To explore the effects of solvent-ionomer interactions in catalyst inks on the structure and performance of Cu catalyst layers (CLs) for CO₂ electrolysis, we used a “like for like” rationale to select acetone and methanol as dispersion solvents with a distinct affinity for the ionomer backbone or sulfonated ionic heads, respectively, of the perfluorinated sulfonic acid (PFSA) ionomer Aquivion. First, we characterized the morphology and wettability of Aquivion films drop-cast from acetone- and methanol-based inks on flat Cu foils and glassy carbons. On a flat surface, the ionomer films cast from the Aquivion and acetone mixture were more continuous and hydrophobic than films cast from methanol-based inks. Our study’s second stage compared the performance of Cu nanoparticle CLs prepared with acetone and methanol on gas diffusion electrodes (GDEs) in a flow cell electrolyzer. The effects of the ionomer-solvent interaction led to a more uniform and flooding-tolerant GDE when acetone was the dispersion solvent (acetone-CL) than when we used methanol (methanol-CL). As a result, acetone-CL yielded a higher selectivity for CO₂ electrolysis to C₂₊ products at high current density, up to 25% greater than methanol-CL at 500 mA cm^-2. Ethylene was the primary product for both CLs, with a Faradaic efficiency for ethylene of 47.4 ± 4.0% on the acetone-CL and that of 37.6 ± 5.5% on the methanol-CL at a current density of 300 mA cm^-2. We attribute the enhanced C₂₊ selectivity of the acetone-CL to this electrode’s better resistance to electrolyte flooding, with zero seepage observed at tested current densities. Our findings reveal the critical role of solvent-ionomer interaction in determining the film structure and hydrophobicity, providing new insights into the CL design for enhanced multicarbon production in high current densities in CO₂ electrolysis processes.

Electrochemical reduction of CO₂ presents an attractive way to store renewable energy in chemical bonds in a potentially carbon-neutral way. However, the available electrolyzers suffer from intrinsic problems, like flooding and salt accumulation, that must be overcome to industrialize the technology. To mitigate flooding and salt precipitation issues, researchers have used super-hydrophobic electrodes based on either expanded polytetrafluoroethylene (ePTFE) gas-diffusion layers (GDL’s), or carbon-based GDL’s with added PTFE. While the PTFE backbone is highly resistant to flooding, the non-conductive nature of PTFE means that without additional current collection the catalyst layer itself is responsible for electron-dispersion, which penalizes system efficiency and stability. In this work, we present operando results that illustrate that the current distribution and electrical potential distribution is far from a uniform distribution in thin catalyst layers (~50 nm) deposited onto ePTFE GDL’s. We then compare the effects of thicker catalyst layers (~500 nm) and a newly developed non-invasive current collector (NICC). The NICC can maintain more uniform current distributions with 10-fold thinner catalyst layers while improving stability towards ethylene (≥ 30%) by approximately two-fold.

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.

Achieving operational stability at high current densities remains a challenge in CO2 electrolyzers due to flooding of the gas diffusion layer (GDL) that supports the electrocatalyst. We mitigated electrode flooding at high current densities using a vacuum-assisted infiltration method to embed 200-400 nm-sized polytetrafluoroethylene (PTFE) particles at the interface of the microporous layer (MPL) and carbon cloth in a commercial GDL. In CO2 electrolysis to CO over a silver nanoparticle catalyst on the GDL, the PTFE-embedded GDL not only just exhibited less than 10% of the electrolyte seepage rates observed in untreated GDLs at a current density of 300 mA·cm-2 but also expanded the electrochemical active area across the testing conditions. The PTFE-embedded GDL also maintained a Faradaic efficiency for CO2 electrolysis to CO above 80% for more than 100 h at 100 mA·cm-2, which was a 50-fold improvement in the stable operation time of the electrolyzer.

Regulating the rational wettability on gas-diffusion electrodes (GDEs) plays a pivotal role to improve the efficiency of CO₂RR via fine-tuning the reaction zone and boosting the formation of triple-phase interfaces. Herein, we present a wettability regulation strategy that modulates the triple-phase reaction zone in the catalyst layer of GDEs. This strategy was employed on a flow-through hollow fiber GDE coated with a Bi-embedded catalyst layer. Compared to other ex-situ methods (e.g., adding wetting agents) affecting the bulk of electrocatalysts or catalyst layer, we create distinctive hydrophilic-hydrophobic regions within the catalyst layer. Catalyst layer with hydrophilic-hydrophobic regions outperforms the fully hydrophilic one by facilitating the species transport, boosting triple-phase interface formation, and maximizing the active sites. This regulation strategy showed stable wettability during CO₂RR cathodic conditions, evidenced by the direct measurement of penetration depth. The electrode with the regulated wettability exhibited over 80% catalyst utilization and 4 times higher formate partial current density (~150 mA cm⁻² with FE_formate> 90%) compared to the untreated electrode, outperforming other GDEs employed for CO₂RR to formate in the same concentrations of bicarbonate. The finding of this versatile microenvironment regulation strategy can be extended to GDEs used for other gas-phase reactions.

Understanding the relationship between gas diffusion electrode (GDE) structures and the performance of electrochemical CO₂ reduction reaction (CO₂RR) is crucial to developing industrial-scale technologies to convert CO₂ to valuable products. We studied how the microporous layer (MPL) on GDE's coated with silver nanoparticle catalysts affects the electrochemical CO₂ conversion to CO in a flow cell electrolyser. We demonstrate a convenient method to measure the rate of catholyte seepage through a GDE during CO₂RR experiments and used this method to show how the MPL thickness affects flooding of the GDE. We found the GDE with the thickest MPL (39BB) had the best selectivity for CO and stability at current densities above 100 mA cm⁻² as the thick MPL minimized flooding. However, at low current densities the 39BB electrode achieved a lower CO selectivity than the GDE with thinner MPL. These results suggest opportunities to improve CO₂ electrolyser performances at high current by optimisation of the MPL structure and wettability.

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.