文献类型：期刊文献

英文题名：The kinetic basis of bifunctional OX-ZEO catalysts for syngas conversion to light olefins

作者：Lai, Zhuangzhuang[1,2,3];Xiong, Danfeng[1,2];Hu, Peijun[1,2,4];Chen, Jianfu[1,2];Wang, Haifeng[1,2]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai, Peoples R China;[3]Shanghai Univ Engn Sci, Sch Chem & Chem Engn, Shanghai, Peoples R China;[4]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast, North Ireland

年份：2026

外文期刊名：NATURE CATALYSIS

收录：;EI(收录号：20262320839006);WOS:【SCI-EXPANDED(收录号:WOS:001780871900001)】；

基金：This project was supported by the National Key R&D Program of China (2021YFA1500700), NSFC (91945302, 92045303, 22525202, 22473043 and 22203031) and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Catalysts - Chemical bonds - Diffusion - Light olefins - Reaction kinetics - Zinc compounds

摘要：Despite considerable progress in oxide-zeolite (OX-ZEO) bifunctional catalysts for ketene-mediated syngas conversion, the origin of inter-component synergy and its dependence on spatial proximity remain unclear. Here we develop a diffusion-bridged, two-component microkinetic model that incorporates the entire reaction network over the ZnCrOx/mordenite (MOR) catalyst. The model captures the coupled reaction-diffusion dynamics and quantitatively elucidates the synergetic mechanism underlying selective syngas-to-light-olefin conversion. We show that MOR enhances light-olefin selectivity by overcoming the thermodynamic limitation of CH2CO formation on the oxide via a more favourable pathway. Furthermore, the model predicts an inverted U-shaped dependence of light-olefin selectivity with proximity, arising from a balance between intermediate transfer and Zn migration, the latter generating [ZnOH]+ species that promote undesired hydrogenation. More broadly, we establish a general reaction-diffusion coupling kinetic framework that quantifies the optimal combination principles for OX-ZEO systems. The predictions agree well with experimental observations and provide guidance for designing high-performance bifunctional catalysts.