磷酸铝分子筛AlPO_4-5的常压快速合成及晶化过程的原位热重-质谱研究  

Rapid Synthesis of Aluminophosphate Molecular Sieve AlPO_4-5 Under Ambient Pressure and In situ Thermogravimetric-Mass Spectroscopy Investigation of the Crystallization

作　　者：郭俊辉 闫文付[1] 师唯[2] 徐如人[1] GUO Junhui;YAN Wenfu;SHI Wei;XU Ruren(State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China;Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education, College of Chemistry, Nankai University, Tianjin 300071, China)

机构地区：[1]吉林大学无机合成与制备化学国家重点实验室化学学院,长春130012 [2]南开大学先进能源材料化学教育部重点实验室化学学院,天津300071

出　　处：《高等学校化学学报》2018年第5期841-848,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21571075;21320102001;21621001);国家重大研究发展计划项目(批准号:2016YFB0701100);高等学校学科创新引智计划项目(批准号:B17020和B12015);吉林大学高层次科技创新团队项目资助~~

摘　　要：分别以三乙胺、环己胺和四乙基氢氧化铵为结构导向剂,二缩三乙二醇为溶剂,研究了3种溶剂热合成体系在常压和自生压力条件下的晶化行为.在常压加热条件下,从分别含有三乙胺、环己胺和四乙基氢氧化铵的初始凝胶中快速晶化出了高结晶度的磷酸铝分子筛AlPO_4-5.在自生压力加热条件下,从相同的初始凝胶中分别晶化出了三维开放骨架磷酸铝JDF-20、二维层状磷酸铝UT-5以及含有磷酸铝分子筛AlPO_4-5的混相.含有三乙胺的初始凝胶晶化过程的原位热重-质谱研究表明,常压条件下磷酸铝分子筛AlPO_4-5主要在150~300℃之间生成.实验表明,自生压力会对有机胺(铵)的结构导向效应产生显著影响,这加深了对分子筛以及开放骨架生成过程及机理的认识.The crystallization behavior of the initial gels containing the structure-directing agents of triethylamine,cyclohexylamine or tetraethylammonium hydroxide under ambient pressure and autogenous pressure at elevated temperature was investigated. At 300 or 180 ℃ under ambient pressure,highly crystalline aluminophosphate molecular sieve AlPO_4-5 was rapidly crystallized from the initial gels containing triethylamine,cyclohexylamine or tetraethylammonium hydroxide. When the same initial gels were loaded into autoclaves and heated at 180 ℃ in an oven,three-dimensional open-framework aluminophosphate JDF-20,layered aluminophosphate UT-5,and a mixture containing aluminophosphate molecular sieve AlPO_4-5,were obtained,respectively. The crystallization process of the initial gel containing triethylamine under ambient pressure was investigated with in situ thermogravimetric-mass spectroscopy analysis. It was confirmed that the formation of aluminophosphate molecular sieve AlPO_4-5 under ambient pressure was mainly occurred in the stage of 150—300 ℃.We found that the pressure can significantly affect the structure-directing effect of amines. This finding greatly enhanced the understanding on the formation process and crystallization mechanism of zeolites and openframework crystals.

关 键 词：磷酸铝 分子筛 常压 自生压力 热重-质谱 

分 类 号：O611.4[理学—无机化学]