多电子、多底物分子催化电化学反应：总催化态下的形式动力学分析。
Multielectron, multisubstrate molecular catalysis of electrochemical reactions: Formal kinetic analysis in the total catalysis regime.
机构信息
Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche Université-CNRS No.7591, Université Paris Diderot, Sorbonne Paris Cité, 75205 Paris Cedex 13, France;
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138
出版信息
Proc Natl Acad Sci U S A. 2017 Oct 24;114(43):11303-11308. doi: 10.1073/pnas.1711129114. Epub 2017 Oct 9.
Abstract
Cyclic voltammetry responses are derived for two-electron, two-step homogeneous electrocatalytic reactions in the total catalysis regime. The models developed provide a framework for extracting kinetic information from cyclic voltammograms (CVs) obtained in conditions under which the substrate or cosubstrate is consumed in a multielectron redox process, as is particularly prevalent for very active catalysts that promote energy conversion reactions. Such determination of rate constants in the total catalysis regime is a prerequisite for the rational benchmarking of molecular electrocatalysts that promote multielectron conversions of small-molecule reactants. The present analysis is illustrated with experimental systems encompassing various limiting behaviors.
摘要
针对总催化状态下的两电子、两步均相电催化反应，推导出了循环伏安响应。所开发的模型为从循环伏安图（CV）中提取动力学信息提供了一个框架，这些 CV 是在底物或共底物在多电子氧化还原过程中消耗的条件下获得的，这种情况在促进能量转换反应的非常活跃的催化剂中尤为普遍。在总催化状态下确定速率常数是合理基准化促进小分子反应物多电子转化的分子电催化剂的前提条件。本分析通过包含各种极限行为的实验系统进行说明。
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