The Role of Frustrated Lewis Pair in Catalytic Transfer Hydrogenation of Furfural using Nickel Single‐Atom Catalysts: A Theoretical Study

Abstract

The burgeoning field of frustrated Lewis pair (FLP) heterogeneous catalysts has garnered significant interest in recent years, primarily due to their inherent ability to activate H‐source molecules, such as H2, thereby facilitating hydrogenation reactions. However, the application of single metal atom catalysts incorporating FLP sites has been relatively under‐explored. In this study, non‐precious transition metal atoms were anchored onto a C2N framework with an intrinsic cavity and a defective N‐C sheet. Theoretical calculations substantiated energy barriers as low as 0.10 eV for isopropanol activation, thereby positioning these catalysts as highly promising candidates for catalytic transfer hydrogenation of furfural. Electronic structure analyses revealed that the H‐O bond breakage in isopropanol molecules was significantly facilitated by the presence of FLP sites within the catalysts. Notably, both Ni‐C2N and Ni‐N6‐C demonstrated exceptional potential as selective catalysts for the hydrogenation of furfural into furfuryl alcohol, exhibiting remarkably low barriers of only 0.65‐0.72 eV for the rate‐determining steps, which are notably lower than those observed in many traditional catalysts. Theoretical investigations strongly imply that the construction of single atom catalysts with FLP sites could significantly enhance the activity and selectivity for hydrogenation reactions, thus stimulating the experimental synthesis of such catalysts.