Engineering interfacial hydrogen spillover for sulfur‑tolerant hydrogenation of nitroarenes with ppm‑level Pt

Intra-particle hydrogen (H) spillover is widely exploited in supported metal catalysts to boost hydrogenation performance, yet interfacial hydrogen spillover between particles remains less explored in liquid-phase hydrogenation. In this study, we demonstrate the activity enhancement achieved by rational regulation of intra/inter-particle H spillover of Pt/TiO 2 using 5-nitrobenzothiazole (NBZ) hydrogenation as a model reaction. By regulating intraparticle hydrogen spillover, we achieved a 17-fold increase in the reaction rate of Pt/TiO 2 with ppm-level Pt. Further leveraging interparticle hydrogen spillover between Pt/TiO 2 and Fe-TiO 2 enhanced the activity by an additional 2.3-fold, resulting in a conversion rate of 5232 h⁻ 1 . Detailed characterizations revealed that the balanced density of Ti 3+ and Pt exposure degree, and enhanced electron transfer properties significantly amplify interparticle H spillover capability. The generality of this strategy is confirmed by extending interparticle H spillover–promoted nitro group hydrogenation to CeO 2 , another prototypical reducible metal oxide. This work demonstrates that carefully tuning intra/inter-particle H spillover can unlock exceptional performance in the hydrogenation of strongly coordinating substrates having N or S atom that can be strongly adsorbed on the Pt surface.