Heterostructural metal/metal oxides are the very promising substituents of noble-metal catalysts;h owever, generation and further stabilization of accessible metal/metal oxide heterojunctions are very difficult. As trategy to encapsulate and stabilizeCu/Cu 2 Onanojunctions in porous organic frameworks in situ is developed by tuning the acrylate contents in copper-based metal-organic frameworks (Cu-MOFs) and the pyrolytic conditions.T he acrylate groups play important roles on improvingt he polymerization degree of organic frameworks and generating and stabilizing highly dispersed and accessible Cu/Cu 2 Oh eteronanojunctions.A saresult, pyrolysis of the MOF ZJU-199, consisting of three acrylates per ligand, generates abundant heterostructural Cu/Cu 2 O discrete domains inside porous organic matrices at 350 8 8C, demonstrating excellent catalytic properties in liquid-phase hydrogenation of furfural into furfuryl alcohol, whicha re muchs uperior to the non-noble metal-based catalysts. Results and DiscussionTheC u-MOF ZJU-199 (ZJU = Zhejiang University) is built from [Cu 2 (COO) 4 ]p addle-wheel secondary building Angewandte Chemie Research Articles Figure 6. Kinetic studies of FAL hydrogenation over ZJU-199-350 catalyst:a )reaction rates of ZJU-199-350 at different temperatures (inset:A rrheniusp lot for the FAL hydrogenation). Reaction conditions: 2.5 mmol FAL, 5mLi sopropanol, 25 mmol catalyst, 1MPa H 2 ,100-130 8 8C, 2h.b)The recyclability of ZJU-199-350 for the hydrogenation of FAL. Reaction conditions: 1.0 mmol FAL, 25 mmol catalyst, 2mL isopropanol, 1MPa H 2 ,130 8 8C, 3h.

Incorporating metal nanoparticles (MNPs) inside metal-organic frameworks (MOFs) demonstrates superior catalytic properties in numerous reactions; however, the size and distribution of MNPs could not be well controlled, resulting in low product selectivity in catalysis by undergoing different catalytic reaction pathways. We report herein a facile strategy for integrating lattice-mismatched MOFs together to fabricate homogeneously distributed “dual-MOFs,” which are the ideal precursors for the preparation of MNPs@MOFs with unique catalytic properties. As a proof of concept, we successfully synthesize a dual-MOF HKUST-1/ZIF-8 for in situ creation of redox-active Cu NPs inside hierarchical porous ZIF-8 under controlled pyrolytic conditions. Combining the advantages of size-tunable Cu NPs in the molecular sieving matrix of ZIF-8, Cu@ZIF-8 demonstrates high activity and selectivity for transformation of alkynes into alkenes without overhydrogenation, which surpasses most of the catalysts in the literature. Therefore, this work paves a new pathway for developing highly efficient and selective heterogeneous catalysts to produce highly value-added chemicals.

Heterostructural metal/metal oxides are the very promising substituents of noble‐metal catalysts; however, generation and further stabilization of accessible metal/metal oxide heterojunctions are very difficult. A strategy to encapsulate and stabilize Cu/Cu2O nanojunctions in porous organic frameworks in situ is developed by tuning the acrylate contents in copper‐based metal–organic frameworks (Cu‐MOFs) and the pyrolytic conditions. The acrylate groups play important roles on improving the polymerization degree of organic frameworks and generating and stabilizing highly dispersed and accessible Cu/Cu2O heteronanojunctions. As a result, pyrolysis of the MOF ZJU‐199, consisting of three acrylates per ligand, generates abundant heterostructural Cu/Cu2O discrete domains inside porous organic matrices at 350 °C, demonstrating excellent catalytic properties in liquid‐phase hydrogenation of furfural into furfuryl alcohol, which are much superior to the non‐noble metal‐based catalysts.

Metal-organic frameworks (MOFs) are a class of crystalline porous coordination materials with systematically designable network structures and tunable properties, demonstrating great potential for applications in diverse fields. However, the generally...