Boosting Toluene Selectivity over Mo-Modified Ni@Silicalite-1 Catalysts in Hydrogenolysis of Vapor-Phase m -Cresol

作者：Jimei Zhang, Yanchun Shi, Junwen Chen, Sihan Sun, Bi Wu, Lei Wang, Qiang Chen · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.5c03303 · 被引用次数：3 · 研究领域：Catalysis and Hydrodesulfurization Studies、Catalytic Processes in Materials Science、Catalysis for Biomass Conversion

The hydrogenolysis of biobased phenolics into high-value arenes is considered as the potential alternative strategy to petroleum-based arenes, but the widely used Ni-based catalysts generally suffer from a poor arenes yield. Herein, we demonstrated a strategy by introducing Mo species into Ni@Silicalite-1 (Ni@S-1) to drive the diffusion of Ni particles embedded at the external surface layer of S-1 into its deeper internal crystals to form uniformly confined NiMo bimetallic nanoparticles (2–5 nm) with rich oxygen vacancies. As for hydroxyl hydrogenolysis of vapor-phase m -cresol as an example, NiMo@S-1 presented a remarkable toluene production rate of 480.3 μmol [toluene] ·g [Ni] –1 ·s –1 with a hydroxyl hydrogenolysis rate of 501.9 μmol [ m -cresol] ·g [Ni] –1 ·s –1 at 350 °C under reported minimal metal Ni loading, suggesting the achievement of the highest hydroxyl hydrogenolysis rate over disclosed Ni-based catalysts by far. As analyzed, such induced confined structures enforce the m -cresol adsorbed onto the metal surface via the vertical geometry for the shape-selective effect of zeolites, and the oxygenophilic oxygen vacancies of NiMo@Silicalite-1 further strengthen the vertically oriented m -cresol to interact with active sites through the hydroxyl group rather than the phenyl group, thus greatly enhancing the desired hydroxyl hydrogenolysis process.