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

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

doi:10.1021/jacs.2c10458

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

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Borodin, Dmitriy
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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Auerbach, Daniel J.
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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Kandratsenka, Alexander
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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Schwarzer, Dirk
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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Kitsopoulos, Theofanis N.
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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Wodtke, Alec M.
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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Citation

Borodin, D., Galparsoro, O., Rahinov, I., Fingerhut, J., Schwarzer, M., Horandl, S., et al. (2022). Steric Hindrance of NH₃ Diffusion on Pt(111) by Co-Adsorbed O-Atoms. Journal of the American Chemical Society, 144(47), 21791-21799. doi:10.1021/jacs.2c10458.

Cite as: https://hdl.handle.net/21.11116/0000-000C-45FD-A

Abstract

A detailed velocity-resolved kinetics study of NH₃ thermal desorption rates from p(2 × 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 × 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 × 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 × 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems.