Physico-chemical principles of AC electrosynthesis

06 February 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Electrolysis integrates renewable energy into chemical manufacturing and is key towards sustainable chemistry. Controlling the waveform beyond direct current addresses the long-standing obstacle of chemoselectivity, yet it also expands the parameter set to optimise, creating a demand for theoretical predictions. Here, we report the first analytical theory for predicting chemoselectivity in alternating current electrosynthesis. The mechanism is a selective reversal of the unwanted redox reaction during periods of opposite polarity. Notably, we find regimes within which a square waveform can not only bias but also reverse the chemoselectivity compared to direct current approaches, favouring overoxidation/overreduction. Sinusoidal waves exhibit the opposite effect. These trends are consistent with existing experimental works. Therefore, we find alternating current to be a promising avenue for achieving the ultimate control over reaction pathways.


AC electrosynthesis


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