Polymer-Regulated Electrochemical Reduction of CO₂ on Ag

The influence of polymer overlayers on the catalytic activity of Ag for electrochemical CO₂ reduction to CO is explored. Polystyrene and poly(4-vinylpyridine) films of varying thicknesses are applied as catalysis-directing overlayers atop Ag electrodes. For polystyrene, substantial suppression of CO₂ reduction activity is observed while the hydrogen evolution reaction (HER) increases. The addition of a nitrogen heteroatom into the phenyl groups of polystyrene (e.g., a pyridine ring) results in an increase in the conversion of CO₂ to CO and suppression of HER. Block copolymer variants containing both phenyl and pyridyl functionalities exhibit similar activity for CO evolution but appear to suppress HER further than the polymer layer containing only pyridine groups. The size of the blocks for the copolymer influences the catalytic output of the Ag electrode, suggesting that the hierarchical structure that forms in the block copolymer layer plays a role in catalytic activity at the electrode surface. Analysis of the polymer overlayers suggests that polystyrene significantly inhibits all ion transport to the metal electrode, while poly(4-vinylpyridine) enables CO₂ transport while modifying the electronics of the Ag active site. Therefore, the engineered application of polymer overlayers, especially those containing heteroatoms, enables new avenues of electrochemical CO₂ reduction to be explored.