Steric Hindrance of NH3Diffusion on Pt(111) by Co-Adsorbed O-Atoms

Dmitriy Borodin; Oihana Galparsoro; Igor Rahinov; Jan Fingerhut; Michael Schwarzer; Stefan Hörandl; Daniel J. Auerbach; Alexander Kandratsenka; Dirk Schwarzer; Theofanis N. Kitsopoulos; Alec M. Wodtke

doi:10.1021/jacs.2c10458

Steric Hindrance of NH₃Diffusion on Pt(111) by Co-Adsorbed O-Atoms

Dmitriy Borodin, Oihana Galparsoro, Igor Rahinov, Jan Fingerhut, Michael Schwarzer, Stefan Hörandl, Daniel J. Auerbach, Alexander Kandratsenka, Dirk Schwarzer, Theofanis N. Kitsopoulos, Alec M. Wodtke

Chemistry

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

Abstract

A detailed velocity-resolved kinetics study of NH₃thermal desorption rates from p(2 × 2) O/Pt(111) is presented. We find a large reduction in the NH₃desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH₃and O-atoms explains these observations. By fitting the model to the derived desorption rate constants, we find an NH₃stabilization on p(2 × 2) O/Pt(111) of 0.147_-0.014^+0.023eV compared to Pt(111) and a rotational barrier of 0.084_-0.022^+0.049eV, which is not present on Pt(111). The model also quantitatively predicts the steric hindrance of NH₃diffusion on Pt(111) due to co-adsorbed O-atoms. The derived diffusion barrier of NH₃on p(2 × 2) O/Pt(111) is 1.10_-0.13^+0.22eV, which is 0.39_-0.14^+0.22eV 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 NH₃binding energies at Pt(111) and p(2 × 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems.

Original language	English
Pages (from-to)	21791-21799
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	144
Issue number	47
DOIs	https://doi.org/10.1021/jacs.2c10458
State	Published - 30 Nov 2022

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© 2022 American Chemical Society. All rights reserved.

Keywords

Adsorption
Diffusion
Kinetics

Access to Document

10.1021/jacs.2c10458

Cite this

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title = "Steric Hindrance of NH3Diffusion on Pt(111) by Co-Adsorbed O-Atoms",

abstract = "A detailed velocity-resolved kinetics study of NH3thermal desorption rates from p(2 × 2) O/Pt(111) is presented. We find a large reduction in the NH3desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH3and O-atoms explains these observations. By fitting the model to the derived desorption rate constants, we find an NH3stabilization on p(2 × 2) O/Pt(111) of 0.147-0.014+0.023eV compared to Pt(111) and a rotational barrier of 0.084-0.022+0.049eV, which is not present on Pt(111). The model also quantitatively predicts the steric hindrance of NH3diffusion on Pt(111) due to co-adsorbed O-atoms. The derived diffusion barrier of NH3on p(2 × 2) O/Pt(111) is 1.10-0.13+0.22eV, which is 0.39-0.14+0.22eV 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 NH3binding energies at Pt(111) and p(2 × 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems.",

keywords = "Adsorption, Diffusion, Kinetics",

author = "Dmitriy Borodin and Oihana Galparsoro and Igor Rahinov and Jan Fingerhut and Michael Schwarzer and Stefan H{\"o}randl and Auerbach, {Daniel J.} and Alexander Kandratsenka and Dirk Schwarzer and Kitsopoulos, {Theofanis N.} and Wodtke, {Alec M.}",

year = "2022",

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doi = "10.1021/jacs.2c10458",

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T1 - Steric Hindrance of NH3Diffusion on Pt(111) by Co-Adsorbed O-Atoms

AU - Borodin, Dmitriy

AU - Galparsoro, Oihana

AU - Rahinov, Igor

AU - Fingerhut, Jan

AU - Schwarzer, Michael

AU - Hörandl, Stefan

AU - Auerbach, Daniel J.

AU - Kandratsenka, Alexander

AU - Schwarzer, Dirk

AU - Kitsopoulos, Theofanis N.

AU - Wodtke, Alec M.

PY - 2022/11/30

Y1 - 2022/11/30

N2 - A detailed velocity-resolved kinetics study of NH3thermal desorption rates from p(2 × 2) O/Pt(111) is presented. We find a large reduction in the NH3desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH3and O-atoms explains these observations. By fitting the model to the derived desorption rate constants, we find an NH3stabilization on p(2 × 2) O/Pt(111) of 0.147-0.014+0.023eV compared to Pt(111) and a rotational barrier of 0.084-0.022+0.049eV, which is not present on Pt(111). The model also quantitatively predicts the steric hindrance of NH3diffusion on Pt(111) due to co-adsorbed O-atoms. The derived diffusion barrier of NH3on p(2 × 2) O/Pt(111) is 1.10-0.13+0.22eV, which is 0.39-0.14+0.22eV 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 NH3binding energies at Pt(111) and p(2 × 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems.

AB - A detailed velocity-resolved kinetics study of NH3thermal desorption rates from p(2 × 2) O/Pt(111) is presented. We find a large reduction in the NH3desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH3and O-atoms explains these observations. By fitting the model to the derived desorption rate constants, we find an NH3stabilization on p(2 × 2) O/Pt(111) of 0.147-0.014+0.023eV compared to Pt(111) and a rotational barrier of 0.084-0.022+0.049eV, which is not present on Pt(111). The model also quantitatively predicts the steric hindrance of NH3diffusion on Pt(111) due to co-adsorbed O-atoms. The derived diffusion barrier of NH3on p(2 × 2) O/Pt(111) is 1.10-0.13+0.22eV, which is 0.39-0.14+0.22eV 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 NH3binding energies at Pt(111) and p(2 × 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems.

KW - Adsorption

KW - Diffusion

KW - Kinetics

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JO - Journal of the American Chemical Society

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ER -