Mechanistic Insights Into Sustainable Catalytic Pyrolysis of Biomass‐Derived Ferulic Acid: The Role of Alumina Regeneration
7 affiliations
- 1Cardiff Catalysis Institute School of Chemistry Translational Research Hub Cardiff University Cardiff Wales UK
- 2Chuiko Institute of Surface Chemistry of National Academy of Science of Ukraine Kyiv Ukraine
- 3Institute of Molecular Biology and Genetics National Academy of Science of Ukraine Kyiv Ukraine
- 4Biophysics Group Department of Physics and Astronomy University College London London UK
- 5UCL Healthcare Biomagnetics and Nanomaterials Laboratories London UK
- 6National University of Science and Technology Polytehnica Bucharest Bucharest Romania
- 7Universidad ECOTEC Samborondón Ecuador
Abstract
A fundamental understanding of catalyst deactivation and regeneration is essential for developing sustainable catalytic pyrolysis processes for lignocellulosic biomass conversion. Herein, the effect of alumina regeneration on the catalytic pyrolysis of ferulic acid, a lignin‐derived model compound, was investigated using kinetic analysis combined with FTIR, TPD–MS, XPS, TEM, XRD, thermogravimetry, and DFT calculations. Comparative kinetic analysis showed that the apparent activation energies of key reactions, including decarboxylation, demethoxylation, and the formation of 4‐vinylguaiacol, guaiacol, phenol, and other aromatic products, increase by 4–23 kJ mol− 1 after catalyst regeneration, indicating partial modification of the alumina surface. DFT calculations revealed that 4‐vinylguaiacol formation proceeds preferentially via a surface‐assisted acidic decarboxylation pathway involving alumina‐bound intermediates, whereas alternative surface interactions generate strongly bound species that may contribute to catalyst deactivation. Combined experimental and theoretical evidence indicates that surface‐bound phenolate complexes act as precursors to carbon deposition. These species undergo styrene‐like polymerization on alumina, forming a polymeric carbonaceous layer that decomposes upon heating, releasing aromatic products and progressively forming extended polyaromatic carbon domains. The proposed mechanism is supported by TEM, FTIR, XPS, and TPD–MS results. These findings establish a unified mechanistic framework linking catalytic decarboxylation, carbon‐layer formation, and catalyst deactivation during biomass conversion.
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BibTeX
@article{kulik2026mechanistic,
title = {{Mechanistic Insights Into Sustainable Catalytic Pyrolysis of Biomass‐Derived Ferulic Acid: The Role of Alumina Regeneration}},
author = {Tetiana V. Kulik and Borys B. Palianytsia and Mykola M. Ilchenko and Nataliia S. Nastasiienko and David J. Morgan and Liudmila P. Storozhuk and David J. Willock and Greg Shaw and Duncan F. Wass and Rafael Luque and Philip R. Davies and Mykola T. Kartel},
journal = {Chemistry (Weinheim an Der Bergstrasse, Germany)},
year = {2026},
month = jul,
doi = {10.1002/chem.71397},
url = {https://doi.org/10.1002/chem.71397},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Mechanistic Insights Into Sustainable Catalytic Pyrolysis of Biomass‐Derived Ferulic Acid: The Role of Alumina Regeneration
AU - Tetiana V. Kulik
AU - Borys B. Palianytsia
AU - Mykola M. Ilchenko
AU - Nataliia S. Nastasiienko
AU - David J. Morgan
AU - Liudmila P. Storozhuk
AU - David J. Willock
AU - Greg Shaw
AU - Duncan F. Wass
AU - Rafael Luque
AU - Philip R. Davies
AU - Mykola T. Kartel
PY - 2026
DA - 2026/07/14
JO - Chemistry (Weinheim an Der Bergstrasse, Germany)
DO - 10.1002/chem.71397
UR - https://doi.org/10.1002/chem.71397
AB - A fundamental understanding of catalyst deactivation and regeneration is essential for developing sustainable catalytic pyrolysis processes for lignocellulosic biomass conversion. Herein, the effect of alumina regeneration on the catalytic pyrolysis of ferulic acid, a lignin‐derived model compound, was investigated using kinetic analysis combined with FTIR, TPD–MS, XPS, TEM, XRD, thermogravimetry, and DFT calculations. Comparative kinetic analysis showed that the apparent activation energies of key reactions, including decarboxylation, demethoxylation, and the formation of 4‐vinylguaiacol, guaiacol, phenol, and other aromatic products, increase by 4–23 kJ mol− 1 after catalyst regeneration, indicating partial modification of the alumina surface. DFT calculations revealed that 4‐vinylguaiacol formation proceeds preferentially via a surface‐assisted acidic decarboxylation pathway involving alumina‐bound intermediates, whereas alternative surface interactions generate strongly bound species that may contribute to catalyst deactivation. Combined experimental and theoretical evidence indicates that surface‐bound phenolate complexes act as precursors to carbon deposition. These species undergo styrene‐like polymerization on alumina, forming a polymeric carbonaceous layer that decomposes upon heating, releasing aromatic products and progressively forming extended polyaromatic carbon domains. The proposed mechanism is supported by TEM, FTIR, XPS, and TPD–MS results. These findings establish a unified mechanistic framework linking catalytic decarboxylation, carbon‐layer formation, and catalyst deactivation during biomass conversion.
SN - 0947-6539
SN - 1521-3765
ER -