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.
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We thank T. Wesley and Y. Román for helpful discussions. This work was supported primarily by the Air Force Office of Scientific Research (AFOSR) under award number FA9550-20-1-0291. The online mass spectrometry studies were supported by the Air Force Office of Scientific Research (AFOSR) under award number FA9550-18-1-0420. J.R. acknowledges support from a Samsung Scholarship. C.J.K is supported by the National Science Foundation Graduate Research Fellowship under grant number 1122374.
The authors declare no competing interests.
Peer review information Nature Catalysis thanks Jun Hui Park and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Ryu, J., Bregante, D.T., Howland, W.C. et al. Thermochemical aerobic oxidation catalysis in water can be analysed as two coupled electrochemical half-reactions. Nat Catal 4, 742–752 (2021). https://doi.org/10.1038/s41929-021-00666-2
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