Controlled Encapsulation of Flower-like Rh-Ni Alloys with MOFs via Tunable Template Dealloying for Enhanced Selective Hydrogenation of Alkyne.

For new composite materials with functional nanoparticles (NPs) embedded in metal organic frameworks (MOFs), rational design and precise control over their architectures are imperative for achieving enhanced performance and novel functions. Especially in catalysis, the activity and selectivity of such composite materials are strongly determined by the encapsulation state and thickness of the MOF shell, which greatly influences the diffusion and adsorption of substance molecules onto the NP surface. In this study, MOF-74(Ni)-encapsulated Rh-Ni hierarchical heterostructures (Rh-Ni@MOF-74(Ni)) were successfully constructed using magnetic Rh-Ni-alloyed nanoflowers (NFs) as a self-sacrificial template. Strikingly, the encapsulation state and thickness of the formed MOF shell were well-tuned via template dealloying by changing the Ni content in the Rh-Ni NFs template. More interestingly, such unique Rh-Ni composites encapsulated with MOFs as catalysts could be magnetically recyclable and exhibited enhanced catalytic performance for the selective hydrogenation of alkynes to cis products, owing to the confinement effect of the MOF shell, as compared to their pristine counterparts.