Chen Xiaoyu, Feng Shuoshuo, Yan Jiaying, Zou Yanhong, Wang Linlin, Qiao Jinli, Liu Yuyu
Institute for Sustainable Energy, College of Sciences, Shanghai University, Baoshan District, Shanghai 200444, China.
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Environmental Science and Engineering, Donghua University, 2999 Ren'min North Road, Shanghai 201620, China; Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China.
J Colloid Interface Sci. 2025 Jan 15;678(Pt A):757-766. doi: 10.1016/j.jcis.2024.08.220. Epub 2024 Aug 28.
The electrochemical reduction of CO (ERCO) has emerged as one of the most promising methods for achieving both renewable energy storage and CO recovery. However, achieving both high selectivity and stability of catalysts remains a significant challenge. To address this challenge, this study investigated the selective synthesis of formate via ERCO at the interface of InO and BiO in the InBiO composite material. Moreover, InBiO was synthesized using indium-based metal-organic frameworks as precursor, which underwent continuous processing through ion exchange and thermal reduction. The results revealed that the formate Faradaic efficiency (FE) of InBiO reached nearly 100 % at -0.86 V vs. reversible hydrogen electrode (RHE) and remained above 90 % after continuous 317-h electrolysis, which exceeded those of previously reported indium-based catalysts. Additionally, the InBiO composite material exhibited an FE exceeding 80 % across a wide potential range of 500 mV from -0.76 to -1.26 V vs. RHE. Density-functional theory analysis confirmed that the heterogeneous interface of InBiO played a role in achieving optimal free energies for *OCHO on its surface. Furthermore, the addition of Bi to the InBiO matrix facilitated electron transfer and altered the electronic structure of InO, thereby enhancing the adsorption, decomposition, and formate production of *OCHO.
电化学还原CO（ERCO）已成为实现可再生能源存储和CO回收最有前景的方法之一。然而，实现催化剂的高选择性和稳定性仍然是一个重大挑战。为应对这一挑战，本研究考察了在InBiO复合材料中InO和BiO界面处通过ERCO选择性合成甲酸盐的情况。此外，以铟基金属有机框架为前驱体合成了InBiO，并通过离子交换和热还原对其进行连续处理。结果表明，InBiO在相对于可逆氢电极（RHE）为-0.86 V时甲酸盐法拉第效率（FE）接近100%，在连续电解317小时后仍保持在90%以上，超过了先前报道的铟基催化剂。此外，InBiO复合材料在相对于RHE为-0.76至-1.26 V的500 mV宽电位范围内FE超过80%。密度泛函理论分析证实，InBiO的异质界面在实现其表面OCHO的最佳自由能方面发挥了作用。此外，向InBiO基体中添加Bi促进了电子转移并改变了InO的电子结构，从而增强了OCHO的吸附、分解和甲酸盐生成。
