Unveiling Surface Reaction Networks in Biomass-Derived Compound Upgrading
- 1Center for Chemical Catalysis-C3, University of Bologna, Via P. Gobetti 85, Bologna, Italy, 40129
- 2Department of Industrial Chemistry “Toso Montanari, University of Bologna, Via P. Gobetti 85, Bologna, Italy, 40129
- 3Italian Institute of Technology, Via E. Melen 83, Genoa, Italy, 16152
Abstract
Biomass-derived platform molecules often undergo complex surface reactions in which productive routes compete with catalyst deactivation, limiting catalyst selectivity and stability. Identifying the molecular origins of these competing processes remains challenging, as conventional computational approaches generally rely on chemical intuition and hypothesis-driven rules, while strongly adsorbed intermediates and poisoning species remain difficult to characterize experimentally. Here, we combine enhanced sampling reaction discovery techniques with machine learning interatomic potentials, experimental catalytic tests, and in situ DRIFTS to unravel the surface reaction network controlling methyl levulinate conversion on zirconia. Our simulations reveal a highly interconnected network of elementary transformations in which surface Lewis acidic Zr sites and basic oxides cooperatively promote carbonyl activation and α-deprotonation, giving rise to competing pathways toward cyclization and catalyst poisoning. This mechanistic picture is supported by experimental evidence, which reveal a progressive decrease in angelica-lactone formation and the accumulation of persistent carboxylate-like surface species. Our results show that the same cooperative acid base surface motif which activates the substrate and promotes productive cyclization, also induces irreversible surface trapping leading to catalyst poisoning. By revealing this intrinsic competition at the molecular level, our work provides a clue on how to steer zirconia reactivity toward selective biomass conversion while suppressing the formation of the persistent surface species responsible for deactivation. More broadly, our work establishes a general strategy to tackle complex reaction networks in heterogeneous catalysis.
Related
- Porosity Engineering of Eggshell-Derived Nanostructured Hydroxyapatite for Ethanol Upgrading: Structural, Textural and Surface Characterization
- General Preparation of Nickel-Based Compound/Carbon Nanotube Catalysts for the Urea Oxidation Reaction
- Unveiling the Influence of Graphitic Nanocarbon Structures, Defects, and Surface Functional Groups on Supercapacitive Performance in LiTFSI Electrolyte
- Unveiling the reactivity of Cu(In 0.7 Ga 0.3 )Se 2 Absorbers Induced by High Relative Humidity and Illumination: Insights From Surface to Bulk
- Surface Reconstruction Activates Bridge Sites of Rutile IrO2(110) for Oxygen Evolution Reaction
BibTeX
@misc{loprete2026unveiling,
title = {{Unveiling Surface Reaction Networks in Biomass-Derived Compound Upgrading}},
author = {Fabio Loprete and Axel Tosello Gardini and Luca Visentin and Umberto Raucci and Lorenzo Mauro and Riccardo Tarroni and Fabrizio Cavani and Tommaso Tabanelli and Ivan Rivalta and Michele Parrinello},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008286/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008286/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Unveiling Surface Reaction Networks in Biomass-Derived Compound Upgrading
AU - Fabio Loprete
AU - Axel Tosello Gardini
AU - Luca Visentin
AU - Umberto Raucci
AU - Lorenzo Mauro
AU - Riccardo Tarroni
AU - Fabrizio Cavani
AU - Tommaso Tabanelli
AU - Ivan Rivalta
AU - Michele Parrinello
PY - 2026
DA - 2026/09/04
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008286/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008286/v1
AB - Biomass-derived platform molecules often undergo complex surface reactions in which productive routes compete with catalyst deactivation, limiting catalyst selectivity and stability. Identifying the molecular origins of these competing processes remains challenging, as conventional computational approaches generally rely on chemical intuition and hypothesis-driven rules, while strongly adsorbed intermediates and poisoning species remain difficult to characterize experimentally. Here, we combine enhanced sampling reaction discovery techniques with machine learning interatomic potentials, experimental catalytic tests, and in situ DRIFTS to unravel the surface reaction network controlling methyl levulinate conversion on zirconia. Our simulations reveal a highly interconnected network of elementary transformations in which surface Lewis acidic Zr sites and basic oxides cooperatively promote carbonyl activation and α-deprotonation, giving rise to competing pathways toward cyclization and catalyst poisoning. This mechanistic picture is supported by experimental evidence, which reveal a progressive decrease in angelica-lactone formation and the accumulation of persistent carboxylate-like surface species. Our results show that the same cooperative acid base surface motif which activates the substrate and promotes productive cyclization, also induces irreversible surface trapping leading to catalyst poisoning. By revealing this intrinsic competition at the molecular level, our work provides a clue on how to steer zirconia reactivity toward selective biomass conversion while suppressing the formation of the persistent surface species responsible for deactivation. More broadly, our work establishes a general strategy to tackle complex reaction networks in heterogeneous catalysis.
ER -