A Durable Nickel Single‐Atom Catalyst for Hydrogenation Reactions and Cellulose Valorization under Harsh Conditions. (9th May 2018)

• Record Type: Journal Article
• Authors: Liu, Wengang; Chen, Yinjuan; Qi, Haifeng; Zhang, Leilei; Yan, Wensheng; Liu, Xiaoyan; Yang, Xiaofeng; Miao, Shu; Wang, Wentao; Liu, Chenguang; Wang, Aiqin; Li, Jun; Zhang, Tao
• Is Part Of: Angewandte Chemie. Volume 130:Number 24(2018)
• Page Start: 7189
• Page End: 7193
• Publication Date: 2018-05-09
• Subjects: Aktive Zentren -- Biomasseumwandlung -- Einzelatomkatalysatoren -- Nickel -- XANES-Simulation; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201802231
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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.