助熔剂法合成钨氧氯化合物Li23CuW10O40Cl5  

Flux Growth of Tungsten Oxychloride Li23CuW10O40Cl5

作　　者：李淑芳 赵爽 李满荣 LI Shufang;ZHAO Shuang;LI Manrong(Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education,School of Chemistry,Sun Yat-Sen University,Guangzhou 510275,China)

机构地区：[1]中山大学化学学院,生物无机和合成化学教育部重点实验室,广州510275

出　　处：《无机材料学报》2020年第7期834-838,共5页Journal of Inorganic Materials

基　　金：National Natural Science Foundation of China(2180153)。

摘　　要：由于不同阴离子之间的电负性、离子半径、极化率和氧化态之间的差异,混合阴离子化合物可以产生不同于单一类型阴离子的新特性。混合阴离子金属材料在电子、湿度探测器、气体传感器、太阳能电池电极等领域有着广泛的应用前景。助熔剂方法是一种广泛应用于混合离子晶体生长的方法,它以适当的金属盐作为助熔剂,在较温和的条件下进行复分解反应。助熔剂法在混合阴离子化合物的合成中具有重要意义。钨氧氯化合物Li23CuW10O40Cl5单晶以高质量的Li4WO5为前驱体,以CuCl2为助熔剂通过两步法合成。通过X射线单晶衍射确定其晶体结构。结果表明, Li23CuW10O40Cl5结晶属于P63/mcm空间群,晶胞参数分别为a=1.02846(3) nm, c=1.98768(9) nm,V=1.82076(11) nm3, Z=2。单胞中分别包含五个晶体学独立的Li原子,两个W原子,一个Cu原子,两个Cl原子以及五个O原子。结构中, W(1)原子和一个Cl原子及五个O原子相连接,形成畸变八面体,而W(2)原子与四个O原子相连接形成四面体,Cu原子与六个O原子相连形成八面体。因此,Li23CuW10O40Cl5的晶体结构主要由[CuO6]和[W(1)O5Cl]八面体以及[W(2)O4]四面体构成。助熔剂法合成钨氧氯化合物Li23CuW10O40Cl5对今后探索新型的混合阴离子化合物具有重要意义。Mixed anion compounds can generate the emergence of novel properties that differ from those with mono-type anion due to the difference of electronegativities,ionic radii,polarizabilities,and oxidation states between unlike anions.Abundant research has been conducted on metallic mixed-anion materials with potential application in electronics,detectors of moisture,gas sensors,electrodes for solar batteries,etc.The flux method has been widely applied for mixed-anion crystal growth,which based on metathetical reaction with appropriate metal-salts flux under mild conditions.It is meaningful to synthesize the mixed anion compounds by the flux method.Single crystals of tungsten oxychloride Li23CuW10O40Cl5 were prepared via CuCl2 flux-growth method by two steps,which using high quality and phase-pure polycrystalline Li4WO5 as precursor.The crystal structure was determined by single-crystal X-ray diffraction analysis,which indicates that Li23CuW10O40Cl5 crystallizes in P63/mcm space group(a=1.02846(3)nm,c=1.98768(9)nm,V=1.82076(11)nm3,and Z=2).There are crystallographically independent five Li,two W,one Cu,two Cl,and five O atoms in the unit cell,where W(1)atoms are coordinated with one Cl and five O atoms in a distorted octahedra geometry,while W(2)atoms are connected with four O atoms in a tetrahedral coordination.The Cu atoms are connected with six O atoms forming[CuO6]octahedra.Thus,the crystal structure of the titled compound consists of[CuO6]and[W(1)O5Cl]octahedra,and[W(2)O4]tetrahedra.The successful synthesis of tungsten oxychloride Li23CuW10O40Cl5 through flux-growth method is meaningful for explore new mixed anion compounds in future.

关 键 词：钨氧氯化合物 CuCl2助熔剂 晶体结构 X射线衍射 

分 类 号：TQ174[化学工程—陶瓷工业]