The Formation of CO by Thermal Decomposition of Formic Acid under Electrochemical Conditions of CO2 Reduction

•We report that the thermal decomposition of formic acid to CO may occur under electrochemically-relevant conditions.•IR visual thermometry provides evidence of heating effects during electrolytic experiments.•Electrolytic experiments may experience product distribution artifacts caused by resistive, local heating and illumination.

We report that the thermal decomposition of formic acid to CO may occur under electrochemically-relevant conditions by mild heating. These thermal effects may play a role in the outcome of electrolytic experiments as an artifact of resistive, local heating and illumination. This non-Faradaic reactivity pathway may therefore need consideration in the analysis of electrochemical data on CO2 reduction to formic acid and CO and may become a hindrance in scaleup efforts of these chemical transformations. IR visual thermometry provides evidence of macroscopic heating effects during electrolytic experiments.

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