Guo Weiwei, Tan Xingxing, Bi Jiahui, Xu Liang, Yang Dexin, Chen Chunjun, Zhu Qinggong, Ma Jun, Tayal Akhil, Ma Jingyuan, Huang Yuying, Sun Xiaofu, Liu Shoujie, Han Buxing
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
J Am Chem Soc. 2021 May 12;143(18):6877-6885. doi: 10.1021/jacs.1c00151. Epub 2021 Apr 15.
Electrochemical reduction of CO to chemicals and fuels is an interesting and attractive way to mitigate greenhouse gas emissions and energy shortages. In this work, we report the use of atomic In catalysts for CO electroreduction to CO. The atomic In catalysts were anchored on N-doped carbon (In/NC) through pyrolysis of In-based metal-organic frameworks (MOFs) and dicyandiamide. It was discovered that In/NC had outstanding performance for selective CO production in the mixed electrolyte of ionic liquid/MeCN. It is different from those common In-based materials, in which formate/formic acid is formed as the main product. The faradaic efficiency (FE) of CO and total current density were 97.2% and 39.4 mA cm, respectively, with a turnover frequency (TOF) of ∼40 000 h. It is one of the highest TOF for CO production to date for all of the catalysts reported. In addition, the catalyst had remarkable stability. Detailed study indicated that In/NC had higher double-layer capacitance, larger CO adsorption capacity, and lower interfacial charge transfer resistance, leading to high activity for CO reduction. Control experiments and theoretical calculations showed that the In-N site of In/NC is not only beneficial for dissociation of COOH* to form CO but also hinders formate formation, leading to high selectivity toward CO instead of formate.
将二氧化碳电化学还原为化学品和燃料是一种减轻温室气体排放和能源短缺的有趣且有吸引力的方法。在这项工作中，我们报道了使用原子铟催化剂将二氧化碳电还原为一氧化碳。通过基于铟的金属有机框架（MOF）和双氰胺的热解，将原子铟催化剂锚定在氮掺杂碳（In/NC）上。研究发现，In/NC在离子液体/乙腈混合电解质中对选择性生成一氧化碳具有出色的性能。它不同于那些以甲酸盐/甲酸作为主要产物的常见铟基材料。一氧化碳的法拉第效率（FE）和总电流密度分别为97.2%和39.4 mA/cm²，周转频率（TOF）约为40000 h⁻¹。这是迄今为止所有报道的催化剂中用于一氧化碳生成的最高TOF之一。此外，该催化剂具有显著的稳定性。详细研究表明，In/NC具有更高的双层电容、更大的一氧化碳吸附容量和更低的界面电荷转移电阻，从而导致一氧化碳还原的高活性。对照实验和理论计算表明，In/NC的In-N位点不仅有利于COOH*解离形成CO，而且阻碍甲酸盐的形成，从而导致对CO而非甲酸盐的高选择性。
