Electroreduction of Captured CO2on Silver Catalysts: Influence of the Capture Agent and Proton Source

In the context of carbon reutilization, the direct electroreduction of captured CO2(c-CO2RR) appears as an appealing approach since it avoids the energetically costly separation of CO2from the capture agent. In this process, CO2is directly reduced from its captured form. Here, we investigate the influence of the capture agent and proton source on that reaction from a combination of theory and experiment. Specifically, we consider methoxide-captured CO2, NH3-captured CO2, and bicarbonate on silver electrocatalysts. We show that the proton source plays a key role in the interplay of the chemistries for the electroreduction of protons, free CO2, and captured CO2. Our density functional theory calculations, including the influence of the potential, demonstrate that a proton source with smaller pKaimproves the reactivity for c-CO2RR, but also increases the selectivity toward the hydrogen evolution reaction (HER) on silver surfaces. Since c-CO2RR requires an additional chemical protonation step, the influence of the proton source is stronger than that of the HER. However, c-CO2RR cannot compete with the HER on Ag, Experimentally, the dominant product observed is H2with low amounts of CO being produced. Through a rotating cylinder electrode cell of well-defined mass-transport properties, we conclude that although methanol solvent exhibits a lower HER activity, HER remains dominant over c-CO2RR. Our work suggests that methoxide is a potential alternative capture agent to NH3for direct reduction of captured CO2, though challenges in catalyst design, particularly in reducing the onset potential of c-CO2RR to surpass the HER, remain to be addressed.