Hydrogen Activation via Dihydride Formation on a Rh ₁ /Fe ₃ O ₄ (001) Single‐Atom Catalyst

Hydrogen activation is a key elementary step in catalytic hydrogenation. In heterogeneous catalysis, it usually proceeds through dissociative adsorption on metal nanoparticles followed by surface diffusion or spillover, whereas homogeneous catalysts activate H₂ through dihydride or dihydrogen intermediates at a single metal center. Here, we show that isolated Rh adatoms supported on Fe₃O₄(001) activate hydrogen through formation of a stable dihydride species without atomic H spillover. Temperature-programmed desorption, x-ray photoelectron spectroscopy, and scanning tunneling microscopy collectively reveal strong (≈1 eV) hydrogen adsorption exclusively at isolated Rh₁ sites, while isotope-exchange experiments further demonstrate that hydrogen remains localized. Density-functional theory-based calculations indicate a barrierless conversion from molecular H₂ to the dihydride, and random-phase approximation calculations further confirm the relative stability of the dihydride. Together, these results show that single-atom Rh sites cleave hydrogen through a dihydride pathway analogous to homogeneous complexes, establishing a mechanistic bridge between homogeneous and heterogeneous catalysis.