Wu Daofu, Liu Xiaoqing, Tian Changqing, Zhou Jinchen, Lai Junan, Ran Hongmei, Gao Bo, Zhou Miao, Huang Qiang, Tang Xiaosheng
Key Laboratory of Optoelectronic Technology & Systems (Ministry of Education), College of Optoelectronic Engineering, Chongqing University, Chongqing 400044, China.
College of Optoelectronic Engineering, Chongqing University of Posts and Telecommunications, Chongqing 400065, China.
iScience. 2023 Jul 10;26(8):107355. doi: 10.1016/j.isci.2023.107355. eCollection 2023 Aug 18.
Lead halide perovskites are prospective candidates for CO photoconversion. Herein, we report copper-doped lead-free CsAgSbCl double perovskite microcrystals (MCs) for gas-solid phase photocatalytic CO reduction. The 0.2Cu@CsAgSbCl double perovskite MCs display unprecedented CO photoreduction capability with CO and CH yields of 412 and 128 μmol g, respectively. The ultrafast transient absorption spectroscopy reveals the enhanced separation of photoexcited carriers in copper-doped CsAgSbCl MCs. The active sites and reaction intermediates on the surface of the doped CsAgSbCl are dynamically monitored and precisely unraveled based on the Fourier transform infrared spectroscopy investigation. In combination with density functional theory calculations, it is revealed that the copper-doped CsAgSbCl MCs facilitate sturdy CO adsorption and activation and strikingly enhance the photocatalytic performance. This work offers an in-depth interpretation of the photocatalytic mechanism of CsAgSbCl doped with copper, which may provide guidance for future design of high-performance photocatalysts for solar fuel production.
卤化铅钙钛矿是一氧化碳光催化转化的潜在候选材料。在此，我们报道了用于气固相光催化一氧化碳还原的铜掺杂无铅CsAgSbCl双钙钛矿微晶（MCs）。0.2Cu@CsAgSbCl双钙钛矿微晶展现出前所未有的一氧化碳光还原能力，一氧化碳和甲烷的产率分别为412和128 μmol g。超快瞬态吸收光谱揭示了铜掺杂CsAgSbCl微晶中光激发载流子的分离增强。基于傅里叶变换红外光谱研究，对掺杂CsAgSbCl表面的活性位点和反应中间体进行了动态监测并精确解析。结合密度泛函理论计算结果表明，铜掺杂CsAgSbCl微晶促进了一氧化碳的牢固吸附和活化，并显著提高了光催化性能。这项工作对铜掺杂CsAgSbCl的光催化机理进行了深入阐释，可为未来太阳能燃料生产高性能光催化剂的设计提供指导。
