Pressure dependence in aqueous-based electrochemical CO<sub>2</sub> reduction.

Huang, Liang; Gao, Ge; Yang, Chaobo; Li, Xiao-Yan; Miao, Rui Kai; Xue, Yanrong; Xie, Ke; Ou, Pengfei et al. · Nat Commun · 2023

basic_science · Level V

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Abstract

Electrochemical CO<sub>2</sub> reduction (CO<sub>2</sub>R) is an approach to closing the carbon cycle for chemical synthesis. To date, the field has focused on the electrolysis of ambient pressure CO<sub>2</sub>. However, industrial CO<sub>2</sub> is pressurized-in capture, transport and storage-and is often in dissolved form. Here, we find that pressurization to 50 bar steers CO<sub>2</sub>R pathways toward formate, something seen across widely-employed CO<sub>2</sub>R catalysts. By developing operando methods compatible with high pressures, including quantitative operando Raman spectroscopy, we link the high formate selectivity to increased CO<sub>2</sub> coverage on the cathode surface. The interplay of theory and experiments validates the mechanism, and guides us to functionalize the surface of a Cu cathode with a proton-resistant layer to further the pressure-mediated selectivity effect. This work illustrates the value of industrial CO<sub>2</sub> sources as the starting feedstock for sustainable chemical synthesis.