物理化学学报 >> 2022, Vol. 38 >> Issue (10): 2206019.doi: 10.3866/PKU.WHXB202206019

所属专题: 生物质催化转化

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利用空间位阻和氢溢流协同作用促进5-羟甲基糠醛选择性加氢制备5-甲基糠醛

李少鹏1,2,3, 杜靖3, 张彬1, 刘艳贞1, 梅清清1, 孟庆磊1,3, 董明华1,2, 杜鹃1, 赵志娟1, 郑黎荣4, 韩布兴1,2,5, 赵美廷3,*(), 刘会贞1,2,5,*()   

  1. 1 中国科学院化学研究所胶体界面与热力学重点实验室, 北京分子科学国家实验室, 北京 100190
    2 中国科学院大学化学科学学院, 北京 100049
    3 天津大学分子聚集态科学研究院, 天津 300072
    4 中国科学院高能物理研究所, 北京 100049
    5 怀柔综合性国家科学中心物理科学实验室, 北京 101407
  • 收稿日期:2022-06-14 录用日期:2022-07-21 发布日期:2022-07-29
  • 通讯作者: 赵美廷,刘会贞 E-mail:mtzhao@tju.edu.cn;liuhz@iccas.ac.cn
  • 基金资助:
    国家重点研发计划(2017YFA0403003);国家重点研发计划(2017YFA0403101);国家自然科学基金(21871277);国家自然科学基金(21603235);国家自然科学基金(21403248);国家自然科学基金(21905195);中国博士后科学基金(2021M702435);北京市科技计划(Z191100007219009)

Selective Hydrogenation of 5-(Hydroxymethyl)furfural to 5-Methylfurfural by Exploiting the Synergy between Steric Hindrance and Hydrogen Spillover

Shaopeng Li1,2,3, Jing Du3, Bin Zhang1, Yanzhen Liu1, Qingqing Mei1, Qinglei Meng1,3, Minghua Dong1,2, Juan Du1, Zhijuan Zhao1, Lirong Zheng4, Buxing Han1,2,5, Meiting Zhao3,*(), Huizhen Liu1,2,5,*()   

  1. 1 Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
    2 School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
    3 Institute of Molecular Aggregation Science, Tianjin University, Tianjin 300072, China
    4 Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
    5 Physical Science Laboratory, Huairou National Comprehensive Science Center, Beijing 101407, China
  • Received:2022-06-14 Accepted:2022-07-21 Published:2022-07-29
  • Contact: Meiting Zhao,Huizhen Liu E-mail:mtzhao@tju.edu.cn;liuhz@iccas.ac.cn
  • About author:Huizhen Liu, E-mail: liuhz@iccas.ac.cn
    Meiting Zhao, E-mail: mtzhao@tju.edu.cn
  • Supported by:
    the National Key Research and Development Program of China(2017YFA0403003);the National Key Research and Development Program of China(2017YFA0403101);National Natural Science Foundation of China(21871277);National Natural Science Foundation of China(21603235);National Natural Science Foundation of China(21403248);National Natural Science Foundation of China(21905195);China Postdoctoral Science Foundation(2021M702435);Beijing Municipal Science & Technology Commission(Z191100007219009)

摘要:

化学工业生产中,用氢气为还原剂,通过选择性加氢可以制备多种重要化学品。5-羟甲基糠醛是重要的生物质基平台化合物,而5-甲基糠醛是用途广泛的化学品。由5-羟甲基糠醛加氢得到5-甲基糠醛是一条非常理想的路径,但是选择性活化C-OH非常困难。本文设计并制备了Pt@PVP/Nb2O5(PVP: 聚乙烯吡咯烷酮)催化剂,该催化体系巧妙地结合了位阻效应、氢溢流和催化剂界面的电子效应,系统研究了该催化剂对5-羟甲基糠醛选择性加氢制备5-甲基糠醛催化性能,在最优条件下,5-甲基糠醛的选择性可达92%。利用密度泛函理论计算研究了5-羟甲基糠醛选择性加氢制备5-甲基糠醛反应路径。

关键词: 生物质, 5-羟甲基糠醛, 选择性加氢脱氧反应, 空间位阻, 氢溢流

Abstract:

Selective hydrogenation is a vital class of reaction. Various unsaturated functional groups in organic compounds, such as aromatic rings, alkynyl (C≡C), carbonyl (C=O), nitro (-NO2), and alkenyl (C=C) groups, are typical targets in selective hydrogenation. Therefore, selectivity is a key indicator of the efficiency of a designed hydrogenation reaction. 5-(Hydroxymethyl)furfural (HMF) is an important platform compound in the context of biomass conversion, and recently, the hydrogenation of HMF to produce fuels and other valuable chemicals has received significant attention. Controlling the selectivity of HMF hydrogenation is paramount because of the different reducible functional groups (C=O, C-OH, and C=C) in HMF. Moreover, the exploration of new routes for hydrogenating HMF to valuable chemicals is becoming attractive. 5-Methylfurfural (MF) is also an important organic compound; thus, the selective hydrogenation of HMF to MF is an essential synthetic route. However, this reaction has challenging thermodynamic and kinetic aspects, making it difficult to realize. Herein, we propose a strategy to design a highly efficient catalytic system for selective hydrogenation by exploiting the synergy between steric hindrance and hydrogen spillover. The design and preparation of the Pt@PVP/Nb2O5 catalyst (PVP = polyvinyl pyrrolidone; Nb2O5 = niobium(V) oxide) were also conducted. Surprisingly, HMF could be converted to MF with 92% selectivity at 100% HMF conversion. The reaction pathway was revealed through the combination of control experiments and density functional theory calculations. Although PVP blocked HMF from accessing the surface of Pt, hydrogen (H2) could be activated on the surface of Pt due to its small molecular size, and the activated H2 could migrate to the surface of Nb2O5 through a phenomenon called H2 spillover. The Lewis acidic surface of Nb2O5 could not adsorb the C=O group but could adsorb and activate the C-OH group of HMF; therefore, when HMF was adsorbed on Nb2O5, the C-OH groups were hydrogenated by the spilled over H2 to form MF. The high selectivity of this reaction was realized because of the unique combination of steric effects, hydrogen spillover, and tuning of the electronic states of the Pt and Nb2O5 surfaces. This new route for producing MF has great potential for practical application owing to its discovered advantages. We believe that this novel strategy can be used to design catalysts for other selective hydrogenation reactions. Furthermore, this study demonstrates a significant breakthrough in selective hydrogenation, which will be of interest to researchers working on the utilization of biomass, organic synthesis, catalysis, and other related fields.

Key words: Biomass, 5-Hydroxymethylfurfural, Selective hydrodeoxygenation, Steric hindrance, Hydrogen spillover

MSC2000: 

  • O643