&#x003b1;&#x02014;O&#x02014;4型木质素二聚体分子间相互作用机理研究

崔达; 尹鹤霖; 吴爽; 刘斌; 王琦; 王擎

doi:10.19912/j.0254-0096.tynxb.2023-0679

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太阳能学报 ›› 2024, Vol. 45 ›› Issue (9) : 595-602. DOI: 10.19912/j.0254-0096.tynxb.2023-0679

α—O—4型木质素二聚体分子间相互作用机理研究

崔达¹, 尹鹤霖¹, 吴爽¹, 刘斌², 王琦², 王擎¹

作者信息 +

STUDY ON MECHANISM OF INTERMOLECULAR INTERACTION IN α—O—4 TYPE LIGNIN DIMER

Cui Da¹, Yin Helin¹, Wu Shuang¹, Liu Bin², Wang Qi², Wang Qing¹

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文章历史 +

摘要

不同于传统单分子分解机制,聚焦双分子反应热解机理,采用密度泛函理论（DFT）的GGA/RPBE方法,选取α—O—4型木质素二聚体模型化合物苄基苯基醚（BPE）为研究对象,确定其中存在的分子间相互作用关系以及关键产物在热解过程中形成的化学途径,并重点研究木质素中取代基对分子间相互作用关系产生的影响。研究结果表明,在单分子反应中,取代基会提高各个键的活性,CH₃取代基会促进C—O键的均裂。木质素分子与自由基之间存在强烈的相互作用,但取代基会抑制分子间相互作用关系,且取代基上H自由基参与反应的意向弱于木质素连接键上的H自由基。4种α—O—4型木质素脱氢二聚体自由基主要可能发生均裂的键是O—C_芳香族键,而非C_α—O键。

Abstract

Different from the traditional unimolecular decomposition mechanism, focusing on the bimolecular reaction pyrolysis mechanism, the α—O—4 type lignin dimer model compound benzyl phenyl ether （BPE） is selected as the research object. The density functional theory （DFT） GGA/RPBE method and DNP basis set are used to perform geometric optimization and frequency calculations on the reactants, intermediates, transition states, and products during the pyrolysis process. The study focuses on the impact of substituents in lignin on the intermolecular interaction relationships. The results show that substituents will increase the activity of each chemical bond in unimolecular reactions, for example, CH₃ substituents will significantly promote the homolytic cleavage of C—O bonds. For bimolecular reactions, although intense interactions exist between lignin molecules and free radicals, it is proved that the presence of substituents can inhibit the molecular interaction relationship. Furthermore, the H radicals on the substituents display weaker reactivity compared to those on the lignin—linked bonds. The O—C_aromatic homolytic cleavage dominates the primary reaction pathway for dehydrodimer radicals, rather than the C_α—O bond.

导出引用

崔达, 尹鹤霖, 吴爽, 刘斌, 王琦, 王擎. α—O—4型木质素二聚体分子间相互作用机理研究[J]. 太阳能学报. 2024, 45(9): 595-602 https://doi.org/10.19912/j.0254-0096.tynxb.2023-0679

Cui Da, Yin Helin, Wu Shuang, Liu Bin, Wang Qi, Wang Qing. STUDY ON MECHANISM OF INTERMOLECULAR INTERACTION IN α—O—4 TYPE LIGNIN DIMER[J]. Acta Energiae Solaris Sinica. 2024, 45(9): 595-602 https://doi.org/10.19912/j.0254-0096.tynxb.2023-0679

中图分类号： TK6

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