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Thermochemical aerobic oxidation catalysis in water can be analysed as two coupled electrochemical half-reactions
Nature Catalysis ( IF 37.8 ) Pub Date : 2021-09-06 , DOI: 10.1038/s41929-021-00666-2
Jaeyune Ryu 1 , Daniel T. Bregante 1 , William C. Howland 1 , Ryan P. Bisbey 1 , Corey J. Kaminsky 1 , Yogesh Surendranath 1
Affiliation  

Heterogeneous aqueous-phase aerobic oxidations are important catalytic transformations; however, their mechanisms and the role of O2 remain unclear. Here we show that thermochemical aerobic oxidations of organic small molecules can be analysed as two coupled electrochemical half-reactions for O2 reduction and substrate oxidation. We find that the polarization curves of the two half-reactions closely predict the mixed potential of the catalyst measured during thermochemical catalysis across diverse reaction conditions, catalysts and reactant identity. Additionally, we find that driving the substrate oxidation electrochemically without O2 at the mixed potential leads to similar rates and selectivities as for the corresponding thermochemical reactions. These findings indicate that O2 acts as an electron scavenger to supply the electrochemical driving force for substrate oxidation. These studies provide a quantitative and predictive link between thermochemical and electrochemical catalysis, thereby enabling the design of new aerobic oxidation schemes by applying the principles of electrochemistry.



中文翻译:

水中的热化学有氧氧化催化可以分析为两个耦合的电化学半反应

多相水相好氧氧化是重要的催化转化。然而,它们的机制和O 2的作用仍不清楚。在这里,我们表明有机小分子的热化学需氧氧化可以分析为 O 2还原和底物氧化的两个耦合电化学半反应。我们发现,这两个半反应的极化曲线密切预测了在不同反应条件、催化剂和反应物同一性的热化学催化过程中测量的催化剂的混合电位。此外,我们发现在没有 O 2的情况下以电化学方式驱动底物氧化在混合电位下会导致与相应的热化学反应相似的速率和选择性。这些发现表明O 2作为电子清除剂为底物氧化提供电化学驱动力。这些研究提供了热化学和电化学催化之间的定量和预测联系,从而能够通过应用电化学原理设计新的好氧氧化方案。

更新日期:2021-09-06
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