Interfacial Dipole Engineering of Single‐Atom Co–N–C and Ru Nanoparticles for Enhanced Hydrogenation of Levulinic Acid to γ ‐Valerolactone

ABSTRACT

The catalytic hydrogenation of levulinic acid (LA) constitutes the central pathway for its conversion into high‐value γ ‐valerolactone (GVL); however, the prevailing challenge lies in enhancing its catalytic activity and stability under mild conditions. Herein, an interfacial dipole effect was established when single‐atom Co ₁ –N–C was used as a support to anchor Ru nanoparticles (Ru _NPs /Co ₁ –N–C), which led to the transfer of electrons from Co ₁ –N–C to Ru nanoparticles and maintenance of electron‐rich Ru. The Ru _NPs /Co ₁ –N–C catalyst exhibits enhanced catalytic performance in LA hydrogenation, achieving nearly complete conversion and 100% selectivity toward GVL under ambient conditions. The Ru _NPs /Co ₁ –N–C catalyst maintained its catalytic activity and selectivity over 10 consecutive cycles without noticeable deactivation, and the other 5 biomass‐derived compounds could also be effectively converted into corresponding lactone compounds. Density functional theory calculations reveal that the interfacial dipole effect of Ru _NPs /Co ₁ –N–C lowers the barriers of key kinetically relevant steps, particularly enabling near‐zero‐barrier H ₂ dissociation while lowering the activation barriers for subsequent hydrogenation and final dehydration steps. Therefore, through interfacial dipole engineering between the single‐atom support and nanoparticles, the electronic structure of the metal sites can be adjusted, thereby enhancing the activity and stability of the catalyst in biomass upgrading and hydrogenation reactions.