【作者】 白音孟和；

【导师】 安永林；

【作者基本信息】 大连理工大学 ， 无机化学， 2005， 硕士

【摘要】 由于硫属化物具有独特的物理化学性质,在半导体、光电导、非线性光学、催化和离子交换等领域有广阔的应用前景,这类材料的合成与结构研究越来越受人们的关注。本课题旨在总结以往硫属化物研究的基础上,通过选择合适的溶剂和模板剂,探索合成具有新型结构的硫属化物,丰富硫属化物的结构化学,同时探索硫属化物的合成规律,开发新的合成路线。 以乙二胺为模板剂在二巯基丙醇-乙醇混合溶液中合成了一种新型结构的类二硼烷结构的化合物（EnH₂）₂Ge₂S₆。单晶结构解析表明,它属于单斜晶系,空间群P2₁/n,晶胞参数:a=6.7125（5）（?）,b=11.2290（4）（?）,c=10.7518（4）（?）,α=90°,β=92.288（2）°,γ=90°。（EnH₂）₂Ge₂S₆中含有孤立Ge₂S₆^4-离子,这种离子具有类乙硼烷的几何结构,由GeS₄四面体通过共边聚合而成。同时对化合物还进行了EDS,IR,DSC-TG,粉末XRD,半导体性质表征,结果表明该合成方法能够合成纯相,并该化合物在200℃以下能够稳定存在,其近拟带隙为3.9eV。 以四甲基铵为模板剂在水溶液中合成了一种双链结构的化合物[（CH₃）₄N]As₃S₅,单晶结构解析表明,三斜晶系,空间群为P1,晶胞参数为:a=9.554（3）（?）,b=10.4874（18）（?）,c=14.027（2）（?）,α=91.873（15）°,β=91.879（19）°,γ=92.86（2）°。化合物[（CH₃）₄N]As₃S₅结构中聚合阴离子由邻近的¹_∞[As₃S₅]^-通过平面环As₂S₂连接形成¹_∞[As₆S₁₀]^2-链,这种链通过每第二个结构单元环状As₃S₃结构单元的As原子连接组成双链结构,其结构中可观察到赝三角锥配位的ψ-AsS₄。 我们详细讨论了硫属化物合成中的主要影响因素,典型的因素包括:溶剂、模板剂、温度和pH值等,总结了一些合成硫属化物的规律,为进一步开发硫属化物提供了一定的基础。更多还原

【Abstract】 Studies on syntheses and structures of chalcogenides are of increasing interest because of their unique physical and chemical properties which are promising for applications in semiconductors, photoconductivity, non-linear optics, catalysis and ion exchange. This work focuses on the synthesis and characterization of some main-group elemental chalcogenides by using solvothermal or hydrothermal technique through selecting suitable solvent and templating agents. We aim to develop new chalcogenides with novel stuctures.Using ethylenediamine as a structure-directing agent in the mixture organic solvent, we have synthesized a new compound (EnH2)2Ge2S6 and crystal structure was determined by single crystal X-ray diffraction method. Structure analysis indicates that it crystallizes in a monoclinic system, space group P21/n with a=6.7125(5)A, b=11.2290(4) A, c=10.7518(4) A, α=90°, β=92.288(2)°, γ=90°.The compound comprises of isolated diborane-like Ge2S64-formed by edge-sharing of two tetrahedral GeS4. It is further characterized by EDS, IR, DSC-TG, powder XRD, the results indicate that the compound is stable below 200 °C and a semiconductor with an estimated bad gap of 3.9 eV.Using tetramethylammonium as a structure-directing agent, hydrothermal technique was used for the synthesis of double chain compound [(CH3)4N]As3S5 and crystal structure was determined by single crystal X-ray diffraction method. Structure analysis indicates that it crystallizes in triclinic, space group P1, a =9.554(3)A, b =10.4874(18) A, c =14.027(2) A, α=91.873(15)°, β=91.879(19) °, γ=92.86(2)°. The polymeric anion of [(CH3)4N]As3S5 consists of adjacent 1∞[AS3S5]- chains linked together into a 1∞ [As6S10]2- double chains through planar As2S2 rings . A relatively undistorted Ψ-AsS4 trigonal bipyramidal geometry is observed for the participating As atoms.Furthermore, we have discussed the synthetic factors affecting the crystallization of chalcogenides, such as solvent, structure-directing agent, temperature and pH value etc, and further summarized some synthetic regularities in synthesizing chalcogenides, which will be helpful for the design and synthesis of new chalcogenides.更多还原