物理化学学报2022，Vol.38Issue(10)：65-72,8.DOI:10.3866/PKU.WHXB202206019
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
Selective Hydrogenation of 5-(Hydroxymethyl)furfural to 5-Methylfurfural by Exploiting the Synergy between Steric Hindrance and Hydrogen Spillover
摘要
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 hvdrogenation 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.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Key words
Biomass/5-Hydroxymethylfurfural/Selective hydrodeoxygenation/Steric hindrance/Hydrogen spillover分类
化学化工引用本文复制引用
李少鹏,郑黎荣,韩布兴,赵美廷,刘会贞,杜靖,张彬,刘艳贞,梅清清,孟庆磊,董明华,杜鹃,赵志娟..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[J].物理化学学报,2022,38(10):65-72,8.基金项目
Foundation of China(21871277,21603235,21403248,21905195),China Postdoctoral Science Foundation(2021M702435),and Beijing Municipal Science&Technology Commission(Z191100007219009).国家重点研发计划(2017YFA0403003,2017YFA0403101),国家自然科学基金(21871277,21603235,21403248,21905195),中国博士后科学基金(2021M702435)及北京市科技计划(Z191100007219009)资助 （21871277,21603235,21403248,21905195）
