Structural Screening and Design of Dendritic Micro-Mesoporous Composites for Efficient Hydrodesulfurization of Dibenzothiophene and 4,6-Dimethyldibenzothiophene

Novel dendritic micro-mesoporous TS-1/dendritic mesoporous silica nanoparticles (DMSNs) composites (TD) were assembled by TS-1 nanocrystals with ultrasmall particle size and strong acidity. TS-1 seeds and DMSNs were composited via the Ti-O-Si chemical bond, which stimulate on the generation of Brønsted (B) and Lewis (L) acid. The spillover d-electrons produced by The Ti element of TS-1 seeds produced a spillover of d-electrons, which could interact with the surface of MoS2 phases, thereby reducing Mo-S interactions and creat sulfur vacancies that are favorable for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions. The increased B&L acid amount of NiMo/TD-2.0 with Cetyltrimethylammonium bromide/Sodium salicylate molar ratio of 2.0 played a important role in facilitating the hydrogenation (HYD) route of DBT HDS and the isomerization (ISO) route of 4,6-DMDBT HDS, which is more favorable to the reduction of steric hindrance of DBT and 4,6-DMDBT reactants in the HDS reaction process. The NiMo/TD-2.0 catalyst exhibited the highest turn-over frequency (TOF) value and HDS reaction rate constant (kHDS) of DBT and 4,6-DMDBT due to its ultrasmall particle size, uniform spherical dendritic morphology, strong B&L acidities and good stacking degree.