Identification of the active sites and mechanism for partial methane oxidation to methanol over copper-exchanged CHA zeolites

作     者：Yu Mao P.Hu Yu Mao;P.Hu

作者机构：School of Chemistry and Chemical EngineeringThe Queen’s University of BelfastBelfastUK 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2020年第63卷第6期

页      面：850-859页

核心收录：

学科分类：081702[工学-化学工艺] 081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the Queen’s University of Belfast and Chinese Scholarship Council for a Joint Scholarship 

主　　题：DFT heterogeneous catalysis methane-to-methanol CHA zeolites 

摘      要：To make methane a suitable energy carrier and transport less costly,it is an urgent and challenging task for us to convert methane to liquid under mild conditions *** this study,we explored partial methane oxidation to methanol by density functional theory(DFT)calculations using a hybrid functional(HSE06)with van der Waals(vdW)*** stabilities of different active sites over SSZ-13 and SAPO-34,two CHA type zeolites,are thoroughly investigated by ab initio molecular dynamics(AIMD)simulations and ab initio thermodynamics *** possible active sites,namely[CuOHCu]2+,[Cu(OH)2Cu]2+,[CuOCu]2+and[CuOH]+,are identified ***-to-methanol reaction mechanisms are further studied upon these most stable active sites,among which[CuOCu]2+and[CuOH]+are proved to be *** migration of species among zeolite pores are also discussed,which accounts for the activity on[CuOH]+*** concept may represent a more complete picture of catalytic reactions over zeolites in general.