林产化学与工业2017，Vol.37Issue(1)：43-53,11.DOI:10.3969/j.issn.0253-2417.2017.01.006
磷酸催化β-D-吡喃葡萄糖热解脱水反应的密度泛函理论研究
Pyrolytic Dehydration Reactions of β-D-Glucopyranose Catalyzed byPhosphoric Acid Using Density Functional Theory
摘要
Abstract
In order to investigate the catalytic mechanism that the dehydration reactions will be promoted by phosphoric acid in pyrolysis process, β-D-glucopyranose is selected as the model compound of cellulose, and the mechanism of pyrolytic dehydration reactions catalyzed by phosphoric acid is investigated using density functional theory method.The results indicate that during catalytic pyrolysis process, β-D-glucopyranose and phosphoric acid will interact to form several possible reaction complexes through hydrogen bonds.Different reaction complexes can initiate different 1,2-dehydration and 1,3-dehydration reactions of β-D-glucopyranose.Compared with the non-catalytic process, the activation energies of dehydration reactions decrease greatly in the phosphoric acid catalyzed process.The activation energies decrease by 79-129 kJ/mol for the eight 1,2-dehydration reactions, and 28~60 kJ/mol for the two 1,3-dehydration reactions.In addition, 1,2-dehydration is easier to occur than 1,3-dehydration in the catalytic process.And the 1,2-dehydration at 4-OH+3-H, 1-OH+2-H and 3-OH+2-H/4-H sites are predominant in the catalytic pyrolysis process.关键词
催化热解/磷酸/脱水反应/纤维素/葡萄糖/密度泛函理论Key words
catalytic pyrolysis/phosphoric acid/dehydration reactions/cellulose/glucose/density functional theory分类
化学化工引用本文复制引用
胡斌,陆强,蒋晓燕,张镇西,董长青..磷酸催化β-D-吡喃葡萄糖热解脱水反应的密度泛函理论研究[J].林产化学与工业,2017,37(1):43-53,11.基金项目
国家自然科学基金资助项目(51576064) （51576064）
中央高校基本科研业务费专项资金资助(2016YQ05,2015ZZD02) （2016YQ05,2015ZZD02）
