具有开放骨架结构氟化磷酸钛的水热合成及分子动力学辅助确定骨架中模板剂的位置  

Hydrothermal Synthesis of a Three-dimensional Open-framework Oxyfluorinated Titanium Phosphate and ComputerSimulation of the Template Positions

作　　者：陈超[1] 丁红[1] 李光华[1] 毕明辉[1] 伊卓[1] 李乙[1] 李守贵[1] 孟河[1] 刘丽[1] 庞文琴[1] 

机构地区：[1]吉林大学无机合成与制备国家重点实验室,长春130012

出　　处：《高等学校化学学报》2005年第7期1189-1193,M003,共6页Chemical Journal of Chinese Universities

基　　金：国家重大基础研究"九七三"计划项目(批准号:G200077507);国家自然科学基金(批准号:20233030)资助

摘　　要：在水热体系中,制备了一个具有三维开放骨架结构的氟化磷酸钛化合物T i4(PO4)4(HPO4)2F2.[(CH3)2N(CH2)2NH3][H3O](简称TP-J3 J=Jilin un ivers ity).用X射线粉末衍射、元素分析、热重分析和X射线单晶衍射对其进行了表征.单晶结构分析表明,该化合物属于三斜晶系,P 1空间群,晶胞参数a=0.635 3(1)nm,b=0.869 9(2)nm,c=1.106 9(2)nm,α=93.94(3),β=90.13(3),γ=107.96(3),V=0.580 4(2)nm3,Z=2,R1=0.039 1,wR2=0.095 9,GOF=1.052.TP-J3的骨架结构可以看作是由次级结构单元(SBU)[T i2(PO4)2(HPO4)F]通过氧桥共顶点相连构筑而成的,在a和c方向形成了两种不同的八元环孔道,两种孔道相互交叉,形成了一种“类笼”结构.通过计算模拟确定双质子化的模板剂存在于“类笼”中,模板剂与骨架原子之间存在强烈的氢键作用,可稳定骨架的结构.Ti_4(PO_4)_4(HPO_4)_2F_2·[(CH_3)_2N(CH_2)_2NH_3][H_3O](denoted TP-J3), a oxyfluorinated titanium phosphate compound, with a three-dimensional open framework was hydrothermally synthesized. It was characterized by X-ray powder diffraction, inductively coupled plasma, elemental analysis(CHN), and thermogravimetric analysis. The structure was determined by single-crystal X-ray diffraction analysis, which crystallizes in the trigonal space group P1 with a0.635 3(1) nm, b0.869 9 (2) nm, c{1.106 9(2)} nm, α{93.94(3)}, β{90.13(3)}, γ{107.96(3)}, V{0.580 4(2)} nm+3, Z2, R_1{0.039 1}, {wR_2}0.095 9, GOF1.052. The structure was constructed from the secondary building units(SBUs, [Ti_2(PO_4)_2(HPO_4)F]. There exist two types of eight-membered ring channels along the b and c axes, which forms a 'cage-like structure'. The computer simulation was used to determine the possible positions of the organic template within the cages.

关 键 词：水热合成 氟化磷酸钛 分子动力学 计算模拟 模板剂 

分 类 号：O614[理学—无机化学]