A density functional theory study on the H2S molecule adsorption onto small gold clusters

An all-electron scalar relativistic calculation on Au_nH₂S (n = 1-13) clusters has been performed by using density functional theory with the generalized gradient approximation at PW91 level. The small gold cluster would like to bond with sulfur in the same plane and the H₂S molecule prefers to occupy the on-top and single fold coordination site in the cluster. The Au_n structures and H₂S molecule in all Au_nH₂S clusters are only slightly perturbed and still maintain their structural integrity. After adsorption, the S-H, H-H bond-lengths and most Au-Au bond-lengths are elongated, only a few Au-Au bond-lengths far from H₂S molecule are shortened. The reactivity enhancement of H₂S molecule is obvious and the strong gold-sulfur bond is observed expectedly. The most favorable adsorption takes place in the case that the H₂S molecule is adsorbed by an even-numbered Au_n cluster and becomes Au_nH₂S cluster with even number of valence electrons. It is believed that the strong scalar relativistic effect is favorable to H₂S molecule adsorption onto small gold clusters and is also one of the important reasons for the strong gold-sulfur bond.     

钇覆盖Si@Al12团簇的贮氢性能

利用密度泛函理论系统地研究了Y_mSi@Al₁₂ (m=1—3)团簇及其贮氢性质. 结果表明, 在所研究的尺度范围内, 钇原子未在Si@Al₁₂团簇上团聚; 每个钇原子按18电子规则吸附氢分子, 其中Y₃Si@Al₁₂团簇可以吸附16个完整氢分子, 贮氢质量分数为5.0 %, 平均吸附能处于0.324—0.527 eV之间, 较为理想的吸附能说明在室温条件下吸氢和脱氢是可行的.     

H2在Al7-团簇解离吸附的理论研究

利用高精度从头计算方法研究了H₂分子在Al₇^-阴离子团簇上的吸附及解离过程, 确定了分子吸附及解离吸附的稳定结构,并分析了各结构的光电子能谱. 计算表明H₂在Al₇^-上为弱的物理吸附,吸附能约为0.02 eV;解离过程的能垒约为0.75 eV. 对团簇及解离吸附结构的态密度与实验得到的光电子能谱的比较表明二者能够很好地符合, 确定H₂与激光烧蚀产生的团簇直接反应时能在Al₇^-上发生解离. 关键词： 7^-')" href="#">Al₇^- 2')" href="#">H₂ 解离吸附 从头计算     

Adsorption of water and ammonia on TiO2-anatase cluster models

Density functional theory (DFT) calculations performed at B3LYP/6-31G^∗∗ level are employed to study water and ammonia adsorption and dissociation on (1 0 1) and (0 0 1) TiO₂ anatase surfaces both represented by totally fixed and partially relaxed Ti₂O₉H₁₀ cluster models. PM3 semiempirical calculations were also conducted both on Ti₂O₉H₁₀ and Ti₉O₃₃H₃₀ clusters in order to assess the effect of cluster size. Following dissociation, the adsorption of H₂O and NH₃ by H-bonding on previously H₂O and NH₃ dissociated systems, respectively are also considered. It is found that the adsorption energies and geometries of water and ammonia molecules on (1 0 1) and (0 0 1) anatase cluster models depend on surface relaxation. The vibration frequency values are also calculated for the optimized geometries. The adsorption energies and vibration frequency values computed are compared with the available theoretical and experimental literature.     

锂原子修饰B6团簇的储氢性能研究

利用密度泛函理论研究B₆和Li_mB₆ (m= 1–2)团簇的结构及其储氢性能. 结果表明, 氢分子在B₆团簇的三种可能结构中均发生解离吸附, Li原子在B₆团簇表面不发生团聚,每一个Li原子均吸附几个氢分子. 其中以两个Li原子修饰笼形B₆团簇吸附完整氢分子数最多,储氢质量分数为20.38%, 氢分子的平均吸附能为1.683 kcal/mol,表明了它在常温常压条件下作为储氢材料的可行性. 关键词： mB₆ (m=1-2)团簇')" href="#">Li_mB₆ (m=1-2)团簇 密度泛函理论(DFT) 吸附能 储氢性能     

Correlation between Li+ adsorption capacity and the preparation conditions of spinel lithium manganese precursor

Spinel lithium manganese oxides can be used as Li⁺ adsorbent with topotactical extraction of lithium. In this paper, the solid state methods were introduced to prepare spinel lithium manganese precursors with Li₂CO₃ and LiOH·H₂O as different Li sources. The Li⁺ uptake was studied to clarify the correction between Li⁺ adsorption capacity and the preparation conditions of precursors, including different Li sources, Li/Mn mole ratios and heating time. The results indicated that the Li⁺-extracted materials prepared with LiOH·H₂O and MnCO₃ usually have higher Li⁺ adsorption capacity than Li₂CO₃ and MnCO₃, and an ascending trend was found in Li⁺ uptake with increasing Li/Mn mole ratio in the preparation of the precursor, but it is not proportional. The Mn₂O₃ impurities could be the primary reason for decreasing Li⁺ adsorption capacity. Furthermore, it is concluded that the Li⁺-extracted materials obtained from spinel manganese oxides synthesized with Li/Mn = 1.0 can serve as selective Li⁺ absorbents due to its high selectivity and large adsorption capacity.     

Computer study of acetylene and ethane adsorption by disperse water medium

Adsorption of acetylene and ethane molecules by water clusters has been investigated by the molecular dynamics method at T=233 K. With the help of determination of statistical weights the cluster systems are created. In the frequency range of 0?ω?1000 cm⁻¹ the integral absorption coefficient of IR-radiation increases after the adsorption of acetylene or ethane molecules by the ultra disperse water system. The dissipation power of IR-radiation by cluster systems increases if C₂H₂ molecules are adsorbed, and it reduces in the case of C₂H₆ molecules' adsorption.     

Density functional study of the cysteine adsorption on Au nanoclusters

The adsorption of the cysteine amino acid (H–SC_βH₂–C_αH–NH₂–COOH) on the Au₅₅ cluster is investigated through density functional theory calculations. Two isomers, with icosahedral (I_h) and chiral (C₁) geometries, of the Au₅₅ cluster are used to calculate the adsorption energy of the cysteine on different facets of these isomers. Results, only involving the S(thiolate)-Au bonding show that the higher adsorption energies are obtained when the sulfur atom is bonded to an asymmetrical bridge site at the facet containing Au atoms with the lowest coordination of the C₁ cluster isomer.     

Reactions of small gold cluster cations with propylene, methane, and hydrogen: permissive and competitive coadsorption effects

Coadsorption effects of molecular hydrogen and small hydrocarbons, CH₄ and C₃H₆, on free Au₃ ⁺ and Au₅ ⁺ were investigated in an octopole ion trap under multi-collision conditions. For hydrogen and methane the observations indicate that both molecules coadsorb on the same adsorption site, i.e., the same atom of the cluster. This type of molecular adsorption on free clusters is termed permissive coadsorption, in contrast to competitive coadsorption, in which two molecules compete for the same adsorption site. The latter case was observed for hydrogen and propylene: already trace amounts of propylene were able to completely saturate the clusters preventing the coadsorption of H₂. The size dependent adsorbate coverage is discussed and implications on the cluster structure are deduced from time and temperature dependent reaction measurements.     

Ethylene adsorption on the Pt-Cu bimetallic catalysts. Density functional theory cluster study

The adsorption of ethylene on Cu₁₂Pt₂ clusters has been studied within the density functional theory (DFT) approach to understand the high ethylene selectivity of Cu-rich Pt-Cu catalyst particles in the reaction of hydrogen-assisted 1,2-dichloroethane dechlorination. The structural parameters for Cu₁₂Pt₂ clusters with D_4h, D_2d, and C_3v symmetry have been calculated. The relative stability of the isomeric Cu₁₂Pt₂ clusters follows the order: C_3v > D_2d > D_4h. Each isomer has an active site for ethylene adsorption that consists of a single Pt atom surrounded by Cu atoms. The interaction of ethylene with the active site yields a π-C₂H₄ adsorption complex. The strongest π-C₂H₄ complex forms with the cluster of C_3v symmetry; the bonding energy, ΔE_π(C₂H₄), is −15.6 kcal mol⁻¹. The bonding energies for the π-C₂H₄ complex with Cu₁₄ and Pt₁₄ clusters are −6.5 and −18.8 kcal mol⁻¹, respectively.The addition of Pt to Cu modifies the valence spd-band of the cluster as compared to a Cu₁₄ cluster. The DOS near the Fermi level increases when C₂H₄ adsorbs on the Cu₁₂Pt₂ cluster. As well, the center of the d-band shifts toward lower binding energies. Ethylene adsorption also induces a number of states below the d-band. These states correspond to those of gas-phase C₂H₄.The vibrational frequencies of C₂H₄ adsorbed on the clusters of D_4h and C_3v symmetry have been calculated. The phonon vibrations occur below 250 cm⁻¹. The intense bands around 200 cm⁻¹ are attributed to stretching vibrations of the Pt-Cu bonds normal to the cluster surface. The stretching vibrations of the Pt-C bonds depend on the local structure of the active site: ν_s(Pt-C) = 268 cm⁻¹ and ν_as(Pt-C) = 357 cm⁻¹ for the cluster of the D_4h symmetry; ν_s(Pt-C) = 335 cm⁻¹ and ν_as(Pt-C) = 397 cm⁻¹ for the cluster of the C_3v symmetry. Bands in the range of 800-3100 cm⁻¹ are attributed to vibrations of the adsorbed C₂H₄ molecule. The signature frequencies of the π-C₂H₄ adsorption complex are the δ_s(CH₂) deformation vibration at ∼1200 cm⁻¹ and the ν(C-C) stretching vibration at ∼1500 cm⁻¹. These vibration are absent for di-σ-C₂H₄ adsorption complexes.     

Surface complexes between O2, H2O and lithium

The He(I) photoelectron spectra of lithium and its surfaces as a function of exposure to O₂ or to H₂O are reported in this paper. The spectra provide evidence for the formation of a stable complex between H₂O and lithium rather than for formation of a product such as LiOH. The spectral evidence for the H₂O/Li complex is supported by calculations using several ten atom models of binding sites on unreconstructed lithium surfaces bearing H₂O in various conformations.     

The adsorption kinetics of C2H2, and C2H4 on W(110) at 1100 K

The adsorption kinetics of C₂H₂ and C₂H₄ gases on W(110) have been studied using Auger electron spectroscopy and qualitative LEED. Below 1100 K, adsorption of either C₂H₂; or C₂H₄ does not follow any simple kinetic model to saturation. At 1100 K adsorption is identical for both gases and follows first order monolayer kinetics with unity sticking coefficient and a carbon-to-tungsten atomic ratio of 0.64 ± 0.05. This carbon is present as a surface carbide which starts to in-diffuse about 1500 K and has completely dissolved after a few seconds at 2400 K.     

Hybrid-DFT study for the initial oxidation steps on silicon cluster surface

We performed a hybrid density functional theory calculation for the successive adsorption of nitrous oxide (N₂O) on Si(1 0 0)-Si₉H₁₂O_x (x = 0 and 1) cluster surfaces to elucidate N₂O decomposition and the subsequent surface oxidation processes. N₂O decomposed into N₂ and O fragments, and the latter fragment inserted into either surface-dimer bonds or back-bonds with similar activation barriers on both the clean and partially oxidized Si surfaces. The Si₉H₁₂ cluster surface was eventually oxidized to five distinct structures of Si₉H₁₂O₂.     

Activation de l'hydrogène moléculaire par une petite particule de nickel

The electronic structure of an icosaedral cluster of 13 nickel atoms is studied using an Extended Hückel method. Near the highest occupied level at ?7.65 eV, h and t orbitals are accidentally degenerate so that the fundamental state possesses a high spin multiplicity (2S + 1 = 9) accounting for the magnetism of the particule. We have considered several geometries for a hydrogen molecule approaching the cluster at a minimum distance of 1.47 Å. In all cases the H-H bond is weakened because of electron transfer from the nickel towards the hydrogen atoms and partial filling of the antibonding orbital of h₂. During the increase of the H-H distance the weakening is easier than in the absence of a nickel catalyst leading to the dissociative adsorption of the molecule. The activation mechanism of H₂ requires participation of both the s and d orbitals of the metal and leads to a lowering of the spin multiplicity. Finally, we have shown that a dissociative adsorption is obtained when the H₂ molecule approaches a triangular face. After breaking of the H-H bond, the more stable system corresponds to atomic H adsorption on two opposite vertices.     

Structural stability and electronic properties of Au5Hn (n=1–10) clusters

A systematic study on the geometrical structures, electronic and magnetic properties of Au₅H _n (n=1–10) clusters has been performed by using the all-electron scalar relativistic density functional theory with generalized gradient approximation at the PW91 level. It is found that all Au₅H _n clusters prefer to keep the planar structures like pure Au₅ cluster, the Au₅ structures in Au₅H₄, Au₅H₅ and Au₅H₆ clusters are distorted obviously. The adsorption of a number of hydrogen atoms enhances the stability of Au₅ cluster and all Au₅H _n clusters are more stable than pure Au₅ cluster energetically. The odd-even alteration of magnetic moment is observed in Au₅H _n clusters and may be served as the material with tunable code capacity of “0” and “1” by adsorbing odd or even number of H atoms. It seems that the most favorable adsorption between Au₅ cluster and a number of hydrogen atoms takes place in the case that the odd number of hydrogen atoms is adsorbed onto Au₅ cluster and becomes Au₅H _n cluster with even number of valence electrons.     

(TiO2)n(n=3—6)团簇吸附水分子的理论研究

给出了优化小分子在团簇表面吸附结构的遗传算法.结合经验势函数,搜寻了水分子在(TiO₂)_n(n=3—6)团簇上可能的吸附方式;利用B3LYP/6-31G^**方法对各种吸附结构进行了优化.结果表明水分子主要通过O原子以非解离方式吸附到团簇中配位数较低或位置比较凸出的Ti原子上.分子轨道分析表明,水分子与团簇之间的成键主要来自吸附位Ti原子3s3p轨道的贡献,水分子的轨道保持了气相水分子中的基本特征,但离域化程度增大 关键词： 2团簇')" href="#">TiO₂团簇 2O吸附')" href="#">H₂O吸附 遗传算法 DFT     

Study on transformation mechanism of lithium titanate modified with hydrochloric acid

The effects of the concentration of hydrochloric acid and treatment time on the transformation of Li₂TiO₃ were studied in detail. The results demonstrate that lithium ions are easily removed from the (?133) and (?206) planes. In contrast, Li⁺ extraction requires a longer time for the (002) and (?131) planes. A mixture of the anatase and rutile phases, pure rutile, and pure anatase can be generated by treating Li₂TiO₃ with a suitable concentration of hydrochloric acid for an appropriate amount of time. The phase(s) that are present significantly affect the cyclic adsorption performance of a titanium lithium ion sieve and the dissolution of Ti. The transformation from H₂TiO₃ particles to TiO₂ primarily occurs via the dissolution-recrystallization process. The electrophilic H⁺ and highly electronegative Cl^? affect the Ti–O bond, resulting in the destruction of the Ti–O bond in TiO₆ octahedrons, promoting the structural rearrangement of anatase to rutile TiO₂.     

Structural,energetic, and electronic properties of hydrogenated aluminum arsenide clusters

The chemisorptions of hydrogen on aluminum arsenide clusters are studied with density functional theory (DFT). The on-top site is identified to be the most favorable chemisorptions site for hydrogen. And the Al-top site is the preferred one in the most cases for one hydrogen adsorption in (AlAs) _n (n = 2, 5, 6, 8–15) clusters. Top on the neighboring Al and As atoms ground-state structures are found for two hydrogen adsorption on (AlAs) _n except for (AlAs)₂ cluster. The Al–As bond lengths decrease generally as the size of the cluster increases. And there is a slight increase in the mean Al–As bond lengths after H adsorption on the lowest-energy sites of the most AlAs clusters. In general, the binding energy of H and 2H are both found to decrease with an increase in the cluster size. And the result shows that large binding energies (BE) of a single hydrogen atom on small AlAs clusters and large highest occupied and lowest unoccupied molecular-orbital gaps for (AlAs)H and (AlAs)₃H make these species behaving like magic clusters. Calculations on two hydrogen atoms on (AlAs) _n clusters show large BE for (AlAs) _n H₂ with an odd number of n. The stability of these complexes is further studied from the fragmentation energies. (AlAs)₇H₂ and (AlAs)₉H₂ clusters are again suggested to be the stable clusters. On the other hand both the fragmentation energy and the binding energy for (AlAs)₁₃H are close to the lowest values.     

Adsorption of thiophene on silica-supported Mo clusters

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. H₄C₄S 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 × 10¹³/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 H₄C₄S. The second reaction pathway, the decomposition of thiophene, starts at 250 K. Utilizing multimass TDS, H₂, H₂S, and mostly alkynes are detected in the gas phase as decomposition products. H₄C₄S 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 H₄C₄S adsorption/desorption cycles, the uptake of molecular thiophene decreases as well as the H₂ and H₂S production ceases. Thus, silica-supported sulfided Mo clusters are less reactive than metallic clusters. The poisoned catalyst can be partially reactivated by annealing in O₂. However, Mo oxides also appear to form, which passivate the catalyst further. On the other hand, while annealing a used catalyst in H/H₂, it is poisoned even more (i.e., the S AES signal increases). By means of adsorption transients, the initial adsorption probability, S₀, of C₄H₄S has been determined. At thermal impact energies (E_i = 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 capture zone model. The temperature dependence of S₀(T_s) consists of two regions consistent with molecular adsorption of thiophene at low temperatures and its decomposition above 250 K. Fitting S₀(T_s) curves allows one to determine the bond activation energy for the first elementary decomposition step of C₄H₄S, which amounts to (79 ± 2) kJ/mol and (52 ± 4) kJ/mol for small and large Mo clusters, respectively. Thus, larger clusters are more active for decomposing C₄H₄S than are smaller clusters.     

Heterogeneous adsorption and catalytic oxidation of benzene, toluene and xylene over spent and chemically regenerated platinum catalyst supported on activated carbon

The heterogeneous adsorption and catalytic oxidation of benzene, toluene and o-xylene (BTX) over the spent platinum catalyst supported on activated carbon (Pt/AC) as well as the chemically treated spent catalysts were studied to understand their catalytic and adsorption activities. Sulfuric aqueous acid solution (0.1N, H₂SO₄) was used to regenerate the spent Pt/AC catalyst. The physico-chemical properties of the catalysts in the spent and chemically treated states were analyzed by using nitrogen adsorption-desorption isotherm and elemental analysis (EDX). The gravimetric adsorption and the light-off curve analysis were employed to study the BTX adsorption and oxidation on the spent catalyst and its modified Pt/AC catalysts. The experimental results indicate that the spent Pt/AC catalyst treated with the H₂SO₄ aqueous solution has a higher toluene adsorption and conversion ability than that of the spent Pt/AC catalyst. A further studies of H₂SO₄ treated Pt/AC catalyst on their catalytic and heterogeneous adsorption behaviours for BTX revealed that the activity of the H₂SO₄ treated Pt/AC catalyst follows the sequence of benzene > toluene > o-xylene. The adsorption equilibrium isotherms of BTX on the H₂SO₄ treated Pt/AC were measured at different temperatures ranging from 120 to 180 °C. To correlate the equilibrium data and evaluate their adsorption affinity for BTX, the two sites localized Langmuir (L2m) isotherm model was employed. The heterogeneous surface feature of the H₂SO₄ treated Pt/AC was described in detail with the information obtained from the results of isosteric enthalpy of adsorption and adsorption energy distributions. Furthermore, the activity of H₂SO₄ treated Pt/AC about BTX was found to be directly related to the Henry's constant, isosteric enthalpy of adsorption and adsorption energy distribution functions.