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Main Authors: Rafsanjani-Abbasi, Ali, Buchner, Florian, Lewis, Faith J., Puntscher, Lena, Kraushofer, Florian, Sombut, Panukorn, Eder, Moritz, Pavelec, Jiri, Rheinfrank, Erik, Franceschi, Giada, Birschitzky, Viktor C., Riva, Michele, Franchini, Cesare, Schmid, Michael, Diebold, Ulrike, Meier, Matthias, Madsen, Georg K. H., Parkinson, Gareth S.
Format: Preprint
Published: 2024
Subjects:
Online Access:https://arxiv.org/abs/2406.18525
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author Rafsanjani-Abbasi, Ali
Buchner, Florian
Lewis, Faith J.
Puntscher, Lena
Kraushofer, Florian
Sombut, Panukorn
Eder, Moritz
Pavelec, Jiri
Rheinfrank, Erik
Franceschi, Giada
Birschitzky, Viktor C.
Riva, Michele
Franchini, Cesare
Schmid, Michael
Diebold, Ulrike
Meier, Matthias
Madsen, Georg K. H.
Parkinson, Gareth S.
author_facet Rafsanjani-Abbasi, Ali
Buchner, Florian
Lewis, Faith J.
Puntscher, Lena
Kraushofer, Florian
Sombut, Panukorn
Eder, Moritz
Pavelec, Jiri
Rheinfrank, Erik
Franceschi, Giada
Birschitzky, Viktor C.
Riva, Michele
Franchini, Cesare
Schmid, Michael
Diebold, Ulrike
Meier, Matthias
Madsen, Georg K. H.
Parkinson, Gareth S.
contents Determining the local coordination of the active site is a pre-requisite for the reliable modeling of single-atom catalysts (SACs). Obtaining such information is difficult on powder-based systems, so much emphasis is placed on density functional theory-based computations based on idealized low-index surfaces of the support. In this work, we investigate how Pt atoms bind to the (1-102) facet of Fe2O3, a common support material in SAC. Using a combination of scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), and an extensive computational evolutionary search, we find that Pt atoms significantly reconfigure the support lattice to facilitate a pseudo-linear coordination to surface oxygen atoms. Despite breaking three surface Fe-O bonds, this geometry is favored by 0.84 eV over the best configuration involving an unperturbed support. We suggest that the linear O-Pt-O configuration is common in reactive Pt-based SAC systems because it balances thermal stability with the ability to adsorb reactants from the gas phase, and that extensive structural searches are likely necessary to determine realistic active site geometry in single-atom catalysis.
format Preprint
id arxiv_https___arxiv_org_abs_2406_18525
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Digging its own Site: Linear Coordination Stabilizes a Pt1/Fe2O3 Single-Atom Catalyst
Rafsanjani-Abbasi, Ali
Buchner, Florian
Lewis, Faith J.
Puntscher, Lena
Kraushofer, Florian
Sombut, Panukorn
Eder, Moritz
Pavelec, Jiri
Rheinfrank, Erik
Franceschi, Giada
Birschitzky, Viktor C.
Riva, Michele
Franchini, Cesare
Schmid, Michael
Diebold, Ulrike
Meier, Matthias
Madsen, Georg K. H.
Parkinson, Gareth S.
Materials Science
Determining the local coordination of the active site is a pre-requisite for the reliable modeling of single-atom catalysts (SACs). Obtaining such information is difficult on powder-based systems, so much emphasis is placed on density functional theory-based computations based on idealized low-index surfaces of the support. In this work, we investigate how Pt atoms bind to the (1-102) facet of Fe2O3, a common support material in SAC. Using a combination of scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), and an extensive computational evolutionary search, we find that Pt atoms significantly reconfigure the support lattice to facilitate a pseudo-linear coordination to surface oxygen atoms. Despite breaking three surface Fe-O bonds, this geometry is favored by 0.84 eV over the best configuration involving an unperturbed support. We suggest that the linear O-Pt-O configuration is common in reactive Pt-based SAC systems because it balances thermal stability with the ability to adsorb reactants from the gas phase, and that extensive structural searches are likely necessary to determine realistic active site geometry in single-atom catalysis.
title Digging its own Site: Linear Coordination Stabilizes a Pt1/Fe2O3 Single-Atom Catalyst
topic Materials Science
url https://arxiv.org/abs/2406.18525