Regulation of the\nProperties of Hydrogen Dissociation\nand Transfer in the Presence of S Atoms for Efficient Hydrogenations

The dissociation and spillover process of hydrogen is\none of the\nkey processes in hydrogenation reactions, but this process is very\nchallenging or even impossible in the presence of a S atom, as S atoms\ncan severely poison the surface of supported metal catalysts. Herein,\nwe report that the efficient dissociation and transfer of hydrogen\ncan be achieved in the presence of S poisoning over the synergetic\nprocess of hydrogen transfer units together with H<sub>2</sub> dissociation\nunits in the hydrogenation of 5-nitrobenzothiazole catalyzed by Pt/MoO<sub>3</sub>. Pt/MoO<sub>3</sub> showcases 99% conversion with ∼99%\nselectivity under mild reaction conditions and is one of the most\nactive catalysts reported so far for the hydrogenation of sulfur atom-containing\ncompounds. Mechanism studies, in situ characterization, and density\nfunctional theory calculations collectively demonstrate that the MoO<sub>3</sub> support, with H<sub>1.68</sub>MoO<sub>3</sub> as an intermediate,\nacts as a bridge for transferring H species between Pt sites and nitrobenzothiazole.\nThe unique H proton storage and release properties of in situ formed\nH<sub>1.68</sub>MoO<sub>3</sub> not only accelerate the breaking of\nthe N–O bond for the hydrogenation of 5-nitrobenzothiazole\nbut also prevent sulfur poisoning. This work provides a promising\nstrategy to tackle the current challenges in the catalytic hydrogenation\nof sulfur atom-containing compounds.