A Bifunctional UiO‐66 Platform Enabled by Schiff‐Base Engineering for CO ₂ Conversion and Epoxide–Anhydride Copolymerization

ABSTRACT

In this study, we report a series of bifunctional UiO‐66‐based metal–organic framework (MOF) catalysts, functionalized with Schiff‐base ligands and coordinated with divalent metal ions (M = Zn, Cu, Ni), for the sustainable transformation of epoxides via ring‐opening copolymerization (ROCOP) with anhydrides and coupling with CO ₂ . The rational integration of Lewis acidic metal centers and tunable porosity within the UiO‐66 framework enables enhanced catalytic activity and selectivity. These catalysts achieve high conversions and excellent selectivity toward polyesters and cyclic carbonates under mild conditions (80°C for CO ₂ coupling; 110°C for ROCOP), with minimal by‐products. Importantly, the catalysts exhibit robust recyclability, maintaining structural integrity and performance over multiple cycles. This work demonstrates a versatile and durable MOF platform for green polymerization and CO ₂ valorization, aligning with principles of sustainable catalysis and circular carbon utilization.