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

Wengang Liu; Yinjuan Chen; Haifeng Qi; Leilei Zhang; Wensheng Yan; Xiaoyan Liu; Xiaofeng Yang; Shu Miao; Wentao Wang; Chenguang Liu; Aiqin Wang; Jun Li; Tao Zhang

doi:10.1002/anie.201802231

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

Angew Chem Int Ed Engl. 2018 Jun 11;57(24):7071-7075. doi: 10.1002/anie.201802231. Epub 2018 May 9.

Authors

Wengang Liu^{1

2}, Yinjuan Chen^{3

4}, Haifeng Qi^{1

2}, Leilei Zhang¹, Wensheng Yan⁵, Xiaoyan Liu¹, Xiaofeng Yang¹, Shu Miao¹, Wentao Wang¹, Chenguang Liu⁴, Aiqin Wang¹, Jun Li³, Tao Zhang¹

Affiliations

¹ State Key Laboratory of Catalysis, and Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 ZhongShan Road, Dalian, 116023, China.
² University of Chinese Academy of Sciences, Beijing, 100049, China.
³ Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
⁴ State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (East China), Qingdao, Shandong, 266580, China.
⁵ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, China.

PMID: 29683255
DOI: 10.1002/anie.201802231

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.

Keywords: XANES simulation; active sites; biomass conversion; nickel; single-atom catalysts.

Publication types

Research Support, Non-U.S. Gov't