Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms

A detailed velocity-resolved kinetics study of NH3 thermal desorption rates from p(2 x 2) O/Pt(111) is presented. We find a large reduction in the NH3 desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH3 and O-atoms explains these...

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Autores: Borodin, Dmitriy, Galparsoro Larraza, Oihana, Rahinov, Igor, Fingerhut, Jan, Schwarzer, Michael, Horandl, Stefan, Auerbach, Daniel J., Kandratsenka, Alexander, Schwarzer, Dirk, Kitsopoulos, Theofanis N., Wodtke, Alec M.
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/59324
Acceso en línea:http://hdl.handle.net/10810/59324
Access Level:acceso abierto
Palabra clave:total energy calculations
ultrasoft pseudopotentials
wave
transition
adsorption
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spelling Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-AtomsBorodin, DmitriyGalparsoro Larraza, OihanaRahinov, IgorFingerhut, JanSchwarzer, MichaelHorandl, StefanAuerbach, Daniel J.Kandratsenka, AlexanderSchwarzer, DirkKitsopoulos, Theofanis N.Wodtke, Alec M.total energy calculationsultrasoft pseudopotentialswavetransitionadsorptionA detailed velocity-resolved kinetics study of NH3 thermal desorption rates from p(2 x 2) O/Pt(111) is presented. We find a large reduction in the NH3 desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH3 and O-atoms explains these observations. By fitting the model to the derived desorption rate constants, we find an NH3 stabilization on p(2 x 2) O/Pt(111) of 0.147-0.014 +0.023 eV compared to Pt(111) and a rotational barrier of 0.084-0.022 +0.049 eV, which is not present on Pt(111). The model also quantitatively predicts the steric hindrance of NH3 diffusion on Pt(111) due to co-adsorbed O-atoms. The derived diffusion barrier of NH3 on p(2 x 2) O/Pt(111) is 1.10-0.13 +0.22 eV, which is 0.39-0.14 +0.22 eV higher than that on pristine Pt(111). We find that Perdew Burke Ernzerhof (PBE) and revised Perdew Burke Ernzerhof (RPBE) exchange-correlation functionals are unable to reproduce the experimentally observed NH3-O adsorbate-adsorbate interactions and NH3 binding energies at Pt(111) and p(2 x 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems.D.B., J.F., A.K., and T.N.K. acknowledge support from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreement no. [833404]). O.G. acknowledges financial support by the Spanish Ministerio de Ciencia e Innovación [Grant no. PID2019-107396GB-I00/AEI/10.13039/501100011033]. I.R. gratefully acknowledges the support by Israel Science Foundation, ISF (grant No. 2187/19), and by the Open University of Israel Research Authority (grant No. 31044). M.S. thanks the BENCh graduate school, funded by the DFG (389479699/GRK2455). Open access funded by Max Planck Society.American Chemical SocietyEuropean Commission202320232022info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/59324reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/EC/ERC/833404info:eu-repo/grantAgreement/MICINN/PID2019-107396GB-I0/https://pubs.acs.org/doi/10.1021/jacs.2c10458info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/3.0/es/© 2022 The Authors. Published by American Chemical Society. Attribution 4.0 International (CC BY 4.0)Atribución 3.0 Españaoai:addi.ehu.eus:10810/593242026-06-18T09:23:17Z
dc.title.none.fl_str_mv Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms
title Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms
spellingShingle Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms
Borodin, Dmitriy
total energy calculations
ultrasoft pseudopotentials
wave
transition
adsorption
title_short Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms
title_full Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms
title_fullStr Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms
title_full_unstemmed Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms
title_sort Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms
dc.creator.none.fl_str_mv Borodin, Dmitriy
Galparsoro Larraza, Oihana
Rahinov, Igor
Fingerhut, Jan
Schwarzer, Michael
Horandl, Stefan
Auerbach, Daniel J.
Kandratsenka, Alexander
Schwarzer, Dirk
Kitsopoulos, Theofanis N.
Wodtke, Alec M.
author Borodin, Dmitriy
author_facet Borodin, Dmitriy
Galparsoro Larraza, Oihana
Rahinov, Igor
Fingerhut, Jan
Schwarzer, Michael
Horandl, Stefan
Auerbach, Daniel J.
Kandratsenka, Alexander
Schwarzer, Dirk
Kitsopoulos, Theofanis N.
Wodtke, Alec M.
author_role author
author2 Galparsoro Larraza, Oihana
Rahinov, Igor
Fingerhut, Jan
Schwarzer, Michael
Horandl, Stefan
Auerbach, Daniel J.
Kandratsenka, Alexander
Schwarzer, Dirk
Kitsopoulos, Theofanis N.
Wodtke, Alec M.
author2_role author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv European Commission
dc.subject.none.fl_str_mv total energy calculations
ultrasoft pseudopotentials
wave
transition
adsorption
topic total energy calculations
ultrasoft pseudopotentials
wave
transition
adsorption
description A detailed velocity-resolved kinetics study of NH3 thermal desorption rates from p(2 x 2) O/Pt(111) is presented. We find a large reduction in the NH3 desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH3 and O-atoms explains these observations. By fitting the model to the derived desorption rate constants, we find an NH3 stabilization on p(2 x 2) O/Pt(111) of 0.147-0.014 +0.023 eV compared to Pt(111) and a rotational barrier of 0.084-0.022 +0.049 eV, which is not present on Pt(111). The model also quantitatively predicts the steric hindrance of NH3 diffusion on Pt(111) due to co-adsorbed O-atoms. The derived diffusion barrier of NH3 on p(2 x 2) O/Pt(111) is 1.10-0.13 +0.22 eV, which is 0.39-0.14 +0.22 eV higher than that on pristine Pt(111). We find that Perdew Burke Ernzerhof (PBE) and revised Perdew Burke Ernzerhof (RPBE) exchange-correlation functionals are unable to reproduce the experimentally observed NH3-O adsorbate-adsorbate interactions and NH3 binding energies at Pt(111) and p(2 x 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems.
publishDate 2022
dc.date.none.fl_str_mv 2022
2023
2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/59324
url http://hdl.handle.net/10810/59324
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/EC/ERC/833404
info:eu-repo/grantAgreement/MICINN/PID2019-107396GB-I0/
https://pubs.acs.org/doi/10.1021/jacs.2c10458
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by/3.0/es/
Atribución 3.0 España
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/3.0/es/
Atribución 3.0 España
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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