Hydrogen/Oxygen Transfer Mechanisms and Endogenous Methyl Features in Dealkaline Lignin Pyrolysis Revealed by Isotope Tracing

Lignin pyrolysis is a pivotal route for biomass valorization, yet the intricate radical reaction network involved results in ambiguous hydrogen/oxygen transfer pathways and product formation mechanisms, severely impeding precise control over directed conversion processes. This study employed a combination of multi-isotope tracing techniques and GC-MS analysis to elucidate the formation mechanisms of four phenolic products during the 500 °C hydrothermal pyrolysis of dealkaline lignin. Experiments using D2O and H218O revealed that the M + 2 signal was predominantly derived from double deuterium substitution, with an abundance difference spanning 13–81 folds. Phenol exhibited the highest M + 1 abundance (3.947) due to the full exposure of its exchangeable hydrogen sites, while its M + 2 abundance ranked second only to that of 2-methylphenol. For 2-methylphenol, the hyperconjugation effect of the ortho-methyl group activated the phenolic structure, leading to the highest M + 2 abundance among all products (M + 2/M + 1 = 2.3). In contrast, 3-methylphenol showed relatively low abundances (M + 2/M + 1 = 1.67) because the meta-methyl group lacked activating effects and introduced steric hindrance. For guaiacol, the steric hindrance of the methoxy group completely overshadowed its electronic activation effect, resulting in the lowest M + 2 abundance (1.545). CD3OD tracing experiments and the absence of detectable M + 3 peaks confirmed that the methyl groups in 2-methylphenol and 3-methylphenol were entirely endogenous to the structural units of lignin itself. By precisely tracking the migration pathways of hydrogen and oxygen, this study revealed that hydrogen transfer dominated the pyrolysis process, while oxygen transfer was hindered and methyl groups exhibited endogenous characteristics. These findings establish a mechanistic foundation for designing efficient catalysts tailored to lignin pyrolysis and for rationally steering product selectivity.