过氧氨三乙酸钛配合物分子前体热分解制备纯钛基复氧化物  

Pure Ti-based Mixed Oxides Prepared from the Thermal Decompositions of Molecular Precursors of Peroxo Complexes Coordinated with Tris(hydroxycarbonylmethyl)amine Trivalent Anion Titanate(Ⅳ)

作　　者：周朝晖[1] 洪麒明[1] 邓远富[1] 

机构地区：[1]厦门大学化学系,固体表面物理化学国家重点实验室,厦门361005

出　　处：《化学学报》2004年第24期2379-2385,共7页Acta Chimica Sinica

基　　金：国家重点基础研究发展规划 (No.0 0 1CB1 0 890 6);国家自然科学基金 (No.2 0 0 2 1 0 0 2 )资助项目

摘　　要：在pH =2 5～ 4 0的条件下 ,以四氯化钛、过氧化氢和氨三乙酸为原料反应得到四种过氧酸钛配合物 (NH4) 4 [Ti2 O (O2 ) 2 (ta) 2 ]·4H2 O (1) ,K4[Ti2 O(O2 ) 2 (ta) 2 ]·6H2 O (2 ) ,Sr2 [Ti2 O(O2 ) 2 (ta) 2 ]·10H2 O (3 )和Ba2 [Ti2 O(O2 ) 2 (ta) 2 ]·10H2 O (4 )(H3 ta =C6H6O6N) .配合物的EA ,UV vis,IR和X射线单晶分析表明它们含有相同的双核过氧氨三乙酸钛的阴离子结构 ,钛原子与过氧基团、四齿氨三乙酸和桥氧七配位 .3和 4中的阳离子锶和钡分别与周围的水分子和羧基氧形成九配位和十配位 .配合物 1,3和 4在空气中 60 0℃分解 ,XRD分析表明分别得到金红石型TiO2 ,SrTiO3 和四方BaTiO3 纯相 .Different peroxo titanate(Ⅳ) complexes coordinated with tris(hydroxycarbonylmethyl)amine trivalent anion including ammonium, potassium, strontium and barium salts (NH 4) 4[Ti 2O(O 2) 2(ta) 2]·4H 2O (1), K 4[Ti 2O^(O 2) 2^(ta) 2]·6H 2O (2), Sr 2[Ti 2O(O 2) 2(ta) 2]·10H 2O (3) and Ba 2[Ti 2O(O 2) 2(ta) 2]·10H 2O (4) were obtained directly from the triad system of TiCl 4-H 2O 2-H 3ta [H 3ta=tris(hydroxycarbonylmethyl)amine] in pH 2.5～4.0. These complexes were characterized with elemental analysis, UV-vis and IR spectra. X-ray structural analysis shows that all complexes contain a similar dimeric anion structure, in which titanium atom is coordinated heptagonally by a peroxo group, a tetradenatate tris(hydroxycarbonylmethyl)amine trivalent anion ligand and a bridging oxygen atom. The cation Sr 2+ and Ba 2+ are coordinated enneahedrally and decagonally by water molecules and carboxyl groups of tris^(hydroxycarbonylmethyl)amine trivalent anion ligand respectively. The ammonium, strontium and barium salts can be decomposed stoichiometrically into the expected low-temperature phases of rutile TiO 2, SrTiO 3 and tetragonal BaTiO 3 at the temperature of 600 ℃ respectively, which has been confirmed by XRD characterization.

关 键 词：钛配合物 氨三乙酸 配位 双核 C6H6 原子 钛基 前体 金红石型TIO2 制备 

分 类 号：O641.4[理学—物理化学]