A1 Journal article (refereed)
Computational insight into the selectivity of γ-valerolactone hydrodeoxygenation over Rh(111) and Ru(0001) (2025)

Kauppinen, M. M., Szlapa, E. N., González, E. J. L., Puurunen, R. L., & Honkala, K. (2025). Computational insight into the selectivity of γ-valerolactone hydrodeoxygenation over Rh(111) and Ru(0001). Surface Science, 751, Article 122624. https://doi.org/10.1016/j.susc.2024.122624

JYU authors or editors

Kauppinen, Minttu
Szlapa, Ewa
Honkala, Karoliina

Publication details

All authors or editors: Kauppinen, Minttu M.; Szlapa, Ewa N.; González, Escobedo José Luis; Puurunen, Riikka L.; Honkala, Karoliina

Journal or series: Surface Science

ISSN: 0039-6028

eISSN: 1879-2758

Publication year: 2025

Publication date: 16/10/2024

Volume: 751

Article number: 122624

Publisher: Elsevier

Publication country: Netherlands

Publication language: English

DOI: https://doi.org/10.1016/j.susc.2024.122624

Research data link: https://doi.org/10.23729/ea2e013c-52ac-49d3-9c70-106b49e98920

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/98222

Abstract

The observed difference in the selectivity towards alkane, ketone, and alcohol hydrodeoxygenation products over Ru and Rh catalysts is explored using a combination of density functional theory and microkinetics. Using
γ-valerolactone as a model compound, we investigate the reaction mechanism in order to identify selectivity determining species. The effect of the coadsorbed water molecule as well as the higher adsorbate surface coverage on reaction barriers and energies is explored as well. The performed calculations suggest that the desired alkane product is formed from a ketone intermediate on Ru, and through both ketone and alcohol on Rh, although the selectivity towars alkane on Rh is much lower than on Ru.

Keywords: biomass (industry); density functional theory; catalysts; hydrocarbons; selectivity; coverage; computational chemistry