The ability to maintain high efficiencies while simultaneously tuning the selectivity of the electrochemical reduction of CO₂ (ERC) using low cost electrodes has proven to be one of the greatest obstacles to the widespread commercialization of this technology. In this study, we prepare dendritic copper-indium and copper-bismuth alloys of various compositions and investigate their catalytic activity and selectivity towards the reduction of CO₂. The Cu-In electrocatalysts are increasingly dendritic with higher In fraction and, depending on composition, consist of mixed phases of Cu, In and Cu-In intermetallic phases. ERC at these electrodes produces formate at high efficiencies (up to 62% with a 80 at% alloy, -1 V)) while also tuning the CO/H₂ ratio to achieve an ideal syngas composition with a 40 at% In alloy, -1 V. The observed product distribution as a function of alloy composition and applied potential is rationalized in terms of the relative adsorption strengths of CO and COOH intermediates at Cu and In sites, and their distinct variation with applied potential may be induced by the differences in electronic structure.

We also studied dendritic Cu, Bi, and Cu-Bi alloys with various compositions. The dendritic structures exhibit a high density of defect sites such as grain boundaries and twins, with these defects being increased at alloy dendrites. While the pure metals exhibited high H₂ production and relatively high formate formation, the alloys exhibit a lower overall current density and a much higher selectivity towards formate, up to about 90%. Most importantly we show in this work that a combination of a d metal (Cu) with a p-block metal (In, Bi) with intimate contact between the two components is capable to tune the relative adsorption strength of the intermediates, thus steering the product distribution towards formate. The relatively purity of this product would be of interest for the direct feed of a direct formate fuel cell. Differences between In and Bi will be discussed in terms of the affinity for oxygen.

This study highlights the opportunities of using alloys to enhance control over the product distribution and suggests that suitable alloys could be promising catalysts for the inexpensive and efficient production of fuels.