Electrochemical CO2 reduction is a promising process to store intermittent renewable energy in the form of chemical bonds and to meet the demand for hydrocarbon chemicals without relying on fossil fuels. Researchers in the field have used gas diffusion electrodes (GDEs) to supply CO2 to the catalyst layer from the gas phase. This approach allows us to bypass mass transfer limitations imposed by the limited solubility and diffusion of CO2 in the liquid phase at a laboratory scale. However, at a larger scale, pressure differences across the porous gas diffusion layer can occur. This can lead to flooding and electrolyte breakthrough, which can decrease performance. The aim of this study is to understand the effects of the GDE structure on flooding behavior and CO2 reduction performance. We approach the problem by preparing GDEs from commercial substrates with a range of structural parameters (carbon fiber structure, thickness, and cracks). We then determined the liquid breakthrough pressure and measured the Faradaic efficiency for CO at an industrially relevant current density. We found that there is a trade-off between flooding resistance and mass transfer capabilities that limits the maximum GDE height of a flow-by electrolyzer. This trade-off depends strongly on the thickness and the structure of the carbon fiber substrate. We propose a design strategy for a hierarchically structured GDE, which might offer a pathway to an industrial scale by avoiding the trade-off between flooding resistance and CO2 reduction performance.

Electrochemical CO2 reduction has the potential to use excess renewable electricity to produce hydrocarbon chemicals and fuels. Gas diffusion electrodes (GDEs) allow overcoming the limitations of CO2 mass transfer but are sensitive to flooding from (hydrostatic) pressure differences, which inhibits upscaling. We investigate the effect of the flooding behavior on the CO2 reduction performance. Our study includes six commercial gas diffusion layer materials with different microstructures (carbon cloth and carbon paper) and thicknesses coated with a Ag catalyst and exposed to differential pressures corresponding to different flow regimes (gas breakthrough, flow-by, and liquid breakthrough). We show that physical electrowetting further limits the flow-by regime at commercially relevant current densities (≥200 mA cm-2), which reduces the Faradaic efficiency for CO (FECO) for most carbon papers. However, the carbon cloth GDE maintains its high CO2 reduction performance despite being flooded with the electrolyte due to its bimodal pore structure. Exposed to pressure differences equivalent to 100 cm height, the carbon cloth is able to sustain an average FECO of 69% at 200 mA cm-2 even when the liquid continuously breaks through. CO2 electrolyzers with carbon cloth GDEs are therefore promising for scale-up because they enable high CO2 reduction efficiency while tolerating a broad range of flow regimes.

Electrochemical reduction of carbon dioxide (CO₂R) poses substantial promise to convert abundant feedstocks (water and CO₂) to value-added chemicals and fuels using solely renewable energy. However, recent membrane-electrode assembly (MEA) devices that have been demonstrated to achieve high rates of CO₂R are limited by water management within the cell, due to both consumption of water by the CO₂R reaction and electro-osmotic fluxes that transport water from the cathode to the anode. Additionally, crossover of potassium (K⁺) ions poses concern at high current densities where saturation and precipitation of the salt ions can degrade cell performance. Herein, a device architecture incorporating an anion-exchange membrane (AEM) with internal water channels to mitigate MEA dehydration is proposed and demonstrated. A macroscale, two-dimensional continuum model is used to assess water fluxes and local water content within the modified MEA, as well as to determine the optimal channel geometry and composition. The modified AEMs are then fabricated and tested experimentally, demonstrating that the internal channels can both reduce K⁺ cation crossover as well as improve AEM conductivity and therefore overall cell performance. This work demonstrates the promise of these materials, and operando water-management strategies in general, in handling some of the major hurdles in the development of MEA devices for CO₂R.

Automation and microfluidic tools potentially enable efficient, fast, and focused reaction development of complex chemistries, while minimizing resource- and material consumption. The introduction of automation-assisted workflows will contribute to the more sustainable development and scale-up of new and improved catalytic technologies. Herein, the application of automation and microfluidics to the development of a complex asymmetric hydrogenation reaction is described. Screening and optimization experiments were performed using an automated microfluidic platform, which enabled a drastic reduction in the material consumption compared to conventional laboratory practices. A suitable catalytic system was identified from a library of Ru^II-diamino precatalysts. In situ precatalyst activation was studied with ¹H/³¹P nuclear magnetic resonance (NMR), and the reaction was scaled up to multigram quantities in a batch autoclave. These reactions were monitored using an automated liquid-phase sampling system. Ultimately, in less than a week of total experimental time, multigram quantities of the target enantiopure alcohol product were provided by this automation-assisted approach.