Encapsulated Platinum–Tin Nanoparticles in Silicalite-1 Zeolite for Methylcyclohexane Dehydrogenation

Catalytic dehydrogenation of methylcyclohexane (MCH) is of great importance for hydrogen storage and transportation, but currently used Pt-based nanoparticle catalysts still suffer from insufficient activity, low selectivity, and short-term stability. In this study, we encapsulated Pt–Sn nanoparticles into the silicalite-1 (S-1) matrix and incorporated Sn into the zeolite framework through one-pot hydrothermal synthesis to overcome the above problems. These Pt–Sn bimetallic catalysts were designed for the first time with a high Sn content (2.8–3.9 wt %, Sn/Pt ratio = 6–8) in zeolite mother gel for MCH dehydrogenation. The introduction of Sn significantly improved the activity and durability of Pt@S-1. Especially, the PtSn@S-1 (Sn/Pt ratio = 6) catalyst showed high MCH conversion (>80% for 2 h) and toluene (TOL) selectivity (∼100%) without cofeeding H2. Even after a long-term stability test for 33 h under a weight hourly space velocity (WHSV) of 120,000 mL/g/h, no obvious deactivation was observed, and this catalyst retained a superior H2 evolution rate normalized with a surface Pt content of 1343 mmolH2/gPt/min. The structure–catalytic property relationship of PtSn@S-1 catalysts was systematically studied. Upon Sn introduction, PtOx species on Pt@S-1 were transformed into the PtSn alloy. With the further increase of the Sn/Pt ratio from 1 to 6, Sn was gradually incorporated into the zeolite framework, and this PtSn alloy evolved into a core–shell structure with a Pt core and a Sn shell. Despite the reduced proportion of surface Pt, these unique structures enabled the modification of the Pt local structure, promoted TOL desorption, and enhanced the stability of Pt–Sn nanoparticles, therefore achieving high activity, selectivity, and durability for MCH dehydrogenation.