Reactivity of silicon‐doped carbon nanotubes toward small gaseous molecules in the atmosphere

The reactivities of the pristine and silicon doped (Si‐doped) single‐walled carbon nanotubes (CNTs) toward small gaseous molecules in the atmosphere, such as formaldehyde, carbon monoxide, and hydrogen sulfide, were studied by performing density functional theory calculations. Compared with the physisorptions on the pristine (8, 0) CNT, these small molecules present strong chemical interactions with the Si‐doped (8, 0) tube. Doping intrinsic CNTs with silicon is expected to be a potential strategy for improving the property of pristine CNTs and expanding the application of CNTs in nanoscience and nanotechnology. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Density functional theory study on the possibility of Si‐, Ge‐, and Sn‐doped carbon nanotubes as efficient support materials for platinum

PBEPBE‐D3 calculations were performed to investigate how platinum (Pt) interacts with the internal and external surfaces of single‐walled pristine, Si‐, Ge‐, and Sn‐doped (6,6) carbon nanotubes (CNTs). Our calculations showed that atomic Pt demonstrates stronger binding strength on the external surfaces than the internal surface adsorption for the same type of nanotube. In cases of external surface adsorptions, Si‐, Ge‐, and Sn‐doped CNTs show comparable binding energies for Pt, at least 1.40 eV larger than pristine CNT. This enhancement can be rationalized by the strong covalent interactions between Pt and X? C (X = Si, Ge, and Sn) pairs based on structural and projected density of states analysis. In terms of internal surface adsorptions, Ge and Sn doping could significantly enhance the binding of Pt. Pt atom shows much more delocalized and bonding states inside Ge‐ and Sn‐doped CNTs, indicating multiple‐site interaction pattern when atomic Pt is confined inside the nanotubes. However, the internal surface of Si‐doped CNT presents limited enhancement in Pt adsorption with respect to that of pristine CNT because of their similar binding geometries. © 2016 Wiley Periodicals, Inc.     

Influence of silicon defects on the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons: a theoretical study using thiophene + coronene as the simplest model

Physisorption and chemisorption processes of thiophene on coronene and 2Si-coronene have been studied using density functional theory and MP2 methods. These systems have been chosen as the simplest models to describe the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons (PAHs). The calculated data suggest that the presence of silicon atoms in PAHs could favor their interaction with thiophene and similar compounds. Small stabilization energies have been found for several physisorbed complexes. The thiophene chemisorption on coronene seems very unlikely to occur, while that on 2Si-coronene leads to addition products which are very stable, with respect to the isolated reactants. These chemisorption processes were found to be exoergic (DeltaG < 0) in the gas phase and in the nonpolar liquid phase. The results reported in this work suggest that silicon defects on extended polycyclic aromatic hydrocarbons, such as graphite, soot, and large-diameter carbon nanotubes, could make them useful in the removal processes of aromatic sulfur compounds from oil hydrocarbons.     

Enhanced Li Adsorption and Diffusion in Single‐Walled Silicon Nanotubes: An ab Initio Study

We report a first‐principles investigation of Li adsorption and diffusion in single‐walled Si nanotubes (SWSiNTs) of interest to Li‐ion battery anodes. We calculate Li insertion characteristics in SWSiNTs and compare them with the respective ones in carbon nanotubes (CNTs) and other silicon nanostructures. From our calculations, SWSiNTs show higher reactivity toward the adsorption of Li adatoms than CNTs and Si nanoclusters. Considering the importance of Li kinetics, we demonstrate that the interior of SWSiNTs may serve as a fast Li diffusion channel. The important advantage of SWSiNTs over their carbon analogues is a sevenfold reduction in the energy barrier for the penetration of the Li atoms into the nanotube interior through the sidewalls. This prepossesses easier Li diffusion inside the tube and subsequent utilization of the interior sites, which enhances Li storage capacity of the system. The improvements in both Li uptake and Li mobility over their analogues support the great potential of SWSiNTs as Li‐ion battery anodes.     

Electronic properties of Si and Ge atoms doped in clusters: In(n)Si(m) and In(n)Ge(m)

Electronic properties of silicon and germanium atom doped indium clusters, In(n)Si(m) and In(n)Ge(m), were investigated by photoionization spectroscopy of the neutrals and photoelectron spectroscopy of the anions. Size dependence of ionization energy and electron affinity for In(n)Si(1) and In(n)Ge(1) exhibit pronounced even-odd alternation at cluster sizes of n = 10-16, as compared to those for pure In(n) clusters. This result shows that symmetry lowering with the doped atom of Si or Ge results in undegeneration of electronic states in the 1d shell formed by monovalent In atoms.     

Cu(I), Ag(I)/分子筛化学吸附脱硫的π-络合机理

应用DFT 研究了一系列含硫的杂环化合物(噻吩、苯并噻吩、二苯并噻吩和4, 6-二甲基二苯并噻吩)以及苯分子在Cu(I)-Y、Ag(I)-Y 分子筛上的化学吸附. 计算采用16T 分子筛簇模型(H22Si15AlO22), 对过渡金属采用了赝势基组, 在BLYP/DNP水平上完成. 相互作用能的结果表明, 阳离子交换的分子筛对含硫杂环芳香族化合物吸附能力的顺序为Cu(I)-Y >Ag(I)-Y. 两种吸附剂对噻吩类分子的吸附能力大于苯分子. 噻吩衍生物的吸附能顺序依次为, 4, 6-二甲基二苯并噻吩<二苯并噻吩约噻吩<苯并噻吩, 与实验结果相近. 通过自然键轨道计算,研究了分子筛上担载的Cu(I)、Ag(I)金属离子与噻吩和苯分子之间的π-络合作用, 分析比较了自然键电子给体-受体之间的二阶微扰稳定化能, 并探索其络合机理.     

Reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride

The effect of substituents at the silicon and germanium atoms in reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride was studied. The only occurring process is the exchange of the chlorine atoms at Ge for the phenyl groups from Si; an increase in the number of methyl groups or chlorine atoms at Si promotes formation of phenyltrichlorogermane, and an increase in the number of phenyl groups or replacement of the chlorine atom at the Si atom by hydrogen leads to the formation of di-and triphenylchlorogermanes. Neither phenyl nor other radicals are transferred back from Ge to Si in the course of reactions of phenylgermanes with methylchlorosilanes in the presence of aluminum chloride; the only occurring processes are the exchange of the phenyl or methyl radicals bonded to Ge for the Cl atom bonded to Al and the disproportionation of phenylchlorogermanes.     

Theoretical calculation of simple and doped CNTs with the potential adsorption of various ions for water desalination technologies

Structural Chemistry - In this work, the interactions between simple carbon nanotubes (CNTs) and doped carbon nanotubes (DCNTs; with sulfur, boron, aluminum, silicon, phosphorus, or nitrogen) as...     

High reaction activity of nitrogen-doped carbon nanotubes toward the electrooxidation of nitric oxide

Carbon nanotubes doped with N (NCNTs) enable 1.5 times faster electron-transfer kinetics for the oxidation of NO compared to pristine carbon nanotubes (CNTs), which may be due to the low adsorption energy for a NO on pyridinic NCNT(5,5) allowing NO to lose electrons readily and facilitate the following oxidation to nitrate.     

The pristine and carbon,silicon or germanium-substituted (10, 0) BN nanotube: A computational DFT study of NMR parameters

The geometrical structure and nuclear magnetic resonance (NMR) parameters of the pristine as well as carbon, silicon and germanium-doped (10, 0) boron-nitride (BN) nanotubes have been studied using a DFT-B3LYP method for the first time. When either a Ge, C or Si atom is substituted for a single B or N in the BN nanotube, the dopant atom extends outward from the surface of the nanotube. Our results show that Ge extends more from the surface than C or Si. It was found that the NMR parameters are significantly changed for those B and N nuclei that bond directly to C, Si or a Ge dopant. The calculations were carried out using the Gaussian 03 software package.     

Electrolytic Formation of Crystalline Silicon/Germanium Alloy Nanotubes and Hollow Particles with Enhanced Lithium‐Storage Properties

Crystalline silicon(Si)/germanium(Ge) alloy nanotubes and hollow particles are synthesized for the first time through a one‐pot electrolytic process. The morphology of these alloy structures can be easily tailored from nanotubes to hollow particles by varying the overpotential during the electro‐reduction reaction. The continuous solid diffusion governed by the nanoscale Kirkendall effect results in the formation of inner void in the alloy particles. Benefitting from the compositional and structural advantages, these SiGe alloy nanotubes exhibit much enhanced lithium‐storage performance compared with the individual solid Si and Ge nanowires as the anode material for lithium‐ion batteries.     

平面五配位硅、 锗XBe5H6(X=Si,Ge)团簇

采用密度泛函理论PBE0方法, 在aug-cc-pVTZ水平上理论预测了含平面五配位硅和锗原子的XBe₅H₆ (X=Si, Ge)团簇. 势能面系统搜索及高精度量化计算表明, 它们均为全局极小结构. XBe₅H₆(X=Si, Ge)团簇整体呈完美的扇形结构: Si/Ge原子被5个金属Be原子配位; 4个H原子以桥基方式与Be原子相键连, 剩余的2个 H原子以端基方式与两端的Be原子成键. 化学键分析表明, XBe₅H₆(X=Si, Ge) 团簇中XBe₅单元具有完全离域的1个π及3个σ键, 外围铍氢间形成4个Be—H—Be 三中心二电子(3c-2e)键及2个定域的Be—H键. XBe₅单元上离域的2π及6σ电子赋予体系π和σ双重芳香性, 并使Si/Ge原子满足八隅律（或八电子规则）. 能量分解-化学价自然轨道分析揭示, Si/Ge和Be₅H₆之间主要为电子共享键.     

Hydrogen desorption kinetics from the Si(1-x)Gex(100)-(2x1) surface

We study the influence of germanium atoms upon molecular hydrogen desorption energetics using density functional cluster calculations. A three-dimer cluster is used to model the Si((1-x))Ge(x)(100)-(2x1) surface. The relative stabilities of the various monohydride and clean surface configurations are computed. We also compute the energy barriers for desorption from silicon, germanium, and mixed dimers with various neighboring configurations of silicon and germanium atoms. Our results indicate that there are two desorption channels from mixed dimers, one with an energy barrier close to that for desorption from germanium dimers and one with an energy barrier close to that for desorption from silicon dimers. Coupled with the preferential formation of mixed dimers over silicon or germanium dimers on the surface, our results suggest that the low barrier mixed dimer channel plays an important role in hydrogen desorption from silicon-germanium surfaces. A simple kinetics model is used to show that reasonable thermal desorption spectra result from incorporating this channel into the mechanism for hydrogen desorption. Our results help to resolve the discrepancy between the surface germanium coverage found from thermal desorption spectra analysis, and the results of composition measurements using photoemission experiments. We also find from our cluster calculations that germanium dimers exert little influence upon the hydrogen desorption barriers of neighboring silicon or germanium dimers. However, a relatively larger effect upon the desorption barrier is observed in our calculations when germanium atoms are present in the second layer.     

沸石桥羟基和硅羟基与噻吩相互作用的理论研究

采用密度泛函理论和模型簇法研究了噻吩和沸石分子筛桥羟基和硅羟基的相互作用.对噻吩吸附在硅羟基H3SiOH可能的两种配位方式及吸附在沸石模型簇H3Si(OH)Al(OH)2OSiH3桥羟基B酸上可能的两种配位方式进行了比较分析.所有模型簇采用B3LYP混合方法对氢原子在6-31G基组水平上,对硅原子、铝原子、氧原子、碳原子、硫原子在6-31 G(d)基组水平上进行了全优化和频率分析.着重考察了噻吩与硅羟基及分子筛桥羟基模型簇不同配位方式所形成的配合物的结构及能量变化.计算结果表明由于在形成沸石-噻吩和硅羟基-噻吩配合物的结构和性质变化不明显,所以它们之间的相互作用为范德华作用力.从噻吩在沸石分子筛的桥羟基和硅羟基与噻吩的相互作用的吸附热可以推断,噻吩优先吸附在桥羟基上,只有桥羟基吸附饱和后方吸附在硅羟基上.由频率分析结果和实验结果的一致性可以证明所推测吸附模型的正确性.     

Reaction of ferrocenylmethyl derivatives of silicon and germanium with methanol: Solvolysis of the metal-carbon bond in the presence of ferric ions

Nine ferrocenylmethyl derivatives of silicon and germanium were prepared and found to undergo methanolysis of their C---M (M = Si or Ge) bonds in the presence of ferric ions to give ferrocenylmethyl methyl ether. For this reaction, relative rate studies and polarographic studies of the pertinent ferrocene derivatives were carried out to obtain some insight into the reaction mechanism. The substituted ferricenium ion intermediate which is formed by oxidation with ferric ions can readily undergo nucleophilic attack by methanol on the metal (Si or Ge) atom. The observed higher reactivity of the germanium derivative relative to the silicon congener in this reaction is not that expected for the usual base-catalyzed attack at the metal atom, and may be reasonably interpreted in terms of a possible change in the transition state depending on the nature of the leaving group, viz. on the acidity of the corresponding hydrocarbon acid, in the solvolysis of the C---M bond.     

二次合成Y型杂原子分子筛的吸附脱硫研究

采用液-固相同晶取代反应制备骨架含Ga的Y型分子筛(AlY),研究其吸附脱除硫质量分数为500×10^-6模拟燃料中的硫化物。AlY处理含噻吩、四氢噻吩(THT)、4,6-二甲基二苯并噻吩(4,6-DMDBT)、二苯并噻吩(DBT)、苯并噻吩(BT)和4-甲基二苯并噻吩(4-MDBT)的模拟燃料时的吸附容量分别为7.0、17.4、14.5、16.9、6.9 和5.8mg(S)/g吸附剂。采用密度泛函理论(DFT)中的广义梯度近似方法(GGA)计算各分子中硫原子上的电荷数,噻吩、四氢噻吩、4,6-二甲基二苯并噻吩(4,6-DMDBT)、二苯并噻吩(DBT)、苯并噻吩(BT)和4-甲基二苯并噻吩(4-MDBT)中硫原子上电荷数分别为-0.159、-0.298、-0.214、-0.211、-0.193、-0.188。四氢噻吩和4,6-DMDBT中硫原子上的电子密度大于噻吩中硫原子上的电子密度,这就使得四氢噻吩和4,6-DMDBT中的硫原子与吸附位间的作用会明显大于噻吩中的硫原子与吸附位间的作用。采用AlY处理催化裂化汽油时的脱硫率可达68%。     

Synthesis and properties of n-trimethylgermylmethyl-n-nitrosourea,a germanium analogue of n-neopentyl-n-nitrosourea

The rate for hydrolysis, chemoselectivitly toward nucleophiles, and partition property of N-neopentyl-, N-trimethylsilylmethyl-, and N-trimethylgermylmethyl-N-nitrosoureas were compared. The latter two compounds are silicon and germanium analogues of the neopentyl derivative. The substitution effect of Ge in place of Si or C are discussed on the chemical and physicochemical properties.     

A computational investigation of copper-doped germanium and germanium clusters by the density-functional theory

The geometries, stabilities, and electronic properties of Ge(n) and CuGe(n) (n = 2-13) clusters have been systematically investigated by using density-functional approach. According to optimized CuGe(n) geometries, growth patterns of Cu-capped Ge(n) or Cu-substituted Ge(n+1) clusters for the small- or middle-sized CuGe(n) clusters as well as growth patterns of Cu-concaved Ge(n) or Ge-capped CuGe(n-1) clusters for the large-sized CuGe(n) clusters are apparently dominant. The average atomic binding energies and fragmentation energies are calculated and discussed; particularly, the relative stabilities of CuGe10 and Ge10 are the strongest among all different sized CuGe(n) and Ge(n) clusters, respectively. These findings are in good agreement with the available experimental results on CoGe10- and Ge10 clusters. Consequently, unlike some transition metal (TM)Si12, the hexagonal prism CuGe12 is only low-lying structure; however, the basket-like structure is located as the lowest-energy structure. Different from some TM-doped silicon clusters, charge always transfers from copper to germanium atoms in all different sized clusters. Furthermore, the calculated highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO-LUMO) gaps are obviously decreased when Cu is doped into the Ge(n) clusters, together with the decrease of HOMO-LUMO gaps, as the size of clusters increases. Additionally, the contribution of the doped Cu atom to bond properties and polarizabilities of the Ge(n) clusters is also discussed.