Department of Mechanical and Industrial Engineering, University of Toronto, 5 King's College Road, Toronto, ON, M5S 3G8, Canada.
Department of Electrical and Computer Engineering, University of Toronto, 10 King's College Road, Toronto, ON, M5S 3G4, Canada.
Nat Commun. 2018 Nov 5;9(1):4614. doi: 10.1038/s41467-018-07032-0.
The electrochemical reduction of carbon monoxide is a promising approach for the renewable production of carbon-based fuels and chemicals. Copper shows activity toward multi-carbon products from CO reduction, with reaction selectivity favoring two-carbon products; however, efficient conversion of CO to higher carbon products such as n-propanol, a liquid fuel, has yet to be achieved. We hypothesize that copper adparticles, possessing a high density of under-coordinated atoms, could serve as preferential sites for n-propanol formation. Density functional theory calculations suggest that copper adparticles increase CO binding energy and stabilize two-carbon intermediates, facilitating coupling between adsorbed *CO and two-carbon intermediates to form three-carbon products. We form adparticle-covered catalysts in-situ by mediating catalyst growth with strong CO chemisorption. The new catalysts exhibit an n-propanol Faradaic efficiency of 23% from CO reduction at an n-propanol partial current density of 11 mA cm.
一氧化碳的电化学还原是一种很有前途的可再生方法，可以用于生产碳基燃料和化学品。铜对多碳产物的 CO 还原具有活性，反应选择性有利于二碳产物；然而，要将 CO 高效转化为更高碳的产物，例如液体燃料正丙醇，还有待实现。我们假设铜 adatoms（原子簇）具有高密度的欠配位原子，可以作为正丙醇形成的优先位点。密度泛函理论计算表明，铜 adatoms 增加了 CO 的结合能并稳定了二碳中间体，促进了吸附的*CO 和二碳中间体之间的耦合，形成三碳产物。我们通过用强 CO 化学吸附来介导催化剂生长，原位形成 adatoms 覆盖的催化剂。新催化剂在 CO 还原时，在 11 mA cm 的正丙醇分电流密度下，正丙醇的法拉第效率达到 23%。
