Peng Chen, Yang Songtao, Luo Gan, Yan Shuai, Shakouri Mohsen, Zhang Junbo, Chen Yangshen, Li Weihan, Wang Zhiqiang, Sham Tsun-Kong, Zheng Gengfeng
Laboratory of Advanced Materials, Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Faculty of Chemistry and Materials Science, Fudan University, Shanghai, 200438, P. R. China.
Henan Engineering Center of New Energy Battery Materials, Henan D&A Engineering Center of Advanced Battery Materials, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, 476000, P. R. China.
Adv Mater. 2022 Sep;34(39):e2204476. doi: 10.1002/adma.202204476. Epub 2022 Aug 25.
The high-rate electrochemical CO conversion to ethanol with high partial current density is attractive but challenging, which requires competing with other reduction products as well as hydrogen evolution. This work demonstrates the in situ reconstruction of KCuF perovskite under CO electroreduction conditions to fabricate a surface fluorine-bonded, single-potassium-atom-modified Cu(111) nanocrystal (K-F-Cu-CO ). Density functional theory calculations reveal that the co-modification of both F and K atoms on the Cu(111) surface can promote the ethanol pathway via stabilization of the CO bond and selective hydrogenation of the CC bond in the CH CHO* intermediate, while the single modification of either F or K is less effective. The K-F-Cu-CO electrocatalyst exhibits an outstanding CO -to-ethanol partial current density of 423 ± 30 mA cm with the corresponding Faradaic efficiency of 52.9 ± 3.7%, and a high electrochemical stability at large current densities, thus suggesting an attractive means of surface co-modification of halide anions and alkali-metal cations on Cu catalysts for high-rate CO -to-ethanol electrosynthesis.
将高比例电流密度的电化学CO转化为乙醇具有吸引力，但也具有挑战性，因为这需要与其他还原产物以及析氢反应竞争。这项工作展示了在CO电还原条件下KCuF钙钛矿的原位重构，以制备表面氟键合、单钾原子修饰的Cu(111)纳米晶体（K-F-Cu-CO）。密度泛函理论计算表明，Cu(111)表面的F和K原子共同修饰可以通过稳定CO键和选择性氢化CH CHO*中间体中的CC键来促进乙醇生成途径，而单独修饰F或K的效果较差。K-F-Cu-CO电催化剂表现出出色的CO到乙醇的部分电流密度为423±30 mA cm，相应的法拉第效率为52.9±3.7%，并且在大电流密度下具有高电化学稳定性，因此表明在Cu催化剂上对卤化物阴离子和碱金属阳离子进行表面共修饰是实现高速率CO到乙醇电合成的一种有吸引力的方法。
