Morphology‐Engineering Construction of Anti‐Aggregated Co/N‐Doped Hollow Carbon from Metal‐Organic Frameworks for Efficient Biomass Upgrading

Abstract The controlled pyrolysis of metal/carbon‐containing precursors is commonly used for fabricating multifunctional metal/carbon‐based catalysts, nevertheless, the inevitable agglomeration of these precursors in pyrolysis is extremely negative for efficient catalysis. This study reports the first example of suppressing the interfacial fusion and agglomeration of metal/carbon‐based catalyst in its pyrolysis‐involved fabrication process by developing a facile morphology‐engineering strategy. Metal‐organic framework precursors are chosen as a proof of concept and five Co/N‐doped hollow carbons with different morphologies (rhombic dodecahedron, cube, plate, interpenetration twin, and rod) are synthesized via the pyrolysis of their corresponding core‐shell ZIF‐8@ZIF‐67 precursors. It is demonstrated that the interpenetration twin precursor shows the minimum interfacial contact of interparticles due to its partly‐concave morphology with abundant facets, which endows it with the best resistibility from interfacial fusion and thus aggregation of interparticles during pyrolysis. Benefiting from its unique anti‐aggregated structure with high specific surface area, abundant fully‐exposed active sites, and good dispersibility, the resultant 36‐facet Co/N‐doped hollow carbon exhibit remarkably improved catalytic property for biomass upgrading as compared with its aggregated counterparts. This study highlights the crucial role of engineering morphology to prevent metal/carbon‐containing precursors from detrimental agglomeration during pyrolysis, demonstrating a new approach to constructing anti‐aggregated metal/carbon‐based catalysts.