De novo assembly of frustrated Lewis pair bearing metal-organic frameworks for atmospheric CO2 cycloaddition

Porous frustrated Lewis pairs (FLPs) have been demonstrated as cutting-edge heterogeneous catalysts in acidic–basic catalysis, which, yet faces great challenges in synthesis. Herein, we propose a one-step de novo assembly strategy for constructing porous FLPs by capping monodentate ionic liquids (ILs) on metal clusters during the synthesis of metal–organic frameworks (MOFs). The capping of ILs makes adjacent metal sites on MOFs transforming to coordinatively-unsaturated metal Lewis acids, producing FLPs containing Lewis basic Cl − ions from ILs and metal sites. The distribution of ILs on the framework of MOFs endows the catalysts with large surface areas (up to 2125 m 2 g −1 ), open channels and good stability. The porous FLPs behave unprecedented activity for atmospheric CO 2 activation and coupling with epoxides (25–40°C, 1 bar, without cocatalyst). This de novo assembly strategy exhibits good universality for synthesizing porous FLPs from different kinds of ILs, paving a facile approach for designing high-efficiency acidic–basic catalysts.