Selective production of olefins from methanol over a heteroatomic SAPO-34 zeolite  

单原子钼掺杂分子筛高效催化甲醇制烯烃

作　　者：Zhaodong Zhu Mengtian Fan Meng He Bing An Yinlin Chen Shaojun Xu Tianze Zhou Alena M.Sheveleva Meredydd Kippax-Jones Lutong Shan Yongqiang Cheng Hamish Cavaye Jeff Armstrong Svemir Rudić Stewart F.Parker William Thornley Evan Tillotson Matthew Lindley Shenglong Tian Daniel Lee Shiyu Fu Mark D.Frogley Floriana Tuna Eric J.L.McInnes Sarah J.Haigh Sihai Yang 朱兆栋;樊梦天;贺萌;安冰;陈胤霖;徐少军;周天择;Alena M.Sheveleva;Meredydd Kippax-Jones;单路通;程永强;Hamish Cavaye;Jeff Armstrong;Svemir Rudić;Stewart F.Parker;William Thornley;Evan Tillotson;Matthew Lindley;田胜龙;Daniel Lee;付时雨;Mark D.Frogley;Floriana Tuna;Eric J.L.McInnes;Sarah J.Haigh;杨四海

机构地区：[1]Department of Chemistry,University of Manchester,Manchester,M139PL,UK [2]Departmentof Chemical Engineering,University of Manchester,Manchester,M139PL,UK [3]Photon Science Institute,University of Manchester,Manchester,M139PL,UK [4]The Chemical and Engineering Materials Division(CEMD),Neutron Sciences Directorate,Oak Ridge National Laboratory,Oak Ridge,TN 37831,USA [5]ISIS Facility,STFC Rutherford Appleton Laboratory,Didcot,OX110QX,UK [6]Department of Materials,University of Manchester,Manchester,M139PL,UK [7]CAS Key Laboratory of Science and Technology on Applied Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China [8]State Key Laboratory of Pulp and Paper Engineering,South China University of Technology,Guangzhou 510641,China [9]Diamond Light Source,Harwell Science Campus,Didcot,OX110DE,UK [10]College of Chemistry and Molecular Engineering,Beijing National Laboratory for Molecular Sciences,Peking University,Beijing 100871,China

出　　处：《Science Bulletin》2025年第5期694-703,共10页科学通报(英文版)

基　　金：University of Manchester,the National Natural Science Foundation of China and BNLMS for funding,and the EPSRC for funding of the EPSRC National EPR Facility at Manchester(EP/W014532/1 and EP/X034623/1);We are grateful to the STFC/ISIS Facility and Diamond Light Source for access to the beamlines TOSCA/MAPS,and I11/B18/B22,respectively;We are grateful to the STFC/ISIS Facility and Diamond Light Source for access to the beamlines TOSCA/MAPS,and I11/B18/B22,respectively;We acknowledge the UK catalysis Hub Block Allocation Group(BAG)Programme Mode Application for provision of beamtime at B18 for collection of the data presented in this work and the initial discussion of the data;The UK Catalysis Hub is kindly thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC grant:EP/R026939,EP/R026815,EP/R026645,EP/R027129 and EP/M013219(biocatalysis);We acknowledge the support of The University of Manchester's Dalton Cumbrian Facility(DCF),a partner in the National Nuclear User Facility;We recognise Dr.R.Edge for the assistance during the 60Co-irradiation processes;We thank M.Kibble for help at ISIS beamlines;TEM access was supported by the Henry Royce Institute for Advanced Materials,funded through EPSRC grants EP/R00661X,EP/S019367,EP/P025021 and EP/P025498;Zhaodong Zhu thanks the President's Doctoral Scholar award of University of Manchester for funding;Meng He and Lutong Shan thank the China Scholarship Council(CSC)for funding.

摘　　要：The methanol-to-olefins(MTO)process has the potential to bridge future gaps in the supply of sustainable lower olefins.Promoting the selectivity of propylene and ethylene and revealing the catalytic role of active sites are challenging goals in MTO reactions.Here,we report a novel heteroatomic silicoaluminophosphate(SAPO)zeolite,SAPO-34-Ta,which incorporates active tantalum(V)sites within the framework to afford an optimal distribution of acidity.SAPO-34-Ta exhibits a remarkable total selectivity of 85.8%for propylene and ethylene with a high selectivity of 54.9%for propylene on full conversion of methanol at 400°C.In situ and operando synchrotron powder X-ray diffraction,diffuse reflectance infrared Fourier transform spectroscopy and inelastic neutron scattering,coupled with theoretical calculations,reveal trimethyloxonium as the key reaction intermediate,promoting the formation of first carbon-carbon bonds in olefins.The tacit cooperation between tantalum(V)and Brønsted acid sites within SAPO-34 provides an efficient platform for selective production of lower olefins from methanol.

关 键 词：METHANOL-TO-OLEFIN SAPO-34 PROPYLENE Inelastic neutron scattering Trimethyloxonium 

分 类 号：O64[理学—物理化学]