Wang Yan, Wang Chun, Wei Yi, Wei Fang, Kong Lichun, Feng Jiuju, Lu Ji-Qing, Zhou Xiaocheng, Yang Fa
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua, Zhejiang, 321004, China.
Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing, Jiangsu, 210023, China.
Chemistry. 2022 Oct 18;28(58):e202201832. doi: 10.1002/chem.202201832. Epub 2022 Aug 23.
Metal halide perovskites, primarily used as optoelectronic devices, have not been applied for electrochemical conversion due to their insufficient stability in moisture. Herein, two bismuth-based perovskites are introduced as novel electrocatalysts to convert CO into HCOOH in aqueous acidic media (pH 2.5), exhibiting a high Faradaic efficiency for HCOOH of >80 % in a wide potential range from -0.75 to -1.25 V. Their structural evolution against water was dynamically monitored by in situ spectra. Theoretical calculations further reveal that the formation of intermediate OCHO* on bismuth sites of Cs Bi Br (111) play a pivotal role toward HCOOH production, which has a lower energy barrier than that on Cs AgBiBr (001) surfaces. Significantly, CO reacts with protons instead of water which can enhance CO reduction rate and suppress hydrogen evolution by avoiding carbonate formation in acidic electrolytes. This work paves the way for the extensive investigation of halide perovskites in aqueous systems.
金属卤化物钙钛矿主要用作光电器件，由于其在潮湿环境中稳定性不足，尚未应用于电化学转换。在此，引入了两种铋基钙钛矿作为新型电催化剂，用于在酸性水溶液（pH 2.5）中将CO转化为HCOOH，在-0.75至-1.25 V的宽电位范围内，对HCOOH表现出>80%的高法拉第效率。通过原位光谱动态监测了它们对水的结构演变。理论计算进一步表明，Cs Bi Br (111)铋位点上中间产物OCHO*的形成对HCOOH的生成起着关键作用，其能垒低于Cs AgBiBr (001)表面。值得注意的是，CO与质子而非水反应，通过避免在酸性电解质中形成碳酸盐，可提高CO还原速率并抑制析氢。这项工作为在水体系中广泛研究卤化物钙钛矿铺平了道路。
