We report a new strategy to improve the reactivity and durability of a membrane electrode assembly (MEA)-type electrolyzer for CO2 electrolysis to CO by modifying the silver catalyst layer with urea. Our experimental and theoretical results show that mixing urea with the silver catalyst can promote electrochemical CO2 reduction (CO2R), relieve limitations of alkali cation transport from the anolyte, and mitigate salt precipitation in the gas diffusion electrode in long-term stability tests. In a 10 mM KHCO3 anolyte, the urea-modified Ag catalyst achieved CO selectivity 1.3 times better with energy efficiency 2.8-fold better than an untreated Ag catalyst, and operated stably at 100 mA cm-2 with a faradaic efficiency for CO above 85% for 200 h. Our work provides an alternative approach to fabricating catalyst interfaces in MEAs by modifying the catalyst structure and the local reaction environment for critical electrochemical applications such as CO2 electrolysis and fuel cells.

The electrochemical reduction of carbon dioxide (CO₂RR) requires access to ample gaseous CO₂and liquid water to fuel reactions at high current densities for industrial-scale applications. Substantial improvement of the CO₂RR rate has largely arisen from positioning the catalyst close to gas-liquid interfaces, such as in gas-diffusion electrodes. These requirements add complexity to an electrode design that no longer consists of only a catalyst but also a microporous and nanoporous network of gas-liquid-solid interfaces of the electrode. In this three-dimensional structure, electrode wettability plays a pivotal role in the CO₂RR because the affinity of the electrode surface by water impacts the observed electrode reactivity, product selectivity, and long-term stability. All these performance metrics are critical in an industrial electrochemical process. This review provides an in-depth analysis of electrode wettability's role in achieving an efficient, selective, and stable CO₂RR performance. We first discuss the underlying mechanisms of electrode wetting phenomena and the foreseen ideal wetting conditions for the CO₂RR. Then we summarize recent advances in improving cathode performance by altering the wettability of the catalyst layer of gas-diffusion electrodes. We conclude the review by discussing the current challenges and opportunities to develop efficient and selective cathodes for CO₂RR at industrially relevant rates. The insights generated from this review could also benefit the advancement of other critical electrochemical processes that involve multiple complex flows in porous electrodes, such as electrochemical reduction of carbon monoxide, oxygen, and nitrogen.