Boosting Photocatalytic CO2 Cycloaddition via Dual-Active Site Coordination over Amino-Functionalized UiO-66(Zr).

CO2 cycloaddition with epoxides offers a sustainable route for CO2 utilization, yet the simultaneous activation of both substrates remains challenging. Herein, using UiO-66(Zr)-NH2 (denoted as UZN) as a model system, we illustrate that dual-active sites consisting of unsaturated Zr4+ centers and amine groups can efficiently accelerate CO2 fixation with epoxides under visible light. The unique ensemble in UZN optimizes light harvesting, promotes charge carrier separation, and enriches bifunctional active sites for efficient adsorption and activation of epoxides and CO2. Consequently, UZN exhibits significantly improved CO2-epoxide cycloaddition performance compared to UiO-66(Zr)-H (denoted as UZH), achieving a PC yield of 99.5%, with a production rate of 9.97 mmol·g-1·h-1. This work establishes a clear coordination-photocatalytic synergy in MOF-based systems and provides fundamental insights and a generalizable strategy for designing advanced catalysts for CO2 transformation.