Acetic acid (CH₃COOH) is an important industrial chemical that is widely used in the generation of various products including medicals, food, solvent, synthetic fibers and fabrics. Although most acetic acid production today relies on the carbonylation process of methanol¹, electrochemical synthesis method is a promising direction owing to its uniqueness in ambient conditions, utilization of renewable energy, and compatibility with bioengineering². Cupper has the capability to electrochemically reduce CO₂ to various C₂ products but with low selectivity. The critical steps for acetate molecule generation from CO₂/CO are the CO-dimerization and the nucleophilic attack of hydroxide ion on a ketene intermediate³, in which acetate production could be enhanced by electroreducing CO in alkaline electrolyte as compared to CO₂ electroreduction in pH neutral solution. Meanwhile, the use of flow electrolyzer further improved the gas transport process by employing gas diffusion electrode, boosting the current and yield rate of products to industrial level. However, electrochemical reduction of CO to acetate on Cu-based electrocatalysts still suffers from low faradaic efficiency (<50%).⁴

In this talk, we will present our recent work on CO electroreduction to acetate by commercial Cu catalyst in flow electrolyzer. Parameters in terms of electrolyte molarity, catalyst loading, catalyst deposition method, and ionomer were manipulated to maximize the acetate production. Acetate was favored in high pH electrolyte by facilitating the nucleophilic attack of hydroxide ion process and suppressing competing proton transfer process towards ethylene and ethanol. Catalyst loading on gas diffusion electrode had great influence on the products selectivity, where low catalyst loading leans to ethylene generation, intermediate catalyst loading is selective to produce acetate, and high catalyst loading improves alcohol yield. A record 68% faradaic efficiency of acetate from CO with partial current density of 102 mA/cm² was reached.

Reference

1. A. Dimian and A. Kiss, Chem. Eng. Res. Des., 159 (2020).
2. S. Guo, T. Asset, and P. Atanassov, ACS Catal., 5172–5188 (2021) https://pubs.acs.org/doi/abs/10.1021/acscatal.0c04862.
3. M. Jouny et al., Nat. Chem., 11, 846–851 (2019) https://doi.org/10.1038/s41557-019-0312-z.
4. W. Luc et al., Nat. Catal., 2, 423–430 (2019) https://doi.org/10.1038/s41929-019-0269-8.