Thermal Regulation of CO₂ Activation Pathways via Interfacial Water Restructuring Enables Ampere-Level, Near-Unity CO...

Electrochemical reduction of CO₂ to CO is a key step in carbon utilization technologies, yet maintaining high CO selectivity under elevated temperatures relevant to industrial membrane-electrode-assembly (MEA) electrolyzers remains challenging due to the competing hydrogen evolution reaction (HER). Additionally, the temperature dependence of CO selectivity on Cu-based catalysts has remained largely unexplored. Here, we demonstrate that incorporating atomic In or Sn into Cu fundamentally reshapes the selectivity of Cu catalysts at elevated temperatures. Dilute alloy catalysts, In₁Cu and Sn₁Cu, achieve >95% FE of CO over a broad current-density window (0.1-1.1 A cm^-2) at 60 °C in MEA electrolyzers, far exceeding their performance at ambient temperature. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy suggests that elevating temperature depletes interfacial water activity, which favors a shift in CO₂ activation from a proton-coupled *COOH pathway toward an electron-driven *COO^--associated pathway, while also suppressing HER and CO hydrogenation. In contrast, benchmark CO-selective catalysts such as Ag exhibit minimal temperature-induced changes in CO production at 20-60 °C. These findings identify temperature as an unavoidable yet previously underutilized operating parameter in MEA electrolyzers for high-rate, selective CO production on Cu-based catalysts.