Computational study of bond dissociation enthalpies for a large range of native and modified Lignins

Seonah Kim, Stephen Chmely, Mark R. Nimlos, Yannick J. Bomble, Thomas D. Foust, Robert S. Paton, Gregg T. Beckham

Research output: Contribution to journalArticle

197 Scopus citations

Abstract

Lignin is a major component of plant cell walls that is typically underutilized in selective conversion strategies for renewable fuels and chemicals. The mechanisms by which thermal and catalytic treatments deconstruct lignin remain elusive, which is where quantum mechanical calculations can offer fundamental insights. Here, we compute homolytic bond dissociation enthalpies (BDEs) for four prevalent linkages in 69 lignin model compounds, including β-O-4, α-O-4, β-5, and biphenyl bonds, with a large range of natural and oxidized substituents. These calculations include ab initio benchmark values extrapolated to the complete basis set limit and full conformational searches for each compound. The results quantify both the relative BDEs among common lignin bonds and the effect of native and oxidized substituents on the functional groups in lignin. These data yield insights into thermal lignin deconstruction for a large range of prevalent linkages and aid in the identification of targets for catalytic cleavage.

Original languageEnglish (US)
Pages (from-to)2846-2852
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume2
Issue number22
DOIs
StatePublished - Nov 17 2011

All Science Journal Classification (ASJC) codes

  • Materials Science(all)

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