Investigation of hydrogen spillover in atomically dispersed metal on <scp>WO₃</scp> for selective hydrogenation

Abstract Optimizing kinetic barriers of hydrogen spillover for selective hydrogenation on supported catalysts with dual‐active sites faces a significant challenge due to inherent contradiction between H 2 activation and *H transformation from metal to support. Herein, the adsorption energy of *H ( E ad (H)) on metal has been demonstrated as a viable descriptor for understanding hydrogenation on the WO 3 surface with dual‐active sites of single‐atom metals and oxygen vacancies. Theoretical simulations rationalize the optimized value of E ad (H) of −2.49 eV for these dual‐active sites. Furthermore, the absolute value (|Δ E ad (H)|) between E ad (H) and −2.49 eV was calculated to directly explore the catalytic activity of M 1 /NR‐WO 3 . Among them, the Pt 1 /NR‐WO 3 catalysts with the lowest |Δ E ad (H)| exhibited the weakened *H adsorption and enabled efficient H 2 activation, resulting in a TOF value of 170,480 h −1 and &gt;99.9% selectivity for the hydrogenation of p ‐chloronitrobenzene to p ‐chloroaniline. These findings provide new insights into the hydrogen spillover‐promoted selective hydrogenation.