Hierarchically micro- and mesoporous metal–organic framework-supported alloy nanocrystals as bifunctional catalysts: Toward cooperative catalysis

[Display omitted] •Hierarchically micro- and mesoporous MOF immobilize bimetallic alloy nanoparticles (NPs).•The combination of MOF and alloy NPs shows cooperative catalysis of oxidant-free dehydrogenation of alcohols.•The highly dispersed PtPd bimetallic alloy nanoparticles (NPs) exhibit synergistically enhanced catalysis. Metal–organic frameworks (MOFs) in most metal nanoparticles (NPs)/MOFs composite catalysis systems serve only as supports to protect NPs from agglomeration. Up to now, most MOFs have still been largely restricted to the microporous regime, which limits the diffusion and mass transfer of substrates and products. Here, we use hierarchically micro- and mesoporous MOFs for the first time to immobilize highly dispersed PtPd bimetallic alloy nanoparticles (NPs). The obtained composites as bifunctional catalysts based on the combination of MOFs and alloy NPs show synergistic enhanced catalysis of oxidant-free dehydrogenation of alcohols. The mesopores facilitate diffusion and accessibility of substrates and products, while the micropores provide large pore volumes and high surface areas to create more active sites to enhance the catalytic activity.