Dynamic Hydrogen Management System: Atomic-Level AlO Site In Situ Construction of Brønsted Acid Optimizes Co 3 S 4 @AlO-CoMoS Hydrogen Spillover for Low-Temperature Hydrogenation Reaction

The rational modulation of catalysts with efficient hydrogen activation and controllable management properties is essential to improve the hydrogenation performance. Herein, we have employed a gradient diffusion-in situ reconstruction strategy to prepare the YS-Co3S4@AlO-CoMoS catalyst with an efficient hydrogen spillover network. The coordinated dissociation of Co-hybrid nanospheres during sulfidation promotes gradient diffusion of Co2+ and drives its binding with small-sized (NH4)3[AlMo6O24·6H2O]·7H2O, generating abundant CoMoS active phases. Subsequently, the in situ reconstruction of the Co3S4 core and the AlO-CoMoS shells was achieved in nanospace, resulting in atomic-level coupling between acid and CoMoS sites. Combining multiple characterizations and theoretical calculations confirms that the Co3S4 core activates H2 and triggers the hydrogen spillover effect and the active hydrogen (H*) is transported into the AlO-CoMoS shells to improve the hydrogenation performance. The AlO sites as a secondary hub of hydrogen spillover are in situ activated by H* to create the Brønsted acid sites, dynamically regulating the supply and consumption balance of H* to prevent over-hydrogenation of substrates. The 1T-MoS2 with short slab length and low stacking provides abundant “rim” sites that promote substrate adsorption and enhance the apparent activity of the catalyst. The unique electronic structure of 1T-MoS2 facilitates H* migration and enhances the intrinsic activity of the catalyst, promoting the dynamic regeneration of −SH, Mo−H, and sulfur vacancy sites by cleaving its weak Mo−S bonds. Therefore, the YS-Co3S4@AlO-CoMoS catalyst exhibited excellent hydrogenation ability and achieved simultaneous conversion of 4,6-dimethyldibenzothiophene (96.8%) and anthracene (98.9%) at moderate conditions (300 °C, 6.5 MPa). The 4,6-dimethyldibenzothiophene products were primarily 3,3'-dimethylcyclohexylbenzene (54.1%), indicating that the catalyst effectively promoted the desulfurization and prevented excessive hydrogenation of the substrate. This strategy realizes the dynamic management of H* by precisely constructing the hydrogen spillover network, providing a practical concept for exploring the efficient hydrogenation catalysts and promoting the quality of oil.