燃料化学学报2013，Vol.41Issue(6)：657-666,10.
木质素模化物紫丁香酚热解机理的量子化学研究
Studies on pyrolysis mechanism of syringol as lignin model compound by quantum chemistry
摘要
Abstract
The pyrolysis of syringol as lignin model compound was investigated using density functional theory methods at B3LYP/6-31 G++ (d,p) level.Three possible pyrolytic pathways were proposed and the equilibrium geometries of the reactants,transition states,intermediate and products were fully optimized.The standard kinetic parameters in each reaction pathway were calculated and the formation and evolution mechanism of main pyrolysis products were analyzed.Bond dissociation energies calculation results show that the bond dissociation energy of CH3-O of syringol is the lowest and the order of all kinds of bond dissociation energy is CH3-O ＜ O-H ＜ CH3O-Caroomatic＜ CH2-H ＜ HO-Caromatic＜ Caromatic-H.In reaction pathway 1 and 2,the main pyrolysis product is 3-methoxycatechol and 2-methoxy-6-methylphenol,respectively.The total energy barrier is 366.6 and 474.8 kJ/mol in pathway 1 and 2,respectively.For reaction pathway 3,the total energy barrier of omethoxyphenol formation is as low as 21.4 kJ/mol,which shows that addition of hydrogen to the carbon atom connected with methoxyl can effectively lower the reaction energy barrier of demethoxy reaction of lignin model syringol.关键词
木质素/紫丁香酚/热解机理/密度泛函理论Key words
lignin/ syringol/ pyrolysis mechanism/ density functional theory分类
能源与动力引用本文复制引用
黄金保,刘朝,任丽蓉,童红,李伟民,伍丹..木质素模化物紫丁香酚热解机理的量子化学研究[J].燃料化学学报,2013,41(6):657-666,10.基金项目
国家自然科学基金(51266002) （51266002）
贵州省科学技术基金(黔科合J字[2012]2188号) （黔科合J字[2012]2188号）
低品位能源利用技术及系统教育部重点实验室开放基金(LLEUTS-201303). （LLEUTS-201303）
