TiHx(x=2,3,4)的从头计算研究

过渡金属氢化物分子与诸多催化过程密切相关[1].而过渡金属氢化物本身是一种颇有潜力的能源材料,即贮氢材料,如钛系、钒系贮氢材料在工业上已得到了广泛的应用 [2].但对于金属与氢的相互作用的机理研究的报道甚少.     

过渡金属膦配合物在硅氢化反应中的应用研究

过渡金属膦配合物在有机合成和催化反应中的应用非常广泛, 大量含膦杂原子配体被设计合成, 利用其特定的配位能力, 和过渡金属配位成过渡金属膦配合物, 并测试其对特定有机化学反应的催化性能. 硅氢加成反应是有机硅化学中的重要反应, 多种过渡金属包括铂、钯、铑、钌等的膦配合物对于硅氢加成反应均有催化活性. 综述了近几年来过渡金属膦配合物在硅氢加成反应中的应用进展.     

氮配位过渡金属配合物在硅氢加成反应中的应用研究

氮配位过渡金属配合物在近十几年来得到迅速的发展。 通过设计不同的含氮配体与不同过渡金属进行配位形成的氮配位过渡金属配合物,在硅氢加成反应中有很大应用研究价值。本文综述了氮配位铑、铁、铼、钴、锌等过渡金属配合物在酮或者烯烃的硅氢加成反应中的新进展。二 NFDA1 唑啉及二氢吡咯等含氮配体的优化设计必将大大促进含氮铁、铼、钴配合物在酮或者亚胺的硅氢加成反应中的应用。     

储氢研究进展

氢能是21世纪主要的新能源之一。作为一种新型的清洁能源,氢的廉价制取、安全高效储存与输送及规模应用是当今研究的重点课题,而氢的储存是氢能应用的关键。储氢材料能可逆地大量吸放氢,在氢的储存与输送过程中是一种重要载体。本文综述了目前所采用或正在研究的主要储氢材料与技术,如高压气态储氢、低温液态储氢、金属氢化物储氢、化学氢化物储氢、吸附储氢、金属有机骨架储氢等,比较了各种储氢的优缺点,并指出其相关发展趋势。     

储氢研究进展

氢能是21世纪主要的新能源之一.作为一种新型的清洁能源,氢的廉价制取、安全高效储存与输送及规模应用是当今研究的重点课题,而氢的储存是氢能应用的关键.储氢材料能可逆地大量吸放氢,在氢的储存与输送过程中是一种重要载体.本文综述了目前所采用或正在研究的主要储氢材料与技术,如高压气态储氢、低温液态储氢、金属氢化物储氢、化学氢化物储氢、吸附储氢、金属有机骨架储氢等,比较了各种储氢的优缺点,并指出其相关发展趋势.     

储氢研究进展

氢能是21世纪主要的新能源之一。作为一种新型的清洁能源,氢的廉价制取、安全高效储存与输送及规模应用是当今研究的重点课题,而氢的储存是氢能应用的关键。储氢材料能可逆地大量吸放氢,在氢的储存与输送过程中是一种重要载体。本文综述了目前所采用或正在研究的主要储氢材料与技术,如高压气态储氢、低温液态储氢、金属氢化物储氢、化学氢化物储氢、吸附储氢、金属有机骨架储氢等,比较了各种储氢的优缺点,并指出其相关发展趋势。     

表面有机金属化学(Ⅱ)

简要总结和评述了硅胶表面负载的一些过渡金属氢化物的烷烃碳-碳键和碳-氢键活化、金属铑和铂表面负载的有机锡物种的选择加氢和脱氢及有机金属化合物的沸石分子筛内外表面改性方面的研究进展,指出了今后拟重点研究的一些问题。     

过渡金属配合物断裂双链DNA及其机理

本文讨论了过渡金属配合物导致ＤＮＡ双链断裂的各种攫氢反应及碱基氧化机理,对由水解过程促进ＤＮＡ断裂的过渡金属配合物也作了介绍。     

我国金属氢化物化学研究

综述了我国金属氢化物化学的发展。我国是从50年代中期开始研究离子型金属氢化物的合成、性能和应用的,发展了一些合成方法,获得了多项中国专利。储氢合金的化学研究是70年代中期开始的。在储氢合金的化学合成、吸放氢热力学与动力学、储氢合金氢化催化和电化学方面都有较深入的研究,特别是储氢电极合金电化学及其在Ni/MH可逆电池中的应用研究,在国家863计划强有力的支持下,某些方面进入了国际先进行列。     

具有18电子结构的镁基过渡金属氢化物*

本文综述了近年来备受关注的具有18电子结构和高储氢容量的镁基过渡金属氢化物Mg₂NiH₄、Mg₂CoH₅和Mg₂FeH₆的研究进展,特别从材料组成、制备工艺、热力学及动力学性能等方面进行了综合评述。提出了该类金属氢化物在实际应用中存在的一些问题,如吸/放氢温度均较高,反应动力学性能较差,对于Mg₂CoH₅和Mg₂FeH₆的制备较困难,且可逆性不好。最后展望了对于具有18电子结构的镁基过渡金属氢化物在今后研究中的发展方向。     

Ion Segregation and Electrostatic Imbalance in Metal Hydrides

Crystal chemical indices of ion segregation and electrostatic imbalance after Beck help to rationalize inorganic crystal structures and sometimes even to predict them. Metal hydrides, from hydrido‐aluminates and ‐gallates, to complex transition metal hydrides, ternary ionic magnesium hydrides and mixed anionic hydrides, were investigated using these tools. Beck's ion segregation and electrostatic imbalance indices are found to work well in explaining crystal structures of most metal hydrides, although the electronegativity differences between cations and hydride anions are often much smaller in ionic metal hydrides, as compared to metal fluorides and oxides. This includes complex transition metal hydrides, despite the fact that formal oxidation states do not describe the actual charges properly. Rare cases of violations can be explained by the chemical bonding situation, e.g. the presence of weak metal–metal bonds in Li₃RhH₄.     

Hydrides with the perovskite structure: General bonding and stability considerations and the new representative CaNiH3

The stability and electronic structure of perovskite hydrides ABH₃ were investigated by means of first-principles density functional calculations. Two types of perovskite hydrides are distinguished: (1) When A and B are alkali and alkaline earth metals, the hydrides are ionic compounds with calculated band gaps of around 2 eV and higher. Their stability trend follows basically the concept of Goldschmidt's tolerance factor. (2) When A is one of the heavier alkaline earth metals (Ca, Sr, Ba) and B a transition metal, stable compounds ABH₃ result only when B is from the Fe, Co, or Ni groups. This stability trend is basically determined by effects associated with d band filling of both the transition metal and the hydride. In contrast to group (1) perovskites, the transition metal-containing compounds are metals. The synthesis of CaNiH₃ and its structure determination from CaNiD₃ is reported. This compound is a type (2) perovskite hydride with a fully occupied hydrogen position (CaNiD₃: a=3.551(4) Å, d_Ni-D=1.776(2) Å). Its stability is discussed with respect to transition metal hydrides with complex anions (e.g., Mg₂NiH₄, Na₂PdH₂, Sr₂PdH₄).     

Superconductivity of light‐metal hydrides

Hydrogen‐rich materials are potential high‐temperature superconductors at pressures lower than metal hydrogen, mainly because hydrogen atoms can provide strong electron–phonon coupling and high phonon frequencies in hydrogen‐rich materials. This review provides a systematic overview of the crystal type, stability, pressure‐induced transition, metallization and superconductivity of binary light‐metal hydrides under high pressure.     

Die Raumchemie des Wasserstoffs in Metallhydriden im Vergleich mit entsprechenden Fluoriden und Chloriden

The Atomic Volume of Hydrogen in Metal Hydrides in Comparison with Corresponding Fluorides and Chlorides The atomic volume of hydrogen in metal hydrides is calculated by using the atomic volumes of the metal cations as given by Biltz. The exceptional polarizability of hydrogen ligands is the reason for its adaptability when forming different bond structures in metal hydrides. The atomic volume of hydrogen decreases from 13.7 cm³mol^?1 in salt-like caesium hydride to 3.9 cm³mol^?1 in metallic palladium hydride. This variation is significantly higher for metal hydrides than for metal chlorides, although the volume of a hydrogen ion is comparable to that of a fluoride ion, that shows an almost constant value in its compounds. For structurally related hydrides an examination of the atomic volume of hydrogen allows the re-examination of a given composition and therefore the disclosure of a wrong atomic arrangement.     

Orbital‐Like Motion of Hydride Ligands around Low‐Coordinate Metal Centers

Hydrogen atoms in the coordination sphere of a transition metal are highly mobile ligands. Here, a new type of dynamic process involving hydrides has been characterized by computational means. This dynamic event consists of an orbital‐like motion of hydride ligands around low‐coordinate metal centers containing N‐heterocyclic carbenes. The hydride movement around the carbene–metal–carbene axis is the lowest energy mode connecting energy equivalent isomers. This understanding provides crucial information for the interpretation of NMR spectra.     

Reactivity of Coinage Metal Hydrides for the Production of H2 Molecules

The formation of molecular hydrogen as well as the possibility of using coinage metal hydrides as a prospective complex to produce hydrogen was presented in this work. Therefore, the reactions involving the interaction between two coinage metal hydrides, MH (M=Cu, Ag and Au, homo and heterodimers), were studied. The free energy profiles corresponding to aforementioned complexation were analysed by means of ab initio methods of quantum chemistry. The characteristics of these intermediates, final complexes and the electron density properties of the established interactions were discussed.     

Low-temperature hydrodechlorination of 2,3-dichlorodibenzo-p-dioxin and chlorobenzene with hydrides catalyzed by transition metal compounds

Hydrodechlorination of chlorobcnzene by chemically bound hydrogen in the presence of transition metal compounds was studied. Alkali and alkaline earth metal hydrides (NaH, MgH₂, LiAlH₄, NaH(LiAlH₄)/12) were used as the sources of the chemically bound hydrogen. The effect of the natures of the hydride and of the transition metal on the activity was studied under comparable conditions. The Pd/C-NaH(LiAlH₄1/2 catalytic system was found to be the most active. This system made it possible to perform the quantitative dechlorination of 2,3-dichlorodibenzo-p-dioxin at 70 °C.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1391–1394, June, 1996.     

Hydrogen and dihydrogen bonding of transition metal hydrides

Intermolecular interactions between a prototypical transition metal hydride WH(CO)₂NO(PH₃)₂ and a small proton donor H₂O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20–30% of the bond energy and to 30–40% of the bond enthalpy. An energy decomposition analysis reveals that the H?H bond of transition metal hydrides contains both covalent and electrostatic contributions.     

Tailoring Thermodynamics and Kinetics for Hydrogen Storage in Complex Hydrides towards Applications

Solid‐state hydrogen storage using various materials is expected to provide the ultimate solution for safe and efficient on‐board storage. Complex hydrides have attracted increasing attention over the past two decades due to their high gravimetric and volumetric hydrogen densities. In this account, we review studies from our lab on tailoring the thermodynamics and kinetics for hydrogen storage in complex hydrides, including metal alanates, borohydrides and amides. By changing the material composition and structure, developing feasible preparation methods, doping high‐performance catalysts, optimizing multifunctional additives, creating nanostructures and understanding the interaction mechanisms with hydrogen, the operating temperatures for hydrogen storage in metal amides, alanates and borohydrides are remarkably reduced. This temperature reduction is associated with enhanced reaction kinetics and improved reversibility. The examples discussed in this review are expected to provide new inspiration for the development of complex hydrides with high hydrogen capacity and appropriate thermodynamics and kinetics for hydrogen storage.