Chemical Modifications of Ag Catalyst Surfaces with Imidazolium Ionomers Modulate H2 Evolution Rates during Electrochemical CO2 Reduction

Bridging polymer design with catalyst surface science is a promising direction for tuning and optimizing electrochemical reactors that could impact long-term goals in energy and sustainability. Particularly, the interaction between inorganic catalyst surfaces and organic-based ionomers provides an avenue to both steer reaction selectivity and promote activity. Here, we studied the role of imidazolium-based ionomers for electrocatalytic CO₂ reduction to CO (CO₂R) on Ag surfaces and found that they produce no effect on CO₂R activity yet strongly promote the competing hydrogen evolution reaction (HER). By examining the dependence of HER and CO₂R rates on concentrations of CO₂ and HCO₃^–, we developed a kinetic model that attributes HER promotion to intrinsic promotion of HCO₃^– reduction by imidazolium ionomers. We also show that varying the ionomer structure by changing substituents on the imidazolium ring modulates the HER promotion. This ionomer-structure dependence was analyzed via Taft steric parameters and density functional theory calculations, which suggest that steric bulk from functionalities on the imidazolium ring reduces access of the ionomer to both HCO₃^– and the Ag surface, thus limiting the promotional effect. Our results help develop design rules for ionomer–catalyst interactions in CO₂R and motivate further work into precisely uncovering the interplay between primary and secondary coordination in determining electrocatalytic behavior.