Shaopeng Li1,2, Minghua Dong1,2, Junjuan Yang1, Xiaomeng Cheng1,2, Xiaojun Shen1,2, Shulin Liu1,2, Zhi-Qiang Wang3, Xue-Qing Gong4, Huizhen Liu5,6,7, Buxing Han8,9,10. 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.
n class="Chemical">5-Methylfurfural (n class="Chemical">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 atomiccatalysts (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 Nb2O5are 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 Ptsites near the interface in the Pt1/Nb2O5-Ov. The Pt atoms are responsible for the activation of H2 and the Nbsites 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.
Authors: Junyi Du; Yan Huang; Zixiang Huang; Geng Wu; Bei Wu; Xiao Han; Cai Chen; Xusheng Zheng; Peixin Cui; Yuen Wu; Jun Jiang; Xun Hong Journal: JACS Au Date: 2022-05-06