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PubMed2001

Adsorption of Molybdenum on Titania from Aqueous Solutions.

The adsorption of Mo from dilute aqueous solutions (10(-3) to 3x10(-2) M) is effected on three samples of titania, two are anatase and the third is P25, which is composed of rutile and anatase. The adsorption isotherms at 298, 318, and 338 K are analyzed using a Langmuir linear equation. The isotherms on P25 showed a distinct inflection point that is reproduced by two linear portions, indicating different adsorption regimes. This adsorption behavior is explained as follows: with low amount adsorbed the adsorption is initiated by protonation of the basic hydroxyls on which the negatively charged MoO(4)(2-')s are adsorbed, and this is accompanied by an increase in the pH of the impregnating solution. At higher adsorption the coordinatively unsaturated Ti(4+) sites participate in the process, leading to a decline in the initial increase in pH. In the case of the two anatase samples the low surface area resulted in poor distribution of adsorption sites; consequently, the distinction between the two modes of adsorption was not entirely clear. The higher adsorption site density in the case of anatase is accompanied by a lower surface coverage, θ, than that for P25. The heat of adsorption, Q, on the three titania samples showed a linear increase with θ, which is represented by the regression equation: -Q=95.77θ-4.25 (R(2)=0.993). Copyright 2001 Academic Press.

Journal Article↗
PubMed2002

Dependence of the adsorption of polymer mixtures from solution on the amount of an adsorbent.

Simultaneous competitive adsorption from solutions of mixtures of poly(butyl methacrylate) and polystyrene and adsorption of each component from binary solutions have been studied for three ratios of the adsorbent mass to the solution volume, A/V. It was found that adsorption from both binary and ternary solutions strongly depends on the amount of an adsorbent, adsorption of poly(butyl methacrylate) being preferential. The characteristic adsorption isotherms of both polymers were constructed under conditions of equal equilibrium concentration of each component to estimate the parameters of preferential adsorption and their dependence on the A/V ratio. It was found that the A/V effect plays an important role in adsorption from polymer mixtures and determines the peculiarities of adsorption from polymer mixtures as well as from solution of single polymers. Changing the A/V ratio may be one way to regulate the composition of an adsorption layer consisting of two chemically different polymers. The reasons for the A/V effect are considered in the framework of the concept of the plurality of adsorption equilibria between two chemically different components and between fractions of different molecular mass of each component having various absorbability.

Journal Article↗
PubMed2002

Kinetics of adsorption of high molecular weight anionic polyacrylamide onto kaolinite: the flocculation process.

The adsorption kinetics of anionic polyacrylamide flocculant onto kaolinite clay are examined as a function of flocculant dosage and pH. Special attention has been given to the flocculation effect during the adsorption process and the resulting inhibition of further adsorption. At pH 8.5 the adsorption capacity of anionic polyacrylamide on kaolinite is low while at pH 4.5, the adsorption capacity increases. Flocculant adsorption has been shown to be related to the amount of available surface area, pH, flocculant dosage, and the resulting floc strength, which controls the rate of new surface area exposure and hence the continuation of further adsorption. At both pH 4.5 and pH 8.5, complete adsorption is achieved at low flocculant dosages and adsorption equilibrium is achieved at high flocculant dosages after 1 day. In contrast, at intermediate flocculant dosages adsorption equilibrium is not reached over a 7-day period, due to a continuously increasing surface area.

Journal Article↗
PubMed2002

A single-site model for divalent transition and heavy metal adsorption over a range of metal concentrations.

Metal adsorption data over a range of surface coverages typically are characterized by curvilinear metal adsorption isotherms. These isotherms generally have a slope of 1 at low surface coverage and a shallower slope at higher surface coverages. The curvature of metal adsorption isotherms with increasing surface coverage is frequently interpreted in terms of sequential adsorption onto different types of surface sites, multinuclear surface complexation, or nonideality of metal adsorption. We demonstrate that the curvature of metal adsorption isotherms can also be attributed to changes in surface charge and potential that depend on the predominant type of metal surface complex. A single-site extended triple-layer model is used to reinterpret previously studied metal adsorption isotherms and pH edges for a wide variety of metals (Cd2+, Co2+, Cu2+, Pb2+, and Zn2+) and solids (goethite, hydrous ferric oxide, corundum, and magnetite) in different electrolyte solutions (NaNO3 and NaClO4). Only metal adsorption on ferrihydrite at very low surface coverages is not consistent with the single-site triple-layer model. This discrepancy might be explained if ferrihydrite is in fact not a single phase but a mixture of two or more phases. Metal surface coverages ranging from 10(-4) to 10.2 mmol/m2 on the other minerals can be accounted for with a single-site extended triple-layer model if appropriate metal adsorption reactions are chosen. In addition, several examples suggest that, within the context of the model, surface complexation schemes can be established that describe metal adsorption over both a wide range of surface coverage and a wide range of ionic strength.

Journal Article↗
PubMed2004

Polymer and particle adsorption at the PDMS droplet-water interface.

Polymer and particle adsorption at the polydimethylsiloxane (PDMS) droplet-water interface has been investigated. Adsorption isotherms and adsorbed layer structure are reported for a range of PEO-PPO-PEO block copolymers, and hydrophilic and hydrophobic silica "nanoparticles". The influence of solution conditions on the adsorption behaviour has indicated the thermodynamics of polymer-droplet and particle-droplet interactions. The influence of droplet cross-linking (deformability) has indicated the role of interfacial penetration in controlling adsorption at the droplet-water interface. The plateau adsorbed amount (Gamma(max)) and adsorbed layer thickness (delta(max)) of PEO-PPO-PEO copolymers are dependent on the copolymer structure and the level of cross-linking within droplets. For a wide range of copolymer structures, Gamma(max) values are in the range 2 to 20 mg m(-2). For delta(max), values range from 2 to 20 nm and are directly proportional to the PEO block length. Droplet cross-linking significantly reduces Gamma and delta values; this is considered to be due to the influence of interfacial penetrability on the adsorbed copolymer conformation. Hydrophilic silica particles adsorb onto PDMS droplets with plateau surface coverages that correspond to their hard sphere radius+double layer thickness, i.e. lateral silica-silica interactions control particle packing. Free energies of adsorption (DeltaG(ads)) are concurrent with a physical adsorption mechanism. Surface coverages, DeltaG(ads) and particle packing at the interface are only weakly influenced by pH, but are significantly influenced by salt addition. Droplet cross-linking reduced particle adsorption only at higher salt concentrations; this was attributed to the increased likelihood of silica particles wetting PDMS. Freeze fracture SEM revealed that individual silica particles are adsorbed at the droplet interface with negligible interfacial aggregation. Densely packed adsorbed particle layers are only observed when the double layer thickness is a few nanometers. Adsorption of hydrophobic particles at the PDMS droplet-water interface is more pronounced (greater adsorbed amounts and DeltaG(ads) values) than for hydrophilic particles and displays a pH dependency in line with 'DLVO behaviour'. The surface coverage values correspond to multiple close packed layers and are significantly influenced by droplet cross-linking, conferring extensive interfacial penetration (confirmed by SEM). Densely packed adsorbed particle layers with interfacial aggregation are observed over a wide range of solution conditions. Interfacial particle saturation occurred at a salt concentration two orders of magnitude less than the critical coagulation concentration (ccc) for silica in water. This phenomenon was observed for both liquid and cross-linked PDMS droplets indicating that particle interaction through the water phase plays a decisive role in particle packing at the interface. SEM indicated the presence of a rigid interfacial crust layer at the salt concentration corresponding to interfacial saturation and a multi-layered interfacial particle wall at salt concentrations >/= ccc. The PDMS droplets under consideration, having inherent colloid stability in the absence of added stabilisers, are an excellent model system for characterising polymer and particle adsorption at the droplet-water interface. The insight gained concerning adsorption thermodynamics at the droplet-water interface is not available from more conventional emulsions.

Journal Article↗
PubMed2004

Adsorption of bilayers and multilayers of cationic and anionic co-polymers of acrylamide on silicon oxide.

Silica surfaces were consecutively treated with copolymers of cationic and anionic polyacrylamides (C-PAM and A-PAM, respectively) and the layer-by-layer build-up was continuously monitored with the aid of stagnation point adsorption reflectometry (SPAR). Four different charge densities of the cationic polymer and one charge density of the anionic polymer were studied. The solid substrate used in the investigation was an oxidized Si wafer, the charge of which was varied by performing the measurements at different pH. Adsorption measurements were performed both in deionized water and with a background electrolyte concentration of 0.01 M NaCl. The results show that the adsorption of C-PAM at pH 6 was dominated by electrostatic interactions. However, a significant nonionic contribution to the adsorption of C-PAM on SiO(2) was detected-when the results of adsorption measurements conducted in deionized water and in 0.01 M NaCl were compared. At pH 9, the adsorption of C-PAM onto SiO(2) was found to be geometrically restricted since the adsorption stoichiometry between the polymer charges and the charges on the surface was less than 1 irrespective of the charge of the C-PAM. Adsorption of the A-PAM onto the C-PAM covered surface increases as a function of the adsorbed charges in the first layer. Experiments showed that it was possible to form multilayers of polyelectrolytes on the SiO(2) surface provided the charge of the C-PAM was high enough. The critical charge of the polyelectrolyte for the formation of multilayers was also dependent on the charge of the substrate; that is, the lower the surface charge the higher the critical charge of the C-PAM. The substrate affected the amount of polyelectrolyte adsorbed up to the fifth layer. For further layers there was almost a stoichiometric relationship between the charges of the polyelectrolytes in consecutive layers. Results from studies of the formed multilayers with a quartz crystal microbalance (QCM-D) indicated that there was a close correlation between energy dissipation into the multilayers and a decrease in the adsorption as detected with SPAR. This in turn indicates that a decrease in the reflectometer signal does not necessarily indicate a decrease in adsorption.

Journal Article↗
PubMed2005

Adsorption of metal ions onto Moroccan stevensite: kinetic and isotherm studies.

The aim of this paper is to study the adsorption of the heavy metals (Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II)) from aqueous solutions by a natural Moroccan stevensite called locally rhassoul. We carried out, first, a mineralogical and physicochemical characterization of stevensite. The surface area is 134 m2/g and the cation exchange capacity (CEC) is 76.5 meq/100 g. The chemical formula of stevensite is Si3.78Al0.22Mg2.92Fe0.09Na0.08K0.08O10(OH)2.4H2O. Adsorption tests of Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II) in batch reactors were carried out at ambient temperature and at constant pH. Two simplified models including pseudo-first-order and pseudo-second- order were used to test the adsorption kinetics. The equilibrium time and adsorption rate of adsorption were determined. The increasing order of the adsorption rates follows the sequence Mn(II) > Pb(II) > Zn(II) > Cu(II) > Cd(II). The Dubinin-Radushkevich (D-R), Langmuir, and Redlich-Peterson (R-P) models were adopted to describe the adsorption isotherms. The maximal adsorption capacities at pH 4.0 determined from the D-R and Langmuir models vary in the following order: Cu(II) > Mn(II) > Cd(II) > Zn(II) > Pb(II). The equilibrium data fitted well with the three-parameter Redlich-Peterson model. The values of mean energy of adsorption show mainly an ion-exchange mechanism. Also, the influence of solution pH on the adsorption onto stevensite was studied in the pH range 1.5-7.0.

Journal Article↗
PubMed2005

Effect of Cr(VI) anions on adsorption and desorption behavior of Cu(II) in the colloidal systems of two authentic variable charge soils.

Heavy metals in wastes exist as multiple pollutants. The study of the interactions between multiple pollutants and soils should be of significance in practice. In the present study, the effect of chromate on adsorption and desorption behavior of Cu(II) in two variable charge soils was investigated, with the emphasis on the adsorption and desorption equilibria of Cu(II). The results showed that chromate can affect adsorption and desorption of Cu(II) in the colloidal systems of two variable charge soils. The extent of the effect was related to the initial concentrations of chromate and Cu(II), the system pH, and the nature of the soils. The presence of chromate led to an increase in the adsorption of Cu(II). For example, in the presence of 0.5, 0.8, 1.0, and 1.5 mmol L(-1) of chromate, for the rhodic ferralsol the adsorption of Cu(II) increased by 15.3, 18.0, 19.0, and 20.2%, respectively. For the hyperrhodic ferrasol, the corresponding figures were 11.9, 17.0, 20.3, and 26.1%, respectively. The presence of chromate also caused an increase in the desorption of Cu(II). For instance, in the presence of 0.5, 1.0, and 1.5 mmol L(-1) of chromate, the desorption for the rhodic ferralsol increased by 16.9, 27.5, and 34.1%, respectively. For the hyperrhodic ferralsol, the corresponding figures were 18.1, 35.6, and 51.4%, respectively. The increments of the adsorption and desorption increased with the increase in equilibrium concentration of Cu(II) in the solution. For instance, when the equilibrium concentrations were 0.5, 1.0, 1.5, and 2.0 mmol L(-1), the increments for the rhodic ferralsol were 2.5, 3.2, 3.3, and 3.0 mmol kg(-1), respectively. For the hyperrhodic ferralsol, the corresponding figures were 2.9, 3.5, 4.0, and 4.2 mmol kg(-1), respectively. The effect of chromate for the hyperrhodic ferralsol was greater than that for the rhodic ferralsol. This is caused by the difference in the content of iron oxides for the two soils. The increments of the adsorption and the desorption of Cu(II) increased with the rise in pH, reaching a maximum value, and then decreased. It can be assumed that the increment of the adsorption was caused by the change in surface charge of the soils induced by the adsorption of chromate and the cooperative adsorption of chromate adsorbed and Cu(II). The increase of electrostatically adsorbed Cu(II) was responsible for the increase in the desorption of Cu(II).

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PubMed2006

Adsorption of reactive dyes on titania-silica mesoporous materials.

This paper presents a study on the adsorption of two basic dyes, methylene blue (MB) and rhodamine B (RhB), from aqueous solution onto mesoporous silica-titania materials. The effect of dye structure, adsorbent particle size, TiO(2) presence, and temperature on adsorption was investigated. Adsorption data obtained at different solution temperatures (25, 35, and 45 degrees C) revealed an irreversible adsorption that decreased with the increment of T. The presence of TiO(2) augmented the adsorption capacity (q(e)). This would be due to possible degradation of the dye molecule in contact with the TiO(2) particles in the adsorbent interior. The adsorption enthalpy was relatively high, indicating that interaction between the sorbent and the adsorbate molecules was not only physical but chemical. Both Langmuir and Freundlich isotherm equations were applied to the experimental data. The obtained parameters and correlation coefficients showed that the adsorption of the two reactive dyes (MB and RhB) on the adsorbent systems at the three work temperatures was best predicted by the Langmuir isotherm, but not in all cases. The kinetic adsorption data were processed by the application of two simplified kinetic models, first and second order, to investigate the adsorption mechanism. It was found that the adsorption kinetics of methylene blue and rhodamine B onto the mesoporous silica-titania materials surface under different operating conditions was best described by the first-order model.

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PubMed2006

Reflectometric study of the adsorption of poly(vinyl imidazole) on a gold electrode, effects of pH, and applied potential.

The adsorption-desorption behavior of poly(vinyl imidazole), a weak polybase (pH-dependent positive charge), on a gold electrode was investigated using optical fixed-angle reflectometry. Using an instrument comprising an impinging-jet system, the hydrodynamic conditions were well defined, making it possible to study the adsorption rate. Comparison between the actual adsorption rate and that of a purely diffusion-controlled process revealed the occurrence and the change of an electrostatic barrier in the adsorption process. The surface charge of the gold electrode was varied by means of an externally applied potential. The surface charge density was evaluated by separate electrochemical impedance spectroscopy. The uptake and the adsorption rate were very sensitive to pH and electrode polarization. At pH 3, the adsorption of the fully charged polymer increased fairly regularly with cathodic polarization, whereas it remained at about 0.4 mg m(-2) in the anodic zone At pH 8, the adsorption of the uncharged polymer decreased with the negative charge of the electrode due to the more favorable adsorption of potassium ions on the charged electrode. Discrepancies in adsorption-desorption measurements taken while cycling the pH were due to an electrostatic adsorption barrier.

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PubMed2006

New methodology to determine the rate-limiting adsorption kinetics mechanism from experimental dynamic surface tension data.

We present a new methodology to determine the rate-limiting adsorption kinetics mechanism (diffusion-controlled vs mixed diffusion-barrier controlled), including deducing the kinetics parameters (the diffusion coefficient, D, and the energy-barrier parameter, beta), from the experimental short-time dynamic surface tension (DST) data. The new methodology has the following advantages over the existing procedure used to analyze the experimental DST data: (a) it does not require using a model for the equilibrium adsorption isotherm, and (b) it only requires using the experimental short-time DST data measured at two initial surfactant bulk solution concentrations. We apply the new methodology to analyze the experimental short-time DST data of the following alkyl poly(ethylene oxide), CiEj, nonionic surfactants: C12E4, C12E6, C12E8, and C10E8 measured using the pendant-bubble apparatus. We find that for C12E4 and C12E6, the effect of the energy barrier on the overall rate of surfactant adsorption can be neglected for surfactant bulk solution concentrations below their respective critical micelle concentrations (CMCs), and therefore, that the rate-limiting adsorption kinetics mechanism for C12E4 and C12E6 is diffusion-controlled at any of their premicellar surfactant bulk solution concentrations. On the other hand, for C12E8 and C10E8, we find that their respective CMC values are large enough to observe a significant effect of the energy barrier on the overall rate of surfactant adsorption. In other words, for C12E8 and C10E8, the rate-limiting adsorption kinetics mechanism shifts from diffusion-controlled to mixed diffusion-barrier controlled as their premicellar surfactant bulk solution concentrations increase. We test the new methodology by predicting the short-time DST profiles at other initial surfactant bulk solution concentrations, and then comparing the predicted DST profiles with those measured experimentally. Very good agreement is obtained for the four CiEj nonionic surfactants considered. We also compare the results of implementing the new methodology with those of implementing the existing procedure, and conclude that using a model for the equilibrium adsorption isotherm can lead not only to different values of D and beta, but it can also lead to a completely different determination of the rate-limiting adsorption kinetics mechanism. Since the new methodology proposed here does not require using a model for the equilibrium adsorption isotherm, we conclude that it should provide a more reliable determination of the rate-limiting adsorption kinetics mechanism, including the deduced kinetics parameters, D and beta.

Journal Article↗
PubMed2003

Adsorption of polyethylene glycol (PEG) from aqueous solution onto hydrophobic zeolite.

In the present study, a hydrophobic zeolite was used as an adsorbent for the adsorption of polyethylene glycol (PEG) in water solution and electroplating solution at 25 degrees C. The adsorption capacities were determined through the adsorption isotherms in a thermostated shaker. The rate of adsorption, on the other hand, was investigated in a batch adsorber under controlled process parameters such as initial PEG concentration (30, 70, 110, 150, 200, and 300 mg x dm(-3)), agitation speed (200, 800, and 1000 rpm), and adsorbent particle size (0.72, 1.44, and 2.03 mm). A batch kinetic model, according to a pseudo-second-order mechanism, has been tested to predict the rate constant of adsorption, equilibrium adsorption capacity, time of half-adsorption, and equilibrium concentration by the fitting of the experimental data. The results of the adsorption isotherm and kinetic studies show that the adsorption process can well be described with the Langmuir and Freundlich models and the pseudo-second-order equation, respectively. Comparing the values of adsorption parameters of PEG in water solution and electroplating solution, there are no significant differences. In addition, the effective diffusion coefficient of the PEG molecule in the microporous adsorbent has been estimated at about 3.20 x 10(-8) cm(2)s(-1) based on the restrictive diffusion model.

Journal Article↗
PubMed2003

Further insights into the role of carbon surface functionalities in the mechanism of phenol adsorption.

The presented study describes the temperature as well as pH dependence of phenol adsorption (and adsorption kinetics) on four carbons with different chemical compositions of the surface layer but almost identical porosity. In the first part, it is shown, applying the most sophisticated method of carbon porosity characterization (i.e., the method of Do and co-workers-ND method), that the porosity does not change much after the chemical modification of carbons. Then it is shown that the ND method leads to the same results as the DFT (density functional theory) does. Next, the TPD results for D43/1 carbons (initial, modified with HNO(3), fuming H(2)SO(4), and with NH(3)) are described. The TPD results for carbon modified with fuming sulphuric acid has not been reported yet by others. The deconvolution of peaks is performed. The obtained results, together with those already published, lead to the chemical structures of surface functionalities for all studied carbons. The thermogravimetric analysis of phenol adsorption shows that the amount of chemically bonded molecules is small. Then it is shown that the adsorption at the acidic pH (1.5) level is lower for all studied carbons than that at the neutral one. The description of the isotherms applying adsorbability, quasi-Freundlich and DA models, together with enthalpy measurements, lead to the mechanism of phenol adsorption at both pH values. The mechanism is, furthermore, confirmed by some empirical correlations. The analysis of the average hysteresis on adsorption-desorption isotherms as well as the comparison of phenol adsorption in oxic and anoxic conditions leads to the mechanism of irreversible phenol adsorption. It is suggested that the irreversibility is caused by two effects: the creation of strong complexes between phenol and surface carbonyl and lactones as well as by the polymerization. The last effect is due to the ability of carbon to adsorb the oxygen from solution and form superoxo ions. Finally, the kinetics is considered. The analytical solution of Fick's law of diffusion for adsorption in cylindrical particles is applied, the diffusion coefficients are calculated. It is shown that phenol diffusion is mixed between a surface process and a pore one. The obtained energy of diffusion is correlated with the values of the physicochemical parameters of studied carbons. As a final point, it is concluded that the mechanism of phenol adsorption is not only determined by so called "pi-pi interactions" and "donor-acceptor complex formation" but also by (strongly depending on temperature) the "solvent effect" balancing the influence of the two mentioned factors on this mechanism.

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PubMed2001

Adsorption of protein/surfactant complexes at the air/aqueous interface.

We use optical reflectometry and surface pressure techniques to measure co-adsorption of the anionic surfactant sodium dodecyl sulfate (SDS) and the protein lysozyme at the air-aqueous interface. We observe lysozyme/SDS co-adsorption behavior in two different buffers for which solution-phase binding data are available in the literature. The co-adsorption of lysozyme/SDS complexes is controlled by the mode of protein/surfactant binding that occurs in solution. In a pH 5.0 acetate buffer, the extent of co-adsorption is weakly dependent on SDS concentration throughout the specific and transitional binding regimes. In a pH 6.9 phosphate buffer, the extent of co-adsorption is weakly dependent on SDS concentration in the specific binding regime, but it increases dramatically, giving rise to multilayer co-adsorption, in the transitional binding regime. In both buffers, the extent of co-adsorption dramatically decreases in the cooperative binding regime. Lysozyme/SDS co-adsorption is strongly influenced by kinetically trapped non-equilibrium adsorbed layer states, such that adsorbed amounts are markedly path-dependent. Surface pressure measurements by themselves do not capture the variations in adsorption in the different binding regimes, nor do they capture the path-dependency of co-adsorption.

Journal Article↗
PubMed2001

The effects of pH and surface composition on Pb adsorption to natural freshwater biofilms.

Two dominant variables that control the adsorption of toxic trace metals to suspended particulate materials and aquatic surface coatings are surface composition and solution pH. A model for the pH-dependent adsorption of Pbto heterogeneous particulate surface mixtures was derived from experimental evaluation of Pb adsorption to laboratory-derived surrogates. The surrogate materials were selected to represent natural reactive surface components. Pb adsorption to both the laboratory surrogates and natural biofilms was determined in chemically defined solutions under controlled laboratory conditions. Pb adsorption was measured over a pH range of 5-8, with an initial Pb concentration in solution of 2.0 microM. The surface components considered include amorphous Fe oxide, biogenic Mn oxide produced by a Mn(II) oxidizing bacterium (Leptothrix discophora SS-1), Al oxide, the common green alga Chlorella vulgaris, and Leptothrix discophora SS-1 cells. A linearization of Pb adsorption data for each adsorbent was used to quantify the relationship between Pb adsorption and pH. The parameters for individual adsorbents were incorporated into an additive model to predict the total Pb adsorption in multiple-adsorbent natural surface coatings that were collected from Cayuga Lake, NY. Pb adsorption experiments on the natural surface coatings at variable pH were utilized to verify the additive model predictions based on the pH dependent behavior of the experimental laboratory surrogates. Observed Pb adsorption is consistent with the model predictions (within 1-24%) over the range of solution pH values considered. The experimental results indicate that the combination of Fe and biogenic Mn oxides can contribute as much as 90% of Pb adsorbed on Cayuga Lake biofilms, with the dominant adsorbent switching from Mn to Fe oxide with increasing pH.

Biofilms↗
PubMed2005

Study of adsorption and decomposition of H2O on Ge(100).

The adsorption and decomposition of water on Ge(100) have been investigated using real-time scanning tunneling microscopy (STM) and density-functional theory (DFT) calculations. The STM results revealed two distinct adsorption features of H2O on Ge(100) corresponding to molecular adsorption and H-OH dissociative adsorption. In the molecular adsorption geometry, H2O molecules are bound to the surface via Ge-O dative bonds between the O atom of H2O and the electrophilic down atom of the Ge dimer. In the dissociative adsorption geometry, the H2O molecule dissociates into H and OH, which bind covalently to a Ge-Ge dimer on Ge(100) in an H-Ge-Ge-OH configuration. The DFT calculations showed that the dissociative adsorption geometry is more stable than the molecular adsorption geometry. This finding is consistent with the STM results, which showed that the dissociative product becomes dominant as the H2O coverage is increased. The simulated STM images agreed very well with the experimental images. In the real-time STM experiments, we also observed a structural transformation of the H2O molecule from the molecular adsorption to the dissociative adsorption geometry.

Journal Article↗
PubMed2006

Three-stage multilayer formation kinetics during adsorption of an anionic fluorinated surfactant onto germanium. 1. Concentration effect.

The adsorption of tetraethylammonium perfluorooctylsulfonate (TEA-FOS) from aqueous solution onto hydroxylated germanium is studied using in situ polarized attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The adsorption is monitored at a series of bulk solution concentrations spanning from well below to above the critical micelle concentration (CMC; 1.0 mM). The kinetics of adsorption is followed by monitoring the intensity of the fluorocarbon bands. The orientation of the fluorocarbon director with respect to the germanium surface is determined by circular dichroism measurements of CF2 stretching bands. At bulk concentrations ranging from 10% of the CMC to at least 500% of the CMC, the adsorption occurs in an unusual sequence of three stages. Initially, rapid adsorption occurs within 200 min, leading to coverage of a monolayer or less. A long period of slow adsorption follows, during which we hypothesize that surfactant molecules form clusters, some of which serve as nuclei for multilayer growth. This stage concludes suddenly with an acceleration in the rate of adsorption, which eventually leads to multilayer formation. Because this is an anionic surfactant adsorbing onto a negatively charged surface at pH 6, the tetraethylammonium ions must mediate the interactions between the surfactant headgroups and the surface. The dichroism measurements show that TEA-FOS is initially oriented randomly or somewhat parallel to the surface, but over time adopts an orientation somewhat normal to the surface. This behavior is consistent with initial adsorption at isolated sites, followed by aggregation into isotropic admicelles, and finally growth into flattened admicelles. The sudden onset of accelerated adsorption can be explained either by autoaccelerating adsorption or nucleation and growth of a hydrophobic multilayer structure.

Journal Article↗
PubMed2006

Liquid-phase adsorption of multi-ring thiophenic sulfur compounds on carbon materials with different surface properties.

This work examines the effects of structural and surface properties of carbon materials on the adsorption of benzothiophene (BT), dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT) in the presence of 10 wt % of aromatics in liquid alkanes that simulate sulfur compounds in diesel fuels. The equilibrium-adsorption capacity varies significantly, from 1.7 to 7.0 mg-S/g-A. The results show that different carbon materials have significantly different sulfur-adsorption capacities and selectivities that depend not only on textural structure but also on surface functional groups. The adsorption of multi-ring sulfur compounds on carbon materials was found to obey the Langmuir isotherm. On the basis of adsorption tests and the characterization of carbon materials by BET and XPS, the oxygen-containing functional groups on the surface appear to play an important role in increasing sulfur-adsorption capacity. The adsorption-selectivity trend of the carbon materials for various compounds increases in the order of BT < naphthalene < 2-methylnaphthalene < DBT < 4-MDBT < 4,6-DMDBT, regardless of carbon material types. This selectivity trend for sulfur compounds is dramatically different and almost opposite from that previously observed for adsorption over nickel-based adsorbents. The regeneration of spent activated carbons was also conducted by solvent washing. The high-adsorption capacity and selectivity for methyl DBTs indicate that certain activated carbons are promising adsorbents for selective adsorption for removing sulfur (SARS) as a new approach to ultra deep desulfurization of diesel fuels.

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