Cooperative S-S coupling and H2 production from photocatalytic dehydrogenation of thiols over ReSe2/ZnIn2S4 heterostructure

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2024-11, Vol.499, p.155687, Article 155687
• Main Authors: Yang, Xin, Jin, Yanchao, Ke, Sunzai, Li, Mengqing, Yang, Xuhui, Shen, Lijuan, Yang, Min-Quan
• Format: Article
• Language: English
• Subjects: Aerobic oxidation; Disulfides; Hydrogen production; Photocatalysis; ReSe2/ZnIn2S4 heterostructure; Thiols
• ISSN: 1385-8947
• DOI: 10.1016/j.cej.2024.155687

A ReSe2/ZnIn2S4 heterostructure is designed for anaerobic dehydrogenation of p-toluenethiol (PTT) into p-tolyl disulfide (PTD) and H2, which realizes the simultaneous utilization of photogenerated electrons and holes and establishes a closed-loop system with zero waste discharge. [Display omitted] •ReSe2/ZnIn2S4 is first constructed for photocatalytic dehydrogenation of thiols.•Cooperative S-S coupling and H2 production is realized devoid of waste discharge.•The emergence of the robust IEF drives the spatial charge separation.•ReSe2 provides active sites to promote H2 evolution and enhances thiols adsorption.•The ReSe2/ZnIn2S4 delivers 5 times higher photocatalytic activity than the blank ZIS. Photocatalytic anaerobic dehydrogenation provides a new avenue to cooperatively produce clean fuels and fine chemicals, while minimizing waste discharge and reducing environmental impact. Here, we demonstrate an efficient co-production of disulfides and H2 via photocatalytic S-S dehydrogenation of thiols using a two-dimensional (2D) heterostructure of ultrathin ZnIn2S4 (ZIS) nanosheets decorated with dispersed (1T phase) ReSe2 nanoparticles. Experimental characterizations and DFT calculations reveal that integrating ReSe2 with ZIS leads to the formation of a robust internal electric field (IEF) within the ReSe2/ZIS heterostructure. The distorted 1T phase ReSe2 with abundant active Se sites and a high Fermi level induces downward band bending of ZIS at the interface, which promotes charge separation and expedites H2 evolution. Moreover, the introduction of ReSe2 provides more adsorptive sites, increasing the concentration of reactants on the catalyst surface. This enhancement fosters surface interactions between the catalyst and p-toluenethiol (PTT), ultimately accelerating the reaction rate. The optimal H2 and S-S coupling p-tolyl disulfide (PTD) production rates of the 5 wt% ReSe2/ZIS composite reach 2275 and 2303 µmol g−1h−1, respectively, approximately 5 times greater than those of blank ZIS. Importantly, the selectivity of PTD reaches 98.4 %. This visible-light-driven dehydrogenation process aligns with the principles and objectives of green chemistry, realizing high atom economy without generating byproducts. It is anticipated to open new sustainable and friendly routes for synthesizing high-value chemicals and producing clean energy.