Abstract

The current mechanism for the CO2 reduction reaction (CO2RR) via electrified plasma/liquid interface (electrochemical discharge) does not explain the favorable formic acid synthesis in aqueous acid media, bringing imprecision on the theoretical predictions of CO2RR selectivity in acid electrolytes. For this reason, this work proposes three CO2RR mechanisms toward formic acid, one of them being a long-stand established in the radiolysis field and passes to analyze the cases employing numerical simulation of their respective chemical dynamic models. With it, it is possible to identify two routes substantially contributing to the global formic acid production, namely the disproportionation-like and radical cross-combination reactions related to the last step. Despite studied here as two separate mechanisms, these two routes combined serve to propose an assertive mechanism of CO2RR in acid media.

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