Impregnating Subnanometer Metallic Nanocatalysts into Self-Pillared Zeolite Nanosheets

Impregnation is the most commonly used approach to prepare supported metal catalysts in industry. However, this method suffers from the formation of large metal particles with uneven dispersion, poor thermal stability, and thus unsatisfied catalytic performance. Here, we demonstrate that the self-pillared MFI zeolite (silicalite-1 and ZSM-5) nanosheets with larger surface area and abundant Si-OH groups are ideal supports to immobilize ultrasmall monometallic (e.g., Rh and Ru) and various bimetallic clusters via simple incipient wetness impregnation method. The loaded subnanometric metal clusters are uniformly dispersed within sinusoidal five-membered rings of MFI and remain stable at high temperatures. The Rh/SP-S-1 is highly efficient in ammonia borane (AB) hydrolysis, showing a TOF value of 430 mol(H2) mol(Rh)(-1) min(-1) at 298 K, which is more than 6-fold improvement over that of nanosized zeolite-supported Rh catalyst and even comparable with that of zeolite-supported Rh single-atom catalyst. Because of the synergistic effect between bimetallic Rh-Ru clusters and zeolite acidity, the H-2 generation rate from AB hydrolysis over Rh0.8Ru0.2/SP-ZSM-5-100 reaches up to 1006 mol(H2) mol(metal)(-1) min(-1) at 298 K, and also shows record activities in cascade hydrogenation of various nitroarenes by coupling with the hydrolysis of AB. This work demonstrates that zeolite nanosheets are excellent supports to anchor diverse ultrasmall metallic species via the simple impregnation method, and the obtained nanocatalysts can be applied in various industrially important catalytic reactions.

Automated summary

Supported metal catalysts prepared using impregnation method often suffer from poor dispersion and thermal stability. In this study, it was demonstrated that self-pillared MFI zeolite nanosheets are ideal supports for immobilizing ultrasmall metal clusters, exhibiting excellent catalytic performance in various reactions.