Regulating the Active Sites of Cs2 AgBiCl6 by Doping for Efficient Coupling of Photocatalytic CO2 Reduction and Benzyl Alcohol Oxidation.
Regulating the Active Sites of Cs2 AgBiCl6 by Doping for Efficient Coupling of Photocatalytic CO2 Reduction and Benzyl Alcohol Oxidation.
复制标题
DOI：
10.1002/smll.202304756
复制
发表时间：
2023-08
期刊：
影响因子：
13.3
通讯作者：
Zhihao Chen;Malik Zeeshan Shahid;Xinyan Jiang;Meng Zhang;Danrui Pan;Hongpeng Xu;Guocan Jiang
中科院分区：
文献类型：
--
作者：
Zhihao Chen;Malik Zeeshan Shahid;Xinyan Jiang;Meng Zhang;Danrui Pan;Hongpeng Xu;Guocan Jiang
卤化物钙钛矿具有优异的光电性能，使其成为光催化CO2还原和苯甲醇（BA）氧化的理想选择。然而，在卤化物钙钛矿上同时实现上述氧化还原偶联反应仍然是一个巨大的挑战，因为它需要不同的催化位点用于不同的目标反应。在此，Cs2 AgBiCl 6（CABC）的催化位点是通过掺杂Fe调节的光催化CO2还原和BA氧化的有效耦合。Fe掺杂的CABC（Fe：CABC）表现出增强的可见光响应和有效的电荷分离。实验结果和理论计算揭示了Bi和Fe位之间的协同作用，其中Bi和Fe位具有较低的CO2还原和BA氧化的活化能。进一步的研究表明，在光照条件下，电子和空穴分别倾向于在Bi位和Fe位聚集，这为促进CO2还原和BA氧化创造了有利条件.所得Fe：CABC对CO（18.5 µmol g-1 h-1）和BD（1.1 mmol g-1 h-1）的生成具有很高的光催化性能，超过了大多数最先进的卤化物光催化剂。这一工作展示了一种调控氧化还原偶联反应催化位点的简单策略，为设计卤化物类钙钛矿结构材料提供了一条新的途径。
Halide perovskites exhibit outstanding optoelectronic properties, which make them an ideal choice for photocatalytic CO2 reduction and benzyl alcohol (BA) oxidation. Nevertheless, the simultaneous realization of the above redox coupling reactions on halide perovskites remains a great challenge, as it requires distinct catalytic sites for different target reactions. Herein, the catalytic sites of Cs2 AgBiCl6 (CABC) are regulated by doping Fe for efficient coupling of photocatalytic CO2 reduction and BA oxidation. The Fe-doped CABC (Fe: CABC) exhibits an enhanced visible-light response and effective charge separation. Experimental results and theoretical calculations reveal a synergistic interplay between Bi and Fe sites, where the Bi and Fe sites have lower activation energies toward CO2 reduction and BA oxidation. Further investigations demonstrate that electrons and holes prefer to accumulate at the Bi site and Fe site under light irradiation, respectively, which creates favorable conditions for facilitating CO2 reduction and BA oxidation. The resultant Fe: CABC achieves a high photocatalytic performance toward CO (18.5 µmol g-1 h-1 ) and BD (1.1 mmol g-1 h-1 ) generation, which surpasses most of the state-of-the-art halide photocatalysts. This work demonstrates a facile strategy for regulating the catalytic site for redox coupling reactions, which will pave a new way for designing halide perovskites for photocatalysis.