文献类型：期刊文献

英文题名：DFT insights into competitive pathways of gas evolution and char precursor formation in lignin pyrolysis

作者：Liu, Xuesong[1,2];Sun, Zhuang[3];Hungwe, Douglas[4];Tang, Longfei[1];Chen, Xueli[1];Wang, Yifei[1];Yu, Guangsuo[1];Wang, Fuchen[1];Ding, Lu[1,2,5]

机构：[1]East China Univ Sci & Technol, Inst Clean Coal Technol, Shanghai 200237, Peoples R China;[2]Engn Res Ctr Resource Utilizat Carbon Containing W, Shanghai 200237, Peoples R China;[3]Inst Sci Tokyo, Sch Environm & Soc, Dept Transdisciplinary Sci & Engn, 2-12-1 Ookayama,Meguro Ku, Tokyo 1528550, Japan;[4]Hosei Univ, Res & Dev Ctr, 4342 Aihara, Machida, Tokyo 1940298, Japan;[5]State Key Lab Chem Engn & Low Carbon Technol, Shanghai 200237, Peoples R China

年份：2025

卷号：526

外文期刊名：CHEMICAL ENGINEERING JOURNAL

收录：;EI(收录号：20254819590259);WOS:【SCI-EXPANDED(收录号:WOS:001630439100001)】；

基金：This work was supported by the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Lignin pyrolysis; Density functional theory; Competitive pathways; Char precursor formation; Gas evolution

摘要：This study systematically decodes the molecular-scale competition between volatile release and char formation during lignin pyrolysis via density functional theory (DFT) calculations on an S-type beta-O-4 lignin dimer. It reveals that initial dehydration generates a conjugated vinyl ether structure, which stabilizes the adjacent C beta-O bond (III-TS2: 348.72 kJ/mol) through p-pi conjugation and diverts pathway selectivity from ether cleavage to decarboxylation. The energy barriers and kinetic characteristics of major initiation reactions, including C beta-O bond scission (as low as 217.36 kJ/mol), decarboxylation (272.90 kJ/mol), and decarbonylation (318.84 kJ/ mol), were quantified and their good agreement with experimental gas evolution profiles was demonstrated. Diels-Alder cyclization-mediated condensation is kinetically and thermodynamically feasible, yet significantly influenced by steric and electronic effects. These insights provide a mechanistic basis for directing product distribution by regulating specific hydrogen-transfer events and pyrolysis conditions, facilitating the rational design of lignin valorization strategies.