Prolonged Stability of Pb-Catalyzed CO2 Electroreduction to Methyl Formate in Acidic Methanol

Hofsommer, Dillon T.; Gautam, Manu; Uttarwar, Sandesh S.; Grapperhaus, Craig A.; Spurgeon, Joshua M.

doi:10.1021/acsaem.3c00166

Prolonged Stability of Pb-Catalyzed CO₂ Electroreduction to Methyl Formate in Acidic Methanol

Journal Article · Wed Feb 15 00:00:00 EST 2023 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.3c00166· OSTI ID:1970182

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Univ. of Louisville, KY (United States); University of Louisville
Univ. of Louisville, KY (United States)

Electrochemical CO₂ reduction from renewable energy is a promising route to mitigate greenhouse gas emissions from waste sources while generating value-added products. CO₂ electroreduction in methanol is particularly interesting due to the increased CO₂ solubility compared to water and the propensity to form methyl formate, a product absent in aqueous electrolysis. Here, four factors have been identified as critical to achieving prolonged high selectivity for methyl formate production on a Pb cathode in methanol: high pH near the electrode, low bulk pH, low water content, and regeneration of Pb²⁺ sites. Increasing concentration of the formic acid product was observed to induce a selectivity shift towards hydrogen, which was mitigated by the in-situ conversion of the formic acid to methyl formate via an esterification reaction. Furthermore, co-electrolysis of CO₂ with dilute molecular oxygen (4% O₂) led to Pb catalyst repair through in-situ surface oxidation. Using CO₂ and dilute O₂ along with single-pass catholyte flow to maintain a low formic acid concentration, sustained high selectivity for methyl formate was attained at ~60% faradaic efficiency at -20 mA cm^-2 for over 72 hours.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Louisville, KY (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FE0031916

OSTI ID:: 1970182

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 4 Vol. 6; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 reduction
catalyst repair
catalyst stability
electroreduction
heterogeneous catalysis
methyl formate
nonaqueous acidity