以1,6-己二胺为模板剂的层状磷酸锆晶体的合成与表征  

Synthesis and Characterization of Layered Zirconium Phosphate Crystal with 1,6-Hexyldiamine as Template

作　　者：王锦航[1] 刘中民[1] 孙振刚[1] 杨越[1] 何艳丽[1] 许磊[1] 齐越[1] 

机构地区：[1]中国科学院大连化学物理研究所天然气化工与应用催化研究室,辽宁大连116023

出　　处：《催化学报》2004年第5期387-392,共6页

基　　金：中国科学院知识创新工程项目 (DICPK2 0 0 0B3 )

摘　　要：采用水热法合成了以 1,6 己二胺 (HDA)为模板剂的层状磷酸锆晶体 [(HDA)H2 ]0 5[Zr(PO4) (HPO4) ]·1 5H2 O ,并用单晶及粉末XRD ,IR和TG DTA等对其结构和性质进行了表征 .该晶体是由磷酸锆无机层、有机胺以及水分子三部分构成的层状结构 ,层间距约为 1 77nm ,无机层结构为γ 型 .位于有机胺两端的氮与无机层表面部分羟基的氧以氢键连接 ,水分子占据磷酸锆层间的两种位置 .单晶结构模拟得到的XRD谱与从粉末样品采集的XRD谱基本吻合 .此晶体在 180℃下脱去水分子 ,在 2 2 0℃下加热 3h其结构未发生明显变化 ;有机胺模板剂在 2 5 0℃下开始分解 .A novel layered zirconium phosphate crystal with organic di-protonated 1,6-hexyldiamine (HDA) cation, 0.5 [Zr(PO 4)(HPO 4)]·1 5H 2O (abbreviated to γ-(HDA)ZrP), was synthesized under hydrothermal conditions and characterized by single-crystal and powder XRD, IR and TG-DTA. The crystal is in orthorhombic space group Imm2 with a= 3 433?8 nm, b= 0 533?8 nm, c= 0 662?0 nm, V= 1 213?42 nm3, Z=2, R= 0 055?4 and R W= 0 075?4. The title compound was of γ-type layered structure which was formed by corner-sharing ZrO 6 octahedron and PO 4, PO 3(OH) tetrahedron units, and the layer-to-layer distance was about 1 77 nm. The HDA molecule, which was perpendicular to the zirconium phosphate layer and bent a little like a bow, supported and connected the zirconium phosphate layer by the hydrogen bonds between the two end nitrogen atoms of HDA molecule and one of the two oxygen atoms stretching out of the zirconium phosphate layers. The water molecules occupied two positions between the layers. One was the cavities formed by HPO 2- 4 tetrahedrons on the surface of the zirconium phosphate layer, and the other was amid HDA molecules with four water molecules in one group. The XRD pattern simulated from the single crystal structure analysis result was in accordance with that collected from the powder sample synthesized. The absorption bands of organic amine and water appeared in the IR spectrum of γ-(HDA)ZrP, corroborated the crystal structure determined by XRD analysis. On heating, one and a half water molecules were lost at 180 ℃ and the HDA began to decompose at 250 ℃. After getting rid of the water molecules by heating at 220 ℃ for 3 h, no obvious change in the crystal structure was observed.

关 键 词：水热合成 己二胺 模板剂 磷酸锆 晶体结构 

分 类 号：O643[理学—物理化学]