木质纤维素中C–O键选择性活化和高效转化制化学品（英文）  

Selective activation of the C–O bonds in lignocellulosic biomass for the efficient production of chemicals

作　　者：邓卫平[1] 张宏喜[2] 薛来奇[2] 张庆红[1] 王野[1] 

机构地区：[1]厦门大学化学化工学院,能源材料化学协同创新中心,固体表面物理化学国家重点实验室,醇醚酯化工清洁生产国家工程实验室,福建厦门361005 [2]昌吉学院化学与应用化学系,新疆昌吉831100

出　　处：《催化学报》2015年第9期1440-1460,共21页

基　　金：supported by National Natural Science Foundation of China(21173172,21473141);the Research Fund for the Doctorial Program of Higher Education(20130121130001);the Program for Innovative Research Team in University(IRT_14R31)~~

摘　　要：高效转化来源丰富且可再生的木质纤维素制备化学品和燃料对建立可持续发展社会具有重要意义.木质纤维素利用的一条理想途径是将其主要成分纤维素、半纤维素和木质素在温和条件下高选择性地催化转化为关键平台化学品.本文综述了近年报道的有关纤维素、半纤维素和木质素或其模型分子中C–O键选择性活化生成葡萄糖、葡萄糖衍生物(包括葡萄糖苷、六元醇和葡萄糖酸)、木糖、阿拉伯糖和芳香化合物的新催化剂和新策略,阐述了决定催化性能的关键因素.本文还讨论了相关反应机理以深入理解C–O键选择性活化.纤维素由葡萄糖单元通过β-1,4-糖苷键连接而成,通过水解反应,选择性切断这些糖苷键可以获得葡萄糖或其低聚物.鉴于葡萄糖在水热条件下不稳定,发展纤维素温和条件下水解的酸催化剂至关重要.众多研究表明,均相酸催化剂(如无机酸,杂多酸等)具有强Br?nsted酸,在该水解反应中显示高的催化活性.另一方面,拥有强酸性基团-SO3H的固体酸也表现出优异的水解糖苷键性能,但是-SO3H官能团易于流失,限制了这类固体酸催化剂的循环使用.最近研究显示,一些催化剂尤其是碳材料上引入能够与纤维素形成氢键的官能团时,其催化纤维素水解性能显著增强.设计合成这类具备酸性位和氢键位协同效应的稳定固体酸催化剂是纤维素水解转化的一个颇具前景的研究方向.以醇替代水为溶剂实施纤维素醇解制葡萄糖苷是高效活化糖苷键的有效策略.杂多酸被证实为该醇解反应的高性能催化剂.在相同反应条件下,醇解产物葡萄糖苷较水解产物葡萄糖更为稳定,因此可以获得高的葡萄糖苷收率.开发稳定可重复利用的固体酸催化剂是纤维素醇解的关键.耦合水解与加氢或氧化反应可以直接将纤维素转化为相对稳定且具有广泛用途的多元醇或有机酸.目前已有一系The efficient transformation of abundant and renewable lignocellulosic biomass for the production of chemicals and fuels is of considerable importance for establishing a sustainable society. The selective catalytic conversion of the major components of lignocellulosic biomass, including cellulose, hemicellulose and lignin, into key platform chemicals under mild conditions represents an ideal route for the utilization of this abundant resource. Cellulose is composed of multiple glucose units, which are linked together through β-1,4-glycosidic bonds, and the selective cleavage of these glycosidic bonds would therefore provide access to glucose and glucose derivatives. Hemicellulose is a heteropolysaccharide composed of different sugar units such as glucose, mannose, xylose, arabinose and galactose. The selective cleavage of the glycosidic bonds in hemicelluloses would therefore provide a mixture of different sugars. In contrast to cellulose and hemicellulose, lignin is a complex macropolymer consisting of methoxylated phenylpropane structures. Furthermore, lignin contains a variety of different C–O bond types, including β-O-4, α-O-4 and 4-O-5 bonds, which connect the primary aromatic units in lignin. The selective cleavage of these C–O bonds would therefore lead to the formation of high-value aromatic compounds. In this review article, we have provided a detailed summary of recent advances towards the development of new catalysts and novel strategies for the selective cleavage of the C–O bonds in cellulose, hemicellulose and lignin, as well as closely related model systems, for the production of glucose, glucose derivatives（including alkyl glucosides, hexitols and gluconic acid）, xylose, arabinose and aromatic compounds. The key factors determining catalytic performances have been described in detail. The reaction mechanisms have also been discussed to provide the reader with a deeper understanding of the processes involved in the selective activation of C–O bonds.

关 键 词：生物质 纤维素 半纤维素 木质素 碳-氧键活化 

分 类 号：O636.11[理学—高分子化学]