Synergistic Cu/Ag dual-sites in MOF-253 for high-efficiency carbonylative cyclization of CO2 under ambient conditions

Developing heterogeneous catalysts capable of activating inert CO 2 under mild conditions remains a central challenge in sustainable chemistry. Herein, we report the rational design of a robust bimetallic platform, MOF-253-0.5(Cu/Ag), constructed by post-synthetic incorporation of synergistic Cu(II) and Ag(I) sites within the 2,2′-bipyridine pockets of the MOF-253 framework. The catalyst exhibits high turnover frequencies (TOF) of 260 h −1 under ambient conditions, ranking among the highest reports. It also maintains robust stability over 5 cycles, achieving a cumulative turnover number (TON) of 999.2. Even under diluted CO 2 conditions mimicking industrial flue gas, its catalytical activity remains largely unaffected. 1 H NMR mechanistic analysis was used to monitor the reaction processes. Comparative experiments with monometallic and pristine MOF confirm the superior performance of the bimetallic system, attributed to Cu/Ag synergy that activates both the C≡C bond and CO 2 . Furthermore, comprehensive density functional theory (DFT) calculations provided clear insights into the energetics and elementary steps of the catalytic cycles. This work highlights the power of site-isolated bimetallic MOFs in CO 2 chemical fixation.