Integrating MOF-Based Catalysis with Nanocavity-Confined Pd Catalysis over Multifunctional Pd-MOF-Fe for Acceptorless Dehydrogenation of Alcohols under Visible Light

Graphical Ultrafine Pd nanoparticles (1.41 nm)-embedded MIL-100(Fe) (Pd-MOF-Fe) nanocomposites are synthesized via a double-solvent impregnation integrated with photo-reduction approach. Coupling MOF-based catalysis with Pd-based catalysis, the resultant Pd-MOF-Fe shows excellent catalytic efficiency and high stability toward visible-light-induced dehydrogenation of alcohols to hydrogen evolution and value-added carbonyl chemical production. Solar-driven hydrogen (H 2 ) evolution combined with synchronously selective oxidation for fine chemicals production is of great significance in energy and synthetic chemistry. Herein, ultrafine Pd nanoparticles-encapsulated MIL-100(Fe) (Pd-MOF-Fe) nanocomposites are synthesized through double-solvent impregnation integrated with photo-reduction method. Integrating MOF-based catalysis and Pd-based catalysis, the Pd-MOF-Fe can serve as multifunctional catalyst for photoinduced alcohol dehydrogenation reaction. Optimal generation rates of H 2 (3.61 mmol g −1 h −1 ) and benzaldehyde (3.40 mmol g −1 h −1 ) are gained over Pd-MOF-Fe, ca. 4.1 times that of the Pd/MOF-Fe, in which Pd crystals with size ranging from 3 to 6 nm are immobilized on the intersurface of MOFs. Besides, controlled experiments reveal the pivotal role of the opened FeO 6 nodes of MIL-100(Fe) as Lewis acid sites toward alcohol activation. This work provides a controllable approach for metal nanoparticle immobilization. Furthermore, considering the diversified MOF structures, this study also highlights the infinite possibility of metal nanoparticle/MOFs as multifunctional platform for solar energy conversion and chemicals production.