Spatial Separation of Metal–MOF Tuning Catalytic Selectivity in CO2 Hydrogenation and Methanol Partial Oxidation

Abstract Tuning the interactions between metal nanoparticles (NPs) and metal–organic frameworks (MOFs) is pivotal for selective catalysis, yet systematic regulation of metal–MOF spatial separation remains largely unexplored. Here, we demonstrate that systematically regulating the metal–MOF separation enables controlled modulation of catalytic activity and reaction selectivity. A series of MOF-encapsulated Pt catalysts with adjusted Pt–MOF separations were designed and synthesized by varying the surface coverage of capping agents on Pt NPs. Both CO2 hydrogenation and methanol partial oxidation exhibit volcano-type dependencies of catalytic performance on Pt–MOF separation, revealing the existence of an optimal spatial window for catalytic cooperation between Pt NPs and MOF nodes. Theoretical calculations indicate that an appropriate Pt–MOF separation facilitates the formation of key reaction intermediates, thereby governing catalytic selectivity. This work establishes metal–MOF spatial separation as an important structural parameter for catalyst design and provides a practical strategy for developing proximity-engineered NP–MOF catalysts with tunable reaction selectivity.