铋
格式化
密度泛函理论
材料科学
催化作用
空位缺陷
无机化学
化学物理
化学
光化学
物理化学
计算化学
结晶学
有机化学
冶金
作者
Xiaowen Wang,Yangyang Zhang,Wei Shao,Yifan Li,Yafei Feng,Zhifeng Dai,Yanxu Chen,Xiangmin Meng,Jing Xia,Genqiang Zhang
标识
DOI:10.1002/anie.202407665
摘要
Bismuth‐based materials have emerged as promising catalysts in the electrocatalytic reduction of CO2 to formate. However, the reasons for the reconstruction of Bi‐based precursors to form bismuth nanosheets are still puzzling, especially the formation of defective bismuth sites. Herein, we prepare bismuth nanosheets with vacancy‐rich defects (V‐Bi NS) by rapidly reconstructing Bi19Cl3S27 under negative potential. Theoretical analysis reveals that the introduction of chlorine induces the generation of intrinsic electric field in the precursor, thereby increasing the electron transfer rate and further promoting the metallization of trivalent bismuth. Meanwhile, in situ Raman and ex situ XRD tests verify that Bi19Cl3S27 has a faster reconstruction rate than Bi2S3. The formed V‐Bi NS exhibits up to 96% HCOO‐ Faraday efficiency and 400 mA cm‐2 HCOO‐ partial current densities, and its ECSA normalized formate current density and yield are 2.2 times higher than those of intact bismuth nanosheets (I‐Bi NS). Density functional theory (DFT) calculations indicate that bismuth vacancies with electron‐rich aggregation reduce the activation energy of CO2 to *CO2‐ radicals and stabilize the adsorption of the key intermediate *OCHO, thus facilitating the reaction kinetics of formate production.
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