A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry.

PubMed

Goverapet Srinivasan, Sriram; Shivaramaiah, Radha; Kent, Paul R C; Stack, Andrew G; Riman, Richard; Anderko, Andre; Navrotsky, Alexandra; Bryantsev, Vyacheslav S

2017-03-15

Bastnäsite, a fluoro-carbonate mineral, is the single largest mineral source of light rare earth elements (REE), La, Ce and Nd. Enhancing the efficiency of separation of the mineral from gangue through froth flotation is the first step towards meeting an ever increasing demand for REE. To design and evaluate collector molecules that selectively bind to bastnäsite, a fundamental understanding of the structure and surface properties of bastnäsite is essential. In our earlier work (J. Phys. Chem. C, 2016, 120, 16767), we carried out an extensive study of the structure, surface stability and water adsorption energies of La-bastnäsite. In this work, we make a comparative study of the surface properties of Ce-bastnäsite, La-bastnäsite, and calcite using a combination of density functional theory (DFT) and water adsorption calorimetry. Spin polarized DFT+U calculations show that the exchange interaction between the electrons in Ce 4f orbitals is negligible and that these orbitals do not participate in bonding with the oxygen atom of the adsorbed water molecule. In agreement with calorimetry, DFT calculations predict larger surface energies and stronger water adsorption energies on Ce-bastnäsite than on La-bastnäsite. The order of stabilities for stoichiometric surfaces is as follows: [101[combining macron]0] > [101[combining macron]1] > [101[combining macron]2] > [0001] > [112[combining macron]2] > [101[combining macron]4] and the most favorable adsorption sites for water molecules are the same as for La-bastnäsite. In agreement with water adsorption calorimetry, at low coverage water molecules are strongly stabilized via coordination to the surface Ce 3+ ions, whereas at higher coverage they are adsorbed less strongly via hydrogen bonding interaction with the surface anions. Due to similar water adsorption energies on bastnäsite [101[combining macron]1] and calcite [101[combining macron]4] surfaces, the design of collector molecules that selectively bind to

Adsorption energies of benzene on close packed transition metal surfaces using the random phase approximation

NASA Astrophysics Data System (ADS)

Garrido Torres, José A.; Ramberger, Benjamin; Früchtl, Herbert A.; Schaub, Renald; Kresse, Georg

2017-11-01

The adsorption energy of benzene on various metal substrates is predicted using the random phase approximation (RPA) for the correlation energy. Agreement with available experimental data is systematically better than 10% for both coinage and reactive metals. The results are also compared with more approximate methods, including van der Waals density functional theory (DFT), as well as dispersion-corrected DFT functionals. Although dispersion-corrected DFT can yield accurate results, for instance, on coinage metals, the adsorption energies are clearly overestimated on more reactive transition metals. Furthermore, coverage dependent adsorption energies are well described by the RPA. This shows that for the description of aromatic molecules on metal surfaces further improvements in density functionals are necessary, or more involved many-body methods such as the RPA are required.

Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test.

PubMed

Nam, Sangchul; Namkoong, Wan; Kang, Jeong-Hee; Park, Jin-Kyu; Lee, Namhoon

2013-10-01

Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane. Copyright © 2013 Elsevier Ltd. All rights reserved.

Adsorption of nicotine from aqueous solution onto hydrophobic zeolite type USY

NASA Astrophysics Data System (ADS)

Lazarevic, Natasa; Adnadjevic, Borivoj; Jovanovic, Jelena

2011-07-01

The isothermal adsorption of nicotine from an aqueous solution onto zeolite type USY was investigated. The adsorption isotherms of nicotine onto the zeolite at different temperatures ranging from 298 to 322 K were determined. It was found that the adsorption isotherms can be described by the model of Freundlich adsorption isotherm. Based on the adsorption isotherms the changes of adsorption heat, free energy and entropy with adsorption degree were determined. The determined decrease of adsorption heat with adsorption degree can be explained by the presence of the adsorption centers of different energy and concentration on interface of zeolite-nicotine solution. It was found that the probability function of density distribution of the heat of adsorption (DDF) has exponential form. It was concluded that the possibility of fitting the adsorption isotherms of nicotine onto the zeolite by Freundlich adsorption isotherm was a direct consequence of that. The determined increase in entropy with the increase in adsorption degree can be explained with the change of phase state of adsorbed nicotine.

Strong Selective Adsorption of Polymers.

PubMed

Ge, Ting; Rubinstein, Michael

2015-06-09

polymers strongly overlap. We anticipate the formation of a self-similar carpet and with increasing l / d a two-layer structure with a brush of loops covered by a self-similar carpet. As l / d exceeds the threshold determined by the adsorption energy, the brush of loops under the carpet reaches a saturated state, resulting in a l / d -independent brush-under-carpet structure, which can also be applied to describe adsorbed multisticker polymers in nonselective adsorption where a sticker can strongly bind to any place on the adsorption surface. We examine the adsorbed amount Γ of multisticker polymers in different regimes for selective adsorption. If the adsorbed multisticker polymers are nonoverlapping mushrooms, the adsorbed amount Γ increases linearly with the surface density of adsorption sites Σ ≈ 1/ d 2 . In the self-similar carpet regime, Γ increases sublinearly as Σ 0.15 in a good solvent, while only logarithmically in a theta solvent. Formation of a brush layer under the carpet contributes an additional adsorbed amount. This additional amount increases linearly with Σ and eventually dominates the overall adsorbed amount Γ before saturating at a plateau value controlled by the adsorption energy.

Phenolic resin-based porous carbons for adsorption and energy storage applications

NASA Astrophysics Data System (ADS)

Wickramaratne, Nilantha P.

The main objective of this dissertation research is to develop phenolic resin based carbon materials for range of applications by soft-templating and Stober-like synthesis strategies. Applications Studied in this dissertation are adsorption of CO2, bio-molecular and heavy metal ions, and energy storage devices. Based on that, our goal is to design carbon materials with desired pore structure, high surface area, graphitic domains, incorporated metal nanoparticles, and specific organic groups and heteroatoms. In this dissertation the organic-organic self-assembly of phenolic resins and triblock copolymers under acidic conditions will be used to obtain mesoporous carbons/carbon composites and Stober-like synthesis involving phenolic resins under basic condition will be used to prepare polymer/carbon particles and their composites. The structure of this dissertation consists of an introductory chapter (Chapter 1) discussing the general synthesis of carbon materials, particularly the soft-templating strategy and Stober-like carbon synthesis. Also, Chapter 1 includes a brief outline of applications namely adsorption of CO2, biomolecule and heavy metal ions, and supercapacitors. Chapter 2 discusses the techniques used for characterization of the carbon materials studied. This chapter starts with nitrogen adsorption analysis, which is used to measure the specific surface area, pore volume, distribution of pore sizes, and pore width. In addition to nitrogen adsorption, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution thermogravimetric analysis (HR-TGA), cyclic voltammetry (CV) and CHNS elemental analysis (EA) are mentioned too. Chapter 3 is focused on carbon materials for CO2 adsorption. There are different types of porous solid materials such as silicate, MOFs, carbons, and zeolites studied for CO2 adsorption. However, the carbon based materials are considered to be the best candidates for CO 2 adsorption to the industrial point of

DFT-based method for more accurate adsorption energies: An adaptive sum of energies from RPBE and vdW density functionals

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

Hensley, Alyssa J. R.; Ghale, Kushal; Rieg, Carolin

In recent years, the popularity of density functional theory with periodic boundary conditions (DFT) has surged for the design and optimization of functional materials. However, no single DFT exchange–correlation functional currently available gives accurate adsorption energies on transition metals both when bonding to the surface is dominated by strong covalent or ionic bonding and when it has strong contributions from van der Waals interactions (i.e., dispersion forces). Here we present a new, simple method for accurately predicting adsorption energies on transition-metal surfaces based on DFT calculations, using an adaptively weighted sum of energies from RPBE and optB86b-vdW (or optB88-vdW) densitymore » functionals. This method has been benchmarked against a set of 39 reliable experimental energies for adsorption reactions. Our results show that this method has a mean absolute error and root mean squared error relative to experiments of 13.4 and 19.3 kJ/mol, respectively, compared to 20.4 and 26.4 kJ/mol for the BEEF-vdW functional. For systems with large van der Waals contributions, this method decreases these errors to 11.6 and 17.5 kJ/mol. Furthermore, this method provides predictions of adsorption energies both for processes dominated by strong covalent or ionic bonding and for those dominated by dispersion forces that are more accurate than those of any current standard DFT functional alone.« less

DFT-based method for more accurate adsorption energies: An adaptive sum of energies from RPBE and vdW density functionals

DOE PAGES

Hensley, Alyssa J. R.; Ghale, Kushal; Rieg, Carolin; ...

2017-01-26

In recent years, the popularity of density functional theory with periodic boundary conditions (DFT) has surged for the design and optimization of functional materials. However, no single DFT exchange–correlation functional currently available gives accurate adsorption energies on transition metals both when bonding to the surface is dominated by strong covalent or ionic bonding and when it has strong contributions from van der Waals interactions (i.e., dispersion forces). Here we present a new, simple method for accurately predicting adsorption energies on transition-metal surfaces based on DFT calculations, using an adaptively weighted sum of energies from RPBE and optB86b-vdW (or optB88-vdW) densitymore » functionals. This method has been benchmarked against a set of 39 reliable experimental energies for adsorption reactions. Our results show that this method has a mean absolute error and root mean squared error relative to experiments of 13.4 and 19.3 kJ/mol, respectively, compared to 20.4 and 26.4 kJ/mol for the BEEF-vdW functional. For systems with large van der Waals contributions, this method decreases these errors to 11.6 and 17.5 kJ/mol. Furthermore, this method provides predictions of adsorption energies both for processes dominated by strong covalent or ionic bonding and for those dominated by dispersion forces that are more accurate than those of any current standard DFT functional alone.« less

[Adsorption kinetics and mechanism of lead (II) on polyamine-functionalized mesoporous activated carbon].

PubMed

Li, Kun-Quan; Wang, Yan-Jin; Yang, Mei-Rong; Zhu, Zhi-Qiang; Zheng, Zheng

2014-08-01

Bagasse mesoporous carbon was prepared by microwave assisted H3 PO4 activation. Amido and imido groups were modified with ethanediamine on the channels' surface of mesoporous carbon through nitric oxidation and amide reaction. The influence of Pb(II) concentration, adsorption time on Pb(II) adsorption on the ethanediamine-modified mesoporous carbon (AC-EDA) was investigated. The adsorption kinetics and mechanism were also discussed. The results showed that AC-EDA had a great performance for Pb(II) adsorption, and more than 70% of Pb(II) was adsorbed in 5 minutes. The adsorption amount of Pb(II) on the carbon increased with the increase of solution pH in acidic conditions. It was found that AC-EDA had different binding energies on different adsorption sites for Pb(II) separation. The Pb(II) adsorption process on AC-EDA was controlled by intra-particle diffusion in the first 3 min, and then film diffusion played the important pole on the adsorption. The adsorption amount increased with the increase of temperature, indicating the adsorption was an endothermic reaction. The high adsorption energy (> 11 kJ x mol(-1)) implied that the) adsorption was a chemical adsorption. The XPS of AC-EDA before and after Pb(II) adsorption showed that the polyamine group was involved in the adsorption, and should be a main factor of the high efficient adsorption.

Microgravimetric Analysis Method for Activation-Energy Extraction from Trace-Amount Molecule Adsorption.

PubMed

Xu, Pengcheng; Yu, Haitao; Li, Xinxin

2016-05-03

Activation-energy (Ea) value for trace-amount adsorption of gas molecules on material is rapidly and inexpensively obtained, for the first time, from a microgravimetric analysis experiment. With the material loaded, a resonant microcantilever is used to record in real time the adsorption process at two temperatures. The kinetic parameter Ea is thereby extracted by solving the Arrhenius equation. As an example, two CO2 capture nanomaterials are examined by the Ea extracting method for evaluation/optimization and, thereby, demonstrating the applicability of the microgravimetric analysis method. The achievement helps to solve the absence in rapid quantitative characterization of sorption kinetics and opens a new route to investigate molecule adsorption processes and materials.

Binding free energy and counterion release for adsorption of the antimicrobial peptide lactoferricin B on a POPG membrane.

PubMed

Tolokh, Igor S; Vivcharuk, Victor; Tomberli, Bruno; Gray, C G

2009-09-01

Molecular dynamics (MD) simulations are used to study the interaction of an anionic palmitoyl-oleoyl-phosphatidylglycerol (POPG) bilayer with the cationic antimicrobial peptide bovine lactoferricin (LFCinB) in a 100 mM NaCl solution at 310 K. The interaction of LFCinB with a POPG bilayer is employed as a model system for studying the details of membrane adsorption selectivity of cationic antimicrobial peptides. Seventy eight 4 ns MD production run trajectories of the equilibrated system, with six restrained orientations of LFCinB at 13 different separations from the POPG membrane, are generated to determine the free energy profile for the peptide as a function of the distance between LFCinB and the membrane surface. To calculate the profile for this relatively large system, a variant of constrained MD and thermodynamic integration is used. A simplified method for relating the free energy profile to the LFCinB-POPG membrane binding constant is employed to predict a free energy of adsorption of -5.4+/-1.3 kcal/mol and a corresponding maximum adsorption binding force of about 58 pN. We analyze the results using Poisson-Boltzmann theory. We find the peptide-membrane attraction to be dominated by the entropy increase due to the release of counterions and polarized water from the region between the charged membrane and peptide, as the two approach each other. We contrast these results with those found earlier for adsorption of LFCinB on the mammalianlike palmitoyl-oleoyl-phosphatidylcholine membrane.

Binding free energy and counterion release for adsorption of the antimicrobial peptide lactoferricin B on a POPG membrane

NASA Astrophysics Data System (ADS)

Tolokh, Igor S.; Vivcharuk, Victor; Tomberli, Bruno; Gray, C. G.

2009-09-01

Molecular dynamics (MD) simulations are used to study the interaction of an anionic palmitoyl-oleoyl-phosphatidylglycerol (POPG) bilayer with the cationic antimicrobial peptide bovine lactoferricin (LFCinB) in a 100 mM NaCl solution at 310 K. The interaction of LFCinB with a POPG bilayer is employed as a model system for studying the details of membrane adsorption selectivity of cationic antimicrobial peptides. Seventy eight 4 ns MD production run trajectories of the equilibrated system, with six restrained orientations of LFCinB at 13 different separations from the POPG membrane, are generated to determine the free energy profile for the peptide as a function of the distance between LFCinB and the membrane surface. To calculate the profile for this relatively large system, a variant of constrained MD and thermodynamic integration is used. A simplified method for relating the free energy profile to the LFCinB-POPG membrane binding constant is employed to predict a free energy of adsorption of -5.4±1.3kcal/mol and a corresponding maximum adsorption binding force of about 58 pN. We analyze the results using Poisson-Boltzmann theory. We find the peptide-membrane attraction to be dominated by the entropy increase due to the release of counterions and polarized water from the region between the charged membrane and peptide, as the two approach each other. We contrast these results with those found earlier for adsorption of LFCinB on the mammalianlike palmitoyl-oleoyl-phosphatidylcholine membrane.

Apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption

DOEpatents

Wegeng, Robert S.; Rassat, Scot D.; Stenkamp, Victoria S.; TeGrotenhuis, Ward E.; Matson, Dean W.; Drost, M. Kevin; Viswanathan, Vilayanur V.

2005-12-13

The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

Method for thermal swing adsorption and thermally-enhanced pressure swing adsorption

DOEpatents

Wegeng, Robert S.; Rassat, Scot D.; Stenkamp, Victoria S.; TeGrotenhuis, Ward E.; Matson, Dean W.; Drost, M. Kevin; Viswanathan, Vilayanur V.

2003-10-07

The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

Adsorption of methanol molecule on graphene: Experimental results and first-principles calculations

NASA Astrophysics Data System (ADS)

Zhao, X. W.; Tian, Y. L.; Yue, W. W.; Chen, M. N.; Hu, G. C.; Ren, J. F.; Yuan, X. B.

2018-04-01

Adsorption properties of methanol molecule on graphene surface are studied both theoretically and experimentally. The adsorption geometrical structures, adsorption energies, band structures, density of states and the effective masses are obtained by means of first-principles calculations. It is found that the electronic characteristics and conductivity of graphene are sensitive to the methanol molecule adsorption. After adsorption of methanol molecule, bandgap appears. With the increasing of the adsorption distance, the bandgap, adsorption energy and effective mass of the adsorption system decreased, hence the resistivity of the system decreases gradually, these results are consistent with the experimental results. All these calculations and experiments indicate that the graphene-based sensors have a wide range of applications in detecting particular molecules.

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.

Charge induced enhancement of adsorption for hydrogen storage materials

NASA Astrophysics Data System (ADS)

Sun, Xiang

2009-12-01

The rising concerns about environmental pollution and global warming have facilitated research interest in hydrogen energy as an alternative energy source. To apply hydrogen for transportations, several issues have to be solved, within which hydrogen storage is the most critical problem. Lots of materials and devices have been developed; however, none is able to meet the DOE storage target. The primary issue for hydrogen physisorption is a weak interaction between hydrogen and the surface of solid materials, resulting negligible adsorption at room temperature. To solve this issue, there is a need to increase the interaction between the hydrogen molecules and adsorbent surface. In this study, intrinsic electric dipole is investigated to enhance the adsorption energy. The results from the computer simulation of single ionic compounds with hydrogen molecules to form hydrogen clusters showed that electrical charge of substances plays an important role in generation of attractive interaction with hydrogen molecules. In order to further examine the effects of static interaction on hydrogen adsorption, activated carbon with a large surface area was impregnated with various ionic salts including LiCl, NaCl, KCl, KBr, and NiCl2 and their performance for hydrogen storage was evaluated by using a volumetric method. Corresponding computer simulations have been carried out by using DFT (Density Functional Theory) method combined with point charge arrays. Both experimental and computational results prove that the adsorption capacity of hydrogen and its interaction with the solid materials increased with electrical dipole moment. Besides the intrinsic dipole, an externally applied electric field could be another means to enhance hydrogen adsorption. Hydrogen adsorption under an applied electric field was examined by using porous nickel foil as electrodes. Electrical signals showed that adsorption capacity increased with the increasing of gas pressure and external electric voltage

Electron Localization States in Asymmetric Shape Carbon Nanotubes Caused by Hydrogen Adsorption

NASA Astrophysics Data System (ADS)

Pan, L. J.; Chen, W. G.

2017-12-01

In this paper, we presented pseudopotential-based density functional theory studies on energy, structure, energy band structure of hydrogenated single-walled carbon nanotube. The stability of the configuration mainly depends on hydrogen coverage. According to the adsorption energies, the stability deteriorates with the increase of the hydrogen adsorption. The cross section of configurations become various shapes such as “beetle” or “lip” appearance without the balanced effects of hydrogen atoms. We also explored the energy band structures of configurations in three typical adsorption patterns, showing that the disparate trends of energy band gap as the hydrogen atoms concentrate. For C32H24, the band gap may reach the large value of 2.79 eV for the adsorption pattern A configuration and reduce to be zero for the adsorption pattern C case, the values of band gap for pattern A configurations decrease, which is opposite of the pattern B configurations as the adsorption hydrogen becomes more disperse. It is deduced that the hydrogen adsorption has significant effect on the electrical properties of the carbon nanotube.

More accurate depiction of adsorption energy on transition metals using work function as one additional descriptor.

PubMed

Shen, Xiaochen; Pan, Yanbo; Liu, Bin; Yang, Jinlong; Zeng, Jie; Peng, Zhenmeng

2017-05-24

The reaction mechanism and properties of a catalytic process are primarily determined by the interactions between reacting species and catalysts. However, the interactions are often challenging to be experimentally measured, especially for unstable intermediates. Therefore, it is of significant importance to establish an exact relationship between chemical-catalyst interactions and catalyst parameters, which will allow calculation of these interactions and thus advance their mechanistic understanding. Herein we report the description of adsorption energy on transition metals by considering both ionic bonding and covalent bonding contributions and introduce the work function as one additional responsible parameter. We find that the adsorption energy can be more accurately described using a two-dimensional (2D) polynomial model, which shows a significant improvement compared with the current adsorption energy-d-band center linear correlation. We also demonstrate the utilization of this new 2D polynomial model to calculate oxygen binding energy of different transition metals to help understand their catalytic properties in oxygen reduction reactions.

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.

Adsorption behaviour of hydrogarnet for humic acid

NASA Astrophysics Data System (ADS)

Maeda, Hirotaka; Kurosaki, Yuichi; Nakayama, Masanobu; Ishida, Emile Hideki; Kasuga, Toshihiro

2018-04-01

Discharge of humic acid (HA) in aqueous environments is a key health and aesthetic issue. The present work investigates the use of hydrogarnet as a novel adsorbent for HA. Hydrogarnet was hydrothermally synthesized with different solvents to control the chemical composition. Hydrogarnet with three types of chemical compositions had better adsorption properties for HA than hydrogarnet with a single chemical composition. Controlling the chemical composition of hydrogarnet increased the number of hydroxyl groups and the overall binding energy of the system, leading to changes in the zeta potential. The enhancement of these adsorption properties is related to the increased numbers of hydroxyl groups on the surface and their diverse binding energies.

Dimethyl Methylphosphonate Adsorption Capacities and Desorption Energies on Ordered Mesoporous Carbons.

PubMed

Huynh, Kim; Holdren, Scott; Hu, Junkai; Wang, Luning; Zachariah, Michael R; Eichhorn, Bryan W

2017-11-22

In this study, we determine effective adsorption capacities and desorption energies for DMMP with highly ordered mesoporous carbons (OMCs), 1D cylindrical FDU-15, 3D hexagonal CMK-3, 3D bicontinuous CMK-8, and as a reference, microporous BPL carbon. After exposure to DMMP vapor at room temperature for approximately 70 and 800 h, the adsorption capacity of DMMP for each OMC was generally proportional to the total surface area and pore volume, respectively. Desorption energies of DMMP were determined using a model-free isoconversional method applied to thermogravimetric analysis (TGA) data. Our experiments determined that DMMP saturated carbon will desorb any weakly bound DMMP from pores >2.4 nm at room temperature, and no DMMP will adsorb into pores smaller than 0.5 nm. The calculated desorption energies for high surface coverages, 25% DMMP desorbed from pores ≤2.4 nm, are 68-74 kJ mol -1 , which is similar to the DMMP heat of vaporization (52 kJ mol -1 ). At lower surface coverages, 80% DMMP desorbed, the DMMP desorption energies from the OMCs are 95-103 kJ mol -1 . This is overall 20-30 kJ mol -1 higher in comparison to that of BPL carbon, due to the pore size and diffusion through different porous networks.

Parameterization of an interfacial force field for accurate representation of peptide adsorption free energy on high-density polyethylene

PubMed Central

Abramyan, Tigran M.; Snyder, James A.; Yancey, Jeremy A.; Thyparambil, Aby A.; Wei, Yang; Stuart, Steven J.; Latour, Robert A.

2015-01-01

Interfacial force field (IFF) parameters for use with the CHARMM force field have been developed for interactions between peptides and high-density polyethylene (HDPE). Parameterization of the IFF was performed to achieve agreement between experimental and calculated adsorption free energies of small TGTG–X–GTGT host–guest peptides (T = threonine, G = glycine, and X = variable amino-acid residue) on HDPE, with ±0.5 kcal/mol agreement. This IFF parameter set consists of tuned nonbonded parameters (i.e., partial charges and Lennard–Jones parameters) for use with an in-house-modified CHARMM molecular dynamic program that enables the use of an independent set of force field parameters to control molecular behavior at a solid–liquid interface. The R correlation coefficient between the simulated and experimental peptide adsorption free energies increased from 0.00 for the standard CHARMM force field parameters to 0.88 for the tuned IFF parameters. Subsequent studies are planned to apply the tuned IFF parameter set for the simulation of protein adsorption behavior on an HDPE surface for comparison with experimental values of adsorbed protein orientation and conformation. PMID:25818122

A Universal Isotherm Model to Capture Adsorption Uptake and Energy Distribution of Porous Heterogeneous Surface.

PubMed

Ng, Kim Choon; Burhan, Muhammad; Shahzad, Muhammad Wakil; Ismail, Azahar Bin

2017-09-06

The adsorbate-adsorbent thermodynamics are complex as it is influenced by the pore size distributions, surface heterogeneity and site energy distribution, as well as the adsorbate properties. Together, these parameters defined the adsorbate uptake forming the state diagrams, known as the adsorption isotherms, when the sorption site energy on the pore surfaces are favorable. The available adsorption models for describing the vapor uptake or isotherms, hitherto, are individually defined to correlate to a certain type of isotherm patterns. There is yet a universal approach in developing these isotherm models. In this paper, we demonstrate that the characteristics of all sorption isotherm types can be succinctly unified by a revised Langmuir model when merged with the concepts of Homotattic Patch Approximation (HPA) and the availability of multiple sets of site energy accompanied by their respective fractional probability factors. The total uptake (q/q*) at assorted pressure ratios (P/P s ) are inextricably traced to the manner the site energies are spread, either naturally or engineered by scientists, over and across the heterogeneous surfaces. An insight to the porous heterogeneous surface characteristics, in terms of adsorption site availability has been presented, describing the unique behavior of each isotherm type.

Effect of electric field on adsorption of formaldehyde by β-cellobiose in micro-scale

NASA Astrophysics Data System (ADS)

Xu, Bo; Chen, Zhenqian

2018-05-01

To provide a microcosmic theoretical support for the reduction of formaldehyde in building material by the effect of electric fields, the adsorption between formaldehyde molecule and β-cellobiose was studied by density function theory (DFT). Details of geometric structures, molecule bonds and adsorption energy were discussed respectively. The obtained results indicated the energy of formaldehyde molecule decreased while the energy of β-cellobiose increased with greater electric intensity. In addition, the adsorption energy between formaldehyde molecule and β-cellobiose was greatly influenced by external electric field. The adsorption energy reduced gradually with greater electric intensity, and the changing curve of adsorption energy could be fitted as an exponential function, verified by the experiment. The results of this study confirmed the external electric field would be a good strategy for decreasing formaldehyde within building materials in the microcosmic view.

Adsorption energies of poly(ethylene oxide)-based surfactants and nanoparticles on an air-water surface.

PubMed

Zell, Zachary A; Isa, Lucio; Ilg, Patrick; Leal, L Gary; Squires, Todd M

2014-01-14

The self-assembly of polymer-based surfactants and nanoparticles on fluid-fluid interfaces is central to many applications, including dispersion stabilization, creation of novel 2D materials, and surface patterning. Very often these processes involve compressing interfacial monolayers of particles or polymers to obtain a desired material microstructure. At high surface pressures, however, even highly interfacially active objects can desorb from the interface. Methods of directly measuring the energy which keeps the polymer or particles bound to the interface (adsorption/desorption energies) are therefore of high interest for these processes. Moreover, though a geometric description linking adsorption energy and wetting properties through the definition of a contact angle can be established for rigid nano- or microparticles, such a description breaks down for deformable or aggregating objects. Here, we demonstrate a technique to quantify desorption energies directly, by comparing surface pressure-density compression measurements using a Wilhelmy plate and a custom-microfabricated deflection tensiometer. We focus on poly(ethylene oxide)-based polymers and nanoparticles. For PEO-based homo- and copolymers, the adsorption energy of PEO chains scales linearly with molecular weight and can be tuned by changing the subphase composition. Moreover, the desorption surface pressure of PEO-stabilized nanoparticles corresponds to the saturation surface pressure for spontaneously adsorbed monolayers, yielding trapping energies of ∼10(3) k(B)T.

Adsorption of hexavalent chromium on cationic cross-linked starches of different botanic origins.

PubMed

Klimaviciute, Rima; Bendoraitiene, Joana; Rutkaite, Ramune; Zemaitaitis, Algirdas

2010-09-15

The influence of origin of native starch used to obtain cationic cross-linked starch (CCS) on the adsorption of Cr(VI) onto CCS has been investigated. CCS granule size is influenced by the botanic source of native starch. The equilibrium adsorption of Cr(VI) onto CCS was described by the Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models. The more equal the adsorption energy of the quaternary ammonium groups in CCS granule as indicated by low value of change of Temkin adsorption energy DeltaE(T) the greater amount of Cr(VI) was adsorbed onto CCS. The value of DeltaE(T) decreased and sorption capacity of CCS increased with the decrease of CCS granule size and with the increase of number of amorphous regions in CCS granules. The affinity of dichromate anions increases and adsorption proceeds more spontaneously when Cr(VI) is adsorbed onto more amorphous CCS. Adsorption process of Cr(VI) onto such CCS is more exothermic and order of system undergoes major changes during adsorption. After the adsorption on CCS Cr(VI) could be regenerated by incineration at temperature of 800 degrees C. Copyright 2010 Elsevier B.V. All rights reserved.

Adsorption of organic molecules on a porous polymer surface modified with the supramolecular structure of melamine-cyanuric acid

NASA Astrophysics Data System (ADS)

Gainullina, Yu. Yu.; Guskov, V. Yu.

2017-10-01

The adsorption of organic molecules on the surface of a porous polymeric sorbent modified with a mixed cyanuric acid-melamine supramolecular structure is studied. The parameters of thermodynamic adsorption are considered and the contributions from intermolecular interactions to the Helmholtz energy of adsorption are assessed. Analysis of the molar changes in internal energy and adsorption entropy shows that the supramolecular structure formed on the surface could not exhibit dimension effects, indicating there were no cavities. The contributions from nonspecific interactions to the Helmholtz energy of adsorption generally fall, while those of specific interactions increase, indicating an increase in the polarity of the sorbent surface.

Internal Surface Adsorption of Methane in the Microporous and the Mesoporous Montmorillonite Models

NASA Astrophysics Data System (ADS)

Shao, Changjin; Nie, Dakai; Zhai, Zengqiang; Yang, Zhenqing

2018-05-01

Due to the rising worldwide energy demands and the shortage of natural gas resources, the development of shale gas has become the new research focus in the field of novel energy resources. To understand the adsorption mechanism of shale gas in the reservoir, we use grand canonical Monte Carlo (GCMC) method to investigate the internal surface adsorption behavior of methane (main component of shale gas) in microporous and mesoporous montmorillonite materials for changing pressure, temperature and surface spacing. The results show that the adsorption capacity of methane decreases with increasing temperature while increasing as the surface spacing increases. Especially, the adsorption isotherm of the microporous model has a mutation when the surface spacing is about 10 ˚A. According to the trend for the change in the adsorption capacity, the best scheme for the exploitation of shale gas can be selected so that the mining efficiency is greatly improved.

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

NASA Astrophysics Data System (ADS)

Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

2016-01-01

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes.

A fundamental study of the impact of pressure on the adsorption mechanism in reversed-phase liquid chromatography.

PubMed

Åsberg, Dennis; Samuelsson, Jörgen; Fornstedt, Torgny

2016-07-29

A fundamental investigation of the pressure effect on individual adsorption sites was undertaken based on adsorption energy distribution and adsorption isotherm measurements. For this purpose, we measured adsorption equilibrium data at pressures ranging from 100 to 1000bar at constant flow and over a wide concentration range for three low-molecular-weight solutes, antipyrine, sodium 2-naphthalenesulfonate, and benzyltriethylammonium chloride, on an Eternity C18 stationary phase. The adsorption energy distribution was bimodal for all solutes, remaining clearly so at all pressures. The bi-Langmuir model best described the adsorption in these systems and two types of adsorption sites were identified, one with a low and another with a high energy of interaction. Evidence exists that the low-energy interactions occur at the interface between the mobile and stationary phases and that the high-energy interactions occur nearer the silica surface, deeper in the C18 layer. The contribution of each type of adsorption site to the retention factor was calculated and the change in solute molar volume from the mobile to stationary phase during the adsorption process was estimated for each type of site. The change in solute molar volume was 2-4 times larger at the high-energy site, likely because of the greater loss of solute solvation layer when penetrating deeper into the C18 layer. The association equilibrium constant increased with increasing pressure while the saturation capacity of the low-energy site remained almost unchanged. The observed increase in saturation capacity for the high-energy site did not affect the column loading capacity, which was almost identical at 50- and 950-bar pressure drops over the column. Copyright © 2016 Elsevier B.V. All rights reserved.

Measurement of the adsorption energy difference between ortho- and para-D2 on an amorphous ice surface.

PubMed

Amiaud, L; Momeni, A; Dulieu, F; Fillion, J H; Matar, E; Lemaire, J-L

2008-02-08

Molecular hydrogen interaction on water ice surfaces is a major process taking place in interstellar dense clouds. By coupling laser detection and classical thermal desorption spectroscopy, it is possible to study the effect of rotation of D(2) on adsorption on amorphous solid water ice surfaces. The desorption profiles of ortho- and para-D(2) are different. This difference is due to a shift in the adsorption energy distribution of the two lowest rotational states. Molecules in J''=1 rotational state are on average more strongly bound to the ice surface than those in J''=0 rotational state. This energy difference is estimated to be 1.4+/-0.3 meV. This value is in agreement with previous calculation and interpretation. The nonspherical wave function J'' =1 has an interaction with the asymmetric part of the adsorption potential and contributes positively in the binding energy.

Adsorption of arsenic(III) into modified lamellar Na-magadiite in aqueous medium-Thermodynamic of adsorption process

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

Lima Guerra, Denis; Azevedo Pinto, Alane; Airoldi, Claudio

2008-12-15

Synthetic Na-magadiite sample was used for organofunctionalization process with N-propyldiethylenetrimethoxysilane and bis[3-(triethoxysilyl)propyl]tetrasulfide, after expanding the interlayer distance with polar organic solvents such as dimethylsulfoxide (DMSO). The resulted materials were submitted to process of adsorption with arsenic solution at pH 2.0 and 298{+-}1 K. The adsorption isotherms were adjusted using a modified Langmuir equation with regression nonlinear; the net thermal effects obtained from calorimetric titration measurements were adjusted to a modified Langmuir equation. The adsorption process was exothermic ({delta}{sub int}H=-4.15-5.98 kJ mol{sup -1}) accompanied by increase in entropy ({delta}{sub int}S=41.32-62.20 J k{sup -1} mol{sup -1}) and Gibbs energy ({delta}{sub int}G=-22.44-24.56 kJmore » mol{sup -1}). The favorable values corroborate with the arsenic (III)/basic reactive centers interaction at the solid-liquid interface in the spontaneous process. - Grapical Abstract: The results suggest that the adsorption capacities increased with an increase of reactive basic centers in the pendant organic chains of the intercalated agent.« less

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

PubMed Central

Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

2016-01-01

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes. PMID:26796523

Behavior of the Enthalpy of Adsorption in Nanoporous Materials Close to Saturation Conditions

PubMed Central

2017-01-01

Many important industrial separation processes based on adsorption operate close to saturation. In this regime, the underlying adsorption processes are mostly driven by entropic forces. At equilibrium, the entropy of adsorption is closely related to the enthalpy of adsorption. Thus, studying the behavior of the enthalpy of adsorption as a function of loading is fundamental to understanding separation processes. Unfortunately, close to saturation, the enthalpy of adsorption is hard to measure experimentally and hard to compute in simulations. In simulations, the enthalpy of adsorption is usually obtained from energy/particle fluctuations in the grand-canonical ensemble, but this methodology is hampered by vanishing insertions/deletions at high loading. To investigate the fundamental behavior of the enthalpy and entropy of adsorption at high loading, we develop a simplistic model of adsorption in a channel and show that at saturation the enthalpy of adsorption diverges to large positive values due to repulsive intermolecular interactions. However, there are many systems that can avoid repulsive intermolecular interactions and hence do not show this drastic increase in enthalpy of adsorption close to saturation. We find that the conventional grand-canonical Monte Carlo method is incapable of determining the enthalpy of adsorption from energy/particle fluctuations at high loading. Here, we show that by using the continuous fractional component Monte Carlo, the enthalpy of adsorption close to saturation conditions can be reliably obtained from the energy/particle fluctuations in the grand-canonical ensemble. The best method to study properties at saturation is the NVT energy (local-) slope methodology. PMID:28521093

Method Evaluations for Adsorption Free Energy Calculations at the Solid/Water Interface through Metadynamics, Umbrella Sampling, and Jarzynski's Equality.

PubMed

Wei, Qichao; Zhao, Weilong; Yang, Yang; Cui, Beiliang; Xu, Zhijun; Yang, Xiaoning

2018-03-19

Considerable interest in characterizing protein/peptide-surface interactions has prompted extensive computational studies on calculations of adsorption free energy. However, in many cases, each individual study has focused on the application of free energy calculations to a specific system; therefore, it is difficult to combine the results into a general picture for choosing an appropriate strategy for the system of interest. Herein, three well-established computational algorithms are systemically compared and evaluated to compute the adsorption free energy of small molecules on two representative surfaces. The results clearly demonstrate that the characteristics of studied interfacial systems have crucial effects on the accuracy and efficiency of the adsorption free energy calculations. For the hydrophobic surface, steered molecular dynamics exhibits the highest efficiency, which appears to be a favorable method of choice for enhanced sampling simulations. However, for the charged surface, only the umbrella sampling method has the ability to accurately explore the adsorption free energy surface. The affinity of the water layer to the surface significantly affects the performance of free energy calculation methods, especially at the region close to the surface. Therefore, a general principle of how to discriminate between methodological and sampling issues based on the interfacial characteristics of the system under investigation is proposed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of aqueous copper on peanut hulls

NASA Astrophysics Data System (ADS)

Davis, Kanika Octavia

A method was established for measuring the adsorption of Cu(II) from aqueous solution to unmodified and modified peanut hulls at constant temperature and pH. Modification of the hulls was performed by oxidation with alkaline hydrogen peroxide. During the modification process, the hydrogen peroxide solubilizes the lignin component, making the surface more porous which increases the availability of binding sites, while simultaneously oxidizing the cellulose. The oxidation of alcohol groups creates more binding sites by creating functional groups such as COO-, which increases chelation to metal ions. Fourier transform infrared spectroscopy confirms delignification of the peanut hulls by the disappearance of carboxyl peaks of the modified hulls, which were originally produced from the lignin content. Although, oxidation is not fully confirmed, it is not ruled out because the expected carboxylate peak (1680 cm-1) maybe overshadowed by a broad peak due to OH bending of water adsorbed to the hulls. Hulls adsorbed copper from solutions in the concentration range of 50-1000 ppm of CuCl2. Concentrations of pre- and post-adsorption solutions were determined using inductively coupled plasma optical emission spectroscopy. The adsorption isotherms were fit to known two and three-parameter models, evaluated and the binding mechanism was inferred. Maximum surface coverage was 3.5 +/- 0.6 mg Cu2+ /g hull for unmodified hulls and 11 +/- 1 mg Cu2+/g hull for modified hulls. The adsorption for the hulls is best described by the Langmuir model, suggesting monolayer, homogeneous adsorption. With a free energy of adsorption of 10.5 +/- 0.9 kJ/mol for unmodified hulls and 14.5 +/-0.4 kJ/mol for modified hulls, the process is categorized as chemisorption for both types of hulls. The adsorption for both hulls is also described by the Redlich-Peterson model, giving beta nearer to 1 than 0, which further suggests homogeneous adsorption described by the Langmuir model. After rinsing the hulls

Water and Carbon Dioxide Adsorption at Olivine Surfaces

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

Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

2013-11-14

Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbonmore » dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.« less

Method and apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption

DOEpatents

Wegeng, Robert S.; Rassat, Scot D.; TeGrotenhuis, Ward E.; Drost, Kevin; Vishwanathan, Vilayanur V.

2004-06-08

The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. In another aspect, the apparatus or methods utilize heat exchange channels of varying lengths that have volumes controlled to provide equal heat fluxes. Methods of fuel cell startup are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

Enhanced charge efficiency and reduced energy use in capacitive deionization by increasing the discharge voltage.

PubMed

Kim, T; Dykstra, J E; Porada, S; van der Wal, A; Yoon, J; Biesheuvel, P M

2015-05-15

Capacitive deionization (CDI) is an electrochemical method for water desalination using porous carbon electrodes. A key parameter in CDI is the charge efficiency, Λ, which is the ratio of salt adsorption over charge in a CDI-cycle. Values for Λ in CDI are typically around 0.5-0.8, significantly less than the theoretical maximum of unity, due to the fact that not only counterions are adsorbed into the pores of the carbon electrodes, but at the same time coions are released. To enhance Λ, ion-exchange membranes (IEMs) can be implemented. With membranes, Λ can be close to unity because the membranes only allow passage for the counterions. Enhancing the value of Λ is advantageous as this implies a lower electrical current and (at a fixed charging voltage) a reduced energy use. We demonstrate how, without the need to include IEMs, the charge efficiency can be increased to values close to the theoretical maximum of unity, by increasing the cell voltage during discharge, with only a small loss of salt adsorption capacity per cycle. In separate constant-current CDI experiments, where after some time the effluent salt concentration reaches a stable value, this value is reached earlier with increased discharge voltage. We compare the experimental results with predictions of porous electrode theory which includes an equilibrium Donnan electrical double layer model for salt adsorption in carbon micropores. Our results highlight the potential of modified operational schemes in CDI to increase charge efficiency and reduce energy use of water desalination. Copyright © 2014 Elsevier Inc. All rights reserved.

Metal-phthalocyanine ordered layers on Au(110): Metal-dependent adsorption energy

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

Massimi, Lorenzo, E-mail: lorenzo.massimi@uniroma1.it; Angelucci, Marco; Gargiani, Pierluigi

2014-06-28

Iron-phthalocyanine and cobalt-phthalocyanine chains, assembled along the Au(110)-(1×2) reconstructed channels, present a strong interaction with the Au metallic states, via the central metal ion. X-ray photoemission spectroscopy from the metal-2p core-levels and valence band high-resolution ultraviolet photoelectron spectroscopy bring to light signatures of the interaction of the metal-phthalocyanine single-layer with gold. The charge transfer from Au to the molecule causes the emerging of a metal-2p core level component at lower binding energy with respect to that measured in the molecular thin films, while the core-levels associated to the organic macrocycle (C and N 1s) are less influenced by the adsorption,more » and the macrocycles stabilize the interaction, inducing a strong interface dipole. Temperature Programmed Desorption experiments and photoemission as a function of temperature allow to estimate the adsorption energy for the thin-films, mainly due to the molecule-molecule van der Waals interaction, while the FePc and CoPc single-layers remain adsorbed on the Au surface up to at least 820 K.« less

Adsorption Energies of Carbon, Nitrogen, and Oxygen Atoms on the Low-temperature Amorphous Water Ice: A Systematic Estimation from Quantum Chemistry Calculations

NASA Astrophysics Data System (ADS)

Shimonishi, Takashi; Nakatani, Naoki; Furuya, Kenji; Hama, Tetsuya

2018-03-01

We propose a new simple computational model to estimate the adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3 P), nitrogen (4 S), and oxygen (3 P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14,100 ± 420 K for carbon, 400 ± 30 K for nitrogen, and 1440 ± 160 K for oxygen. The adsorption energy of oxygen is consistent with experimentally reported values. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption, in which a chemical bond to an O atom of a water molecule is formed. That of an oxygen atom has a dual character, with both physisorption and chemisorption. The chemisorption of atomic carbon also implies the possibility of further chemical reactions to produce molecules bearing a C–O bond, though this may hinder the formation of methane on water ice via sequential hydrogenation of carbon atoms. These properties would have a large impact on the chemical evolution of carbon species in interstellar environments. We also investigated the effects of newly calculated adsorption energies on the chemical compositions of cold dense molecular clouds with the aid of gas-ice astrochemical simulations. We found that abundances of major nitrogen-bearing molecules, such as N2 and NH3, are significantly altered by applying the calculated adsorption energy, because nitrogen atoms can thermally diffuse on surfaces, even at 10 K.

Adsorption of ion pairs onto graphene flakes and impacts of counterions during the adsorption processes

NASA Astrophysics Data System (ADS)

Zhu, Chang; Yun, Jiena; Wang, Qian; Yang, Gang

2018-03-01

Although cations and anions are two integral constituents for all electrolytes, adsorption of ion pairs onto carbonaceous materials gains obviously less attention than adsorption of only cations or anions. Here DFT calculations are employed finding that four adsorption configurations emerge for KI onto graphene flakes (GF) instead of three for the other ion pairs. Reservation of ionic bonds is critical to their stabilities, and the bilateral configurations, where GFs couple with both cations and anions, are disfavored due to rupture of ionic bonds. Relative stabilities of two vertical configurations can be regulated and even reversed through edge-functionalization. Surprisingly, the horizontal adsorption configurations, which are global energy minima as long as present, are non-existent for a majority of ion pairs, and their existence or not is determined by the adsorption differences between halide ions and alkali ions (△Ead). Counterions effects for both cations and anions increase with the atomic electronegativities and cations correspond to stronger counterion effects; e.g., Li+ added on the other side of GFs promotes the adsorption of F- more pronouncedly than edge-functionalization. Mechanisms of electron transfers are also discussed, and three alteration patterns by counterions are observed for each type of adsorption configurations. Furthermore, addition of counterions causes band gaps to vary within a wider range that may be useful to design electronic devices.

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

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

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

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

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

Trends in Adsorption Energies of the Oxygenated Species on Single Platinum Atom Embedded in Carbon Nanotubes

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

Siahrostami, Samira; Li, Guo-Ling; Nørskov, Jens K.

Herein we study the effect of strain on the catalytic activity of different Pt-doped single wall metallic carbon nanotubes (SWCNT) towards the oxygen reduction reaction (ORR). We consider the possibility of the Pt-doped at single vacancy inside the SWCNT to investigate the effect of confinement on the reaction mechanism. Density functional theory calculations indicate that for the SWCNTs with tube diameters below 7 Å, the strain energy varies significantly influencing the adsorption energies of the key intermediates of the ORR reaction. For the SWCNTs with tube diameters above 7 Å, on the other hand, both the calculated strain and themore » adsorption energies are almost constant. We furthermore find that the adsorption energies are strongly affected by confinement effects as shown for Pt-doped systems that are located inside the SWCNT. We show that the Pt-doped at single vacancy of the SWCNT strongly binds the oxygenated species under ORR potentials and therefore the active species is covered by oxo- or hydroxo group. Because the presence of Pt atoms doped at the single and double vacancies of the SWCNT is equivalently probable we also studied the Pt-doped at double vacancy. We find that the most active motif is the Pt-doped at double vacancy of SWCNT with 0.24V overpotenital.« less

Trends in Adsorption Energies of the Oxygenated Species on Single Platinum Atom Embedded in Carbon Nanotubes

DOE PAGES

Siahrostami, Samira; Li, Guo-Ling; Nørskov, Jens K.; ...

2017-09-30

Herein we study the effect of strain on the catalytic activity of different Pt-doped single wall metallic carbon nanotubes (SWCNT) towards the oxygen reduction reaction (ORR). We consider the possibility of the Pt-doped at single vacancy inside the SWCNT to investigate the effect of confinement on the reaction mechanism. Density functional theory calculations indicate that for the SWCNTs with tube diameters below 7 Å, the strain energy varies significantly influencing the adsorption energies of the key intermediates of the ORR reaction. For the SWCNTs with tube diameters above 7 Å, on the other hand, both the calculated strain and themore » adsorption energies are almost constant. We furthermore find that the adsorption energies are strongly affected by confinement effects as shown for Pt-doped systems that are located inside the SWCNT. We show that the Pt-doped at single vacancy of the SWCNT strongly binds the oxygenated species under ORR potentials and therefore the active species is covered by oxo- or hydroxo group. Because the presence of Pt atoms doped at the single and double vacancies of the SWCNT is equivalently probable we also studied the Pt-doped at double vacancy. We find that the most active motif is the Pt-doped at double vacancy of SWCNT with 0.24V overpotenital.« less

DNA adsorption characteristics of hollow spherule allophane nano-particles.

PubMed

Matsuura, Yoko; Iyoda, Fumitoshi; Arakawa, Shuichi; John, Baiju; Okamoto, Masami; Hayashi, Hidetomo

2013-12-01

To understand the propensity of natural allophane to adsorb the DNA molecules, the adsorption characteristics were assessed against natural allophane (AK70), using single-stranded DNA (ss-DNA) and adenosine 5'-monophosphate (5'-AMP) as a reference molecule. The adsorption capacity of ss-DNA on AK70 exhibited one order of magnitude lower value as compared with that of 5'-AMP. The adsorption capacity of ss-DNA decreased with increasing pH due to the interaction generated between phosphate groups of ss-DNA and functional Al-OH groups on the wall perforations through deprotonating, associated with higher energy barrier for the adsorption of ss-DNA. The adsorption morphologies consisting of the individual ss-DNA with mono-layer coverage of the clustered allophane particle were observed successfully through transmission electron microscopy analysis. © 2013.

Alcohol molecules adsorption on graphane nanosheets - A first-principles investigation

NASA Astrophysics Data System (ADS)

Nagarajan, V.; Chandiramouli, R.

2018-05-01

The geometric structure, electronic and adsorption properties of methanol, ethanol and 1-propanol molecules on hydrogenated graphene (graphane) were investigated using first-principles calculations. The stability of graphane base material is confirmed using formation energy and phonon band structures. The adsorption of alcohol molecules on bare graphane and hydrogen vacant graphane nanosheet is found to be prominent and the selectivity of alcohol molecules can be achieved using bare or hydrogen vacant graphane nanosheet. Moreover, the interaction of alcohol molecules on bare and hydrogen vacant graphane nanosheets is studied using the adsorption energy, energy band gap variation, Bader charge transfer and average energy band gap variation. The adsorption energy ranges from -0.149 to -0.383 eV upon alcohol adsorption. The energy gap varies from 4.71 to 2.62 eV for bare graphane and from 4.02 to 3.60 eV for hydrogen vacant graphane nanosheets upon adsorption of alcohol molecules. The adsorption properties of alcohol molecules provide useful information for the possible application of graphane nanosheet as a base material for the detection of alcohol molecules.

Heavy metal adsorption changes of EAF steel slag after phosphorus adsorption.

PubMed

Song, Guanling; Cao, Lijing; Chen, Xiao; Hou, Wenhua; Wang, Qunhui

2012-01-01

A kind of electric arc furnace (EAF) steel slag was phosphated, and its isothermal and dynamic adsorptions of copper, cadmium, and lead ions were measured to determine if heavy metal adsorption changes after phosphorus adsorption. The surface area increased greatly after the slag was phosphated. Isothermal adsorption experiments showed that the theoretical Q(max) of the EAF steel slag on Cu(2+), Cd(2+), and Pb(2+) improved 59, 50, and 89% respectively after it was phosphated. Dynamic adsorption results showed that the greatest adsorption capacities of unit volume of Cu(2+), Cd(2+), and Pb(2+) were 2.2, 1.8, and 1.8 times that of the column packed with original EAF steel slag when the column was packed with phosphate EAF steel slag at the same heavy metal ion concentration. The breakthrough time, the exhaustion time and elution efficiency of the column also increased when the column was packed with phosphated EAF steel slag compared with that packed with original EAF steel slag. Phosphorus adsorption could further improve the heavy metal ion adsorption of the EAF steel slag.

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: kinetics, isotherms and thermodynamics.

PubMed

Yu, Fei; Wu, Yanqing; Ma, Jie; Zhang, Chi

2013-01-01

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qmSSA) and SSA-normalized adsorption coefficient (Kd/SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (deltaG0) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (deltaH0), deltaG0 and free energy of adsorption (Ea), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and Kd/SSA or qm/SSA.

Kinetics and Thermodynamics of Reserpine Adsorption onto Strong Acidic Cationic Exchange Fiber

PubMed Central

Guo, Zhanjing; Liu, Xiongmin; Huang, Hongmiao

2015-01-01

The kinetics and thermodynamics of the adsorption process of reserpine adsorbed onto the strong acidic cationic exchange fiber (SACEF) were studied by batch adsorption experiments. The adsorption capacity strongly depended on pH values, and the optimum reserpine adsorption onto the SACEF occurred at pH = 5 of reserpine solution. With the increase of temperature and initial concentration, the adsorption capacity increased. The equilibrium was attained within 20 mins. The adsorption process could be better described by the pseudo-second-order model and the Freundlich isotherm model. The calculated activation energy Ea was 4.35 kJ/mol. And the thermodynamic parameters were: 4.97<ΔH<7.44 kJ/mol, -15.29<ΔG<-11.87 kJ/mol and 41.97<ΔS<47.35 J/mol·K. The thermodynamic parameters demonstrated that the adsorption was an endothermic, spontaneous and feasible process of physisorption within the temperature range between 283 K and 323 K and the initial concentration range between 100 mg/L and 300 mg/L. All the results showed that the SACEF had a good adsorption performance for the adsorption of reserpine from alcoholic solution. PMID:26422265

Mechanics of adsorption-deformation coupling in porous media

NASA Astrophysics Data System (ADS)

Zhang, Yida

2018-05-01

This work extends Coussy's macroscale theory for porous materials interacting with adsorptive fluid mixtures. The solid-fluid interface is treated as an independent phase that obeys its own mass, momentum and energy balance laws. As a result, a surface strain energy term appears in the free energy balance equation of the solid phase, which further introduces the so-called adsorption stress in the constitutive equations of the porous skeleton. This establishes a fundamental link between the adsorption characteristics of the solid-fluid interface and the mechanical response of the porous media. The thermodynamic framework is quite general in that it recovers the coupled conduction laws, Gibbs isotherm and the Shuttleworth's equation for surface stress, and imposes no constraints on the magnitude of deformation and the functional form of the adsorption isotherms. A rich variety of coupling between adsorption and deformation is recovered as a result of combining different poroelastic models (isotropic vs. anisotropic, linear vs. nonlinear) and adsorption models (unary vs. mixture adsorption, uncoupled vs. stretch-dependent adsorption). These predictions are discussed against the backdrop of recent experimental data on coal swelling subjected to CO2 and CO2sbnd CH4 injections, showing the capability and versatility of the theory in capturing adsorption-induced deformation of porous materials.

Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111).

PubMed

Geweke, Jan; Shirhatti, Pranav R; Rahinov, Igor; Bartels, Christof; Wodtke, Alec M

2016-08-07

In this work we seek to examine the nature of collisional energy transfer between HCl and Au(111) for nonreactive scattering events that sample geometries near the transition state for dissociative adsorption by varying both the vibrational and translational energy of the incident HCl molecules in the range near the dissociation barrier. Specifically, we report absolute vibrational excitation probabilities for HCl(v = 0 → 1) and HCl(v = 1 → 2) scattering from clean Au(111) as a function of surface temperature and incidence translational energy. The HCl(v = 2 → 3) channel could not be observed-presumably due to the onset of dissociation. The excitation probabilities can be decomposed into adiabatic and nonadiabatic contributions. We find that both contributions strongly increase with incidence vibrational state by a factor of 24 and 9, respectively. This suggests that V-T as well as V-EHP coupling can be enhanced near the transition state for dissociative adsorption at a metal surface. We also show that previously reported HCl(v = 0 → 1) excitation probabilities [Q. Ran et al., Phys. Rev. Lett. 98, 237601 (2007)]-50 times smaller than those reported here-were influenced by erroneous assignment of spectroscopic lines used in the data analysis.

Linear solvation energy relationships (LSER) for adsorption of organic compounds by carbon nanotubes.

PubMed

Ersan, Gamze; Apul, Onur G; Karanfil, Tanju

2016-07-01

The objective of this paper was to create a comprehensive database for the adsorption of organic compounds by carbon nanotubes (CNTs) and to use the Linear Solvation Energy Relationship (LSER) technique for developing predictive adsorption models of organic compounds (OCs) by multi-walled carbon nanotubes (MWCNTs) and single-walled carbon nanotubes (SWCNTs). Adsorption data for 123 OCs by MWCNTs and 48 OCs by SWCNTs were compiled from the literature, including some experimental results obtained in our laboratory. The roles of selected OCs properties and CNT types were examined with LSER models. The results showed that the r(2) values of the LSER models displayed small variability for aromatic compounds smaller than 220 g/mol, after which a decreasing trend was observed. The data available for aliphatics was mainly for molecular weights smaller than 250 g/mol, which showed a similar trend to that of aromatics. The r(2) values for the LSER model on the adsorption of aromatic and aliphatic OCs by SWCNTs and MWCNTs were relatively similar indicating the linearity of LSER models did not depend on the CNT types. Among all LSER model descriptors, V term (molecular volume) for aromatic OCs and B term (basicity) for aliphatic OCs were the most predominant descriptors on both type of CNTs. The presence of R term (excess molar refractivity) in LSER model equations resulted in decreases for both V and P (polarizability) parameters without affecting the r(2) values. Overall, the results demonstrate that successful predictive models can be developed for the adsorption of OCs by MWCNTs and SWCNTs with LSER techniques. Copyright © 2016 Elsevier Ltd. All rights reserved.

Adsorption of arsenic(III) into modified lamellar Na-magadiite in aqueous medium—Thermodynamic of adsorption process

NASA Astrophysics Data System (ADS)

Guerra, Denis Lima; Pinto, Alane Azevedo; Airoldi, Claudio; Viana, Rúbia Ribeiro

2008-12-01

Synthetic Na-magadiite sample was used for organofunctionalization process with N-propyldiethylenetrimethoxysilane and bis[3-(triethoxysilyl)propyl]tetrasulfide, after expanding the interlayer distance with polar organic solvents such as dimethylsulfoxide (DMSO). The resulted materials were submitted to process of adsorption with arsenic solution at pH 2.0 and 298±1 K. The adsorption isotherms were adjusted using a modified Langmuir equation with regression nonlinear; the net thermal effects obtained from calorimetric titration measurements were adjusted to a modified Langmuir equation. The adsorption process was exothermic (Δ intH=-4.15-5.98 kJ mol -1) accompanied by increase in entropy (Δ intS=41.32-62.20 J k -1 mol -1) and Gibbs energy (Δ intG=-22.44-24.56 kJ mol -1). The favorable values corroborate with the arsenic (III)/basic reactive centers interaction at the solid-liquid interface in the spontaneous process.

New findings on the influence of carbon surface curvature on energetics of benzene adsorption from gaseous phase

NASA Astrophysics Data System (ADS)

Terzyk, Artur P.; Furmaniak, Sylwester; Wiśniewski, Marek; Werengowska, Karolina; Gauden, Piotr A.; Kowalczyk, Piotr

2016-02-01

In this Letter, new results of calorimetric study on benzene adsorption from the gaseous phase are presented. According to some of recently published reports, the energy of solid-fluid, interactions increases with the rise in carbon nanotube curvature during adsorption. The recent considerations [Chem. Phys. Lett. 619 (2015) 219] on thermodynamics of adsorption from aqueous solutions on a series of carbon nanotubes have confirmed this observation. Although comparable 'energy-tube diameter' relations for benzene adsorption from the solution and from the gaseous phase are observed, remarkable differences between the mechanisms of the both processes caused by surface heterogeneity are noticeable.

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.

Determination of the Adsorption Free Energy for Peptide–Surface Interactions by SPR Spectroscopy

PubMed Central

Wei, Yang; Latour, Robert A.

2009-01-01

To understand and predict protein adsorption behavior, we must first understand the fundamental interactions between the functional groups presented by the amino acid residues making up a protein and the functional groups presented by the surface. Limited quantitative information is available, however, on these types of submolecular interactions. The objective of this study was therefore to develop a reliable method to determine the standard state adsorption free energy (ΔG°ads) of amino acid residue–surface interactions using surface plasma resonance (SPR) spectroscopy. Two problems are commonly encountered when using SPR for peptide adsorption studies: the need to account for “bulk-shift” effects and the influence of peptide–peptide interactions at the surface. Bulk-shift effects represent the contribution of the bulk solute concentration to the SPR response that occurs in addition to the response due to adsorption. Peptide–peptide interactions, which are assumed to be zero for Langmuir adsorption, can greatly skew the isotherm shape and result in erroneous calculated values of ΔG°ads. To address these issues, we have developed a new approach for the determination of ΔG°ads using SPR that is based on the chemical potential. In this article, we present the development of this new approach and its application for the calculation of ΔG°ads for a set of peptide–surface systems where the peptide has a host–guest amino acid sequence of TGTG-X-GTGT (where G and T are glycine and threonine residues and X represents a variable residue) and the surface consists of alkanethiol self-assembled monolayers (SAMs) with methyl (CH3) and hydroxyl (OH) functionality. This new approach enables bulk-shift effects to be directly determined from the raw SPR versus peptide concentration data plots and the influence of peptide–peptide interaction effects to be minimized, thus providing a very straightforward and accurate method for the determination of ΔG �

Adsorption of thiophene on silica-supported Mo clusters

NASA Astrophysics Data System (ADS)

Komarneni, M.; Kadossov, E.; Justin, J.; Lu, M.; Burghaus, U.

2010-07-01

The adsorption/decomposition kinetics/dynamics of thiophene has been studied on silica-supported Mo and MoS x clusters. Two-dimensional cluster formation at small Mo exposures and three-dimensional cluster growth at larger exposures would be consistent with the Auger electron spectroscopy (AES) data. Thermal desorption spectroscopy (TDS) indicates two reaction pathways. H 4C 4S desorbs molecularly at 190-400 K. Two TDS features were evident and could be assigned to molecularly on Mo sites, and S sites adsorbed thiophene. Assuming a standard preexponential factor (ν = 1 × 10 13/s) for first-order kinetics, the binding energies for adsorption on Mo (sulfur) sites amount to 90 (65) kJ/mol for 0.4 ML Mo exposure and 76 (63) kJ/mol for 2 ML Mo. Thus, smaller clusters are more reactive than larger clusters for molecular adsorption of H 4C 4S. The second reaction pathway, the decomposition of thiophene, starts at 250 K. Utilizing multimass TDS, H 2, H 2S, and mostly alkynes are detected in the gas phase as decomposition products. H 4C 4S bond activation results in partially sulfided Mo clusters as well as S and C residuals on the surface. S and C poison the catalyst. As a result, with an increasing number of H 4C 4S adsorption/desorption cycles, the uptake of molecular thiophene decreases as well as the H 2 and H 2S production ceases. Thus, silica-supported sulfided Mo clusters are less reactive than metallic clusters. The poisoned catalyst can be partially reactivated by annealing in O 2. However, Mo oxides also appear to form, which passivate the catalyst further. On the other hand, while annealing a used catalyst in H/H 2, it is poisoned even more (i.e., the S AES signal increases). By means of adsorption transients, the initial adsorption probability, S0, of C 4H 4S has been determined. At thermal impact energies ( Ei = 0.04 eV), S0 for molecular adsorption amounts to 0.43 ± 0.03 for a surface temperature of 200 K. S0 increases with Mo cluster size, obeying the

On irreversible adsorption of electron-donating compounds in aqueous solution

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

Tamon, Hajime; Atsushi, Masanori; Okazaki, Morio

Activated carbons and synthetic adsorbents have been used for liquid purification and wastewater treatment. The feasibility of an adsorption process depends greatly on the cost of regeneration of spent adsorbents. If irreversible adsorption occurs, regeneration of spent adsorbent is very difficult. Hence, it is very important to understand why irreversible adsorption appears in aqueous solution. In the adsorption of electron-donating compounds such as phenol, aniline, L-phenylalanine, and L-tyrosine from aqueous solution, irreversibility was observed on activated carbon and graphite. The compounds, except L-tyrosine, were reversibly adsorbed on a synthetic adsorbent. In the case where the carbonaceous adsorbents contacted the aqueousmore » solution containing electron-donating compounds for a long time, the irreversible amount adsorbed increased with the contact time. A two-state adsorption model was used to explain why the irreversible adsorption of electron-donating compound appears in aqueous solution. First, the compound is adsorbed in the precursor state for irreversible adsorption, and then moves into its irreversible state over a potential energy barrier after a long contact time. The appearance of irreversible adsorption was qualitatively explained by the two-state adsorption model.« less

Dynamic surface tension and adsorption mechanism of surfactin biosurfactant at the air-water interface.

PubMed

Onaizi, Sagheer A

2018-03-01

The dynamic adsorption of the anionic biosurfactant, surfactin, at the air-water interface has been investigated in this work and compared to those of two synthetic surfactants: the anionic sodium dodecylbenzenesulfonate (SDBS) and the nonionic octaethylene glycol monotetradecyl ether (C 14 E 8 ). The results revealed that surfactin adsorption at the air-water interface is purely controlled by diffusion mechanism at the initial stage of the adsorption process (i.e., [Formula: see text]), but shifts towards a mixed diffusion-barrier mechanism when surface tension approaches equilibrium (i.e., [Formula: see text]) due to the development of an energy barrier for adsorption. Such energy barrier has been found to be a function of the surfactin bulk concentration (increases with increasing surfactin concentration) and it is estimated to be in the range of 1.8-9.5 kJ/mol. Interestingly, such a trend (pure diffusion-controlled mechanism at [Formula: see text] and mixed diffusion-barrier mechanism at [Formula: see text]) has been also observed for the nonionic C 14 E 8 surfactant. Unlike the pure diffusion-controlled mechanism of the initial surfactin adsorption, which was the case in the presence and the absence of the sodium ion (Na + ), SDBS showed a mixed diffusion-barrier controlled at both short and long time, with an energy barrier of 3.0-9.0 and 3.8-18.0 kJ/mol, respectively. Such finding highlights the nonionic-like adsorption mechanism of surfactin despite its negative charge.

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

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

Nitrile versus isonitrile adsorption at interstellar grain surfaces. II. Carbonaceous aromatic surfaces

NASA Astrophysics Data System (ADS)

Bertin, M.; Doronin, M.; Michaut, X.; Philippe, L.; Markovits, A.; Fillion, J.-H.; Pauzat, F.; Ellinger, Y.; Guillemin, J.-C.

2017-12-01

Context. Almost 20% of the 200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Of these 37 molecules, 30 are nitrile R-CN compounds, the remaining 7 belonging to the isonitrile R-NC family. How these species behave in their interactions with the grain surfaces is still an open question. Aims: In a previous work, we have investigated whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of various nature and morphologies. This study is a follow up of this work, where we focus on the adsorption on carbonaceous aromatic surfaces. Methods: The question is addressed by means of a concerted experimental and theoretical approach of the adsorption energies of CH3CN and CH3NC on the surface of graphite (with and without surface defects). The experimental determination of the molecule and surface interaction energies is carried out using temperature-programmed desorption in an ultra-high vacuum between 70 and 160 K. Theoretically, the question is addressed using first-principle periodic density functional theory to represent the organised solid support. Results: The adsorption energy of each compound is found to be very sensitive to the structural defects of the aromatic carbonaceous surface: these defects, expected to be present in a large numbers and great diversity on a realistic surface, significantly increase the average adsorption energies to more than 50% as compared to adsorption on perfect graphene planes. The most stable isomer (CH3CN) interacts more efficiently with the carbonaceous solid support than the higher energy isomer (CH3NC), however.

Dissociative adsorption of water on Au/MgO/Ag(001) from first principles calculations

NASA Astrophysics Data System (ADS)

Nevalaita, J.; Häkkinen, H.; Honkala, K.

2015-10-01

The molecular and dissociative adsorption of water on a Ag-supported 1 ML, 2 ML and 3 ML-a six atomic layer-thick MgO films with a single Au adatom is investigated using density functional theory calculations. The obtained results are compared to a bulk MgO(001) surface with an Au atom. On thin films the negatively charged Au strengthens the binding of the polar water molecule due to the attractive Au-H interaction. The adsorption energy trends of OH and H with respect to the film thickness depend on an adsorption site. In the case OH or H binds atop Au on MgO/Ag(001), the adsorption becomes more exothermic with the increasing film thickness, while the reverse trend is seen when the adsorption takes place on bare MgO/Ag(001). This behavior can be explained by different bonding mechanisms identified with the Bader analysis. Interestingly, we find that the rumpling of the MgO film and the MgO-Ag interface distance correlate with the charge transfer over the thin film and the interface charge, respectively. Moreover, we employ a modified Born-Haber-cycle to analyze the effect of film thickness to the adsorption energy of isolated Au and OH species on MgO/Ag(001). The analysis shows that the attractive Coulomb interaction between the negatively charged adsorbate and the positive MgO-Ag-interface does not completely account for the weaker binding with increasing film thickness. The redox energy associated with the charge transfer from the interface to the adsorbate is more exothermic with the increasing film thickness and partly compensates the decrease in the attractive Coulomb interaction.

Theoretical insight of adsorption thermodynamics of multifunctional molecules on metal surfaces

NASA Astrophysics Data System (ADS)

Loffreda, David

2006-05-01

Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries.

[Adsorption of Congo red from aqueous solution on hydroxyapatite].

PubMed

Zhan, Yan-Hui; Lin, Jian-Wei

2013-08-01

The adsorption of Congo red (CR) from aqueous solution on hydroxyapatite was investigated using batch experiments. The hydroxyapatite was effective for CR removal from aqueous solution. The adsorption kinetics of CR on hydroxyapatite well followed a pseudo-second-order model. The equilibrium adsorption data of CR on hydroxyapatite could be described by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and showed that the adsorption of CR on hydroxyapatite was spontaneous and exothermic in nature. The CR adsorption capacity for hydroxyapatite decreased significantly with increasing pH from 8 to 10. Thermal regeneration showed that hydroxyapatite could be used for six desorption-adsorption cycles with high removal efficiency for CR in each cycle. The mechanisms for CR adsorption on hydroxyapatite with pH value below the pH at point of zero charge (pH(PZC)) include electrostatic attraction, hydrogen bonding and Lewis acid-base interaction. The mechanisms for CR adsorption on hydroxyapatite with pH value above its pH(PZC) include hydrogen bonding and Lewis acid-base interaction. Results of this work indicate that hydroxyapatite is a promising adsorbent for CR removal from aqueous solution.

Free energy landscape of dissociative adsorption of methane on ideal and defected graphene from ab initio simulations

NASA Astrophysics Data System (ADS)

Wlazło, M.; Majewski, J. A.

2018-03-01

We study the dissociative adsorption of methane at the surface of graphene. Free energy profiles, which include activation energies for different steps of the reaction, are computed from constrained ab initio molecular dynamics. At 300 K, the reaction barriers are much lower than experimental bond dissociation energies of gaseous methane, strongly indicating that the graphene surface acts as a catalyst of methane decomposition. On the other hand, the barriers are still much higher than on the nickel surface. Methane dissociation therefore occurs at a higher rate on nickel than on graphene. This reaction is a prerequisite for graphene growth from a precursor gas. Thus, the growth of the first monolayer should be a fast and efficient process while subsequent layers grow at a diminished rate and in a more controllable manner. Defects may also influence reaction energetics. This is evident from our results, in which simple defects (Stone-Wales defect and nitrogen substitution) lead to different free energy landscapes at both dissociation and adsorption steps of the process.

Toward Accurate Adsorption Energetics on Clay Surfaces

PubMed Central

2016-01-01

Clay minerals are ubiquitous in nature, and the manner in which they interact with their surroundings has important industrial and environmental implications. Consequently, a molecular-level understanding of the adsorption of molecules on clay surfaces is crucial. In this regard computer simulations play an important role, yet the accuracy of widely used empirical force fields (FF) and density functional theory (DFT) exchange-correlation functionals is often unclear in adsorption systems dominated by weak interactions. Herein we present results from quantum Monte Carlo (QMC) for water and methanol adsorption on the prototypical clay kaolinite. To the best of our knowledge, this is the first time QMC has been used to investigate adsorption at a complex, natural surface such as a clay. As well as being valuable in their own right, the QMC benchmarks obtained provide reference data against which the performance of cheaper DFT methods can be tested. Indeed using various DFT exchange-correlation functionals yields a very broad range of adsorption energies, and it is unclear a priori which evaluation is better. QMC reveals that in the systems considered here it is essential to account for van der Waals (vdW) dispersion forces since this alters both the absolute and relative adsorption energies of water and methanol. We show, via FF simulations, that incorrect relative energies can lead to significant changes in the interfacial densities of water and methanol solutions at the kaolinite interface. Despite the clear improvements offered by the vdW-corrected and the vdW-inclusive functionals, absolute adsorption energies are often overestimated, suggesting that the treatment of vdW forces in DFT is not yet a solved problem. PMID:27917256

Analysis of Adsorbate-Adsorbate and Adsorbate-Adsorbent Interactions to Decode Isosteric Heats of Gas Adsorption.

PubMed

Madani, S Hadi; Sedghi, Saeid; Biggs, Mark J; Pendleton, Phillip

2015-12-21

A qualitative interpretation is proposed to interpret isosteric heats of adsorption by considering contributions from three general classes of interaction energy: fluid-fluid heat, fluid-solid heat, and fluid-high-energy site (HES) heat. Multiple temperature adsorption isotherms are defined for nitrogen, T=(75, 77, 79) K, argon at T=(85, 87, 89) K, and for water and methanol at T=(278, 288, 298) K on a well-characterized polymer-based, activated carbon. Nitrogen and argon are subjected to isosteric heat analyses; their zero filling isosteric heats of adsorption are consistent with slit-pore, adsorption energy enhancement modelling. Water adsorbs entirely via specific interactions, offering decreasing isosteric heat at low pore filling followed by a constant heat slightly in excess of water condensation enthalpy, demonstrating the effects of micropores. Methanol offers both specific adsorption via the alcohol group and non-specific interactions via its methyl group; the isosteric heat increases at low pore filling, indicating the predominance of non-specific interactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Designing transition metal surfaces for their adsorption properties and chemical reactivity

NASA Astrophysics Data System (ADS)

Montemore, Matthew M.

Many technological processes, such as catalysis, electrochemistry, corrosion, and some materials synthesis techniques, involve molecules bonding to and/or reacting on surfaces. For many of these applications, transition metals have proven to have excellent chemical reactivity, and this reactivity is strongly tied to the surface's adsorption properties. This thesis focuses on predicting adsorption properties for use in the design of transition metal surfaces for various applications. First, it is shown that adsorption through a particular atom (e.g, C or O) can be treated in a unified way. This allows predictions of all C-bound adsorbates from a single, simple adsorbate, such as CH3. In particular, consideration of the adsorption site can improve the applicability of previous approaches, and gas-phase bond energies correlate with adsorption energies for similarly bound adsorbates. Next, a general framework is presented for understanding and predicting adsorption through any atom. The energy of the adsorbate's highest occupied molecular orbital (HOMO) determines the strength of the repulsion between the adsorbate and the surface. Because adsorbates with similar HOMO energies behave similarly, their adsorption energies correlate. This can improve the efficiency of predictions, but more importantly it constrains catalyst design and suggests strategies for circumventing these constraints. Further, the behavior of adsorbates with dissimilar HOMO energies varies in a systematic way, allowing predictions of adsorption energy differences between any two adsorbates. These differences are also useful in surface design. In both of these cases, the dependence of adsorption energies on surface electronic properties is explored. This dependence is used to justify the unified treatments mentioned above, and is used to gain further insight into adsorption. The properties of the surface's d band and p band control variations in adsorption energy, as does the strength of the

Adsorption of alcohols on a two-dimensional SiO2 single crystal - Alcohol adsorption on silicatene

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Influence of surface roughness on cetyltrimethylammonium bromide adsorption from aqueous solution.

PubMed

Wu, Shuqing; Shi, Liu; Garfield, Lucas B; Tabor, Rico F; Striolo, Alberto; Grady, Brian P

2011-05-17

The influence of surface roughness on surfactant adsorption was studied using a quartz crystal microbalance with dissipation (QCM-D). The sensors employed had root-mean-square (R) roughness values of 2.3, 3.1, and 5.8 nm, corresponding to fractal-calculated surface area ratios (actual/nominal) of 1.13, 1.73, and 2.53, respectively. Adsorption isotherms measured at 25 °C showed that adsorbed mass of cetyltrimethylammonium bromide per unit of actual surface area below 0.8 cmc, or above 1.2 cmc, decreases as the surface roughness increases. At the cmc, both the measured adsorbed amount and the measured dissipation increased dramatically on the rougher surfaces. These results are consistent with the presence of impurities, suggesting that roughness exacerbates well-known phenomena reported in the literature of peak impurity-related adsorption at the cmc. The magnitude of the increase, especially in dissipation, suggests that changes in adsorbed amount may not be the only reason for the observed results, as aggregates at the cmc on rougher surfaces are more flexible and likely contain larger amounts of solvent. Differences in adsorption kinetics were also found as a function of surface roughness, with data showing a second, slower adsorption rate after rapid initial adsorption. A two-rate Langmuir model was used to further examine this effect. Although adsorption completes faster on the smoother surfaces, initial adsorption at zero surface coverage is faster on the rougher surfaces, suggesting the presence of more high-energy sites on the rougher surfaces.

Kinetic and geometric isotope effects originating from different adsorption potential energy surfaces: cyclohexane on Rh(111).

PubMed

Koitaya, Takanori; Shimizu, Sumera; Mukai, Kozo; Yoshimoto, Shinya; Yoshinobu, Jun

2012-06-07

Novel isotope effects were observed in desorption kinetics and adsorption geometry of cyclohexane on Rh(111) by the use of infrared reflection absorption spectroscopy, temperature programmed desorption, photoelectron spectroscopy, and spot-profile-analysis low energy electron diffraction. The desorption energy of deuterated cyclohexane (C(6)D(12)) is lower than that of C(6)H(12). In addition, the work function change by adsorbed C(6)D(12) is smaller than that by adsorbed C(6)H(12). These results indicate that C(6)D(12) has a shallower adsorption potential than C(6)H(12) (vertical geometric isotope effect). The lateral geometric isotope effect was also observed in the two-dimensional cyclohexane superstructures as a result of the different repulsive interaction between interfacial dipoles. The observed isotope effects should be ascribed to the quantum nature of hydrogen involved in the C-H···metal interaction.

Study of gas adsorption on as-produced and modified carbon nanotubes

NASA Astrophysics Data System (ADS)

Rawat, Dinesh Singh

Volumetric adsorption isotherm measurements were used to study the adsorption characteristics of Ethane (C2H6) and Butane (C 4H10) on as-produced single-walled carbon nanotubes. The binding energy of the adsorbed alkane molecule was found to increase with increasing carbon chain length. Two adsorption substeps were obtained for each alkane molecule. However, the size of the high pressure substep was found to be gradually smearing with the increase in size of the adsorbed molecule. This phenomenon is interpreted as size entropy effect for linear molecules. This interpretation was also verified by determining the specific surface area of the substrate using linear molecules of different sizes. Kinetics measurements of alkane adsorption on SWNTs were also conducted and their dependence on the molecular length was determined. Similar adsorption measurements were performed for Argon (Ar) on as-produced single-walled carbon nanotubes and nanotubes that were structurally modified using acid treatment. Enhancement of the sorptive capacity and the presence of two distinct kinetics of gas adsorption verified partial opening of single walled carbon nanotubes as a result of chemical treatment. Mutiwalled carbon nanotubes were exposed to oxygen plasma treatment for varying time periods. Afterwards, adsorption measurements of Methane (CH 4) were conducted on untreated and oxygen plasma treated tubes. The presence of an additional substep, after exposing multiwalled carbon nanotubes to oxygen plasma for varying time periods, suggested progressive cleaning of nanotube surface.

Adsorption enhancement of elemental mercury onto sulphur-functionalized silica gel adsorbents.

PubMed

Johari, Khairiraihanna; Saman, Norasikin; Mat, Hanapi

2014-01-01

In this study, elemental mercury (EM) adsorbents were synthesized using tetraethyl orthosilicate (TEOS) and 3-mercaptopropyl trimethoxysilane as silica precursors. The synthesized silica gel (SG)-TEOS was further functionalized through impregnation with elemental sulphur and carbon disulphide (CS2). The SG adsorbents were then characterized by using scanning electron microscope, Fourier transform infra-red spectrophotometer, nitrogen adsorption/desorption, and energy-dispersive X-ray diffractometer. The EM adsorption of the SG adsorbents was determined using fabricated fixed-bed adsorber. The EM adsorption results showed that the sulphur-functionalized SG adsorbents had a greater Hgo breakthrough adsorption capacity, confirming that the presence of sulphur in silica matrices can improve Hgo adsorption performance due to their high affinity towards mercury. The highest Hgo adsorption capacity was observed for SG-TEOS(CS2) (82.62 microg/g), which was approximately 2.9 times higher than SG-TEOS (28.47 microg/g). The rate of Hgo adsorption was observed higher for sulphur-impregnated adsorbents, and decreased with the increase in the bed temperatures.

Organic molecules on metal and oxide semiconductor substrates: Adsorption behavior and electronic energy level alignment

NASA Astrophysics Data System (ADS)

Ruggieri, Charles M.

Modern devices such as organic light emitting diodes use organic/oxide and organic/metal interfaces for crucial processes such as charge injection and charge transfer. Understanding fundamental physical processes occurring at these interfaces is essential to improving device performance. The ultimate goal of studying such interfaces is to form a predictive model of interfacial interactions, which has not yet been established. To this end, this thesis focuses on obtaining a better understanding of fundamental physical interactions governing molecular self-assembly and electronic energy level alignment at organic/metal and organic/oxide interfaces. This is accomplished by investigating both the molecular adsorption geometry using scanning tunneling microscopy, as well as the electronic structure at the interface using direct and inverse photoemission spectroscopy, and analyzing the results in the context of first principles electronic structure calculations. First, we study the adsorption geometry of zinc tetraphenylporphyrin (ZnTPP) molecules on three noble metal surfaces: Au(111), Ag(111), and Ag(100). These surfaces were chosen to systematically compare the molecular self-assembly and adsorption behavior on two metals of the same surface symmetry and two surface symmetries of one metal. From this investigation, we improve the understanding of self-assembly at organic/metal interfaces and the relative strengths of competing intermolecular and molecule-substrate interactions that influence molecular adsorption geometry. We then investigate the electronic structure of the ZnTPP/Au(111), Ag(111), and Ag(100) interfaces as examples of weakly-interacting systems. We compare these cases to ZnTPP on TiO2(110), a wide-bandgap oxide semiconductor, and explain the intermolecular and molecule-substrate interactions that determine the electronic energy level alignment at the interface. Finally we study tetracyanoquinodimethane (TCNQ), a strong electron acceptor, on TiO2

NH3 adsorption on anatase-TiO2(101)

NASA Astrophysics Data System (ADS)

Koust, Stig; Adamsen, Kræn C.; Kolsbjerg, Esben Leonhard; Li, Zheshen; Hammer, Bjørk; Wendt, Stefan; Lauritsen, Jeppe V.

2018-03-01

The adsorption of ammonia on anatase TiO2 is of fundamental importance for several catalytic applications of TiO2 and for probing acid-base interactions. Utilizing high-resolution scanning tunneling microscopy (STM), synchrotron X-ray photoelectron spectroscopy, temperature-programmed desorption (TPD), and density functional theory (DFT), we identify the adsorption mode and quantify the adsorption strength on the anatase TiO2(101) surface. It was found that ammonia adsorbs non-dissociatively as NH3 on regular five-fold coordinated titanium surface sites (5f-Ti) with an estimated exothermic adsorption energy of 1.2 eV for an isolated ammonia molecule. For higher adsorbate coverages, the adsorption energy progressively shifts to smaller values, due to repulsive intermolecular interactions. The repulsive adsorbate-adsorbate interactions are quantified using DFT and autocorrelation analysis of STM images, which both showed a repulsive energy of ˜50 meV for nearest neighbor sites and a lowering in binding energy for an ammonia molecule in a full monolayer of 0.28 eV, which is in agreement with TPD spectra.

Adsorption of fibrinogen on a biomedical-grade stainless steel 316LVM surface: a PM-IRRAS study of the adsorption thermodynamics, kinetics and secondary structure changes.

PubMed

Desroches, Marie-Josee; Omanovic, Sasha

2008-05-14

Polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) was employed to investigate the interaction of serum protein fibrinogen with a biomedical-grade 316LVM stainless steel surface, in terms of the adsorption thermodynamics, kinetics and secondary structure changes of the protein. Apparent Gibbs energy of adsorption values indicated a highly spontaneous and strong adsorption of fibrinogen onto the surface. The kinetics of fibrinogen adsorption were successfully modeled using a pseudo first-order kinetic model. Deconvolution of the amide I bands indicated that the adsorption of fibrinogen on 316LVM results in significant changes in the protein's secondary structure that occur predominantly within the first minute of adsorption. Among the investigated structures, the alpha-helix structure undergoes the smallest changes, while the beta-sheet and beta-turns structures undergo significant changes. It was shown that lateral interactions between the adsorbed molecules do not play a role in controlling the secondary structure changes. An increase in temperature induced changes in the secondary structure of the protein, characterized by a loss of the alpha-helical content and its transformation into the beta-turns structure.

Effect of water on methane adsorption on the kaolinite (0 0 1) surface based on molecular simulations

NASA Astrophysics Data System (ADS)

Zhang, Bin; Kang, Jianting; Kang, Tianhe

2018-05-01

CH4 adsorption isotherms of kaolinite with moisture contents ranging from 0 to 5 wt% water, the effects of water on maximum adsorption capacity, kaolinite swelling, and radial distribution function were modelled by the implementing combined Monte Carlo (MC) and molecular dynamics (MD) simulations at 293.15 K (20 °C) and a pressure range of 1-20 MPa. The simulation results showed that the absolute adsorption of CH4 on both dry and moist kaolinite followed a Langmuir isotherm within the simulated pressure range, and both the adsorption capacity and the rate of CH4 adsorption decreased with the water content increases. The adsorption isosteric heats of CH4 on kaolinite decreased linearly with increasing water content, indicating that at higher water contents, the interaction energy between the CH4 and kaolinite was weaker. The interaction between kaolinite and water dominates and was the main contributing factor to kaolinite clay swelling. Water molecules were preferentially adsorbed onto oxygen and hydrogen atoms in kaolinite, while methane showed a tendency to be adsorbed only onto oxygen. The simulation results of our study provide the quantitative analysis of effect of water on CH4 adsorption capacity, adsorption rate, and interaction energy from a microscopic perspective. We hope that our study will contribute to the development of strategies for the further exploration of coal bed methane and shale gas.

Predicting Multicomponent Adsorption Isotherms in Open-Metal Site Materials Using Force Field Calculations Based on Energy Decomposed Density Functional Theory.

PubMed

Heinen, Jurn; Burtch, Nicholas C; Walton, Krista S; Fonseca Guerra, Célia; Dubbeldam, David

2016-12-12

For the design of adsorptive-separation units, knowledge is required of the multicomponent adsorption behavior. Ideal adsorbed solution theory (IAST) breaks down for olefin adsorption in open-metal site (OMS) materials due to non-ideal donor-acceptor interactions. Using a density-function-theory-based energy decomposition scheme, we develop a physically justifiable classical force field that incorporates the missing orbital interactions using an appropriate functional form. Our first-principles derived force field shows greatly improved quantitative agreement with the inflection points, initial uptake, saturation capacity, and enthalpies of adsorption obtained from our in-house adsorption experiments. While IAST fails to make accurate predictions, our improved force field model is able to correctly predict the multicomponent behavior. Our approach is also transferable to other OMS structures, allowing the accurate study of their separation performances for olefins/paraffins and further mixtures involving complex donor-acceptor interactions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thiophenic compounds adsorption on Na(I)Y and rare earth exchanged Y zeolites: a density functional theory study.

PubMed

Gao, Xionghou; Geng, Wei; Zhang, Haitao; Zhao, Xuefei; Yao, Xiaojun

2013-11-01

We have theoretically investigated the adsorption of thiophene, benzothiophene, dibenzothiophene on Na(I)Y and rare earth exchanged La(III)Y, Ce(III)Y, Pr(III)Y Nd(III)Y zeolites by density functional theory calculations. The calculated results show that except benzothiophene adsorbed on Na(I)Y with a stand configuration, the stable adsorption structures of other thiophenic compounds on zeolites exhibit lying configurations. Adsorption energies of thiophenic compounds on the Na(I)Y are very low, and decrease with the increase of the number of benzene rings in thiophenic compounds. All rare earth exchanged zeolites exhibit strong interaction with thiophene. La(III)Y and Nd(III)Y zeolites are found to show enhanced adsorption energies to benzothiophene and Pr(III)Y zeolites are favorable for dibenzothiophene adsorption. The analysis of the electronic total charge density and electron orbital overlaps show that the thiophenic compounds interact with zeolites by π-electrons of thiophene ring and exchanged metal atom. Mulliken charge populations analysis reveals that adsorption energies are strongly dependent on the charge transfer of thiophenic molecule and exchanged metal atom.

Wettability modification of Wender lignite by adsorption of dodecyl poly ethoxylated surfactants with different degree of ethoxylation: A molecular dynamics simulation study.

PubMed

Zhang, Lei; Li, Bao; Xia, Yangchao; Liu, Shengyu

2017-09-01

Lignite is an important and useful fossil fuel in the world and the strong hydrophilicity of it limits its applications. Surfactant adsorption on lignite is an effective way to make it hydrophobic. In this work, aiming to examine the effect of the degree of ethoxylation on the adsorption behavior of dodecyl poly ethoxylated surfactants on lignite and the wettability modification of modified lignite by surfactant adsorption, different combined systems formed by surfactants, water and a model surface of Wender lignite have been studied using molecular dynamics simulation. The adsorption configurations vary with the degree of ethoxylation. At the same adsorption amounts, increasing the degree of ethoxylation can make the adsorption layer more compactness and bring stronger adsorption strength. The results of binding energy and its components show that the adsorption of alkyl polyoxyethylene ethers surfactant on lignite is physically adsorbed rather than electrostatically or chemisorbed. Meanwhile, van der Waals interaction plays a dominant role in the adsorption. The addition of surfactant could reduce the possibility of the interaction between water and lignite. Compared to the original lignite, the interaction between them is weakened after surfactant adsorption in water/surfactant/lignite system, thus strengthening the hydrophobicity of lignite. Similar to the adsorption strength, hydrophobicity of modified lignite increases with the increase of the degree of ethoxylation. The lignite surface properties are changed due to surfactant adsorption by analyzing the compositions of interaction energy and the change of hydrogen bonds. Copyright © 2017 Elsevier Inc. All rights reserved.

Thermodynamics of adsorption of dithiocarbamates at the hanging mercury drop.

PubMed

Giannakopoulos, Evangelos; Deligiannakis, Yiannis

2007-02-27

Two dimethyldithiocarbamate (DMDTC) pesticides, thiram and ziram, are adsorbed onto a Hg drop via an entropically driven process. The adsorption isotherms are described by the Frumkin equation. For both molecules, the adsorption is characterized by a nonlinear pseudosigmoid temperature dependence of the Gibbs free energy. For the temperature range of 273-313 K, DeltaGADS varies between -43.4 and -56.71 kJ/mol for thiram and -42.60 and -55.67 kJ/mol for ziram. This variation of DeltaGADS reveals that the adsorption strength is increased at higher temperatures. During the adsorption of either molecule, strong lateral interactions are developed between neighboring adsorbates, which are severely weakened as the temperature increases. A unified reaction scheme is suggested for both ziram and thiram that predicts the formation and adsorption of a surface complex, (DMDTC)2Hg. In the case of thiram, two DMDTC molecules are formed by the cleavage of the disulfide S-S bond near the Hg electrode. The thermodynamic and structural parameters reveal that there are two limiting thermodynamic regimes for the adsorbed (DMDTC)2Hg species that originate from two limiting adsorption conformations of the adsorbates on the Hg surface. A transition occurs between these two conformations at temperatures in the region of 285-295 K. This transition is accompanied by large entropic and enthalpic changes.

Nitrotyrosine adsorption on carbon nanotube: a density functional theory study

NASA Astrophysics Data System (ADS)

Majidi, R.; Karami, A. R.

2014-05-01

We have studied the effect of nitrotyrosine on electronic properties of different single-wall carbon nanotubes by density functional theory. Optimal adsorption configurations of nitrotyrosine adsorbed on carbon nanotube have been determined by calculation of adsorption energy. Adsorption energies indicate that nitrotyrosine is chemisorbed on carbon nanotubes. It is found that the nitrotyrosine adsorption modifies the electronic properties of the semiconducting carbon nanotubes significantly and these nanotubes become n-type semiconductors, while the effect of nitrotyrosine on metallic carbon nanotubes is not considerable and these nanotubes remain metallic. Results clarify sensitivity of carbon nanotubes to nitrotyrosine adsorption and suggest the possibility of using carbon nanotubes as biosensor for nitrotyrosine detection.

Adsorption laboratory experiment for undergraduate chemical engineering: Introducing kinetic, equilibrium and thermodynamic concepts

NASA Astrophysics Data System (ADS)

Muryanto, S.; Djatmiko Hadi, S.

2016-11-01

Adsorption laboratory experiment for undergraduate chemical engineering program is discussed. The experiment demonstrated adsorption of copper ions commonly found in wastewater using bio-sorbent, i.e. agricultural wastes. The adsorption was performed in a batch mode under various parameters: adsorption time (up to 120 min), initial pH (2 to 6), adsorbent dose (2.0 to 12.0 g L-1), adsorbent size (50 to 170 mesh), initial Cu2+ concentration (25 to 100 ppm) and temperatures (room temp to 40°C). The equilibrium and kinetic data of the experiments were calculated using the two commonly used isotherms: Langmuir and Lagergren pseudo-first-order kinetics. The maximum adsorption capacity for Cu2+ was found as 94.34 mg g-1. Thermodynamically, the adsorption process was spontaneous and endothermic. The calculated activation energy for the adsorption was observed as high as 127.94 kJ mol-1. Pedagogically, the experiment was assumed to be important in increasing student understanding of kinetic, equilibrium and thermodynamic concepts.

Molecular Simulation of Cesium Adsorption at the Basal Surface of Phyllosilicate Minerals

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

Kerisit, Sebastien N.; Okumura, Masahiko; Rosso, Kevin M.

2016-08-16

A better understanding of the thermodynamics of radioactive cesium uptake at the surfaces of phyllosilicate minerals is needed to understand mechanisms of its selective adsorption and help guide the development of practical and inexpensive decontamination techniques. In this work, molecular dynamics simulations were carried out to determine the thermodynamics of adsorption of Cs + at the basal surface of six 2:1 phyllosilicate minerals, namely pyrophyllite, illite, muscovite, phlogopite, celadonite, and margarite. These minerals were selected to isolate the effects of the magnitude of the permanent layer charge (≤ 2), its location (tetrahedral versus octahedral sheet), and the structure of themore » octahedral sheet (dioctahedral versus trioctahedral). Good agreement was obtained with experiment in terms of the hydration free energy of Cs + and the structure and thermodynamics of Cs + adsorption at the muscovite basal surface, for which published data were available for comparison. With the exception of pyrophyllite, which did not exhibit an inner-sphere free energy minimum, all phyllosilicate minerals showed similar behavior with respect to Cs + adsorption; notably, Cs + adsorption was predominantly inner-sphere whereas outer-sphere adsorption was very weak with the simulations predicting the formation of an extended outer-sphere complex. For a given location of the layer charge, the free energy of adsorption as an inner-sphere complex was found to vary linearly with the magnitude of the layer charge. For a given location and magnitude of the layer charge, adsorption at phlogopite (trioctahedral sheet structure) was much less favorable than at muscovite (dioctahedral sheet structure) due to the electrostatic repulsion between the adsorbed Cs + and the hydrogen atom of the hydroxyl group directly below the six-membered siloxane ring cavity. For a given magnitude of the layer charge and structure of the octahedral sheet, adsorption at celadonite (layer charge

Organophilic treatments of bentonite increase the adsorption of aflatoxin B1 and protect stem cells against cellular damage.

PubMed

Nones, Janaína; Nones, Jader; Poli, Anicleto; Trentin, Andrea Gonçalves; Riella, Humberto Gracher; Kuhnen, Nivaldo Cabral

2016-09-01

Bentonite clays exhibit high adsorptive capacity for contaminants, including aflatoxin B1 (AFB1), a mycotoxin responsible for causing severe toxicity in several species including pigs, poultry and man. Organophilic treatments is known to increase the adsorption capacity of bentonites, and the primary aim of this study was to evaluate the ability of Brazilian bentonite and two organic salts - benzalkonium chloride (BAC) and cetyltrimethylammonium bromide (CTAB) to adsorb AFB1. For this end, 2(2) factorial designs were used in order to analyze if BAC or CTAB was able to increase AFB1 adsorption when submitted in different temperature and concentration. Both BAC and CTAB treatment (at 30°C and 2% of salt concentration) were found to increase the adsorption of AFB1 significantly compared with untreated bentonite. After organophilic bentonite treatments with BAC or CTAB, a vibration of CH stretch (2850 and 2920cm(-1)) were detected. A frequency of the SiO stretch (1020 and 1090cm(-1)) was changed by intercalation of organic cation. Furthermore, the interlayer spacing of bentonite increases to 1.23nm (d001 reflection at 2θ=7.16) and 1.22 (d001 reflection at 2θ=7.22) after the addition of BAC and CTAB, respectively. Another aim of the study was to observe the effects of these two bentonite salts in neural crest stem cell cultures. The two materials that were created by organophilic treatments were not found to be toxic to stem cells. Furthermore the results indicate that the two materials tested may protect the neural crest stem cells against damage caused by AFB1. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular dynamics simulation on adsorption of pyrene-polyethylene onto ultrathin single-walled carbon nanotube

NASA Astrophysics Data System (ADS)

Cai, Lu; Lv, Wenzhen; Zhu, Hong; Xu, Qun

2016-07-01

The mechanism of the adsorption of pyrene-polyethylene (Py-PE) onto ultrathin single-walled carbon nanotube (SWNT) was studied by using all-atom molecular dynamics (MD) simulations. We found that solvent polarity and pyrene group are two critical factors in the Py-PE decoration on ultrathin SWNT. Combined MD simulations with free energy calculations, our results indicate that larger solvent polarity can decrease the contribution of conformation entropy, but contributes little to the interaction energy, moreover, larger SWNT diameter can decrease the contribution of conformation entropy but lead to the increasing of the interaction energy. In polar organic solvent (N, N-Dimethylacetamide), the pyrene group plays a key role in the adsorption of Py-PE onto ultrathin SWNT, not only facilitates the spontaneous adsorption of Py-PE onto ultrathin SWNT, but also helps to form compact structure between themselves in the final adsorption states. While in aqueous solution, pyrene group no longer works as an anchor, but still affects a lot to the final adsorption conformation. Our present work provides detailed theoretical clue to understand the noncovalent interaction between aromatic segment appended polymer and ultrathin SWNT, and helps to explore the potential application of ultrathin SWNT in the fields of hybrid material, biomedical and electronic materials.

Adsorption and structure of the adsorbed layer of ionic surfactants.

PubMed

Ivanov, Ivan B; Ananthapadmanabhan, Kavssery P; Lips, Alex

2006-11-16

Our goal in this study was to investigate theoretically and experimentally the adsorption of ionic surfactants and the role of different factors in the mechanism of adsorption, the adsorption parameters and the structure of the adsorbed layer. We used available literature data for the interfacial tension, sigma, vs. concentration, C(s), for sodium dodecyl sulfate (SDS) in three representative systems with Air/Water (A/W), Oil/Water (O/W) and Oil/Water + 0.1 M NaCl (O/WE) interfaces. We derived 6 new adsorption isotherms and 6 new equations of state (EOS) based on the adsorption isotherms for non-ionic surfactants of Langmuir, Volmer and Helfand-Frisch-Lebowitz (HFL) with interaction term betatheta2/2 in the EOS, theta=alphaGamma being the degree of coverage, with Gamma--adsorption and alpha--minimum area per molecule. We applied Gouy equation for high surface potentials and modified it to account for partial penetration of the counterions in the adsorbed layer. The equations were written in terms of the effective concentration C=[C(s)(C(s)+C(el))](1/2), where C(s) and C(el) are, respectively concentrations of the surfactant and the electrolyte. We showed that the adsorption constant K was model independent and derived an equation for the effective thickness of the adsorbed layer, delta(s). We found also that the minimum area per molecule, alpha, is larger than the true area, alpha(0), which depends on the adsorption model and is a function of the adsorption Gamma. The interaction term betatheta2/2 in the Langmuir EOS was found to be exact for small beta<1, but for the Volmer EOS it turned out to be only a crude approximation. Semi-quantitative considerations about the interaction between adsorbed discrete charges revealed that at A/W interface part of the adsorbed surfactant molecules are partially immersed in water, which leads to decreased repulsion and increased adsorption Gamma. At O/W the larger adsorption energy keeps the surfactant molecules on the surface

Water adsorption on goethite: Application of multilayer adsorption models

NASA Astrophysics Data System (ADS)

Hatch, C. D.; Tumminello, R.; Meredith, R.

2016-12-01

Adsorbed water on the surface of atmospheric mineral dust has recently been shown to significantly affect the ability of mineral dust aerosol to act as cloud condensation nuclei. We have studied water adsorption as a function of relative humidity (RH) on goethite (α-FeO(OH)), a common component of atmospheric mineral dust. The goethite surface area and particle size was determined using BET analysis and with N2 as an adsorbate and scanning electron microscopy, respectively. Water adsorption on the sample was monitored using horizontal attenuated total reflectance Fourier transform infrared (HATR-FTIR) spectroscopy equipped with a flow cell. Water content was determined using Beer's law and the optical constants for bulk water. The results were analyzed using Type II adsorption isotherms to model multilayer adsorption, including BET (Brunauer, Emmet and Teller), FHH (Frenkel, Halsey and Hill) and Freundlich. BET fits to experimental data provide parameters of monolayer coverage, while the FHH and Freundlich isotherms provide insights into multilayer adsorption mechanisms. Results indicate that goethite contains 5% H2O by mass at 50% RH, which increases to 12% by mass at 90% RH. Adsorption parameters and experimental results will be presented.

Electrical swing adsorption gas storage and delivery system

DOEpatents

Judkins, Roddie R.; Burchell, Timothy D.

1999-01-01

Systems and methods for electrical swing natural gas adsorption are described. An apparatus includes a pressure vessel; an electrically conductive gas adsorptive material located within the pressure vessel; and an electric power supply electrically connected to said adsorptive material. The adsorptive material can be a carbon fiber composite molecular sieve (CFCMS). The systems and methods provide advantages in that both a high energy density and a high ratio of delivered to stored gas are provided.

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

USGS Publications Warehouse

Balistrieri, L.S.; Chao, T.T.

1990-01-01

is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.

Characterization of biochars derived from agriculture wastes and their adsorptive removal of atrazine from aqueous solution: A comparative study.

PubMed

Liu, Na; Charrua, Alberto Bento; Weng, Chih-Huang; Yuan, Xiaoling; Ding, Feng

2015-12-01

The physicochemical properties of biochars produced from soybeans (SBB), corn stalks (CSB), rice stalks (RSB), poultry manure (PMB), cattle manure (CMB), and pig manure (PgMB) and their adsorption characteristics of atrazine were investigated. The adsorption capacity increased with the increase of temperature and initial atrazine concentration. More atrazine was removed from basic solutions than acidic solutions, due to the effects of adsorption and hydrolysis. The Freundlich isotherm adsorption parameters indicated that the adsorption capacity decreased in the order SBB>RSB>CMB>CSB>PMB>PgMB, which is associated to the pore volume of biochars. The total pore volume and biochar pH were concluded to play important roles in determining the adsorption capacity, and they may have contributed to physical adsorption mechanisms dominating the overall adsorption process (the low activation energy for all of the biochars). Modified Freundlich and intraparticle diffusion models were used to describe the kinetics of the adsorption process. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nanometer polymer surface features: the influence on surface energy, protein adsorption and endothelial cell adhesion

NASA Astrophysics Data System (ADS)

Carpenter, Joseph; Khang, Dongwoo; Webster, Thomas J.

2008-12-01

Current small diameter (<5 mm) synthetic vascular graft materials exhibit poor long-term patency due to thrombosis and intimal hyperplasia. Tissue engineered solutions have yielded functional vascular tissue, but some require an eight-week in vitro culture period prior to implantation—too long for immediate clinical bedside applications. Previous in vitro studies have shown that nanostructured poly(lactic-co-glycolic acid) (PLGA) surfaces elevated endothelial cell adhesion, proliferation, and extracellular matrix synthesis when compared to nanosmooth surfaces. Nonetheless, these studies failed to address the importance of lateral and vertical surface feature dimensionality coupled with surface free energy; nor did such studies elicit an optimum specific surface feature size for promoting endothelial cell adhesion. In this study, a series of highly ordered nanometer to submicron structured PLGA surfaces of identical chemistry were created using a technique employing polystyrene nanobeads and poly(dimethylsiloxane) (PDMS) molds. Results demonstrated increased endothelial cell adhesion on PLGA surfaces with vertical surface features of size less than 18.87 nm but greater than 0 nm due to increased surface energy and subsequently protein (fibronectin and collagen type IV) adsorption. Furthermore, this study provided evidence that the vertical dimension of nanometer surface features, rather than the lateral dimension, is largely responsible for these increases. In this manner, this study provides key design parameters that may promote vascular graft efficacy.

Adsorption and inhibitive properties of sildenafil (Viagra) for zinc in hydrochloric acid solution

NASA Astrophysics Data System (ADS)

Fouda, A. S.; Ibrahim, H.; Atef, M.

Sildenafil (Viagra) was investigated as corrosion inhibitor for Zn in 1 M HCl solution using chemical and electrochemical methods at 25 °C. Electrochemical results showed that this drug is efficient inhibitor for Zn in HCl and the inhibition efficiency (IE) reached to 91% at 300 ppm. The IE increases with the drug concentration and decreases with increasing temperature. The adsorption of this drug on Zn surface follows Langmuir adsorption isotherm. The polarization plots revealed that Sildenafil acts as a mixed-type inhibitor. The thermodynamic parameters of activation and adsorption were calculated and discussed. The surface morphology of the Zn specimens was evaluated using scanning electron microscope (SEM), energy dispersive X-ray (EDX), atomic force microscopy (AFM) and Fourier transform infrared spectroscopy (FTIR) techniques.

Electrical swing adsorption gas storage and delivery system

DOEpatents

Judkins, R.R.; Burchell, T.D.

1999-06-15

Systems and methods for electrical swing natural gas adsorption are described. An apparatus includes a pressure vessel; an electrically conductive gas adsorptive material located within the pressure vessel; and an electric power supply electrically connected to said adsorptive material. The adsorptive material can be a carbon fiber composite molecular sieve (CFCMS). The systems and methods provide advantages in that both a high energy density and a high ratio of delivered to stored gas are provided. 5 figs.

Adsorption and diffusion of lithium in a graphene/blue-phosphorus heterostructure and the effect of an external electric field.

PubMed

Fan, Kaimin; Tang, Jing; Wu, Shiyun; Yang, Chengfu; Hao, Jiabo

2016-12-21

The adsorption and diffusion behaviors of lithium (Li) in a graphene/blue-phosphorus (G/BP) heterostructure have been investigated using a first principles method based on density functional theory (DFT). The effect of an external electric field on the adsorption and diffusion behaviors has also been investigated. The results show that the adsorption energy of Li on the graphene side of the G/BP heterostructure is higher than that on monolayer graphene, and Li adsorption on the BP side of the G/BP/Li system is slightly stronger than that on monolayer BP (BP/Li). The adsorption energy of Li reaches 2.47 eV, however, the energy barriers of Li diffusion decrease in the interlayer of the G/BP heterostructure. The results mentioned above suggest that the rate performance of the G/BP heterostructure is better than that of monolayer graphene. Furthermore, the adsorption energies of Li atoms in the three different most stable sites, i.e., H G , T P and H 1 sites, increase by about 0.49 eV, 0.26 eV, and 0.13 eV, respectively, as the electric field intensity reaches 0.6 V Å -1 . The diffusion energy barrier is significantly decreased by an external electric field. It is demonstrated that the external electric field can not only enhance the adsorption but can also modulate the diffusion barriers of Li atoms in the G/BP heterostructure.

Thermodynamic properties of rhamnolipid micellization and adsorption.

PubMed

Mańko, Diana; Zdziennicka, Anna; Jańczuk, Bronisław

2014-07-01

of the surface tension, density, viscosity and conductivity of aqueous solutions of rhamnolipid at natural and controlled pH were made at 293 K. On the basis of the obtained results the critical micelle concentration of rhamnolipid and its Gibbs surface excess concentration at the water-air interface were determined. The maximal surface excess concentration was considered in the light of the size of rhamnolipid molecule. Next the Gibbs standard free energy of rhamnolipid adsorption at this interface was determined on the basis of the different approaches to this energy. The standard free energy of adsorption was also deduced on the basis of the surface tension of n-hexane and water-n-hexane interface tension. Standard free energy obtained in this way was close to those determined by using the Langmuir, Szyszkowski, Aronson and Rosen, Gu and Zhu as well as modified Gamboa and Olea equations. The standard free energy of rhamnolipid adsorption at the water-air interface was compared to its standard free energy of micellization which was determined from the Philips equation taking into account the degree of rhamnolipid dissociation in the micelles. Copyright © 2014 Elsevier B.V. All rights reserved.

First-principles characterization of formate and carboxyl adsorption on the stoichiometric CeO2(111) and CeO2(110) surfaces

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

Mei, Donghai

2013-05-20

Molecular adsorption of formate and carboxyl on the stoichiometric CeO2(111) and CeO2(110) surfaces was studied using periodic density functional theory (DFT+U) calculations. Two distinguishable adsorption modes (strong and weak) of formate are identified. The bidentate configuration is more stable than the monodentate adsorption configuration. Both formate and carboxyl bind at the more open CeO2(110) surface are stronger. The calculated vibrational frequencies of two adsorbed species are consistent with experimental measurements. Finally, the effects of U parameters on the adsorption of formate and carboxyl over both CeO2 surfaces were investigated. We found that the geometrical configurations of two adsorbed species aremore » not affected by using different U parameters (U=0, 5, and 7). However, the calculated adsorption energy of carboxyl pronouncedly increases with the U value while the adsorption energy of formate only slightly changes (<0.2 eV). The Bader charge analysis shows the opposite charge transfer occurs for formate and carboxyl adsorption where the adsorbed formate is negatively charge whiled the adsorbed carboxyl is positively charged. Interestingly, with the increasing U parameter, the amount of charge is also increased. This work was supported by the Laboratory Directed Research and Development (LDRD) project of the Pacific Northwest National Laboratory (PNNL) and by a Cooperative Research and Development Agreement (CRADA) with General Motors. The computations were performed using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at PNNL in Richland, Washington. Part of the computing time was also granted by the National Energy Research Scientific Computing Center (NERSC)« less

Pyrolysis conditions and ozone oxidation effects on ammonia adsorption in biomass generated chars.

PubMed

Kastner, James R; Miller, Joby; Das, K C

2009-05-30

Ammonia adsorbents were generated via pyrolysis of biomass (peanut hulls and palm oil shells) over a range of temperatures and compared to a commercially available activated carbon (AC) and solid biomass residuals (wood and poultry litter fly ash). Dynamic ammonia adsorption studies (i.e., breakthrough curves) were performed using these adsorbents at 23 degrees C from 6 to 17 ppmv NH(3). Of the biomass chars, palm oil char generated at 500 degrees C had the highest NH(3) adsorption capacity (0.70 mg/g, 6 ppmv, 10% relative humidity (RH)), was similar to the AC, and contrasted to the other adsorbents (including the AC), the NH(3) adsorption capacity significantly increased if the relative humidity was increased (4 mg/g, 7 ppmv, 73% RH). Room temperature ozone treatment of the chars and activated carbon significantly increased the NH(3) adsorption capacity (10% RH); resultant adsorption capacity, q (mg/g) increased by approximately 2, 6, and 10 times for palm oil char, peanut hull char (pyrolysis only), and activated carbon, respectively. However, water vapor (73% RH at 23 degrees C) significantly reduced NH(3) adsorption capacity in the steam and ozone treated biomass, yet had no effect on the palm shell char generated at 500 degrees C. These results indicate the feasibility of using a low temperature (and thus low energy input) pyrolysis and activation process for the generation of NH(3) adsorbents from biomass residuals.

Interplay between strong correlation and adsorption distances: Co on Cu(001)

NASA Astrophysics Data System (ADS)

Bahlke, Marc Philipp; Karolak, Michael; Herrmann, Carmen

2018-01-01

Adsorbed transition metal atoms can have partially filled d or f shells due to strong on-site Coulomb interaction. Capturing all effects originating from electron correlation in such strongly correlated systems is a challenge for electronic structure methods. It requires a sufficiently accurate description of the atomistic structure (in particular bond distances and angles), which is usually obtained from first-principles Kohn-Sham density functional theory (DFT), which due to the approximate nature of the exchange-correlation functional may provide an unreliable description of strongly correlated systems. To elucidate the consequences of this popular procedure, we apply a combination of DFT with the Anderson impurity model (AIM), as well as DFT + U for a calculation of the potential energy surface along the Co/Cu(001) adsorption coordinate, and compare the results with those obtained from DFT. The adsorption minimum is shifted towards larger distances by applying DFT+AIM, or the much cheaper DFT +U method, compared to the corresponding spin-polarized DFT results, by a magnitude comparable to variations between different approximate exchange-correlation functionals (0.08 to 0.12 Å). This shift originates from an increasing correlation energy at larger adsorption distances, which can be traced back to the Co 3 dx y and 3 dz2 orbitals being more correlated as the adsorption distance is increased. We can show that such considerations are important, as they may strongly affect electronic properties such as the Kondo temperature.

Surface Complexation Modeling of Fluoride Adsorption by Soil and the Role of Dissolved Aluminum on Adsorption

NASA Astrophysics Data System (ADS)

Padhi, S.; Tokunaga, T.

2017-12-01

Adsorption of fluoride (F) on soil can control the mobility of F and subsequent contamination of groundwater. Hence, accurate evaluation of adsorption equilibrium is a prerequisite for understanding transport and fate of F in the subsurface. While there have been studies for the adsorption behavior of F with respect to single mineral constituents based on surface complexation models (SCM), F adsorption to natural soil in the presence of complexing agents needs much investigation. We evaluated the adsorption processes of F on a natural granitic soil from Tsukuba, Japan, as a function of initial F concentration, ionic strength, and initial pH. A SCM was developed to model F adsorption behavior. Four possible surface complexation reactions were postulated with and without including dissolved aluminum (Al) and Al-F complex sorption. Decrease in F adsorption with the increase in initial pH was observed in between the initial pH range of 4 to 9, and a decrease in the rate of the reduction of adsorbed F with respect to the increase in the initial pH was observed in the initial pH range of 5 to 7. Ionic strength variation in the range of 0 to 100mM had insignificant effect on F removal. Changes in solution pH were observed by comparing the solution before and after F adsorption experiments. At acidic pH, the solution pH increased, whereas at alkaline pH, the solution pH decreased after equilibrium. The SCM including dissolved Al and the adsorption of Al-F complex can simulate the experimental results quite successfully. Also, including dissolved Al and the adsorption of Al-F complex to the model explained the change in solution pH after F adsorption.

Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies

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

Srinivasan, Sriram Goverapet; Shivaramaiah, Radha; Kent, Paul R. C.

2016-07-11

Bastnasite is a fluoro-carbonate mineral that is the largest source of rare earth elements such as Y, La and Ce. With increasing demand for REE in many emerging technologies, there is an urgent need for improving the efficiency of ore beneficiation by froth flotation. In order to design improved flotation agents that can selectively bind to the mineral surface, a fundamental understanding of the bulk and surface properties of bastnasite is essential. Density functional theory calculations using the PBEsol exchange correlation functional and the DFT-D3 dispersion correction reveal that the most stable form of La bastnsite is isomorphic to themore » structure of Ce bastnasite belonging to the P2c space group, while the Inorganic Crystal Structure Database structure in the P2m space group is ca. 11.3 kJ/mol higher in energy per LaFCO 3 formula unit. We report powder X-ray diffraction measurements on synthetic of La bastnasite to support these theoretical findings. Six different surfaces are studied by DFT, namely [100], [0001], [101], [102], [104] and [112]. Among these, the [100] surface is the most stable with a surface energy of 0.73 J/m 2 in vacuum and 0.45 J/m 2 in aqueous solution. We predicted the shape of a La bastnasite nanoparticle via thermodynamic Wulff construction to be a hexagonal prism with [100] and [0001] facets, chiseled at its ends by the [101] and [102] facets. The average surface energy of the nanoparticle in the gas phase is estimated to be 0.86 J/m 2, in good agreement with a value of 1.11 J/m 2 measured by calorimetry. The calculated adsorption energy of a water molecule varies widely with the surface plane and specific adsorption sites on a given surface. Moreover, the first layer of water molecules is predicted to adsorb strongly on the La-bastnasite surface, in agreement with water adsorption calorimetry experiments. Our work provides an important step towards a detailed atomistic understanding of the bastnasite water interface and

Application of low energy ion blocking for adsorption site determination of Na Atoms on a Cu(111) surface

NASA Astrophysics Data System (ADS)

Zhang, R.; Makarenko, B.; Bahrim, B.; Rabalais, J. W.

2010-07-01

Ion blocking in the low keV energy range is demonstrated to be a sensitive method for probing surface adsorption sites by means of the technique of time-of-flight scattering and recoiling spectroscopy (TOF-SARS). Adsorbed atoms can block the nearly isotropic backscattering of primary ions from surface atoms in the outmost layers of a crystal. The relative adsorption site position can be derived unambiguously by simple geometrical constructs between the adsorbed atom site and the surface atom sites. Classical ion trajectory simulations using the scattering and recoiling imaging code (SARIC) and molecular dynamics (MD) simulations provide the detailed ion trajectories. Herein we present a quantitative analysis of the blocking effects produced by sub-monolayer Na adsorbed on a Cu(111) surface at room temperature. The results show that the Na adsorption site preferences are different at different Na coverages. At a coverage θ = 0.25 monolayer, Na atoms preferentially populate the fcc threefold surface sites with a height of 2.7 ± 0.1 Å above the 1st layer Cu atoms. At a lower coverage of θ = 0.10 monolayer, there is no adsorption site preference for the Na atoms on the Cu(111) surface.

Macromolecule simulation and CH4 adsorption mechanism of coal vitrinite

NASA Astrophysics Data System (ADS)

Yu, Song; Yan-ming, Zhu; Wu, Li

2017-02-01

The microscopic mechanism of interactions between CH4 and coal macromolecules is of significant practical and theoretical importance in CBM development and methane storage. Under periodic boundary conditions, the optimal energy configuration of coal vitrinite, which has a higher torsion degree and tighter arrangement, can be determined by the calculation of molecular mechanics (MM) and molecular dynamics (MD), and annealing kinetics simulation based on ultimate analysis, 13C NMR, FT IR and HRTEM. Macromolecular stabilization is primarily due to the van der Waals energy and covalent bond energy, mainly consisting of bond torsion energy and bond angle energy. Using the optimal configuration as the adsorbent, GCMC simulation of vitrinite adsorption of CH4 is conducted. A saturated state is reached after absorbing 17 CH4s per coal vitrinite molecule. CH4 is preferentially adsorbed on the edge, and inclined to gathering around the branched chains of the inner vitrinite sites. Finally, the adsorption parameters are calculated through first principle DFT. The adsorbability order is as follows: aromatic structure> heteroatom rings > oxygen functional groups. The adsorption energy order is as follows: Top < Bond < Center, Up < Down. The order of average RDF better reflects the adsorption ability and that of [-COOH] is lower than those of [sbnd Cdbnd O] and [Csbnd Osbnd C]. CH4 distributed in the distance of 0.99-16 Å to functional groups in the type of monolayer adsorption and the average distance order manifest as [sbnd Cdbnd O] (1.64 Å) < [Csbnd Osbnd C] (1.89 Å) < [sbnd COOH] (3.78 Å) < [-CH3] (4.11 Å) according to the average RDF curves. CH4 enriches around [sbnd Cdbnd O] and [Csbnd O-C] whereas is rather dispersed about [-COOH] and [CH3]. Simulation and experiment data are both in strong agreement with the Langmuir and D-A isothermal adsorption model and the D-A model fit better than Langmuir model. Preferential adsorption sites and orientations in vitrinite are

Kinetic and thermodynamic studies on the adsorption of anionic surfactant on quaternary ammonium cationic cellulose.

PubMed

Zhang, Yuanzhang; Shi, Wenjian; Zhou, Hualan; Fu, Xing; Chen, Xuan

2010-06-01

Removal of anionic surfactants from aqueous solutions by adsorption onto quaternary ammonium cationic cellulose (QACC) was investigated. The effects of solution acidity, initial concentration, adsorption time, and temperature on the adsorption of sodium dodecyl-benzene sulfonate (SDBS), sodium lauryl sulfate (SLS), and sodium dodecyl sulfonate (SDS) were studied. The kinetic experimental data fit well with the pseudo-second-order model; the rate constant of the adsorption increased with temperature. The values of apparent activation energy for the adsorption were calculated as ranging from 10.2 to 17.4 kJ/ mol. The adsorption isotherm can be described by the Langmuir isotherm. The values of thermodynamic parameters (deltaH0, deltaS0, and deltaG0) for the adsorption indicated that this process was spontaneous and endothermic. At 318 K, the saturated adsorption capacities of QACC for SDBS, SLS, and SDS were 1.75, 1.53, and 1.39 mmol/g, respectively. The adsorption process was mainly chemisorption and partially physisorption. The results show that QACC is effective for the removal of anionic surfactants.

Effects of carbon nanotubes on phosphorus adsorption behaviors on aquatic sediments.

PubMed

Qian, Jin; Li, Kun; Wang, Peifang; Wang, Chao; Shen, Mengmeng; Liu, Jingjing; Tian, Xin; Lu, Bianhe

2017-08-01

Aquatic sediments are believed to be an important sink for carbon nanotubes (CNTs). With novel properties, CNTs can potentially disturb the fate and mobility of the co-existing contaminants in the sediments. Only toxic pollutants have been investigated previously, and to the best of our knowledge, no data has been published on how CNTs influence phosphorus (P) adsorption on aquatic sediments. In this study, multi-walled carbon nanotubes (MWCNTs) were selected as model CNTs. Experimental results indicated that compared to pseudo-first order and intraparticle diffusion models, the pseudo-second-order model is better for describing the adsorption kinetics of sediments and MWCNT-contaminated sediments. Adsorption isotherm studies suggested that the Langmuir model fits the isotherm data well. With the increase in the MWCNT-to-sediment ratio from 0.0% to 5.0%, the theoretical maximum monolayer adsorption capacity (Q max ) for P increased from 0.664 to 0.996mg/g. However, the Langmuir isotherm coefficient (K L ) significantly decreased from 4.231L/mg to 2.874L/mg, indicating the decrease in the adsorption free energy of P adsorbed on the sediments after MWCNT contamination. It was suggested that P was released more easily to the overlying water after the re-suspension of sediments. Moreover, the adsorption of sediments and sediment-MWCNT mixture was endothermic and physical in nature. Results obtained herein suggested that the change in the specific surface area and zeta potential of sediments is related to MWCNT contamination, and the large adsorption capacity of MWCNTs is probably the main factor responsible for the variation in the adsorption of P on aquatic sediments. Copyright © 2017 Elsevier Inc. 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.

Interaction of polyhydroxy fullerenes with ferrihydrite: adsorption and aggregation.

PubMed

Liu, Jing; Zhu, Runliang; Xu, Tianyuan; Laipan, Mingwang; Zhu, Yanping; Zhou, Qing; Zhu, Jianxi; He, Hongping

2018-02-01

The rapid development of nanoscience and nanotechnology, with thousands types of nanomaterials being produced, will lead to various environmental impacts. Thus, understanding the behaviors and fate of these nanomaterials is essential. This study focused on the interaction between polyhydroxy fullerenes (PHF) and ferrihydrite (Fh), a widespread iron (oxyhydr)oxide nanomineral and geosorbent. Our results showed that PHF were effectively adsorbed by Fh. The adsorption isotherm fitted the D-R model well, with an adsorption capacity of 67.1mg/g. The adsorption mean free energy of 10.72kJ/mol suggested that PHF were chemisorbed on Fh. An increase in the solution pH and a decrease of the Fh surface zeta potential were observed after the adsorption of PHF on Fh; moreover, increasing initial solution pH led to a reduction of adsorption. The Fourier transform infrared spectra detected a red shift of C-O stretching from 1075 to 1062cm -1 and a decrease of Fe-O bending, implying the interaction between PHF oxygenic functional groups and Fh surface hydroxyls. On the other hand, PHF affected the aggregation and reactivity of Fh by changing its surface physicochemical properties. Aggregation of PHF and Fh with individual particle sizes increasing from 2nm to larger than 5nm was measured by atomic force microscopy. The uniform distribution of C and Fe suggested that the aggregates of Fh were possibly bridged by PHF. Our results indicated that the interaction between PHF and Fh could evidently influence the migration of PHF, as well as the aggregation and reactivity of Fh. Copyright © 2017. Published by Elsevier B.V.

Adsorption calorimetry during metal vapor deposition on single crystal surfaces: Increased flux, reduced optical radiation, and real-time flux and reflectivity measurements

NASA Astrophysics Data System (ADS)

Sellers, Jason R. V.; James, Trevor E.; Hemmingson, Stephanie L.; Farmer, Jason A.; Campbell, Charles T.

2013-12-01

Thin films of metals and other materials are often grown by physical vapor deposition. To understand such processes, it is desirable to measure the adsorption energy of the deposited species as the film grows, especially when grown on single crystal substrates where the structure of the adsorbed species, evolving interface, and thin film are more homogeneous and well-defined in structure. Our group previously described in this journal an adsorption calorimeter capable of such measurements on single-crystal surfaces under the clean conditions of ultrahigh vacuum [J. T. Stuckless, N. A. Frei, and C. T. Campbell, Rev. Sci. Instrum. 69, 2427 (1998)]. Here we describe several improvements to that original design that allow for heat measurements with ˜18-fold smaller standard deviation, greater absolute accuracy in energy calibration, and, most importantly, measurements of the adsorption of lower vapor-pressure materials which would have previously been impossible. These improvements are accomplished by: (1) using an electron beam evaporator instead of a Knudsen cell to generate the metal vapor at the source of the pulsed atomic beam, (2) changing the atomic beam design to decrease the relative amount of optical radiation that accompanies evaporation, (3) adding an off-axis quartz crystal microbalance for real-time measurement of the flux of the atomic beam during calorimetry experiments, and (4) adding capabilities for in situ relative diffuse optical reflectivity determinations (necessary for heat signal calibration). These improvements are not limited to adsorption calorimetry during metal deposition, but also could be applied to better study film growth of other elements and even molecular adsorbates.

Adsorption calorimetry during metal vapor deposition on single crystal surfaces: increased flux, reduced optical radiation, and real-time flux and reflectivity measurements.

PubMed

Sellers, Jason R V; James, Trevor E; Hemmingson, Stephanie L; Farmer, Jason A; Campbell, Charles T

2013-12-01

Thin films of metals and other materials are often grown by physical vapor deposition. To understand such processes, it is desirable to measure the adsorption energy of the deposited species as the film grows, especially when grown on single crystal substrates where the structure of the adsorbed species, evolving interface, and thin film are more homogeneous and well-defined in structure. Our group previously described in this journal an adsorption calorimeter capable of such measurements on single-crystal surfaces under the clean conditions of ultrahigh vacuum [J. T. Stuckless, N. A. Frei, and C. T. Campbell, Rev. Sci. Instrum. 69, 2427 (1998)]. Here we describe several improvements to that original design that allow for heat measurements with ~18-fold smaller standard deviation, greater absolute accuracy in energy calibration, and, most importantly, measurements of the adsorption of lower vapor-pressure materials which would have previously been impossible. These improvements are accomplished by: (1) using an electron beam evaporator instead of a Knudsen cell to generate the metal vapor at the source of the pulsed atomic beam, (2) changing the atomic beam design to decrease the relative amount of optical radiation that accompanies evaporation, (3) adding an off-axis quartz crystal microbalance for real-time measurement of the flux of the atomic beam during calorimetry experiments, and (4) adding capabilities for in situ relative diffuse optical reflectivity determinations (necessary for heat signal calibration). These improvements are not limited to adsorption calorimetry during metal deposition, but also could be applied to better study film growth of other elements and even molecular adsorbates.

Comparative study on the copper activation and xanthate adsorption on sphalerite and marmatite surfaces

NASA Astrophysics Data System (ADS)

Liu, Jian; Wang, Yu; Luo, Deqiang; Chen, Luzheng; Deng, Jiushuai

2018-05-01

The copper activation and potassium butyl xanthate (PBX) adsorption on sphalerite and marmatite surfaces were comparatively investigated using in situ local electrochemical impedance spectroscopy (LEIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and surface adsorption tests. Comparing the LEIS and surface adsorption results, it was found that the activation time is a key factor influencing the copper activation and PBX adsorption on marmatite surface, but it has a negligible influence on sphalerite. For a short activation time within 10 min, the Fe impurity in marmatite shows an adverse influence on the speed of Cu adsorption and ion exchange as well as on the subsequent PBX adsorption. For a long activation time of 30 min, the LEIS, ToF-SIMS and surface adsorption results suggested that the Fe impurity in marmatite enhances the copper adsorption, whereas such enhanced copper adsorption of marmatite cannot result in corresponding enhancing of PBX adsorption. DFT result showed that the Fe impurity in marmatite has harmful influence on the PBX interaction with the Cu-activated surface by increasing the interaction energy. ToF-SIMS result further indicated that the Cu distribution in the outermost surface of marmatite is less than that of the sphalerite, which also results in the less PBX adsorption for the marmatite.

Protein adsorption to poly(ethylenimine)-modified Sepharose FF: VI. Partial charge neutralization drastically increases uptake rate.

PubMed

Zhao, Yangyang; Dong, Xiaoyan; Yu, Linling; Sun, Yan

2016-01-04

The adsorption and elution behaviors of bovine serum albumin (BSA) on poly(ethylenimine) (PEI)-grafted Sepharose FF resins were recently studied and a critical ionic capacity (cIC; 600 mmol/L) was found, above which the uptake rate increased drastically due to the occurrence of significant "chain delivery" effect. Moreover, above the cIC value, higher salt concentrations were required for protein elution due to the high charge density of the resins. In this work, we have reduced the charge density on the PEI chains of a PEI-grafted resin by neutralization of the amine groups with sodium acetate. PEI-modified resin with IC of 740 mmol/L (FF-PEI-L740, IC>cIC) was chosen as the starting material, and three resins with residual IC values of 660, 560 and 440 mmol/L (FF-PEI-R440) were obtained. The adsorption and chromatographic behaviors of these resins for BSA were investigated. It was found that, with IC decreasing from 740 to 440 mmol/L, the adsorption capacity kept almost unchanged; the effective protein diffusivity (De) also showed negligible variations as IC decreased from 740 to 560 mmol/L (De/D0=0.38 ± 0.04). However, it was interesting to observe a three-fold increase of the De value for FF-PEI-R440 (De/D0=1.23 ± 0.08). It is considered that the occurrence of the drastic uptake rate increase in FF-PEI-R440 was attributed to the decreased available binding sites for protein molecule, which led to the decrease of binding strength, thus facilitated the happenings of "chain delivery" effect of bound proteins. Besides, a study on the effect of ionic strength clarified that the lower the IC value, the higher the sensitivity of protein binding to salt concentration due to the easily screened electrostatic interactions at low surface charge densities. The ionic strength at the elution peak also decreased with decreasing IC in accordance with the salt sensitivity order. Column breakthrough studies demonstrated that the dynamic adsorption capacity of FF-PEI-R440 was

Improvement of pesticide adsorption capacity of cellulose fibre by high-energy irradiation-initiated grafting of glycidyl methacrylate

NASA Astrophysics Data System (ADS)

Takács, Erzsébet; Wojnárovits, László; Koczog Horváth, Éva; Fekete, Tamás; Borsa, Judit

2012-09-01

Cellulose as a renewable raw material was used for preparation of adsorbent of organic impurities in wastewater treatment. Hydrophobic surface of cellulose substrate was developed by grafting glycidyl methacrylate in simultaneous grafting using gamma irradiation initiation. Water uptake of cellulose significantly decreased while adsorption of phenol and a pesticide molecule (2,4-dichlorophenoxyacetic acid: 2,4-D) increased upon grafting. Adsorption equilibrium data fitted the Freundlich isotherm for both solutes.

Adsorption Isotherm Studies of Methyl Bromide on MgO

NASA Astrophysics Data System (ADS)

Burns, Teresa; Larese, John

2003-11-01

The adsorption of methyl bromine onto highly-uniform magnesium oxide powder was studied using a high-precision computer-controlled gas adsorption system. Methyl bromide was condensed onto the MgO substrate at temperatures between 165 K and 180 K. The layering behavior, iosthermal compressibility, and isosteric heat of adsorption were determined. Isotherms will be presented and future work discussed. TEB research sponsored by the Department of Energy EPSCOR Grant No. DE-FG02-01ER45895. JZL research sponsored by start-up funds from the University of Tennessee - Knoxville and by the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy, under contract No. DE-AC05-00OR22725 with Oak Ridge National Laboratory, managed and operated by UT-Battelle, LLC.

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

Adsorption kinetics, isotherms and thermodynamics of atrazine removal using a banana peel based sorbent.

PubMed

Chaparadza, Allen; Hossenlopp, Jeanne M

2012-01-01

Atrazine removal from water by treated banana peels was studied. The effect of pH, contact time, initial atrazine concentration, and temperature were investigated. Batch experiments demonstrated that 15 g L(-1) adsorbent dosage removed 90-99% of atrazine from 1-150 ppm aqueous solutions. The removal was both pH and temperature dependent with the most atrazine removed between pH 7 and 8.2 and increased with increasing temperature. Equilibrium data fitted well to the Langmuir and Redlich-Peterson models in the concentration and temperature ranges investigated, with a maximum adsorption capacity of 14 mg g(-1). Simple mass transfer models were applied to the experimental data to examine the adsorption mechanism and it was found that both external mass transfer and intraparticle diffusion played important roles in the adsorption mechanisms. The enthalpy of atrazine adsorption was evaluated to be 67.8 ± 6.3 kJ mol(-l) with a Gibbs free energy of -5.7 ± 1.2 kJ mol(-1).

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.

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE PAGES

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.; ...

2018-01-19

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

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

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« 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

Evaluation of ferrolysis in arsenate adsorption on the paddy soil derived from an Oxisol.

PubMed

Jiang, Jun; Dai, Zhaoxia; Sun, Rui; Zhao, Zhenjie; Dong, Ying; Hong, Zhineng; Xu, Renkou

2017-07-01

Iron oxides are dominant effective adsorbents for arsenate in iron oxide-rich variable charge soils. Oxisol-derived paddy soils undergo intensive ferrolysis, which results in high leaching and transformation of iron oxides. However, little information is available concerning the effect of ferrolysis on arsenate adsorption by paddy soil and parent Oxisol. In the present study, we examined the arsenate affinity of soils using arsenate adsorption/desorption isotherms, zeta potential, adsorption kinetics, pH effect and phosphate competition experiments. Results showed that ferrolysis in an alternating flooding-drying Oxisol-derived paddy soil resulted in a significant decrease of free iron oxides and increase of amorphous iron oxides in the surface and subsurface layers. There were more reactive sites exposed on amorphous than on crystalline iron oxides. Therefore, disproportionate ratios of arsenate adsorption capacities and contents of free iron oxides were observed in the studied Oxisols compared with paddy soils. The Gibbs free energy values corroborated that both electrostatic and non-electrostatic adsorption mechanisms contributed to the arsenate adsorption by bulk soils, and the kinetic adsorption data further suggested that the rate-limiting step was chemisorption. The zeta potential of soil colloids decreased after arsenate was adsorbed on the surfaces, forming inner-sphere complexes and thus transferring their negative charges to the soil particle surfaces. The adsorption/desorption isotherms showed that non-electrostatic adsorption was the main mechanism responsible for arsenate binding to the Oxisol and derived paddy soils, representing 91.42-94.65% of the adsorption capacities. Further studies revealed that arsenate adsorption was greatly inhibited by increasing suspension pH and incorporation of phosphate. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorption of bentazon on CAT and CARBOPAL activated carbon: Experimental and computational study

NASA Astrophysics Data System (ADS)

Spaltro, Agustín; Simonetti, Sandra; Torrellas, Silvia Alvarez; Rodriguez, Juan Garcia; Ruiz, Danila; Juan, Alfredo; Allegretti, Patricia

2018-03-01

Removal of the bentazon by adsorption on two different types of activated carbon was investigated under various experimental conditions.Kinetics of adsorption is followed and the adsorption isotherms of the pesticide are determined. The effects of the changes in pH, ionic strength and temperature are analyzed. Computational simulation was employed to analyze the geometry and the energy of pesticide absorption on activated carbon. Concentration of bentazon decreases while increase all the variables, from the same initial concentration. Experimental data for equilibrium was analyzed by three models: Langmuir, Freundlich and Guggenheim-Anderson-de Boer isotherms. Pseudo-first and pseudo-second-order kinetics are tested with the experimental data, and pseudo-second-order kinetics was the best for the adsorption of bentazon by CAT and CARBOPAL with coefficients of correlation R2 = 0.9996 and R2 = 0.9993, respectively. The results indicated that both CAT and CARBOPAL are very effective for the adsorption of bentazon from aqueous solutions, but CAT carbon has the greater capacity.

Adsorption characteristics of sol gel-derived zirconia for cesium ions from aqueous solutions.

PubMed

Yakout, Sobhy M; Hassan, Hisham S

2014-07-01

Zirconia powder was synthesized via a sol gel method and placed in a batch reactor for cesium removal investigation. X-ray analysis and Fourier transform infrared spectroscopy were utilized for the evaluation of the developed adsorbent. The adsorption process has been investigated as a function of pH, contact time and temperature. The adsorption is strongly dependent on the pH of the medium whereby the removal efficiency increases as the pH turns to the alkaline range. The process was initially very fast and the maximum adsorption was attained within 60 min of contact. A pseudo-second-order model and homogeneous particle diffusion model (HPDM) were found to be the best to correlate the diffusion of cesium into the zirconia particles. Furthermore, adsorption thermodynamic parameters, namely the standard enthalpy, entropy, and Gibbs free energy, were calculated. The results indicate that cesium adsorption by zirconia is an endothermic (ΔH>0) process and good affinity of cesium ions towards the sorbent (ΔS>0) was observed.

Anharmonicity and confinement in zeolites: Structure, spectroscopy, and adsorption free energy of ethanol in H-ZSM-5

DOE PAGES

Alexopoulos, Konstantinos; Lee, Mal -Soon; Liu, Yue; ...

2016-03-21

Here, to account for thermal and entropic effects caused by the dynamics of the motion of the reaction intermediates, ethanol adsorption on the Brønsted acid site of the H-ZSM-5 catalyst has been studied at different temperatures and ethanol loadings using ab initio molecular dynamics (AIMD) simulations, infrared (IR) spectroscopy and calorimetric measurements. At low temperatures (T ≤ 400 K) and ethanol loading, a single ethanol molecule adsorbed in H-ZSM-5 forms a Zundel-like structure where the proton is equally shared between the oxygen of the zeolite and the oxygen of the alcohol. At higher ethanol loading, a second ethanol molecule helpsmore » to stabilize the protonated ethanol at all temperatures by acting as a solvating agent. The vibrational density of states (VDOS), as calculated from the AIMD simulations, are in excellent agreement with measured IR spectra for C 2H 5OH, C 2H 5OD and C 2D 5OH isotopomers and support the existence of both monomers and dimers. A quasi-harmonic approximation (QHA), applied to the VDOS obtained from the AIMD simulations, provides estimates of adsorption free energy within ~10 kJ/mol of the experimentally determined quantities, whereas the traditional approach, employing harmonic frequencies from a single ground state minimum, strongly overestimates the adsorption free energy by at least ~30 kJ/mol. This discrepancy is traced back to the inability of the harmonic approximation to represent the contributions to the vibrational motions of the ethanol molecule upon confinement in the zeolite. KA, MFR, GBM were supported by the Long Term Structural Methusalem Funding by the Flemish Government – grant number BOF09/01M00409. MSL, VAG, RR and JAL were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational resources were provided at W. R. Wiley

Spin asymmetric band gap opening in graphene by Fe adsorption

NASA Astrophysics Data System (ADS)

del Castillo, E.; Cargnoni, F.; Achilli, S.; Tantardini, G. F.; Trioni, M. I.

2015-04-01

The adsorption of Fe atom on graphene is studied by first-principles Density Functional Theory. The structural, electronic, and magnetic properties are analyzed at different coverages, all preserving C6v symmetry for the Fe adatom. We observed that binding energies, magnetic moments, and adsorption distances rapidly converge as the size of the supercell increases. Among the considered supercells, those constituted by 3n graphene unit cells show a very peculiar behavior: the adsorption of a Fe atom induces the opening of a spin-dependent gap in the band structure. In particular, the gap amounts to tenths of eV in the majority spin component, while in the minority one it has a width of about 1 eV for the 3 × 3 supercell and remains significant even at very low coverages (0.25 eV for θ ≃ 2%). The charge redistribution upon Fe adsorption has also been analyzed according to state of the art formalisms indicating an appreciable charge transfer from Fe to the graphene layer.

The effect of carbon surface chemical composition on the adsorption of acetanilide.

PubMed

Terzyk, Artur P

2004-04-01

The study of acetanilide adsorption-desorption performed at three temperatures (300, 310, and 320 K) and at two pH levels (7.0 and 1.5) on the series of D43/1 carbons (initial and modified with HNO3, fuming H2SO4, and gaseous NH3) is reported. Sorption data are additionally supplemented with the results of thermal analysis and calorimetric and kinetic measurements. It is shown that, generally, acetanilide adsorption at the neutral pH level is reversible (only on the more acidic carbons and at the lowest temperature does hysteresis occur due to the formation of hydrogen bonds with surface OH groups), and it decreases for the chemically modified carbons. In contrast, at the acidic pH level acetanilide adsorption is irreversible. A mechanism of irreversibility is proposed and it is shown that hysteresis is caused by the chemical reaction between the nucleophile (carbon) and the protonized acetanilide molecules. For all studied carbons, at the acidic pH level, adsorption increases and this is caused by the weakly basic character of acetanilide molecule. Adsorption results are described applying adsorbability and Dubinin-Astakhov, quasi-Freundlich and solution analogue of the Toth adsorption isotherm equations. Using the kinetic data, the effective diffusion coefficients and the energy of diffusion are calculated. It is shown that the diffusion is mainly a surface process, and the contribution of the pore diffusion increases with the rise in temperature. By applying different correlations between the parameters obtained from the theoretical description of experimental data and those characterizing the chemical composition of the studied carbons, the role of the latter in the adsorption and kinetics of acetanilide adsorption is determined.

A comparative study of fibrinogen adsorption onto metal oxide thin films

NASA Astrophysics Data System (ADS)

Silva-Bermudez, P.; Muhl, S.; Rodil, S. E.

2013-10-01

One of the first events occurring upon foreign material-biological medium contact is the adsorption of proteins, which evolution greatly determines the cells response to the material. Protein-surface interactions are a complex phenomenon driven by the physicochemical properties of the surface, protein(s) and liquid medium involve in the interaction. In this article the adsorption of fibrinogen (Fbg) onto Ta2O5, Nb2O5, TiO2 and ZrO2 thin films is reported. The adsorption kinetics and characteristics of the adsorbed fibrinogen layer were studied in situ using dynamic and spectroscopic ellipsometry. The films wettability, surface energy (γLW/AB) and roughness were characterized aiming to elucidate their correlations with Fbg adsorption. The adsorption rate changed accordingly to the film; the fastest adsorption rate and highest Fbg surface mass concentration (Γ) was observed on ZrO2. The hydrophobic/hydrophilic character of the oxide highly influenced Fbg adsorption. On Ta2O5, Nb2O5 and TiO2, which were either hydrophilic or in the breaking-point between hydrophilicity and hydrophobicity, Γ was correlated to the polar component of γLW/AB and roughness of the surface. On ZrO2, clearly hydrophobic, Γ increased significantly off the correlation observed for the other films. The results indicated different adsorption dynamics and orientations of the Fbg molecules dependent on the surface hydrophobic/hydrophilic character.

Densely-packed ZnTPPs Monolayer on the Rutile TiO2(110)-(1×1) Surface: Adsorption Behavior and Energy Level Alignment

PubMed Central

Rangan, Sylvie; Ruggieri, Charles; Bartynski, Robert; Martínez, José Ignacio; Flores, Fernando; Ortega, José

2016-01-01

The adsorption of a densely packed Zinc(II) tetraphenylporphyrin monolayer on a rutile TiO2(110)-(1×1) surface has been studied using a combination of experimental and theoretical methods, aimed at analyzing the relation between adsorption behavior and barrier height formation. The adsorption configuration of ZnTPP was determined from scanning tunnel microscopy (STM) imaging, density functional theory (DFT) calculations and STM image simulation. The corresponding energy alignment was experimentally determined from X-ray and UV-photoemission spectroscopies and inverse photoemission spectroscopy. These results were found in good agreement with an appropriately corrected DFT model, pointing to the importance of local bonding and intermolecular interactions in the establishment of barrier heights. PMID:26998188

Adsorption of antimony onto iron oxyhydroxides: adsorption behavior and surface structure.

PubMed

Guo, Xuejun; Wu, Zhijun; He, Mengchang; Meng, Xiaoguang; Jin, Xin; Qiu, Nan; Zhang, Jing

2014-07-15

Antimony is detected in soil and water with elevated concentration due to a variety of industrial applications and mining activities. Though antimony is classified as a pollutant of priority interest by the United States Environmental Protection Agency (USEPA) and Europe Union (EU), very little is known about its environmental behavior and adsorption mechanism. In this study, the adsorption behaviors and surface structure of antimony (III/V) on iron oxides were investigated using batch adsorption techniques, surface complexation modeling (SCM), X-ray photon spectroscopy (XPS) and extended X-ray absorption fine structure spectroscopy (EXAFS). The adsorption isotherms and edges indicated that the affinity of Sb(V) and Sb(III) toward the iron oxides depended on the Sb species, solution pH, and the characteristics of iron oxides. Sb(V) adsorption was favored at acidic pH and decreased dramatically with increasing pH, while Sb(III) adsorption was constant over a broad pH range. When pH is higher than 7, Sb(III) adsorption by goethite and hydrous ferric oxide (HFO) was greater than Sb(V). EXAFS analysis indicated that the majority of Sb(III), either adsorbed onto HFO or co-precipitated by FeCl3, was oxidized into Sb(V) probably due to the involvement of O2 in the long duration of sample preservation. Only one Sb-Fe subshell was filtered in the EXAFS spectra of antimony adsorption onto HFO, with the coordination number of 1.0-1.9 attributed to bidentate mononuclear edge-sharing ((2)E) between Sb and HFO. Copyright © 2014 Elsevier B.V. All rights reserved.

Batch and fixed-bed adsorption of tartrazine azo-dye onto activated carbon prepared from apricot stones

NASA Astrophysics Data System (ADS)

Albroomi, H. I.; Elsayed, M. A.; Baraka, A.; Abdelmaged, M. A.

2017-07-01

This work describes the potential of utilizing prepared activated carbon from apricot stones as an efficient adsorbent material for tartrazine (TZ) azo-dye removal in a batch and dynamic adsorption system. The results revealed that activated carbons with well-developed surface area (774 m2/g) and pore volume (1.26 cm3/g) can be manufactured from apricot stones by H3PO4 activation. In batch experiments, effects of the parameters such as initial dye concentration and temperature on the removal of the dye were studied. Equilibrium was achieved in 120 min. Adsorption capacity was found to be dependent on the initial concentration of dye solution, and maximum adsorption was found to be 76 mg/g at 100 mg/L of TZ. The adsorption capacity at equilibrium ( q e) increased from 22.6 to 76 mg/g with an increase in the initial dye concentrations from 25 to 100 mg/L. The thermodynamic parameters such as change in free energy (Δ G 0), enthalpy (Δ H 0) and entropy (Δ S 0) were determined and the positive value of (Δ H) 78.1 (K J mol-1) revealed that adsorption efficiency increased with an increase in the process temperature. In fixed-bed column experiments, the effect of selected operating parameters such as bed depth, flow rate and initial dye concentration on the adsorption capacity was evaluated. Increase in bed height of adsorption columns leads to an extension of breakthrough point as well as the exhaustion time of adsorbent. However, the maximum adsorption capacities decrease with increases of flow rate. The breakthrough data fitted well to bed depth service time and Thomas models with high coefficient of determination, R 2 ≥ 94.

Aluminum and iron doped graphene for adsorption of methylated arsenic pollutants

NASA Astrophysics Data System (ADS)

Cortés-Arriagada, Diego; Toro-Labbé, Alejandro

2016-11-01

The ability of Al and Fe-doped graphene for the adsorption of trivalent and pentavalent methylated arsenic compounds was studied by quantum chemistry computations. The adsorption of trivalent methylarsenicals is reached with adsorption energies of 1.5-1.7 eV at neutral conditions; while, adsorption of pentavalent methylarsenicals reaches adsorption energies of 3.3-4.2 eV and 1.2-2.4 eV from neutral to low pH conditions, respectively. Moreover, the weakening of the interacting σAssbnd O bond in the pollutant structure played an important role in the stability of the adsorbent-adsorbate systems, determining the adsorption strength. In addition, the pollutant adsorption appears to be efficient in aqueous environments, with even high stability at ambient temperature; in this regard, it was determined that the trivalent and petavalent forms are mainly adsorbed in their neutral and anionic forms at neutral pH, respectively. Therefore, Al and Fe-doped graphene are considered as potential future materials for the removal of methylated arsenic pollutants.

Study of carbon dioxide adsorption on a Cu-nitroprusside polymorph

DOE PAGES

Roque-Malherbe, R.; Lozano, C.; Polanco, R.; ...

2011-03-26

A careful structural characterization was carried out to unequivocally determine the structure of the synthesized material. The TGA, DRIFTS and a Pawley fitting of the XRD powder profiles indicate that the hydrated and in situ dehydrated polymorph crystallizes in the orthorhombic space group Pnma. Meanwhile, the CO 2 isosteric heat of adsorption appears to be independent of loading with an average value of 30 kJ/mol. This translates to a physisorption type interaction, where the adsorption energy corresponding to wall and lateral interactions are mutually compensated to produce, an apparently, homogeneous adsorption energy. The somewhat high adsorption energy is probably duemore » to the confinement of the CO 2 molecules in the nitroprusside pores. Statistical Physics and the Dubinin theory for pore volume filling allowed model the CO 2 equilibrium adsorption process in Cu-nitroprusside. A DRIFTS test for the adsorbed CO 2 displayed a peak at about 2338 cm -1 that was assigned to a contribution due to physical adsorption of the molecule. Another peak found at 2362 cm -1 evidenced that this molecule interacts with the Cu 2+, which appears to act as an electron accepting Lewis acid site. In conclusion, the aim of the present paper is to report a Pnma stable Cu-nitroprusside polymorph obtained by the precipitation method that can adsorb carbon dioxide.« less

Gas adsorption capacity of wood pellets

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

Yazdanpanah, F.; Sokhansanj, Shahabaddine; Lim, C. Jim

In this paper, temperature-programmed desorption (TPD) analysis was used to measure and analyze the adsorption of off-gases and oxygen by wood pellets during storage. Such information on how these gases interact with the material helps in the understanding of the purging/stripping behavior of off-gases to develop effective ventilation strategies for wood pellets. Steam-exploded pellets showed the lowest carbon dioxide (CO 2) uptake compared to the regular and torrefied pellets. The high CO 2 adsorption capacity of the torrefied pellets could be attributed to their porous structure and therefore greater available surface area. Quantifying the uptake of carbon monoxide by pelletsmore » was challenging due to chemical adsorption, which formed a strong bond between the material and carbon monoxide. The estimated energy of desorption for CO (97.8 kJ/mol) was very high relative to that for CO 2 (7.24 kJ/mol), demonstrating the mechanism of chemical adsorption and physical adsorption for CO and CO 2, respectively. As for oxygen, the strong bonds that formed between the material and oxygen verified the existence of chemical adsorption and formation of an intermediate material.« less

Gas adsorption capacity of wood pellets

DOE PAGES

Yazdanpanah, F.; Sokhansanj, Shahabaddine; Lim, C. Jim; ...

2016-02-03

In this paper, temperature-programmed desorption (TPD) analysis was used to measure and analyze the adsorption of off-gases and oxygen by wood pellets during storage. Such information on how these gases interact with the material helps in the understanding of the purging/stripping behavior of off-gases to develop effective ventilation strategies for wood pellets. Steam-exploded pellets showed the lowest carbon dioxide (CO 2) uptake compared to the regular and torrefied pellets. The high CO 2 adsorption capacity of the torrefied pellets could be attributed to their porous structure and therefore greater available surface area. Quantifying the uptake of carbon monoxide by pelletsmore » was challenging due to chemical adsorption, which formed a strong bond between the material and carbon monoxide. The estimated energy of desorption for CO (97.8 kJ/mol) was very high relative to that for CO 2 (7.24 kJ/mol), demonstrating the mechanism of chemical adsorption and physical adsorption for CO and CO 2, respectively. As for oxygen, the strong bonds that formed between the material and oxygen verified the existence of chemical adsorption and formation of an intermediate material.« less

Adsorption kinetics of SO2 on powder activated carbon

NASA Astrophysics Data System (ADS)

Li, Bing; Zhang, Qilong; Ma, Chunyuan

2018-02-01

The flue gas SO2 adsorption removal by powder activated carbon is investigated based on a fixed bed reactor. The effect of SO2 inlet concentration on SO2 adsorption is investigated and the adsorption kinetics is analyzed. The results indicated that the initial SO2 adsorption rate and the amount of SO2 adsorbed have increased with increased in SO2 inlet concentration. Gas diffusion, surface adsorption and catalytic oxidation reaction are involved in SO2 adsorption on powder activated carbon, which play a different role in different stage. The Bangham kinetics model can be used to predict the kinetics of SO2 adsorption on powder activated carbon.

Early stages of Cs adsorption mechanism for GaAs nanowire surface

NASA Astrophysics Data System (ADS)

Diao, Yu; Liu, Lei; Xia, Sihao; Feng, Shu

2018-03-01

In this study, the adsorption mechanism of Cs adatoms on the (100) surface of GaAs nanowire with [0001] growth direction is investigated utilizing first principles method based on density function theory. The adsorption energy, work function, atomic structure and electronic property of clean surface and Cs-covered surfaces with different coverage are discussed. Results show that when only one Cs is adsorbed on the surface, the most favorable adsorption site is BGa-As. With increasing Cs coverage, work function gradually decreases and gets its minimum at 0.75 ML, then rises slightly when Cs coverage comes to 1 ML, indicating the existence of 'Cs-kill' phenomenon. According to further analysis, Cs activation process can effectively reduce the work function due to the formation of a downward band bending region and surface dipole moment directing from Cs adatom to the surface. As Cs coverage increases, the conduction band minimum and valence band maximum both shift towards lower energy side, contributed by the orbital hybridization between Cs-5s, Cs-5p states and Ga-4p, As-4s, As-4p states near Fermi level. The theoretical calculations and analysis in this study can improve the Cs activation technology for negative electron affinity optoelectronic devices based on GaAs nanowires, and also provide a reference for the further Cs/O or Cs/NF3 activation process.

Effects of structure of fatty acid collectors on the adsorption of fluorapatite (0 0 1) surface: A first-principles calculations

NASA Astrophysics Data System (ADS)

Xie, Jun; Li, Xianhai; Mao, Song; Li, Longjiang; Ke, Baolin; Zhang, Qin

2018-06-01

Effects of carbon chain length, carbon chain isomerism, Cdbnd C double bonds number on fatty acid adsorption on FAP (0 0 1) surface have been investigated based on DFT. The results revealed that fatty acid collector can form stable adsorption configuration at Ca1 (surf) site. Chemical adsorption was formed between O (mole) of fatty acid collector and the Ca1 (surf) of fluorapatite (0 0 1) surface; hydrogen bond adsorption was formed between the H (mole) of fatty acid and the O (surf) of-[PO4]- of FAP (0 0 1) surface. Fatty acid collectors and FAP (0 0 1) surface are bonding by means of the hybridization of O (mole) 2p and Ca (surf) 4d orbitals, H (mole) 1s and O (surf) 2p orbital. The analysis of adsorption energy, DOS, electron density, Mulliken charge population and Mulliken bond population revealed that with the carbon chain growing within certain limits, the absolute value of the adsorption energy and the overlapping area between the DOS curve of O (mole) and Ca (surf) was greater, while that of H (mole) 1s and O (surf) 2p basically remained unchanged. As Cdbnd C double bonds of fatty acids increased within certain limits, the adsorption energy and the overlapping area between the state density curve of O (mole) and Ca (surf), H (mole) and O (surf) basically remained unchanged. The substituent groups of fatty acid changed, the absolute value of the adsorption energy and the overlapping area between the state density curve had a major change. The influence of fatty acids adsorption on FAP (0 0 1) surface depends mainly on the interaction between O (mole) and Ca (surf).

Adsorption and dissociation of H2O on the (001) surface of uranium mononitride: energetics and mechanism from first-principles investigation.

PubMed

Bo, Tao; Lan, Jian-Hui; Zhang, Yu-Juan; Zhao, Yao-Lin; He, Chao-Hui; Chai, Zhi-Fang; Shi, Wei-Qun

2016-05-21

The interfacial interaction of uranium mononitride (UN) with water from the environment unavoidably leads to corrosion of nuclear fuels, which affects a lot of processes in the nuclear fuel cycle. In this work, the microscopic adsorption behaviors of water on the UN(001) surface as well as water dissociation and accompanying H2 formation mechanisms have been investigated on the basis of DFT+U calculations and ab initio atomistic thermodynamics. For adsorption of one H2O monomer, the predicted adsorption energies are -0.88, -2.07, and -2.07 eV for the most stable molecular, partially dissociative, and completely dissociative adsorption, respectively. According to our calculations, a water molecule dissociates into OH and H species via three pathways with small energy barriers of 0.78, 0.72, and 0.85 eV, respectively. With the aid of the neighboring H atom, H2 formation through the reaction of H* + OH* can easily occur via two pathways with energy barriers of 0.61 and 0.36 eV, respectively. The molecular adsorption of water shows a slight coverage dependence on the surface while this dependence becomes obvious for partially dissociative adsorption as the water coverage increases from 1/4 to 1 ML. In addition, based on the "ab initio atomistic thermodynamic" simulations, increasing H2O partial pressure will enhance the stability of the adsorbed system and water coverage, while increasing temperature will decrease the H2O coverage. We found that the UN(001) surface reacts easily with H2O at room temperature, leading to dissolution and corrosion of the UN fuel materials.

Single-component and binary CO2 and H2O adsorption of amine-functionalized cellulose.

PubMed

Gebald, Christoph; Wurzbacher, Jan A; Borgschulte, Andreas; Zimmermann, Tanja; Steinfeld, Aldo

2014-02-18

A fundamental analysis of single-component and binary CO2 and H2O adsorption of amine-functionalized nanofibrillated cellulose is carried out in the temperature range of 283-353 K and at CO2 partial pressures in the range of 0.02-105 kPa, where the ultralow partial pressure range is relevant for the direct capture of CO2 from atmospheric air. Single-component CO2 and H2O adsorption experimental data are fitted to the Toth and Guggenheim-Anderson-de Boer models, respectively. Corresponding heats of adsorption, derived from explicit solutions of the van't Hoff equation, are -50 kJ/mol CO2 and -48.8 kJ/mol H2O. Binary CO2/H2O adsorption measurements for humid air reveal that the presence of H2O at 2.55 kPa enhances CO2 adsorption, while the presence of CO2 at 0.045 kPa does not influence H2O adsorption. The energy demand of the temperature-vacuum-swing adsorption/desorption cycle for delivering pure CO2 from air increases significantly with H2O adsorption and indicates the need to reduce the hygroscopicity of the adsorbent.

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

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

Removal of carbonyl sulfide using activated carbon adsorption.

PubMed

Sattler, Melanie L; Rosenberk, Ranjith Samuel

2006-02-01

Wastewater treatment plant odors are caused by compounds such as hydrogen sulfide (H2S), methyl mercaptans, and carbonyl sulfide (COS). One of the most efficient odor control processes is activated carbon adsorption; however, very few studies have been conducted on COS adsorption. COS is not only an odor causing compound but is also listed in the Clean Air Act as a hazardous air pollutant. Objectives of this study were to determine the following: (1) the adsorption capacity of 3 different carbons for COS removal; (2) the impact of relative humidity (RH) on COS adsorption; (3) the extent of competitive adsorption of COS in the presence of H2S; and (4) whether ammonia injection would increase COS adsorption capacity. Vapor phase react (VPR; reactivated), BPL (bituminous coal-based), and Centaur (physically modified to enhance H2S adsorption) carbons manufactured by Calgon Carbon Corp. were tested in three laboratory-scale columns, 6 in. in depth and 1 in. in diameter. Inlet COS concentrations varied from 35 to 49 ppmv (86-120 mg/m3). RHs of 17%, 30%, 50%, and 90% were tested. For competitive adsorption studies, H2S was tested at 60 ppmv, with COS at 30 ppmv. COS, RH, H2S, and ammonia concentrations were measured using an International Sensor Technology Model IQ-350 solid state sensor, Cole-Parmer humidity stick, Interscan Corp. 1000 series portable analyzer, and Drager Accuro ammonia sensor, respectively. It was found that the adsorption capacity of Centaur carbon for COS was higher than the other two carbons, regardless of RH. As humidity increased, the percentage of decrease in adsorption capacity of Centaur carbon, however, was greater than the other two carbons. The carbon adsorption capacity for COS decreased in proportion to the percentage of H2S in the gas stream. More adsorption sites appear to be available to H2S, a smaller molecule. Ammonia, which has been found to increase H2S adsorption capacity, did not increase the capacity for COS.

Quantitatively identifying the roles of interfacial water and solid surface in governing peptide adsorption.

PubMed

Xu, Zhijun; Yang, Xiao; Wei, Qichao; Zhao, Weilong; Cui, Beiliang; Yang, Xiaoning; Sahai, Nita

2018-06-11

Understanding the molecular mechanism of protein adsorption on solids is critical to their applications in materials synthesis and tissue engineering. Though the water phase at the surface/water interface has been recognized as three types: free water in the bulk region, intermediate water phase and surface-bound water layers adjacent to the surface, the roles of the water and surface in determining the protein adsorption are not clearly identified, particularly at the quantitative level. Herein, we provide a methodology involving the combination of microsecond strengthen sampling simulation and force integration to quantitatively characterize the water-induced contribution and the peptide-surface interactions into the adsorption free energy. Using hydroxyapatite and graphene surfaces as examples, we demonstrate how the distinct interfacial features dominate the delicate force balance between these two thermodynamics parameters, leading to surface preference/resistance to peptide adsorption. Specifically, the water layer provides sustained repelling force against peptide adsorption, as indicated by a monotonic increase in the water-induced free energy profile, whereas the contribution to the free energy from the surface effect is thermodynamically favorable, thus acting as the dominant driving force for peptide adsorptions. More importantly, the revealed adsorption mechanism is critically dictated by the distribution of water phase at the solid/water interface, which plays a crucial role in establishing the force balance between the interactions of the peptide with the water layer and the surface. For the HAP surface, the charged peptide exhibits strong binding affinity to the surface, which is ascribed to the controlling contribution of peptide-surface interaction in the intermediate water phase and the surface-bound water layers are observed as the origin of bioresistance of solid surfaces towards the adsorption of charge-neutral peptides. The preferred peptide

Adsorption of diclofenac and nimesulide on activated carbon: Statistical physics modeling and effect of adsorbate size

NASA Astrophysics Data System (ADS)

Sellaoui, Lotfi; Mechi, Nesrine; Lima, Éder Cláudio; Dotto, Guilherme Luiz; Ben Lamine, Abdelmottaleb

2017-10-01

Based on statistical physics elements, the equilibrium adsorption of diclofenac (DFC) and nimesulide (NM) on activated carbon was analyzed by a multilayer model with saturation. The paper aimed to describe experimentally and theoretically the adsorption process and study the effect of adsorbate size using the model parameters. From numerical simulation, the number of molecules per site showed that the adsorbate molecules (DFC and NM) were mostly anchored in both sides of the pore walls. The receptor sites density increase suggested that additional sites appeared during the process, to participate in DFC and NM adsorption. The description of the adsorption energy behavior indicated that the process was physisorption. Finally, by a model parameters correlation, the size effect of the adsorbate was deduced indicating that the molecule dimension has a negligible effect on the DFC and NM adsorption.

Theoretical Studies about Adsorption on Silicon Surface

NASA Astrophysics Data System (ADS)

Huang, Yan; Chen, Xiaoshuang; Zhu, Xiao Yan; Duan, He; Zhou, Xiao Hao; Lu, Wei

In this review paper, we address the important research topic of adsorption on the silicon surface. The deposition of single Si ad-species (adatom and ad-dimer) on the p(2×2) reconstructed Si(100) surface has been simulated by the empirical tight-binding method. Using the clean and defective Si surfaces as the deposition substrates, the deposition energies are mapped out around the clean surface, dimer vacancies, steps and kink structures. The binding sites, saddle points and several possible diffusion paths are obtained from the calculated energy. With further analysis of the deposition and diffusion behaviors, the influences of the surface defects can be found. Then, by adopting the first-principle calculations, the adsorptions of the II-VI group elements on the clean and As-passivated Si(211) substrates have been calculated as the example of adsorption on the high-miller-index Si surface.

The influence of CO adsorption on the surface composition of cobalt/palladium alloys

NASA Astrophysics Data System (ADS)

Murdoch, A.; Trant, A. G.; Gustafson, J.; Jones, T. E.; Noakes, T. C. Q.; Bailey, P.; Baddeley, C. J.

2016-04-01

Segregation induced by the adsorption of gas phase species can strongly influence the composition of bimetallic surfaces and can therefore play an important role in influencing heterogeneous catalytic reactions. The addition of palladium to cobalt catalysts has been shown to promote Fischer Tropsch catalysis. We investigate the adsorption of CO onto bimetallic CoPd surfaces on Pd{111} using a combination of reflection absorption infrared spectroscopy and medium energy ion scattering. The vibrational frequency of adsorbed CO provides crucial information on the adsorption sites adopted by CO and medium energy ion scattering probes the surface composition before and after CO exposure. We show that cobalt segregation is induced by CO adsorption and rationalise these observations in terms of the strength of adsorption of CO in various surface adsorption sites.

Adsorption of Antibiotics on Graphene and Biochar in Aqueous Solutions Induced by π-π Interactions

PubMed Central

Peng, Bingquan; Chen, Liang; Que, Chenjing; Yang, Ke; Deng, Fei; Deng, Xiaoyong; Shi, Guosheng; Xu, Gang; Wu, Minghong

2016-01-01

The use of carbon based materials on the removal of antibiotics with high concentrations has been well studied, however the effect of this removal method is not clear on the actual concentration of environments, such as the hospital wastewater, sewage treatment plants and aquaculture wastewater. In this study, experimental studies on the adsorption of 7 antibiotics in environmental concentration of aqueous solutions by carbon based materials have been observed. Three kinds of carbon materials have shown very fast adsorption to antibiotics by liquid chromatography–tandem mass spectrometry (LC-MS-MS) detection, and the highest removal efficiency of antibiotics could reach to 100% within the range of detection limit. Surprisedly, the adsorption rate of graphene with small specific surface area was stronger than other two biochar, and adsorption rate of the two biochar which have approximate specific surface and different carbonization degree, was significantly different. The key point to the present observation were the π-π interactions between aromatic rings on adsorbed substance and carbon based materials by confocal laser scanning microscope observation. Moreover, adsorption energy markedly increased with increasing number of the π rings by using the density functional theory (DFT), showing the particular importance of π-π interactions in the adsorption process. PMID:27534975

Adsorption of Antibiotics on Graphene and Biochar in Aqueous Solutions Induced by π-π Interactions

NASA Astrophysics Data System (ADS)

Peng, Bingquan; Chen, Liang; Que, Chenjing; Yang, Ke; Deng, Fei; Deng, Xiaoyong; Shi, Guosheng; Xu, Gang; Wu, Minghong

2016-08-01

The use of carbon based materials on the removal of antibiotics with high concentrations has been well studied, however the effect of this removal method is not clear on the actual concentration of environments, such as the hospital wastewater, sewage treatment plants and aquaculture wastewater. In this study, experimental studies on the adsorption of 7 antibiotics in environmental concentration of aqueous solutions by carbon based materials have been observed. Three kinds of carbon materials have shown very fast adsorption to antibiotics by liquid chromatography-tandem mass spectrometry (LC-MS-MS) detection, and the highest removal efficiency of antibiotics could reach to 100% within the range of detection limit. Surprisedly, the adsorption rate of graphene with small specific surface area was stronger than other two biochar, and adsorption rate of the two biochar which have approximate specific surface and different carbonization degree, was significantly different. The key point to the present observation were the π-π interactions between aromatic rings on adsorbed substance and carbon based materials by confocal laser scanning microscope observation. Moreover, adsorption energy markedly increased with increasing number of the π rings by using the density functional theory (DFT), showing the particular importance of π-π interactions in the adsorption process.

Adsorption of goethite onto quartz and kaolinite

USGS Publications Warehouse

Goldberg, M.C.; Weiner, Eugene R.; Boymel, P.M.

1984-01-01

The adsorption of colloidal goethite onto quartz and kaolinite substrates has been studied as a function of pH and NaCl concentration. Goethite adsorption was measured quantitatively by Fourier-transform infrared spectroscopy. The results indicate that adsorption onto both substrates is due primarily to coulombic forces; however, the pH dependence of adsorption is very different for the two substrates. This is explained by the fact that the surface charge on quartz is entirely pH-dependent, while kaolinite has surface faces which carry a permanent negative charge. Adsorption of goethite on to kaolinite increases markedly with increasing NaCl concentration, while adsorption onto quartz is relatively independent of NaCl concentration. This can be explained by the influence of NaCl concentration upon the development of surface charge on the substrates. A method is described for separating surface-bound goethite from free goethite.

Theoretical Study of Trimethylacetic Acid Adsorption on CeO 2 (111) Surface

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

Wang, Weina; Thevuthasan, S.; Wang, Wenliang

We investigated trimethylacetic acid (TMAA) adsorption on stoichiometric and oxygen-deficient CeO 2(111) surfaces using density functional theory that accounts for the on-site Coulomb interaction via a Hubbard term (DFT+U) and long-range dispersion correction. Both the molecular state and dissociative state (TMAA → TMA– + H +) were identified on stoichiometric and oxygen-deficient CeO 2(111) surfaces. For the stoichiometric surface, two thermodynamically favorable configurations with adsorption energies of the order of -30 kcal/mol are identified; one is a molecule adsorption state, and the other one is a dissociative state. For the oxygen-deficient surface, dissociative states are more favorable than molecular states.more » Moreover, the most favorable configuration is the dissociative adsorption of TMAA with the adsorption energy of the order of -77 kcal/mol. The dissociated TMA moiety takes the position of oxygen vacancy, forming three Ce–O bonds. The signature vibrational frequencies for these thermodynamically stable structures are reported as well as their electronic structures. The effects of long-range dispersion interactions are found to be negligible for geometries but important for adsorption energies.« less

Theoretical Study of Trimethylacetic Acid Adsorption on CeO 2 (111) Surface

DOE PAGES

Wang, Weina; Thevuthasan, S.; Wang, Wenliang; ...

2016-01-11

We investigated trimethylacetic acid (TMAA) adsorption on stoichiometric and oxygen-deficient CeO 2(111) surfaces using density functional theory that accounts for the on-site Coulomb interaction via a Hubbard term (DFT+U) and long-range dispersion correction. Both the molecular state and dissociative state (TMAA → TMA– + H +) were identified on stoichiometric and oxygen-deficient CeO 2(111) surfaces. For the stoichiometric surface, two thermodynamically favorable configurations with adsorption energies of the order of -30 kcal/mol are identified; one is a molecule adsorption state, and the other one is a dissociative state. For the oxygen-deficient surface, dissociative states are more favorable than molecular states.more » Moreover, the most favorable configuration is the dissociative adsorption of TMAA with the adsorption energy of the order of -77 kcal/mol. The dissociated TMA moiety takes the position of oxygen vacancy, forming three Ce–O bonds. The signature vibrational frequencies for these thermodynamically stable structures are reported as well as their electronic structures. The effects of long-range dispersion interactions are found to be negligible for geometries but important for adsorption energies.« less

Selective adsorption and separation of chromium (VI) on the magnetic iron-nickel oxide from waste nickel liquid.

PubMed

Wei, Linsen; Yang, Gang; Wang, Ren; Ma, Wei

2009-05-30

The selective adsorption of Cr (VI) from the wastewater of Cr (VI)-Ni (II) by magnetically iron-nickel oxide was investigated in this study. Synthetic iron-nickel oxide magnetic particles in the co-sedimentation method were used as adsorbent to remove hexavalent chromium ions. The characteristic of adsorption was evaluated by Langmuir, Freundlich isotherm and Dubinin-Kaganer-Radushkevich (DKR) equations in the simulation wastewater of Cr (VI)-Ni (II) bi-system. The energy spectra and FT-IR analysis were used to test adsorbent before and after adsorption. The obtained results suggest that the uptake of chromium (VI) effect is obvious from phosphate anions and that from others is unobvious. The maximum adsorption capacity of hexavalent chromium is about 30 mg/g at pH 5.00+/-0.02, and it was reduced by increasing the total dissolved substance (TDS) of system. Adsorption energies E are about 10.310-21.321 kJ/mol which were obtained from DKR equation in difference TDS conditions. The regeneration shows that the iron-nickel oxide has good reuse performance and the hexavalent chromium was recycled. The major adsorption mechanism proposed was the ions exchange; however the surface coordination was a main role in the condition of TDS less than 200mg/L.

Phosphate adsorption performance of a novel filter substrate made from drinking water treatment residuals.

PubMed

Wang, Wendong; Ma, Cui; Zhang, Yinting; Yang, Shengjiong; Shao, Yue; Wang, Xiaochang

2016-07-01

Phosphate is one of the most predominant pollutants in natural waters. Laboratory experiments were conducted to investigate the phosphate adsorption performance of a (NFS) made from drinking water treatment residuals. The adsorption of phosphate on the NFS fitted well with the Freundlich isotherm and pseudo second-order kinetic models. At pH7.0, the maximum adsorption capacity of 1.03mg/g was achieved at 15°C corresponding to the wastewater temperature in cold months, and increased notably to 1.31mg/g at 35°C. Under both acidic conditions (part of the adsorption sites was consumed) and basic conditions (negative charges formed on the surface of NFS, which led to a static repulsion of PO4(3-) and HPO4(2-)), the adsorption of phosphate was slightly inhibited. Further study showed that part of the adsorption sites could be recovered by 0.25mol/L NaOH. The activation energy was calculated to be above 8.0kJ/mol, indicating that the adsorption of phosphate on NFS was probably a chemical process. Considering the strong phosphate adsorption capacity and recoverability, NFS showed great promise on enhancing phosphate removal from the secondary treated wastewater in the filtration process. Copyright © 2016. Published by Elsevier B.V.

Adsorption of cadmium(II) on waste biomaterial.

PubMed

Baláž, M; Bujňáková, Z; Baláž, P; Zorkovská, A; Danková, Z; Briančin, J

2015-09-15

Significant increase of the adsorption ability of the eggshell biomaterial toward cadmium was observed upon milling, as is evidenced by the value of maximum monolayer adsorption capacity of 329mgg(-1), which is markedly higher than in the case of most "green" sorbents. The main driving force of the adsorption was proven to be the presence of aragonite phase as a consequence of phase transformation from calcite occurring during milling. Cadmium is adsorbed in a non-reversible way, as documented by different techniques (desorption tests, XRD and EDX measurements). The optimum pH for cadmium adsorption was 7. The adsorption process was accompanied by the increase of the value of specific surface area. The course of adsorption has been described by Langmuir, Freundlich and Dubinin-Radushkevich isotherms. The adsorption kinetics was evaluated using three models, among which the best correlation coefficients and the best normalized standard deviation values were achieved for the pseudo-second order model and the intraparticle diffusion model, respectively. Copyright © 2015 Elsevier Inc. All rights reserved.

The Influence of Salt Anions on Heavy Metal Ion Adsorption on the Example of Nickel

PubMed Central

Mende, Mandy; Schwarz, Dana; Steinbach, Christine; Schwarz, Simona

2018-01-01

The biodegradable polysaccharide chitosan possesses protonated and natural amino groups at medium pH values and has therefore been used as an adsorbing material for nickel salts in water treatment. Nickel is a problematic heavy metal ion which can cause various diseases and disorders in living organisms. Here, we show the influence of oxyanions (e.g., nitrate and sulfate) to the adsorption of nickel ions. Hence, simultaneously we are addressing the increasing global problem of nitrate and sulfate ion pollution in groundwater and surface water. A series of adsorption experiments was carried out in order to determine (i) the adsorption equilibrium, (ii) the adsorption capacity in dependence on the initial nickel ion concentration, and (iii) the influence of the anion presented in solution for the adsorption capacity. Surface morphology of chitosan flakes before and after the adsorption process has been studied with SEM-EDX analysis. The chitosan flakes exhibited promising adsorption capacities of 81.9 mg·g−1 and 21.2 mg·g−1 for nickel (sulfate) and nickel (nitrate), respectively. The calculated values of Gibbs free energy change ΔG0 confirm the higher adsorption of nickel ions in presence of sulfate ions. Hence, higher anion valence leads to a higher adsorption capacity. PMID:29510485

Comparison of 4-chloro-2-nitrophenol adsorption on single-walled and multi-walled carbon nanotubes

PubMed Central

2012-01-01

The adsorption characteristics of 4-chloro-2-nitrophenol (4C2NP) onto single-walled and multi-walled carbon nanotubes (SWCNTs and MWCNTs) from aqueous solution were investigated with respect to the changes in the contact time, pH of solution, carbon nanotubes dosage and initial 4C2NP concentration. Experimental results showed that the adsorption efficiency of 4C2NP by carbon nanotubes (both of SWCNTs and MWCNTs) increased with increasing the initial 4C2NP concentration. The maximum adsorption took place in the pH range of 2–6. The linear correlation coefficients of different isotherm models were obtained. Results revealed that the Langmuir isotherm fitted the experimental data better than the others and based on the Langmuir model equation, maximum adsorption capacity of 4C2NP onto SWCNTs and MWCNTs were 1.44 and 4.42 mg/g, respectively. The observed changes in the standard Gibbs free energy, standard enthalpy and standard entropy showed that the adsorption of 4C2NP onto SWCNTs and MWCNTs is spontaneous and exothermic in the temperature range of 298–328 K. PMID:23369489

A study of equilibrium and FTIR, SEM/EDS analysis of trimethoprim adsorption onto K10

NASA Astrophysics Data System (ADS)

Bekçi, Zehra; Seki, Yoldaş; Kadir Yurdakoç, M.

2007-02-01

The sorption behavior of K10, a type of montmorillonite for trimethoprim (TMP) drug, was studied by using batch technique under different pH and temperature. The interaction between K10 and TMP was investigated using SEM, and FTIR. It was observed that adsorption was increased between pH 2.5 and 6.3. By performing kinetic experiments, the pseudo-second-order kinetic model provides the best fit for TMP adsorption onto K10 montmorillonite. The sorption of TMP reached the equilibrium state after 6 h sorption time and has been described by using Langmuir, Freundlich and Dubinin-Radushkevich equations to obtain adsorption capacity values. The results indicate that the relative adsorption capacity values ( Kf) are decreasing with the increase of temperature in the range of 298-318 K. The sorption energy values obtained from DR isotherm show that sorption of TMP onto K10 can be explained by ion exchange mechanism at 298, 308 and 318 K. The thermodynamic studies were conducted to find the thermodynamic parameters Δ H°, Δ S° and Δ G°. It was determined that adsorption process is spontaneous and exothermic in nature.

Effect of hydrophobicity of pharmaceuticals and personal care products for adsorption on activated carbon: Adsorption isotherms, kinetics and mechanism.

PubMed

Kaur, Harkirat; Bansiwal, Amit; Hippargi, Girivyankatesh; Pophali, Girish R

2017-09-11

Adsorption of three pharmaceuticals and personal care products (PPCPs), namely caffeine, ibuprofen and triclosan on commercial powdered activated carbon was examined in aqueous medium. The contaminants were chosen based on their diverse log K ow (octanol-water partition coefficient) viz. - 0.07 for caffeine, 3.97 for ibuprofen and 4.76 for triclosan to examine the role of hydrophobicity on adsorption process. The adsorbent characterisation was achieved using BET surface area, SEM, pore size distribution studies and FTIR. Influence of mass of PAC, contact time, solution pH and initial concentration on adsorption capacity of PAC was studied. Adsorption isotherms and kinetics were applied to establish the mechanism of adsorption. The kinetics followed pseudo-second order with physisorption occurring through particle diffusion. The Freundlich model fitted best among the isotherm models. The adsorption capacity increased in the order CFN < IBU < TCS which correlates with increasing hydrophobicity (log K ow ), molecular weight and decreasing water solubility, respectively. We conclude that micro-pollutant hydrophobicity contributes towards adsorption on activated carbon.

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 xenon on vicinal copper and platinum surfaces

NASA Astrophysics Data System (ADS)

Baker, Layton

The adsorption of xenon was studied on Cu(111), Cu(221), Cu(643) and on Pt(111), Pt(221), and Pt(531) using low energy electron diffraction (LEED), temperature programmed desorption (TPD) of xenon, and ultraviolet photoemission of adsorbed xenon (PAX). These experiments were performed to study the atomic and electronic structure of stepped and step-kinked, chiral metal surfaces. Xenon TPD and PAX were performed on each surface in an attempt to titrate terrace, step edge, and kink adsorption sites by adsorption energetics (TPD) and local work function differences (PAX). Due to the complex behavior of xenon on the vicinal copper and platinum metal surfaces, adsorption sites on these surfaces could not be adequately titrated by xenon TPD. On Cu(221) and Cu(643), xenon desorption from step adsorption sites was not apparent leading to the conclusion that the energy difference between terrace and step adsorption is minuscule. On Pt(221) and Pt(531), xenon TPD indicated that xenon prefers to bond at step edges and that the xenon-xenon interaction at step edges in repulsive but no further indication of step-kink adsorption was observed. The Pt(221) and Pt(531) TPD spectra indicated that the xenon overlayer undergoes strong compression near monolayer coverage on these surfaces due to repulsion between step-edge adsorbed xenon and other encroaching xenon atoms. The PAX experiments on the copper and platinum surfaces demonstrated that the step adsorption sites have lower local work functions than terrace adsorption sites and that higher step density leads to a larger separation in the local work function of terrace and step adsorption sites. The PAX spectra also indicated that, for all surfaces studied at 50--70 K, step adsorption is favored at low coverage but the step sites are not saturated until monolayer coverage is reached; this observation is due to the large entropy difference between terrace and step adsorption states and to repulsive interactions between xenon atoms

Exhaustively sampling peptide adsorption with metadynamics.

PubMed

Deighan, Michael; Pfaendtner, Jim

2013-06-25

Simulating the adsorption of a peptide or protein and obtaining quantitative estimates of thermodynamic observables remains challenging for many reasons. One reason is the dearth of molecular scale experimental data available for validating such computational models. We also lack simulation methodologies that effectively address the dual challenges of simulating protein adsorption: overcoming strong surface binding and sampling conformational changes. Unbiased classical simulations do not address either of these challenges. Previous attempts that apply enhanced sampling generally focus on only one of the two issues, leaving the other to chance or brute force computing. To improve our ability to accurately resolve adsorbed protein orientation and conformational states, we have applied the Parallel Tempering Metadynamics in the Well-Tempered Ensemble (PTMetaD-WTE) method to several explicitly solvated protein/surface systems. We simulated the adsorption behavior of two peptides, LKα14 and LKβ15, onto two self-assembled monolayer (SAM) surfaces with carboxyl and methyl terminal functionalities. PTMetaD-WTE proved effective at achieving rapid convergence of the simulations, whose results elucidated different aspects of peptide adsorption including: binding free energies, side chain orientations, and preferred conformations. We investigated how specific molecular features of the surface/protein interface change the shape of the multidimensional peptide binding free energy landscape. Additionally, we compared our enhanced sampling technique with umbrella sampling and also evaluated three commonly used molecular dynamics force fields.

Adsorption Behavior, Thermodynamics, and Kinetics of the Methanol Decomposition Reaction on defective graphene-supported Pt13

NASA Astrophysics Data System (ADS)

Gasper, Raymond; Ramasubramaniam, Ashwin

Defective graphene has been shown experimentally to be an excellent support for transition-metal electrocatalysts in direct methanol fuel cells. Prior computational modeling has shown that the improved catalytic activity of graphene-supported metal clusters is in part due to increased resistance to catalyst sintering and CO poisoning, but the increased reaction rate for the methanol decomposition reaction (MDR) is not yet fully explained. Using DFT, we investigate the adsorption of MDR intermediates and reaction thermodynamics on defective graphene-supported Pt13 nanoclusters with realistic, low-symmetry morphologies. We find that the support-induced shifts in Pt13 electronic structure correlate well with a rigid shift in adsorption of MDR intermediates, and that adsorption energy scaling relationships perform well on the low-symmetry surface. We investigate the reaction kinetics and thermodynamics, including testing the effectiveness of scaling relationships for predicting reaction barriers on the nanoclusters. Using these fundamental data, we perform microkinetic modeling to quantify the effect of the support on the MDR, and to understand how the support influences surface coverages, CO poisoning, and the relationships between reaction pathways. Funded by U.S. Department of Energy under Award Number DE-SC0010610. Computational resources were provided by National Energy Research Scientific Computing Center.

Oxygen adsorption on the Al₉Co₂(001) surface: first-principles and STM study.

PubMed

Villaseca, S Alarcón; Loli, L N Serkovic; Ledieu, J; Fournée, V; Gille, P; Dubois, J-M; Gaudry, E

2013-09-04

Atomic oxygen adsorption on a pure aluminum terminated Al9Co2(001) surface is studied by first-principle calculations coupled with STM measurements. Relative adsorption energies of oxygen atoms have been calculated on different surface sites along with the associated STM images. The local electronic structure of the most favourable adsorption site is described. The preferential adsorption site is identified as a 'bridge' type site between the cluster entities exposed at the (001) surface termination. The Al-O bonding between the adsorbate and the substrate presents a covalent character, with s-p hybridization occurring between the states of the adsorbed oxygen atom and the aluminum atoms of the surface. The simulated STM image of the preferential adsorption site is in agreement with experimental observations. This work shows that oxygen adsorption generates important atomic relaxations of the topmost surface layer and that sub-surface cobalt atoms strongly influence the values of the adsorption energies. The calculated Al-O distances are in agreement with those reported in Al2O and Al2O3 oxides and for oxygen adsorption on Al(111).

Surface Charge-Transfer Doping of Graphene Nanoflakes Containing Double-Vacancy (5-8-5) and Stone-Wales (55-77) Defects through Molecular Adsorption.

PubMed

Shakourian-Fard, Mehdi; Jamshidi, Zahra; Kamath, Ganesh

2016-10-18

The adsorption of six electron donor-acceptor (D/A) organic molecules on various sizes of graphene nanoflakes (GNFs) containing two common defects, double-vacancy (5-8-5) and Stone-Wales (55-77), are investigated by means of ab initio DFT [M06-2X(-D3)/cc-pVDZ]. Different D/A molecules adsorb on a defect graphene (DG) surface with binding energies (ΔE b ) of about -12 to -28 kcal mol -1 . The ΔE b values for adsorption of molecules on the Stone-Wales GNF surface are higher than those on the double vacancy GNF surface. Moreover, binding energies increase by about 10 % with an increase in surface size. The nature of cooperative weak interactions is analyzed based on quantum theory of atoms in molecules, noncovalent interactions plot, and natural bond order analyses, and the dominant interaction is compared for different molecules. Electron density population analysis is used to explain the n- and p-type character of defect graphene nanoflakes (DGNFs) and also the change in electronic properties and reactivity parameters of DGNFs upon adsorption of different molecules and with increasing DGNF size. Results indicate that the HOMO-LUMO energy gap (E g ) of DGNFs decreases upon adsorption of molecules. However, by increasing the size of DGNFs, the E g and chemical hardness of all complexes decrease and the electrophilicity index increases. Furthermore, the values of the chemical potential of acceptor-DGNF complexes decrease with increasing size, whereas those of donor-DGNF complexes increase. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

SeO2 adsorption on CaO surface: DFT and experimental study on the adsorption of multiple SeO2 molecules

NASA Astrophysics Data System (ADS)

Fan, Yaming; Zhuo, Yuqun; Li, Liangliang

2017-10-01

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

High pressure adsorption isotherms of nitrogen onto granular activated carbon for a single bed pressure swing adsorption refrigeration system

NASA Astrophysics Data System (ADS)

Palodkar, Avinash V.; Anupam, Kumar; Roy, Zunipa; Saha, B. B.; Halder, G. N.

2017-10-01

Adsorption characteristics of nitrogen onto granular activated carbon for the wide range of temperature (303-323 K) and pressure (0.2027-2.0265 MPa) have been reported for a single bed pressure swing adsorption refrigeration system. The experimental data were fitted to Langmuir, Dubinin-Astakhov and Dubinin-Radushkevich (D-R) isotherms. The Langmuir and D-R isotherm models were found appropriate in correlating experimental adsorption data with an average relative error of ±2.0541% and ±0.6659% respectively. The isosteric heat of adsorption data were estimated as a function of surface coverage of nitrogen and temperature using D-R isotherm. The heat of adsorption was observed to decrease from 12.65 to 6.98 kJ.mol-1 with an increase in surface concentration at 303 K and it followed the same pattern for other temperatures. It was found that an increase in temperature enhances the magnitude of the heat of adsorption.

Preferred orientation of albumin adsorption on a hydrophilic surface from molecular simulation.

PubMed

Hsu, Hao-Jen; Sheu, Sheh-Yi; Tsay, Ruey-Yug

2008-12-01

In general, non-specific protein adsorption follows a two-step procedure, i.e. first adsorption onto a surface in native form, and a subsequent conformational change on the surface. In order to predict the subsequent conformational change, it is important to determine the preferred orientation of an adsorbed protein in the first step of the adsorption. In this work, a method based on finding the global minimum of the interaction potential energy of an adsorbed protein has been developed to delineate the preferred orientations for the adsorption of human serum albumin (HSA) on a model surface with a hydrophilic self-assembled monolayer (SAM). For computational efficiency, solvation effects were greatly simplified by only including the dampening of electrostatic effects while neglecting contributions due to the competition of water molecules for the functional groups on the surface. A contour map obtained by systematic rotation of a molecule in conjunction with perpendicular motion to the surface gives the minimum interaction energy of the adsorbed molecule at various adsorption orientations. Simulation results show that for an -OH terminated SAM surface, a "back-on" orientation of HSA is the preferred orientation. The projection area of this adsorption orientation corresponds with the "triangular-side-on" adsorption of a heart shaped HSA molecule. The method proposed herein is able to provide results which are consistent with those predicted by Monte Carlo (MC) simulations with a substantially less computing cost. The high computing efficiency of the current method makes it possible to be implemented as a design tool for the control of protein adsorption on surfaces; however, before this can be fully realized, these methods must be further developed to enable interaction free energy to be calculated in place of potential energy, along with a more realistic representation of solvation effects.

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.

Adsorption of heavy metal from aqueous solution by dehydrated root powder of long-root Eichhornia crassipes.

PubMed

Li, Qiang; Chen, Bo; Lin, Peng; Zhou, Jiali; Zhan, Juhong; Shen, Qiuying; Pan, Xuejun

2016-01-01

The root powder of long-root Eichhornia crassipes, as a new kind of biodegradable adsorbent, has been tested for aqueous adsorption of Pb, Zn, Cu, and Cd. From FT-IR, we found that the absorption peaks of phosphorous compounds, carbonyl, and nitrogenous compounds displayed obvious changes before and after adsorption which illustrated that plant characteristics may play a role in binding with metals. Surface properties and morphology of the root powders have been characterized by means of SEM and BET. Energy spectrum analysis showed that the metals were adsorbed on root powders after adsorption. Then, optimum quantity of powder, pH values, and metal ion concentrations in single-system and multi-system were detected to discuss the characteristics and mechanisms of metal adsorption. Freundlich model and the second-order kinetics equation could well describe the adsorption of heavy metals in single-metal system. The adsorption of Pb, Zn, and Cd in the multi-metal system decreased with the concentration increased. At last, competitive adsorption of every two metals on root powder proved that Cu and Pb had suppressed the adsorption performance of Cd and Zn.

Heat of adsorption, adsorption stress, and optimal storage of methane in slit and cylindrical carbon pores predicted by classical density functional theory.

PubMed

Hlushak, Stepan

2018-01-03

Temperature, pressure and pore-size dependences of the heat of adsorption, adsorption stress, and adsorption capacity of methane in simple models of slit and cylindrical carbon pores are studied using classical density functional theory (CDFT) and grand-canonical Monte-Carlo (MC) simulation. Studied properties depend nontrivially on the bulk pressure and the size of the pores. Heat of adsorption increases with loading, but only for sufficiently narrow pores. While the increase is advantageous for gas storage applications, it is less significant for cylindrical pores than for slits. Adsorption stress and the average adsorbed fluid density show oscillatory dependence on the pore size and increase with bulk pressure. Slit pores exhibit larger amplitude of oscillations of the normal adsorption stress with pore size increase than cylindrical pores. However, the increase of the magnitude of the adsorption stress with bulk pressure increase is more significant for cylindrical than for slit pores. Adsorption stress appears to be negative for a wide range of pore sizes and external conditions. The pore size dependence of the average delivered density of the gas is analyzed and the optimal pore sizes for storage applications are estimated. The optimal width of slit pore appears to be almost independent of storage pressure at room temperature and pressures above 10 bar. Similarly to the case of slit pores, the optimal radius of cylindrical pores does not exhibit much dependence on the storage pressure above 15 bar. Both optimal width and optimal radii of slit and cylindrical pores increase as the temperature decreases. A comparison of the results of CDFT theory and MC simulations reveals subtle but important differences in the underlying fluid models employed by the approaches. The differences in the high-pressure behaviour between the hard-sphere 2-Yukawa and Lennard-Jones models of methane, employed by the CDFT and MC approaches, respectively, result in an overestimation of

Enhanced initial protein adsorption on engineered nanostructured cubic zirconia.

PubMed

Sabirianov, R F; Rubinstein, A; Namavar, F

2011-04-14

Motivated by experimentally-observed biocompatibility enhancement of nanoengineered cubic zirconia (ZrO(2)) coatings to mesenchymal stromal cells, we have carried out computational analysis of the initial immobilization of one known structural fragment of the adhesive protein (fibronectin) on the corresponding surface. We constructed an atomistic model of the ZrO(2) nano-hillock of 3-fold symmetry based on Atom Force Microscopy and Transmission Electron Microscopy images. First principle quantum mechanical calculations show a substantial variation of electrostatic potential at the hillock due to the presence of surface features such as edges and vertexes. Using an implemented Monte Carlo simulated annealing method, we found the orientation of the immobilized protein on the ZrO(2) surface and the contribution of the amino acid residues from the protein sequence to the adsorption energy. Accounting for the variation of the dielectric permittivity at the protein-implant interface, we used a model distance-dependent dielectric function to describe the inter-atom electrostatic interactions in the adsorption potential. We found that the initial immobilization of the rigid protein fragment on the nanostructured pyramidal ZrO(2) surface is achieved with a magnitude of adsorption energy larger than that of the protein on the smooth (atomically flat) surface. The strong attractive electrostatic interactions are a major contributing factor in the enhanced adsorption at the nanostructured surface. In the case of adsorption on the flat, uncharged surface this factor is negligible. We show that the best electrostatic and steric fit of the protein to the inorganic surface corresponds to a minimum of the adsorption energy determined by the non-covalent interactions.

A DFT+U investigation of hydrogen adsorption on the LaFeO3(010) surface.

PubMed

Boateng, Isaac W; Tia, Richard; Adei, Evans; Dzade, Nelson Y; Catlow, C Richard A; de Leeuw, Nora H

2017-03-08

The ABO 3 perovskite lanthanum ferrite (LaFeO 3 ) is a technologically important electrode material for nickel-metal hydride batteries, energy storage and catalysis. However, the electrochemical hydrogen adsorption mechanism on LaFeO 3 surfaces remains under debate. In the present study, we have employed spin-polarized density functional theory calculations, with the Hubbard U correction (DFT+U), to unravel the adsorption mechanism of H 2 on the LaFeO 3 (010) surface. We show from our calculated adsorption energies that the preferred site for H 2 adsorption is the Fe-O bridge site, with an adsorption energy of -1.18 eV (including the zero point energy), which resulted in the formation of FeOH and FeH surface species. H 2 adsorption at the surface oxygen resulted in the formation of a water molecule, which leaves the surface to create an oxygen vacancy. The H 2 molecule is found to interact weakly with the Fe and La sites, where it is only physisorbed. The electronic structures of the surface-adsorption systems are discussed via projected density of state and Löwdin population analyses. The implications of the calculated adsorption strengths and structures are discussed in terms of the improved design of nickel-metal hydride (Ni-MH) battery prototypes based on LaFeO 3 .

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.

Adsorption and dissociation of molecular oxygen on α-Pu (0 2 0) surface: A density functional study

NASA Astrophysics Data System (ADS)

Wang, Jianguang; Ray, Asok K.

2011-09-01

Molecular and dissociative oxygen adsorptions on the α-Pu (0 2 0) surface have been systematically studied using the full-potential linearized augmented-plane-wave plus local orbitals (FP-LAPW+lo) basis method and the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional. Chemisorption energies have been optimized for the distance of the admolecule from the Pu surface and the bond length of O-O atoms for four adsorption sites and three approaches of O 2 admolecule to the (0 2 0) surface. Chemisorption energies have been calculated at the scalar relativistic level with no spin-orbit coupling (NSOC) and at the fully relativistic level with spin-orbit coupling (SOC). Dissociative adsorptions are found at the two horizontal approaches (O 2 is parallel to the surface and perpendicular/parallel to a lattice vector). Hor2 (O 2 is parallel to the surface and perpendicular to a lattice vector) approach at the one-fold top site is the most stable adsorption site, with chemisorption energies of 8.048 and 8.415 eV for the NSOC and SOC cases, respectively, and an OO separation of 3.70 Å. Molecular adsorption occurs at the Vert (O 2 is vertical to the surface) approach of each adsorption site. The calculated work functions and net spin magnetic moments, respectively, increase and decrease in all cases upon chemisorption compared to the clean surface. The partial charges inside the muffin-tins, the difference charge density distributions, and the local density of states have been used to investigate the Pu-admolecule electronic structures and bonding mechanisms.

Fibrinogen adsorption on blocked surface of albumin.

PubMed

Holmberg, Maria; Hou, Xiaolin

2011-05-01

We have investigated the adsorption of albumin and fibrinogen onto PET (polyethylene terephthalate) and glass surfaces and how pre-adsorption of albumin onto these surfaces can affect the adsorption of later added fibrinogen. For materials and devices being exposed to blood, adsorption of fibrinogen is often a non-wanted event, since fibrinogen is part of the clotting cascade and unspecific adsorption of fibrinogen can have an influence on the activation of platelets. Albumin is often used as blocking agent for avoiding unspecific protein adsorption onto surfaces in devices designed to handle biological samples, including protein solutions. It is based on the assumption that proteins adsorbs as a monolayer on surfaces and that proteins do not adsorb on top of each other. By labelling albumin and fibrinogen with two different radioactive iodine isotopes that emit gamma radiation with different energies, the adsorption of both albumin and fibrinogen has been monitored simultaneously on the same sample. Information about topography and coverage of adsorbed protein layers has been obtained using AFM (Atomic Force Microscopy) analysis in liquid. Our studies show that albumin adsorbs in a multilayer fashion on PET and that fibrinogen adsorbs on top of albumin when albumin is pre-adsorbed on the surfaces. Copyright © 2010 Elsevier B.V. All rights reserved.

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.

Adsorption isotherms of some alkyl aromatic hydrocarbons and surface energies on partially dealuminated Y faujasite zeolite by inverse gas chromatography.

PubMed

Kondor, Anett; Dallos, András

2014-10-03

Adsorption isotherm data of some alkyl aromatic hydrocarbons (benzene, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene) measured in the temperature range of 423-523K on a partially dealuminated faujasite type DAY F20 zeolite by inverse gas chromatography are presented in this work. The temperature dependent form of Tóth's equation has been fitted to the multiple temperature adsorption isotherms of benzene, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene with standard deviations of 4.6, 5.0, 5.9, 4.3, 5.1 and 6.3mmolkg(-1) and coefficients of determinations (r(2)) of 0.977, 0.971, 0.974, 0.975, 0.991 and 0.991, respectively. The gas-solid equilibria and modeling were interpreted on the basis of the interfacial properties of the zeolite, by dispersive, specific and total surface energy heterogeneity profiles and distributions of the adsorbent measured by surface energy analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

Coverage-dependent adsorption and desorption of oxygen on Pd(100)

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

Dunnen, Angela den; Jacobse, Leon; Wiegman, Sandra

2016-06-28

We have studied the adsorption and desorption of O{sub 2} on Pd(100) by supersonic molecular beam techniques and thermal desorption spectroscopy. Adsorption measurements on the bare surface confirm that O{sub 2} initially dissociates for all kinetic energies between 56 and 380 meV and surface temperatures between 100 and 600 K via a direct mechanism. At and below 150 K, continued adsorption leads to a combined O/O{sub 2} overlayer. Dissociation of molecularly bound O{sub 2} during a subsequent temperature ramp leads to unexpected high atomic oxygen coverages, which are also obtained at high incident energy and high surface temperature. At intermediatemore » temperatures and energies, these high final coverages are not obtained. Our results show that kinetic energy of the gas phase reactant and reaction energy dissipated during O{sub 2} dissociation on the cold surface both enable activated nucleation of high-coverage surface structures. We suggest that excitation of local substrate phonons may play a crucial role in oxygen dissociation at any coverage.« less

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

Linear solvation energy relationship for the adsorption of synthetic organic compounds on single-walled carbon nanotubes in water.

PubMed

Ding, H; Chen, C; Zhang, X

2016-01-01

The linear solvation energy relationship (LSER) was applied to predict the adsorption coefficient (K) of synthetic organic compounds (SOCs) on single-walled carbon nanotubes (SWCNTs). A total of 40 log K values were used to develop and validate the LSER model. The adsorption data for 34 SOCs were collected from 13 published articles and the other six were obtained in our experiment. The optimal model composed of four descriptors was developed by a stepwise multiple linear regression (MLR) method. The adjusted r(2) (r(2)adj) and root mean square error (RMSE) were 0.84 and 0.49, respectively, indicating good fitness. The leave-one-out cross-validation Q(2) ([Formula: see text]) was 0.79, suggesting the robustness of the model was satisfactory. The external Q(2) ([Formula: see text]) and RMSE (RMSEext) were 0.72 and 0.50, respectively, showing the model's strong predictive ability. Hydrogen bond donating interaction (bB) and cavity formation and dispersion interactions (vV) stood out as the two most influential factors controlling the adsorption of SOCs onto SWCNTs. The equilibrium concentration would affect the fitness and predictive ability of the model, while the coefficients varied slightly.

Determination of the effects of water adsorption on the sensitivity and detonation performance of the explosive JOB-9003 by molecular dynamics simulation.

PubMed

Hang, GuiYun; Yu, WenLi; Wang, Tao; Li, Zhen

2016-11-01

In order to determine the adsorption mechanism of water on the crystal surfaces of the explosive JOB-9003 and the effect of this adsorption on the sensitivity and detonation performance of this explosive, a model of the crystal of JOB-9003 was created in the software package Materials Studio (MS). The adsorption process was simulated, and molecular dynamics simulation was performed with the COMPASS force field in the NPT ensemble to calculate the sensitivity and detonation performance of the explosive. The results show that the maximum trigger bond length decreases whereas the interaction energy of the trigger bond and the cohesive energy density increase after adsorption, indicating that the sensitivity of JOB-9003 decreases. The results for the detonation performance show that the detonation pressure, detonation velocity, and detonation heat decrease upon the adsorption of water, thus illustrating that the detonation performance of JOB-9003 is degraded. In summary, the adsorption of water has a positive effect on the sensitivity and safety of the explosive JOB-9003 but a negative effect on its detonation performance.

Energy of adhesion of human T cells to adsorption layers of monoclonal antibodies measured by a film trapping technique.

PubMed Central

Ivanov, I B; Hadjiiski, A; Denkov, N D; Gurkov, T D; Kralchevsky, P A; Koyasu, S

1998-01-01

A novel method for studying the interaction of biological cells with interfaces (e.g., adsorption monolayers of antibodies) is developed. The method is called the film trapping technique because the cell is trapped within an aqueous film of equilibrium thickness smaller than the cell diameter. A liquid film of uneven thickness is formed around the trapped cell. When observed in reflected monochromatic light, this film exhibits an interference pattern of concentric bright and dark fringes. From the radii of the fringes one can restore the shape of interfaces and the cell. Furthermore, one can calculate the adhesive energy between the cell membrane and the aqueous film surface (which is covered by a layer of adsorbed proteins and/or specific ligands), as well as the disjoining pressure, representing the force of interaction per unit area of the latter film. The method is applied to two human T cell lines: Jurkat and its T cell receptor negative (TCR-) derivative. The interaction of these cells with monolayers of three different monoclonal antibodies adsorbed at a water-air interface is studied. The results show that the adhesive energy is considerable (above 0.5 mJ/m2) when the adsorption monolayer contains antibodies acting as specific ligands for the receptors expressed on the cell surface. In contrast, the adhesive energy is close to zero in the absence of such a specific ligand-receptor interaction. In principle, the method can be applied to the study of the interaction of a variety of biological cells (B cells, natural killer cells, red blood cells, etc.) with adsorption monolayers of various biologically active molecules. In particular, film trapping provides a tool for the gentle micromanipulation of cells and for monitoring of processes (say the activation of a T lymphocyte) occurring at the single-cell level. PMID:9649417

Adsorption of Benzoic Acid in Aqueous Solution by Bagasse Fly Ash

NASA Astrophysics Data System (ADS)

Suresh, S.

2012-09-01

This paper reports the studies on the benzoic acid (BA) onto bagasse fly ash (BFA) was studied in aqueous solution in a batch system. Physico-chemical properties including surface area, surface texture of the GAC before and after BA adsorption onto BFA were analysed using X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The optimum initial pH for the adsorption of BA was found to be 5.56. The adsorbent dose was 10 g/l for BFA and the equilibrium time 8 h of reaction. Pseudo first and second order models were used to find the adsorption kinetics. It was found that intraparticle diffusion played important role in the adsorption mechanisms of BA and the adsorption kinetics followed pseudo-second order kinetic model rather than the pseudo first order kinetic model. Isotherm data were generated for BA solution having initial concentrations of BA in the range of 10-200 mg/l for the BFA dosage of 10 g/l at temperatures of 288, 303, and 318 K. The adsorption of BA onto BFA was favorably influenced by an increase in temperature. Equilibrium data were well represented by the Redlich-Peterson isotherm model. Values of the change in entropy ( ΔS 0), heat of adsorption ( ΔH 0) for adsorption of BA on BFA was found to be 120.10 and 19.61 kJ/mol respectively. The adsorption of BA onto BFA was an endothermic reaction. Desorption of BA from BFA was studied by various solvents method. Acetic acid was found to be a better eluant for desorption of BA with a maximum desorption efficiency of 55.2 %. Owing to its heating value, spent BFA can be used as a co-fuel for the production of heat in boiler furnaces.

Effects of van der Waals Interactions in the Adsorption of Isooctane and Ethanol on Fe(100) Surfaces

PubMed Central

2014-01-01

van der Waals (vdW) forces play a fundamental role in the structure and behavior of diverse systems. Because of development of functionals that include nonlocal correlation, it is possible to study the effects of vdW interactions in systems of industrial and tribological interest. Here we simulated within the framework of density functional theory (DFT) the adsorption of isooctane (2,2,4-trimethylpentane) and ethanol on an Fe(100) surface, employing various exchange–correlation functionals to take vdW forces into account. In particular, this paper discusses the effect of vdW forces on the magnitude of adsorption energies, equilibrium geometries, and their role in the binding mechanism. According to our calculations, vdW interactions increase the adsorption energies and reduce the equilibrium distances. Nevertheless, they do not influence the spatial configuration of the adsorbed molecules. Their effect on the electronic density is a nonisotropic, delocalized accumulation of charge between the molecule and the slab. In conclusion, vdW forces are essential for the adsorption of isooctane and ethanol on a bcc Fe(100) surface. PMID:25126156

Cesium adsorption and distribution onto crushed granite under different physicochemical conditions.

PubMed

Tsai, Shih-Chin; Wang, Tsing-Hai; Li, Ming-Hsu; Wei, Yuan-Yaw; Teng, Shi-Ping

2009-01-30

The adsorption of cesium onto crushed granite was investigated under different physicochemical conditions including contact time, Cs loading, ionic strength and temperature. In addition, the distribution of adsorbed Cs was examined by X-ray diffraction (XRD) and EDS mapping techniques. The results showed that Cs adsorption to crushed granite behaved as a first-order reaction with nice regression coefficients (R(2) > or = 0.971). Both Freundlich and Langmuir models were applicable to describe the adsorption. The maximum sorption capacity determined by Langmuir model was 80 micromol g(-1) at 25 degrees C and 10 micromol g(-1) at 55 degrees C. The reduced sorption capacity at high temperature was related to the partial enhancement of desorption from granite surface. In general, Cs adsorption was exothermic (DeltaH<0, with median of -12 kJ mol(-1)) and spontaneous (DeltaG<0, with median of -6.1 at 25 degrees C and -5.0 kJ mol(-1) at 55 degrees C). The presence of competing cations such as sodium and potassium ions in synthetic groundwater significantly reduces the Cs adsorption onto granite. The scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM/EDS) mapping method provided substantial evidences that micaceous minerals (biotite in this case) dominate Cs adsorption. These adsorbed Cs ions were notably distributed onto the frayed edges of biotite minerals. More importantly, the locations of these adsorbed Cs were coincided with the potassium depletion area, implying the displacement of K by Cs adsorption. Further XRD patterns displayed a decreased intensity of signal of biotite as the Cs loading increased, revealing that the interlayer space of biotite was affected by Cs adsorption.

Adsorption of CH4 on nitrogen- and boron-containing carbon models of coal predicted by density-functional theory

NASA Astrophysics Data System (ADS)

Liu, Xiao-Qiang; Xue, Ying; Tian, Zhi-Yue; Mo, Jing-Jing; Qiu, Nian-Xiang; Chu, Wei; Xie, He-Ping

2013-11-01

Graphene doped by nitrogen (N) and/or boron (B) is used to represent the surface models of coal with the structural heterogeneity. Through the density functional theory (DFT) calculations, the interactions between coalbed methane (CBM) and coal surfaces have been investigated. Several adsorption sites and orientations of methane (CH4) on graphenes were systematically considered. Our calculations predicted adsorption energies of CH4 on graphenes of up to -0.179 eV, with the strongest binding mode in which three hydrogen atoms of CH4 direct to graphene surface, observed for N-doped graphene, compared to the perfect (-0.154 eV), B-doped (-0.150 eV), and NB-doped graphenes (-0.170 eV). Doping N in graphene increases the adsorption energies of CH4, but slightly reduced binding is found when graphene is doped by B. Our results indicate that all of graphenes act as the role of a weak electron acceptor with respect to CH4. The interactions between CH4 and graphenes are the physical adsorption and slightly depend upon the adsorption sites on graphenes and the orientations of methane as well as the electronegativity of dopant atoms in graphene.

A pressure-amplifying framework material with negative gas adsorption transitions.

PubMed

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

2016-04-21

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

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.

Study of adsorption of Neon on open Carbon nanohorns aggregates

NASA Astrophysics Data System (ADS)

Ziegler, Carl Andrew

Adsorption isotherms can be used to determine surface area of a substrate and the heat released when adsorption occurs. Our measurements are done determining the equilibrium pressures corresponding to a given amount of gas adsorbed on a substrate at constant temperature. The adsorption studies were done on aggregates of open dahlia-like carbon nanohorns. The nanohorns were oxidized for 9 hours at 550 °C to open them up and render their interior space accessible for adsorption. Volumetric adsorption measurements of Ne were performed at twelve different temperatures between 19 K and 48 K. The isotherms showed two substeps. The first substep corresponds to adsorption on the high energy binding sites in the interior of the nanohorns, near the tip. The second substep corresponds to low energy binding sites both on the outside of the nanotubes and inside the nanotube away from the tip. The isosteric heat measurements obtained from the isotherm data also shows these two distinct substeps. The effective surface area of the open nanotubes was determined from the isotherms using the point-B method. The isosteric heat and surface area data for neon on open nanohorns were compared to two similar experiments of neon adsorbed on aggregates of closed nanohorns.

Adsorption equilibrium and thermodynamics of CO2 and CH4 on carbon molecular sieves

NASA Astrophysics Data System (ADS)

Song, Xue; Wang, Li'ao; Ma, Xu; Zeng, Yunmin

2017-02-01

Carbon molecular sieves (CMS) are widely used in the separation of dioxide carbon and methane. In this research, three commercial CMS were utilized to analyze the pore structure and chemical properties. The adsorption isotherms of CO2 and CH4 were studied at 298 K, 308 K and 318 K over the pressure range of 0-1 MPa by an Intelligent Gravimetric analysis (IGA-100B, UK). Langmuir model was adopted to fit the experimental data. The working capacity and selectivity were employed to evaluate the adsorbents. The adsorption thermodynamics were discussed. The adsorbed amounts of both CO2 and CH4 are found to be highly related with the BET specific surface area and the volume of micropores, and also are interrelated with the total pore volume and micropore surface area. The standard enthalpy change (ΔHΘ), standard Gibbs free energy (ΔGΘ) and standard entropy change (ΔSΘ) at zero surface loading are negative, manifesting the adsorption process is exothermic and spontaneous, and the system tends to be ordered. With the increasing surface coverage, the absolute values of Gibbs free energy (ΔG) decrease whereas the absolute values of enthalpy change (ΔH) and entropy change(ΔS) increase. This indicates that as the adsorbed amount increases, the degree of the spontaneity reduces, the intermolecular forces among the adsorbate molecules increase, the orderliness of the system improves and the adsorbed amount approaches the maximum adsorbed capacity.

Bovine serum albumin adsorption on titania surfaces and its relation to wettability aspects.

PubMed

Valagão Amadeu do Serro, A P; Fernandes, A C; de Jesus Vieira Saramago, B; Norde, W

1999-09-05

The adsorption of bovine serum albumin (BSA) from sodium chloride solution and Hanks' balanced salt solution (HBSS) onto TiO2-silicon surfaces is studied by reflectometry in stagnation point flow. The results are compared with those obtained by dynamic contact-angle (DCA) analysis of titanium substrates. The adsorption isotherms show that the adsorbed amount of protein always is lower in HBSS, that is, in the presence of calcium and phosphate ions. This may be related to the increase in surface hydrophilicity caused by these ions, as suggested by the authors in previous works. The rate of adsorption also is lower in HBSS solutions. Comparison of the initial adsorption rates with the rate of mass transfer to the surface reveals that in both solvents only a small fraction of the protein that arrives at the surface adsorbs onto it. Electrostatic and/or conformational effects can explain the energy barrier to adsorption. The DCA analysis of high concentration (4 mg/mL) protein solutions shows a strong reduction of the contact-angle hysteresis, both in HBSS and in NaCl solutions, which confirms that the immediate adsorption of the protein to the surface forms a stable, hydrophilic film. Copyright 1999 John Wiley & Sons, Inc.

Adsorption Characteristics of Pb(2+) onto Wine Lees-Derived Biochar.

PubMed

Zhu, Qihong; Wu, Jun; Wang, Lilin; Yang, Gang; Zhang, Xiaohong

2016-08-01

Biochar has great advantages in soil amendment and polluted soil remediation. Herein, the pore and adsorption properties of wine lees-derived biochar were explored. Specifically, the adsorption isotherm and kinetics of Pb(2+) onto wine lees-derived biochar were examined. Experimental results revealed that wine lees-derived biochar featured large specific surface area and total pore volume, and high contents of -COOH and -OH on its surface. Adsorption of Pb(2+) onto wine lees-derived biochar proceeded via a multilayer adsorption mechanism, as described by the Freundlich adsorption model. Adsorption kinetics followed the Lagergren pseudo-second-order kinetics model; adsorption equilibrium was achieved within 30-60 min. Furthermore, the effect of solution pH on the adsorption of Pb(2+) was investigated. Within the studied pH range of 3-6, the adsorption capacity increased with increasing pH. Under established optimized conditions, wine lees-derived biochar achieved a Pb(2+) adsorption capacity of 79.12 mg/g.

Adsorption behavior of glycidoxypropyl-trimethoxy-silane on titanium alloy Ti-6.5Al-1Mo-1V-2Zr

NASA Astrophysics Data System (ADS)

Liu, Jian-hua; Zhan, Zhong-wei; Yu, Mei; Li, Song-mei

2013-01-01

The adsorption behavior of glycidoxypropyl-trimethoxy-silane (GTMS) on titanium alloy Ti-6.5Al-1Mo-1V-2Zr was investigated by using X-ray photoelectron spectroscopy (XPS), Tafel polarization test, and electrochemical impedance spectroscopy (EIS). From the XPS results, it was found that the silane coverage on the titanium surface generally increased with GTMS concentration, with a slight decrease at concentration of 0.1%. Based on the relationship between isoelectronic point (IEP) of titanium surface and the pH values of silane solutions, adsorption mechanisms at different concentrations were proposed. The surface coverage data of GTMS on titanium surface was also derived from electrochemical measurements. By linear fitting the coverage data, it revealed that the adsorption of GTMS on the titanium alloy surface at 30 °C was of a physisorption-based mechanism, and obeyed Langmuir adsorption isotherm. The adsorption equilibrium constant (Kads) and free energy of adsorption process (ΔGads) were calculated to elaborate the mechanism of GTMS adsorption.

Influence of Mechanical Stretching on Adsorption Properties of Nitrogen-Doped Graphene

NASA Astrophysics Data System (ADS)

Dolinskii, I. Yu.; Katin, K. P.; Grishakov, K. S.; Prudkovskii, V. S.; Kargin, N. I.; Maslov, M. M.

2018-04-01

This paper presents the results of quantum chemical modeling of chemisorption of atomic hydrogen and epoxy, carboxyl, and hydroxyl functional groups on nitrogen-doped graphene. It is shown that the substitutional nitrogen atom does not bind to adsorbing groups directly, but significantly increases the adsorption activity of neighboring carbon atoms. Mechanical stretching of doped graphene reduces the adsorption energy of all the aforementioned radicals. This reduction is significantly greater for the epoxy group than for the other functional groups. The results obtained confirm that, upon a sufficient stretching of a nitrogen-doped graphene sheet, the dissociation of molecular hydrogen and oxygen with subsequent precipitation of the resulting radicals onto graphene can be energetically favorable.

Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

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

DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.

Quantum chemical calculations were employed to model the interactions of the [(NH 4 +) 4(HSO 4 -) 4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH 4 +) 4(SOmore » 4 -) 4] cluster, is able to adsorb an oxygenated organic molecule. Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.« less

Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

DOE PAGES

DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.; ...

2015-10-21

Quantum chemical calculations were employed to model the interactions of the [(NH 4 +) 4(HSO 4 -) 4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH 4 +) 4(SOmore » 4 -) 4] cluster, is able to adsorb an oxygenated organic molecule. Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.« less

Polycyclic Aromatic Hydrocarbons Adsorption onto Graphene: A DFT and AIMD Study.

PubMed

Li, Bing; Ou, Pengfei; Wei, Yulan; Zhang, Xu; Song, Jun

2018-05-03

Density functional theory (DFT) calculations and ab-initio molecular dynamics (AIMD) simulations were performed to understand graphene and its interaction with polycyclic aromatic hydrocarbons (PAHs) molecules. The adsorption energy was predicted to increase with the number of aromatic rings in the adsorbates, and linearly correlate with the hydrophobicity of PAHs. Additionally, the analysis of the electronic properties showed that PAHs behave as mild n-dopants and introduce electrons into graphene; but do not remarkably modify the band gap of graphene, indicating that the interaction between PAHs and graphene is physisorption. We have also discovered highly sensitive strain dependence on the adsorption strength of PAHs onto graphene surface. The AIMD simulation indicated that a sensitive and fast adsorption process of PAHs can be achieved by choosing graphene as the adsorbent. These findings are anticipated to shed light on the future development of graphene-based materials with potential applications in the capture and removal of persistent aromatic pollutants.

Adsorption of octylamine on titanium dioxide

NASA Astrophysics Data System (ADS)

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

2009-05-01

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

Adsorption of Rh(III) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion-exchange resin Diaion WA21J.

PubMed

Shen, Shaobo; Pan, Tonglin; Liu, Xinqiang; Yuan, Lei; Wang, Jinchao; Zhang, Yongjian; Guo, Zhanchen

2010-07-15

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Rh(III) ions contained in the chloride solutions obtained, thermodynamic and kinetics studies for adsorption of Rh(III) complexes from the chloride solutions on an anionic exchange resin Diaion WA21J were carried out. Rh, Pd, Pt, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The distribution coefficients (K(d)) of Rh(III) decreased with the increase in initial Rh(III) concentration or in adsorption temperature. The isothermal adsorption of Rh(III) was found to fit Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The maximum monolayer adsorption capacities Q(max) based on Langmuir adsorption isotherms were 6.39, 6.61 and 5.81 mg/g for temperatures 18, 28 and 40 degrees C, respectively. The apparent adsorption energy of Rh was about -7.6 kJ/mol and thus Rh(III) adsorption was a physical type. The experimental data obtained could be better simulated by pseudo-first-order kinetic model and the activation energy obtained was 6.54 J/mol. The adsorption rate of Rh(III) was controlled by intraparticle diffusion in most of time of adsorption process. 2010 Elsevier B.V. All rights reserved.

Mechanisms of Polyelectrolyte Enhanced Surfactant Adsorption at the Air-Water Interface

PubMed Central

Stenger, Patrick C.; Palazoglu, Omer A.; Zasadzinski, Joseph A.

2009-01-01

Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids. PMID:19366599

Mechanisms of polyelectrolyte enhanced surfactant adsorption at the air-water interface.

PubMed

Stenger, Patrick C; Palazoglu, Omer A; Zasadzinski, Joseph A

2009-05-01

Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids.

Differential adsorption of CHON isomers at interstellar grain surfaces

NASA Astrophysics Data System (ADS)

Lattelais, M.; Pauzat, F.; Ellinger, Y.; Ceccarelli, C.

2015-06-01

Context. The CHON generic chemical formula covers different isomers such as isocyanic acid (HNCO), cyanic acid (HOCN), fulminic acid (HCNO), and isofulminic acid (HONC); the first three have been identified in a large variety of environments in the interstellar medium (ISM). Several phenomena could be at the origin of the observed abundances, such as different pathways of formation and destruction involving gas phase reactions with different possible activation barriers and/or surface processes depending on the local temperature and the nature of the support. Aims: The scope of this article is to shed some light on the interaction of the CHON isomers with interstellar grains as a function of the nature of the surface and to determine the corresponding adsorption energies in order to find whether this phenomenon could play a role in the abundances observed in the ISM. Methods: The question was addressed by means of numerical simulations using first principle periodic density functional theory (DFT) to represent the grain support as a solid of infinite dimension. Results: Regardless of the nature of the model surface (water ice, graphene, silica), two different classes of isomers were identified: weakly bound (HNCO and HCNO) and strongly bound (HOCN and HONC), with the adsorption energies of the latter group being about twice those of the former. The range of the adsorption energies is (from highest to lowest) HOCN > HONC > HNCO > HCNO. They are totally disconnected from the relative stabilities, which range from HNCO > HOCN > HCNO > HONC. Conclusions: The possibility of hydrogen bonding is the discriminating factor in the trapping of CHON species on grain surfaces. Whatever the environment, differential adsorption is effective and its contribution to the molecular abundances should not be ignored. The theoretical adsorption energies provided here could be profitably used for a more realistic modeling of molecule-surfaces interactions.

Replica-exchange molecular dynamics simulation of basic fibroblast growth factor adsorption on hydroxyapatite.

PubMed

Liao, Chenyi; Zhou, Jian

2014-06-05

The adsorption of basic fibroblast growth factor (bFGF) on the hydroxyapatite (001) surface was investigated by a combination of replica-exchange molecular dynamics (REMD) and conventional molecular dynamics (CMD) methods. In CMD, the protein cannot readily cross the surface water layer, whereas in REMD, the protein can cross the adsorption barrier from the surface water layer and go through weak, medium, then strong adsorption states with three energetically preferred configurations: heparin-binding-up (HP-up), heparin-binding-middle (HP-middle), and heparin-binding-down (HP-down). The HP-middle orientation, with the strongest adsorption energy (-1149 ± 40 kJ·mol(-1)), has the largest adsorption population (52.1-52.6%) and exhibits the largest conformational charge (RMSD of 0.26 ± 0.01 nm) among the three orientations. The HP-down and HP-up orientations, with smaller adsorption energies of -1022 ± 55 and -894 ± 70 kJ·mol(-1), respectively, have smaller adsorption populations of 27.4-27.7% and 19.7-20.5% and present smaller RMSD values of 0.21 ± 0.01 and 0.19 ± 0.01 nm, respectively. The convergent distribution indicates that nearly half of the population (in the HP-middle orientation) will support both FGF/FGFR and DGR-integrin signaling and another half (in the HP-up and HP-down orientations) will support DGR-integrin signaling. The major population (~80%) has the protein dipole directed outward. In the strong adsorption state, there are usually 2 to 3 basic residues that form the anchoring interactions of 210-332 kJ·mol(-1) per residue or that are accompanied by an acidic residue with an adsorption energy of ~207 kJ·mol(-1). Together, the major bound residues form a triangle or a quadrilateral on the surface and stabilize the adsorption geometrically, which indicates topologic matching between the protein and HAP surfaces.

Arsenate adsorption mechanisms at the allophane - Water interface

USGS Publications Warehouse

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

2005-01-01

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

[Adsorption characteristics of acetone and butanone onto honeycomb ZSM-5 molecular sieve].

PubMed

Du, Juan; Luan, Zhi-Qiang; Xie, Qiang; Ye, Ping-Wei; Li, Kai; Wang, Xi-Qin

2013-12-01

Adsorption capacity of acetone and acetone-butanone mixture onto honeycomb ZSM-5 molecular sieve was measured in this paper, and the influences of relative humidity, initial adsorbate concentration and airflow velocity on the adsorption process were investigated. Besides, adsorption performance parameters were calculated by Wheeler's equation. The results showed that relative humidity had no obvious influence on the acetone adsorption performance, which suggests that this material has good hydrophobic ability; in the low concentration range, the dynamic saturated adsorption capacity of acetone increased with the increase of initial concentration, but in the occasion of high concentration of acetone gas (more than 9 mg x L(-1)), the dynamic saturated adsorption capacity maintained at a certain level and did not vary with the increase of initial concentration; the increase of air flow velocity resulted in significant increase of acetone adsorption rate constant, at the same time the critical layer thickness of the adsorbent bed also increased significantly. In the cases of acetone-butanone mixture, the adsorption capacity of butanone onto ZSM-5 was clearly higher than that of acetone.

Effect of Particle Association on 2,2'-Bipyridyl Adsorption onto Kaolinite.

PubMed

Helmy, A. K.; Ferreiro, E. A.; de Bussetti, S. G.

2000-05-15

The effect of particle concentration, in kaolin suspensions, on the adsorption of 2,2'-bipyridyl was studied. Adsorption expressed in units of micromoles per gram decreased as a result of the increase in particle concentration and also as a result of the presence of coagulant (0.25 M NaCl). Dispersion treatment with sodium hexametaphosphate increased the adsorption of bipyridyl. The decrease in adsorption with the increase in particle concentration suggests a possible relation between adsorption and flocculation phenomena. On the basis of classic flocculation theory a straight-line relation was obtained between the square root of the adsorption maximum (mmol/L) and particle concentration (g/L). It is concluded that particle association, which is a function of particle concentration, reduces the surface/aqueous interface and consequently the adsorption of bipyridyl. Copyright 2000 Academic Press.

Protein-Nanoparticle Interactions: Improving Immobilized Lytic Enzyme Activity and Surface Energy Effects

NASA Astrophysics Data System (ADS)

Downs, Emily Elizabeth

Protein-nanostructure conjugates, particularly particles, are a subject of significant interest due to changes in their fundamental behavior compared to bulk surfaces. As the size scale of nano-structured materials and proteins are on the same order of magnitude, nanomaterial properties can heavily influence how proteins adsorb and conform to the surface. Previous work has demonstrated the ability of nanoscale surfaces to modulate protein activity, conformation, and retention by modifying the particle surface curvature, morphology, and surface charge. This work has improved our understanding of the protein material interactions, but a complete understanding is still lacking. The goal of this thesis is to investigate two missing areas of understanding using two distinct systems. The first system utilizes a particle with controlled surface energy to observe the impact of surface energy on protein-particle interactions, while the second system uses a modified Listeria-specific protein to determine how protein structure and flexibility affects protein adsorption and activity on particles. Spherical, amorphous, and uniformly doped Zn-silica particles with tailored surface energies were synthesized to understand the impact of surface energy on protein adsorption behavior. Particle surface energy increased with a decrease in particle size and greater dopant concentrations. Protein adsorption and structural loss increased with both particle size and particle surface energy. Higher surface energies promoted protein-particle association and increased protein unfolding. Particle curvature and protein steric hindrance effects limited adsorption and structural loss on smaller particles. Protein surface charge heterogeneity was also found to be linked to both protein adsorption and unfolding behavior on larger particles. Greater surface charge heterogeneity led to higher adsorption concentrations and multilayer formation. These multilayers transitioned from protein

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.

High capacity adsorption media and method of producing

DOEpatents

Tranter, Troy J.; Mann, Nicholas R.; Todd, Terry A.; Herbst, Ronald S.

2010-10-05

A method of producing an adsorption medium to remove at least one constituent from a feed stream. The method comprises dissolving and/or suspending at least one metal compound in a solvent to form a metal solution, dissolving polyacrylonitrile into the metal solution to form a PAN-metal solution, and depositing the PAN-metal solution into a quenching bath to produce the adsorption medium. The at least one constituent, such as arsenic, selenium, or antimony, is removed from the feed stream by passing the feed stream through the adsorption medium. An adsorption medium having an increased metal loading and increased capacity for arresting the at least one constituent to be removed is also disclosed. The adsorption medium includes a polyacrylonitrile matrix and at least one metal hydroxide incorporated into the polyacrylonitrile matrix.

High capacity adsorption media and method of producing

DOEpatents

Tranter, Troy J [Idaho Falls, ID; Herbst, R Scott [Idaho Falls, ID; Mann, Nicholas R [Blackfoot, ID; Todd, Terry A [Aberdeen, ID

2008-05-06

A method of producing an adsorption medium to remove at least one constituent from a feed stream. The method comprises dissolving at least one metal compound in a solvent to form a metal solution, dissolving polyacrylonitrile into the metal solution to form a PAN-metal solution, and depositing the PAN-metal solution into a quenching bath to produce the adsorption medium. The at least one constituent, such as arsenic, selenium, or antimony, is removed from the feed stream by passing the feed stream through the adsorption medium. An adsorption medium having an increased metal loading and increased capacity for arresting the at least one constituent to be removed is also disclosed. The adsorption medium includes a polyacrylonitrile matrix and at least one metal hydroxide incorporated into the polyacrylonitrile matrix.

Adsorption and self-assembly of bio-organic molecules at model surfaces: A route towards increased complexity

NASA Astrophysics Data System (ADS)

Costa, Dominique; Pradier, Claire-Marie; Tielens, Frederik; Savio, Letizia

2015-12-01

Understanding the bio-physical-chemical interactions at nanostructured biointerfaces and the assembly mechanisms of so-called hybrid nano-composites is nowadays a key issue for nanoscience in view of the many possible applications foreseen. The contribution of surface science in this field is noteworthy since, using a bottom-up approach, it allows the investigation of the fundamental processes at the basis of complex interfacial phenomena and thus it helps to unravel the elementary mechanisms governing them. Nowadays it is well demonstrated that a wide variety of different molecular assemblies can form upon adsorption of small biomolecules at surfaces. The geometry of such self-organized structures can often be tuned by a careful control of the experimental conditions during the deposition process. Indeed an impressive number of studies exists (both experimental and - to a lesser extent - theoretical), which demonstrates the ability of molecular self-assembly to create different structural motifs in a more or less predictable manner, by tuning the molecular building blocks as well as the metallic substrate. In this frame, amino acids and small peptides at surfaces are key, basic, systems to be studied. The amino acids structure is simple enough to serve as a model for the chemisorption of biofunctional molecules, but their adsorption at surfaces has applications in surface functionalization, in enantiospecific catalysis, biosensing, shape control of nanoparticles or in emerging fields such as "green" corrosion inhibition. In this paper we review the most recent advances in this field. We shall start from the adsorption of amino acids at metal surfaces and we will evolve then in the direction of more complex systems, in the light of the latest improvements of surface science techniques and of computational methods. On one side, we will focus on amino acids adsorption at oxide surfaces, on the other on peptide adsorption both at metal and oxide substrates. Particular

Adsorption of amino acids by fullerenes and fullerene nanowhiskers

NASA Astrophysics Data System (ADS)

Hashizume, Hideo; Hirata, Chika; Fujii, Kazuko; Miyazawa, Kun'ichi

2015-12-01

We have investigated the adsorption of some amino acids and an oligopeptide by fullerene (C60) and fullerene nanowhiskers (FNWs). C60 and FNWs hardly adsorbed amino acids. Most of the amino acids used have a hydrophobic side chain. Ala and Val, with an alkyl chain, were not adsorbed by the C60 or FNWs. Trp, Phe and Pro, with a cyclic structure, were not adsorbed by them either. The aromatic group of C60 did not interact with the side chain. The carboxyl or amino group, with the frame structure of an amino acid, has a positive or negative charge in solution. It is likely that the C60 and FNWs would not prefer the charged carboxyl or amino group. Tri-Ala was adsorbed slightly by the C60 and FNWs. The carboxyl or amino group is not close to the center of the methyl group of Tri-Ala. One of the methyl groups in Tri-Ala would interact with the aromatic structure of the C60 and FNWs. We compared our results with the theoretical interaction of 20 bio-amino acids with C60. The theoretical simulations showed the bonding distance between C60 and an amino acid and the dissociation energy. The dissociation energy was shown to increase in the order, Val < Phe < Pro < Asp < Ala < Trp < Tyr < Arg < Leu. However, the simulation was not consistent with our experimental results. The adsorption of albumin (a protein) by C60 showed the effect on the side chains of Try and Trp. The structure of albumin was changed a little by C60. In our study Try and Tyr were hardly adsorbed by C60 and FNWs. These amino acids did not show a different adsorption behavior compared with other amino acids. The adsorptive behavior of mono-amino acids might be different from that of polypeptides.

[Thermodynamic analysis of water adsorption and desorption process of Chinese herbal decoction pieces].

PubMed

Cheng, Lin; Luo, Xiao-Jian; Han, Xiu-Lin; Wang, Wen-Kai; Rao, Xiao-Yong; Xu, Shao-Zhong; He, Yan

2016-09-01

Based on the basic theory of thermodynamics, the thermodynamic parameters and related equations in the process of water adsorption and desorption of Chinese herbal decoction pieces were established, and their water absorption and desorption characteristics were analyzed. The physical significance of the thermodynamic parameters, such as differential adsorption enthalpy, differential adsorption entropy, integral adsorption enthalpy, integral adsorption entropy and the free energy of adsorption, were discussed in this paper to provide theoretical basis for the research on the water adsorption and desorption mechanism, optimum drying process parameters, storage conditions and packaging methods of Chinese herbal decoction pieces. Copyright© by the Chinese Pharmaceutical Association.

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.

Removing polycyclic aromatic hydrocarbons from water using granular activated carbon: kinetic and equilibrium adsorption studies.

PubMed

Eeshwarasinghe, Dinushika; Loganathan, Paripurnanda; Kalaruban, Mahatheva; Sounthararajah, Danious Pratheep; Kandasamy, Jaya; Vigneswaran, Saravanamuthu

2018-05-01

Polycyclic aromatic hydrocarbons (PAHs) constitute a group of highly persistent, toxic and widespread environmental micropollutants that are increasingly found in water. A study was conducted in removing five PAHs, specifically naphthalene, acenaphthylene, acenaphthene, fluorene and phenanthrene, from water by adsorption onto granular activated carbon (GAC). The pseudo-first-order (PFO) model satisfactorily described the kinetics of adsorption of the PAHs. The Weber and Morris diffusion model's fit to the data showed that there were faster and slower rates of intra-particle diffusion probably into the mesopores and micropores of the GAC, respectively. These rates were negatively related to the molar volumes of the PAHs. Batch equilibrium adsorption data fitted well to the Langmuir, Freundlich and Dubinin-Radushkevich models, of which the Freundlich model exhibited the best fit. The adsorption affinities were related to the hydrophobicity of the PAHs as determined by the log K ow values. Free energies of adsorption calculated from the Dubinin-Radushkevich model and the satisfactory kinetic data fitting to the PFO model suggested physical adsorption of the PAHs. Adsorption of naphthalene, acenaphthylene and acenaphthene in fixed-bed columns containing a mixture of GAC (0.5 g) + sand (24.5 g) was satisfactorily simulated by the Thomas model.

Malachite Green Adsorption by Spent Coffee Grounds

NASA Astrophysics Data System (ADS)

Syamimie Atirah Mat, Siti; Zati Hanani Syed Zuber, Sharifah; Rahim, Siti Kartini Enche Ab; Sohaimi, Khairunissa Syairah Ahmad; Halim, Noor Amirah Abdul; Fauziah Zainudin, Nor; Aida Yusoff, Nor; Munirah Rohaizad, Nor; Hidayah Ishak, Noor; Anuar, Adilah; Sarip, Mohd Sharizan Md

2018-03-01

In this work, the ability of spent coffee grounds (SCG) as a low-cost adsorbent to remove malachite green (MG) from aqueous solutions was studied. Batch adsorption tests were carried out to observe the effect of various experimental parameters such as contact time, initial concentration of malachite green and adsorbent dosage on the removal of dye. The results obtained show that the percentage of dye removal will decreased with the increased of initial concentration of dye in the range of 50 mg/L to 250 mg/L. Besides, percentage removal of dye was also found to be increased as the contact time increased until it reached equilibrium condition. The results also showed that the adsorbent dosage in range of 0.2 g to 1.0 g is proportional to the percentage removal of malachite green dye. Study on the kinetic adsorption and isotherm adsorption has also been investigated. The adsorption isotherm data were described by Langmuir isotherm with high-correlation coefficients while the experimental data showed the pseudo-second-order kinetics model was the best model for the adsorption of MG by SCG with the coefficients of correlation R2 > 0.9978.

Effects of hydration and oxygen vacancy on CO2 adsorption and activation on beta-Ga2O3(100).

PubMed

Pan, Yun-xiang; Liu, Chang-jun; Mei, Donghai; Ge, Qingfeng

2010-04-20

The effects of hydration and oxygen vacancy on CO(2) adsorption on the beta-Ga(2)O(3)(100) surface have been studied using density functional theory slab calculations. Adsorbed CO(2) is activated on the dry perfect beta-Ga(2)O(3)(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect beta-Ga(2)O(3)(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect beta-Ga(2)O(3)(100) surface. Adsorption of CO(2) on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slightly repulsive interaction when H(2)O and CO(2) are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the coadsorbed H(2)O to a bicarbonate species, making the CO(2) adsorption exothermic, with an adsorption energy of -0.13 eV. The effect of defects on CO(2) adsorption and activation has been examined by creating an oxygen vacancy on the dry beta-Ga(2)O(3)(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O(2) molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO(2). In the most stable CO(2) adsorption configuration on the dry defective beta-Ga(2)O(3)(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO(2) occupies the oxygen vacancy site, and the CO(2) adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is spontaneous, with a reaction energy of -0.62 eV. These results indicate that, when water and CO(2) are present in the adsorption system simultaneously, water will compete with CO(2) for the oxygen vacancy sites and impact CO(2) adsorption and conversion negatively.

How strong is the edge effect in the adsorption of anticancer drugs on a graphene cluster?

PubMed

Rungnim, Chompoonut; Chanajaree, Rungroj; Rungrotmongkol, Thanyada; Hannongbua, Supot; Kungwan, Nawee; Wolschann, Peter; Karpfen, Alfred; Parasuk, Vudhichai

2016-04-01

The adsorption of nucleobase-analog anticancer drugs (fluorouracil, thioguanine, and mercaptopurine) on a graphene flake (C54H18) was investigated by shifting the site at which adsorption occurs from one end of the sheet to the other end. The counterpoise-corrected M06-2X/cc-pVDZ binding energies revealed that the binding stability decreases in the sequence thioguanine > mercaptopurine > fluorouracil. We found that adsorption near the middle of the sheet is more favorable than adsorption near the edge due to the edge effect. This edge effect is stronger for the adsorption of thioguanine or mercaptopurine than for fluorouracil adsorption. However, the edge effect reduces the binding energy of the drug to the flake by only a small amount, <5 kcal/mol, depending on the adsorption site and the alignment of the drug at this site.

Influence of soil solution cation composition on boron adsorption by soils

USDA-ARS?s Scientific Manuscript database

Boron (B) adsorption on five arid-zone soil samples from California was investigated as a function of solution pH (4-10) and cation composition (Na, Ca, or Mg). Boron adsorption increased with increasing solution pH, reached an adsorption maximum near pH 9, and decreased with further increases with...

Isotherm and thermodynamic studies of Zn (II) adsorption on lignite and coconut shell-based activated carbon fiber.

PubMed

Shrestha, Sohan; Son, Guntae; Lee, Seung Hwan; Lee, Tae Gwan

2013-08-01

The Zn (II) adsorption capacity of lignite and coconut shell-based activated carbon fiber (ACF) was evaluated as a function of initial Zn (II) concentration, temperature and contact time in batch adsorption process in this study. Adsorption uptake increased with initial Zn (II) concentration and temperature. Optimal contact time for the adsorption of Zn (II) ions onto lignite and coconut shell-based ACF was found to be 50 min. Removal percentage decreased from 88.0% to 78.54% with the increment in initial Zn (II) concentration from 5 to 50 mg L(-1). Equilibrium data fit well with Langmuir-I isotherm indicating homogeneous monolayer coverage of Zn (II) ions on the adsorbent surface. Maximum monolayer adsorption capacity of Zn (II) ions on ACF was found to be 9.43 mg g(-1). Surface morphology and functionality of ACF prior to and after adsorption were characterized by electron microscopy and infrared spectroscopy. Various thermodynamic parameters such as standard Gibbs free energy (ΔG°), standard enthalpy (ΔH°), and standard entropy (ΔS°) were evaluated. Copyright © 2013 Elsevier Ltd. All rights reserved.

Microcolumn studies of dye adsorption onto manganese oxides modified diatomite.

PubMed

Al-Ghouti, M A; Khraisheh, M A M; Ahmad, M N; Allen, S J

2007-07-19

The method described here cannot fully replace the analysis of large columns by small test columns (microcolumns). The procedure, however, is suitable for speeding up the determination of adsorption parameters of dye onto the adsorbent and for speeding up the initial screening of a large adsorbent collection that can be tedious if a several adsorbents and adsorption conditions must be tested. The performance of methylene blue (MB), a basic dye, Cibacron reactive black (RB) and Cibacron reactive yellow (RY) was predicted in this way and the influence of initial dye concentration and other adsorption conditions on the adsorption behaviour were demonstrated. On the basis of the experimental results, it can be concluded that the adsorption of RY onto manganese oxides modified diatomite (MOMD) exhibited a characteristic "S" shape and can be simulated effectively by the Thomas model. It is shown that the adsorption capacity increased as the initial dye concentration increased. The increase in the dye uptake capacity with the increase of the adsorbent mass in the column was due to the increase in the surface area of adsorbent, which provided more binding sites for the adsorption. It is shown that the use of high flow rates reduced the time that RY in the solution is in contact with the MOMD, thus allowing less time for adsorption to occur, leading to an early breakthrough of RY. A rapid decrease in the column adsorption capacity with an increase in particle size with an average 56% reduction in capacity resulting from an increase in the particle size from 106-250 microm to 250-500 microm. The experimental data correlated well with calculated data using the Thomas equation and the bed depth-service time (BDST) equation. Therefore, it might be concluded that the Thomas equation and the BDST equations can produce accurate predication for variation of dye concentration, mass of the adsorbent, flow rate and particle size. In general, the values of adsorption isotherm capacity

Insight into the adsorption of chloramphenicol on a vermiculite surface

NASA Astrophysics Data System (ADS)

Tri, Nguyen Ngoc; Carvalho, A. J. P.; Dordio, A. V.; Nguyen, Minh Tho; Trung, Nguyen Tien

2018-05-01

Four stable configurations were found upon adsorption of the chloramphenicol on a period slab model of the vermiculite surface, using the PBE and C09-vdW functionals in a projector-augmented wave (PAW) method approach. The adsorption is a strong chemisorption process, characterized by an adsorption energy of -106.5 kcal mol-1 at the most stable configuration. Stability of configurations contributed mainly by Mg⋯O/Cl attractive electrostatic interactions and C/Osbnd H⋯O hydrogen bonds. It is remarkable that the vermiculite is found to be a solid material with good potential to be used for adsorption and consequent removal of this type of antibiotic drugs.

Adsorption--from theory to practice.

PubMed

Dabrowski, A

2001-10-08

Adsorption at various interfaces has concerned scientists since the beginning of this century. This phenomenon underlies a number of extremely important processes of utilitarian significance. The technological, environmental and biological importance of adsorption can never be in doubt. Its practical applications in industry and environmental protection are of paramount importance. The adsorption of substrates is the first stage in many catalytic processes. The methods for separation of mixtures on a laboratory and on an industrial scale are increasingly based on utilising the change in concentration of components at the interface. Moreover, such vital problems as purification of water, sewages, air and soil are involved here too. On the other hand, many areas in which technological innovation has covered adsorption phenomena have been expanded more through art and craft than through science. A basic understanding of the scientific principles is far behind; in part because the study of interfaces requires extremely careful experimentation if meaningful and reproducible results are to be obtained. In recent years, however, considerable effort has been increasingly directed toward closing the gap between theory and practice. Crucial progress in theoretical description of the adsorption has been achieved, mainly through the development of new theoretical approaches formulated on a molecular level, by means of computer simulation methods and owing to new techniques which examine surface layers or interfacial regions. Moreover, during the last 15 years new classes of solid adsorbents have been developed, such as activated carbon fibres and carbon molecular sieves, fullerenes and heterofullerenes, microporous glasses and nanoporous--both carbonaceous and inorganic--materials. Nanostructured solids are very popular in science and technology and have gained extreme interest due to their sorption, catalytic, magnetic, optical and thermal properties. Although the development

The different adsorption mechanism of methane molecule onto a boron nitride and a graphene flakes

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

Seyed-Talebi, Seyedeh Mozhgan; Neek-Amal, M., E-mail: neekamal@srttu.edu

2014-10-21

Graphene and single layer hexagonal boron-nitride are two newly discovered 2D materials with wonderful physical properties. Using density functional theory, we study the adsorption mechanism of a methane molecule over a hexagonal flake of single layer hexagonal boron-nitride (h-BN) and compare the results with those of graphene. We found that independent of the used functional in our ab-initio calculations, the adsorption energy in the h-BN flake is larger than that for graphene. Despite of the adsorption energy profile of methane over a graphene flake, we show that there is a long range behavior beyond minimum energy in the adsorption energymore » of methane over h-BN flake. This result reveals the higher sensitivity of h-BN sheet to the adsorption of a typical closed shell molecule with respect to graphene. The latter gives insight in the recent experiments of graphene over hexagonal boron nitride.« less

Hydrogen adsorption in metal-decorated silicon carbide nanotubes

NASA Astrophysics Data System (ADS)

Singh, Ram Sevak; Solanki, Ankit

2016-09-01

Hydrogen storage for fuel cell is an active area of research and appropriate materials with excellent hydrogen adsorption properties are highly demanded. Nanotubes, having high surface to volume ratio, are promising storage materials for hydrogen. Recently, silicon carbide nanotubes have been predicted as potential materials for future hydrogen storage application, and studies in this area are ongoing. Here, we report a systematic study on hydrogen adsorption properties in metal (Pt, Ni and Al) decorated silicon carbide nanotubes (SiCNTs) using first principles calculations based on density functional theory. The hydrogen adsorption properties are investigated by calculations of adsorption energy, electronic band structure, density of states (DOS) and Mulliken charge population analysis. Our findings show that hydrogen adsorptions on Pt, Ni and Al-decorated SiCNTs undergo spontaneous exothermic reactions with significant modulation of electronic structure of SiCNTs in all cases. Importantly, according to the Mulliken charge population analysis, dipole-dipole interaction causes chemisorptions of hydrogen in Pt, Ni and Al decorated SiCNTs with formation of chemical bonds. The study is a platform for the development of metal decorated SiCNTs for hydrogen adsorption or hydrogen storage application.

Surface adsorption of poisonous Pb(II) ions from water using chitosan functionalised magnetic nanoparticles.

PubMed

Christopher, Femina Carolin; Anbalagan, Saravanan; Kumar, Ponnusamy Senthil; Pannerselvam, Sundar Rajan; Vaidyanathan, Vinoth Kumar

2017-06-01

In this study, chitosan functionalised magnetic nano-particles (CMNP) was synthesised and utilised as an effective adsorbent for the removal of Pb(II) ions from aqueous solution. The experimental studies reveal that adsorbent material has finer adsorption capacity for the removal of heavy metal ions. Parameters affecting the adsorption of Pb(II) ions on CMNP, such as initial Pb(II) ion concentration, contact time, solution pH, adsorbent dosage and temperature were studied. The adsorption equilibrium study showed that present adsorption system followed a Freundlich isotherm model. The experimental kinetic studies on the adsorption of Pb(II) ions exhibited that present adsorption process best obeyed with pseudo-first order kinetics. The maximum monolayer adsorption capacity of CMNP for the removal of Pb(II) ions was found to be 498.6 mg g -1 . The characterisation of present adsorbent material was done by FTIR, energy disperse X-ray analysis and vibrating sample magnetometer studies. Thermodynamic parameters such as Gibbs free energy (Δ G °), enthalpy (Δ H °) and entropy (Δ S °) have declared that the adsorption process was feasible, exothermic and spontaneous in nature. Sticking probability reported that adsorption of Pb(II) ions on CMNP was favourable at lower temperature and sticking capacity of Pb(II) ions was very high.

On the mechanism of gas adsorption for pristine, defective and functionalized graphene.

PubMed

You, Y; Deng, J; Tan, X; Gorjizadeh, N; Yoshimura, M; Smith, S C; Sahajwalla, V; Joshi, R K

2017-02-22

Defects are no longer deemed an adverse aspect of graphene. Contrarily, they can pave ways of extending the applicability of graphene. Herein, we discuss the effects of three types of defects in graphene including carbon deficiency, adatom (single Fe) dopants and the introduction of functional groups (carbonyl, ether group) on the NO 2 gas adsorption via density functional theory methods. We have observed that introducing Fe on graphene can enhance the NO 2 adsorption process. Adsorption energy calculations suggest that the enhancement in NO 2 adsorption is more profound for Fe-doped mono- and tetra-vacant graphene than that for Fe doped bi- and tri-vacant graphene, which is favourable for NO 2 gas capture applications. The unsaturated carbons in defected graphene as well as the oxygenated functional groups are very active to attract NO 2 molecules. However, though the gas binding strength was not as high as the that found in the Fe-doped graphene structure, the relatively low NO 2 gas adsorption energy is suitable for the practical gas sensors both for gas sensitivity and the sensor recovery rate factor. This theoretical study can potentially be useful for developing adsorption-based applications of graphene.

Three steps to gold: mechanism of protein adsorption revealed by Brownian and molecular dynamics simulations.

PubMed

Ozboyaci, M; Kokh, D B; Wade, R C

2016-04-21

The addition of three N-terminal histidines to β-lactamase inhibitor protein was shown experimentally to increase its binding potency to an Au(111) surface substantially but the binding mechanism was not resolved. Here, we propose a complete adsorption mechanism for this fusion protein by means of a multi-scale simulation approach and free energy calculations. We find that adsorption is a three-step process: (i) recognition of the surface predominantly by the histidine fusion peptide and formation of an encounter complex facilitated by a reduced dielectric screening of water in the interfacial region, (ii) adsorption of the protein on the surface and adoption of a specific binding orientation, and (iii) adaptation of the protein structure on the metal surface accompanied by induced fit. We anticipate that the mechanistic features of protein adsorption to an Au(111) surface revealed here can be extended to other inorganic surfaces and proteins and will therefore aid the design of specific protein-surface interactions.

A First Principles Study of H2 Adsorption on LaNiO3(001) Surfaces

PubMed Central

Pan, Changchang; Chen, Yuhong; Wu, Na; Zhang, Meiling; Yuan, Lihua; Zhang, Cairong

2017-01-01

The adsorption of H2 on LaNiO3 was investigated using density functional theory (DFT) calculations. The adsorption sites, adsorption energy, and electronic structure of LaNiO3(001)/H2 systems were calculated and indicated through the calculated surface energy that the (001) surface was the most stable surface. By looking at optimized structure, adsorption energy and dissociation energy, we found that there were three types of adsorption on the surface. First, H2 molecules completely dissociate and then tend to bind with the O atoms, forming two –OH bonds. Second, H2 molecules partially dissociate with the H atoms bonding to the same O atom to form one H2O molecule. These two types are chemical adsorption modes; however, the physical adsorption of H2 molecules can also occur. When analyzing the electron structure of the H2O molecule formed by the partial dissociation of the H2 molecule and the surface O atom, we found that the interaction between H2O and the (001) surface was weaker, thus, H2O was easier to separate from the surface to create an O vacancy. On the (001) surface, a supercell was constructed to accurately study the most stable adsorption site. The results from analyses of the charge population; electron localization function; and density of the states indicated that the dissociated H and O atoms form a typical covalent bond and that the interaction between the H2 molecule and surface is mainly due to the overlap-hybridization among the H 1s, O 2s, and O 2p states. Therefore, the conductivity of LaNiO3(001)/H2 is stronger after adsorption and furthermore, the conductivity of the LaNiO3 surface is better than that of the LaFeO3 surface. PMID:28772396

Evaluation of natural organic matter adsorption on Fe-Al binary oxide: Comparison with single metal oxides.

PubMed

Kim, Kyung-Jo; Jang, Am

2017-10-01

The adsorption characteristics of three types of standard natural organic matter (NOM) on iron-aluminum (Fe-Al) binary oxide (FAO) and heated aluminum oxide (HAO) under natural surface water condition were investigated using various adsorption isotherms and kinetic models. FAO was synthesized by Fe oxide and Al oxide, mixed using the sol-gel hydrothermal method, and aluminum sulfate was used to make HAO. The amount of adsorbed NOM was increased to 79.6 mg g -1 for humic acid (HA), 101.1 mg g -1 for sodium alginate (SA) in the FAO, but the maximum adsorption capacity of bovine serum albumin (BSA) (461.3 mg g -1 ) was identified on the HAO. The adsorption of HA, BSA, and SA dramatically increased (>70%) on FAO in 5 min and HA was significantly removed (90%) among the three NOM. Mutual interaction among the adsorbed NOM (BSA) occurred on the HAO surface during adsorption due to formation of monolayer by protein molecules at neutral pH. The pseudo second order clearly represented the adsorption kinetics for both adsorbents. The equilibrium isotherm data of FAO was better exhibited by the Langmuir isotherm model than by the Freundlich isotherm, but HAO was a slightly non-linear Langmuir type. Also, the free energy, enthalpy, and entropy of adsorption were determined from the thermodynamic experiments. Adsorption on FAO was spontaneous and an exothermic process. Fluorescence excitation-emission matrix (FEEM) spectra were used to elucidate the variation in organic components. The results obtained suggests that the significant changes in the surface property of the adsorbent (large surface area, increased crystalline intensity, and fine particle size) were effectively determined by the Fe-synthesized Al oxide mixed using the sol-gel hydrothermal method. The results also suggest that the changes enhanced the adsorption capacity, whereby three NOM were notably removed on FAO regardless of NOM characteristics (hydrophobic and hydrophilic). Copyright © 2017 Elsevier

Adsorption of vitamin E on mesoporous titania nanocrystals

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

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

2010-07-15

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

Equilibrium and kinetic adsorption study of Basic Yellow 28 and Basic Red 46 by a boron industry waste.

PubMed

Olgun, Asim; Atar, Necip

2009-01-15

In this study, the adsorption characteristics of Basic Yellow 28 (BY 28) and Basic Red 46 (BR 46) onto boron waste (BW), a waste produced from boron processing plant were investigated. The equilibrium adsorption isotherms and kinetics were investigated. The adsorption equilibrium data were analyzed by using various adsorption isotherm models and the results have shown that adsorption behavior of two dyes could be described reasonably well by a generalized isotherm. Kinetic studies indicated that the kinetics of the adsorption of BY 28 and BR 46 onto BW follows a pseudo-second-order model. The result showed that the BW exhibited high-adsorption capacity for basic dyes and the capacity slightly decreased with increasing temperature. The maximum adsorption capacities of BY 28 and BR 46 are reported at 75.00 and 74.73mgg(-1), respectively. The dye adsorption depended on the initial pH of the solution with maximum uptake occurring at about pH 9 and electrokinetic behavior of BW. Activation energy of 15.23kJ/mol for BY 28 and 18.15kJ/mol for BR 46 were determined confirming the nature of the physisorption onto BW. These results indicate that BW could be employed as low-cost material for the removal of the textile dyes from effluents.

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

Adsorption mechanism in RPLC. Effect of the nature of the organic modifier

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

Gritti, Fabrice; Guiochon, Georges A

2005-07-01

The adsorption isotherms of phenol and caffeine were acquired by frontal analysis on two different adsorbents, Kromasil-C{sub 18} and Discovery-C{sub 18}, with two different mobile phases, aqueous solutions of methanol (MeOH/H{sub 2}O = 40/60 and 30/70, v/v) and aqueous solutions of acetonitrile (MeCN/H{sub 2}O = 30/70 and 20/80, v/v). The adsorption isotherms are always strictly convex upward in methanol/water solutions. The calculations of the adsorption energy distribution confirm that the adsorption data for phenol are best modeled with the bi-Langmuir and the tri-Langmuir isotherm models for Kromasil-C{sub 18} and Discovery-C{sub 18}, respectively. Because its molecule is larger and excluded frommore » the deepest sites buried in the bonded layer, the adsorption data of caffeine follow bi-Langmuir isotherm model behavior on both adsorbents. In contrast, with acetonitrile/water solutions, the adsorption data of both phenol and caffeine deviate far less from linear behavior. They were best modeled by the sum of a Langmuir and a BET isotherm models. The Langmuir term represents the adsorption of the analyte on the high-energy sites located within the C{sub 18} layers and the BET term its adsorption on the low-energy sites and its accumulation in an adsorbed multilayer system of acetonitrile on the bonded alkyl chains. The formation of a complex adsorbed phase containing up to four layers of acetonitrile (with a thickness of 3.4 {angstrom} each) was confirmed by the excess adsorption isotherm data measured for acetonitrile on Discovery-C{sub 18}. A simple interpretation of this change in the isotherm curvature at high concentrations when methanol is replaced with acetonitrile as the organic modifier is proposed, based on the structure of the interface between the C{sub 18} chains and the bulk mobile phase. This new model accounts for all the experimental observations.« less

Study of Adsorption Mechanism of Congo Red on Graphene Oxide/PAMAM Nanocomposite

PubMed Central

Rafi, Mohammad; Samiey, Babak; Cheng, Chil-Hung

2018-01-01

Graphene oxide/poly(amidoamine) (GO/PAMAM) nanocomposite adsorbed high quantities of congo red (CR) anionic dye in 0.1 M NaCl solution, with the maximum adsorption capacity of 198 mg·g−1. The kinetics and thermodynamics of adsorption were investigated to elucidate the effects of pH, temperature, shaking rate, ionic strength, and contact time. Kinetic data were analyzed by the KASRA model and the KASRA, ISO, and pore-diffusion equations. Adsorption adsorption isotherms were studied by the ARIAN model and the Henry, Langmuir, and Temkin equations. It was shown that adsorption sites of GO/PAMAM at experimental conditions were phenolic hydroxyl groups of GO sheets and terminal amine groups of PAMAM dendrimer. Analysis of kinetic data indicated that amine sites were located on the surface, and that hydroxyl sites were placed in the pores of adsorbent. CR molecules interacted with the adsorption sites via hydrogen bonds. The molecules were adsorbed firstly on the amine sites, and then on the internal hydroxyl sites. Adsorption kinetic parameters indicated that the interaction of CR to the –NH3+ sites was the rate-controlling step of adsorption of CR on this site and adsorption activation energies calculated for different parts of this step. On the other hand, kinetic parameters showed that the intraparticle diffusion was the rate-controlling step during the interaction of CR molecules to –OH sites and activation energy of this step was not calculable. Finally, the used GO/PAMAM was completely regenerated by using ethylenediamine. PMID:29587463

A quantum chemical study for exploring the inhibitory effect of nitrogen containing species on the adsorption of polynuclear aromatic hydrocarbons over a Bronsted acid site

NASA Astrophysics Data System (ADS)

Celis-Cornejo, C. M.; Garnica Mantilla, M. M.; Baldovino-Medrano, V. G.; Ramírez-Caballero, G. E.

2016-08-01

The analysis of the inhibitory effect of nitrogenated compounds on the hydroprocessing and hydropurification of oil derived fuels is important to produce cleaner fuels. In this work, density functional theory calculations were performed to investigate the effect of the nitrogen containing molecules on the adsorption of Polynuclear Aromatic Hydrocarbons (PAHs). Mordenite was chosen as a zeolitic structure for simulating a Bronsted acid site. The character of the acid site was confirmed by both a vibrational frequency calculation and a Bader charge analysis. From the adsorption calculations, it was found that the adsorption energy of PAHs increases with the number of aromatic rings in the structure. Also, the nitrogen containing species possibly inhibit more extensively two and three rings PAHs because of their lower adsorption energies. Finally, it was observed that the nitrogen species tend to drag the proton from the mordenite acid site. This explains the inhibitory effect in the adsorption of PAHs and contributes to understanding the dynamics of hydrocarbon hydroprocessing in refineries.

Adsorption and Dissociation of Molecular Hydrogen on the (0001) Surface of DHCP Americium

NASA Astrophysics Data System (ADS)

Dholabhai, Pratik; Ray, Asok

2009-03-01

Hydrogen molecule adsorption on the (0001) surface of double hexagonal closed packed americium has been studied in detail within the framework of density functional theory. Weak molecular hydrogen adsorptions were observed. The most stable configuration corresponded to a Hor2 approach molecular adsorption at the one-fold top site where the molecule's approach is perpendicular to a lattice vector. Adsorption energies and adsorption geometries for different adsorption sites will be discussed. The change in work functions, magnetic moments, partial charges inside muffin-tins, difference charge density distributions and density of states for the bare Am slab and the Am slab after adsorption of the hydrogen molecule will be discussed. Reaction barrier for the dissociation of hydrogen molecule will be presented. The implications of adsorption on Am 5f electron localization-delocalization will be summarized.

Adsorption dynamics of CVD graphene investigated by a contactless microwave method

NASA Astrophysics Data System (ADS)

Black, N. C. G.; Rungger, I.; Li, B.; Maier, S. A.; Cohen, L. F.; Gallop, J. C.; Hao, L.

2018-07-01

We use a contactless microwave dielectric resonator gas sensing platform to study the adsorption dynamics of NO2 gas present in air onto a graphene surface. The use of microwaves removes the need for metal contacts that would otherwise be necessary for traditional conductivity measurements, and therefore allows non-invasive determination of NO2 concentrations to sub parts per million. As a result, gas‑metal interactions and localised graphene doping in the vicinity of metal contacts are eliminated, with the advantage that only graphene‑gas adsorbate interactions are responsible for the measured signal. We show that the sensor response for all considered concentrations can be described using a surface coverage dependent Langmuir model. We demonstrate that the possible variation of the NO2 binding energy, which is frequently considered as the main parameter, plays only a secondary role compared to the rising adsorption energy barrier with increasing NO2 coverage. The continuous distribution of the properties of the graphene adsorption sites used in the theoretical model is supported by our Kelvin probe and Raman surface analysis. Our results demonstrate that the non-invasive microwave method is a promising alternative platform for gas sensing. Moreover it provides valuable insights towards the understanding of the microscopic processes occurring in graphene based gas sensors, which is a key factor in the realization of reproducible and optimized device properties.

Understanding pH Effects on Trichloroethylene and Perchloroethylene Adsorption to Iron in Permeable Reactive Barriers for Groundwater Remediation.

PubMed

Luo, Jing; Farrell, James

2013-01-01

Metallic iron filings are becoming increasing used in permeable reactive barriers for remediating groundwater contaminated by chlorinated solvents. Understanding solution pH effects on rates of reductive dechlorination in permeable reactive barriers is essential for designing remediation systems that can meet treatment objectives under conditions of varying groundwater properties. The objective of this research was to investigate how the solution pH value affects adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) on metallic iron surfaces. Because adsorption is first required before reductive dechlorination can occur, pH effects on halocarbon adsorption energies may explain pH effects on dechlorination rates. Adsorption energies for TCE and PCE were calculated via molecular mechanics simulations using the Universal force field and a self-consistent reaction field charge equilibration scheme. A range in solution pH values was simulated by varying the amount of atomic hydrogen adsorbed on the iron. The potential energies associated TCE and PCE complexes were dominated by electrostatic interactions, and complex formation with the surface was found to result in significant electron transfer from the iron to the adsorbed halocarbons. Adsorbed atomic hydrogen was found to lower the energies of TCE complexes more than those for PCE. Attractions between atomic hydrogen and iron atoms were more favorable when TCE versus PCE was adsorbed to the iron surface. These two findings are consistent with the experimental observation that changes in solution pH affect TCE reaction rates more than those for PCE.

Adsorption of thiophene on transition metal surfaces with the inclusion of van der Waals effects

NASA Astrophysics Data System (ADS)

Malone, Walter; Matos, Jeronimo; Kara, Abdelkader

2018-03-01

We use density functional theory with the inclusion of the van der Waals interaction to study the adsorption of thiophene, C4H4S, on Pt, Rh, Pd, Au, and Ag (100) surfaces. The five van der Waals (vdW) inclusive functionals we employ are optB86b-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, and rPW86-vdW2. For comparison we also run calculations with the GGA- Perdew Burke and Ernzerhof (PBE) functional. We examine several adsorption sites with the plane of the molecule parallel or perpendicular to the surface. The most stable configuration on all metals was the site where the center of the thiophene lies over a 4-fold hollow site with the sulfur atom lying close to a top site. Furthermore, we examine several electronic and geometric properties of the adsorbate including charge transfer, modification of the d-band, adsorption energy, tilt angle, and adsorption height. For the coinage metals PBE gives the lowest adsorption energy. For reactive transition metal substrates, revPBE-vdW and rPW86-vdW2 give lower adsorption energies than PBE.

Ion-specific weak adsorption of salts and water/octanol transfer free energy of a model amphiphilic hexapeptide.

PubMed

Déjugnat, Christophe; Dufrêche, Jean-François; Zemb, Thomas

2011-04-21

An amphiphilic hexapeptide has been used as a model to quantify how specific ion effects induced by addition of four salts tune the hydrophilic/hydrophobic balance and induce temperature-dependant coacervate formation from aqueous solution. The hexapeptide chosen is present as a dimer with low transfer energy from water to octanol. Taking sodium chloride as the reference state in the Hofmeister scale, we identify water activity effects and therefore measure the free energy of transfer from water to octanol and separately the free energy associated to the adsorption of chaotropic ions or the desorption of kosmotropic ions for the same amphiphilic peptide. These effects have the same order of magnitude: therefore, both energies of solvation as well as transfer into octanol strongly depend on the nature of the electrolytes used to formulate any buffer. Model peptides could be used on separation processes based on criteria linked to "Hofmeister" but different from volume and valency.

Molecular adsorption on metal surfaces with van der Waals density functionals

NASA Astrophysics Data System (ADS)

Li, Guo; Tamblyn, Isaac; Cooper, Valentino R.; Gao, Hong-Jun; Neaton, Jeffrey B.

2012-03-01

The adsorption of 1,4-benzenediamine (BDA) on Au(111) and azobenzene on Ag(111) is investigated using density functional theory (DFT) with the nonlocal van der Waals density functional (vdW-DF) and the semilocal Perdew-Burke-Ernzerhof functional. For BDA on Au(111), the inclusion of London dispersion interactions not only dramatically enhances the molecule-substrate binding, resulting in adsorption energies consistent with experimental results, but also significantly alters the BDA binding geometry. For azobenzene on Ag(111), vdW-DFs produce superior adsorption energies compared to those obtained with other dispersion-corrected DFT approaches. These results provide evidence for the applicability of the vdW-DF approach and serve as practical benchmarks for the investigation of molecules adsorbed on noble-metal surfaces.

Adsorption and diffusion of Au atoms on the (001) surface of Ti, Zr, Hf, V, Nb, Ta, and Mo carbides.

PubMed

Florez, Elizabeth; Viñes, Francesc; Rodriguez, Jose A; Illas, Francesc

2009-06-28

The adsorption of atomic Au on the (001) surface of TiC, ZrC, HfC, VC, NbC, TaC, and delta-MoC and the mechanism of diffusion of this adatom through the surface have been studied in terms of a periodic density functional theory based approach. In all the cases, the Au adsorption energies are in the range of 1.90-2.35 eV. The moderately large adsorption energies allow the Au diffusion before desorption could take place. For TiC(001), ZrC(001), and HfC(001), atomic Au is adsorbed directly on top of C atoms and diffusion takes place along the diagonal of the squares formed by M-C-M-C atoms with the transition state located above the hollow sites. For the rest of transition metal carbides the situation is less simple with the appearance of more than one stable adsorption site, as for NbC and TaC, of a small energy barrier for diffusion around the most stable adsorption site and of a more complex diffusion pathway. The small energy barrier for diffusion around the most stable site will result in a highly mobile Au species which could be observed in scanning tunnel microscope experiments. After depositing Au on metal-carbide surfaces, there is a noticeable charge transfer from the substrate to the adsorbed Au atom. The electronic perturbations on Au increase when going from TiC to ZrC or TaC. Our results indicate that metal carbides should be better supports for the chemical activation of Au than metal oxides.

Adsorption of divalent metals to metal oxide nanoparicles: Competitive and temperature effects

NASA Astrophysics Data System (ADS)

Grover, Valerie Ann

The presence of metals in natural waters is becoming a critical environmental and public health concern. Emerging nanotechnology and the use of metal oxide nanoparticles has been identified as a potential remediation technique in removing metals from water. However, practical applications are still being explored to determine how to apply their unique chemical and physical properties for full scale remediation projects. This thesis investigates the sorption properties of Cd(II), Cu(II), Pb(II) and Zn(II) to hematite (alpha-Fe2O3) and titanium dioxide (TiO2) nanoparticles in single- and binary-adsorbate systems. Competitive sorption was evaluated in 1L batch binary-metal systems with 0.05g/L nano-hematite at pH 8.0 and pH 6.0. Results indicate that the presence of a secondary metal can affect the sorption process depending upon the molar ratios, such as increased or reduced adsorption. Thermodynamic properties were also studied in order to better understand the effects of temperature on equilibrium and kinetic adsorption capabilities. Understanding the thermodynamic properties can also give insight to determine if the sorption process is a physical, chemical or ion exchange reaction. Thermodynamic parameters such as enthalpy (DeltaH), entropy (DeltaS), and Gibbs free energy (DeltaG) were evaluated as a function of temperature, pH, and metal concentration. Results indicate that Pb(II) and Cu(II) adsorption to nano-hematite was an endothermic and physical adsorption process, while Zn(II) and Cd(II) adsorption was dependent upon the adsorbed concentration evaluated. However, metal adsorptions to nano-titanium dioxide were all found to be endothermic and physical adsorption processes; the spontaneity of metal adsorption was temperature dependent for both metal oxide nanoparticles.

Effects of Hydration and Oxygen Vacancy on CO2 Adsorption and Activation on β-Ga2O3(100)

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

Pan, Yunxiang; Liu, Chang-jun; Mei, Donghai

The effects of hydration and oxygen vacancy on CO2 adsorption on the β-Ga2O3(100) surface have been studied using density functional theory slab calculations. Adsorbed CO2 is activated on the dry perfect β-Ga2O3(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect β-Ga2O3(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect β-Ga2O3(100) surface. Adsorption of CO2 on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slight repulsive interactionmore » when H2O and CO2 are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the co-adsorbed H2O to a bicarbonate species, making the overall process exothermic with an adsorption energy of -0.13 eV. The effect of defects on CO2 adsorption and activation has been examined by creating an oxygen vacancy on the dry β-Ga2O3(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O2 molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO2. In the most stable CO2 adsorption configuration on the dry defective β-Ga2O3(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO2 occupies the oxygen vacancy site and the CO2 adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is instantaneous with an adsorption energy of -0.62 eV. These results indicate that, when water and CO2 are both present in the adsorption system simultaneously, the water molecule will compete with CO2 for the oxygen vacancy sites and impact CO2 adsorption and conversion negatively. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. A portion of the computing time

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.

Gas adsorption properties of hybrid graphene-MOF materials.

PubMed

Szczęśniak, Barbara; Choma, Jerzy; Jaroniec, Mietek

2018-03-15

Nowadays, hybrid porous materials consisting of metal-organic frameworks (MOFs) and graphene nanosheets become more and more attractive because of their growing applications in adsorption, catalysis and related areas. Incorporation of graphene oxide into MOFs can provide benefits such as increased water resistance and thermal stability as well as enhanced surface area and adsorption properties. Graphene oxide is one of the best additives to other materials owing to its two main virtues: high atomic density and large amount of surface functional groups. Due to its dense array of atoms, graphene oxide can significantly increase dispersion forces in graphene-MOF materials, which is beneficial for adsorption of small molecules. This work presents a concise appraisal of adsorption properties of MOFs and graphene-MOF hybrids toward CO 2 , volatile organic compounds, hydrogen and methane. It shows that the graphene-MOF materials represent an important class of materials with potential applications in adsorption and catalysis. A special emphasis of this article is placed on their adsorption applications for gas capture and storage. A large number of graphene-MOF adsorbents has been so far explored and their appraisal could be beneficial for researchers interested in the development of hybrid adsorbents for adsorption-based applications. Copyright © 2017 Elsevier Inc. All rights reserved.

In situ enzyme aided adsorption of soluble xylan biopolymers onto cellulosic material.

PubMed

Chimphango, Annie F A; Görgens, J F; van Zyl, W H

2016-06-05

The functional properties of cellulose fibers can be modified by adsorption of xylan biopolymers. The adsorption is improved when the degree of biopolymers substitution with arabinose and 4-O-methyl-glucuronic acid (MeGlcA) side groups, is reduced. α-l-Arabinofuranosidase (AbfB) and α-d-glucuronidase (AguA) enzymes were applied for side group removal, to increase adsorption of xylan from sugarcane (Saccharum officinarum L) bagasse (BH), bamboo (Bambusa balcooa) (BM), Pinus patula (PP) and Eucalyptus grandis (EH) onto cotton lint. The AguA treatment increased the adsorption of all xylans by up to 334%, whereas, the AbfB increased the adsorption of the BM and PP by 31% and 44%, respectively. A combination of AguA and AbfB treatment increased the adsorption, but to a lesser extent than achieved with AguA treatment. This indicated that the removal of the glucuronic acid side groups provided the most significant increase in xylan adsorption to cellulose, in particular through enzymatic treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Factors influencing antibiotics adsorption onto engineered adsorbents.

PubMed

Xia, Mingfang; Li, Aimin; Zhu, Zhaolian; Zhou, Qin; Yang, Weiben

2013-07-01

The study evaluated the adsorption of two antibiotics by four engineered adsorbents (hypercrosslinked resin MN-202, macroporous resin XAD-4, activated carbon F-400, and multi-walled carbon nanotubes (MWCNT)) from aqueous solutions. The dynamic results demonstrated the dominant influence of pore size in adsorption. The adsorption amounts of antibiotics on XAD-4 were attributed to the hydrophobic effect, whereas steric hindrance or micropore-filling played a main role in the adsorption of antibiotics by F-400 because of its high microporosity. Aside from F-400, similar patterns of pH-dependent adsorption were observed, implying the importance of antibiotic molecular forms to the adsorption process for adsorbents. Increasing the ionic concentration with CaC12 produced particular adsorption characteristics on MWCNT at pH 2.0 and F-400 at pH 8.0, which were attributed to the highly available contact surfaces and molecular sieving, respectively. Its hybrid characteristics incorporating a considerable portion of mesopores and micropores made hypercross linked MN-202 a superior antibiotic adsorbent with high adsorption capacity. Furthermore, the adsorption capacity of MWCNT on the basis of surface area was more advantageous than that of the other adsorbents because MWCNT has a much more compact molecular arrangement.

Chloride Ion Adsorption Capacity of Anion Exchange Resin in Cement Mortar

PubMed Central

Lee, Hanseung; Jung, Dohyun; Chen, Zhengxin

2018-01-01

This paper presents the effect of anion exchange resin (AER) on the adsorption of chloride ions in cement mortar. The kinetic and equilibrium behaviors of AER were investigated in distilled water and Ca(OH)2 saturated solutions, and then the adsorption of chloride ions by the AER in the mortar specimen was determined. The AER was used as a partial replacement for sand in the mortar specimen. The mortar specimen was coated with epoxy, except for an exposed surface, and then immersed in a NaCl solution for 140 days. The chloride content in the mortar specimen was characterized by energy dispersive X-ray fluorescence analysis and electron probe microanalysis. The results showed that the AER could adsorb the chloride ions from the solution rapidly but had a relatively low performance when the pH of its surrounding environment increased. When the AER was mixed in the cement mortar, its chloride content was higher than that of the cement matrix around it, which confirms the chloride ion adsorption capacity of the AER. PMID:29621188

Chloride Ion Adsorption Capacity of Anion Exchange Resin in Cement Mortar.

PubMed

Lee, Yunsu; Lee, Hanseung; Jung, Dohyun; Chen, Zhengxin; Lim, Seungmin

2018-04-05

This paper presents the effect of anion exchange resin (AER) on the adsorption of chloride ions in cement mortar. The kinetic and equilibrium behaviors of AER were investigated in distilled water and Ca(OH)₂ saturated solutions, and then the adsorption of chloride ions by the AER in the mortar specimen was determined. The AER was used as a partial replacement for sand in the mortar specimen. The mortar specimen was coated with epoxy, except for an exposed surface, and then immersed in a NaCl solution for 140 days. The chloride content in the mortar specimen was characterized by energy dispersive X-ray fluorescence analysis and electron probe microanalysis. The results showed that the AER could adsorb the chloride ions from the solution rapidly but had a relatively low performance when the pH of its surrounding environment increased. When the AER was mixed in the cement mortar, its chloride content was higher than that of the cement matrix around it, which confirms the chloride ion adsorption capacity of the AER.

Determination of adsorption parameters in numerical simulation for polymer flooding

NASA Astrophysics Data System (ADS)

Bao, Pengyu; Li, Aifen; Luo, Shuai; Dang, Xu

2018-02-01

A study on the determination of adsorption parameters for polymer flooding simulation was carried out. The study mainly includes polymer static adsorption and dynamic adsorption. The law of adsorption amount changing with polymer concentration and core permeability was presented, and the one-dimensional numerical model of CMG was established under the support of a large number of experimental data. The adsorption laws of adsorption experiments were applied to the one-dimensional numerical model to compare the influence of two adsorption laws on the historical matching results. The results show that the static adsorption and dynamic adsorption abide by different rules, and differ greatly in adsorption. If the static adsorption results were directly applied to the numerical model, the difficulty of the historical matching will increase. Therefore, dynamic adsorption tests in the porous medium are necessary before the process of parameter adjustment in order to achieve the ideal history matching result.

Adsorption of guanidinium collectors on aluminosilicate minerals - a density functional study.

PubMed

Nulakani, Naga Venkateswara Rao; Baskar, Prathab; Patra, Abhay Shankar; Subramanian, Venkatesan

2015-10-07

In this density functional theory based investigation, we have modelled and studied the adsorption behaviour of guanidinium cations and substituted (phenyl, methoxy phenyl, nitro phenyl and di-nitro phenyl) guanidinium cationic collectors on the basal surfaces of kaolinite and goethite. The adsorption behaviour is assessed in three different media, such as gas, explicit water and pH medium, to understand the affinity of GC collectors to the SiO4 tetrahedral and AlO6 octahedral surfaces of kaolinite. The tetrahedral siloxane surface possesses a larger binding affinity to GC collectors than the octahedral sites due to the presence of surface exposed oxygen atoms that are active in the intermolecular interactions. Furthermore, the inductive electronic effects of substituted guanidinium cations also play a key role in the adsorption mechanism. Highly positive cations result in a stronger electrostatic interaction and preferential adsorption with the kaolinite surfaces than low positive cations. Computed interaction energies and electron densities at the bond critical points suggest that the adsorption of guanidinium cations on the surfaces of kaolinite and goethite is due to the formation of intra/inter hydrogen bonding networks. Also, the electrostatic interaction favours the high adsorption ability of GC collectors in the pH medium than gas phase and water medium. The structures and energies of GC collectors pave an intuitive view for future experimental studies on mineral flotation.

Van der Waals corrected DFT study of adsorption of groups VA and VIA hydrides on graphene monoxide

NASA Astrophysics Data System (ADS)

Notash, M. Yaghoobi; Ebrahimzadeh, A. Rastkar

2016-06-01

Adsorption properties of H2O, H2S, NH3 and PH3 on graphene monoxide (GMO) nano flack are investigated using density functional theory (DFT). Calculations were carried out by van der Waals correction and general gradient approximation. The adsorption energies and charge transfer between species are obtained and discussed for the considered positions of adsorbate molecules. Charge transfer analysis show that the gas molecules act as an electron acceptor in all cases. The analysis of the adsorption energies suggest GMO can be a good candidate for the adsorption of these molecules.

Activated adsorption of methane on clean and oxygen-modified Pt?111? and Pd?110?

NASA Astrophysics Data System (ADS)

Valden, M.; Pere, J.; Hirsimäki, M.; Suhonen, S.; Pessa, M.

1997-04-01

Activated adsorption of CH 4 on clean and oxygen modified Pt{111} and Pd{110} has been studied using molecular beam surface scattering. The absolute dissociation probability of CH 4 was measured as a function of the incident normal energy ( E) and the surface temperature ( Ts). The results from clean Pt{111} and Pd{110} are consistent with a direct dissociation mechanism. The dissociative chemisorption dynamics of CH 4 is addressed by using quantum mechanical and statistical models. The influence of adsorbed oxygen on the dissociative adsorption of CH 4 on both Pt{111} and Pd{110} shows that the dissociation probability decreases linearly with increasing oxygen coverage.

Adsorption of Water on Simulated Moon Dust Samples

NASA Technical Reports Server (NTRS)

Goering, John P.; Sah, Shweta; Burghaus, Uwe; Street, Kenneth W., Jr.

2008-01-01

A lunar regolith simulant dust sample (JSC-1a) supported on a silica wafer (SiO2/Si(111)) has been characterized by scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), and Auger electron spectroscopy (AES). The adsorption kinetics of water has been studied primarily by thermal desorption spectroscopy (TDS) and also by collecting isothermal adsorption transients. The support has been characterized by water TDS. JSC-1a consists mostly of aluminosilicate glass and other minerals containing Fe, Na, Ca, and Mg. The particle sizes span the range from a few microns up to 100 microns. At small exposures, H2O TDS is characterized by broad (100 to 450 K) structures; at large exposures distinct TDS peaks emerge that are assigned to amorphous solid water (145 K) and crystalline ice (165 K). Water dissociates on JSC-1a at small exposures but not on the bare silica support. It appears that rather porous condensed ice layers form at large exposures. At thermal impact energies, the initial adsorption probability amounts to 0.92+/-0.05.

A relativistic density functional study of the role of 5f electrons in atomic and molecular adsorptions on actinide surfaces

NASA Astrophysics Data System (ADS)

Huda, Muhammad Nurul

Atomic and molecular adsorptions of oxygen and hydrogen on actinide surfaces have been studied within the generalized gradient approximations to density functional theory (GGA-DFT). The primary goal of this work is to understand the details of the adsorption processes, such as chemisorption sites, energies, adsorption configurations and activation energies for dissociation of molecules; and the signature role of the plutonium 5f electrons. The localization of the 5f electrons remains one of central questions in actinides and one objective here is to understand the extent to which localizations plays a role in adsorption on actinide surfaces. We also investigated the magnetism of the plutonium surfaces, given the fact that magnetism in bulk plutonium is a highly controversial issue, and the surface magnetism of it is not a well explored territory. Both the non-spin-polarized and spin-polarized calculations have been performed to arrive at our conclusions. We have studied both the atomic and molecular hydrogen and oxygen adsorptions on plutonium (100) and (111) surfaces. We have also investigated the oxygen molecule adsorptions on uranium (100) surface. Comparing the adsorption on uranium and plutonium (100) surfaces, we have seen that O2 chemisorption energy for the most favorable adsorption site on uranium surface has higher chemisorption energy, 9.492 eV, than the corresponding plutonium site, 8.787 eV. Also degree of localization of 5f electrons is less for uranium surface. In almost all of the cases, the most favorable adsorption sites are found where the coordination numbers are higher. For example, we found center sites are the most favorable sites for atomic adsorptions. In general oxygen reacts more strongly with plutonium surface than hydrogen. We found that atomic oxygen adsorption energy on (100) surface is 3.613 eV more than that of the hydrogen adsorptions, considering only the most favorable site. This is also true for molecular adsorptions, as the

Adsorption of sugars on Al- and Ga-doped boron nitride surfaces: A computational study

NASA Astrophysics Data System (ADS)

Darwish, Ahmed A.; Fadlallah, Mohamed M.; Badawi, Ashraf; Maarouf, Ahmed A.

2016-07-01

Molecular adsorption on surfaces is a key element for many applications, including sensing and catalysis. Non-invasive sugar sensing has been an active area of research due to its importance to diabetes care. The adsorption of sugars on a template surface study is at the heart of matter. Here, we study doped hexagonal boron nitride sheets (h-BNNs) as adsorbing and sensing template for glucose and glucosamine. Using first principles calculations, we find that the adsorption of glucose and glucosamine on h-BNNs is significantly enhanced by the substitutional doping of the sheet with Al and Ga. Including long range van der Waals corrections gives adsorption energies of about 2 eV. In addition to the charge transfer occurring between glucose and the Al/Ga-doped BN sheets, the adsorption alters the size of the band gap, allowing for optical detection of adsorption. We also find that Al-doped boron nitride sheet is better than Ga-doped boron nitride sheet to enhance the adsorption energy of glucose and glucosamine. The results of our work can be potentially utilized when designing support templates for glucose and glucosamine.

Comparison of hydrogen and deuterium adsorption on Pd(100).

PubMed

Gladys, M J; Kambali, I; Karolewski, M A; Soon, A; Stampfl, C; O'Connor, D J

2010-01-14

Low energy ion recoil spectroscopy is a powerful technique for the determination of adsorbate position on metal surfaces. In this study, this technique is employed to compare the adsorption sites of hydrogen and deuterium on Pd(100) by detection of either H or D recoil ions produced by Ne(+) bombardment. Comparisons of experimental and Kalypso simulated azimuthal yield distributions show that, at room temperature, both hydrogen isotopes are adsorbed in the fourfold hollow site of Pd(100), however, at different heights above the surface (H-0.20 A and D-0.25 A). The adsorbates remain in the hollow site at all temperatures up to 383 K even though they move up to 0.40-0.45 A above the surface. Density functional theory calculations show a similar coverage dependent adsorption height for both H and D and confirm a real difference between the H and D adsorption heights based on zero point energies.

Removal of Reactofix Navy Blue 2 GFN from aqueous solutions using adsorption techniques.

PubMed

Gupta, Vinod Kumar; Jain, Rajeev; Varshney, Shaily; Saini, Vipin Kumar

2007-03-15

The wheat husk, an agricultural by-product, has been activated and used as an adsorbent for the adsorption of Reactofix Navy Blue 2 GFN from aqueous solution. In this work, adsorption of Reactofix Navy Blue 2 GFN on wheat husk and charcoal has been studied by using batch studies. The equilibrium adsorption level was determined to be a function of the solution pH, adsorbent dosage, dye concentration and contact time. The equilibrium adsorption capacities of wheat husk and charcoal for dye removal were obtained using Freundlich and Langmuir isotherms. Thermodynamic parameters such as the free energies, enthalpies and entropies of adsorption were also evaluated. Adsorption process is considered suitable for removing color, COD from waste water.

Enhanced Adsorption and Photocatalytic Activities of Co-Doped TiO2 Immobilized on Silica for Paraquat

NASA Astrophysics Data System (ADS)

Nghia, Nguyen Manh; Negishi, Nobuaki; Hue, Nguyen Thi

2018-01-01

We studied the adsorption and photocatalysis of paraquat in an aqueous solution with cobalt-doped TiO2 supported on mesoporous silica gel. With Co concentration increasing from 0% to 9%, it was found that the TiO2 anatase phase remained unchanged and the Co was uniformly distributed, while the band gap energy decreased from 3.32 eV to 2.64 eV. The drop in band gap energy leads to the Co-TiO2/silica gel photocatalyst oxidation of paraquat to NH4 + and NO3 - products under visible light. Relative to TiO2, the incorporation of Co into TiO2 led to an increase in the adsorption ability against the paraquat. A possible mechanism of the paraquat degradation may be that the paraquat was selectively adsorbed onto the Co-TiO2/silica gel photocatalyst before light irradiation and after that the paraquat was continuously photodecomposed.

First-principles study of structure, electronic properties and stability of tungsten adsorption on TiC(111) surface with disordered vacancies

NASA Astrophysics Data System (ADS)

Ilyasov, Victor V.; Pham, Khang D.; Zhdanova, Tatiana P.; Phuc, Huynh V.; Hieu, Nguyen N.; Nguyen, Chuong V.

2017-12-01

In this paper, we systematically investigate the atomic structure, electronic and thermodynamic properties of adsorbed W atoms on the polar Ti-terminated TixCy (111) surface with different configurations of adsorptions using first principle calculations. The bond length, adsorption energy, and formation energy for different reconstructions of the atomic structure of the W/TixCy (111) systems were established. The effect of the tungsten coverage on the electronic structure and the adsorption mechanism of tungsten atom on the TixCy (111) are also investigated. We also suggest the possible mechanisms of W nucleation on the TixCy (111) surface. The effective charges on W atoms and nearest-neighbor atoms in the examined reconstructions were identified. Additionally, we have established the charge transfer from titanium atom to tungsten and carbon atoms which determine by the reconstruction of the local atomic and electronic structures. Our calculations showed that the charge transfer correlates with the electronegativity of tungsten and nearest-neighbor atoms. We also determined the effective charge per atom of titanium, carbon atoms, and neighboring adsorbed tungsten atom in different binding configurations. We found that, with reduction of the lattice symmetry associated with titanium and carbon vacancies, the adsorption energy increases by 1.2 times in the binding site A of W/TixCy systems.

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.

Protein adsorption in microengraving immunoassays.

PubMed

Song, Qing

2015-10-16

Microengraving is a novel immunoassay for characterizing multiple protein secretions from single cells. During the immunoassay, characteristic diffusion and kinetic time scales  and  determine the time for molecular diffusion of proteins secreted from the activated single lymphocytes and subsequent binding onto the glass slide surface respectively. Our results demonstrate that molecular diffusion plays important roles in the early stage of protein adsorption dynamics which shifts to a kinetic controlled mechanism in the later stage. Similar dynamic pathways are observed for protein adsorption with significantly fast rates and rapid shifts in transport mechanisms when  is increased a hundred times from 0.313 to 31.3. Theoretical adsorption isotherms follow the trend of experimentally obtained data. Adsorption isotherms indicate that amount of proteins secreted from individual cells and subsequently captured on a clean glass slide surface increases monotonically with time. Our study directly validates that protein secretion rates can be quantified by the microengraving immunoassay. This will enable us to apply microengraving immunoassays to quantify secretion rates from 10⁴-10⁵ single cells in parallel, screen antigen-specific cells with the highest secretion rate for clonal expansion and quantitatively reveal cellular heterogeneity within a small cell sample.

Protein Adsorption in Microengraving Immunoassays

PubMed Central

Song, Qing

2015-01-01

Microengraving is a novel immunoassay forcharacterizing multiple protein secretions from single cells. During the immunoassay, characteristic diffusion and kinetic time scales τD and τK determine the time for molecular diffusion of proteins secreted from the activated single lymphocytes and subsequent binding onto the glass slide surface respectively. Our results demonstrate that molecular diffusion plays important roles in the early stage of protein adsorption dynamics which shifts to a kinetic controlled mechanism in the later stage. Similar dynamic pathways are observed for protein adsorption with significantly fast rates and rapid shifts in transport mechanisms when C0* is increased a hundred times from 0.313 to 31.3. Theoretical adsorption isotherms follow the trend of experimentally obtained data. Adsorption isotherms indicate that amount of proteins secreted from individual cells and subsequently captured on a clean glass slide surface increases monotonically with time. Our study directly validates that protein secretion rates can be quantified by the microengraving immunoassay. This will enable us to apply microengraving immunoassays to quantify secretion rates from 104–105 single cells in parallel, screen antigen-specific cells with the highest secretion rate for clonal expansion and quantitatively reveal cellular heterogeneity within a small cell sample. PMID:26501282

Thermodynamics of organic molecule adsorption on sorbents modified with 5-hydroxy-6-methyluracil by inverse gas chromatography.

PubMed

Gus'kov, Vladimir Yu; Gainullina, Yulia Yu; Ivanov, Sergey P; Kudasheva, Florida Kh

2014-08-22

The thermodynamic features of organic molecule adsorption from the gaseous phase of sorbents modified with 5-hydroxy-6-methyluracil (HMU) were studied. Molar internal energy and entropy of adsorption variation analyses showed that with every type surface, except for silica gel, layers of supramolecular structure have cavities equal in size with the ones revealed in HMU crystals by X-ray diffraction. Adsorption thermodynamics on HMU-modified sorbents depended on the amount of impregnated HMU and on the polarity, but not the porosity, of the initial sorbent. Polarity of the modified surface increased as a function of HMU quantity and initial sorbent mean pore size, but become appreciably lower if the initial surface is capable of hydrogen bonding. Copyright © 2014 Elsevier B.V. All rights reserved.

In silico approach to investigating the adsorption mechanisms of short chain perfluorinated sulfonic acids and perfluorooctane sulfonic acid on hydrated hematite surface.

PubMed

Feng, Hongru; Lin, Yuan; Sun, Yuzhen; Cao, Huiming; Fu, Jianjie; Gao, Ke; Zhang, Aiqian

2017-05-01

Short chain perfluorinated sulfonic acids (PFSAs) that were introduced as alternatives for perfluorooctane sulfonic acid (PFOS) have been widely produced and used. However, few studies have investigated the environmental process of short chain PFSAs, and the related adsorption mechanisms still need to be uncovered. The water-oxide interface is one of the major environmental interfaces that plays an important role in affecting the adsorption behaviour and transport potential of the environmental pollutant. In this study, we performed molecular dynamics simulations and quantum chemistry calculations to investigate the adsorption mechanisms of five PFSAs and their adsorption on hydrated hematite surface as well. Different to the vertical configuration reported for PFOS on titanium oxide, all PFSAs share the same adsorption configuration as the long carbon chains parallel to the surface. The formation of hydrogen bonds between F and inter-surface H helps to stabilize the unique configuration. As a result, the sorption capacity increases with increasing C-F chain length. Moreover, both calculated adsorption energy and partial density of states (PDOS) analysis demonstrate a PFSAs adsorption mechanism in between physical and chemical adsorption because the hydrogen bonds formed by the overlap of F (p) orbital and H (s) orbital are weak intermolecular interactions while the physical adsorption are mainly ascribed to the electrostatic interactions. This massive calculation provides a new insight into the pollutant adsorption behaviour, and in particular, may help to evaluate the environmental influence of pollutants. Copyright © 2017. Published by Elsevier Ltd.

First-principles calculations of the indigo encapsulation and adsorption by MgO nanotubes

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

Sánchez-Ochoa, F., E-mail: fsanchez@ifuap.buap.mx; Cocoletzi, Gregorio H.; Canto, Gabriel I.

2014-06-07

We have performed ab-initio calculations to investigate the structural and electronic properties of (m,m) chiral magnesium oxide nanotubes, (m,m)MgONTs, to explore the encapsulation, inclusion, and adsorption of dyes (organic molecules) such as Indigo (IND). Studies start by determining the structural parameters of the MgO nanotubes with different diameters and the IND. The indigo encapsulation into the MgONT is studied considering four (m,m) chiralities which yield 4 different NT diameters. In the endohedral functionalization, the indigo is within the NT at a tilt angle as in previous theoretical studies of organic molecules inside carbon and boron-nitride nanotubes. Results show that themore » encapsulation is a strong exothermic process with the m = 6 case exhibiting the largest encapsulation energy. It is also explored the indigo adsorption on the NT surface in the parallel and perpendicular configurations. The perpendicular configuration of the IND adsorption on the (8,8)MgONT exhibits the largest energy. The indigo inclusion within the NTs meets a potential barrier when m < 6, however this barrier diminishes as the index increases. Additionally, we have determined the total density of states (DOS), partial DOS, electron charge redistributions, and the highest occupied molecular orbital–lowest unoccupied molecular orbital levels for the NTs with m = 6. Very strong binding energies and electron charge transfer from the IND to NTs is present in the atomic structures.« less

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.

Mechanism of ion adsorption to aqueous interfaces: Graphene/water vs. air/water.

PubMed

McCaffrey, Debra L; Nguyen, Son C; Cox, Stephen J; Weller, Horst; Alivisatos, A Paul; Geissler, Phillip L; Saykally, Richard J

2017-12-19

The adsorption of ions to aqueous interfaces is a phenomenon that profoundly influences vital processes in many areas of science, including biology, atmospheric chemistry, electrical energy storage, and water process engineering. Although classical electrostatics theory predicts that ions are repelled from water/hydrophobe (e.g., air/water) interfaces, both computer simulations and experiments have shown that chaotropic ions actually exhibit enhanced concentrations at the air/water interface. Although mechanistic pictures have been developed to explain this counterintuitive observation, their general applicability, particularly in the presence of material substrates, remains unclear. Here we investigate ion adsorption to the model interface formed by water and graphene. Deep UV second harmonic generation measurements of the SCN - ion, a prototypical chaotrope, determined a free energy of adsorption within error of that for air/water. Unlike for the air/water interface, wherein repartitioning of the solvent energy drives ion adsorption, our computer simulations reveal that direct ion/graphene interactions dominate the favorable enthalpy change. Moreover, the graphene sheets dampen capillary waves such that rotational anisotropy of the solute, if present, is the dominant entropy contribution, in contrast to the air/water interface.

Adsorption of Atoms of 3 d Metals on the Surfaces of Aluminum and Magnesium Oxide Films

NASA Astrophysics Data System (ADS)

Ramonova, A. G.; Kibizov, D. D.; Kozyrev, E. N.; Zaalishvili, V. B.; Grigorkina, G. S.; Fukutani, K.; Magkoev, T. T.

2018-01-01

The adsorption and formation of submonolayer structures of Ti, Cr, Fe, Ni, Cu on the surfaces of aluminum and magnesium oxide films formed on Mo(110) under ultrahigh vacuum conditions are studied via X-ray, ultraviolet photo-, and Auger electron spectroscopy (XPS, UVES, AES); spectroscopy of energy losses of high-resolution electrons (SELHRE); spectroscopy of the backscattering of low-energy ions (SBSLEI); infrared absorption spectroscopy (IAS); and the diffraction of slow electrons (DSE). Individual atoms and small clusters of all the investigated metals deposited on oxides acquire a positive charge, due presumably to interaction with surface defects. As the concentration of adatoms increases when the adsorption centers caused by defects are filled, charge transfer from adatoms to substrates is reduced. This is accompanied by further depolarization caused by the lateral interaction of adatoms.

Design and analysis of siloxanes removal by adsorption from landfill gas for waste-to-energy processes.

PubMed

Elwell, Anthony C; Elsayed, Nada H; Kuhn, John N; Joseph, Babu

2018-03-01

Separation of volatile methyl siloxanes from landfill gas using fixed adsorption beds was modeled with the objective of identifying appropriate technology and the economics associated with this purification step. A general adsorption model assuming plug flow and radial symmetry was developed and used to conduct a parametric sweep of 162 unique cases. The varied parameters were adsorbent type (activated carbon and silica gel), bed height (3.05-9.15 m/10-30 ft), inlet siloxane concentration (5-15 mg/m 3 ), moisture content (0-100% relative humidity at STP or RH), and siloxane tolerance limit (0.094-9.4 mg/m 3 ) that correlated to three distinct energy conversion technologies (electricity production using engines or fuels cells or catalytic conversion to liquid hydrocarbon fuels). Due to the detrimental effect of RH on siloxane absorption, the maximum allowable moisture content of LFG before purification is 50% RH and moisture removal processes are also required. The design calculations using a selected case study show that the adsorption bed height required needed for 6 months minimum breakthrough time for catalytic fuel production is twice that for engine applications. Fuel cell applications require 3 times the bed height compared to engine applications. However, the purification costs amounted to 94%, 16% and 52% of recovered product value for engine, liquefaction, and fuel cell applications, respectively indicating the need for a high value product to justify purification costs. The approaches and conclusions can be extended to specific process conditions for landfill gas purification and to other processes that use biogas produced from waste as a feedstock. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorption of catechol and comparative solutes on hydroxyapatite.

PubMed

Chirdon, William M; O'Brien, William J; Robertson, Richard E

2003-08-15

Contemporary medical and dental adhesives often have difficulty sticking to wet surfaces or weaken with long-term exposure to water. Substantial research has been dedicated to finding a means of achieving adhesion in an aqueous environment. A study evaluates the adsorption of catechol relative to other chemical groups as means of gauging how effective they may be as adsorptive groups in adhesives. Contact angle and surface-tension measurements of solutions of catechols and other chemical groups were used to determine their works of adhesion. Adsorption isotherms were also constructed to ascertain Langmuir constants. Solutes containing catechol groups were compared to solutes containing other polar groups to see how well catechol adsorbs to hydroxyapatite, the mineral component of bones and teeth, relative to other chemical groups found in adhesives. The results of this study show that catechol and molecules containing catechol groups have higher rates and energies of adsorption to hydroxyapatite than do groups such as alcohols, amines, and carboxylic acids. Copyright 2003 Wiley Periodicals, Inc.

[Characteristics of Adsorption Leaching and Influencing Factors of Dimethyl Phthalate in Purple Soil].

PubMed

Wang, Qiang; Song, Jiao-yan; Zeng, Wei; Wang, Fa

2016-02-15

The typical soil-purple soil in Three Gorges Reservoir was the tested soil, the characteristics of adsorption leaching of dimethyl phthalate (DMP) in contaminated water by the soil, and the influencing factors in the process were conducted using soil column leaching experiment. The results showed that the parabolic equation was the best equation describing adsorption kinetics of DMP by soils. The concentration of DMP in the leaching solution had significant effect on the adsorption amounts of DMP. With the increasing concentration of DMP in the leaching solution, the adsorption capacities of DMP by purple soil increased linearly. The ionic strength and pH in leaching solution had significant effects on adsorption of DMP. On the whole, increasing of the ionic strength restrained the adsorption. The adsorption amounts at pH 5.0-7.0 were more than those under other pH condition. The addition of exogenous organic matter (OM) in purple soil increased the adsorption amount of DMP by purple soil. However, the adsorption amount was less than those with other addition amounts of exogenous OM when the addition of exogenous OM was too high (> or = 30 g x kg(-1)). The addition of surfactant sodium dodecylbenzene sulfonic acid (SDBS) in purple soil increased the adsorption amount of DMP by purple soil. The adsorption amount was maximal when the addition amount of SDBS was 50 mg x kg(-1). However, the adsorption amounts decreased with increasing addition amounts of SDBS although the adsorption amounts were still more than that of the control group, and the adsorption amount was almost equal to that of the control group when the addition amount of SDBS was 800 mg x kg(-1). Continuous leaching time affected the vertical distribution of DMP in the soil column. When the leaching time was shorter, the upper soil column adsorbed more DMP, while the DMP concentrations in upper and lower soil columns became similar with the extension of leaching time.

Protein Adsorption and Subsequent Fibroblasts Adhesion on Hydroxyapatite Nanocrystals

NASA Astrophysics Data System (ADS)

Tagaya, Motohiro; Ikoma, Toshiyuki; Takemura, Taro; Hanagata, Nobutaka; Yoshioka, Tomohiko; Tanaka, Junzo

2011-10-01

Quartz crystal microbalance with dissipation (QCM-D) technique was employed for protein adsorption and subsequent fibroblast adhesion on hydroxyapatite (HAp) nanocrystals. The pre-adsorption of three proteins (albumin (BSA) or fibronectin (Fn) or collagen (Col)) and subsequent adsorption of fetal bovine serum (FBS), and the adhesion of fibroblasts on the surface were in situ monitored, and evaluated with the frequency shift (Δf) and dissipation energy shift (ΔD), and the viscoelastic change as ΔD-Δf plot. The Col adsorption showed larger Δf and ΔD values compared with BSA or Fn adsorption, and the subsequent FBS adsorption depended on the pre-adsorbed proteins. The ΔD-Δf plot of the cell adhesion also showed the different behaviour on the surfaces, indicating the process affected by cell-protein interactions. The confocal laser scanning microscope images of adherent cells showed the different morphology and pseudopod on the surfaces. The cells adhered on the surfaces modified with Fn and Col had the uniaxially expanded shape with fibrous pseudopods, while those modified with BSA had round shape. The different cell-protein interaction would cause the arrangement of extracellular matrix and cytoskeleton changes at the interfaces.

Dopant Adsorption and Incorporation at Irradiated GaN Surfaces

NASA Astrophysics Data System (ADS)

Sun, Qiang; Selloni, Annabella; Myers, Thomas; Doolittle, W. Alan

2006-03-01

Mg and O are two of the common dopants in GaN, but, in spite of extensive investigation, the atomic scale understanding of their adsorption and incorporation is still incomplete. In particular, high-energy electron irradiation, such as occurring during RHEED, has been reported to have an important effect on the incorporation of these impurities, but no study has addressed the detailed mechanisms of this effect yet. Here we use DFT calculations to study the adsorption and incorporation of Mg and O at the Ga- and N-polar GaN surfaces under various Ga, Mg and O coverage conditions as well as in presence of light or electron beam-induced electronic excitation. We find that the adsorption and incorporation of the two impurities have opposite surface polarity dependence: substitutional Mg prefers to incorporate at the GaN(0001) surface, while O prefers to adsorb and incorporate at the N-polar surface. In addition, our results indicate that in presence of light irradiation the tendency of Mg to surface-segregate is reduced. The O adsorption energy on the N-polar surface is also significantly reduced, consistent with the experimental observation of a much smaller concentration of oxygen in the irradiated samples.

Study on Adsorption of Chromium (VI) by Activated Carbon from Cassava Sludge

NASA Astrophysics Data System (ADS)

Yang, Jinhui; Li, Chuanshu; Yang, Bin; Kang, Sijun; Zhang, Zhen

2018-03-01

In this paper, a new type of adsorbent prepared by waste sludge from alcohol production industry was used to adsorb Cr (VI) in activated carbon from cassava sludge. A series of static adsorption experiments were carried out on the initial concentration of solution Cr (VI), pH value of solution, adsorption time and dosage of adsorbent. The results of single factor experiments show that the removal rate of Cr (VI) increases with the initial concentration of Cr(VI), while the adsorption amount is opposite. When the pH value of the solution is low, the adsorption effect of activated carbon is better.The adsorption time should be controlled within 40-60min. When the activated carbon dosage is increased, the removal rate increases but the adsorption capacity decreases.

How soil organic matter composition controls hexachlorobenzene-soil-interactions: adsorption isotherms and quantum chemical modeling.

PubMed

Ahmed, Ashour A; Kühn, Oliver; Aziz, Saadullah G; Hilal, Rifaat H; Leinweber, Peter

2014-04-01

Hazardous persistent organic pollutants (POPs) interact in soil with the soil organic matter (SOM) but this interaction is insufficiently understood at the molecular level. We investigated the adsorption of hexachlorobenzene (HCB) on soil samples with systematically modified SOM. These samples included the original soil, the soil modified by adding a hot water extract (HWE) fraction (soil+3 HWE and soil+6 HWE), and the pyrolyzed soil. The SOM contents increased in the order pyrolyzed soiladsorption. The pyrolyzed soil adsorbed more HCB than the other samples at low initial concentrations, but at higher concentrations the HCB adsorption became weaker than in the samples with HWE addition. This adsorption combined with the differences in the chemical composition between the soil samples suggested that alkylated aromatic, phenol, and lignin monomer compounds contributed most to the HCB adsorption. To obtain a molecular level understanding, a test set has been developed on the basis of elemental analysis which comprises 32 representative soil constituents. The calculated binding energy for HCB with each representative system shows that HCB binds to SOM stronger than to soil minerals. For SOM, HCB binds to alkylated aromatic, phenols, lignin monomers, and hydrophobic aliphatic compounds stronger than to polar aliphatic compounds confirming the above adsorption isotherms. Moreover, quantitative structure-activity relationship (QSAR) of the binding energy with independent physical properties of the test set systems for the first time indicated that the polarizability, the partial charge on the carbon atoms, and the molar volume are the most important properties controlling HCB-SOM interactions. Copyright © 2013 Elsevier B.V. All rights reserved.

Overcoming Rapid Inactivation of Lung Surfactant: Analogies Between Competitive Adsorption and Colloid Stability

PubMed Central

Zasadzinski, Joseph A.; Stenger, Patrick C.; Shieh, Ian; Dhar, Prajnaparamita

2009-01-01

Lung surfactant (LS) is a mixture of lipids and proteins that line the alveolar air-liquid interface, lowering the interfacial tension to levels that make breathing possible. In acute respiratory distress syndrome (ARDS), inactivation of LS is believed to play an important role in the development and severity of the disease. This review examines the competitive adsorption of LS and surface-active contaminants, such as serum proteins, present in the alveolar fluids of ARDS patients, and how this competitive adsorption can cause normal amounts of otherwise normal LS to be ineffective in lowering the interfacial tension. LS and serum proteins compete for the air-water interface when both are present in solution either in the alveolar fluids or in a Langmuir trough. Equilibrium favors LS as it has the lower equilibrium surface pressure, but the smaller proteins are kinetically favored over multi-micron LS bilayer aggregates by faster diffusion. If albumin reaches the interface, it creates an energy barrier to subsequent LS adsorption that slows or prevents the adsorption of the necessary amounts of LS required to lower surface tension. This process can be understood in terms of classic colloid stability theory in which an energy barrier to diffusion stabilizes colloidal suspensions against aggregation. This analogy provides qualitative and quantitative predictions regarding the origin of surfactant inactivation. An important corollary is that any additive that promotes colloid coagulation, such as increased electrolyte concentration, multivalent ions, hydrophilic non-adsorbing polymers such as PEG, dextran, etc. or polyelectrolytes such as chitosan, added to LS, also promotes LS adsorption in the presence of serum proteins and helps reverse surfactant inactivation. The theory provides quantitative tools to determine the optimal concentration of these additives and suggests that multiple additives may have a synergistic effect. A variety of physical and chemical

Adsorption and co-adsorption of graphene oxide and Ni(II) on iron oxides: A spectroscopic and microscopic investigation.

PubMed

Sheng, Guodong; Huang, Chengcai; Chen, Guohe; Sheng, Jiang; Ren, Xuemei; Hu, Baowei; Ma, Jingyuan; Wang, Xiangke; Huang, Yuying; Alsaedi, Ahmed; Hayat, Tasawar

2018-02-01

Graphene oxide (GO) may strongly interact with toxic metal ions and mineral particles upon release into the soil environment. We evaluated the mutual effects between GO and Ni (Ni(II)) with regard to their adsorption and co-adsorption on two minerals (goethite and hematite) in aqueous phase. Results indicated that GO and Ni could mutually facilitate the adsorption of each other on both goethite and hematite over a wide pH range. Addition of Ni promoted GO co-adsorption mainly due to the increased positive charge of minerals and cation-π interactions, while the presence of GO enhanced Ni co-adsorption predominantly due to neutralization of positive charge and strong interaction with oxygen-containing functional groups on adsorbed GO. Increasing adsorption of GO and Ni on minerals as they coexist may thus reduce their mobility in soil. Extended X-ray absorption fine structure (EXAFS) spectroscopy data revealed that GO altered the microstructure of Ni on minerals, i.e., Ni formed edge-sharing surface species (at R Ni-Fe ∼3.2 Å) without GO, while a GO-bridging ternary surface complexes (at R Ni-C ∼2.49 Å and R Ni-Fe ∼4.23 Å) was formed with GO. These findings improved the understanding of potential fate and toxicity of GO as well as the partitioning processes of Ni ions in aquatic and soil environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorption of Pd(II) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion exchange resin Diaion WA21J.

PubMed

Shen, Shaobo; Pan, Tonglin; Liu, Xinqiang; Yuan, Lei; Zhang, Yongjian; Wang, Jinchao; Guo, Zhanchen

2010-05-01

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Pd(II) contained in the chloride solution obtained from the dry chlorination process, thermodynamic and kinetics studies for adsorption of Pd(II) complexes from the chloride solutions on anionic exchange resin Diaion WA21J were carried out. It was found that Pd, Pt, Rh, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The isothermal adsorption of Pd(II) was found to fit Freundlich, Langmuir and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The adsorption of Pd(II) on the resin was favorable according to the values of 1/n and R(L) from Freundlich and Langmuir adsorption isotherms, respectively. The maximum monolayer adsorption capacities Q(max) based on Langmuir adsorption isotherms were 5.70, 4.84 and 4.05 mg/g and the corresponding value X(m) based on Dubinin-Kaganer-Radushkevich were 5.55, 4.69 and 4.01 mg/g at temperatures 18 degrees C, 28 degrees C and 40 degrees C, respectively. The apparent adsorption energies (E(ad)) based on Dubinin-Kaganer-Radushkevich isotherm were -15.43, -16.22 and -23.57 kJ/mol for the temperatures 18 degrees C, 28 degrees C and 40 degrees C, respectively. Chemical adsorption was a main mechanism involved in the adsorption process. Pd(II) adsorption on the resin could be accelerated by increasing the adsorption temperature. The adsorption of Pd(II) from the chloride solution on the resin underwent pseudo-first order kinetic process and the apparent adsorption activation energy E(a) was 15.0 kJ/mol. The intra-particle diffusion was a main rate controlling step in the Pd(II) adsorption process under the adsorption conditions. Copyright 2010 Elsevier Inc. All rights reserved.

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.

Adsorption of Cd2+ ions on plant mediated SnO2 nanoparticles

NASA Astrophysics Data System (ADS)

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

2016-10-01

Plant mediated SnO2 nanoparticles were synthesized by using SnCl4.5H2O as a precursor material. The nanoparticles were then characterized for BET surface area measurements, energy dispersive x-rays (EDX), scanning electron microscopy (SEM), UV-vis diffuse reflectance (DRS) spectra and x-rays diffraction (XRD) analysis. The successful synthesis of SnO2 nanoparticles was confirmed by EDX analysis. The particle sizes were in the range 19-27 nm whereas the crystallite size computed from XRD measurement was found to be 19.9 nm. Batch adsorption technique was employed for the removal of Cd2+ ions from aqueous solution. The sorption studies of Cd2+ ions were performed at pHs 4 and 6. The equilibrium concentration of Cd2+ ions was determined by atomic absorption spectrometer (flame mode). The uptake of Cd2+ ions was affected by initial concentration, pH and temperature of the electrolytic solution. It was observed that the adsorption of Cd2+ ions enhanced with increase in the initial concentration of Cd2+ ions whereas a decrease in the percent adsorption was detected. From the thermodynamic parameters, the adsorption process was found spontaneous and endothermic in nature. The n values confirmed 2:1 exchange mechanism between surface protons and Cd2+ ions.

Understanding the Adsorption Interface of Polyelectrolyte Coating on Redox Active Nanoparticles Using Soft Particle Electrokinetics and Its Biological Activity

PubMed Central

2015-01-01

The application of cerium oxide nanoparticles (CNPs) for therapeutic purposes requires a stable dispersion of nanoparticles in a biological environment. The objective of this study is to tailor the properties of polyelectrolyte coated CNPs as a function of molecular weight to achieve a stable and catalytic active dispersion. The coating of CNPs with polyacrylic acid (PAA) has increased the dispersion stability of CNPs and enhanced the catalytic ability. The stability of PAA coating was analyzed using the change in the Gibbs free energy computed by the Langmuir adsorption model. The adsorption isotherms were determined using soft particle electrokinetics which overcomes the challenges presented by other techniques. The change in Gibbs free energy was highest for CNPs coated with PAA of 250 kg/mol indicating the most stable coating. The change in free energy for PAA of 100 kg/mol coated CNPs was 85% lower than the PAA of 250 kg/mol coated CNPs. This significant difference is caused by the strong adsorption of PAA of 100 kg/mol on CNPs. Catalytic activity of PAA-CNPs is assessed by the catalase enzymatic mimetic activity of nanoparticles. The catalase activity was higher for PAA coated CNPs as compared to bare CNPs which indicated preferential adsorption of hydrogen peroxide induced by coating. This indicates that the catalase activity is also affected by the structure of the coating layer. PMID:24673655

Adsorption, folding, and packing of an amphiphilic peptide at the air/water interface.

PubMed

Engin, Ozge; Sayar, Mehmet

2012-02-23

Peptide oligomers play an essential role as model compounds for identifying key motifs in protein structure formation and protein aggregation. Here, we present our results, based on extensive molecular dynamics simulations, on adsorption, folding, and packing within a surface monolayer of an amphiphilic peptide at the air/water interface. Experimental results suggest that these molecules spontaneously form ordered monolayers at the interface, adopting a β-hairpin-like structure within the surface layer. Our results reveal that the β-hairpin structure can be observed both in bulk and at the air/water interface. However, the presence of an interface leads to ideal partitioning of the hydrophobic and hydrophilic residues, and therefore reduces the conformational space for the molecule and increases the stability of the hairpin structure. We obtained the adsorption free energy of a single β-hairpin at the air/water interface, and analyzed the enthalpic and entropic contributions. The adsorption process is favored by two main factors: (1) Free-energy reduction due to desolvation of the hydrophobic side chains of the peptide and release of the water molecules which form a cage around these hydrophobic groups in bulk water. (2) Reduction of the total air/water contact area at the interface upon adsorption of the peptide amphiphile. By performing mutations on the original molecule, we demonstrated the relative role of key design features of the peptide. Finally, by analyzing the potential of mean force among two peptides at the interface, we investigated possible packing mechanisms for these molecules within the surface monolayer. © 2012 American Chemical Society

Adsorption of HMF from water/DMSO solutions onto hydrophobic zeolites: experiment and simulation.

PubMed

Xiong, Ruichang; León, Marta; Nikolakis, Vladimiros; Sandler, Stanley I; Vlachos, Dionisios G

2014-01-01

The adsorption of 5-hydroxymethylfurfural (HMF), DMSO, and water from binary and ternary mixtures in hydrophobic silicalite-1 and dealuminated Y (DAY) zeolites at ambient conditions was studied by experiments and molecular modeling. HMF and DMSO adsorption isotherms were measured and compared to those calculated using a combination of grand canonical Monte Carlo and expanded ensemble (GCMC-EE) simulations. A method based on GCMC-EE simulations for dilute solutions combined with the Redlich-Kister (RK) expansion (GCMC-EE-RK) is introduced to calculate the isotherms over a wide range of concentrations. The simulations, using literature force fields, are in reasonable agreement with experimental data. In HMF/water binary mixtures, large-pore hydrophobic zeolites are much more effective for HMF adsorption but less selective because large pores allow water adsorption because of H2 O-HMF attraction. In ternary HMF/DMSO/water mixtures, HMF loading decreases with increasing DMSO fraction, rendering the separation of HMF from water/DMSO mixtures by adsorption difficult. The ratio of the energetic interaction in the zeolite to the solvation free energy is a key factor in controlling separation from liquid mixtures. Overall, our findings could have an impact on the separation and catalytic conversion of HMF and the rational design of nanoporous adsorbents for liquid-phase separations in biomass processing. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of Heavy Metal Ions from Aqueous Solutions by Bentonite Nanocomposites.

PubMed

Ma, Jing; Su, Guojun; Zhang, Xueping; Huang, Wen

2016-08-01

A series of bentonite nanocomposites have been synthesized by modifying bentonite with hexadecyltrimethylammonium bromide (CTMAB) and the common complexing agents, complexone (ethylene diamine tetraacetic acid, EDTA) or mercaptocomplexant (2-Mercaptobenzothiazole, MBT). These adsorbents are used to remove heavy metal ions (Cu(2+), Zn(2+), Mn(2+),Co(2+)). The Bent-CTMAB-MBT adsorbed metal ions are higher than Bent-CTMAB-EDTA under the same ion concentration in AAS. Compared with the single ion system, the adsorption of the mixed ion system of Cu(2+), Zn(2+), Mn(2+), Co(2+) had decreased differently. In the mixed system, the adsorption of Mn(2+) is significantly lower, but the adsorption of Cu(2+) was highest. The adsorption sequence of these four metal ions was Cu(2+) > Zn(2+) > Co(2+) > Mn(2+), and the selective adsorption was closely related to the hydration energy of heavy metal ions. We could remove more metal ions in different stages with the adsorption sequence.

Adsorption de gaz sur les materiaux microporeux modelisation, thermodynamique et applications

NASA Astrophysics Data System (ADS)

Richard, Marc-Andre

2009-12-01

Nos travaux sur l'adsorption de gaz dans les materiaux microporeux s'inscrivent dans le cadre des recherches visant a augmenter l'efficacite du stockage de l'hydrogene a bord des vehicules. Notre objectif etait d'etudier la possibilite d'utiliser l'adsorption afin d'ameliorer l'efficacite de la liquefaction de l'hydrogene des systemes a petite echelle. Nous avons egalement evalue les performances d'un systeme de stockage cryogenique de l'hydrogene base sur la physisorption. Comme nous avons affaire a des plages de temperatures particulierement etendues et a de hautes pressions dans la region supercritique du gaz, nous avons du commencer par travailler sur la modelisation et la thermodynamique de l'adsorption. La representation de la quantite de gaz adsorbee en fonction de la temperature et de la pression par un modele semi-empirique est un outil utile pour determiner la masse de gaz adsorbee dans un systeme mais egalement pour calculer les effets thermiques lies a l'adsorption. Nous avons adapte le modele Dubinin-Astakhov (D-A) pour modeliser des isothermes d'adsorption d'hydrogene, d'azote et de methane sur du charbon actif a haute pression et sur une grande plage de temperatures supercritiques en considerant un volume d'adsorption invariant. Avec cinq parametres de regression (incluant le volume d'adsorption Va), le modele que nous avons developpe permet de tres bien representer des isothermes experimentales d'adsorption d'hydrogene (de 30 a 293 K, jusqu'a 6 MPa), d'azote (de 93 a 298 K, jusqu'a 6 MPa) et de methane (de 243 a 333 K, jusqu'a 9 MPa) sur le charbon actif. Nous avons calcule l'energie interne de la phase adsorbee a partir du modele en nous servant de la thermodynamique des solutions sans negliger le volume d'adsorption. Par la suite, nous avons presente les equations de conservation de la niasse et de l'energie pour un systeme d'adsorption et valide notre demarche en comparant des simulations et des tests d'adsorption et de desorption. En plus de l'energie

Incorporating water-release and lateral protein interactions in modeling equilibrium adsorption for ion-exchange chromatography.

PubMed

Thrash, Marvin E; Pinto, Neville G

2006-09-08

The equilibrium adsorption of two albumin proteins on a commercial ion exchanger has been studied using a colloidal model. The model accounts for electrostatic and van der Waals forces between proteins and the ion exchanger surface, the energy of interaction between adsorbed proteins, and the contribution of entropy from water-release accompanying protein adsorption. Protein-surface interactions were calculated using methods previously reported in the literature. Lateral interactions between adsorbed proteins were experimentally measured with microcalorimetry. Water-release was estimated by applying the preferential interaction approach to chromatographic retention data. The adsorption of ovalbumin and bovine serum albumin on an anion exchanger at solution pH>pI of protein was measured. The experimental isotherms have been modeled from the linear region to saturation, and the influence of three modulating alkali chlorides on capacity has been evaluated. The heat of adsorption is endothermic for all cases studied, despite the fact that the net charge on the protein is opposite that of the adsorbing surface. Strong repulsive forces between adsorbed proteins underlie the endothermic heat of adsorption, and these forces intensify with protein loading. It was found that the driving force for adsorption is the entropy increase due to the release of water from the protein and adsorbent surfaces. It is shown that the colloidal model predicts protein adsorption capacity in both the linear and non-linear isotherm regions, and can account for the effects of modulating salt.

Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

PubMed Central

2012-01-01

The rapid increase in the use of engineered nanoparticles [ENPs] has resulted in an increasing concern over the potential impacts of ENPs on the environmental and human health. ENPs tend to adsorb a large variety of toxic chemicals when they are emitted into the environment, which may enhance the toxicity of ENPs and/or adsorbed chemicals. The study was aimed to investigate the adsorption and desorption behaviors of arsenic on ceria NPs in aqueous solution using batch technique. Results show that the adsorption behavior of arsenic on ceria NPs was strongly dependent on pH and independent of ionic strength, indicating that the electrostatic effect on the adsorption of these elements was relatively not important compared to surface chemical reactions. The adsorption isotherms fitted very well to both the Langmuir and Freundlich models. The thermodynamic parameters (ΔH0, ΔS0, and ΔG0) for the adsorption of arsenic were determined at three different temperatures of 283, 303, and 323 K. The adsorption reaction was endothermic, and the process of adsorption was favored at high temperature. The desorption data showed that desorption hysteresis occurred at the initial concentration studied. High adsorption capacity of arsenic on ceria NPs suggests that the synergistic effects of ceria NPs and arsenic on the environmental systems may exist when they are released into the environment. PMID:22269298

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.

Computational screening of biomolecular adsorption and self-assembly on nanoscale surfaces.

PubMed

Heinz, Hendrik

2010-05-01

The quantification of binding properties of ions, surfactants, biopolymers, and other macromolecules to nanometer-scale surfaces is often difficult experimentally and a recurring challenge in molecular simulation. A simple and computationally efficient method is introduced to compute quantitatively the energy of adsorption of solute molecules on a given surface. Highly accurate summation of Coulomb energies as well as precise control of temperature and pressure is required to extract the small energy differences in complex environments characterized by a large total energy. The method involves the simulation of four systems, the surface-solute-solvent system, the solute-solvent system, the solvent system, and the surface-solvent system under consideration of equal molecular volumes of each component under NVT conditions using standard molecular dynamics or Monte Carlo algorithms. Particularly in chemically detailed systems including thousands of explicit solvent molecules and specific concentrations of ions and organic solutes, the method takes into account the effect of complex nonbond interactions and rotational isomeric states on the adsorption behavior on surfaces. As a numerical example, the adsorption of a dodecapeptide on the Au {111} and mica {001} surfaces is described in aqueous solution. Copyright 2009 Wiley Periodicals, Inc.

Linear free energy relationships for the adsorption of volatile organic compounds onto multiwalled carbon nanotubes at different relative humidities: comparison with organoclays and activated carbon.

PubMed

Li, Mei-Syue; Wang, Reuben; Fu Kuo, Dave Ta; Shih, Yang-Hsin

2017-03-22

Accurate prediction of the sorption coefficients of volatile organic compounds (VOCs) on carbon nanotubes (CNTs) is of major importance for developing an effective VOC removal process and risk assessment of released nanomaterial-carrying contaminants. The linear free energy relationship (LFER) approach was applied to investigate the adsorption mechanisms of VOCs on multiwalled CNTs (MWCNTs). The gas-solid partition coefficients (log K d ) of 17 VOCs were determined at 0%, 55%, and 90% relative humidity (RH). The cavity/dispersion interaction is generally the most influential adsorption mechanism for all RH cases. The hydrogen-accepting interactions declined but with constant hydrogen-donating interactions during the increase of RH, suggesting that the acidity of VOC was important in forming sorptive interaction with the MWCNT surface. Moreover, the comparison of log K d of VOCs on MWCNTs and other sorbents revealed that the sorption performance of MWCNTs is much more stable over a wider range of RHs due to better site availability and site quality. Furthermore, for all 6 adsorbents in all RHs, the positive contribution of hydrogen bonding ability was found as compared to the negative one found for sorbents completely in water, indicating that the hydrogen-bond donor and acceptor on the sorbent surface contribute to the sorption in the gas phase. In conclusion, the LFER-derived coefficients can be useful in predicting the performance of VOC adsorption on adsorbents and in facilitating the design of efficient VOC removal systems.

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

Thermodynamic properties of adsorption and micellization of n-oktyl-β-D-glucopiranoside.

PubMed

Mańko, Diana; Zdziennicka, Anna; Jańczuk, Bronisław

2014-02-01

Measurements of the surface tension, density and viscosity of aqueous solutions of n-oktyl-β-D-glucopiranoside (OGP) were made at 293 K. From the obtained results the Gibbs surface excess concentration of OGP at the water-air interface and its critical micelle concentration were determined. The Gibbs surface excess concentration of OGP used in the Gu and Zhu isotherm equation allowed us to determine the Gibbs standard free energy of OGP adsorption at the water-air interface. The Gibbs standard free energy of OGP adsorption was also determined on the basis of the Langmuir, Szyszkowski, Gamboa and Olea equations as well the surface tension of "hydrophobic" part of OGP and "hydrophobic" part-water interface tension. It appeared that there is an agreement between the values of Gibbs standard free energy of OGP adsorption at the water-air interface determined by using all the above mentioned methods. It also proved that standard free energy of OGP micellization determined from CMC is consistent with that obtained on the basis of the free energy of the interactions between the "hydrophobic" part of the OPG through the water phase. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Adsorption of Bromine on Gold Nanoclusters

NASA Astrophysics Data System (ADS)

Salvo, Christopher; Keagy, Josiah; Yarmoff, Jory

Small metal nanoclusters are extremely effective as catalysts, with rates that rival those of enzymes in biological systems. The first step in a catalytic reaction is the adsorption of a precursor molecule. The neutralization of alkali projectiles during low energy ion scattering (LEIS), which is acutely sensitive to the local electrostatic potential a few Å's above the surface, is used here to probe Au nanoclusters grown on SiO2 as they are reacted with Br2. Previous work had demonstrated very efficient neutralization in scattering from small catalytically active Au clusters, which was interpreted as an indication that the bare clusters are negatively charged. X-ray photoelectron spectroscopy and LEIS show little or no Br signal after exposing SiO2 and Au foil to Br2, suggesting that adsorption does not occur because the Br-Br bond does not break. Dissociative adsorption occurs rapidly, however, when small Au nanoclusters are reacted with Br2. 1.5 keV Na+ ions scattered from the Au clusters show a decrease in the neutralization probability as Br is reacted, indicating that adsorption results in charge being transferred from the cluster to the Br adatom. This material is based upon work supported by the National Science Foundation under CHE - 1611563.

Effective adsorption of phosphate from wastewaters by big composite pellets made of reduced steel slag and iron ore concentrate.

PubMed

Wang, Hongjuan; Shen, Shaobo; Liu, Longhui; Ji, Yilong; Wang, Fuming

2015-01-01

In order to remove phosphate from wastewater, a large plastic adsorption column filled with big phosphate-adsorbing pellets with diameters of 10 mm, heated by electromagnetic induction coils, was conceived. It was found that the prepared big pellets, which were made of reduced steel slag and iron ore concentrate, contain magnetic Fe and Fe3O4. The thermodynamics and kinetics of adsorption of phosphate from synthetic wastewaters on the pellets were studied in this work. The phosphate adsorption on the pellets followed three models of Freundlich, Langmuir and Dubinin-Kaganer-Radushkevick. The maximum phosphate adsorption capacity Qmax of the pellets were 2.46, 2.74 and 2.77 mg/g for the three temperatures of 20°C, 30°C and 40°C, respectively, based on the Langmuir model. The apparent adsorption energies were -12.9 kJ/mol for the three temperatures. It implied that ion exchange was the main mechanism involved in the adsorption processes. The adsorbed phosphate existed on the pellet surface mainly in the form of Fe3(PO4)2. A reduction pre-treatment of the pellet precursor with H2 greatly enhanced pellet adsorption for phosphate. The adsorption kinetics is better represented by a pseudo-first-order model. The adsorbed phosphate amounts were similar for both real and synthetic wastewaters under similar adsorption conditions. The percentage of adsorbed phosphate for a real wastewater increased with increasing pellet concentration and reached 99.2% at a pellet concentration of 64 (g/L). Some specific phosphate adsorption mechanisms for the pellets were revealed and the pellets showed the potential to efficiently adsorb phosphate from a huge amount of real wastewaters in an industrial scale.

Adsorption of methanol, ethanol and water on well-characterized PtSn surface alloys

NASA Astrophysics Data System (ADS)

Panja, Chameli; Saliba, Najat; Koel, Bruce E.

1998-01-01

Adsorption and desorption of methanol (CH 3OH), ethanol (C 2H 5OH) and water on Pt(111) and two, ordered, PtSn alloys has been studied primarily using temperature-programmed desorption (TPD) mass spectroscopy. The two alloys studied were the {p(2 × 2) Sn}/{Pt(111) } and (√3 × √3) R30° {Sn}/{Pt(111) } surface alloys prepared by vapor deposition of Sn on Pt(111), with θSn = 0.25 and 0.33, respectively. All three molecules are weakly bonded and reversibly adsorbed under UHV conditions on all three surfaces, molecularly desorbing during TPD without any decomposition. The two PtSn surface alloys were found to chemisorb both methanol and ethanol slightly more weakly than on the Pt(111) surface. The desorption activation energies measured by TPD, and hence the adsorption energies, of both methanol and ethanol progressively decrease as the surface concentration of Sn increases, compared with Pt(111). The decreased binding energy leads one to expect a lower reactivity for these alcohols on the two alloys. The sticking coefficients and the monolayer coverages of these alcohols on the two alloys were identical to that on Pt(111) at 100 K, independent of the amount of Sn present in the surface layer. Alloying Sn in Pt(111) also slightly weakens the adsorption energy of water. Water clusters are formed even at low coverages on all three surfaces, eventually forming a water bilayer prior to the formation of a condensed ice phase. These results are relevant to a molecular-level explanation for the reactivity of Sn-promoted Pt surfaces that have been used in the electro-oxidation of simple organic molecules.

Electronic theoretical study of the influences of O adsorption on the electronic structure and optical properties of graphene

NASA Astrophysics Data System (ADS)

Shuang, Zhou; Guili, Liu; Dazhi, Fan

2017-02-01

The electronic structure and optical properties of adsorbing O atoms on graphene with different O coverage are researched using the density functional theory based upon the first-principle study to obtain further insight into properties of graphene. The adsorption energies, band structures, the density of states, light absorption coefficient and reflectivity of each system are calculated theoretically after optimizing structures of each system with different O coverage. Our calculations show that adsorption of O atoms on graphene increases the bond length of C-C which adjacent to the O atoms. When the O coverage is 9.4%, the adsorption energy (3.91 eV) is the maximum, which only increases about 1.6% higher than that of 3.1% O coverage. We find that adsorbed O atoms on pristine graphene opens up indirect gap of about 0.493-0.952 eV. Adsorbing O atoms make pristine graphene from metal into a semiconductor. When the O coverage is 9.4%, the band gap (0.952 eV) is the maximum. Comparing with pristine graphene, we find the density of states at Fermi level of O atoms adsorbing on graphene with different coverage are significantly increased. We also find that light absorption coefficient and reflectivity peaks are significantly reduced, and the larger the coverage, the smaller the absorption coefficient and reflectivity peaks are. And the blue shift phenomenon appears.

Impact of the interaction with the positive charge in adsorption of benzene and other organic compounds from aqueous solutions on carbons

NASA Astrophysics Data System (ADS)

Terzyk, Artur P.; Ćwiertnia, Magdalena S.; Wiśniewski, Marek; Gauden, Piotr A.; Rychlicki, Gerhard; Szymański, Grzegorz S.

2007-02-01

We present the results of benzene adsorption at the acidic pH level determined on the series of chemically modified activated carbons and at three temperatures. The influence of carbon surface chemical composition on benzene adsorption is discussed. It is shown that the decrease in the pH level from 7 up to 1.5 increases benzene adsorption and the only exception is carbon modified with gaseous ammonia. Basing on the results of current work and those published previously (for phenol, paracetamol, acetanilide and aniline) and using the results of quantum chemistry calculations (DFT, Gaussian 98) we show, that the value of the energy of interaction with unit positive charge is crucial during the analysis of the influence of pH level on adsorption. Obtained results allow to predict the changes in adsorption of aromatics on carbons with the decrease in the pH level.

Mechanism of tyramine adsorption on Ca-montmorillonite.

PubMed

Chang, Po-Hsiang; Jiang, Wei-Teh; Li, Zhaohui

2018-06-10

Tyramine (TY) adsorption on a Ca-montmorillonite (SAz-2) was investigated with batch experiments and complementary analyses utilizing ultra-high performance liquid chromatography, ion chromatography, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetry (TG). The adsorption reached equilibrium in 8 h, complying with the pseudo-second-order rate equation, and came to an adsorption capacity of 682 mmol kg -1 at pH 6-8.1, utilizing the Langmuir isotherm model. The adsorption of TY and desorption of exchangeable cations exhibited a linear relationship with a slope of 0.9, implying that the adsorption was largely influenced by a cation exchange mechanism. The effective adsorption was further verified by the characteristic TY bands in the FTIR spectra and the signals of mass loss due to TY decomposition in the TG measurements of the clay after adsorption experiments. Intercalation of hydrated TY into the clay interlayer was confirmed by XRD and TG analyses of the heated samples loaded with TY. The adsorption reached only 0.57 cation exchange capacity of the clay which was probably limited by the low charge density of TY as compared to the negative charge density of the clay surface and by the steric effects arising from the hydration of TY that increased its molecular size. Adsorption of TY on montmorillonite can make TY more resistant to thermal decomposition and possibly better preserved in aquatic and soil environments. Copyright © 2018 Elsevier B.V. All rights reserved.

Surface Curvature Relation to Protein Adsorption for Carbon-based Nanomaterials

NASA Astrophysics Data System (ADS)

Gu, Zonglin; Yang, Zaixing; Chong, Yu; Ge, Cuicui; Weber, Jeffrey K.; Bell, David R.; Zhou, Ruhong

2015-06-01

The adsorption of proteins onto carbon-based nanomaterials (CBNs) is dictated by hydrophobic and π-π interactions between aliphatic and aromatic residues and the conjugated CBN surface. Accordingly, protein adsorption is highly sensitive to topological constraints imposed by CBN surface structure; in particular, adsorption capacity is thought to increase as the incident surface curvature decreases. In this work, we couple Molecular Dynamics (MD) simulations with fluorescence spectroscopy experiments to characterize this curvature dependence in detail for the model protein bovine serum albumin (BSA). By studying BSA adsorption onto carbon nanotubes of increasing radius (featuring descending local curvatures) and a flat graphene sheet, we confirm that adsorption capacity is indeed enhanced on flatter surfaces. Naïve fluorescence experiments featuring multi-walled carbon nanotubes (MWCNTs), however, conform to an opposing trend. To reconcile these observations, we conduct additional MD simulations with MWCNTs that match those prepared in experiments; such simulations indicate that increased mass to surface area ratios in multi-walled systems explain the observed discrepancies. In reduction, our work substantiates the inverse relationship between protein adsorption capacity and surface curvature and further demonstrates the need for subtle consideration in experimental and simulation design.

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.

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.

Enantiospecific adsorption of propranolol enantiomers on naturally chiral copper surface: A molecular dynamics simulation investigation

NASA Astrophysics Data System (ADS)

Sedghamiz, Tahereh; Bahrami, Maryam; Ghatee, Mohammad Hadi

2017-04-01

Adsorption of propranolol enantiomers on naturally chiral copper (Cu(3,1,17)S) and achiral copper (Cu(100)) surfaces were studied by molecular dynamics simulation to unravel the features of adsorbate-adsorbent enantioselectivity. Adsorption of S- and R-propranolol on Cu(3,1,17)S terraces (with 100 plane) leads mainly to endo- and exo-conformers, respectively. Simulated pair correlation function (g(r)) and mean square displacement (MSD) were analyzed to identify adsorption sites of enantiomers on Cu(3,1,17)S substrate surface, and their simulated binding energies were used to access the adsorption strength. According to (g(r)), R-propranolol adsorbs via naphtyl group while S-propranolol mainly adsorbs through chain group. R-enantiomer binds more tightly to the chiral substrate surface than S-enantiomer as indicated by a higher simulated binding energy by 2.74 kJ mol-1 per molecule. The difference in binding energies of propranolol enantiomers on naturally chiral Cu(3,1,17)S is almost six times larger than on the achiral Cu(100) surface, which substantiates the appreciably strong specific enantioselective adsorption on the former surface.

Mechanisms of chain adsorption on porous substrates and critical conditions of polymer chromatography.

PubMed

Cimino, Richard T; Rasmussen, Christopher J; Brun, Yefim; Neimark, Alexander V

2016-11-01

Polymer adsorption is a ubiquitous phenomenon with numerous technological and healthcare applications. The mechanisms of polymer adsorption on surfaces and in pores are complex owing to a competition between various entropic and enthalpic factors. Due to adsorption of monomers to the surface, the chain gains in enthalpy yet loses in entropy because of confining effects. This competition leads to the existence of critical conditions of adsorption when enthalpy gain and entropy loss are in balance. The critical conditions are controlled by the confining geometry and effective adsorption energy, which depends on the solvent composition and temperature. This phenomenon has important implications in polymer chromatography, since the retention at the critical point of adsorption (CPA) is chain length independent. However, the mechanisms of polymer adsorption in pores are poorly understood and there is an ongoing discussion in the theoretical literature about the very existence of CPA for polymer adsorption on porous substrates. In this work, we examine the mechanisms of chain adsorption on a model porous substrate using Monte Carlo (MC) simulations. We distinguish three adsorption mechanisms depending on the chain location: on external surface, completely confined in pores, and also partially confined in pores in so-called "flower" conformations. The free energies of different conformations of adsorbed chains are calculated by the incremental gauge cell MC method that allows one to determine the partition coefficient as a function of the adsorption potential, pore size, and chain length. We confirm the existence of the CPA for chain length independent separation on porous substrates, which is explained by the dominant contributions of the chain adsorption at the external surface, in particular in flower conformations. Moreover, we show that the critical conditions for porous and nonporous substrates are identical and depend only on the surface chemistry. The theoretical

A Novel Nanocomposite as an Efficient Adsorbent for the Rapid Adsorption of Ni(II) from Aqueous Solution

PubMed Central

Wang, Ximing; Chen, Zhangjing

2017-01-01

A sulfhydryl-lignocellulose/montmorillonite (SLT) nanocomposite was prepared using a chemical intercalation reaction. The SLT nanocomposite was characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Transmission Electron Microscopy (TEM), the results demonstrated that an intercalated-exfoliated nanostructure was formed in the SLT nanocomposite. Batch experiments were conducted to optimize parameters such as SLT nanocomposite dosage, the initial concentration of Ni(II), solution pH, temperature, and time. The results indicated that the attractive adsorption capacity reached 1134.08 mg/g with 0.05 g of SLT at an initial concentration of Ni(II) of 700 mg/L, solution pH of 5.5, adsorption temperature of 50 °C, and adsorption time of 40 min, meanwhile, the Ni(II) adsorption capacity significantly decreased with the increase in ionic strength. The pseudo-second order kinetic model could describe the whole adsorption process well, and the isotherm adsorption equilibrium conformed to the Freundlich model. The adsorption mechanism of SLT was also discussed by means of FTIR and Energy-Dispersive X-Ray (EDX). Dramatically, the introduction of sulfhydryl achieves the increased activated functional groups content of SLT nanocomposite, leading to remarkably higher adsorption amount on Ni(II). The desorption capacity of SLT was dependent on parameters such as HNO3 concentration, desorption temperature, and ultrasonic desorption time. The satisfactory desorption capacity and desorption efficiency of 458.21 mg/g and 40.40% were obtained at an HNO3 concentration, desorption temperature, and ultrasonic desorption time of 0.4 mol/L, 40 °C, and 30 min, respectively. The regeneration studies showed that the adsorption capacity of SLT was consistent for four cycles without any appreciable loss and confirmed that the SLT was reusable. Owing to such outstanding features, the novel SLT nanocomposite proved the

Adsorption of Organic Molecules to van der Waals Materials: Comparison of Fluorographene and Fluorographite with Graphene and Graphite

PubMed Central

2017-01-01

Understanding strength and nature of noncovalent binding to surfaces imposes significant challenge both for computations and experiments. We explored the adsorption of five small nonpolar organic molecules (acetone, acetonitrile, dichloromethane, ethanol, ethyl acetate) to fluorographene and fluorographite using inverse gas chromatography and theoretical calculations, providing new insights into the strength and nature of adsorption of small organic molecules on these surfaces. The measured adsorption enthalpies on fluorographite range from −7 to −13 kcal/mol and are by 1–2 kcal/mol lower than those measured on graphene/graphite, which indicates higher affinity of organic adsorbates to fluorographene than to graphene. The dispersion-corrected functionals performed well, and the nonlocal vdW DFT functionals (particularly optB86b-vdW) achieved the best agreement with the experimental data. Computations show that the adsorption enthalpies are controlled by the interaction energy, which is dominated by London dispersion forces (∼70%). The calculations also show that bonding to structural features, like edges and steps, as well as defects does not significantly increase the adsorption enthalpies, which explains a low sensitivity of measured adsorption enthalpies to coverage. The adopted Langmuir model for fitting experimental data enabled determination of adsorption entropies. The adsorption on the fluorographene/fluorographite surface resulted in an entropy loss equal to approximately 40% of the gas phase entropy. PMID:28145699

Theoretical study of ozone adsorption on the surface of Fe, Co and Ni doped boron nitride nanosheets

NASA Astrophysics Data System (ADS)

Farmanzadeh, Davood; Askari Ardehjani, Nastaran

2018-06-01

In this work, the adsorption of ozone molecule on Fe, Co and Ni doped boron nitride nanosheets (BNNSs) were investigated using density functional theory. The most stable adsorption configurations, charge transfer and adsorption energy of ozone molecule on pure and doped BNNSs are calculated. It is shown that ozone molecule has no remarkable interaction with pure boron nitride nanosheet, it tends to be chemisorbed on Fe, Co and Ni doped BNNSs with adsorption energy in the range of -249.4 to -686.1 kJ/mol. In all configurations, the adsorption of ozone molecule generates a semiconductor by reducing Eg in the pure and Fe, Co and Ni doped boron nitride nanosheet. It shows that the conductance of BNNSs change over the adsorption of ozone molecule. The obtained results in this study can be used in developing BN-based sheets for ozone molecule removal.

Albumin (BSA) adsorption onto graphite stepped surfaces

NASA Astrophysics Data System (ADS)

Rubio-Pereda, Pamela; Vilhena, J. G.; Takeuchi, Noboru; Serena, Pedro A.; Pérez, Rubén

2017-06-01

Nanomaterials are good candidates for the design of novel components with biomedical applications. For example, nano-patterned substrates may be used to immobilize protein molecules in order to integrate them in biosensing units. Here, we perform long MD simulations (up to 200 ns) using an explicit solvent and physiological ion concentrations to characterize the adsorption of bovine serum albumin (BSA) onto a nano-patterned graphite substrate. We have studied the effect of the orientation and step size on the protein adsorption and final conformation. Our results show that the protein is stable, with small changes in the protein secondary structure that are confined to the contact area and reveal the influence of nano-structuring on the spontaneous adsorption, protein-surface binding energies, and protein mobility. Although van der Waals (vdW) interactions play a dominant role, our simulations reveal the important role played by the hydrophobic lipid-binding sites of the BSA molecule in the adsorption process. The complex structure of these sites, that incorporate residues with different hydrophobic character, and their flexibility are crucial to understand the influence of the ion concentration and protein orientation in the different steps of the adsorption process. Our study provides useful information for the molecular engineering of components that require the immobilization of biomolecules and the preservation of their biological activity.

Adsorption of cesium on cement mortar from aqueous solutions.

PubMed

Volchek, Konstantin; Miah, Muhammed Yusuf; Kuang, Wenxing; DeMaleki, Zack; Tezel, F Handan

2011-10-30

The adsorption of cesium on cement mortar from aqueous solutions was studied in series of bench-scale tests. The effects of cesium concentration, temperature and contact time on process kinetics and equilibrium were evaluated. Experiments were carried out in a range of initial cesium concentrations from 0.0103 to 10.88 mg L(-1) and temperatures from 278 to 313 K using coupons of cement mortar immersed in the solutions. Non-radioactive cesium chloride was used as a surrogate of the radioactive (137)Cs. Solution samples were taken after set periods of time and analyzed by inductively coupled plasma mass spectroscopy. Depending on the initial cesium concentration, its equilibrium concentration in solution ranged from 0.0069 to 8.837 mg L(-1) while the respective surface concentration on coupons varied from 0.0395 to 22.34 μg cm(-2). Equilibrium test results correlated well with the Freundlich isotherm model for the entire test duration. Test results revealed that an increase in temperature resulted in an increase in adsorption rate and a decrease in equilibrium cesium surface concentration. Among several kinetic models considered, the pseudo-second order reaction model was found to be the best to describe the kinetic test results in the studied range of concentrations. The adsorption activation energy determined from Arrhenius equation was found to be approximately 55.9 kJ mol(-1) suggesting that chemisorption was the prevalent mechanism of interaction between cesium ions and cement mortar. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

Adsorption studies of volatile organic compounds on germanene nanotube emitted from banana fruit for quality assessment - A density functional application.

PubMed

Srimathi, U; Nagarajan, V; Chandiramouli, R

2018-06-01

We report the density functional application of adsorption behavior of volatile organic compounds (VOCs) emitted from the different ripening stages of banana fruit on germanene nanotube (GNT). Initially, the geometric structural stability of GNT is ascertained and the tunable electronic properties lead to the application of GNT as a base material in order to know the adsorption features of VOCs. We further explored the adsorption behavior of VOCs on to GNT through charge transfer, adsorption energy and band gap variation. The energy band structure and density of states (DOS) spectrum shows a noteworthy variation upon adsorption of different VOCs on to the GNT. Also, the electron density variation is noticed upon adsorption of VOCs emitted from the banana on to the GNT base material. Besides, the difference in the energy band gap of GNT upon emission of VOCs from banana leads to the use of GNT as a chemiresistor to assess fruit freshness with adsorption studies. Moreover, we suggest the use of GNT to discriminate the fruit freshness of banana through the adsorption process of VOCs on to GNT. Copyright © 2018 Elsevier Inc. All rights reserved.

Theoretical evaluation on selective adsorption characteristics of alkali metal-based sorbents for gaseous oxidized mercury.

PubMed

Tang, Hongjian; Duan, Yufeng; Zhu, Chun; Cai, Tianyi; Li, Chunfeng; Cai, Liang

2017-10-01

Alkali metal-based sorbents are potential for oxidized mercury (Hg 2+ ) selective adsorption but show hardly effect to elemental mercury (Hg 0 ) in flue gas. Density functional theory (DFT) was employed to investigate the Hg 0 and HgCl 2 adsorption mechanism over alkali metal-based sorbents, including calcium oxide (CaO), magnesium oxide (MgO), potassium chloride (KCl) and sodium chloride (NaCl). Hg 0 was found to weakly interact with CaO (001), MgO (001), KCl (001) and NaCl (001) surfaces while HgCl 2 was effectively adsorbed on top-O and top-Cl sites. Charge transfer and bond population were calculated to discuss the covalency and ionicity of HgCl 2 bonding with the adsorption sites. The partial density of states (PDOS) analysis manifests that HgCl 2 strongly interacts with surface sites through the orbital hybridizations between Hg and top O or Cl. Frontier molecular orbital (FMO) energy and Mulliken electronegativity are introduced as the quantitative criteria to evaluate the reactivity of mercury species and alkali metal-based sorbents. HgCl 2 is identified as a Lewis acid and more reactive than Hg 0 . The Lewis basicity of the four alkali metal-based sorbents is predicted as the increasing order: NaCl < MgO < KCl < CaO, in consistence with the trend of HgCl 2 adsorption energies. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Accelerated Late Adsorption of Pulmonary Surfactant

PubMed Central

2011-01-01

Adsorption of pulmonary surfactant to an air−water interface lowers surface tension (γ) at rates that initially decrease progressively, but which then accelerate close to the equilibrium γ. The studies here tested a series of hypotheses concerning mechanisms that might cause the late accelerated drop in γ. Experiments used captive bubbles and a Wilhelmy plate to measure γ during adsorption of vesicles containing constituents from extracted calf surfactant. The faster fall in γ reflects faster adsorption rather than any feature of the equation of state that relates γ to surface concentration (Γ). Adsorption accelerates when γ reaches a critical value rather than after an interval required to reach that γ. The hydrophobic surfactant proteins (SPs) represent key constituents, both for reaching the γ at which the acceleration occurs and for producing the acceleration itself. The γ at which rates of adsorption increase, however, is unaffected by the Γ of protein in the films. In the absence of the proteins, a phosphatidylethanolamine, which, like the SPs, induces fusion of the vesicles with the interfacial film, also causes adsorption to accelerate. Our results suggest that the late acceleration is characteristic of adsorption by fusion of vesicles with the nascent film, which proceeds more favorably when the Γ of the lipids exceeds a critical value. PMID:21417351

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.

Adsorption characteristics of Bisphenol-A on tailored activated carbon in aqueous solutions.

PubMed

Yan, Liang; Lv, Di; Huang, Xinwen; Shi, Huixiang; Zhang, Geshan

2016-10-01

The adsorption behavior of pharmaceuticals and personal care product, Bisphenol-A (BPA), according to four coal-based and four wood-based granular activated carbons modified using outgassing treatment, acidic treatment or alkaline treatment was studied. The adsorption isotherm results indicated that carbon surface acidity played a very important role in the adsorption of BPA. It was found that increasing surface acidity would increase the hydrogen bonding effects and increase adsorption of BPA on activated carbon. The acidic modified sample (F600-A and OLC-A) represented the best adsorption capacity, and the equilibrium adsorption amounts reached 346.42 and 338.55 mg/g, respectively. Further, effects of surface charge and surface basicity were examined. It was found that the adsorbed amount of BPA decreased with the increase of surface charge. Finally, there appeared to be a significant oligomerization phenomenon with BPA molecules onto the surface of activated carbon. OLC and OLC-OG, which have higher micropore percentages, are very effective in hampering the oligomerization of BPA under oxic conditions.

Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

PubMed

Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

2018-03-07

The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

Features of the adsorption of naproxen enantiomers on weak chiral anion-exchangers in nonlinear chromatography

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

Asnin, Leonid; Kaczmarski, Krzysztof; Guiochon, Georges A

The retention mechanism of the enantiomers of naproxen on a Pirkle-type chiral stationary phase (CSP) was studied. This CSP is made of a porous silica grafted with quinidine carbamate. It can interact with the weak organic electrolyte naproxen either by adsorbing it or by ion-exchange. Using frontal chromatography, we explored the adsorption equilibrium under such experimental conditions that naproxen dissociates or cannot dissociate. Under conditions preventing ionic dissociation, the adsorption isotherms were measured, the adsorption energy distributions determined, and the chromatographic profiles calculated. Three different types of the adsorption sites were found for both enantiomers. The density and the bindingmore » energy of these sites depend on the nature of the organic modifier. Different solute species, anions, neutral molecules, solvent-ion associates, and solute dimers can coexist in solution, giving rise to different forms of adsorption. This study showed the unexpected occurrence of secondary steps in the breakthrough profiles of S-naproxen in the adsorption mode at high concentrations. Being enantioselective, this phenomenon was assumed to result from the association of solute molecules involving a chiral selector moiety. A multisite Langmuir adsorption model was used to calculate band profiles. Although this model accounts excellently for the experimental adsorption isotherms, it does not explain all the features of the breakthrough profiles. A comparison between the calculated and experimental profiles allowed useful conclusions concerning the effects of the adsorbate-adsorbate and adsorbate-solvent interactions on the adsorption mechanism.« less

Investigation of carboxylation of carbon nanotube in the adsorption of anti-cancer drug: A theoretical approach

NASA Astrophysics Data System (ADS)

Hesabi, Maryam; Behjatmanesh-Ardakani, Reza

2018-01-01

Nowadays, an important process applied in the design of novel composite materials and drug delivery fields is the carboxylation of carbon nanotubes. In this work, we study the interaction of the anti-cancer drug hydroxyurea with carboxyl-functionalized zigzag carbon nanotubes (CNTs) by employing the method of the density functional theory (DFT) at B3LYP and CAM-B3LYP levels in gas and solvent phases. The results show that all complexes are energetically favorable, especially in the aqueous phase. The enthalpy energy values are negative in all cases, which indicate their exothermic adsorption nature. The presence of sbnd COOH groups would create enough free space on the nanotube surface for the adsorption between interacting atoms. Thus, these can increase the activity of CNTs. Data indicates that adsorption is dependent on the carboxyl sites of the nanotube as well as on the sites of the drug. Furthermore, the hydrogen-bonding interactions between drug and sbnd COOH-CNTs play an important role for the different kinds of adsorption observed.

Adsorption of Cr(III) on ozonised activated carbon. Importance of Cpi-cation interactions.

PubMed

Rivera-Utrilla, J; Sánchez-Polo, M

2003-08-01

The adsorption of Cr(III) in aqueous solution was investigated on a series of ozonised activated carbons, analysing the effect of oxygenated surface groups on the adsorption process. A study was carried out to determine the adsorption isotherms and the influence of the pH on the adsorption of this metal. The adsorption capacity and affinity of the adsorbent for Cr(III) increased with the increase in oxygenated acid groups on the surface of the activated carbon. These findings imply that electrostatic-type interactions predominate in the adsorption process, although the adsorption of Cr(III) on the original (basic) carbon indicates that other forces also participate in the adsorption process. Thus, the ionic exchange of protons in the -Cpi-H3O(+) interaction for Cr(III) accounts for the adsorption of cationic species in basic carbons with positive charge density. Study of the influence of pH on the adsorption of Cr(III) showed that, in each system, the maximum adsorption occurred when the charge of the carbon surface was opposite that of the species of Cr(III) present at the pH of the experiment. These results confirmed that electrostatic interactions predominate in the adsorption process.

Influence of Soil Solution Salinity on Molybdenum Adsorption by Soils

USDA-ARS?s Scientific Manuscript database

Molybdenum (Mo) adsorption on five arid-zone soils from California was investigated as a function of equilibrium solution Mo concentration (0-30 mg L-1), solution pH (4-8), and electrical conductivity (EC = 0.3 or 8 dS m-1). Molybdenum adsorption decreased with increasing pH. An adsorption maximum...

Oxygen adsorption onto pure and doped Al surfaces--the role of surface dopants.

PubMed

Lousada, Cláudio M; Korzhavyi, Pavel A

2015-01-21

Using density functional theory (DFT) with the PBE0 density functional we investigated the role of surface dopants in the molecular and dissociative adsorption of O2 onto Al clusters of types Al50, Al50Alad, Al50X and Al49X, where X represents a dopant atom of the following elements Si, Mg, Cu, Sc, Zr, and Ti. Each dopant atom was placed on the Al(111) surface as an adatom or as a substitutional atom, in the last case replacing a surface Al atom. We found that for the same dopant geometry, the closer is the ionization energy of the dopant element to that of elemental Al, the more exothermic is the dissociative adsorption of O2 and the stronger are the bonds between the resulting O atoms and the surface. Additionally we show that the Mulliken concept of electronegativity can be applied in the prediction of the dissociative adsorption energy of O2 on the doped surfaces. The Mulliken modified second-stage electronegativity of the dopant atom is proportional to the exothermicity of the dissociative adsorption of O2. For the same dopant element in an adatom position the dissociation of O2 is more exothermic when compared to the case where the dopant occupies a substitutional position. These observations are discussed in view of the overlap population densities of states (OPDOS) computed as the overlap between the electronic states of the adsorbate O atoms and the clusters. It is shown that a more covalent character in the bonding between the Al surface and the dopant atom causes a more exothermic dissociation of O2 and stronger bonding with the O atoms when compared to a more ionic character in the bonding between the dopant and the Al surface. The extent of the adsorption site reconstruction is dopant atom dependent and is an important parameter for determining the mode of adsorption, adsorption energy and electronic structure of the product of O2 adsorption. The PBE0 functional could predict the existence of the O2 molecular adsorption product for many of the cases

Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics Driven by Soft Vibration Modes

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

Woo, Sung-Jae; Lee, Eui-Sup; Yoon, Mina

2013-01-01

It is widely accepted that room-temperature hydrogen storage on nanostructured or porous materials requires enhanced dihydrogen adsorption. In this work we reveal that room-temperature hydrogen storage is possible not only by the enhanced adsorption, but also by making use of the vibrational free energy from soft vibration modes. These modes exist for example in the case of metallo-porphyrin-incorporated graphenes (M-PIGs) with out-of-plane ( buckled ) metal centers. There, the in-plane potential surfaces are flat because of multiple-orbital-coupling between hydrogen molecules and the buckled-metal centers. This study investigates the finite-temperature adsorption/desorption thermodynamics of hydrogen molecules adsorbed on M-PIGs by employing first-principlesmore » total energy and vibrational spectrum calculations. Our results suggest that the current design strategy for room-temperature hydrogen storage materials should be modified by explicitly taking finite-temperature vibration thermodynamics into account.« less

Atomic adsorption on pristine graphene along the Periodic Table of Elements - From PBE to non-local functionals

NASA Astrophysics Data System (ADS)

Pašti, Igor A.; Jovanović, Aleksandar; Dobrota, Ana S.; Mentus, Slavko V.; Johansson, Börje; Skorodumova, Natalia V.

2018-04-01

The understanding of atomic adsorption on graphene is of high importance for many advanced technologies. Here we present a complete database of the atomic adsorption energies for the elements of the Periodic Table up to the atomic number 86 (excluding lanthanides) on pristine graphene. The energies have been calculated using the projector augmented wave (PAW) method with PBE, long-range dispersion interaction corrected PBE (PBE+D2, PBE+D3) as well as non-local vdW-DF2 approach. The inclusion of dispersion interactions leads to an exothermic adsorption for all the investigated elements. Dispersion interactions are found to be of particular importance for the adsorption of low atomic weight earth alkaline metals, coinage and s-metals (11th and 12th groups), high atomic weight p-elements and noble gases. We discuss the observed adsorption trends along the groups and rows of the Periodic Table as well some computational aspects of modelling atomic adsorption on graphene.

Adsorption Isotherm Studies of Methyl Bromide on MgO

NASA Astrophysics Data System (ADS)

Burns, Teresa; Larese, John

2004-03-01

The adsorption of methyl bromine onto highly-uniform magnesium oxide powder was studied. Methyl bromide was condensed onto the MgO substrate at temperatures between 164 K and 179 K. The layering behavior of the gas molecules was studied by a series of vapor pressure isotherms, using a high-accuracy, computer-controller system. The isotherms clearly show first layer formation at all temperatures, with second layer formation at higher temperatures; the 2D compressibility and isosteric heat of adsorption were determined. TEB sponsored by the Department of Energy EPSCOR Grant No. DE-FG02-01ER45895. JZL sponsored by start-up funds from the University of Tennessee - Knoxville and by the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy, under contract No. DE-AC05-00OR22725 with Oak Ridge National Laboratory, managed and operated by UT-Battelle, LLC.

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.

KOH catalysed preparation of activated carbon aerogels for dye adsorption.

PubMed

Ling, Sie King; Tian, H Y; Wang, Shaobin; Rufford, Thomas; Zhu, Z H; Buckley, C E

2011-05-01

Organic carbon aerogels (CAs) were prepared by a sol-gel method from polymerisation of resorcinol, furfural, and hexamethylenetetramine catalysed by KOH at around pH 9 using ambient pressure drying. The effect of KOH in the sol-gel on CA synthesis was studied. It was found that addition of KOH prior to the sol-gel polymerisation process improved thermal stability of the gel, prevented the crystallinity of the gel to graphite, increased the microporosity of CA and promoted activation of CA. The CAs prepared using the KOH catalyst exhibited higher porosity than uncatalysed prepared samples. Activation in CO(2) at higher temperature also enhanced the porosity of CAs. Adsorption tests indicated that the CAs were effective for both basic and acid dye adsorption and the adsorption increased with increasing surface area and pore volume. The kinetic adsorption of dyes was diffusion control and could be described by the second-order kinetic model. The equilibrium adsorption of dyes was higher than activated carbon. Copyright © 2011 Elsevier Inc. All rights reserved.

The adsorption behavior of U(VI) on granite.

PubMed

Fan, Q H; Hao, L M; Wang, C L; Zheng, Z; Liu, C L; Wu, W S

2014-03-01

The effects of pH, counter ions and temperature on the adsorption of U(VI) on Beishan granite (BsG) were investigated in the presence and absence of fulvic acid (FA) and humic acid (HA). The adsorption edge of U(VI) on BsG suggested that U(VI) adsorption was mainly controlled by ion exchange and outer-sphere complexation at low pH, whereas inner-sphere complex was the dominant adsorption species in the pH range of 4.0-9.0. Above pH 9.0, Na2U2O7 might play an important role in the rise of U(VI) adsorption again. Counter ions such as Cl(-), SO4(2-) and PO4(3-) can provoke U(VI) adsorption on BsG to some extent, which was directly correlated to the complexing ability of U(VI)-ligand. More noticeably, the large enhancement of U(VI) adsorption in the presence of phosphate can be attributed to the ternary complex formation (BsG-PO4-UO2), precipitation ((UO2)3(PO4)2(s)) and secondary phase (Na-autunite). Both FA and HA can slightly increase U(VI) adsorption at low pH, whereas they strongly inhibited U(VI) adsorption at high pH range. Artificial synthesized granite (AsG) prepared in the laboratory is impossible to use as an analogue of natural granite because of the large difference in the adsorption and surface properties.

Studies of the water adsorption on Lampung’s natural zeolite of Indonesia for cooling application

NASA Astrophysics Data System (ADS)

Wulandari, D. A.; Nasruddin; Lemington

2018-03-01

Part of minerals that originally formed from volcanic rock and ash layers reacting further with alkaline groundwater is called natural zeolite, where its sources are not always available in all countries. Indonesia is located in the ring of fire which have a huge sources of zeolite, one of the area is Lampung, South Sumatra. Natural zeolite has been considered as one of potential heat adsorbent medium which can contribute to the energy consumption and reduce air pollution in the using of cooling application. The characteristic of this Lampung natural zeolite such as adsorption kinetics, adsorption water uptake, and adsorption capacity were test with ASAP 2020 system. Sorption kinetics by this experiment of zeolite samples were carried out in a constant temperature and humidity chamber. The chamber can supply constant air condition with deviations of ±0.5 °C for temperature and ±3% for relative humidity. The data based on rate of adsorption and the defined working condition was set as 20°C and 70% RH. Pore volume is a significant parameter for determining the limitation of water uptake, which can describe the saturated condition of zeolite. Sorption isotherm models used to describe sorption phenomena are commonly deduced from the Polanyi potential theory were investigated. The water adsorption quantity increased with the increase of relative pressure. To sum up, this pure zeolite has a less heat and mass transfer performance so its need to be activated before using in cooling application to get their great potential and by being coated in a desiccant heat exchanger systems.

Subnanopore filling during water vapor adsorption on microporous silica thin films as seen by low-energy positron annihilation

NASA Astrophysics Data System (ADS)

Ito, Kenji; Yoshimoto, Shigeru; O'Rourke, Brian E.; Oshima, Nagayasu; Kumagai, Kazuhiro

2018-02-01

Positron annihilation lifetime spectroscopy (PALS) using a low-energy positron microbeam extracted into air was applied to elucidating molecular-level pore structures formed in silicon-oxide-backboned microporous thin films under controlled humidity conditions; as a result, a direct observation of the interstitial spaces in the micropores filled with water molecules was achieved. It was demonstrated that PALS using a microbeam extracted into air in combination with water vapor adsorption is a powerful tool for the in-situ elucidation of both open and closed subnanoscaled pores of functional thin materials under practical conditions.

Adsorption and Exchange Kinetics of Hydrophilic and Hydrophobic Phosphorus Ligands on Gold Surface

NASA Astrophysics Data System (ADS)

Zhuge, X. Q.; Bian, Z. C.; Luo, Z. H.; Mu, Y. Y.; Luo, K.

2017-02-01

The adsorption kinetics process of hydrophobic ligand (triphenylphosphine, PPh3) and hydrophilic ligand (tris(hydroxymethyl)phosphine oxide, THPO) on the surface of gold electrode were estimated by using electrical double layer capacitance (EDLC). Results showed that the adsorption process of both ligands included fast and slow adsorption processes, and the fast adsorption process could fit the first order kinetic equation of Langmuir adsorption isotherm. During the slow adsorption process, the surface coverage (θ) of PPh3 was higher than that of THPO due to the larger adsorption kinetic constant of PPh3 than that of THPO, which implied that PPh3 could replace THPO on the gold electrode. The exchange process of both ligands on the surface of gold electrode proved that PPh3 take the place of THPO by testing the variation of EDLC which promote the preparation of Janus gold, and the theoretic simulation explained the reason of ligands exchange from the respect of energy..

Response to Extreme Temperatures of Mesoporous Silica MCM-41: Porous Structure Transformation Simulation and Modification of Gas Adsorption Properties.

PubMed

Zhang, Shenli; Perez-Page, Maria; Guan, Kelly; Yu, Erick; Tringe, Joseph; Castro, Ricardo H R; Faller, Roland; Stroeve, Pieter

2016-11-08

Molecular dynamics (MD) and Monte Carlo (MC) simulations were applied together for the first time to reveal the porous structure transformation mechanisms of mesoporous silica MCM-41 subjected to temperatures up to 2885 K. Silica was experimentally characterized to inform the models and enable prediction of changes in gas adsorption/separation properties. MD simulations suggest that the pore closure process is activated by a collective diffusion of matrix atoms into the porous region, accompanied by bond reformation at the surface. Degradation is kinetically limited, such that complete pore closure is postponed at high heating rates. We experimentally observe decreased gas adsorption with increasing temperature in mesoporous silica heated at fixed rates, due to pore closure and structural degradation consistent with simulation predictions. Applying the Kissinger equation, we find a strong correlation between the simulated pore collapse temperatures and the experimental values which implies an activation energy of 416 ± 17 kJ/mol for pore closure. MC simulations give the adsorption and selectivity for thermally treated MCM-41, for N 2 , Ar, Kr, and Xe at room temperature within the 1-10 000 kPa pressure range. Relative to pristine MCM-41, we observe that increased surface roughness due to decreasing pore size amplifies the difference of the absolute adsorption amount differently for different adsorbate molecules. In particular, we find that adsorption of strongly interacting molecules can be enhanced in the low-pressure region while adsorption of weakly interacting molecules is inhibited. This then results in higher selectivity in binary mixture adsorption in mesoporous silica.

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.

Adsorption of Potassium on the MoS2(100) Surface: A First-Principles Investigation

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

Andersen, Amity; Kathmann, Shawn M.; Lilga, Michael A.

2011-04-15

Periodic density functional theory calculations were performed to investigate the interaction that potassium with the Mo and S edges of the MoS2(100) surface. Both neutral and cationic (+1) charged potassium-promoted systems at different sulfur coverages were considered. Our calculations indicate that the potassium atom readily donates its single 4s valence electron to the MoS2 structure for the neutral potassium-promoted system, and the neutral and cationic potassium-promoted systems demonstrate a similar adsorption behavior. Moreover, potassium changes the magnetic properties known to occur at the metallic edge surface, which have implications for electron spin dependent surface characterization methods (i.e., electron spin/paramagnetic spectroscopy).more » Potassium in both the neutral and cationic systems tends to maximize its interactions with the available sulfur atoms at the edge surface, preferring sites over four-fold S hollows on fully sulfided Mo and S edges and over the interstitial gap where two to four edge surface S atoms are available for coordination. As the potassium coverage increases, the adsorption energy per potassium atom, surface work function, and transfer of the K 4s electron to the MoS2(100) surface decreases, which is in line with an increased metallization of the potassium adlayer. The potassium adlayer tends to form chains along the interstitial with K-K distances ~1 Å, which is notably less than those of bulk bcc K metal (4.61 Å). Density of states for the potassium-saturated surface suggests enhanced involvement of broad K 3d states beginning just above the Fermi level. Potassium-promotion of MoS2(100) has implications for alcohol catalysis: increasing the surface basicity by increasing the electron charge of the surface, providing hydrogenation-promoting CO site, blocking edge surface that dissociate CO and lead to methanation, and limiting H2 dissociative adsorption to the edge surface and possibly inhibiting the H2

Adsorption of surfactants and polymers at interfaces

NASA Astrophysics Data System (ADS)

Rojas, Orlando Jose

Surface tension and high-resolution laser light scattering experiments were used to investigate the adsorption of isomeric sugar-based surfactants at the air/liquid interface in terms of surfactant surface packing and rheology. Soluble monolayers of submicellar surfactant solutions exhibited a relatively viscous behavior. It was also proved that light scattering of high-frequency thermally-induced capillary waves can be utilized to study surfactant exchange between the surface and the bulk solution. Such analysis revealed the existence of a diffusional relaxation mechanism. A procedure based on XPS was developed for quantification, on an absolute basis, of polymer adsorption on mica and Langmuir-Blodgett cellulose films. The adsorption of cationic polyelectrolytes on negatively-charged solid surfaces was highly dependent on the polymer ionicity. It was found that the adsorption process is driven by electrostatic mechanisms. Charge overcompensation (or charge reversal) of mica occurred after adsorption of polyelectrolytes of ca. 50% charge density, or higher. It was demonstrated that low-charge-density polyelectrolytes adsorb on solid surfaces with an extended configuration dominated by loops and tails. In this case the extent of adsorption is limited by steric constraints. The conformation of the polyelectrolyte in the adsorbed layer is dramatically affected by the presence of salts or surfactants in aqueous solution. The phenomena which occur upon increasing the ionic strength are consistent with the screening of the electrostatic attraction between polyelectrolyte segments and solid surface. This situation leads to polyelectrolyte desorption accompanied by both an increase in the layer thickness and the range of the steric force. Adsorbed polyelectrolytes and oppositely charged surfactants readily associate at the solid/liquid interface. Such association induces polyelectrolyte desorption at a surfactant concentration which depends on the polyelectrolyte charge

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.

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.

Mercury adsorption properties of sulfur-impregnated adsorbents

USGS Publications Warehouse

Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

2002-01-01

Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

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.

Adsorption of pentacene on (100) vicinal surfaces: role of coordination, surface chemistry and vdWs effects

NASA Astrophysics Data System (ADS)

Matos, Jeronimo; Kara, Abdelkader

2015-03-01

In contrast to low miller index surfaces, vicinal surfaces are characterized by steps and step edges that not only present an interesting atomic landscape for the adsorption organic molecules, but also a unique electronic structure resulting in part from the low coordinated atoms at the step edges. The adsorption of pentacene on the stepped (511), (711), (911) surfaces (respectively 3, 4 and 5-atom wide terraces) of Cu and Ag (coinage transition metals); Pt (reactive transition metal); and Ni (reactive, magnetic transition metal) are studied using density functional theory, in order to investigate the support effects arising from differing surface chemistry. We compare the adsorption energy, adsorption geometry and electronic structure predicted by the PBE functional with those obtained from one of the optimized vdW-DF methods: optB88-vdW. Work supported by the U.S. Department of Energy Basic Energy Science under Contract No. DE-FG02-11ER16243.

The adsorption of HCl on volcanic ash

NASA Astrophysics Data System (ADS)

Gutiérrez, Xochilt; Schiavi, Federica; Keppler, Hans

2016-03-01

Understanding the interaction between volcanic gases and ash is important to derive gas compositions from ash leachates and to constrain the environmental impact of eruptions. Volcanic HCl could potentially damage the ozone layer, but it is unclear what fraction of HCl actually reaches the stratosphere. The adsorption of HCl on volcanic ash was therefore studied from -76 to +150 °C to simulate the behavior of HCl in the dilute parts of a volcanic plume. Finely ground synthetic glasses of andesitic, dacitic, and rhyolitic composition as well as a natural obsidian from Vulcano (Italy) served as proxies for fresh natural ash. HCl adsorption is an irreversible process and appears to increase with the total alkali content of the glass. Adsorption kinetics follow a first order law with rate constants of 2.13 ṡ10-6 s-1 to 1.80 ṡ10-4 s-1 in the temperature range investigated. For dacitic composition, the temperature and pressure dependence of adsorption can be described by the equation ln ⁡ c = 1.26 + 0.27 ln ⁡ p - 715.3 / T, where c is the surface concentration of adsorbed HCl in mg/m2, T is temperature in Kelvin, and p is the partial pressure of HCl in mbar. A comparison of this model with a large data set for the composition of volcanic ash suggests that adsorption of HCl from the gas phase at relatively low temperatures can quantitatively account for the majority of the observed Cl concentrations. The model implies that adsorption of HCl on ash increases with temperature, probably because of the increasing number of accessible adsorption sites. This temperature dependence is opposite to that observed for SO2, so that HCl and SO2 are fractionated by the adsorption process and the fractionation factor changes by four orders of magnitude over a temperature range of 250 K. The assumption of equal adsorption of different species is therefore not appropriate for deriving volcanic gas compositions from analyses of adsorbates on ash. However, with the experimental

Adsorption of aquatic humic substances on colloidal-size aluminum oxide particles: Influence of solution chemistry

NASA Astrophysics Data System (ADS)

Schlautman, Mark A.; Morgan, James J.

1994-10-01

The adsorption of Suwannee River humic substances (HS) on colloidal-size aluminum oxide particles was examined as a function of solution chemistry. The amount of humic acid (HA) or fulvic acid (FA) adsorbed decreased with increasing pH for all solutions of constant ionic strength. In NaCl solutions at fixed pH values, the adsorption of HA and FA increased with increasing ionic strength. The presence of Ca 2+ enhanced the adsorption of HA but had little effect on FA. For identical solution conditions, the amount (by mass) of HA adsorbed to alumina was always greater than FA. Adsorption densities for both HA and FA showed good agreement with the Langmuir equation, and interpretations of adsorption processes were made from the model parameters. For FA, ligand exchange appears to be the dominant adsorption reaction for the conditions studied here. Ligand exchange is also a major adsorption reaction for HA; however, other reactions contribute to adsorption for some solution compositions. At high pH, cation and water bridging become increasingly important for HA adsorption with increasing amounts of Na + and Ca 2+, respectively. At low to neutral pH values, increases in these same two cations make hydrophobic bonding more effective. Calculations of HS carboxyl group densities in the adsorbed layer support the proposed adsorption reactions. From the adsorption data it appears that fewer than 3.3 HS-COO - groups per nm 2 can be bound directly as inner-sphere complexes by the alumina surface. We propose that the influence of aqueous chemistry on HS adsorption reactions, and therefore on the types of HS surface complexes formed, affects the formation and nature of organic coatings on mineral surfaces.

Adsorption of phenanthrene on activated carbon increases mineralization rate by specific bacteria.

PubMed

Leglize, Pierre; Alain, Saada; Jacques, Berthelin; Corinne, Leyval

2008-03-01

Bioavailability of polycyclic aromatic hydrocarbons (PAH) in soil is affected by PAH sorption to solid phase. We studied the influence of activated carbon (AC) on phenanthrene (PHE) mineralization by five degrading bacterial strains isolated from contaminated soil. PHE adsorption on AC was important and reduced PHE aqueous concentration up to 90%. PHE degradation was improved in the presence of activated carbon with three of the bacterial strains, named NAH1, MATE3 and MATE7, which produced biofilms, whereas it was not improved with the two other ones, which did not produce biofilms, MATE10 and MATE12. Monitoring PHE distribution during incubation showed that aqueous PHE concentration was significantly higher with the biofilm-producing NAH1 than with MATE10. Bacterial adhesion on AC was also investigated. The precoating of AC with PHE increased NAH1 and MATE3 adhesion to the solid surface (>16 and >13%, respectively). Bacterial properties, such as biofilm production and adhesion to AC capacity seemed to be related to their ability to optimize PHE degradation by improving PHE diffusion and reducing diffusion path length.

Adsorption of methylene blue on an agro-waste oiltea shell with and without fungal treatment

NASA Astrophysics Data System (ADS)

Liu, Jiayang; Li, Enzhong; You, Xiaojuan; Hu, Changwei; Huang, Qingguo

2016-12-01

A lignocellulosic waste oiltea shell (OTS) was evaluated as an inexpensive sorbent to remove methylene blue (MB) from aqueous solution. Fungal treatment of OTS increased the MB adsorption by modifying the physicochemical properties of OTS and simultaneously produced laccase as a beneficial co-product. Without fungal treatment, the maximum amount of adsorption (qm) of MB by OTS was 64.4 mg/g, whereas the treatment with fungus Pycnoporus sp. and Trametes versicolor increased qm up to 72.5 mg/g and 85.7 mg/g, respectively. This is because of the improved surface area and pore sizes as well as altered chemical compositions. The equilibrium sorption data for OTS both with and without treatment fitted to the Langmuir model, and the sorption rate data well fitted to the pseudo second-order kinetic model. The changes in free energy (ΔG°) and separation factor (RL) indicated that the sorption was spontaneous and favorable. Scanning electron microscopy and Fourier transform infrared spectroscopy showed the changes in the surface morphology and functional groups of OTS after fungal treatment. The agro-waste OTS could be utilized as a low-cost adsorbent for efficient dye removal, and fungal treatment can serve as a mild and clean technique to increase the adsorptive capacity of OTS.

Characterization and adsorption of Lactobacillus virulent phage P1.

PubMed

Chen, X; Xi, Y; Zhang, H; Wang, Z; Fan, M; Liu, Y; Wu, W

2016-09-01

Bacteriophage infection of lactic acid bacteria is considered an important problem worldwide in the food fermentation industry, as it may produce low quality or unsafe foods, cause fermentation failure, and result in economic losses. To increase current knowledge on the properties of Lactobacillus virulent phages, we evaluated the effect of divalent cations, temperature, pH, and chloramphenicol on the adsorption ability of Lactobacillus virulent phage P1. Phage P1 was isolated from the abnormal fermentation liquid of Lactobacillus plantarum IMAU10120. The results showed that this phage belonged to the Siphoviridae family. The latent period of this phage was 45min, and the burst time was 90min. Burst size was 132.88±2.37 phage counts expressed per milliliter per infective center. This phage showed good tolerance at different temperatures, but incubation at 50°C only affected its adsorption. Adsorption rate reached a maximum value between 30 and 42°C. A high adsorption value of phage infectivity was obtained from pH 6 to 8. Moreover, calcium ions promoted and increased the adsorption capacity of phage P1, but magnesium ions had negative effects. Chloramphenicol had no effect on phage adsorption. This study increased current knowledge on the characterization and biological aspects of Lactobacillus virulent phages, and may provide some basic information that can be used to design successful antiphage strategies in the food industry. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Adsorption of arginine, glycine and aspartic acid on Mg and Mg-based alloy surfaces: A first-principles study

NASA Astrophysics Data System (ADS)

Fang, Zhe; Wang, Jianfeng; Yang, Xiaofan; Sun, Qiang; Jia, Yu; Liu, Hairong; Xi, Tingfei; Guan, Shaokang

2017-07-01

Studying the adsorption behaviors of biomolecules on the surface of Mg and Mg-based alloy has a fundamental and important role for related applications in biotechnology. In the present work, we systematically investigate and compare the adsorption properties of three typical amino acids, i.e., Arg (arginine), Gly (glycine) and Asp (aspartic acid), which form RGD tripeptide, on the Mg (0 0 0 1) surface with various doping (Zn, Y, and Nd), and aim to realize proper binding between biomolecules and Mg and Mg-based biomedical materials. Our results show that flat adsorption configurations of the functional groups binding to the surfaces are favored in energy for all the three selected amino acids. In specific, for the amino acids adsorped on clean Mg (0 0 0 1) surface, the adsorption energy (Eads) of Arg is found to be -1.67 eV for the most stable configuration, with amino and guanidyl groups binding with the surface. However, Gly (Asp) is found to binding with the surface through amino and carboxyl groups, with a -1.16 eV (-1.15 eV) binding energy. On the 2% Zn doped Mg (0 0 0 1) alloy surface (Mg-Zn (2%)), the Eads are significantly increased to be -1.91 eV, -1.32 eV and -1.35 eV for Arg, Gly and Asp, respectively. While the Mg-Y (1%) and Mg-Nd (1%) slightly weaken the adsorption of three amino acids. Moreover, we have performed detail discussions of the binding properties between amino acids and surfaces by projected density of states (PDOS) combined with charge transfer analyses. Our studies provide a comprehensive understanding on the interactions between amino acids and Mg and Mg-based alloy surfaces, with respect to facilitate the applications of Mg and Mg-based biomedical alloys in biosensing, drug delivery, biomolecule coating and other fields in biotechnology.

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

Selective adsorption of bovine hemoglobin on functional TiO2 nano-adsorbents: surface physic-chemical properties determined adsorption activity

NASA Astrophysics Data System (ADS)

Guo, Shiguang; Zhang, Jianghua; Shao, Mingxue; Zhang, Xia; Liu, Yufeng; Xu, Junli; Meng, Hao; Han, Yide

2015-04-01

Surface functionalized nanoparticles are efficient adsorbents which have shown good potential for protein separation. In this work, we chose two different types of organic molecules, oleic acid (OA) and 3-glycidoxypropyltrimethoxy silane (GPTMS), to functionalize the surface of TiO2 nanoparticles, and we studied the effects of this modification on their surface physicochemical properties in correlation with their selective adsorption of proteins. The results showed that the surface zeta potential and the surface water wettability of the modified TiO2 were significantly changed in comparison with the original TiO2 nanoparticles. The adsorption activities of bovine hemoglobin (BHb) and bovine serum albumin (BSA) on these functionalized TiO2 samples were investigated under different conditions, including pH values, contact time, ion strength, and initial protein concentration. In comparison with the non-specific adsorption of original TiO2, however, both the OA-TiO2 and GPTMS-TiO2 exhibited increased BHb adsorption and decreased BSA adsorption at the same time. Using a binary protein mixture as the adsorption object, a higher separation factor (SF) was obtained for OA-TiO2 under optimum conditions. The different adsorption activities of BHb and BSA on the modified TiO2 were correlated with different interactions at the protein/solid interface, and the chemical force as well as the electrostatic force played an important role in the selective adsorption process.