Computational Insights into Catalytic Hydrogenation over M6O8-Node MOFs: From Active-Site Engineering to Data-Driven Catalyst Design

Abstract Metal–organic frameworks (MOFs) containing M6O8 secondary building units (SBUs) have attracted considerable attention as hydrogenation catalysts because of their structural robustness, tunable coordination environments, and diverse opportunities for active-site engineering. In recent years, density functional theory (DFT) and related computational approaches have become indispensable tools for elucidating catalytic mechanisms and guiding catalyst design. This review summarizes recent theoretical advances in catalytic hydrogenation over M6O8-node MOFs, with particular emphasis on active-site engineering strategies, including metal doping, single-atom anchoring, metal cluster encapsulation, and ligand functionalization. Their effects on key catalytic processes, such as H2 activation, intermediate stabilization, and reaction energy barriers, are systematically discussed. We further highlight the electronic structure origins of catalytic performance, focusing on descriptors such as charge transfer, d-band center modulation, and frontier orbital interactions that govern activity and selectivity. In addition, emerging data-driven approaches are reviewed for their potential to establish structure–property relationships, enable high-throughput screening, and accelerate catalyst discovery. Current challenges in theoretical studies, including model idealization and the limited description of realistic reaction environments, are also discussed.