Artificial photosynthesis in carbon dioxide(CO_(2))conversion into value-added chemicals attracts considerable attention but suffers from the low activity induced by sluggish separation of photogenerated carriers and ...Artificial photosynthesis in carbon dioxide(CO_(2))conversion into value-added chemicals attracts considerable attention but suffers from the low activity induced by sluggish separation of photogenerated carriers and the kinetic bottleneck-induced unsatisfied selectivity.Herein,we prepare a new-style Bi/TiO_(2) catalyst formed by pinning bismuth clusters on TiO_(2) nanowires through being confined by pores,which exhibits high activity and selectivity towards photocatalytic production of CH_(4) from CO_(2).Boosted charge transfer from TiO_(2) through Bi to the reactants is revealed via in situ X-ray photon spectroscopy and time-resolved photoluminescence(PL).Further,in situ Fourier transform infrared results confirm that Bi/TiO_(2) not only overcomes the multi-electron kinetics challenge of CO_(2) to CH_(4) via boosting charge transfer,but also facilitates proton production and transfer as well as the intermediates*CHO and*CH_(3)O generation,ultimately achieving the tandem catalysis towards methanation.Theoretical calculation also underlies that the more favorable reaction step from*CO to*CHO on Bi/TiO_(2) results in CH_(4) production with higher selectivity.Our work brings new insights into rational design of photocatalysts with high performance and the formation mechanism of CO_(2) to CH_(4) for solar energy storage in future.展开更多
基金supported in part by the National Natural Science Foundation of China(Nos.52125103,52071041 and 12074048)the Project for Fundamental and Frontier Research in Chongqing(Nos.cstc2020jcyj-msxmX0777 and cstc2020jcyj-msxmX0796).
文摘Artificial photosynthesis in carbon dioxide(CO_(2))conversion into value-added chemicals attracts considerable attention but suffers from the low activity induced by sluggish separation of photogenerated carriers and the kinetic bottleneck-induced unsatisfied selectivity.Herein,we prepare a new-style Bi/TiO_(2) catalyst formed by pinning bismuth clusters on TiO_(2) nanowires through being confined by pores,which exhibits high activity and selectivity towards photocatalytic production of CH_(4) from CO_(2).Boosted charge transfer from TiO_(2) through Bi to the reactants is revealed via in situ X-ray photon spectroscopy and time-resolved photoluminescence(PL).Further,in situ Fourier transform infrared results confirm that Bi/TiO_(2) not only overcomes the multi-electron kinetics challenge of CO_(2) to CH_(4) via boosting charge transfer,but also facilitates proton production and transfer as well as the intermediates*CHO and*CH_(3)O generation,ultimately achieving the tandem catalysis towards methanation.Theoretical calculation also underlies that the more favorable reaction step from*CO to*CHO on Bi/TiO_(2) results in CH_(4) production with higher selectivity.Our work brings new insights into rational design of photocatalysts with high performance and the formation mechanism of CO_(2) to CH_(4) for solar energy storage in future.
