Density Functional Theory Study of the Concerted Pyrolysis Mechanism for Lignin Models
Density Functional Theory Study of the Concerted Pyrolysis Mechanism for Lignin Models
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DOI：
10.1021/ef5013648
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发表时间：
2014-08-01
期刊：
影响因子：
5.3
通讯作者：
Beste, Ariana
中科院分区：
文献类型：
--
作者：
Elder, Thomas;Beste, Ariana
对木质素模型化合物热解机理的研究主要集中在初始均解裂解反应上。然而，已经注意到，协同机制也可以解释观察到的产物形成。在本工作中，通过应用密度泛函理论对全取代木素模型进行计算，对后一种过程进行了检验，并与前一种过程进行了比较。结果表明，协同反应的活化能略低于均解反应的键离解能。动力学分析表明，这一协同途径是逆转的裂解机制。
Studies on the pyrolysis mechanisms of lignin model compounds have largely focused on initial homolytic cleavage reactions. It has been noted, however, that concerted mechanisms may also account for observed product formation. In the current work, the latter processes are examined and compared to the former, by the application of density functional theory calculations to fully substituted lignin models. Results show that activation energies for the concerted reactions are somewhat lower than the bond dissociation energies of the homolysis reactions. Kinetic analysis revealed that the concerted pathway is the retro-ene fragmentation mechanism.