English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
Add to Basket
 Local TagsRelease HistoryDetailsSummary
  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.

Item is

 

show all hide all

Basic

show hide
Item Permalink: https://hdl.handle.net/21.11116/0000-000A-67A1-C Version Permalink: https://hdl.handle.net/21.11116/0000-000A-67A4-9
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 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              

Content

show
hide
Free keywords: -
 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.

Details

show
hide
Language(s): eng - English
 Dates: 2021-09-012021-10-212021-11-03
 Publication Status: Issued
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.1c09269
 Degree: -

Event

show

Legal Case

show

Project information

show hide
Project name : PSBICH 3219 (KID)
Grant ID : -
Funding program : Horizon 2020 (H2020)
Funding organization : European Commission (EC)
Project name : BENCh gradute school
Grant ID : -
Funding program : DFG (389479699/GRK2455)
Funding organization : Deutsche Forschungsgemeinschaft
Project name : -
Grant ID : -
Funding program : ISF 2187/19
Funding organization : Israel Science Foundation (ISF)
Project name : -
Grant ID : -
Funding program : Grant 31044
Funding organization : Open University of Israel Research Authority
Project name : -
Grant ID : -
Funding program : Grant PID2019-107396GB-I00/AEI/10.13039/501100011033
Funding organization : Spanish Ministerio de Ciercia e Innovacion

Source 1

show
hide
Title: Journal of the American Chemical Society
  Other :
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: -
Pages: - Volume / Issue: 143 (43) Sequence Number: - Start / End Page: 18305 - 18316 Identifier: -