基于一氧化碳、二氧化碳和氧气分子吸附为探针的碳化钼、碳化钨、氮化钼和氮化钨的表面化学性质：密度泛函理论分析

作为具有吸引力的电极材料,过渡金属碳化物与氮化物被应用在许多电化学储能及能量转换领域. 本工作中,通过密度泛函理论计算,以及一氧化碳 （CO）, 二氧化碳（CO₂）和 氧气（O₂）分子的吸附来表征钼和钨的碳化物及氮化物,如碳化钼（Mo₂C）、碳化钨（W₂C）、氮化钼（Mo₂N）和氮化钨（Mo₂C）的表面化学性质. 这些探针分子可为研究钼和钨的碳化物及氮化物表面在酸性/碱性的氧化还原性质提供衡量方法. 计算结果表明,CO₂分子的吸附发生在路易斯碱位,其碱性降低顺序为α-W₂C(001) > α-W₂N(001) > β-Mo₂C(001) > γ-Mo₂N(100). 此外,CO和O₂分子吸附可用于评估上述碳化物及氮化物的还原能力,其还原性减小顺序为β-W₂C(100) > α-Mo₂C(100) > α-W₂N(001) > α-W₂C(001) > β-Mo₂C(001) > γ-Mo₂N(100). 由于还原本性,使得上述这些碳化物和氮化物成为在各种催化反应中有可能取代贵金属的良好候选材料.     

Oxygen photo-adsorption related quenching of photoluminescence in group-III nitride nanocolumns

GaN and InGaN nanocolumns of various compositions are studied by room-temperature photoluminescence (PL) under different ambient conditions. GaN nanocolumns exhibit a reversible quenching upon exposure to air under constant UV excitation, following a t^−1/2 time dependence and resulting in a total reduction of intensity by 85–90%, as compared to PL measured in vacuum, with no spectral change. This effect is not observed when exposing the samples to pure nitrogen. We attribute this effect to photoabsorption and photodesorption of oxygen that modifies the surface potential bending. InGaN nanocolumns, under the same experimental conditions do not show the same quenching features: The high-energy part of the broad PL line is not modified by exposure to air, whereas a lower-energy part, which does quench by 80–90%, can now be distinguished. We discuss the different behaviors in terms of carrier localization and possible composition or strain gradients in the InGaN nanocolumns.     

新型内嵌混合金属氮化物原子簇富勒烯的合成、结构与性质*

内嵌混合金属氮化物原子簇富勒烯的发现极大地扩展了内嵌富勒烯家族。内嵌混合金属氮化物原子簇富勒烯是一类新型的内嵌富勒烯,其内嵌物为由2-3种不同的金属组成的氮化物原子簇。本文首先介绍了新型内嵌混合金属氮化物原子簇富勒烯的发现、合成和分离方法,并对目前所分离出来的内嵌混合金属氮化物原子簇富勒烯进行了分类。然后总结了目前所报导的内嵌混合金属氮化物原子簇富勒烯的结构表征手段,对于不同的内嵌混合金属氮化物原子簇富勒烯的分子结构分别进行了阐述。最后着重讨论了内嵌混合金属氮化物原子簇富勒烯的特殊电子性质以及物理和化学性质。本文还对内嵌混合金属氮化物原子簇富勒烯潜在的应用前景作了展望,在内嵌具有不同物理性质的两到三种金属原子的基础上,所形成的内嵌混合金属氮化物原子簇富勒烯有可能兼具不同金属原子各自的性质,从而成为多功能综合的功能材料。     

Multiexciton molecules in the hexaborides

We investigate multiexciton bound states in a semiconducting phase of divalent hexaborides. Due to three degenerate valleys in both the conduction and valence bands the binding energy of a 6-exciton molecule is greatly enhanced by the shell effect. The ground state energies of multiexciton molecules are calculated using the density functional formalism. We also show that charged impurities stabilize multiexciton complexes leading to condensation of localized excitons. These complexes can act as nucleation centers of local moments. Received 24 October 2000     

Study of energy-band structures,some thermomechanical properties and chemical bonding for a number of refractory metal carbides by the LMTO-ASA method

The energy-band structures of V, Nb, VC, NbC and WC have been calculated with the use of the linearized method of “muffin-tin” orbitals (LMTO-ASA). The calculated band structures are in good agreement with a previous self-consistent APW calculation. The prominent features of the band structures for WC are a particularly wide 5d W, 2p C band, and also the presence of a separate 5d W band below the Fermi level. The values of the lattice constants, bulk moduli, sound velocities, Debye temperatures and melting temperatures have been calculated and are in reasonable agreement with experiment. It is shown that the high values of the bulk moduli of VC and NbC are explained by the hybridization between s- and p-metal states and 2s C, 2p C states, while the extreme value of the modulus for WC is due mainly to the covalency resulting from 5d W, 2s C and 2p C hybridization.     

Determination of nitrogen and carbon in refractory nitrides and carbonitrides by means of Dumas gas chromatography

The applicability of an automated Dumas-GC method for the determination of nitrogen and carbon in refractory materials was investigated. Analyses were carried out to determine nitrogen and carbon in TiN, ZrN and Ti(C,N) using CuO, V₂O₅ and Pb₃O₄ as oxidizing additives. The reproducibility of the analyses obtained with V₂O₅ was better than ± 1 rel% for major constituents. An estimation of the accuracy of the Dumas-GC method shows that this rapid and low-cost method can compete with other methods, at least for the refractory nitrides and carbonitrides of the transition metals.