Two‐Membrane Dual Non‐Aqueous/Aqueous Electrolyte Flow Cell Operation for Electrochemical Conversion of CO2 to Methyl Formate

Gautam, Manu; Nkurunziza, Francois; Mulvehill, Matthew C.; Uttarwar, Sandesh S.; Hofsommer, Dillon T.; Grapperhaus, Craig A.; Spurgeon, Joshua M.

doi:10.1002/cssc.202301337

Two‐Membrane Dual Non‐Aqueous/Aqueous Electrolyte Flow Cell Operation for Electrochemical Conversion of CO₂ to Methyl Formate (in EN)

Journal Article · Mon Nov 06 04:00:00 EST 2023 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.202301337· OSTI ID:2575879

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Univ. of Louisville, KY (United States)

Recently, tandem cathodic reactions have been demonstrated in non-aqueous solvents to couple CO₂ reduction to a secondary reaction to create novel species that are not produced in aqueous CO₂ electrolysis. One reaction that can be performed with high selectivity and durability is the electrochemical conversion of CO₂ to formic acid and in-situ esterification with methanol to produce methyl formate. However, the translation to a high-performance flow electrolyzer is far from trivial, as the non-aqueous catholyte leads to reactor challenges including flooding the gas diffusion electrode. Here, in this study, a two-membrane flow electrolyzer with both anion and cation exchange membranes was used with flowing methanol catholyte and aqueous anolyte. This design prevented methanol from flooding the cathode, which was a pervasive limiting issue for electrolyzers with a single membrane. Methyl formate production at 42.9 % faradaic efficiency was achieved with pure methanol in a flow electrolyzer with stable performance beyond 80 min. However, low-water-content catholyte compositions also led to increased cell resistance and lower operating current densities. Thus, with the present ionomer materials there is a tradeoff between methyl formate selectivity and current density depending on water concentration, highlighting a need for new ionomers tailored for desirable non-aqueous solvents such as methanol.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Fossil Energy and Carbon Management (FECM)

Grant/Contract Number:: FE0031916

OSTI ID:: 2575879

Alternate ID(s):: OSTI ID: 2327070

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 6 Vol. 17; ISSN 1864-564X; ISSN 1864-5631

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: EN

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Two‐Membrane Dual Non‐Aqueous/Aqueous Electrolyte Flow Cell Operation for Electrochemical Conversion of CO₂ to Methyl Formate (in EN)