Wang Min, Torbensen Kristian, Salvatore Danielle, Ren Shaoxuan, Joulié Dorian, Dumoulin Fabienne, Mendoza Daniela, Lassalle-Kaiser Benedikt, Işci Umit, Berlinguette Curtis P, Robert Marc
Université de Paris, Laboratoire d'Electrochimie Moléculaire, CNRS, F-75013, Paris, France.
Department of Chemical and Biological Engineering, The University of British Columbia, 2360 East Mall, Vancouver, BC, V6Y 1Z3, Canada.
Nat Commun. 2019 Aug 9;10(1):3602. doi: 10.1038/s41467-019-11542-w.
Molecular catalysts that combine high product selectivity and high current density for CO electrochemical reduction to CO or other chemical feedstocks are urgently needed. While earth-abundant metal-based molecular electrocatalysts with high selectivity for CO to CO conversion are known, they are characterized by current densities that are significantly lower than those obtained with solid-state metal materials. Here, we report that a cobalt phthalocyanine bearing a trimethyl ammonium group appended to the phthalocyanine macrocycle is capable of reducing CO to CO in water with high activity over a broad pH range from 4 to 14. In a flow cell configuration operating in basic conditions, CO production occurs with excellent selectivity (ca. 95%), and good stability with a maximum partial current density of 165 mA cm (at -0.92 V vs. RHE), matching the most active noble metal-based nanocatalysts. These results represent state-of-the-art performance for electrolytic carbon dioxide reduction by a molecular catalyst.
迫切需要能够将一氧化碳电化学还原为一氧化碳或其他化学原料并兼具高产物选择性和高电流密度的分子催化剂。虽然已知对一氧化碳转化为一氧化碳具有高选择性的富含地球元素的金属基分子电催化剂，但其特征在于电流密度明显低于固态金属材料所获得的电流密度。在此，我们报告一种在酞菁大环上带有三甲基铵基团的钴酞菁能够在pH值从4到14的宽范围内，在水中将一氧化碳高效还原为一氧化碳。在碱性条件下运行的流动电解槽配置中，一氧化碳的产生具有优异的选择性（约95%），并且具有良好的稳定性，最大分电流密度为165 mA cm²（相对于可逆氢电极在-0.92 V时），与最具活性的贵金属基纳米催化剂相当。这些结果代表了分子催化剂在电解二氧化碳还原方面的最先进性能。
