Energetics of cellulose and cyclodextrin glycosidic bond cleavage

Cheng Zhu, Christoph Krumm, Gregory G. Facas, Matthew Neurock, Paul J. Dauenhauer

Research output: Contribution to journalArticlepeer-review

26 Scopus citations


Thermochemical conversion of lignocellulosic materials for production of biofuels and renewable chemicals utilizes high temperature to thermally decompose long-chain cellulose to volatile organic compounds. Cellulose undergoes two distinct kinetic regimes of intra-chain scission: low-temperature glycosidic bond cleavage (T < 467 °C) associated with a low apparent activation energy and high-temperature glycosidic bond cleavage (T > 467 °C) associated with a high apparent activation energy. In this work, the initial breakdown kinetics of cellulose were examined from 385 °C to 505 °C using a millisecond, thin-film reactor called PHASR (pulse-heated analysis of solid/surface reactions). Using the cellulose surrogate, α-cyclodextrin, the energetics of each kinetic regime were characterized by measuring the conversion between 20 ms and 2.0 seconds. The low temperature kinetic regime exhibited glycosidic bond cleavage (Ea,1 = 23.2 ± 1.9 kcal mol-1, k0,1 = 2.0 × 107 s-1), while the high temperature kinetic regime (Ea,2 = 53.7 ± 1.1 kcal mol-1, k0,2 = 2.4 × 1016 s-1) was consistent with four reaction mechanisms including concerted transglycosylation. Apparent energetics were compared with computed literature values.

Original languageEnglish (US)
Pages (from-to)201-214
Number of pages14
JournalReaction Chemistry and Engineering
Issue number2
StatePublished - Apr 2017

Bibliographical note

Funding Information:
We acknowledge financial support from the U.S. National Science Foundation, CBET – Process Systems, Reaction Engineering and Molecular Thermodynamics under Award Number 1534930.

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