Oxygen-Resistant CO2 Reduction Enabled by Electrolysis of Liquid Feedstocks.

Abstract

Electrolytic CO2 reduction fails in the presence of O2. This failure occurs because the reduction of O2 is thermodynamically favored over the reduction of CO2. Consequently, O2 must be removed from the CO2 feed prior to entering an electrolyzer, which is expensive. Here, we show that the use of liquid bicarbonate feedstocks (e.g., aqueous 3.0 M KHCO3), rather than gaseous CO2 feedstocks, enables efficient and selective CO2 reduction without additional procedures for removing O2. This effect is made possible because liquid bicarbonate solutions, which serve as a liquid CO2 carrier, deliver high concentrations of captured CO2 to the cathode, while the low solubility of O2 in aqueous media maintains a low O2 concentration at the same cathode surface. Consequently, electrolyzers fed with liquid bicarbonate feedstocks create an environment at the cathode that favors the reduction of CO2 over O2. We validate this claim by electrochemically converting CO2 into CO with reaction selectivities of 65% at 100 mA cm-2 using a 3.0 M KHCO3 solution bubbled with 100% CO2 or 100% O2. Similar experiments performed with a gaseous CO2 feedstock showed that merely 0.5% of O2 in the feedstock reduced CO selectivity by >90% after 1 h of electrolysis. Our findings demonstrate that a liquid bicarbonate feedstock enables efficient CO2 reduction without the need for expensive O2 removal steps.