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^*

^*Tämän työn vastaava kirjoittaja

University of Jyväskylä

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

70 Lataukset (Pure)

Abstrakti

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.

Alkuperäiskieli	Englanti
Artikkeli	122624
Sivumäärä	9
Julkaisu	Surface Science
Vuosikerta	751
Varhainen verkossa julkaisun päivämäärä	22 lokak. 2024
DOI - pysyväislinkit	https://doi.org/10.1016/j.susc.2024.122624
Tila	Julkaistu - tammik. 2025
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

The computational work was funded by Research Council of Finland (307623) and University of Jyväskylä. The electronic structure calculations were made possible by the computational resources provided by the CSC — IT Center for Science, Espoo, Finland (https://www.csc.fi/en/) and FGCI. The experiments on which this work is based (Supporting Information) were funded by Neste Corporation. J. L. G. E. acknowledges funding from Fortum Foundation, Finland (number 201800142) and from the Finnish Foundation for Technology Promotion, Finland (number 6712).

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10.1016/j.susc.2024.122624Lisenssi: CC BY

CHEM_Kauppinen_et_al_Computational_insight_2024_Surface_ScienceFinal published version, 2,35 MBLisenssi: CC BY

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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",

author = "Kauppinen, \{Minttu M.\} and S{\l}apa, \{Ewa N.\} and \{Gonz{\'a}lez Escobedo\}, \{Jos{\'e} Luis\} and Puurunen, \{Riikka L.\} and Karoliina Honkala",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors",

year = "2025",

month = jan,

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

language = "English",

volume = "751",

journal = "Surface Science",

issn = "0039-6028",

publisher = "Elsevier",

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TY - JOUR

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 - 2025/1

Y1 - 2025/1

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

UR - https://www.scopus.com/pages/publications/85206915761

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

U2 - 10.1016/j.susc.2024.122624

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)

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