Selective hydrogenation of 5-(hydroxymethyl)furfural to 5-methylfurfural over single atomic metals anchored on Nb2O5

Shaopeng Li; Minghua Dong; Junjuan Yang; Xiaomeng Cheng; Xiaojun Shen; Shulin Liu; Zhi-Qiang Wang; Xue-Qing Gong; Huizhen Liu; Buxing Han

doi:10.1038/s41467-020-20878-7

Selective hydrogenation of 5-(hydroxymethyl)furfural to 5-methylfurfural over single atomic metals anchored on Nb₂O₅

Nat Commun. 2021 Jan 26;12(1):584. doi: 10.1038/s41467-020-20878-7.

Authors

Shaopeng Li^{1

2}, Minghua Dong^{1

2}, Junjuan Yang¹, Xiaomeng Cheng^{1

2}, Xiaojun Shen^{1

2}, Shulin Liu^{1

2}, Zhi-Qiang Wang³, Xue-Qing Gong⁴, Huizhen Liu^{5

6

7}, Buxing Han^{8

9

10}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China.
² School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, 100190, Beijing, China.
³ Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 200237, Shanghai, China. zhiqiangwang@ecust.edu.cn.
⁴ Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 200237, Shanghai, China. xgong@ecust.edu.cn.
⁵ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China. liuhz@iccas.ac.cn.
⁶ School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, 100190, Beijing, China. liuhz@iccas.ac.cn.
⁷ Physical Science Laboratory, Huairou National Comprehensive Science Center, 101407, Beijing, China. liuhz@iccas.ac.cn.
⁸ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China. hanbx@iccas.ac.cn.
⁹ School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, 100190, Beijing, China. hanbx@iccas.ac.cn.
¹⁰ Physical Science Laboratory, Huairou National Comprehensive Science Center, 101407, Beijing, China. hanbx@iccas.ac.cn.

Abstract

5-Methylfurfural (MF) is a very useful chemical. Selective hydrogenation of biomass platform molecule 5-(hydroxymethyl)furfural (HMF) to MF using H₂ as the reducing agent is very attractive, but challenging because hydrogenation of C=O bond in HMF is more favourable than C-OH both kinetically and thermodynamically, and this route has not been realized. In this work, we prepare isolated single atomic catalysts (SACs) Pt₁/Nb₂O₅-Ov, Pd₁/Nb₂O₅-Ov, and Au₁/Nb₂O₅-Ov, in which single metal atoms are supported on oxygen defective Nb₂O₅ (Nb₂O₅-Ov). It is discovered that the SACs can efficiently catalyze the hydrogenation of HMF to MF using H₂ as the reducing agent with MF selectivity of >99% at complete conversion, while the selectivities of the metal nanocatalysts supported on Nb₂O₅ are very poor. A combination of experimental and density function theory (DFT) studies show that the unique features of the SACs for the reaction result from the cooperation of the Nb and Pt sites near the interface in the Pt₁/Nb₂O₅-Ov. The Pt atoms are responsible for the activation of H₂ and the Nb sites activate C-OH in the reaction. This work opens the way for producing MF by direct hydrogenation of biomass-derived HMF using H₂ as the reductant.

Publication types

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