Detecting Important Intermediates in Pd Catalyzed Depolymerization of a Lignin Model Compound by a Combination of DFT Calculations and Constrained Minima Hopping
| Autor: | Maxim V. Galkin, Pemikar Srifa, Joseph S. M. Samec, Peter Broqvist, Kersti Hermansson |
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| Rok vydání: | 2016 |
| Předmět: |
010405 organic chemistry
Chemistry chemistry.chemical_element Reaction intermediate 010402 general chemistry Photochemistry 01 natural sciences Tautomer Enol 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials Catalysis chemistry.chemical_compound General Energy Computational chemistry Molecule Density functional theory Physical and Theoretical Chemistry Bond cleavage Palladium |
| Zdroj: | The Journal of Physical Chemistry C. 120:23469-23479 |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/acs.jpcc.6b05622 |
| Popis: | Density functional theory (DFT) calculations, combined with a constrained minima hopping algorithm (global minimum search while preserving the molecular identity), have been performed to investigate important reaction intermediates for the heterogeneously catalyzed β-O-4′ bond cleavage in lignin derivatives. More specifically, we have studied the adsorption properties of a keto tautomer (1-methoxypropan-2-one) and its enol form on a catalytically active Pd(111) surface. In agreement with experiments, we find that for the gas-phase molecules the keto tautomer is the most stable. Interestingly, the enol tautomer has a higher affinity to the Pd catalyst than the keto form, and becomes the most stable molecular form when adsorbed on the catalyst surface. The global minimum complex found on the metal surface corresponds to an enolate structure formed when the enol tautomer chemisorbs onto the surface and donates its π-electrons from the C═C region to two adjacent palladium atoms. The actual formation of a chem... |
| Databáze: | OpenAIRE |
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