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Demonstrates that higher proton activity increases formic acid production in acidic media, suggesting a new strategy for carbon dioxide reduction.
The electrochemical carbon dioxide reduction reaction (CO 2 RR) in acidic electrolytes addresses the critical issue of carbonate formation but is intrinsically limited by the parasitic hydrogen evolution reaction (HER). While prevailing strategies aim at suppressing the HER by depleting interfacial proton concentration, this approach is detrimental for products whose formation kinetics are proton‐dependent. We demonstrate that for the electrosynthesis of formic acid (FA), the maintenance of high interfacial proton activity is not merely a challenge but a requirement for higher FA formation rates. We show that, rather than arising from suppression of the competing HER, FA synthesis is directly coupled to proton availability and is strongly enhanced at higher proton activities. Our findings establish that an efficient acidic CO 2 RR to FA requires a distinct design paradigm, which balances the kinetic competition between HER and CO 2 RR while ensuring sufficient proton flux to drive the kinetics of FA formation.
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Mairegger et al. (2026) studied this question.
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