Reid Amelia G, Machan Charles W
Department of Chemistry, University of Virginia, P.O. Box 400319, Charlottesville, Virginia 22904-4319, United States.
J Am Chem Soc. 2023 Feb 1;145(4):2013-2027. doi: 10.1021/jacs.2c10033. Epub 2023 Jan 18.
Homogeneous electrocatalysis has been well studied over the past several decades for the conversion of small molecules to useful products for green energy applications or as chemical feedstocks. However, in order for these catalyst systems to be used in industrial applications, their activity and stability must be improved. In naturally occurring enzymes, redox equivalents (electrons, often in a concerted manner with protons) are delivered to enzyme active sites by small molecules known as redox mediators (RMs). Inspired by this, co-electrocatalytic systems with homogeneous catalysts and RMs have been developed for the conversion of alcohols, nitrogen, unsaturated organic substrates, oxygen, and carbon dioxide. In these systems, the RMs have been shown to both increase the activity of the catalyst and shift selectivity to more desired products by altering catalytic cycles and/or avoiding high-energy intermediates. However, the area is currently underdeveloped and requires additional fundamental advancements in order to become a more general strategy. Here, we summarize the recent examples of homogeneous co-electrocatalysis and discuss possible future directions for the field.
在过去几十年里，均相电催化已得到充分研究，用于将小分子转化为绿色能源应用的有用产品或作为化学原料。然而，为了使这些催化剂体系能够用于工业应用，必须提高它们的活性和稳定性。在天然存在的酶中，氧化还原当量（电子，通常与质子协同作用）通过称为氧化还原介质（RMs）的小分子传递到酶活性位点。受此启发，已开发出具有均相催化剂和RMs的共电催化体系，用于醇、氮、不饱和有机底物、氧和二氧化碳的转化。在这些体系中，RMs已被证明既能提高催化剂的活性，又能通过改变催化循环和/或避免高能中间体，将选择性转向更理想的产物。然而，该领域目前尚不完善，需要更多的基础进展才能成为一种更通用的策略。在此，我们总结了均相共电催化的最新实例，并讨论了该领域未来可能的发展方向。
