TY - JOUR
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.
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
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.
UR - https://www.scopus.com/pages/publications/85142432811
U2 - 10.1021/jacs.2c10458
DO - 10.1021/jacs.2c10458
M3 - Article
C2 - 36399044
AN - SCOPUS:85142432811
SN - 0002-7863
VL - 144
SP - 21791
EP - 21799
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 47
ER -