Synergistic Mediation: Flexible Alkanolamine-Ir Sites for Photocatalytic CO2 Reduction Coupled with Water Oxidation

• • The M-Ir/ACN system achieves a 20-fold increase in CO production compared to pristine ACN, demonstrating a substantial enhancement in photocatalytic CO2 reduction efficiency. • • Sustained stability over 45 hours of continuous operation indicates robust performance, critical for practical solar-to-fuel applications where catalyst longevity is a major economic factor. • • Time-resolved in situ spectroscopy captures rapid carbamate intermediate transformation and sustained IrOOH formation, providing direct evidence of the synergistic mechanism and guiding rational design of dual-site catalysts. • • Microkinetic modeling reveals that the MEA-Ir system creates interconnected H spillover networks, facilitating efficient proton transport that drives *COOH formation with favorable thermodynamics, addressing the bottleneck of proton supply in CO2 photoreduction.