Acidic Media Impedes Tandem Catalysis Reaction Pathways in Electrochemical CO 2 Reduction

Electrochemical CO 2 reduction (CO 2 R) in acidic media with Cu‐based catalysts tends to suffer from lowered selectivity towards multicarbon products. This could in principle be mitigated using tandem catalysis, whereby the *CO coverage on Cu is increased by introducing a CO generating catalyst (e.g. Ag) in close proximity. Although this has seen significant success in neutral/alkaline media, here we report that such a strategy becomes impeded in acidic electrolyte. This was investigated through the co‐reduction of 13 CO 2 / 12 CO mixtures using a series of Cu and CuAg catalysts. These experiments provide strong evidence for the occurrence of tandem catalysis in neutral media and its curtailment under acidic conditions. Density functional theory simulations suggest that the presence of H 3 O + weakens the *CO binding energy of Cu, preventing effective utilization of tandem‐supplied CO. Our findings also provide other unanticipated insights into the tandem catalysis reaction pathway and important design considerations for effective CO 2 R in acidic media.