Elucidating the nature of the active sites in heterogeneous catalysts is fundamental for understanding their reactivity and catalytic performances.Although stannosilicate zeolites have tremendous application potential...Elucidating the nature of the active sites in heterogeneous catalysts is fundamental for understanding their reactivity and catalytic performances.Although stannosilicate zeolites have tremendous application potential for catalyzing biomass-related compounds in aqueous media,the detailed local structures and features of the real active sites and their possible structural variations under reaction conditions are poorly understood to date.In this study,a dynamic transformation of framework Sn−O−Si sites to Sn−OH/Si−OH pairs and subsequently a pseudo-Brønsted acid in stannosilicate zeolites upon molecular adsorption,which is analogous to various adsorbates/reactants under working conditions,was identified by solid-state nuclear magnetic resonance(NMR)spectroscopy for the first time,which challenges the widespread assumption that the active center structures remain rigid/stable during the catalytic process.These results provide new comprehensive insights for the fundamental understanding of the dynamic and flexible active centers and involved reaction mechanisms of novel zeolite catalysts with heterometal atoms,such as Sn,Ti,and Zr.展开更多
基金supported by the National Key R&D Program of China(2021YFA1502600,and 2022YFE0116000)State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC,33600000-20-ZC0607-0024)the National Natural Science Foundation of China(22032005,22125304,22002174,22241801,21991090,and 21991092).
文摘Elucidating the nature of the active sites in heterogeneous catalysts is fundamental for understanding their reactivity and catalytic performances.Although stannosilicate zeolites have tremendous application potential for catalyzing biomass-related compounds in aqueous media,the detailed local structures and features of the real active sites and their possible structural variations under reaction conditions are poorly understood to date.In this study,a dynamic transformation of framework Sn−O−Si sites to Sn−OH/Si−OH pairs and subsequently a pseudo-Brønsted acid in stannosilicate zeolites upon molecular adsorption,which is analogous to various adsorbates/reactants under working conditions,was identified by solid-state nuclear magnetic resonance(NMR)spectroscopy for the first time,which challenges the widespread assumption that the active center structures remain rigid/stable during the catalytic process.These results provide new comprehensive insights for the fundamental understanding of the dynamic and flexible active centers and involved reaction mechanisms of novel zeolite catalysts with heterometal atoms,such as Sn,Ti,and Zr.
