TY - JOUR
T1 - Radicals and molecular products from the gas-phase pyrolysis of lignin model compounds. Cinnamyl alcohol
AU - Khachatryan, Lavrent
AU - Xu, Meng Xia
AU - Wu, Ang Jian
AU - Pechagin, Mikhail
AU - Asatryan, Rubik
N1 - Funding Information:
This work was funded by National Science Foundation under Grant CBET 1330311 . Dr. Lavrent Khachatryan is grateful to Superfund Research Program (#2P42ES013648-03), and Dr. Meng-xia Xu – to RJ Reynolds’ Tobacco Company, for partial support. Ruckenstein fund (SUNY Buffalo) is acknowledged by Dr. Rubik Asatryan for continuous support.
PY - 2016/9/1
Y1 - 2016/9/1
N2 - The experimental results on detection and identification of intermediate radicals and molecular products from gas-phase pyrolysis of cinnamyl alcohol (CnA), the simplest non-phenolic lignin model compound, over the temperature range of 400-800 °C are reported. The low temperature matrix isolation - electron paramagnetic resonance (LTMI-EPR) experiments along with the theoretical calculations, provided evidences on the generation of the intermediate carbon and oxygen centered as well as oxygen-linked, conjugated radicals. A mechanistic analysis is performed based on density functional theory to explain formation of the major products from CnA pyrolysis; cinnamaldehyde, indene, styrene, benzaldehyde, 1-propynyl benzene, and 2-propenyl benzene. The evaluated bond dissociation patterns and unimolecular decomposition pathways involve dehydrogenation, dehydration, 1,3-sigmatropic H-migration, 1,2-hydrogen shift, C-O and C-C bond cleavage processes.
AB - The experimental results on detection and identification of intermediate radicals and molecular products from gas-phase pyrolysis of cinnamyl alcohol (CnA), the simplest non-phenolic lignin model compound, over the temperature range of 400-800 °C are reported. The low temperature matrix isolation - electron paramagnetic resonance (LTMI-EPR) experiments along with the theoretical calculations, provided evidences on the generation of the intermediate carbon and oxygen centered as well as oxygen-linked, conjugated radicals. A mechanistic analysis is performed based on density functional theory to explain formation of the major products from CnA pyrolysis; cinnamaldehyde, indene, styrene, benzaldehyde, 1-propynyl benzene, and 2-propenyl benzene. The evaluated bond dissociation patterns and unimolecular decomposition pathways involve dehydrogenation, dehydration, 1,3-sigmatropic H-migration, 1,2-hydrogen shift, C-O and C-C bond cleavage processes.
KW - Biomass
KW - EPR
KW - Renewable fuel
KW - Spin trapping
KW - Theoretical calculations
UR - http://www.scopus.com/inward/record.url?scp=85027925102&partnerID=8YFLogxK
U2 - 10.1016/j.jaap.2016.07.004
DO - 10.1016/j.jaap.2016.07.004
M3 - Article
AN - SCOPUS:85027925102
SN - 0165-2370
VL - 121
SP - 75
EP - 83
JO - Journal of Analytical and Applied Pyrolysis
JF - Journal of Analytical and Applied Pyrolysis
ER -
