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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