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Cu-based catalysts currently offer the most promising route to actively and selectively produce value-added chemicals via electrochemical reduction of CO2 (eCO2R); yet further improvements are required for their wide-scale deployment in carbon mitigation efforts. Here, we systematically investigate a family of dilute Cu-based alloys to explore their viability as active and selective catalysts for eCO2R through a combined theoretical–experimental approach. Using a quantum–classical modeling approach that accounts for dynamic solvation effects, we assess the stability and activity of model single-atom catalysts under eCO2R conditions. Our calculations identify that the presence of eCO2R intermediates, such as CO*, H*, and OH*, may dynamically influence the local catalyst surface composition. Additionally, we identify through binding energy descriptors of the CO*, CHO*, and OCCO* dimer intermediates that certain elements, such as group 13 elements (B, Al, and Ga), enhance the selectivity of C2+ species relative to pure Cu by facilitating CO dimerization. The theoretical work is corroborated by preliminary testing of eCO2R activity and selectivity of candidate dilute Cu-based alloy catalyst films prepared by electron beam evaporation in a zero-gap gas diffusion electrode-based reactor. Of all studied alloys, dilute CuAl was found to be the most active and selective toward C2+ products like ethylene, consistent with the theoretical predictions. We attribute the improved performance of dilute CuAl alloys to more favorable dimerization reaction energetics of bound CO species relative to that on pure Cu. In a broader context, the results presented here demonstrate the power of our simulation framework in terms of rational catalyst design. [ABSTRACT FROM AUTHOR]

We report on integrating ultrathin monolithic nanoporous gold (npAu) catalyst coatings for CO2 reduction in a large electrode area (25 cm2) electrochemical membrane reactor with gas diffusion electrodes at 100 mA/cm2. The CO Faraday efficiency increases with increasing thickness, from 65% to 75% and 80% for 1, 5, and 10 layers of npAu leaves where each npAu leaf layer is 100 nm thick. For the one npAu leaf layer configuration, this corresponds to an extremely high CO current density of 955 A/g gold thus demonstrating the potential for commercial applications. By device level optimization of catalyst integration we significantly improved the utilization of gold catalysts for electrochemical CO2 reduction to syngas at industrial relevant current densities of 100 mA/cm2. [ABSTRACT FROM AUTHOR]