A unique Co@CoO catalyst for hydrogenolysis of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran

Shuang Xiang, Lin Dong, Zhi-Qiang Wang, Xue Han, Luke L. Daemen, Jiong Li, Yongqiang Cheng, Yong Guo, Xiaohui Liu, Yongfeng Hu, Anibal J. Ramirez-Cuesta, Sihai Yang (), Xue-Qing Gong () and Yanqin Wang ()
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Shuang Xiang: East China University of Science and Technology
Lin Dong: East China University of Science and Technology
Zhi-Qiang Wang: East China University of Science and Technology
Xue Han: University of Manchester
Luke L. Daemen: Oak Ridge National Laboratory
Jiong Li: Chinese Academy of Sciences
Yongqiang Cheng: Oak Ridge National Laboratory
Yong Guo: East China University of Science and Technology
Xiaohui Liu: East China University of Science and Technology
Yongfeng Hu: Sinopec Shanghai Research Institute of Petrochemical Technology
Anibal J. Ramirez-Cuesta: Oak Ridge National Laboratory
Sihai Yang: University of Manchester
Xue-Qing Gong: East China University of Science and Technology
Yanqin Wang: East China University of Science and Technology

Nature Communications, 2022, vol. 13, issue 1, 1-9

Abstract: Abstract The development of precious-metal-free catalysts to promote the sustainable production of fuels and chemicals from biomass remains an important and challenging target. Here, we report the efficient hydrogenolysis of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran over a unique core-shell structured catalyst, Co@CoO that affords the highest productivity among all catalysts, including noble-metal-based catalysts, reported to date. Surprisingly, we find that the catalytically active sites reside on the shell of CoO with oxygen vacancies rather than the metallic Co. The combination of various spectroscopic experiments and computational modelling reveals that the CoO shell incorporating oxygen vacancies not only drives the heterolytic cleavage, but also the homolytic cleavage of H2 to yield more active Hδ− species, resulting in the exceptional catalytic activity. Co@CoO also exhibits excellent activity toward the direct hydrodeoxygenation of lignin model compounds. This study unlocks, for the first time, the potential of simple metal-oxide-based catalysts for the hydrodeoxygenation of renewable biomass to chemical feedstocks.

Date: 2022
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DOI: 10.1038/s41467-022-31362-9

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