物理化学学报2022，Vol.38Issue(10)：21-34,14.DOI:10.3866/PKU.WHXB2022205032
纤维素及其衍生物催化脱氧转化制化学品
Heterogeneous Catalysis for Deoxygenation of Cellulose and Its Derivatives to Chemicals
摘要
Abstract
Biomass,as a renewable carbon resource in nature,has been considered as an ideal starting feedstock to produce various valuable chemicals,fuels,and materials,and thus,can help build a sustainable chemical industry.Because cellulose is one of the richest components in lignocellulosic biomass,the efficient transformation of cellulose plays a crucial role in biomass utilization.However,there are many oxygen-containing groups in cellulose,and therefore,the selective removal of particular functional groups from cellulose becomes an essential step in the synthesis of the chemicals or fuels that can meet the requirements set by current chemical industries.In the past decades,several efficient catalytic systems have been developed to selectively split the C—O bonds inside cellulose and its derivatives,thereby producing various valuable chemicals.In this review article,we highlight recent progress made in the selective deoxygenation of cellulose and its derived key platforms such as glucose and 5-hydroxymethyl furfural(HMF)into ethanol,dimethyl furfural(DMF),1,6-hexanediol(1,6-HD),and adipic acid.The selection of these reactions is primarily because these chemicals are of great significance in chemical industries.More importantly,the formation of these chemicals represents the cleavage of different C—O bonds in biomass molecules.For instance,the synthesis of ethanol requires cleaving of only one C—O bond and two C—C bonds of the glucose unit inside cellulose.If two or more C—O bonds in the sugar or sugar acids are cleaved,olefins,oxygen-reduced sugars,and adipic acid will be attained.HMF has a furan ring linked by hydroxyl/carbonyl groups,and hence,either a furanic compound(e.g.,DMF)or linear products(e.g.,1,6-HD and adipic acid)can be synthesized by selective removal of hydroxyl/carbonyl oxygen or ring oxygen atoms.This article focuses on the selective cleavage of particular C—O bonds via heterogeneous catalysis.Efficient catalytic systems using hydrogenolysis and/or deoxydehydration strategies for these transformations are discussed.Moreover,the functions of typical catalysts and reaction mechanisms are presented to obtain insight into the C—O bond cleavage in these biomass molecules.Additionally,other factors such as reaction conditions that also influence the deoxygenation performance are analyzed.We hope that these knowledge gained on the catalytic deoxygenation of cellulose and its derived platforms will promote the rational design of effective strategies or catalysts in the future utilization of lignocellulosic biomass.关键词
纤维素/糖类化合物/5-羟甲基糠醛/C—O键活化/催化脱氧Key words
Cellulose/Sugars/5-Hydroxymethyl furfural/C—O activation/Catalytic deoxygenation分类
化学化工引用本文复制引用
王伟,王瑶,占自祥,谭天,邓卫平,张庆红,王野..纤维素及其衍生物催化脱氧转化制化学品[J].物理化学学报,2022,38(10):21-34,14.基金项目
The project was supported by the National Key R&D program of China(2018YFB1501602)and the National Natural Science Foundation of China(22121001,22172127,91945301).国家重点研发计划(2018YFB1501602)和国家自然科学基金(22121001,22172127,91945301)资助 （2018YFB1501602）
