Coverage, repulsion, and reactivity of hydrogen on High-Entropy alloys

Frederik C. Østergaard; Frank Abild-Pedersen; Jan Rossmeisl

doi:10.1016/j.jcat.2024.115570

Coverage, repulsion, and reactivity of hydrogen on High-Entropy alloys

Frederik C. Østergaard
, Frank Abild-Pedersen
, Jan Rossmeisl^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › Research › peer-review

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Abstract

Modeling hydrogen evolution reaction (HER) activity probability on IrPdPtRhRu(1 1 1) high-entropy alloys. Determining hydrogen coverages based on ligand effects and generalized hydrogen–hydrogen repulsion. The rate of H₂ formation is highly impacted by the level of hydrogen coverage on the catalyst surface. In search of optimal catalytic properties high-entropy alloys (HEA) are promising candidates that utilize the compositional space of multiple elements. Based on simulations of HEA model (1 1 1) surfaces with a range of hydrogen coverages, distributions of binding energies are used to construct a framework that approximates the probability that adsorbed hydrogen may lead to the formation of H₂ as a function of applied potential. By optimizing the alloy compositions for the highest activity probability at given potentials the best and most efficient catalyst candidates for HER can be identified. Treating hydrogen–hydrogen repulsion effects and binding energy separately, we find that the repulsion is larger for HEAs than for pure metals. Differing isotherm slopes in the mean adsorption and desorption energies demonstrate a possible hysteresis for hydrogen adsorption on HEAs.

Original language	English
Article number	115570
Journal	Journal of Catalysis
Volume	435
Number of pages	11
ISSN	0021-9517
DOIs	https://doi.org/10.1016/j.jcat.2024.115570
Publication status	Published - 2024

Bibliographical note

Funding Information:
F.C.\u00D8. and J.R. acknowledge support from the Danish National Research Foundation Center for High-Entropy Alloy Catalysis (CHEAC) DNRF-149. F.A.-P. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. J.R. acknowledges funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) \u2013 SFB 1625, project number 506711657, subproject A01-Rossmeisl.

Funding Information:
F.C.\u00D8. and J.R. acknowledge support from the Danish National Research Foundation Center for High-Entropy Alloy Catalysis (CHEAC) DNRF-149. F.A.-P. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis.

Publisher Copyright:
© 2024 The Author(s)

Funding

F.C.\u00D8. and J.R. acknowledge support from the Danish National Research Foundation Center for High-Entropy Alloy Catalysis (CHEAC) DNRF-149. F.A.-P. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. J.R. acknowledges funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) \u2013 SFB 1625, project number 506711657, subproject A01-Rossmeisl. F.C.\u00D8. and J.R. acknowledge support from the Danish National Research Foundation Center for High-Entropy Alloy Catalysis (CHEAC) DNRF-149. F.A.-P. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis.

Keywords

Catalysis
Density Functional Theory
Electrocatalysis
Hydrogen Evolution Reaction
Simulation

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Cite this

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title = "Coverage, repulsion, and reactivity of hydrogen on High-Entropy alloys",

abstract = "Modeling hydrogen evolution reaction (HER) activity probability on IrPdPtRhRu(1 1 1) high-entropy alloys. Determining hydrogen coverages based on ligand effects and generalized hydrogen{\textendash}hydrogen repulsion. The rate of H2 formation is highly impacted by the level of hydrogen coverage on the catalyst surface. In search of optimal catalytic properties high-entropy alloys (HEA) are promising candidates that utilize the compositional space of multiple elements. Based on simulations of HEA model (1 1 1) surfaces with a range of hydrogen coverages, distributions of binding energies are used to construct a framework that approximates the probability that adsorbed hydrogen may lead to the formation of H2 as a function of applied potential. By optimizing the alloy compositions for the highest activity probability at given potentials the best and most efficient catalyst candidates for HER can be identified. Treating hydrogen{\textendash}hydrogen repulsion effects and binding energy separately, we find that the repulsion is larger for HEAs than for pure metals. Differing isotherm slopes in the mean adsorption and desorption energies demonstrate a possible hysteresis for hydrogen adsorption on HEAs.",

keywords = "Catalysis, Density Functional Theory, Electrocatalysis, Hydrogen Evolution Reaction, Simulation",

author = "{\O}stergaard, \{Frederik C.\} and Frank Abild-Pedersen and Jan Rossmeisl",

note = "Funding Information: F.C.\textbackslash{}u00D8. and J.R. acknowledge support from the Danish National Research Foundation Center for High-Entropy Alloy Catalysis (CHEAC) DNRF-149. F.A.-P. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. J.R. acknowledges funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) \textbackslash{}u2013 SFB 1625, project number 506711657, subproject A01-Rossmeisl. Funding Information: F.C.\textbackslash{}u00D8. and J.R. acknowledge support from the Danish National Research Foundation Center for High-Entropy Alloy Catalysis (CHEAC) DNRF-149. F.A.-P. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. Publisher Copyright: {\textcopyright} 2024 The Author(s)",

year = "2024",

doi = "10.1016/j.jcat.2024.115570",

language = "English",

volume = "435",

journal = "Journal of Catalysis",

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T1 - Coverage, repulsion, and reactivity of hydrogen on High-Entropy alloys

AU - Østergaard, Frederik C.

AU - Abild-Pedersen, Frank

AU - Rossmeisl, Jan

N1 - Funding Information: F.C.\u00D8. and J.R. acknowledge support from the Danish National Research Foundation Center for High-Entropy Alloy Catalysis (CHEAC) DNRF-149. F.A.-P. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. J.R. acknowledges funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) \u2013 SFB 1625, project number 506711657, subproject A01-Rossmeisl. Funding Information: F.C.\u00D8. and J.R. acknowledge support from the Danish National Research Foundation Center for High-Entropy Alloy Catalysis (CHEAC) DNRF-149. F.A.-P. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. Publisher Copyright: © 2024 The Author(s)

PY - 2024

Y1 - 2024

N2 - Modeling hydrogen evolution reaction (HER) activity probability on IrPdPtRhRu(1 1 1) high-entropy alloys. Determining hydrogen coverages based on ligand effects and generalized hydrogen–hydrogen repulsion. The rate of H2 formation is highly impacted by the level of hydrogen coverage on the catalyst surface. In search of optimal catalytic properties high-entropy alloys (HEA) are promising candidates that utilize the compositional space of multiple elements. Based on simulations of HEA model (1 1 1) surfaces with a range of hydrogen coverages, distributions of binding energies are used to construct a framework that approximates the probability that adsorbed hydrogen may lead to the formation of H2 as a function of applied potential. By optimizing the alloy compositions for the highest activity probability at given potentials the best and most efficient catalyst candidates for HER can be identified. Treating hydrogen–hydrogen repulsion effects and binding energy separately, we find that the repulsion is larger for HEAs than for pure metals. Differing isotherm slopes in the mean adsorption and desorption energies demonstrate a possible hysteresis for hydrogen adsorption on HEAs.

AB - Modeling hydrogen evolution reaction (HER) activity probability on IrPdPtRhRu(1 1 1) high-entropy alloys. Determining hydrogen coverages based on ligand effects and generalized hydrogen–hydrogen repulsion. The rate of H2 formation is highly impacted by the level of hydrogen coverage on the catalyst surface. In search of optimal catalytic properties high-entropy alloys (HEA) are promising candidates that utilize the compositional space of multiple elements. Based on simulations of HEA model (1 1 1) surfaces with a range of hydrogen coverages, distributions of binding energies are used to construct a framework that approximates the probability that adsorbed hydrogen may lead to the formation of H2 as a function of applied potential. By optimizing the alloy compositions for the highest activity probability at given potentials the best and most efficient catalyst candidates for HER can be identified. Treating hydrogen–hydrogen repulsion effects and binding energy separately, we find that the repulsion is larger for HEAs than for pure metals. Differing isotherm slopes in the mean adsorption and desorption energies demonstrate a possible hysteresis for hydrogen adsorption on HEAs.

KW - Catalysis

KW - Density Functional Theory

KW - Electrocatalysis

KW - Hydrogen Evolution Reaction

KW - Simulation

U2 - 10.1016/j.jcat.2024.115570

DO - 10.1016/j.jcat.2024.115570

M3 - Journal article

AN - SCOPUS:85194482160

SN - 0021-9517

VL - 435

JO - Journal of Catalysis

JF - Journal of Catalysis

M1 - 115570

ER -