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The conversion of waste CO2 to value‐added chemicals through electrochemical reduction is a promising technology for mitigating climate change while simultaneously providing economic opportunities. The use of non‐aqueous solvents like methanol allows for higher CO2 availability and novel products. In this work, the electrochemistry of CO2 reduction in acidic methanol catholyte at a Pb working electrode was investigated while using a separate aqueous anolyte to promote a sustainable water oxidation half‐reaction. The selectivity among methyl formate (a product unique to reduction of CO2 in methanol), formic acid, and formate was critically dependent on the catholyte pH, with higher pH conditions leading to formate and low pH favoring methyl formate. The potential dependence of the product distribution in acidic catholyte was also investigated, with a faradaic efficiency for methyl formate as high as 75 % measured at −2.0 V vs. Ag/AgCl.
A question of pH: An electrolytic cell with acidic methanol catholyte and an aqueous anolyte separated by a proton exchange membrane is utilized to produce a methanol unique C2 product, methyl formate, from CO2 on a Pb electrode. High selectivity (≈75 % faradaic efficiency) for methyl formate is attainable as long as the catholyte pH remains low.