Confined Co x S y Cluster on Basal Nanoporous MoS 2 for Mild Hydrodeoxygenation of Lignin Derivatives to Arenes

Abstract Activating the inert basal plane of MoS 2 by introducing a second metal is an effective strategy to enhance the hydrodeoxygenation activity and stability of MoS 2 ‐based catalysts in lignin utilization. In this work, the confinement of the Co x S y cluster on the basal nanoporous MoS 2 (denominated as Co x S y ‐n‐MoS 2 ) is reported through 1T‐MoS 2 phase transformation and in situ sulfurization of the Co dimethylimidazole complex, which exhibited excellent performance, stability, and universality in the hydrodeoxygenation (HDO) of lignin and its derivatives into arenes. Advanced characterizations confirmed that Co is anchored as Co x S y clusters via Co─S covalent bonds adjacent to the basal plane nanopore on the MoS 2 . In the HDO reaction of p ‐cresol, the catalyst achieved 99.9% conversion and 96.7% toluene selectivity under mild conditions (170 °C, 3 MPa H 2 , 10 h) and almost remained unchanged after eight cycles, representing state‐of‐the‐art performance among reported works. Mechanistic studies revealed that the ultrasmall Co x S y clusters served as the dominant active sites, enabling H 2 adsorption/dissociation, p ‐cresol activation, and deoxygenation catalysis, while the nanopores contribute to the weakening of C─O bond via a unique tensile effect to the electron‐rich benzene ring. This work will open up new opportunities for exploring advanced functional MoS 2 ‐based catalysts to achieve lignin utilization.