Enhanced Catalytic Performance through in Situ Encapsulation of Ultrafine Ru Clusters within a High-Aluminum Zeolite

Zeolite-encapsulated metal clusters have been shown to be an effective bifunctional catalyst for tandem catalysis. Nevertheless, the efficient encapsulation of nanometric metal species into a high-aluminum ZSM-5 zeolite still poses a significant challenge. In this contribution, we have prepared well-dispersed and ultra-small Ru clusters encapsulated within a high-aluminum ZSM-5 zeolite (with a Si/Al ratio of ∼30-40) via an in situ two-stage hydrothermal synthesis method. Small Ru clusters with an average size of ∼1 nm have been identified by scanning transmission electron microscopy and hydrogen chemisorption. Shape-selective hydrogenation experiments with different probe molecules reveal a predominant encapsulation (∼90%) of metal clusters within the MFI zeolite cavities, which significantly enhances thermal stability of metal clusters against sintering. 27Al magic angle spinning nuclear magnetic resonance and Brønsted acid site (BAS) titration experiments show the successful incorporation of aluminum species (>99%) into the zeolite framework and build-up of intimacy between the Ru clusters and BASs at a sub-nanometric level. The resulting Ru@H-ZSM-5 shows an enhanced activity and stability for the crucial hydrodeoxygenation (HDO) of phenol to cyclohexane, in biomass valorization. This synthesis strategy could be of great help for the rational design and development of zeolitic bifunctional catalysts and could be extended to other crystalline porous materials.