Uranyl adsorption on solvated edge surfaces of pyrophyllite: a DFT model study

In a computational study we addressed the adsorption of uranyl UO(2)(2+) on solvated (110) and (010) edge surfaces of pyrophyllite, applying a density functional approach to periodic slab models. We explored bidentate adsorption complexes on various partially deprotonated adsorption sites: octahedral Al(O,OH), tetrahedral Si(O,OH), and mixed AlO-SiO. Aluminol sites were determined to be most favorable on the (110) surface of pyrophyllite, while on the (010) surface mixed AlO-SiO sites are preferred. The structural parameters of all low-energy complexes on both surfaces agree rather well with EXAFS results for the structurally similar mineral montmorillonite. We calculate the average U-O distance to surface and aqua ligand oxygen atoms to increase with the increasing coordination number of uranyl whereas EXAFS results indicate the opposite trend. According to our results, several adsorption species, with different coordination numbers on different edge faces, may coexist on clay minerals. This computational finding rationalizes why earlier spectroscopic studies indicated the existence of more than one adsorption species, whereas a single type of adsorption complex was suggested from most EXAFS results.     

Modeling adsorption of the uranyl dication on the hydroxylated alpha-Al2O3(0001) surface in an aqueous medium. Density functional study

As a first step toward modeling the interaction of dissolved actinide contaminants with mineral surfaces, we studied low-coverage adsorption of aqueous uranyl, UO2(2+), on the hydroxylated alpha-Al2O3(0001) surface. We carried out density functional periodic slab model calculations and modeled solvation effects by explicit aqua ligands. We explored the formation of both inner- and outer-sphere complexes and estimated the corresponding adsorption energies. Effects of solvation were accounted for by explicit consideration of the first hydration shell of uranyl and by means of a posteriori corrections for long-range solvent effect. With energetics described at the GGA-PW91 level and under the assumption of a fully protonated ideal surface, we predict a weakly bound outer-sphere adsorption complex.     

Amorphous silica as a versatile supermolecular ligand for Ni(II) amine complexes: toward interfacial molecular recognition.

Selective adsorption of Ni(II) amine complexes used as precursors for supported catalysts was studied on amorphous silica surfaces. The nature of the adsorption sites was probed by [Ni(en)(dien) (H2O)]2+, [Ni(en)2(H2O)2]2+, and [Ni(dien)(H2O)3]2+ (en = ethylenediamine, dien = diethylenetriamine), which respectively contain one, two, and three labile aqua ligands. The silica surface acts as a mono- or polydentate ligand that can substitute the aqua ligands of the Ni(II) complexes in an inner-sphere adsorption mechanism. Room-temperature adsorption isotherms indicate that each nickel complex selects a limited number of adsorption sites; different sites are recognised by the three complexes, even though they have the same charge and comparable sizes. Several spectroscopic techniques (UV/Vis/NIR, EXAFS, and 29Si NMR) were used to confirm the selective character of the interaction of Ni(II) amine complexes with the silica surface. The specific sites include both silanol/silanolate groups in the same number as the original labile ligands and other surface groups that probably act as hydrogen-bond acceptors. These two types of groups cooperate to result in interfacial molecular-recognition phenomena with interactional complementarity.     

铀酰离子吸附在高岭土基面的分子动力学模拟

为研究铀酰离子在高岭土不同基面上的吸附, 对含有0.01 mol·L^-1碳酸铀酰液相和9×9×3个高岭土单胞的粘土固相的模拟盒子进行了分子动力学模拟. 从模拟的截图中直观地观察到了铀酰离子的吸附位点, 由径向分布函数得到了铀酰离子与水中氧原子的配位情况. 利用原子密度剖面图讨论铀酰离子在两个基面上的吸附倾向, 并从原子密度剖面图和均方位移等角度证实了铀酰离子在硅氧面上形成了外界配合物. 从理论上证明了表面配合模型对于吸附位点所做简化的合理性.     

Interaction of Hg Atom with Bare Si（111） Surface

1INTRODUCTION In the past decades,mercury has been a very use-ful electrode material in the fabrication and electrical measurement of molecule modified metal-metal and metal-semiconductor junctions.Majda et al.[1,2]constructed a symmetric Hg-SCn-CnS-Hg junction to study the electron tunneling properties of alkanethio-late bilayers.Whitesides et al.[3～5]fabricated Hg-SAM/SAM-Metal(Ag,Au,Cu)junctions to investi-gate the electrical breakdown voltage of self-assem-bled monolayers(SAMs…     

Theoretical study of adsorption of sarin and soman on tetrahedral edge clay mineral fragments

This study provides details of the structure and interactions of Sarin and Soman with edge tetrahedral fragments of clay minerals. The adsorption mechanism of Sarin and Soman on these mineral fragments containing the Si(4+) and Al(3+) central cations was investigated. The calculations were performed using the B3LYP and MP2 levels of theory in conjunction with the 6-31G(d) basis set. The studied systems were fully optimized. Optimized geometries, adsorption energies, and Gibbs free energies of Sarin and Soman adsorption complexes were computed. The number and strength of formed intermolecular interactions have been analyzed using the AIM theory. The charge of the systems and a termination of the mineral fragment are the main contributing factors on the formation of intermolecular interactions in the studied systems. In the neutral complexes, Sarin and Soman is physisorbed on these mineral fragments due to the formation of C-H...O, and O-H...O hydrogen bonds. The chemical bond is formed between a phosphorus atom of Sarin and Soman and an oxygen atom of the -2 charged clusters containing an Al(3+) central cation and -1 charged complex containing a Si(4+) central cation (chemisorption). Sarin and Soman interact mostly in the same way with the same terminated edge mineral fragments containing different central cations. However, the interaction energies of the complexes with an Al(3+) central cation are larger than these values for the Si(4+) complexes. The interaction enthalpies of all studied systems corrected for the basis set superposition error were found to be negative. However, on the basis of the Gibbs free energy values, only strongly interacting complexes containing a charged edge mineral fragment with an Al(3+) central cation are stable at room temperature. We can conclude that Sarin and Soman will be adsorbed preferably on this type of edge mineral surfaces. Moreover, on the basis of the character of these edge surfaces, a tetrahedral edge mineral fragment can provide effective centers for the dissociation.     

Synthesis and characterization of acidic properties of Al-HMS materials of varying Si/Al ratios

HMS and Al-HMS materials with Si/Al ratio in the range 5-45 were synthesized by neutral templating pathway. The as synthesized as well as calcined samples were examined for pore size distribution, surface area and XRD. These investigations confirmed the hexagonal mesoporous structure formation at all Si/Al ratios. The TGA measurements indicated that two types of template species interacting with Si or Al could be distinguished. The acidity and acid strength distribution studies using microcalorimetric NH₃ adsorption indicated that the acidity increases with Al content in the mesoporous structure. The presence of Al in the structure creates a wide variety of acid sites of varying strengths. The heterogeneity of the sites also increases with Al content of the catalysts. The activities for cumene cracking reaction to test acidity of the materials supported the trend obtained from microcalorimetric NH₃ adsorption results.     

Vibrational Spectroscopy Study of Selenate and Sulfate Adsorption Mechanisms on Fe and Al (Hydr)oxide Surfaces

The coordination and speciation of selenate (SeO(4)) and sulfate (SO(4)) on goethite and Al oxide were studied using Raman and ATR-FTIR spectroscopy. Raman spectra were collected from pastes of suspensions containing 4 mM SeO(4) or SO(4). For SO(4), complementary data were collected by ATR-FTIR spectroscopy in goethite systems with 1 mM SO(4) and in Al oxide systems with 4 mM SO(4). The combined data set of Raman and ATR-FTIR spectra indicate that both inner- and outer-sphere surface complexes of SeO(4) and SO(4) occur on these metal (hydr)oxide surfaces. These spectral data show that SeO(4) and SO(4) have a similar complexation behavior on the same adsorbent. On goethite, these form predominantly monodentate inner-sphere surface complexes at pH <6, while at pH >6 these anions exist predominantly as outer-sphere surface complexes. On Al oxide, in contrast, these anions exist predominantly as outer-sphere surface complexes, but a small fraction is also present as an inner-sphere complex at pH <6. A comparison of the spectral intensities of these anions on goethite and Al oxide shows that complexation of these anions with Al oxide is weaker than with Fe oxide. Copyright 2000 Academic Press.     

Mechanisms of Arsenic Adsorption on Amorphous Oxides Evaluated Using Macroscopic Measurements, Vibrational Spectroscopy, and Surface Complexation Modeling

Arsenic adsorption on amorphous aluminum and iron oxides was investigated as a function of solution pH, solution ionic strength, and redox state. In this study in situ Raman and Fourier transform infrared (FTIR) spectroscopic methods were combined with sorption techniques, electrophoretic mobility measurements, and surface complexation modeling to study the interaction of As(III) and As(V) with amorphous oxide surfaces. The speciation of As(III) and As(V) in aqueous solution was examined using Raman and attenuated total reflectance (ATR)-FTIR methods as a function of solution pH. The position of the As-O stretching bands, for both As(III) and As(V), are strongly pH dependent. Assignment of the observed As-O bands and their shift in position with pH was confirmed using semiempirical molecular orbital calculations. Similar pH-dependent frequency shifts are observed in the vibrational bands of As species sorbed on amorphous Al and Fe oxides. The mechanisms of As sorption to these surfaces based on the spectroscopic, sorption, and electrophoretic mobility measurements are as follows: arsenate forms inner-sphere surface complexes on both amorphous Al and Fe oxide while arsenite forms both inner- and outer-sphere surface complexes on amorphous Fe oxide and outer-sphere surface complexes on amorphous Al oxide. These surface configurations were used to constrain the input parameters of the surface complexation models. Inclusion of microscopic and macroscopic experimental results is a powerful technique that maximizes chemical significance of the modeling approach. Copyright 2001 Academic Press.     

氢在Mg_2Ni(100)面的吸附及扩散

运用第一性原理研究氢在清洁和掺杂Al的Mg2Ni(100)面的吸附及扩散.在清洁Mg2Ni(100)表面,氢原子可稳定地吸附于Mg-Ni桥位和Mg-Mg桥位,吸附能为1.19-1.52eV.在掺杂Al的Mg2Ni(100)表面,氢原子可稳定吸附于Al-Ni、Mg-Ni、Mg-Al桥位,吸附能为0.10-0.29eV.氢在掺杂Al的Mg2Ni(100)表面的吸附能低于其在清洁表面的吸附能,说明掺杂Al后氢原子与表面的相互作用减弱.过渡态计算结果表明,氢原子由清洁的Mg2Ni(100)面及掺杂Al的Mg2Ni(100)面扩散至次表层的势垒分别为0.59及-0.04eV,掺杂Al后氢原子的扩散势垒降低,说明氢原子更易由掺杂Al表面扩散至次表层.Al原子替代Mg2Ni(100)面的Mg原子减弱氢原子与表面的相互作用,降低氢原子由表层扩散至次表层的势垒,这可能是Mg2Ni合金掺杂Al可改善其吸氢动力学性能的主要原因之一.     

Silicon surfaces as electron acceptors: dative bonding of amines with Si(001) and Si(111) surfaces.

The bonding of the trimethylamine (TMA) and dimethylamine (DMA) with crystalline silicon surfaces has been investigated using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy, and density-functional computational methods. XPS spectra show that TMA forms stable dative-bonded adducts on both Si(001) and Si(111) surfaces that are characterized by very high N(1s) binding energies of 402.2 eV on Si(001) and 402.4 eV on Si(111). The highly ionic nature of these adducts is further evidenced by comparison with other charge-transfer complexes and through computational chemistry studies. The ability to form these highly ionic charge-transfer complexes between TMA and silicon surfaces stems from the ability to delocalize the donated electron density between different types of chemically distinct atoms within the surface unit cells. Corresponding studies of DMA on Si(001) show only dissociative adsorption via cleavage of the N-H bond. These results show that the unique geometric structures present on silicon surfaces permit silicon atoms to act as excellent electron acceptors.     

Luminescence investigations of the adsorption properties of disperse Al2O3 surfaces by means of selective laser excitation

A new method for the determination of the adsorption activity of disperse materials by means of inorganic luminescent probes under selective laser excitation has been developed and tested for the investigation of the adsorption properties of disperse Al(2)O(3) surfaces. Water-uranyl complexes have been used as luminescent probes for these experiments, and the photoluminescence spectra of UO(2)(2+) molecular ions adsorbed on the disperse Al(2)O(3) surfaces were investigated. The luminescence properties of this adsorption system, as in the previously studied case of SiO(2), were determined by the type and structure of the adsorption complexes (AC) formed. Different ACs cause many (7 observed) "elementary" luminescence spectra. The water-uranyl-complex adsorption binding energies were obtained. The values of the binding energies and the electric field strength of the surface active centers support the validity of the water-uranyl model of AC and the electrostatic consideration used.     

Beta分子筛中Al的分布和Brφnsted酸的酸性强度

基于量子化学中的密度泛函理论(DFT), 研究了Beta分子筛中骨架Al在9个不同T位的分布和Brφnsted酸的分布及其强度. 计算采用8T 簇模型和B3LYP/6-31G(d,p)方法, 得到了不同T位的Al/Si替代能、(Al, H)/Si替代能和质子亲和势, 以及碱性探针分子NH3在Beta分子筛酸性位的吸附能. 结果表明, 骨架Al和Brφnsted酸优生位于Beta分子筛的T5 和T6 位; 其中酸性最强的位置是Al5-O14-Si9, 最弱的位置是Al7-O3-Si1.     

氢原子在Pt及Pt系双金属催化表面吸附的密度泛函理论研究

采用密度泛函理论(dFT)考察了Pt(100)、(110)、(111)三种表面氢原子的吸附行为, 计算了覆盖度为0.25 ML时氢原子在Pt 三种表面和M-Pt(111)双金属(M=Al, Fe, Co, Ni, Cu, Pd)上的最稳定吸附位、表面能以及吸附前后金属表面原子层间弛豫情况. 分析了氢原子在不同双金属表面吸附前后的局域态密度变化以及双金属表面d 带中心偏离费米能级的程度并与氢吸附能进行了关联. 计算结果表明, 在Pt(100), Pt(110)和Pt(111)表面, 氢原子的稳定吸附位分别为桥位、短桥位和fcc 穴位. 三种表面中以Pt(111)的表面能最低, 结构最稳定. 氢原子在不同M-Pt(111)双金属表面上的最稳定吸附位均为fcc 穴位, 其中在Ni-Pt 双金属表面的吸附能最低, Co-Pt 次之. 表明氢原子在Ni-Pt 和Co-Pt 双金属表面的吸附最稳定. 通过对氢原子在M-Pt(111)双金属表面吸附前后的局域态密度变化的分析, 验证了氢原子吸附能计算结果的准确性. 掺杂金属Ni、Co、Fe 的3d-Pt(111)双金属表面在吸附氢原子后发生弛豫, 第一层和第二层金属原子均不同程度地向外膨胀. 此外, 3d金属的掺入使得其对应的M-Pt(111)双金属表面d带中心与Pt 相比更靠近费米能级, 吸附氢原子能力增强, 表明3d-Pt系双金属表面有可能比Pt具有更好的脱氢活性.     

Uranium(VI) Sorption Complexes on Montmorillonite as a Function of Solution Chemistry

We have investigated the effect of changes in solution chemistry on the nature of uranyl sorption complexes on montmorillonite (SAz-1) at different surface coverages (1.43-53.6 μmol/g). Uranyl uptake onto SAz-1 between pH 3 and 7 was determined in both titration and batch-mode experiments. These pH values result in solutions that contain a range of monomeric and oligomeric aqueous uranyl species. Continuous-wave and time-resolved emission spectroscopies were used to investigate the nature of U(VI) sorbed to SAz-1. A discrete set of uranyl surface complexes has been identified over a wide range of pH values at these low to moderate coverages. For all samples, two surface complexes are detected with spectral characteristics commensurate with an inner-sphere complex and an exchange-site complex; the relative abundance of these two species is similar over these pH values at low coverage (1.43-2.00 μmol/g). In addition, surface species having spectra consistent with polymeric hydroxide-like sorption complexes form at the moderate coverages ( approximately 34-54 μmol/g), increasing in abundance as the capacity of the amphoteric surface sites is exceeded. Furthermore, a species with spectral characteristics anticipated for an outer-sphere surface complex is observed for wet paste samples at low pH (3.7-4.4) and both low ( approximately 2 μmol/g) and moderate ( approximately 40 μmol/g) coverage. There are only subtle differences in the nature of sorption complexes formed at different pH values but similar coverages, despite markedly different uranyl speciation in solution. These results indicate that the speciation in the solution has minimal influence on the nature of the sorption complex under these experimental conditions. The primary control on the nature and abundance of the different uranyl sorption complexes appears to be the relative abundance and reactivity of the different sorption sites. Copyright 2001 Academic Press.     

Interaction of molecular nitrogen and oxygen with extraframework cations in zeolites with double six-membered rings of oxygen-bridged silicon and aluminum atoms: a DFT study

The interaction of N(2) and O(2) with extraframework cations of zeolite frameworks was studied by DFT, using the B3LYP method. The extraframework cation sites located in the vicinity of the double six-member rings (D6R) of FAU zeolites (SI, SI', SIII') were considered and clusters with composition (M(n)(+))(2/)(n)()H(12)Si(10)Al(2)O(18), M = Li(+), Na(+), K(+), Ca(2+), were selected to represent the adsorption centers. The cation sites SII in the center of single six-membered rings (S6R) were modeled by [M(I)H(12)Si(4)Al(2)O(6)](-) and M(II)H(12)Si(4)Al(2)O(6) clusters. The adsorption energy of N(2) and O(2) is the highest for Li(+) cations at the SIII' cation sites, while for the SI' and SII sites the adsorption energies decrease in the order Ca(2+) > Na(+) > Li(+). The calculated small N(2) adsorption energy for Li(+) cations at SII sites suggests that these sites do not take part in the sorption process in agreement with results of NMR studies and Monte Carlo simulations. The N(2) adsorption complexes with the extraframework cations are linear, while those of O(2) are bent regardless of the extraframework cation location. The SIII' cation sites are the most favorable ones with respect to N(2) adsorption capacity and N(2)/O(2) selectivity; the SII sites are less selective and the SI sites are not accessible.     

Surface complexes of phthalic acid at the hematite/water interface

The adsorption of o-phthalic acid at the hematite/water interface was investigated experimentally using batch adsorption experiments and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy over a wide range of solution pH, surface loading, and ionic strength conditions. Molecular orbital calculations for several possible surface complexes were also performed to assign atomistic structures to the features observed in the ATR-FTIR spectra. The results of the batch adsorption experiments exhibit typical anionic characteristics with high adsorption at low pH and low adsorption at high pH. The adsorption of phthalic acid also exhibits a strong dependence on ionic strength, which suggests the presence of outer-sphere complexes. ATR-FTIR spectra provide evidence of three fully deprotonated phthalate surface complexes (an outer-sphere complex and two inner-sphere complexes) under variable chemical conditions. A fully deprotonated outer-sphere complex appears to dominate adsorption in the circumneutral pH region, while two fully deprotonated inner-sphere complexes that shift in relative importance with surface coverage increase in importance at low pH. Comparison of experimental and theoretical calculations suggests the two inner-sphere complexes are best described as a mononuclear bidentate (chelating) complex and a binuclear bidentate (bridging) complex. The mononuclear bidentate inner-sphere complex was favored at relatively low surface coverage. With increasing surface coverage, the relative contribution of the binuclear bidentate inner-sphere complex increased in importance.     

苯分子与Si6O18H12和Al6O24H30团簇模型相互作用的理论研究

粘土矿已经被广泛用来去除有机物,修复和净化被石油碳氢化合物污染的土壤和地下水. 我们选择高岭石作为研究对象,构造了Si₆O₁₈H₁₂和Al₆O₂₄H₃₀两个团簇模型分别代表高岭石的硅氧层表面和铝氧层表面,在MP2/6-31G(d,p)//B3LYP/6-31G(d,p)的理论水平上系统地研究了气态下苯分子和高岭石团簇模型的相互作用. 并进一步分析了苯分子和高岭石表面相互作用的各种气态性质,比如：优化的几何构型、结构参数、吸附能、自然键轨道电荷分布、振动频率变化、静电势、电子密度性质(次级氢键的电子密度和拉普拉斯算符值)和电子密度差分等. 优化的几何构型表明苯分子吸附在高岭石表面的本质可能是次级氢键的形成. 其他性质的结果进一步验证了次级氢键的存在,并指出苯更倾向于吸附在高岭石的铝氧层表面,且苯环和铝氧层表面形成近似90°的夹角.     

Molecular dynamics simulation of uranyl(VI) adsorption equilibria onto an external montmorillonite surface

We used molecular dynamics simulations to study the adsorption of aqueous uranyl species (UO(2)(2+)) onto clay mineral surfaces in the presence of sodium counterions and carbonato ligands. The large system size (10,000 atoms) and long simulation times (10 ns) allowed us to investigate the thermodynamics of ion adsorption, and the atomistic detail provided clues for the observed adsorption behavior. The model system consisted of the basal surface of a low-charge Na-montmorillonite clay in contact with aqueous uranyl carbonate solutions with concentrations of 0.027 M, 0.081 M, and 0.162 M. Periodic boundary conditions were used in the simulations to better represent an aqueous solution interacting with an external clay surface. Uranyl adsorption tendency was found to decrease as the aqueous uranyl carbonate concentration was increased, while sodium adsorption remained constant. The observed behavior is explained by physical and chemical effects. As the ionic strength of the aqueous solution was increased, electrostatic factors prevented further uranyl adsorption once the surface charge had been neutralized. Additionally, the formation of aqueous uranyl carbonate complexes, including uranyl carbonato oligomers, contributed to the decreased uranyl adsorption tendency.