Strong metal-support interaction(SMSI)has a great impact on the activity and selectivity of heterogeneous catalysts,which was usually adjusted by changing reduction temperature or processing catalyst in different atmo...Strong metal-support interaction(SMSI)has a great impact on the activity and selectivity of heterogeneous catalysts,which was usually adjusted by changing reduction temperature or processing catalyst in different atmosphere.However,few researches concentrate on modulating SMSI through regulating the structure of the support.Herein,we show how changing the surface environment of the anatase TiO_(2)(B–TiO_(2))can be used to modulate the SMSI.The moderate TiOx overlayer makes the Ni metal highly dispersed on the high specific surface area of support,resulting in a substantially enhanced CO_(2)methanation rate.Besides,a novel phenomenon was observed that boron dopants promote the for-mation of the B–O–Ti interface site,enhancing the catalytic performance of CO_(2)hydrogenation.DFT calculations confirm that the B–O–Ti structure facilitates the activation of CO_(2)and further hydrogenation to methane.展开更多
An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant s...An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant surface nickel and cobalt components as active sites led to strong Ni-Co interaction with charge transfer from nickel to cobalt.Notably,electron-enriched Coδ-species participated in efficient chemisorption and activation of CO_(2)to generate monodentate carbonate.Simultaneously,plentiful available Ni0sites facilitated H2dissociation,thus CO_(2)and H2were smoothly activated at zones of Coδ-species and Ni0,respectively.Detailed in situ DRIFTS,quasi situ XPS,TPSR,and DFT calculations substantiated a new formate evolution mechanism via monodentate carbonate instead of traditional bidentate carbonate based on synergistic catalysis of Coδ-species and Ni0.The zonal activation of CO_(2)and H2by tuning electron behaviors of double-center catalysts can boost heterogeneous catalytic hydrogenation performance.展开更多
基金supported by National Natural Science Foundation of China(21773053)Advanced Talents Incubation Program of Hebei University(801260201019)+1 种基金Research Innovation Team of College of Chemistry and Environmental Science of Hebei University(hxkytd-py2102)the support of the High-Performance Computing Center of Hebei University。
文摘Strong metal-support interaction(SMSI)has a great impact on the activity and selectivity of heterogeneous catalysts,which was usually adjusted by changing reduction temperature or processing catalyst in different atmosphere.However,few researches concentrate on modulating SMSI through regulating the structure of the support.Herein,we show how changing the surface environment of the anatase TiO_(2)(B–TiO_(2))can be used to modulate the SMSI.The moderate TiOx overlayer makes the Ni metal highly dispersed on the high specific surface area of support,resulting in a substantially enhanced CO_(2)methanation rate.Besides,a novel phenomenon was observed that boron dopants promote the for-mation of the B–O–Ti interface site,enhancing the catalytic performance of CO_(2)hydrogenation.DFT calculations confirm that the B–O–Ti structure facilitates the activation of CO_(2)and further hydrogenation to methane.
基金funded by the Science and Technology Project of Southwest United Graduate School of Yunnan Province(No.202302AQ370002)the National Natural Science Foundation of China(No.22206066)。
文摘An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant surface nickel and cobalt components as active sites led to strong Ni-Co interaction with charge transfer from nickel to cobalt.Notably,electron-enriched Coδ-species participated in efficient chemisorption and activation of CO_(2)to generate monodentate carbonate.Simultaneously,plentiful available Ni0sites facilitated H2dissociation,thus CO_(2)and H2were smoothly activated at zones of Coδ-species and Ni0,respectively.Detailed in situ DRIFTS,quasi situ XPS,TPSR,and DFT calculations substantiated a new formate evolution mechanism via monodentate carbonate instead of traditional bidentate carbonate based on synergistic catalysis of Coδ-species and Ni0.The zonal activation of CO_(2)and H2by tuning electron behaviors of double-center catalysts can boost heterogeneous catalytic hydrogenation performance.
