Targeted fabrication of 1T-MoS2 enriched nanosheets vertically oriented on spiny-shaped nanospheres with sufficient sulfur vacancies and “rim” sites for co-enhancing the hydrodesulfurization activity and hydrogenation selectivity

The 1T-enriched spiny-shaped nanospheres with vertically oriented MoS₂ nanosheets over the surface was successfully prepared with the novel solvent induced micelle-limited Mo-CTA⁺ composites self-assembly (SIMMS) strategy under the dual effects of mixed sulfur sources (thiourea and thioacetamide) and cetyltrimethylammonium bromide (CTAB). In the proposed strategy, the molybdenum source and CTAB are firstly assembled to Mo-CTA⁺ by strong electrostatic attraction to avoid the molybdenum source from polymerization and forming large polymolybdate anions. Meanwhile, the CTAB moleculars self-assemble to spherical micelles, which can adsorb Mo-CTA⁺ through van der Waals force and obtain spherical precursors with a controllable number of nucleation sites. Under the sulfurization from mixed sulfur source, appropriate reducibility can control the formation of crystal seeds and crystal growth during the crystallization process of MoS₂, whereas CTAB can regulate and control the growth behavior and micro-morphology of MoS₂, which is ultimately also retained between the MoS₂ nanolayersto expand their interlayer spacing and stabilize the 1T phase. Therefore, the 1T-enriched spiny-shaped nanospheres with vertically oriented MoS₂ nanosheets can be controllably prepared. In the hydrodesulfurization (HDS) reaction of dibenzothiophene (DBT) over these catalysts, the MoS₂-75%/0.25 catalyst with the highest concentration of sulfur vacancies as well as “rim” and “rim-like” sites can reach the highest HDS activity (99.1%) and HYD/DDS ratio (4.76), which are much higher than those of the MoS₂-H catalyst prepared by conventional hydrothermal method (HDSDBT%=46.0%, HYD/DDS ratio=0.90).