Voltage-Driven Molecular Catalysis: A Promising Approach to Electrosynthesis
Voltage-Driven Molecular Catalysis: A Promising Approach to Electrosynthesis
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DOI：
10.1021/acscatal.3c03644
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发表时间：
2023-11
期刊：
影响因子：
12.9
通讯作者：
Koushik Barman;Yu Chen;Shu Wu;Guoxiang Hu;M. Mirkin
中科院分区：
文献类型：
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作者：
Koushik Barman;Yu Chen;Shu Wu;Guoxiang Hu;M. Mirkin
电催化和分子催化的结合是设计用于电合成过程的催化剂的日益流行的方法。我们最近发现，在双电层的静电势下降有助于驱动力之间的电子转移溶解的反应物和直接固定在电极表面上的分子催化剂。所施加的电极电势可以增加表面结合的分子催化剂的氧化（或还原）能力，从而使其适合于通常不能催化的电荷转移过程。在这篇文章中，我们报道了电压驱动的分子催化在有机电合成中的初步应用。附着在碳电极上的不含金属的纯有机分子催化剂（克里思）对甲苯的氧化表现出依赖于电位的活性，而如果克里思用作均相催化剂，则不会发生这种情况。表面附着的克里思也显示出显着的催化活性，甚至在pH 7的苯甲醇氧化。通过核磁共振、傅立叶变换红外光谱和紫外-可见光谱对甲苯和苯甲醇氧化的产物进行了鉴定，以评价反应的产率和选择性。通过密度泛函理论计算阐明了电极电位对催化过程的影响。
The combination of electrocatalysis and molecular catalysis is an increasingly popular approach to designing catalysts for electrosynthetic processes. We recently found that the electrostatic potential drop across the double layer contributes to the driving force for electron transfer between a dissolved reactant and a molecular catalyst immobilized directly on the electrode surface. The applied electrode potential can increase the oxidizing (or reducing) ability of a surface-bound molecular catalyst, thus making it suitable for charge-transfer processes, which it normally would not be able to catalyze. In this article, we report the initial application of voltage-driven molecular catalysis to electroorganic synthesis. The metal-free, purely organic molecular catalyst (TEMPO) attached to a carbon electrode showed potential-dependent activity for the oxidation of toluene, which does not occur if TEMPO is used as a homogeneous catalyst. Surface-attached TEMPO also shows significant catalytic activity toward benzyl alcohol oxidation even at pH 7. The products of toluene and benzyl alcohol oxidations were identified by nuclear magnetic resonance, Fourier transform infrared, and ultraviolet–visible spectroscopy to evaluate the reaction yield and selectivity. The effect of the applied electrode potential on these catalytic processes was elucidated by density functional theory calculations.