Hydrogen Activation via Dihydride Formation on a Rh₁/Fe₃O₄(001) Single‐Atom Catalyst

Abstract

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 H<inf>2</inf> through dihydride or dihydrogen intermediates at a single metal center. Here, we show that isolated Rh adatoms supported on Fe<inf>3</inf>O<inf>4</inf>(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 Rh<inf>1</inf> sites, while isotope-exchange experiments further demonstrate that hydrogen remains localized. Density-functional theory-based calculations indicate a barrierless conversion from molecular H<inf>2</inf> 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.