一种新型的磷化钼加氢精制催化剂的研究

通过(NH4)Mo7O24·4H2O和(NH4)2HPO4水溶液沉淀、焙烧在923K用H2还原制得磷化钼催化剂.XRD检测表明,用H2还原后有纯的磷化钼生成.在3.0MPa的高压连续微反系统中测定催化剂的加氢活性.以制备的磷化钼为活性组分、γ-Al2O3为稀释剂,考察了空速、反应温度和反应时间对模型化合物的HDN、HDS和HDY性能的影响,结果表明:在合适的条件下,其脱硫脱氮率可达到90%以上.模型化合物为吡啶、噻吩和环己烯,吡啶含量以N计(为0.2%)、噻吩含量以S计(为0.3%),环己烯含量为20%,以环己烷作溶剂.     

Protective Properties of Zinc-Rich Coatings: An Impedance Method Estimate

The impedance of zinc-rich polymer coatings on steel in a 3-% NaCl solution is studied. The electrochemical behavior of the electrode is satisfactorily described by an equivalent circuit that contains a constant-phase element, which reflects fractal properties of the zinc surface in the binder. From the results of calculations of the circuit elements for metal-rich electrodes with different zinc contents computed are fractions of the active area of the surface of the coating and its fractal dimensionality.     

n—InP在Fe^3＋／Fe^2＋溶液中光脉冲暂态行为（Ⅳ）

研究了波长、温度及表面处理对ｎ－ＩｎＰ光脉冲暂态行为的影响。结果表明，波长对时间常数无影响；随着温度升高，峰值下降，衰减变快。讨论了表面处理的影响，并对实验结果作了必要的解释。     

M_nP_m~+原子簇结构的ab initio从头算(M=Cr,Mn,n=1～3,m=2～12)

应用ahinitio计算程序，我们对飞行时间质谱产生的谱图进行了理论分析。稳定的MnnPm+和CrnPm+的结构基本上是多面体，仅有少数结构为环状和平面的。在计算中，我们尚未发现有链状的簇合物，这与风簇绝大多数是多面体是相一致的。因此，单枚金属簇合物的形成机制很大可能是金属进入磷形成的笼簇中。一般地说，除了磷的个别笼状团簇外，金属和磷相互成键是普遍存在的；在二核、多核金属磷簇合物中，金属间相互作用不常见，绝大多数是通过桥磷相连的。     

由非晶态Ni-P低温制备Ni2P催化剂及其对二苯并噻吩加氢脱硫的催化性能

 以非晶态Ni-P合金为前驱体,在低温下通过PH3处理制备了Ni2P/SiO2-Al2O3催化剂,并用X射线衍射(XRD)、 透射电镜(TEM)、 电感耦合等离子体发射光谱、 N2吸附和X射线光电子能谱(XPS)进行了表征,以二苯并噻吩为探针,在小型连续流动固定床反应器上考察了催化剂的加氢脱硫性能. XRD结果表明,在200～300 ℃范围内前驱体都可以完全转化为Ni2P, 随着磷化温度的升高,晶体结构变得越来越完整. TEM观察发现, Ni-P粒子和Ni2P粒子的平均尺寸都在40～50 nm, 并且都能够高分散在SiO2-Al2O3载体上. XPS结果表明,不论是非负载还是SiO2-Al2O3负载的Ni2P, 表层主要为Ni2P和钝化层Ni3(PO4)2. Ni2P/SiO2-Al2O3催化剂在实验范围内表现出很好的二苯并噻吩加氢脱硫性能.     

Covalent Structures of Phosphorus: A Comprehensive Theoretical Study

Starting from earlier work by Baudler we introduce a chemical heuristic for the systematic deduction and classification of covalent partial structures of phosphorus in polycyclic phosphanes, phosphorus-rich polycyclic phosphides, and allotropes of phosphorus except the black forms. This approach is used to direct ab initio techniques (which also confirm the rules) in the quest for as yet unknown forms of molecular or macromolecular phosphorus. Based on calculated stabilities of systematically generated structural alternatives we rationalize the stabilities of Hittorf's phosphorus and of molecular P₄, confirm the possible existence of at least one other crystalline allotropic form of phosphorus, and provide insight into the probable structure of amorphous red phosphorus. In total, the combined approach of chemical heuristics and large scale ab initio calculations presented in this work supplies a coherent chemical understanding of covalent polyphosphorus structures.     

磷化镍晶体结构的密度泛函理论研究

运用密度泛函理论系统地研究了已知的磷化镍晶体如Ni3P、 Ni12P5、 Ni2P、 Ni5P4、 NiP、 NiP2 和 NiP3等的结构、成键以及相关的热力学稳定性，对于结构简易化合物（Ni2P和NiP3）的弹性行为进行了预测。这些数据有助于更好的理解磷化镍的催化活性。     

Ba8Cu16P30 – eine neue ternäre Variante des Clathrat I-Strukturtyps

Ba₈Cu₁₆P₃₀ – a New Ternary Variant of the Clathrate I Type Structure Ba₈Cu₁₆P₃₀ (a = 14.117(1) Å, b = 10.093(1) Å, c = 28.022(2) Å) was prepared by heating a mixture of the elements (800°C; excess of Ba and P; removal of the by-products by acetic acid/H₂O₂). The compound crystallizes orthorhombically (Pbcn; Z = 4) in a new superstructure of the cubic clathrate I type structure with an ordered distribution of the atoms. The structure is characterized by a three-dimensional framework of CuP₄ tetrahedra with cavities in the form of pentagonal dodecahedra and tetrakaidecahedra, which are occupied by the Ba atoms. The compound shows semiconduction, therefore the composition should be Ba₈Cu_15.5P_30.5.     

Solvothermal syntheses of Cu3P via reactions of amorphous red phosphorus with a variety of copper sources

Polycrystalline Cu₃P was successfully prepared under a wide variety of solvothermal conditions. The reaction of red phosphorus with several copper sources (copper metal, copper (I) iodide, copper (I) chloride and copper (II) chloride) at 150-200 °C for 1-2 days in water produced Cu₃P. Products were examined with powder X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Thermal analyses and optical spectroscopy were also performed. A detailed list of reaction conditions, products and impurity phases (where applicable) are reported.     

New metal-rich mixed chalcogenides with an intergrowth structure: Ni<Subscript>5.68</Subscript>SiSe<Subscript>2</Subscript>, Ni<Subscript>5.46</Subscript>GeSe<Subscript>2</Subscript>, and Ni<Subscript>5.42</Subscript>GeTe<Subscript>2</Subscript>

New metal-rich mixed nickel-silicon and nickel-germanium chalcogenides, Ni_5.68SiSe₂, Ni_5.46GeSe₂, and Ni_5.42GeTe₂, were synthesized by high-temperature ceramic techniques. The X-ray diffraction study of single crystals grown from a molten flux revealed that the compounds are isostructural and crystallize in the tetragonal system (space group I4/mmm, Z = 2). These compounds are the first members of the family of M_7−δEX₂-type (M = Ni or Pd; E = Sn or Sb; X is chalcogen) intergrowth structures containing “light” p elements E. Resistivity measurements on pressed textured pellets showed that both selenides are anisotropic metallic conductors in the directions parallel and perpendicular to the heterometallic bond systems. The geometric criteria of stability of the intergrowth structure type under consideration are discussed. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1632–1638, September, 2007.