Pushing the Ag-loading of CO2 electrolyzers to the minimum via molecularly tuned environments

Electrochemically converting CO₂ to renewable synthons is steadily becoming a globally scalable and important CO₂ utilization technology. Nevertheless, most industrial endeavors employ catalysts based on metallic Ag or Au, with few catalytically competitive alternatives, showing similar activity, high mass activity, and cost efficiency. Similarly, this effort is hindered by insufficient testing of promising materials in application-oriented conditions. We herein present a holistic pathway starting from the conceptualization of different Ag(I)-based molecular catalysts to their complete integration into directly industrially applicable cell assemblies. Notably, optimization of not only the catalyst but also the operational conditions allowed us to achieve CO₂ electrolysis for at least 110 h at 300 mA cm⁻² and 80 h at 600 mA cm⁻² with an FE_CO decay rate of 0.01% h⁻¹. Beyond significant mass activity improvements for CO production, we provide the community with a broad toolbox toward improving catalytic and cell performance directly between different cell sizes.