Regulation of excitation energy transfer in Sb-alloyed Cs_(4)MnBi_(2)Cl_(12) perovskites for efficient CO_(2) photoreduction to CO and water oxidation toward H_(2)O_(2)

查看全文 作　　者：Haiwen [1]Wei;Zhen [1]Li;Honglei [1]Wang;Yang [2]Yang;Pengfei [2]Cheng;Peigeng [1]Han;Ruiling [1]Zhang;Feng [1]Liu;Panwang [1]Zhou;Keli [1,2]Han 机构地区：[1]Institute of Molecular Sciences and Engineering,Institute of Frontier and Interdisciplinary Science,Shandong University,Qingdao 266237,Shandong,China;[2]State Key Laboratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,Chinese Academy of Science,Dalian 116023,Liaoning,China 出　　处：《Journal of Energy Chemistry》索引2023年第7期,共8页 基　　金：financially supported by the National Natural Science Foundation of China(22179072,22002070);the Natural Science Foundation of Shandong Province(ZR2021QF006);the Outstanding Youth Science Foundation of Shandong Province(Overseas)(2022HWYQ-006);the Natural Science Foundation of Shandong Province(ZR2020QB059);the Fundamental Research Center of Artificial Photosynthesis(FReCAP)financially supported by the National Natural Science Foundation of China(22088102);the China Postdoctoral Science Foundation(No.2022M711898)。 摘　　要：Lead(Pb)-free halide perovskites have recently attracted increasing attention as potential catalysts for CO_(2) photoreduction to CO due to their potential to capture solar energy and drive catalytic reaction.However,issues of the poor charge transfer still remain one of the main obstacles limiting their performance due to the overwhelming radiative and nonradiative charge-carrier recombination losses.Herein,Pb-free Sb-alloyed all-inorganic quadruple perovskite Cs_(4)Mn(Bi_(1-x)Sb_(x))_(2)Cl_(12)(0≤x≤1)is synthesized as efficient photocatalyst.By Sb alloying,the undesired relaxation of photogenerated electrons from conduction band to emission centers of[MnCl6]^(4-)is greatly suppressed,resulting in a weakened PL emission and enhanced charge transfer for photocatalyst.The ensuing Cs_(4)Mn(Bi_(1-x)Sb_(x))_(2)Cl_(12) photocatalyst accomplishes efficient conversion of CO_(2)into CO,accompanied by a surprising production of H_(2)O_(2),a high valueadded product associated with water oxidation.By optimizing Sb^(3+) concentration,a high CO evolution rate of 35.1μmol g^(-1)h^(-1)is achieved,superior to most other Pb and Pb-free halide perovskites.Our findings provide new insights into the mixed-cation alloying strategies for improved photocatalytic performance of Pb-free perovskites and shed light on the rational design of robust band structure toward efficient energy transfer. 关 键 词：Pb-free perovskites Energy band modulation Perovskite photocatalysis photocatalytic CO_(2)reduction Water oxidation to H_(2)O_(2)