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Therefore, a better understanding of pathway for char formation is significant and highly desired for lignin valorization. In this work, we propose a fundamental mechanistic insight into char formation in lignin depolymerization, using hydrothermal decomposition as model reaction. The results demonstrate that the char featuring a multi\u2010layer construction of coke and oligomer contains mainly G units, primarily generated from native G\u2010lignin and demethoxylation of S\u2010lignin. Instead, H\u2010lignin contributes to the formation of volatile monophenols. Furthermore, new methylene bridges form between the benzene rings in lignin, which consequently results in the formation of recalcitrant char. Based on these observations, a plausible mechanism for char formation is proposed and verified by the density functional theory calculation.<\/jats:p>","DOI":"10.1002\/cssc.202300978","type":"journal-article","created":{"date-parts":[[2023,8,7]],"date-time":"2023-08-07T04:33:53Z","timestamp":1691382833000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Mechanistic Insights into Formation of Residual Solid in Lignin Depolymerization"],"prefix":"10.1002","volume":"16","author":[{"given":"Kaiqi","family":"Lv","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering State Key Laboratory of Pulp and Paper Engineering South China University of Technology  Guangzhou 510640 P.R. 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