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Heterogeneous catalysts with tunable micropores and confined metal sites in micropores are of great significance in sizeselective catalysis but remain difficult to be achieved in organic polymers. In this work, we provide a micropore-confining strategy for the design of size-selective heterogeneous catalysts and investigate their size selectivity on various catalytic reactions. The palladium (Pd) @microporous tetrastyrene polymer (MTP) was synthesized via a Pdcatalyzed coupling reaction, where superfine Pd nanoparticles in situ form in the micropores of MTP. The results demonstrate that Pd@ MTP catalysts not only exhibit greatly enhanced catalytic activity but also present excellent size selectivity on various catalytic systems. This research greatly expands the application scope of microporous organic polymers in size-selective heterogeneous catalysis.

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