Recent advances in thermocatalytic hydrogenation of unsaturated organic compounds with Metal-Organic Frameworks-based materials: Construction strategies and related mechanisms

Metal-Organic Frameworks (MOFs) have become a research hotspot in the field of hydrogenation reactions due to their tunable pore size, structural diversity, large specific surface area, and functional tunability. MOFs can integrate a variety of hydrogenation active sites based on the inherent advantages, including metal nodes, organic ligands, and functionally modified active groups, as well as diverse pore structure-constrained guest species, especially metal nanoparticles (MNPs). One unique feature of MOFs is that they can serve as templates/precursors for controlled thermal transformation into porous carbon materials, metal-based compounds (such as metal oxides, sulfur, and phosphides), and their composites, which can also be turned into single-atom catalysts (SACs) with superior activity. Therefore, these unique properties of MOFs and their derivatives contribute to enhancing the hydrogenation performance and/or broadening the reaction range, making MOFs-based materials a highly versatile catalytic platform for hydrogenation. In this review, the relevant studies related to different hydrogen sources and activation mechanisms for MOFs-based materials are first summarized. The research progress on three broad blocks of intrinsic MOFs with synthesizable post-modification properties, MOFs-metal composites, and MOFs-derived materials for the catalytic hydrogenation of unsaturated organics are systematically described on the basis of different forms of catalytic active sites as the main thread, focusing on their preparation strategies, structural design, and the synergy between active sites and structural properties. Theoretical simulation studies of MOFs-based materials are further briefly presented to reveal the hydrogenation reaction pathways. Finally, the current challenges and development trends of MOFs-based porous materials in the field of hydrogenation are summarized.