A Durable Nickel Single‐Atom Catalyst for Hydrogenation Reactions and Cellulose Valorization under Harsh Conditions

Hydrothermally stable, acid-resistant nickel catalysts are highly desired in hydrogenation reactions, but such a catalyst remains absent owing to the inherent vulnerability of nickel under acidic conditions. An ultra-durable Ni-N-C single-atom catalyst (SAC) has now been developed that possesses a remarkable Ni content (7.5 wt %) required for practical usage. This SAC shows not only high activities for hydrogenation of various unsaturated substrates but also unprecedented durability for the one-pot conversion of cellulose under very harsh conditions (245 °C, 60 bar H2 , presence of tungstic acid in hot water). Using integrated spectroscopy characterization and computational modeling, the active site structure is identified as (Ni-N4)⋅⋅⋅N, where significantly distorted octahedral coordination and pyridinic N constitute a frustrated Lewis pair for the heterolytic dissociation of dihydrogen, and the robust covalent chemical bonding between Ni and N atoms accounts for its ultrastability.