We have devised a straightforward tandem postsynthetic modification strategy for Zr-based metal-organic framework (MOF) materials, which resulted in a series of well-defined 2-in-1 heterogeneous catalysts, cat1-cat8, exhibiting high catalytic activity in the synthesis of cyclic carbonates under solvent-free and co-catalyst-free conditions. The materials feature precisely located co-catalyst moieties decorating the metal nodes throughout the bulk of the MOF and yield cyclic carbonates with up to 99% efficiency at room temperature. We use diffuse reflectance infrared Fourier transform (DRIFT) and solid-state nuclear magnetic resonance (NMR) measurements to elucidate the role of each component in this model catalytic reaction. Establishing a method to precisely control the co-catalyst loading allowed us to observe the cooperativity between Lewis acid sites and the co-catalyst in the 2-in-1 heterogeneous system.
Keywords: carbon dioxide fixation; cycloaddition; heterogeneous catalysis; metal−organic framework; postsynthetic functionalization.