Abstract
Synergistic catalysis occurring in an enzyme pocket shows enhanced performance through supramolecular recognition and flexibility. This study presents an aerogel capable of similar function by fabricating a gel catalyst with hierarchical porosity. Here, the as-prepared Co-MMPG, a Co(II) metal-metalloporphyrin gel, maintains enough conformational flexibility and features a binding pocket formed from the co-facial arrangement of the porphyrin rings, as elucidated through the combined studies of solid-state NMR and X-ray absorption near-edge structure (XANES). The cooperativity between two Co(II) sites within the defined nanospace pocket facilitates the binding of different substrates with a favourable geometry thereby rendering Co-MMPG with excellent performance in the context of synergistic catalysis, especially for the kinetic control stereoselective reactions. Our work thus contributes a different enzyme-mimic design strategy to develop a highly efficient heterogeneous catalyst with high chemo/stereo selectivity.
Highlights
Synergistic catalysis occurring in an enzyme pocket shows enhanced performance through supramolecular recognition and flexibility
The permanent porosity of CoMMPG was confirmed by N2 sorption isotherms collected at 77 K (Fig. 2a), which reveals that Co-metal–metalloporphyrin gel (MMPG) exhibits a Brunauer–Emmett–Teller (BET) surface are of 1343 m2 g−1 (P/P0 = 0.0001–0.1), corresponding to a Langmuir surface area of ~1678 m2 g−1
Field-emission scanning electron microscopy (SEM) images show that Co-MMPG is composed of cross-linked nanofibers with sizes ranging from 200 to 300 nm in diameter (Fig. 2b)
Summary
Synergistic catalysis occurring in an enzyme pocket shows enhanced performance through supramolecular recognition and flexibility. Extensive yet continuous efforts have been dedicated to mimic enzymes for synergistic catalysis, and significant progress has been accomplished in creating active centers with binding/coordination environment similar to enzymes[6–8] It remains a challenge, in the solid state, to combine both binding pocket and flexibility into one system to function like enzymes that feature high specificity, selectivity, and efficiency[9–11]. Metal–organic gels (MOGs)[12–17], a class of soft-hybrid polymer materials are functional porous aerogels that have characteristics of low density, versatile porosity, and high-internal surface area. These polymer materials have shown potential for applications in catalysis[18–21], adsorption/separation[22,23], and others[24,25]. Because porphyrin materials in gel form can be designed with multiple and precisely spaced
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