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  Kinetics of NH3 desorption and diffusion on Pt: Implications for the Ostwald process

Borodin, D., Rahinov, I., Galparsoro, O., Fingerhut, J., Schwarzer, M., Golibrzuch, K., et al. (2021). Kinetics of NH3 desorption and diffusion on Pt: Implications for the Ostwald process. Journal of the American Chemical Society, 143(43), 18305-18316. doi:10.1021/jacs.1c09269.

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 Creators:
Borodin, D.1, Author           
Rahinov, I., Author
Galparsoro, O., Author           
Fingerhut, J., Author
Schwarzer, M., Author
Golibrzuch, K.2, Author           
Skoulatakis, G.3, Author           
Auerbach, D. J.2, Author           
Kandratsenka, A.3, Author           
Kitsopoulos, T. N.2, Author           
Wodtke, A. M.2, Author           
Affiliations:
1Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_persistent22              
2Department of Dynamics at Surfaces, MPI for biophysical chemistry, Max Planck Society, ou_578600              
3Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_578600              

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 Abstract: ABSTRACT: We report accurate time-resolved measurements of NH3 desorption from Pt(111) and Pt(332) and use these results to determine elementary rate constants for desorption from steps, from (111) terrace sites and for diffusion on (111) terraces. Modeling the extracted rate constants with transition state theory, we find that conventional models for partition functions, which rely on uncoupled degrees of freedom (DOFs), are not able to reproduce the experimental observations. The results can be reproduced using a more sophisticated partition function, which couples DOFs that are most sensitive to NH3 translation parallel to the surface; this approach yields accurate values for the NH3 binding energy to Pt(111) (1.13 ± 0.02 eV) and the diffusion barrier (0.71 ± 0.04 eV). In addition, we determine NH3’s binding energy preference for steps over terraces on Pt (0.23 ± 0.03 eV). The ratio of the diffusion barrier to desorption energy is ∼0.65, in violation of the so-called 12% rule. Using our derived diffusion/desorption rates, we explain why established rate models of the Ostwald process incorrectly predict low selectivity and yields of NO under typical reactor operating conditions. Our results suggest that mean-field kinetics models have limited applicability for modeling the Ostwald process.

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Language(s): eng - English
 Dates: 2021-09-012021-10-212021-11-03
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.1c09269
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Project name : PSBICH 3219 (KID)
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Funding program : Horizon 2020 (H2020)
Funding organization : European Commission (EC)
Project name : BENCh gradute school
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Funding program : DFG (389479699/GRK2455)
Funding organization : Deutsche Forschungsgemeinschaft
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Funding program : ISF 2187/19
Funding organization : Israel Science Foundation (ISF)
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Funding program : Grant 31044
Funding organization : Open University of Israel Research Authority
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Funding program : Grant PID2019-107396GB-I00/AEI/10.13039/501100011033
Funding organization : Spanish Ministerio de Ciercia e Innovacion

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Title: Journal of the American Chemical Society
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Source Genre: Journal
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Pages: - Volume / Issue: 143 (43) Sequence Number: - Start / End Page: 18305 - 18316 Identifier: -