Generalized Poisson-Boltzmann Equation Taking into Account Ionic Interaction and Steric Effects

Generalized Poisson-Boltzmann equation which takes into account both ionic interaction in bulk solution and steric effects of adsorbed ions has been suggested.We found that,for inorganic cations adsorption on negatively charged surface,the steric effect is not significant for surface charge density 0.0032 Cdm 2,while the ionic interaction is an important effect for electrolyte concentration 0.15 moll in bulk solution.We conclude that for most actual cases the original PB equation can give reliable result in describing inorganic cation adsorption.     

N2在页岩干酪根上的吸附特征

采用密度泛函理论的wB97XD方法、RDG函数方法和counterpoise correction理论,研究氮气在干酪根C₂₈H₁₄O和氮掺杂干酪根C₂₇H₁₄ON上的吸附特征。结果表明：N₂在干酪根上的活性吸附位点为苯环上方中心位置,吸附能在8~10 kJ·mol^-1之间,N₂和干酪根之间的相互作用主要是范德华相互作用和空间排斥作用。氮掺杂改变了干酪根的构型和电子云分布,导致含氮杂环不再是稳定的活性吸附位点,增强了排斥作用,使吸附能略有减小。研究结果对理解干酪根吸附小分子的特征有重要意义,能够为页岩气的开采提供理论支持。     

Studies on the surface modification of diatomite with polyethyleneimine and trapping effect of the modified diatomite for phenol

The adsorption isotherm of polyethyleneimine (PEI) on diatomite was studied using UV spectrophotometry, the surface of diatomite was modified with polyethyleneimine by using impregnation method, and the trapping behavior of the modified diatomite for phenol was investigated by using 4-aminoantipyrine (4-AAP) spectrophotometric method. The experiment results show that negatively charged diatomite particles have very strong absorption effect for cationic macromolecule PEI, the adsorption isotherm fits in Freundlich equation. The character that there is a maximum value after intitial sharp increase of adsorption capacity on the adsorption curve indicates that there is strong affinity between diatomite particles and polyethyleneimine macromolecules, and it attributes to the strong electrostatic interaction. After modification with PEI, the electric property of diatomite particle surface changes essentially, and the isoelectric point of diatomite particles moves from pH 2.0 to 10.5. In acidic solution, phenol exists as molecular state, and the modified diatomite particles adsorb phenol through hydrogen bond interaction. However, the hydrogen bond interaction between nitrogen atoms on PEI chains and phenol is weaker because of high degree of protonation of polyethyleneimine macromolecules, so the adsorption quantity is lower. In basic solution, phenol exists as negative benzene–oxygen ion, and the modified diatomite particles adsorb phenol through electrostatic interaction. However, the electrostatic interaction between PEI and negative benzene–oxygen ion is very weak because of low degree of protonation of polyethyleneimine macromolecules, so the adsorption quantity is much lower. The modified diatomite particles produce very strong trapping effect for phenol in neutral aqueous solution via the cooperating of strong electrostatic interaction and hydrogen bond interaction, and the saturated adsorption capacity can attain to 92 mg g⁻¹.     

Adsorption of SH and OH and coadsorption of S, O and H on Ni(111)

The adsorption of SH and OH radicals on Ni(111) is treated using an ab initio embedding theory. The Ni(111) surface is modeled as a three-layer, 28-atom cluster with the Ni atoms fixed at bulk lattice sites. The Ni(111) energy surface is very flat for SH adsorption if the H tilt angle is allowed to vary. At both atop and bridge sites, the S---H axis is tilted away from the surface normal by 70°, resulting in the sulfur atom being sp³-hybridized and the adsorption energy being 59 kcal mol⁻¹. For SH at the three-fold site, the S---H axis is normal to the surface, the sulfur is sp-hybridized, and the adsorption energy is 58 kcal mol⁻¹. OH is preferentially adsorbed at the three-fold site. The calculated adsorption energy is 90 kcal mol⁻¹ and the O---H axis is perpendicular to the surface. OH adsorption at the atop and bridge sites is 16 and 5 kcal mol⁻¹ less stable than at the three-fold site, respectively. Atomic H, O and S are preferentially adsorbed at the three-fold site. The calculated adsorption energies are 62, 92 and 87 kcal mol⁻¹, for H, O and S, respectively. The calculated adsorbate---Ni bond distances of 1.86 Å for H, 1.86 Å for O and 2.29 Å for S are in good agreement with experimental data. SH and OH bonding to the surface involves a combination of ionic and covalent contributions and substantial mixing with the Ni 3d orbitals. Dipole-moment calculations indicate strong ionic bonding for the atomic O/Ni system and ionic plus covalent character for the atomic S/Ni interactions. Adsorption of S and O at the three-fold site blocks H adsorption at the nearby surface. Moving H away from the S or O adatom reduces the repulsion. The dissociation of SH_ad → S_ad + H_ad is calculated to be exothermic by 5 kcal mol⁻¹ and OH_ad → O_ad + H_ad to be endothermic by 30 kcal mol⁻¹ for infinite separation between S, O and H.     

Polyelectrolyte adsorption

The problem of charged polymer chains (polyelectrolytes) as they adsorb on a planar surface is addressed theoretically. We review the basic mechanisms and theory underlying polyelectrolyte adsorption on a single surface in two situations: adsorption of a single charged chain, and adsorption from a bulk solution in θ solvent conditions. The behavior of flexible and semi-rigid chains is discussed separately and is expressed as function of the polymer and surface charges, ionic strength of the solution and polymer bulk concentration. We mainly review mean-field results and briefly comment about fluctuation effects. The phenomenon of polyelectrolyte adsorption on a planar surface as presented here is of relevance to the stabilization of colloidal suspensions. In this respect we also mention calculations of the inter-plate force between two planar surfaces in presence of polyelectrolyte. Finally, we comment on the problem of charge overcompensation and its implication to multi-layers formation of alternating positive and negative polyelectrolytes on planar surfaces and colloidal particles.     

Adsorption kinetics in micellar solutions of nonionic surfactants

Standard models of the adsorption kinetics of surfactants at the air-water surface assume that micelles break down into monomers in the bulk solution and that only monomers adsorb. We show here that micelles of the nonionic surfactant C14E8 adsorb to the surface of a liquid jet at a diffusion-controlled rate. Micellar adsorption can be switched off by incorporation of a small amount of ionic surfactant into the micelle and switched on again by addition of salt. More sophisticated models of adsorption processes in micellar solutions are required that permit a kinetic flux of micelles to the air-water interface.     

Application of the statistical rate theory of interfacial transport to investigate the kinetics of divalent metal ion adsorption onto the energetically heterogeneous surfaces of oxides and activated carbons

Divalent metal cation adsorption from solution onto oxides or activated carbons can be described by the Surface Complexation Model (SCM). We assumed that the adsorbent surface is strongly energetically heterogeneous and derived the adsorption isotherm using rectangular distribution of adsorption energy and condensation approximation for the local isotherm equation. Assuming additionally that the bulk concentration of divalent metal ion is low and does not change considerably during the adsorption process and next applying the Statistical Rate Theory of Interfacial Transport (SRT) we derived the Elovich equation—the experimental formula describing adsorption kinetics.     

光度法研究太湖表层沉积物中磷形态分布及动力学特征

表层沉积物是水体污染物的源和汇。研究表明,太湖地区特别是梅梁湾和东太湖表层沉积物中磷等营养元素污染严重。采用SMT法(standards measurements and testing)和钼锑抗分光光度法对太湖18个采样点表层沉积物样品进行前处理和磷形态分析,结合我国、加拿大和美国标准对总磷进行污染评价。通过拟合建立了吸附-解吸动力学特征方程,并在不同pH、水土比的环境条件下获得磷的吸附特性。同时也在不同温度和pH下对磷进行解吸特征研究。结果表明： S₉采样点总磷、无机磷、有机磷和酸磷含量均最高,S₁₁采样点碱磷含量最高。对于所有采样点,各形态磷平均值大小排序为(μg·g-1)： 无机磷(401.43)>酸磷(377.81)>有机磷(175.37)>碱磷(25.53)。污染评价结果表明： 除S₁₂,S₁₄~S₁₆及S₁₈采样点外,其余采样点均有不同程度的污染。表层沉积物对磷的吸附-解吸过程均符合伪二级动力学方程。吸附过程最佳水土比为25∶1,且pH值对吸附和解吸有不同程度的影响。研究结果为掌握太湖梅梁湾和东太湖区域磷的污染现状提供理论依据,同时为研究磷在沉积物-水界面的迁移规律提供可信的实验数据。     

H,Cl和F原子钝化Cu_2ZnSnS_4(112)表面态的第一性原理计算

采用基于密度泛函理论的第一性原理计算方法系统研究了Cu_2ZnSnS_4体相的晶格结构、能带、态密度及表面重构与H,Cl和F原子在Cu_2ZnSnS_4(112)表面上的吸附和钝化机理.计算结果表明:表面重构出现在以金属原子Cu-Zn-Sn终止的Cu_2ZnSnS_4(112)表面上,并且表面重构使表面发生自钝化;当单个H,Cl或F原子吸附在S原子终止的Cu_2ZnSnS_4(112)表面上时,相比于桥位(bridge)、六方密排(hcp)位和面心立方(fcc)位点,三种原子均在特定的顶位(top)吸附位点表现出最佳稳定性.当覆盖度为0.5 ML时,无论H,Cl还是F原子占据Cu_2ZnSnS_4(112)表面的2个顶位均具有最低的吸附能.以S原子终止的Cu_2ZnSnS_4(112)表面在费米能级附近的电子态主要由价带顶部Cu-3d轨道和S-3p轨道电子贡献,此即表面态.当H,Cl或F原子在表面的覆盖度达0.5 ML时,费米能级附近的表面态降低,其中H原子钝化表面态的效果最佳,Cl原子的效果次之,F原子的效果最差.表面态降低的主要原因在于吸附原子从S原子获得电子致使表面Cu原子和S原子在费米能级处的态密度峰几乎完全消失.     

Adsorption of hydrophobic polyelectrolytes onto oppositely charged surfaces

We present a scaling theory for the adsorption of a weakly charged polyelectrolyte chain in a poor solvent onto an oppositely charged surface. Depending on the fraction of charged monomers and on the solvent quality for uncharged monomers, the globule in the bulk of the solution has either a spherical conformation or a necklace structure. At sufficiently high surface charge density, a chain in the globular conformation adsorbs in a flat pancake conformation due to the Coulombic attraction to the oppositely charged surface. Different adsorption regimes are predicted depending on two screening lengths (the Debye screening length monitored by the salt concentration and the Gouy-Chapman length monitored by the surface charge density), on the degree of ionization of the polymer and on the solvent strength. At low bulk ionic strength, an increase in the surface charge density may induce a transition from an adsorbed necklace structure to a uniform pancake due to the enhanced screening of the intra-chain Coulombic repulsion by the counterions localized near the surface. Received 12 April 2001     

Molecular dynamics study of the vibrational relaxation of OCl and OCl in the bulk and the surface of water and acetonitrile

The vibrational relaxation of OCl and OCl⁻ in the bulk and the liquid/vapor interface of water and acetonitrile is studied by molecular dynamics computer simulations. Both equilibrium calculations of the vibrational friction and non-equilibrium simulation of the energy relaxation are used to elucidate the factors that influence the rate of energy relaxation in systems that represent polar ionic and non-ionic solutes in polar protic and non-protic solvents. We find that, in agreement with previous experimental and theoretical studies, the relaxation of the ionic solute is much faster than that of the non-ionic solute in both the solvents. However, while the relaxation is slowed down considerably when the non-ionic solute is transferred from the bulk to the interface, no such surface effect is found in the case of the ionic solute. This behavior can be explained by noting that the ionic solute is able to keep its first solvation shell intact upon transfer to the interface and that the main contribution to the friction is due to the Lennard-Jones part of the intermolecular potential.     

Applicability of the film-diffusion model for description of the adsorption kinetics at the solid/solution interfaces

The adsorption kinetics at the solid/solution interfaces has been described by using the kinetic model based on accepting the existence of the concentration gradient in the region of bulk solution close to the solid surface (external film-diffusion model). This model has also been adopted to explain some behaviours observed in the real adsorption systems. Simultaneously, the pseudo-first order (Lagergren) equation can be derived applying this model. The results indicate that the necessary condition to state that the “diffusion across the liquid film” mechanism is involved in controlling the rate of adsorption process is the linearity of the initial parts of kinetic isotherms plotted as the amount adsorbed vs. the time. The two methods have been proposed to distinguish between this mechanism and the classical Langmuir kinetics. The results presented here might be useful in identifying if the concentration gradient in the bulk solution influences the overall adsorption rate.     

The interaction of C2Cl4 with fe(110)

Quantitative adsorption studies, temperature programmed desorption (TPD) and Auger spectroscopy have been used to study the interaction of C₂Cl₄ with Fe(110) at 90 and 325 K. At 90 K, multilayer C₂Cl₄ adsorption occurs. The following desorption products are observed in the temperature range of 90–1050 K: C₂Cl₄ from the multilayer and the monolayer, FeCl₂, and a high mass iron chloride species with mass spectrometer cracking products FeCl⁺₂, FeCl⁺, and Fe⁺. Irreversible dissociative C₂Cl₄ adsorption occurs at 325 K and the only desorption product which is observed is the high mass iron chloride species. Auger spectroscopy shows that surface carbon from C₂Cl₄ starts to diffuse into the bulk of the crystal at ˜ 480 K while small coverages of chlorine remain on the surface of the crystal even after heating to 1050 K. Comparison of the behavior of C₂Cl₄ and CCl₄ on Fe(110) indicates that radical products (·CCl₃ and :CCl₂) observed to be produced from CCl₄ adsorption are not produced from C₂Cl₄ adsorption. This difference is probably due to the enhanced surface reactivity of the C=C bond in C₂Cl₄. A special reactivity of iron defect sites for C₂Cl₄ is observed through the production of associated FeCl₂ species which desorb via zero-order kinetics with an activation energy of 44.8 ± 8.5 kcal/mol, the sublimation enthalpy of FeCl₂.     

Adsorption of hydrogen and deuterium on potassium-promoted Pd(100) surfaces

The adsorption of H₂ and D₂ has been studied on clean and K-promoted Pd(100) surfaces using thermal desorption, work function changes, ultraviolet photoelectron and Auger spectroscopy. The potassium adlayer significantly lowers the sticking coefficient (from 0.6 to 0.06 at θ_k = 0.2), and the uptake of hydrogen, but increases the desorption energy for H₂ desorption. Calculation showed that each potassium adatom blocks approximately 4–5 adsorption sites for H₂ adsorption. Atomization of hydrogen led to an increase of hydrogen uptake. The adsorption of potassium on the H-covered surface caused a significant decrease in the amount of hydrogen adsorbed on the surface (as indicated by less desorbing hydrogen below 500 K) and promoted the dissolution of H atoms into the bulk of Pd. The dissolved hydrogen was released only above 600–650 K. In the interpetation of the results the extended charge transfer from K-dosed Pd to the adsorbed H atoms and the direct interaction between adsorbed H and K adatoms are taken into account.     

VO2薄膜表面氧缺陷的修复:F4TCNQ分子吸附反应

VO₂表面氧缺陷的存在对VO₂材料具有显著的电子掺杂效应, 极大地影响材料的本征电子结构和相变性质. 通过2, 3, 5, 6-四氟-7, 7', 8, 8'-四氰二甲基对苯醌(F₄TCNQ)分子表面吸附反应, 可以有效消除表面氧缺陷及其电子掺杂效应. 利用同步辐射光电子能谱和X射线吸收谱原位研究了修复过程中电子结构的变化以及界面的化学反应, 发现这种方式使得VO₂薄膜样品氩刻后得到的V³⁺失去电子成功地被氧化成原先的V⁴⁺, 同时F₄TCNQ分子吸附引起电子由衬底向分子层转移, 界面形成带负电荷的分子离子物种. 受电化学性质的制约, F₄TCNQ分子吸附反应修复氧缺陷较氧气氛退火更安全有效, 不会引起表面过度氧化形成V₂O₅.     

Ethylene, sulphur, and chlorine coadsorption on Pd(111): a theoretical study of poisoning and promotion

First principles calculations for the coadsorption of C₂H₄ with S and Cl on Pd(111) are presented. Sulphur poisons adsorption, decreasing the strength of the ethylene–surface interaction. While low coverages of chlorine alone do not appear to affect ethylene adsorption on the otherwise clean palladium surface, chlorine does act as a promoter on the sulphur poisoned surface, increasing the strength of the ethylene–surface interaction. The promotional effect is attributed to changes in the dative bonding of the molecule and the surface and cannot be explained solely in terms of changes in the metal workfunction.     

Stereodynamics in dissociative adsorption of NO on Si(111)

We report results of our study on the surface-temperature dependence of the steric effect in the dissociative adsorption of NO on Si(111)-(7x7). Data presented here show that, at an incident energy of 58 meV, the reactive sticking probability for the N-end collision is larger than that for the O-end collision. Furthermore, this steric preference is quite sensitive to the surface temperature and the surface coverage. This study shows that the transient surface trapping into a shallow precursor well plays a key role in the stereodynamics of the dissociative adsorption at the low energy region.     

Probing the adsorption of methylimidazole at ionic liquids/Cu electrode interface by surface‐enhanced Raman scattering spectroscopy

Two kinds of room‐temperature ionic liquids, 1‐butyl‐3‐methylimidazolium bromide ([BMIM]Br) and 1‐butyl‐3‐methylimidazolium tetrafluoroboride ([BMIM]BF₄), were used as solvent, and the adsorption of the ionic liquids themselves and of N‐methylimidazole (NMIM) were investigated by electrochemical surface‐enhanced Raman scattering (SERS) over a wide potential window. The results revealed that the cation of ionic liquid adsorbed onto Cu surface with different configurations in different potential ranges. When the potential was changed from the negative to the positive range, the orientation underwent a change from flat to vertical, and the onset potential for the orientation change was dependent on the types of anion of the ionic liquid. The ionic liquid in bulk solution exhibited a remarkable effect on the adsorption of NMIM. The electrode surface structure changed from adsorbing the ionic liquid at the negative potential to coadsorbing the ionic liquid and NMIM at relative positive potential for the [BMIM]BF₄ liquids, and formed films of NMIM at extremely positive potential. Due to the strong specific adsorption of Br⁻, the coadsorption of ionic liquid and NMIM was not observed in the system [BMIM]Br. By simulating the electrode surroundings, two surface complexes [Cu(NMIM)₄Br]Br·H₂O and [Cu(NMIM)₄](BF₄)₂ were synthesized by the electrochemical method in the corresponding ionic liquids for modeling the surface coordination chemistry of NMIM. The surface coordination configuration of NMIM and ionic liquids is proposed. Copyright © 2009 John Wiley & Sons, Ltd.