Hybridization of Pd Nanoparticles with UiO-66(Hf) Metal-Organic Framework and the Effect of Nanostructure on the Catalytic Properties.

Metal-organic frameworks (MOFs) have emerged as a new class of supports for metal nanoparticles(NPs) in heterogeneous catalysis because of possible synergetic effects between the two components. In addition, MOFs also can be coated over metal NPs to influence the entire nanoparticle's surface. Herein, NPs were hybridized with UiO-66(Hf) MOF possessing Brønsted acidic sites (on secondary building units) and fabricated Pd@UiO-66 (Hf) core-shell and Pd/UiO-66(Hf) supported catalysts. These hybrid materials exhibited enhanced catalytic properties (TOF increased up to 2.5 times) compared to individual counterparts or their physical mixture for dehydrogenation of ammonia borane(AB) in non-aqueous medium(1,4-dioxane). Further, nanostructure of the hybrid material had pronounced influence on the catalytic properties. The core-shell catalyst exhibited highest activity towards H2 generation from AB owing to greater contact interface between Pd and MOF. Further, phenylacetylene semi-hydrogenation with AB over Pd@UiO-66 (Hf) furnished styrene selectivity as high as 93.2 % at ∼100 % conversion mostly due to the regulated phenylacetylene diffusion through UiO-66(Hf) shell.