Computational insight into the selectivity of γ-valerolactone hydrodeoxygenation over Rh(111) and Ru(0001)

Minttu M. Kauppinen; Ewa N. Słapa; José Luis González Escobedo; Riikka L. Puurunen; Karoliina Honkala

doi:10.1016/j.susc.2024.122624

Computational insight into the selectivity of γ-valerolactone hydrodeoxygenation over Rh(111) and Ru(0001)

Minttu M. Kauppinen, Ewa N. Słapa, José Luis González Escobedo, Riikka L. Puurunen, Karoliina Honkala^*

^*Corresponding author for this work

University of Jyväskylä

Research output: Contribution to journal › Article › Scientific › peer-review

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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 towards alkane on Rh is much lower than on Ru.

Original language	English
Article number	122624
Number of pages	9
Journal	Surface Science
Volume	751
Early online date	22 Oct 2024
DOIs	https://doi.org/10.1016/j.susc.2024.122624
Publication status	E-pub ahead of print - 22 Oct 2024
MoE publication type	A1 Journal article-refereed

Keywords

Biomass
Coverage
Density-functional theory
Hydrocarbons
Hydrodeoxygenation
Microkinetic analysis
Selectivity
γ-valerolactone

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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title = "Computational insight into the selectivity of γ-valerolactone hydrodeoxygenation over Rh(111) and Ru(0001)",

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 towards alkane on Rh is much lower than on Ru.",

keywords = "Biomass, Coverage, Density-functional theory, Hydrocarbons, Hydrodeoxygenation, Microkinetic analysis, Selectivity, γ-valerolactone",

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doi = "10.1016/j.susc.2024.122624",

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T1 - Computational insight into the selectivity of γ-valerolactone hydrodeoxygenation over Rh(111) and Ru(0001)

AU - Kauppinen, Minttu M.

AU - Słapa, Ewa N.

AU - González Escobedo, José Luis

AU - Puurunen, Riikka L.

AU - Honkala, Karoliina

PY - 2024/10/22

Y1 - 2024/10/22

N2 - 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 towards alkane on Rh is much lower than on Ru.

AB - 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 towards alkane on Rh is much lower than on Ru.

KW - Biomass

KW - Coverage

KW - Density-functional theory

KW - Hydrocarbons

KW - Hydrodeoxygenation

KW - Microkinetic analysis

KW - Selectivity

KW - γ-valerolactone

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

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DO - 10.1016/j.susc.2024.122624

M3 - Article

AN - SCOPUS:85206915761

SN - 0039-6028

VL - 751

JO - Surface Science

JF - Surface Science

M1 - 122624

ER -

Computational insight into the selectivity of γ-valerolactone hydrodeoxygenation over Rh(111) and Ru(0001)

Abstract

Keywords

UN SDGs

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