Xue Huan, Zhao Zhen-Hua, Liao Pei-Qin, Chen Xiao-Ming
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, People's Republic of China.
Chemistry and Chemical Engineering Guangdong Laboratory, Shantou 515031, People's Republic of China.
J Am Chem Soc. 2023 Aug 9;145(31):16978-16982. doi: 10.1021/jacs.3c05023. Epub 2023 Aug 1.
The electrochemical CO reduction reaction (eCORR) under acidic conditions has become a promising way to achieve high CO utilization because of the inhibition of undesirable carbonate formation that typically occurs under neutral and alkaline conditions. Herein, unprecedented and highly active ditin(IV) sites were integrated into the nanopores of a metal-organic framework, namely , by a "ship-in-a-bottle" strategy. delivers nearly 100% formic acid Faradaic efficiency at an industry current density of 260 mA cm with a high single-pass CO utilization of 95% in an acidic solution (pH = 1.67). No obvious degradation was observed over 15 hours of continuous operation at the current density of 260 mA cm, representing the remarkable eCORR performance in acidic electrolyte to date. The mechanism study shows that both oxygen atoms of the key intermediate *HCOO can coordinate to the two adjacent Sn atoms in a ditin(IV) site simultaneously. Such bridging coordination is conducive to the hydrogenation of CO, thus leading to high performance.
在酸性条件下的电化学CO还原反应（eCORR）已成为实现高CO利用率的一种有前景的方法，因为它抑制了通常在中性和碱性条件下发生的不希望的碳酸盐形成。在此，通过“瓶中造船”策略，将前所未有的高活性二锡（IV）位点整合到金属有机框架的纳米孔中。在工业电流密度为260 mA cm时，在酸性溶液（pH = 1.67）中具有近100%的甲酸法拉第效率，单次通过CO利用率高达95%。在260 mA cm的电流密度下连续运行15小时未观察到明显降解，这代表了迄今为止在酸性电解质中卓越的eCORR性能。机理研究表明，关键中间体*HCOO的两个氧原子可以同时与二锡（IV）位点中的两个相邻Sn原子配位。这种桥连配位有利于CO的氢化，从而导致高性能。
