extent, which gave rise to an increase in the pH pzc value. The species of the functional groups and relative content of various elements and groups were given further analysis using FTIR and XPS spectra. An increase in the micropores was found at the start, and the micropores were then extended into larger ones, resulting in an increase in the pore volume and average pore size. Adsorption studies showed enhanced adsorption of methylene blue on the modified activated carbons, caused mainly by the enlargement of the micropores. Adsorption isotherm fittings revealed that Langmuir and Freundlich models were applicable for the virgin and modified activated carbons, respectively. Kinetic studies exhibited faster adsorption rate of methylene blue on the modified activated carbons, and the pseudo-second-order model fitted well for all of the activated carbons.

Effect of pre-pyrolysis mode on simultaneous introduction of nitrogen/oxygen-containing functional groups into the structure of bagasse-based mesoporous carbon and its influence on Cu(II) adsorption.

PubMed

Wan, Zeqing; Li, Kunquan

2018-03-01

A convenient effective microwave pre-pyrolysis treatment to synthesize biomass-based mesoporous carbon with higher nitrogen/oxygen-chelating adsorption for Cu(II) is reported here, in which phosphoric acid impregnated bagasse was used as a microwave absorber and porogen. For comparison, conventional electric-heating pyrolyzed carbon was prepared and doped with nitrogen/oxygen groups. Nitrogen adsorption, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS) and batch adsorption were employed to investigate the effects of the two pre-pyrolysis modes on the sample physicochemical and Cu(II) adsorptive properties. The 22-min-microwave-pyrolyzed bagasse mesoporous activated carbon (MBAC, 85.32% mesoporosity) contained 10.52% O, which is 3.94% more than electric-heating pyrolyzed mesoporous activated carbon (89.52% mesoporosity). After electrophilic aromatic substitutions of N/O doping, the former possessed more N (5.83%) and more O (21.40%), confirming that time-saving energy-efficient microwave pyrolysis favors the formation of defective C/O atoms in or at the edges of the graphite layer of MBAC, which are highly active and tend to act as preferred reactive positions for the doping of N/O-containing groups simultaneously compared with conventional electric-heating pyrolysis. These N and O species existed mainly as COOH, OH, NH and NH 2 functional groups, and were confirmed by XPS to be active sites for metal binding via electrostatic attraction, hydrogen bonding, a chelate effect and complexation, resulting in the great enhancement of Cu(II) adsorption. Langmuir isotherm and pseudo-second-order kinetic fitting further proved that Cu(II) adsorption by N/O-doped MBAC is ascribed mainly to chemisorption. Therefore, rapid microwave pre-pyrolysis provides a promising route to prepare excellent-performance N/O-doped carbon adsorbents. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorptive Removal of Nitrate from Aqueous Solution Using Nitrogen Doped Activated Carbon.

PubMed

Machida, Motoi; Goto, Tatsuru; Amano, Yoshimasa; Iida, Tatsuya

2016-01-01

Activated carbon (AC) has been widely applied for adsorptive removal of organic contaminants from aqueous phase, but not for ionic pollutants. In this study, nitrogen doped AC was prepared to increase the adsorption capacity of nitrate from water. AC was oxidized with (NH 4 ) 2 S 2 O 8 solution to maximize oxygen content for the first step, and then NH 3 gas treatment was carried out at 950°C to aim at forming quaternary nitrogen (N-Q) species on AC surface (Ox-9.5AG). Influence of solution pH was examined so as to elucidate the relationship between surface charge and adsorption amounts of nitrate. The results showed that Ox-9.5AG exhibited about twice higher adsorption capacity than non-treatment AC at any initial nitrate concentration and any equilibrium solution pH (pH e ) investigated. The more decrease in pH e value, the more adsorption amount of negatively charged nitrate ion, because the surface charge of AC and Ox-9.5AG could become more positive in acidic solution. The oxidation and consecutive ammonia treatments lead to increase in nitrogen content from 0.35 to 6.4% and decrease in the pH of the point of zero charge (pH pzc ) from 7.1 to 4.0 implying that positively charged N-Q of a Lewis acid was created on the surface of Ox-9.5AG. Based on a Langmuir data analysis, maximum adsorption capacity attained 0.5-0.6 mmol/g of nitrate and adsorption affinity was 3.5-4.0 L/mmol at pH e 2.5 for Ox-9.5AG.

Adsorption of radionuclides on the monolayer MoS2

NASA Astrophysics Data System (ADS)

Zhao, Qiang; Zhang, Zheng; Ouyang, Xiaoping

2018-04-01

How to remove radionuclides from radioactive wastewater has long been a difficult problem, especially in nuclear accidents. In this paper, the adsorption of radionuclides Cs, Sr, and Ba on the monolayer MoS2 was investigated by using the first principles calculation method. Through the calculation of adsorption energy and Hirshfeld charge of the radionuclides on the monolayer MoS2 at six adsorption sites, the results show that all of the radionuclides chemisorbed on the monolayer MoS2, and the adsorption strength of these three kinds of radionuclides on the monolayer MoS2 is Ba > Sr > Cs. This work might shed some light on the treatment of the radioactive wastewater.

A density functional study on adsorption and dissociation of O 2 on Ir(1 0 0) surface

NASA Astrophysics Data System (ADS)

Erikat, I. A.; Hamad, B. A.; Khalifeh, J. M.

2011-06-01

The adsorption and the reaction barrier for the dissociation of O 2 on Ir(1 0 0) surface are studied using periodic self-consistent density functional theory (DFT) calculations. Dissociative adsorption is found to be energetically more favorable compared to molecular adsorption. Parallel approaches Prl1 and Prl2 on a hollow site with the same adsorption energy of -3.93 eV for both of them are found to have the most energetically preferred sites of adsorptions among all the studied cases. Hybridization between p-O 2 and d-metal orbitals is responsible for the dissociative adsorption. The minimum energy path is determined by using the nudge elastic band method (NEB). We found that the dissociation occurs immediately and very early in the dissociation path with a small activation barrier (0.26 eV), which means that molecular adsorption of O 2 on Ir(1 0 0) surface occurs at very low temperatures; this is consistent with previous experimental and theoretical studies on Ir surfaces.

Persimmon leaf bio-waste for adsorptive removal of heavy metals from aqueous solution.

PubMed

Lee, Seo-Yun; Choi, Hee-Jeong

2018-03-01

The aim of this study was to investigate heavy metal removal using waste biomass adsorbent, persimmon leaves, in an aqueous solution. Persimmon leaves, which are biomaterials, have a large number of hydroxyl groups and are highly suitable for removal of heavy metals. Therefore, in this study, we investigated the possibility of removal of Cu, Pb, and Cd in aqueous solution by using raw persimmon leaves (RPL) and dried persimmon leaves (DPL). Removal of heavy metals by RPL and DPL showed that DPL had a 10%-15% higher removal than RPL, and the order of removal efficiency was found to be Pb > Cu > Cd. The pseudo-second order model was a better fit to the heavy metal adsorption experiments using RPL and DPL than the pseudo-first order model. The adsorption of Cu, Pb, and Cd by DPL was more suitable with the Freundlich isothermal adsorption and showed an ion exchange reaction which occurred in the uneven adsorption surface layer. The maximum adsorption capacity of Cu, Pb, and Cd was determined to be 19.42 mg/g, 22.59 mg/g, and 18.26 mg/g, respectively. The result of the adsorption experiments showed that the n value was higher than 2 regardless of the dose, indicating that the heavy metal adsorption on DPL was easy. In the thermodynamic experiment, ΔG° was a negative value, and ΔH° and ΔS° were positive values. It can be seen that the heavy metal adsorption process using DPL was spontaneous in nature and was an endothermic process. Moreover, as the temperature increased, the adsorption increased, and the affinity of heavy metal adsorption to DPL was very good. This experiment, in which heavy metals are removed using the waste biomass of persimmon leaves is an eco-friendly new bioadsorbent method because it can remove heavy metals without using chemicals while utilizing waste recycling. Copyright © 2018 Elsevier Ltd. All rights reserved.

A Comparative Study of the Adsorption of Methylene Blue onto Synthesized Nanoscale Zero-Valent Iron-Bamboo and Manganese-Bamboo Composites

PubMed Central

Shaibu, Solomon E.; Adekola, Folahan A.; Adegoke, Halimat I.; Ayanda, Olushola S.

2014-01-01

In this study, bamboo impregnated with nanoscale zero-valent iron (nZVI) and nanoscale manganese (nMn) were prepared by the aqueous phase borohydride reduction method and characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and PIXE analysis. The synthesized nMn-bamboo and nZVI-bamboo composites were subsequently applied to the sorption of methylene blue (MB) dye from aqueous solution. The adsorption of MB dye was investigated under various experimental conditions such as pH, contact time, initial concentration of MB dye and adsorbent dosage. The results showed that the synthesized nZVI-bamboo composite was more effective than nMn-bamboo composite in terms of higher MB dye adsorption capacity of 322.5 mg/g compared to 263.5 mg/g of nMn-bamboo composite. At a concentration of 140 mg/L MB dye, 0.02 g of nZVI-bamboo and nMn-bamboo composites resulted in 79.6% and 78.3% removal, respectively, at 165 rpm, contact time of 120 min and at a solution pH of 7.6. The equilibrium data was best represented by Freundlich isotherm model and the pseudo-second order kinetic model better explained the kinetic data for both nZVI-bamboo and nMn-bamboo composites. PMID:28788688

ZnO nanowires: Synthesis and charge transfer mechanism in the detection of ammonia vapour

NASA Astrophysics Data System (ADS)

Nancy Anna Anasthasiya, A.; Ramya, S.; Rai, P. K.; Jeyaprakash, B. G.

2018-01-01

ZnO nanowires with hexagonal wurtzite structure were grown on the glass substrate using Successive Ionic Layer Adsorption and Reaction (SILAR) method. Both experimental and theoretical studies demonstrated that NH3 chemisorbed and transferred the charge to the surface of the nanowire via its nitrogen site to the zinc site of ZnO nanowires, leading to the detection of NH3 vapour. The adsorbed ammonia dissociated into NH2 and H due to steric repulsion, and then into N2 and H2 gas. The formation of the N2 gas during the desorption process confirmed by observing peak at 14 and 28 m/z in the GC-MS spectrum.

Gas chromatography using ice-coated fused silica columns: study of adsorption of sulfur dioxide on water ice

NASA Astrophysics Data System (ADS)

Langenberg, Stefan; Schurath, Ulrich

2018-05-01

The well established technique of gas chromatography is used to investigate interactions of sulfur dioxide with a crystalline ice film in a fused silica wide bore column. Peak shape analysis of SO2 chromatograms measured in the temperature range 205-265 K is applied to extract parameters describing a combination of three processes: (i) physisorption of SO2 at the surface, (ii) dissociative reaction with water and (iii) slow uptake into bulk ice. Process (ii) is described by a dissociative Langmuir isotherm. The pertinent monolayer saturation capacity is found to increase with temperature. The impact of process (iii) on SO2 peak retention time is found to be negligible under our experimental conditions. By analyzing binary chromatograms of hydrophobic n-hexane and hydrophilic acetone, the premelt surface layer is investigated in the temperature range 221-263 K, possibly giving rise to irregular adsorption. Both temperature dependencies fit simple van't Hoff equations as expected for process (i), implying that irregular adsorption of acetone is negligible in the investigated temperature range. Adsorption enthalpies of -45 ± 5 and -23±2 kJ mol-1 are obtained for acetone and n-hexane. The motivation of our study was to assess the vertical displacement of SO2 and acetone in the wake of aircraft by adsorption on ice particles and their subsequent sedimentation. Our results suggest that this transport mechanism is negligible.

Effective adsorption of malachite green using magnetic barium phosphate composite from aqueous solution

NASA Astrophysics Data System (ADS)

Zhang, Fan; Wei, Zhong; Zhang, Wanning; Cui, Haiyan

2017-07-01

Magnetic Ba3(PO4)2/Fe3O4-nanoparticle (called BPFN) was prepared, characterized, and developed as a low-cost adsorbent for malachite green (MG) from aqueous solution. Factors such as adsorption temperature, pH of solution, dosage of adsorbent, adsorption kinetics and isotherms were investigated. The maximum adsorption capacity obtained in this work was 1639 mg g- 1 at 45 °C and pH 6. The adsorption process fitted the pseudo-first-order kinetic model and Langmuir isotherm model. Evidences from zeta potential, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) data revealed that the adsorption process was driven by electrostatic attraction, the interaction between Lewis base sbnd N(CH3)2 in MG and Lewis acid Ba sites of BPFN. In addition, the BPFN could be easily regenerated by a magnet and the adsorption capacity maintained at 70% after five cycles. The present study suggests that the BPFN had high potential of removing MG from wastewater.

Experimental screening of porous materials for high pressure gas adsorption and evaluation in gas separations: application to MOFs (MIL-100 and CAU-10).

PubMed

Wiersum, Andrew D; Giovannangeli, Christophe; Vincent, Dominique; Bloch, Emily; Reinsch, Helge; Stock, Norbert; Lee, Ji Sun; Chang, Jong-San; Llewellyn, Philip L

2013-02-11

A high-throughput gas adsorption apparatus is presented for the evaluation of adsorbents of interest in gas storage and separation applications. This instrument is capable of measuring complete adsorption isotherms up to 40 bar on six samples in parallel using as little as 60 mg of material. Multiple adsorption cycles can be carried out and four gases can be used sequentially, giving as many as 24 adsorption isotherms in 24 h. The apparatus has been used to investigate the effect of metal center (MIL-100) and functional groups (CAU-10) on the adsorption of N(2), CO(2), and light hydrocarbons on MOFs. This demonstrates how it can serve to evaluate sample quality and adsorption reversibility, to determine optimum activation conditions and to estimate separation properties. As such it is a useful tool for the screening of novel adsorbents for different applications in gas separation, providing significant time savings in identifying potentially interesting materials.

Nanocomposites of zeolite-titanium(IV) oxides: Preparation, characterization, adsorption, photocatalytic and bactericidal properties

NASA Astrophysics Data System (ADS)

Domoroshchina, Elena; Kravchenko, Galina; Kuz'micheva, Galina

2017-06-01

NT/zeolite nanocomposites (NT - nanosized titanium(IV) oxides: η-phase and Hombifine N with anatase; zeolite: Beta(25), ZSM-5 with different modules Si/Al, MOR, or Y) have been obtained by two methods: modified cold-impregnation method (method 1) and in situ method of introduction of zeolites into the reaction mixture during the synthesis of NT by hydrolysis of TiOSO4×xH2SO4×yH2O or TiOSO4×2H2O aqueous solutions (method 2), performed for the first time. According to the X-ray data, the following differences in the NT:zeolite systems under investigation have been revealed: the mixture of zeolites and NT in nanocrystalline (Hombifine N/zeolite) or amorphous states (η-phase/zeolite, except for η-phase/MOR, where NT peaks are absent) (method 1), and the mixture of Y-zeolite and amorphous NT or only Y-zeolite without NT (method 2), which indicates the different levels of interaction between NT and zeolites in the systems studied. The best characteristics of properties (photocatalytic, adsorption, and antibacterial) have been revealed in the nanocomposites synthesized by the method 2. The correlation between the photoreaction rate constant (the k value) under UV irradiation in the presence of nanocomposites (kmax for NT/ZSM-5(12)) and the type of precursor, its pH, synthesis duration, NT:zeolite ratio, organic dye composition (methyl orange or Rhodamine G) has been established. The highest degree of extraction of P(V) ions from model aqueous systems has been observed in the presence of nanocomposites with the largest total surface area of all particles (Rmax = 99.48% for NT/MOR). The correlation between the sorption degree of P(V) ions and the modulus of zeolite is possible. Antibacterial activity in the dark towards Escherichia coli has been found for Y and Beta(25) zeolites and nanocomposites on their basis (methods 1 and 2) with the maximum diameter of bacterial growth inhibition (18 mm) obtained for NT/Beta(25) (method 2) synthesized only from TiOSO4×xH2SO4×yH2O precursor.

Influence of wide band gap oxide substrates on the photoelectrochemical properties and structural disorder of CdS nanoparticles grown by the successive ionic layer adsorption and reaction (SILAR) method

PubMed Central

Malashchonak, Mikalai V; Korolik, Olga V; Streltsov, Еugene А; Kulak, Anatoly I

2015-01-01

Summary The photoelectrochemical properties of nanoheterostructures based on the wide band gap oxide substrates (ZnO, TiO2, In2O3) and CdS nanoparticles deposited by the successive ionic layer adsorption and reaction (SILAR) method have been studied as a function of the CdS deposition cycle number (N). The incident photon-to-current conversion efficiency (IPCE) passes through a maximum with the increase of N, which is ascribed to the competition between the increase in optical absorption and photocarrier recombination. The maximal IPCE values for the In2O3/CdS and ZnO/CdS heterostructures are attained at N ≈ 20, whereas for TiO2/CdS, the appropriate N value is an order of magnitude higher. The photocurrent and Raman spectroscopy studies of CdS nanoparticles revealed the occurrence of the quantum confinement effect, demonstrating the most rapid weakening with the increase of N in ZnO/CdS heterostructures. The structural disorder of CdS nanoparticles was characterized by the Urbach energy (E U), spectral width of the CdS longitudinal optical (LO) phonon band and the relative intensity of the surface optical (SO) phonon band in the Raman spectra. Maximal values of E U (100–120 meV) correspond to СdS nanoparticles on a In2O3 surface, correlating with the fact that the CdS LO band spectral width and intensity ratio for the CdS SO and LO bands are maximal for In2O3/CdS films. A notable variation in the degree of disorder of CdS nanoparticles is observed only in the initial stages of CdS growth (several tens of deposition cycles), indicating the preservation of the nanocrystalline state of CdS over a wide range of SILAR cycles. PMID:26734517

Influence of wide band gap oxide substrates on the photoelectrochemical properties and structural disorder of CdS nanoparticles grown by the successive ionic layer adsorption and reaction (SILAR) method.

PubMed

Malashchonak, Mikalai V; Mazanik, Alexander V; Korolik, Olga V; Streltsov, Еugene А; Kulak, Anatoly I

2015-01-01

The photoelectrochemical properties of nanoheterostructures based on the wide band gap oxide substrates (ZnO, TiO2, In2O3) and CdS nanoparticles deposited by the successive ionic layer adsorption and reaction (SILAR) method have been studied as a function of the CdS deposition cycle number (N). The incident photon-to-current conversion efficiency (IPCE) passes through a maximum with the increase of N, which is ascribed to the competition between the increase in optical absorption and photocarrier recombination. The maximal IPCE values for the In2O3/CdS and ZnO/CdS heterostructures are attained at N ≈ 20, whereas for TiO2/CdS, the appropriate N value is an order of magnitude higher. The photocurrent and Raman spectroscopy studies of CdS nanoparticles revealed the occurrence of the quantum confinement effect, demonstrating the most rapid weakening with the increase of N in ZnO/CdS heterostructures. The structural disorder of CdS nanoparticles was characterized by the Urbach energy (E U), spectral width of the CdS longitudinal optical (LO) phonon band and the relative intensity of the surface optical (SO) phonon band in the Raman spectra. Maximal values of E U (100-120 meV) correspond to СdS nanoparticles on a In2O3 surface, correlating with the fact that the CdS LO band spectral width and intensity ratio for the CdS SO and LO bands are maximal for In2O3/CdS films. A notable variation in the degree of disorder of CdS nanoparticles is observed only in the initial stages of CdS growth (several tens of deposition cycles), indicating the preservation of the nanocrystalline state of CdS over a wide range of SILAR cycles.

Adsorption and catalytic properties of sulfated aluminum oxide modified with cobalt ions

NASA Astrophysics Data System (ADS)

Lanin, S. N.; Bannykh, A. A.; Vlasenko, E. V.; Krotova, I. N.; Obrezkov, O. N.; Shilina, M. I.

2017-01-01

The adsorption properties of sulfated aluminum oxide (9% SO 4 2- /γ-Al2O3) and a cobalt-containing composite (0.5%Co/SO 4 2- /γ-Al2O3) based on it are studied via dynamic sorption. The adsorption isotherms of such test adsorbates as n-hydrocarbons (C6-C8), benzene, ethylbenzene, chloroform, and diethyl ether are measured, and their isosteric heats of adsorption are calculated. It is shown that the surface sulfation of aluminum oxide substantially improves its electron-accepting properties, and so the catalytic activity of SO 4 2- /γ-Al2O3 in the liquid-phase alkylation of benzene with octene-1 at temperatures of 25-120°C is one order of magnitude higher than for the initial aluminum oxide. It is established that additional modification of sulfated aluminum oxide with cobalt ions increases the activity of this catalyst by 2-4 times. It is shown that adsorption sites capable of strong specific adsorption with both donating (aromatics, diethyl ether chemosorption) and accepting molecules (chloroform) form on the surface of sulfated γ-Al2O3 promoted by cobalt salt.

Adsorption Characteristics of Bixin on Acid- and Alkali-Treated Kaolinite in Aprotic Solvents

PubMed Central

Rahmalia, Winda; Fabre, Jean-François; Usman, Thamrin

2018-01-01

The adsorption of bixin in aprotic solvents onto acid- and alkali-treated kaolinite was investigated. Kaolinite was treated three times, for 6 h each, with 8 M HCl or 5 M KOH. The adsorbents were characterized by XRD, FT-IR, EDS, and BET-N2. The effects of contact time and dye concentration on adsorption capacity and kinetics, electronic transition of bixin before and after adsorption, and also mechanism of bixin-kaolinite adsorption were investigated. Dye adsorption followed pseudo-second order kinetics and was faster in acetone than in dimethyl carbonate. The best adsorption results were obtained for KOH-treated kaolinite. In both of the solvents, the adsorption isotherm followed the Langmuir model and adsorption capacity was higher in dimethyl carbonate (q m = 0.43 mg/g) than in acetone (0.29 mg/g). The adsorption capacity and kinetics of KOH-treated kaolinite (q m = 0.43 mg/g, k 2 = 3.27 g/mg·min) were better than those of HCl-treated kaolinite (q m = 0.21 mg/g, k 2 = 0.25 g/mg·min) and natural kaolinite (q m = 0.18 mg/g, k 2 = 0.32 g/mg·min). There are shift in the band position of maximum intensity of bixin after adsorption on this adsorbent. Adsorption in this system seemed to be based essentially on chemisorption due to the electrostatic interaction of bixin with the strong basic and reducing sites of kaolinite. PMID:29581720

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.

Photoluminescence Probing of Complex H2O Adsorption on InGaN/GaN Nanowires.

PubMed

Maier, Konrad; Helwig, Andreas; Müller, Gerhard; Hille, Pascal; Teubert, Jörg; Eickhoff, Martin

2017-02-08

We demonstrate that the complex adsorption behavior of H 2 O on InGaN/GaN nanowire arrays is directly revealed by their ambient-dependent photoluminescence properties. Under low-humidity, ambient-temperature, and low-excitation-light conditions, H 2 O adsorbates cause a quenching of the photoluminescence. In contrast, for high humidity levels, elevated temperature, and high excitation intensity, H 2 O adsorbates act as efficient photoluminescence enhancers. We show that this behavior, which can only be detected due to the low operation temperature of the InGaN/GaN nanowires, can be explained on the basis of single H 2 O adsorbates forming surface recombination centers and multiple H 2 O adsorbates forming surface passivation layers. Reversible creation of such passivation layers is induced by the photoelectrochemical splitting of adsorbed water molecules and by the interaction of reactive H 3 O + and OH - ions with photoactivated InGaN surfaces. Due to electronic coupling of adsorbing molecules with photoactivated surfaces, InGaN/GaN nanowires act as sensitive nanooptical probes for the analysis of photoelectrochemical surface processes.

Aspartic acid incorporated monolithic columns for affinity glycoprotein purification.

PubMed

Armutcu, Canan; Bereli, Nilay; Bayram, Engin; Uzun, Lokman; Say, Rıdvan; Denizli, Adil

2014-02-01

Novel aspartic acid incorporated monolithic columns were prepared to efficiently affinity purify immunoglobulin G (IgG) from human plasma. The monolithic columns were synthesised in a stainless steel HPLC column (20 cm × 5 mm id) by in situ bulk polymerisation of N-methacryloyl-L-aspartic acid (MAAsp), a polymerisable derivative of L-aspartic acid, and 2-hydroxyethyl methacrylate (HEMA). Monolithic columns [poly(2-hydroxyethyl methacrylate-N-methacryloyl-L-aspartic acid) (PHEMAsp)] were characterised by swelling studies, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The monolithic columns were used for IgG adsorption/desorption from aqueous solutions and human plasma. The IgG adsorption depended on the buffer type, and the maximum IgG adsorption from aqueous solution in phosphate buffer was 0.085 mg/g at pH 6.0. The monolithic columns allowed for one-step IgG purification with a negligible capacity decrease after ten adsorption-desorption cycles. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Adsorption of normal pentane on the surface of rutile. Experimental results and simulations.

PubMed

Rakhmatkariev, G U; Carvalho, A J Palace; Ramalho, J P Prates

2007-07-03

Adsorption isotherms and differential heats of normal pentane adsorption on microcrystalline rutile were measured at 303 K. The heat of adsorption of n-pentane on rutile at zero occupancy is 64 kJ/mol. The differential heats have three descending segments, corresponding to the adsorption of n-pentane on three types of surfaces. At low coverage (first segment), the adsorption is restricted to the rows A of the (110) faces along the 5-fold coordinatively unsaturated (cus) Ti(4+) ions with differential heat showing a linear decrease with increasing occupancy. The second segment is attributed to bonding with atoms of the rows along the remaining faces exposed, (101) and (100). The third segment is related to a multilayer adsorption. The mean molar adsorption entropy of n-pentane is ca. -25 J/mol K less than the entropy of the bulk liquid, thus revealing a hindered state of motion of the n-pentane molecules on the surface of rutile. Simulations of the adsorption of n-pentane on the three most abundant crystallographic faces of rutile were also performed. The adsorption isotherm obtained from the combination of each face's isotherm weighted by the respective abundance was found to be in a good agreement with the experimental data. A structural characterization of n-pentane near the surface was also conducted, and it was found that the substrate, especially for the (110) face, strongly perturbs the distribution of n-pentane conformations, compared to those found for the gas phase. Adsorbed molecules are predominantly oriented with their long axes and their backbone zigzag planes parallel to the surface and are also characterized by fewer gauche conformations than observed in the bulk phase.

Diesel NO(x) aftertreatment by combined process using temperature swing adsorption, NO(x) reduction by nonthermal plasma, and NO(x) recirculation: improvement of the recirculation process.

PubMed

Yoshida, Keiichiro; Kuwahara, Takuya; Kuroki, Tomoyuki; Okubo, Masaaki

2012-09-15

NO(x) emitted from a stationary diesel engine generator was treated with a hybrid system comprising NO(x) reduction by nonthermal plasma (NTP) and temperature swing adsorption (TSA) driven by engine waste heat. TSA produces a low-volume gas mixture of N(2) and highly concentrated NO(x), which is effectively reduced by NTP treatment. Improved treatment performance and efficiency are achieved by re-injecting the NTP-treated gas mixture into the engine intake. The system comprises two switchable adsorption chambers; the operation of this system was simulated by using a one-chamber system. The maximum energy efficiency for NO(x) treatment is 200 g(NO(2))/kWh. The respective contributions of NTP and injection of N(2) and NO(x) to the performance were theoretically analyzed. The analysis predicts that high energy efficiency and high NO(x)-removal efficiency can be simultaneously achieved with this system but miniaturization of the adsorption chambers will be a challenge. Copyright © 2012 Elsevier B.V. All rights reserved.

A simple method for the preparation of activated carbon fibers coated with graphite nanofibers.

PubMed

Kim, Byung-Joo; Park, Soo-Jin

2007-11-15

A simple method is described for the preparation of activated carbon fibers (ACFs) coated with graphite nanofibers (GNFs). Low-pressure-plasma mixed-gas (Ar/O2) treatment of the ACFs led to the growth of GNFs on their surface. The growth was greater at higher power inputs, and from TEM observations the GNFs were seen to be of herringbone type. It was found that the N2 adsorption capacity of the ACFs did not sharply decrease, and that volume resistivity of the ACFs enhanced as a result of this treatment.

Adsorption of sunset yellow FCF from aqueous solution by chitosan-modified diatomite.

PubMed

Zhang, Y Z; Li, J; Li, W J; Li, Y

2015-01-01

Sunset yellow (SY) FCF is a hazardous azo dye pollutant found in food processing effluent. This study investigates the use of diatomaceous earth with chitosan (DE@C) as a modified adsorbent for the removal of SY from wastewater. Fourier transform infrared spectroscopy results indicate the importance of functional groups during the adsorption of SY. The obtained N2 adsorption-desorption isotherm values accord well with IUPAC type II. Our calculations determined a surface area of 69.68 m2 g(-1) for DE@C and an average pore diameter of 4.85 nm. Using response surface methodology, optimized conditions of process variables for dye adsorption were achieved. For the adsorption of SY onto DE@C, this study establishes mathematical models for the optimization of pH, contact time and initial dye concentration. Contact time plays a greater role in the adsorption process than either pH or initial dye concentration. According to the adjusted correlation coefficient (adj-R2>0.97), the models used here are suitable for illustration of the adsorption process. Theoretical experimental conditions included a pH of 2.40, initial dye concentration of 113 mg L(-1) and 30.37 minutes of contact time. Experimental values for the adsorption rate (92.54%) were close to the values predicted by the models (95.29%).

High temperature hydrogen sulfide adsorption on activated carbon - I. Effects of gas composition and metal addition

USGS Publications Warehouse

Cal, M.P.; Strickler, B.W.; Lizzio, A.A.

2000-01-01

Various types of activated carbon sorbents were evaluated for their ability to remove H2S from a simulated coal gas stream at a temperature of 550 ??C. The ability of activated carbon to remove H2S at elevated temperature was examined as a function of carbon surface chemistry (oxidation, thermal desorption, and metal addition), and gas composition. A sorbent prepared by steam activation, HNO3 oxidation and impregnated with Zn, and tested in a gas stream containing 0.5% H2S, 50% CO2 and 49.5% N2, had the greatest H2S adsorption capacity. Addition of H2, CO, and H2O to the inlet gas stream reduced H2S breakthrough time and H2S adsorption capacity. A Zn impregnated activated carbon, when tested using a simulated coal gas containing 0.5% H2S, 49.5% N2, 13% H2, 8.5% H2O, 21% CO, and 7.5% CO2, had a breakthrough time of 75 min, which was less than 25 percent of the length of breakthrough for screening experiments performed with a simplified gas mixture of 0.5% H2S, 50% CO2, and 49.5% N2.

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.

Silica-gel Particles Loaded with an Ionic Liquid for Separation of Zr(IV) Prior to Its Determination by ICP-OES.

PubMed

Marwani, Hadi M; Alsafrani, Amjad E; Asiri, Abdullah M; Rahman, Mohammed M

2016-06-29

A new ionic liquid loaded silica gel amine (SG-APTMS-N,N-EPANTf₂) was developed, as an adsorptive material, for selective adsorption and determination of zirconium, Zr(IV), without the need for a chelating intermediate. Based on a selectivity study, the SG-APTMS-N,N-EPANTf₂ phase showed a perfect selectivity towards Zr(IV) at pH 4 as compared to other metallic ions, including gold [Au(III)], copper [Cu(II)], cobalt [Co(II)], chromium [Cr(III)], lead [Pb(II)], selenium [Se(IV)] and mercury [Hg(II)] ions. The influence of pH, Zr(IV) concentration, contact time and interfering ions on SG-APTMS-N,N-EPANTf₂ uptake for Zr(IV) was evaluated. The presence of incorporated donor atoms in newly synthesized SG-APTMS-N,N-EPANTf₂ phase played a significant role in enhancing its uptake capacity of Zr(IV) by 78.64% in contrast to silica gel (activated). The equilibrium and kinetic information of Zr(IV) adsorption onto SG-APTMS-N,N-EPANTf₂ were best expressed by Langmuir and pseudo second-order kinetic models, respectively. General co-existing cations did not interfere with the extraction and detection of Zr(IV). Finally, the analytical efficiency of the newly developed method was also confirmed by implementing it for the determination of Zr(IV) in several water samples.

Factors Influencing NO2 Adsorption/Reduction on Microporous Activated Carbon: Porosity vs. Surface Chemistry

PubMed Central

Ghouma, Imen; Limousy, Lionel; Bennici, Simona

2018-01-01

The textural properties and surface chemistry of different activated carbons, prepared by the chemical activation of olive stones, have been investigated in order to gain insight on the NO2 adsorption mechanism. The parent chemical activated carbon was prepared by the impregnation of olive stones in phosphoric acid followed by thermal carbonization. Then, the textural properties and surface chemistry were modified by chemical treatments including nitric acid, sodium hydroxide and/or a thermal treatment at 900 °C. The main properties of the parent and modified activated carbons were analyzed by N2-adsorption, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) techniques, in order to enlighten the modifications issued from the chemical and thermal treatments. The NO2 adsorption capacities of the different activated carbons were measured in fixed bed experiments under 500 ppmv NO2 concentrations at room temperature. Temperature programmed desorption (TPD) was applied after adsorption tests in order to quantify the amount of the physisorbed and chemisorbed NO2. The obtained results showed that the development of microporosity, the presence of oxygen-free sites, and the presence of basic surface groups are key factors for the efficient adsorption of NO2. PMID:29670008

Ammonia modification of activated carbon to enhance carbon dioxide adsorption: Effect of pre-oxidation

NASA Astrophysics Data System (ADS)

Shafeeyan, Mohammad Saleh; Daud, Wan Mohd Ashri Wan; Houshmand, Amirhossein; Arami-Niya, Arash

2011-02-01

A commercial granular activated carbon (GAC) was subjected to thermal treatment with ammonia for obtaining an efficient carbon dioxide (CO2) adsorbent. In general, CO2 adsorption capacity of activated carbon can be increased by introduction of basic nitrogen functionalities onto the carbon surface. In this work, the effect of oxygen surface groups before introduction of basic nitrogen functionalities to the carbon surface on CO2 adsorption capacity was investigated. For this purpose two different approaches of ammonia treatment without preliminary oxidation and amination of oxidized samples were studied. Modified carbons were characterized by elemental analysis and Fourier Transform Infrared spectroscopy (FT-IR) to study the impact of changes in surface chemistry and formation of specific surface groups on adsorption properties. The texture of the samples was characterized by conducting N2 adsorption/desorption at -196 °C. CO2 capture performance of the samples was investigated using a thermogravimetric analysis (TGA). It was found that in both modification techniques, the presence of nitrogen functionalities on carbon surface generally increased the CO2 adsorption capacity. The results indicated that oxidation followed by high temperature ammonia treatment (800 °C) considerably enhanced the CO2 uptake at higher temperatures.

Modification of polystyrene-based activated carbon spheres to improve adsorption of dibenzothiophene

NASA Astrophysics Data System (ADS)

Wang, Qin; Liang, Xiaoyi; Qiao, Wenming; Liu, Chaojun; Liu, Xiaojun; Zhang, Rui; Ling, Licheng

2009-01-01

Polystyrene-based activated carbon spheres (PACS) were modified with either air, HNO 3, (NH 4) 2S 2O 8, H 2O 2 or H 2 to improve their adsorption properties of dibenzothiophene (DBT). The texture and surface chemistry of PACS were characterized by N 2 adsorption, scanning electron microscopy (SEM), temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), acid-base titration and elemental analysis. The results showed that HNO 3 and (NH 4) 2S 2O 8 treatments introduced large amount of acidic groups such as carboxylic, lactones and anhydride groups, while air and H 2O 2 had relatively mild effects and introduced a small quantity of phenol, carbonyl and ether groups. In the HNO 3 treatment, the acidic groups might be fixed on the internal and external surface of PACS, which may act as active sites of adsorption, resulting in increase of the adsorption amount by 45%. Whereas H 2O 2 and (NH 4) 2S 2O 8 treatments might fix more oxygen-containing groups on the external surface, which may hinder DBT molecule enter into micropores, leading to rather lower adsorption capacity with the extent of oxidation. So, the concentration, distribution and types of the acidic functional groups are responsible for the removal of DBT.

Simultaneous Online Measurement of H2O and CO2 in the Humid CO2 Adsorption/Desorption Process.

PubMed

Yu, Qingni; Ye, Sha; Zhu, Jingke; Lei, Lecheng; Yang, Bin

2015-01-01

A dew point meter (DP) and an infrared (IR) CO2 analyzer were assembled in a humid CO2 adsorption/desorption system in series for simultaneous online measurements of H2O and CO2, respectively. The humidifier, by using surface-flushing on a saturated brine solution was self-made for the generation of humid air flow. It was found that by this method it became relatively easy to obtain a low H2O content in air flow and that its fluctuation could be reduced compared to the bubbling method. Water calibration for the DP-IR detector is necessary to be conducted for minimizing the measurement error of H2O. It demonstrated that the relative error (RA) for simultaneous online measurements H2O and CO2 in the desorption process is lower than 0.1%. The high RA in the adsorption of H2O is attributed to H2O adsorption on the transfer pipe and amplification of the measurement error. The high accuracy of simultaneous online measurements of H2O and CO2 is promising for investigating their co-adsorption/desorption behaviors, especially for direct CO2 capture from ambient air.

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.

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+.

First-principles study on the structure and electronic property of gas molecules adsorption on Ge2Li2 monolayer

NASA Astrophysics Data System (ADS)

Hu, Yiwei; Long, Linbo; Mao, Yuliang; Zhong, Jianxin

2018-06-01

Using first-principles methods, we have studied the adsorption of gas molecules (CO2, CH4, H2S, H2 and NH3) on two dimensional Ge2Li2 monolayer. The adsorption geometries, adsorption energies, charge transfer, and band structures of above mentioned gas molecules adsorption on Ge2Li2 monolayer are analyzed. It is found that the adsorption of CO2 on Ge2Li2 monolayer is a kind of strong chemisorption, while other gas molecules such as CH4, H2S, H2 and NH3 are physisorption. The strong covalent binding is formed between the CO2 molecule and the nearest Ge atom in Ge2Li2 monolayer. This adsorption of CO2 molecule on Ge2Li2 monolayer leads to a direct energy gap of 0.304 eV. Other gas molecules exhibit mainly ionic binding to the nearest Li atoms in Ge2Li2 monolayer, which leads to indirect energy gap after adsorptions. Furthermore, it is found that the work function of Ge2Li2 monolayer is sensitive with the variation of adsorbents. Our results reveal that the Ge2Li2 monolayer can be used as a kind of nano device for gas molecules sensor.

Adsorption properties of HKUST-1 toward hydrogen and other small molecules monitored by IR.

PubMed

Bordiga, S; Regli, L; Bonino, F; Groppo, E; Lamberti, C; Xiao, B; Wheatley, P S; Morris, R E; Zecchina, A

2007-06-07

Among microporous systems metal organic frameworks are considered promising materials for molecular adsorption. In this contribution infrared spectroscopy is successfully applied to highlight the positive role played by coordinatively unsaturated Cu2+ ions in HKUST-1, acting as specific interaction sites. A properly activated material, obtained after solvent removal, is characterized by a high fraction of coordinatively unsaturated Cu2+ ions acting as preferential adsorption sites that show specific activities towards some of the most common gaseous species (NO, CO2, CO, N2 and H2). From a temperature dependent IR study, it has been estimated that the H2 adsorption energy is as high as 10 kJ mol(-1). A very complex spectral evolution has been observed upon lowering the temperature. A further peculiarity of this material is the fact that it promotes ortho-para conversion of the adsorbed H2 species.

Adsorption of sulfur dioxide on ammonia-treated activated carbon fibers

USGS Publications Warehouse

Mangun, C.L.; DeBarr, J.A.; Economy, J.

2001-01-01

A series of activated carbon fibers (ACFs) and ammonia-treated ACFs prepared from phenolic fiber precursors have been studied to elucidate the role of pore size, pore volume, and pore surface chemistry on adsorption of sulfur dioxide and its catalytic conversion to sulfuric acid. As expected, the incorporation of basic functional groups into the ACFs was shown as an effective method for increasing adsorption of sulfur dioxide. The adsorption capacity for dry SO2 did not follow specific trends; however the adsorption energies calculated from the DR equation were found to increase linearly with nitrogen content for each series of ACFs. Much higher adsorption capacities were achieved for SO2 in the presence of oxygen and water due to its catalytic conversion to H2SO4. The dominant factor for increasing adsorption of SO2 from simulated flue gas for each series of fibers studied was the weight percent of basic nitrogen groups present. In addition, the adsorption energies calculated for dry SO2 were shown to be linearly related to the adsorption capacity of H2SO4 from this flue gas for all fibers. It was shown that optimization of this parameter along with the pore volume results in higher adsorption capacities for removal of SO2 from flue gases. ?? 2001 Elsevier Science Ltd. All rights reserved.

Adsorption of n-butane on graphene/Ru(0001)—A molecular beam scattering study

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

Sivapragasam, Nilushni; Nayakasinghe, Mindika T.; Burghaus, Uwe, E-mail: uwe.burghaus@ndsu.edu

2016-07-15

Adsorption kinetics/dynamics of n-butane on graphene, physical vapor deposited on Ru(0001) (hereafter G/Ru), and bare Ru(0001) (hereafter Ru) are discussed. The chemical activity of the supported-graphene as well as the support was probed by thermal desorption spectroscopy (adsorption kinetics). In addition and to the best of our knowledge, for the first time, molecular beam scattering data of larger molecules were collected for graphene (probing the adsorption dynamics). Furthermore, samples were inspected by x-ray photoelectron spectroscopy and Auger electron spectroscopy. At the measuring conditions used here, n-butane adsorption kinetics/dynamics are molecular and nonactivated. Binding energies of butane on Ru and G/Rumore » are indistinguishable within experimental uncertainty. Thus, G/Ru is “kinetically transparent.” Initial adsorption probabilities, S{sub 0}, of n-butane decrease with increasing impact energy (0.76–1.72 eV) and are adsorption temperature independent for both Ru and G/Ru, again consistent with molecular adsorption. Also, S{sub 0} of Ru and G/Ru are indistinguishable within experimental uncertainty. Thus, G/Ru is “dynamically transparent.” Coverage dependent adsorption probabilities indicate precursor effects for graphene/Ru.« less

[Influence of surface chemical properties and pore structure characteristics of activated carbon on the adsorption of nitrobenzene from aqueous solution].

PubMed

Liu, Shou-Xin; Chen, Xi; Zhang, Xian-Quan

2008-05-01

Commercial activated carbon was treated by HNO3 oxidation and then subsequently heat treated under N2 atmosphere. Effect of surface chemical properties and pore structure on the adsorption performance of nitrobenzene was investigated. N2/77K adsorption isotherm and scanning electron microscopy (SEM) were used to characterize the pore structure and surface morphology of carbon. Boehm titration, Fourier transform infrared spectroscopy (FTIR), the point of zero charge (pH(PZC)) measurement and elemental analysis were used to characterize the surface properties. The results reveal that HNO3 oxidation can modify the surface chemical properties, increase the number of acidic surface oxygen-containing groups and has trivial effect on the pore structure of carbon. Further heat treatment can cause the decomposition of surface oxygen-containing groups, and increase the external surface area and the number of mesopores. Adsorption capacity of nitrobenzene on AC(NO-T), AC(raw) and AC(NO) was 1011.31, 483.09 and 321.54 mg x g(-1), respectively. Larger external surface area and the number of meso-pores, together with the less acid surface oxygen-containing groups were the main reason for the larger adsorption capacity AC(NO-T).