Unraveling the radical chain mechanism in the pyrolysis of β-O-4 linked lignin: The role of aliphatic substituents

Abstract

Lignin pyrolysis involves complex radical reactions, whereas the radical chain process, especially the influence of aliphatic substituents, has been rarely studied. Herein, the typical β-O-4 lignin dimer, phenethyl phenyl ether (PPE), and three aliphatic substituted derivatives of PPE, namely α-OH substituted, β-CH2OH substituted, and α,β-disubstituted PPE (αPPE, βPPE, and αβPPE) were employed as model compounds. DFT calculations, electronic analyses, and fast pyrolysis experiments were combined to investigate three core steps of the radical chain mechanism in lignin pyrolysis, i.e., homolysis, hydrogen abstraction, and radical decomposition. The pathway involving successive Cβ-O homolysis → α-hydrogen abstraction → Cβ-O breakage of α-dehydrogenated radical is dominated for the pyrolysis of aliphatic substituted β-O-4 linked lignin, with the formation of phenolics. The hydrogen abstraction reactions at the Cα site are obviously superior to those at other sites for PPE derivatives, due to the p-π conjugate stability. Notably, α-hydrogen abstraction can be significantly promoted by the π-electron-dispersing α-OH substitution. The decomposition step of dehydrogenated radicals can be facilitated by the electron-donating β-CH2OH substitution, where the Cβ-O breakage of the α-dehydrogenated radical is dominant. Totally, aliphatic substituents can improve the radical growth stage and change the competitiveness of the hydrogen abstraction and radical decomposition reactions. The fast pyrolysis experiments of PPE and αPPE gave direct proof that the generation of characteristic products from the radical chain process, i.e., benzaldehyde and phenylacetaldehyde, was enhanced by the α-OH substitution. The present work offers the potential to give a comprehensive image of the radical chain mechanism in lignin pyrolysis.