Describing H* adsorption on dual-active sites of single-atom-metals and frustrated-Lewis-pairs for reverse water-gas shift reaction

Acquiring descriptors to guide catalyst design is an ideal but challenging topic in the field of heterogeneous catalysis. Herein, the adsorption energy of H* (E_ad(H)) has been established to describe the catalytic activity of dual-active sites of single-atom metals and frustrated Lewis pairs (FLPs) on the porous nanorod of CeO₂ surface (M₁/PN-CeO₂) for reverse water-gas shift (RWGS) reaction. H₂ and CO₂ molecules are adsorbed and activated on single-atom metals and FLP sites, respectively, facilitating the RWGS reaction through the H* spillover from single-atom metals to PN-CeO₂ supports. Mechanistic investigations illustrate that the generation of H* on the single-atom metals and subsequent migration towards FLP are critical steps, determining the performance of M₁/PN–CeO₂ for RWGS reaction. A volcanic correlation is observed between E_ad(H) and catalytic activity of M₁/PN–CeO₂ for RWGS. The Pt₁/PN–CeO₂ catalysts with a minimal deviation of −0.01 eV from the experimentally optimized E_ad(H) of −1.88 eV, exhibited an exceptional turnover frequency of 33,605 h⁻¹ and surpassed a turnover number of 20,000,000 for each Pt active site during a period of 650 h at 600 °C. These findings could pave the way for the rational design of highly active and durable catalysts for RWGS reaction.