O2引发木质素模型化合物气相氧化反应机理的理论研究,International Journal of Quantum Chemistry

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O2引发木质素模型化合物气相氧化反应机理的理论研究
International Journal of Quantum Chemistry ( IF 2.3 ) Pub Date : 2023-12-29 , DOI: 10.1002/qua.27298
Shuqi Dong ₁ , Hui Zhang ₁ , Xia Du ₁ , Tingyu Yao ₁ , Yan Shang ₁ , Liquan Jing ₂ , Jinguang Hu ₂

Affiliation

将可再生木质素转化为高附加值化学品是解决生物质资源利用不足造成的资源浪费的前瞻性策略。在此基础上，研究木质素高效转化为醛/酸及其反应机制已成为一个颇具吸引力的课题。利用密度泛函理论(DFT)在原子和分子水平上系统研究了O ₂引发的三种模型化合物的气相氧化反应机理。进一步详细揭示了酚羟基和羟甲基两个反应位点的氧化行为。在B3LYP/6-311+G( d,p)水平上获得了两条途径的21个可能的反应通道的势能表面信息。估计了取代基效应对反应能垒的影响。计算结果表明，酚羟基的反应活性比羟甲基强，因为反应吉布斯势垒低约4.9~8.7 kcal/mol。酚羟基位点和羟甲基位点的反应能垒随着甲氧基数量的增加而降低。揭示木质素模型化合物的氧化过程将为人们更深入地理解反应机理提供依据，并为进一步将木质素转化为高附加值化学品的实验研究提供理论支撑。

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Theoretical investigation on the reaction mechanisms of O2-initiated gas-phase oxidation of lignin model compounds

Transforming renewable lignin into high value-added chemicals is a forward-looking strategy to address the resource waste caused by insufficient utilization of biomass resources. On this basis, studying the efficient conversion of lignin to aldehydes/acids and their reaction mechanisms has become an attractive topic. A systematic investigation of the gas-phase oxidation reaction mechanisms of the three model compounds initiated by O₂ was carried out at the atomic and molecular levels by using density functional theory (DFT). Further revealing of oxidation behavior on two reaction sites of phenolic hydroxyl group and hydroxymethyl group were accomplished in detail. The potential energy surface information of 21 possible reaction channels of two pathways were obtained at B3LYP/6-311+G(d,p) level. The influence of substituent effects on the reaction energy barrier was estimated. The calculation results showed that the reactivity of phenolic hydroxyl group is stronger than that of hydroxymethyl group, because the reaction Gibbs potential barriers are lower by about 4.9–8.7 kcal/mol. The reaction energy barriers on phenolic hydroxyl group site and hydroxymethyl group site decrease with the increase of the number of methoxy groups. Revealing the oxidation processes of lignin model compounds will provide a deeper understanding on the reaction mechanism and provide theoretical support for further experimental research on the conversion of lignin into high value-added chemicals.

更新日期：2023-12-31

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