Voltage-Driven Molecular Catalysis of Electrochemical Reactions
Voltage-Driven Molecular Catalysis of Electrochemical Reactions
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DOI：
10.1021/jacs.1c07934
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发表时间：
2021-10-13
影响因子：
15
通讯作者：
Mirkin, Michael, V
中科院分区：
文献类型：
--
作者：
Barman, Koushik;Wang, Xiang;Mirkin, Michael, V
多相电催化和分子氧化还原催化已经发展了几十年，作为促进能量转换和存储所必需的电荷转移过程的两种不同方法。电催化反应是由外加电压驱动的，而分子催化过程是由催化剂和反应物的标准电位差驱动的。在这里，我们证明了溶解反应物和直接固定在碳纳米电极表面的分子催化剂之间的电子转移速率是由化学驱动力和双层静电势降共同控制的。DFT计算表明，施加电压的变化改变了表面结合态和溶解态氧化还原态之间的电位降。这些结果为设计下一代杂化分子/电催化剂提供了一条新的途径。
Heterogeneous electrocatalysis and molecular redox catalysis have developed over several decades as two distinct ways to facilitate charge-transfer processes essential for energy conversion and storage. Whereas electrocatalytic reactions are driven by the applied voltage, molecular catalytic processes are driven by the difference between standard potentials of the catalyst and the reactant. Here, we demonstrate that the rate of electron transfer between a dissolved reactant and a molecular catalyst immobilized directly on the surface of a carbon nanoelectrode is governed by combination of chemical driving force and electrostatic potential drop across the double layer. DFT calculations show that varying the applied voltage alters the potential drop between the surfacebound and dissolved redox species. These results suggest a new route for designing next-generation hybrid molecular/electrocatalysts.