Versatile Hollow ZSM-5 Nanoreactors Loaded with Tailorable Metal Catalysts for Selective Hydrogenation Reactions

Zeolites are one of the most commonly used materials in the chemical industry, acting as catalysts or catalyst supports in different applications. Recently, the synthesis and functionalization of hollow zeolites have attracted many research interests, owing to the unique advantages of their hollow morphology. In the development of more sustainable processes, the hollow zeolites are often endowed with additional stability, selectivity, and activity. Herein, we present a stepwise synthetic protocol to prepare a range of complex hollow ZSM-5 catalysts with catalytic nanoparticles. Solid ZSM-5 crystals were first synthesized from Stöber silica spheres. This solid ZSM-5 sample was then loaded with transition metals via the impregnation method. A subsequent hollowing process was carried out in hydrothermal conditions in which hollow ZSM-5 crystals with confined transition metals inside were synthesized. More specifically, after the encapsulation of transition metals inside hollow ZSM-5, two different approaches have been further devised to allow the deposition of noble metals into the interior cavities or onto the exterior surfaces of the hollow ZSM-5. The deposition of Pt on the exterior surface was carried out by mixing the hollow ZSM-5 sample with presynthesized Pt nanoparticles. Loading of Pd in the interior was achieved by the galvanic replacement reaction between the Pd ions and embedded transition metals inside the hollow ZSM-5 sample. The catalytic performance of these reactor-like nanocatalysts has been evaluated with hydrogenation reactions in both liquid and gas phases, and their compositional and structural merits have been illustrated. For the hollow ZSM-5 sample with Pd loaded inside, liquid-phase selective hydrogenation of styrene over 4-vinylbiphenyl has been achieved with the ZSM-5 shell acting as a molecular sieve. The deposition of Pt on the exterior has improved the C₂-C₄ product yield when tested for the gas-phase CO₂ hydrogenation reaction.