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Title: Precise non-steady-state characterization of solid active materials with no preliminary mechanistic assumptions

This paper presents a straightforward and user-friendly procedure for extracting a reactivity characterization of catalytic reactions on solid materials under non-steady-state conditions, particularly in temporal analysis of products (TAP) experiments. The kinetic parameters derived by this procedure can help with the development of detailed mechanistic understanding. The procedure consists of the following two major steps: 1) Three “Laplace reactivities” are first determined based on the moments of the exit flow pulse response data; 2) Depending on a select kinetic model, kinetic constants of elementary reaction steps can then be expressed as a function of reactivities and determined accordingly. In particular, we distinguish two calculation methods based on the availability and reliability of reactant and product data. The theoretical results are illustrated using a reverse example with given parameters as well as an experimental example of CO oxidation over a supported Au/SiO 2 catalyst. The procedure presented here provides an efficient tool for kinetic characterization of many complex chemical reactions.
Authors:
 [1] ;  [2] ;  [3] ;  [3] ;  [4] ;  [3]
  1. Ghent Univ., Gent (Belgium). Dept. of Mathematical Analysis
  2. Saint Louis Univ., Saint Louis, MO (United States). Parks College of Engineering, Aviation and Technology
  3. Idaho National Lab. (INL), Idaho Falls, ID (United States). Biological and Chemical Processing Dept.; Center for Advanced Energy Studies, Idaho Falls, ID (United States)
  4. Ghent Univ., Gent (Belgium). Lab. for Chemical Technology
Publication Date:
Report Number(s):
INL/JOU-16-40798
Journal ID: ISSN 0920-5861; PII: S0920586117302687
Grant/Contract Number:
AC07-05ID14517
Type:
Accepted Manuscript
Journal Name:
Catalysis Today
Additional Journal Information:
Journal Volume: 298; Journal ID: ISSN 0920-5861
Publisher:
Elsevier
Research Org:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org:
USDOE Office of Nuclear Energy (NE); Flemish Government
Country of Publication:
United States
Language:
English
Subject:
03 NATURAL GAS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Nonsteady state kinetics; TAP Reactor; Temporal Analysis of Products (TAP) experiment; Transient kinetics; Catalyst characterization; Pulse response
OSTI Identifier:
1361553

Constales, Denis, Yablonsky, Gregory S., Wang, Lucun, Diao, Weijian, Galvita, Vladimir V., and Fushimi, Rebecca. Precise non-steady-state characterization of solid active materials with no preliminary mechanistic assumptions. United States: N. p., Web. doi:10.1016/j.cattod.2017.04.036.
Constales, Denis, Yablonsky, Gregory S., Wang, Lucun, Diao, Weijian, Galvita, Vladimir V., & Fushimi, Rebecca. Precise non-steady-state characterization of solid active materials with no preliminary mechanistic assumptions. United States. doi:10.1016/j.cattod.2017.04.036.
Constales, Denis, Yablonsky, Gregory S., Wang, Lucun, Diao, Weijian, Galvita, Vladimir V., and Fushimi, Rebecca. 2017. "Precise non-steady-state characterization of solid active materials with no preliminary mechanistic assumptions". United States. doi:10.1016/j.cattod.2017.04.036. https://www.osti.gov/servlets/purl/1361553.
@article{osti_1361553,
title = {Precise non-steady-state characterization of solid active materials with no preliminary mechanistic assumptions},
author = {Constales, Denis and Yablonsky, Gregory S. and Wang, Lucun and Diao, Weijian and Galvita, Vladimir V. and Fushimi, Rebecca},
abstractNote = {This paper presents a straightforward and user-friendly procedure for extracting a reactivity characterization of catalytic reactions on solid materials under non-steady-state conditions, particularly in temporal analysis of products (TAP) experiments. The kinetic parameters derived by this procedure can help with the development of detailed mechanistic understanding. The procedure consists of the following two major steps: 1) Three “Laplace reactivities” are first determined based on the moments of the exit flow pulse response data; 2) Depending on a select kinetic model, kinetic constants of elementary reaction steps can then be expressed as a function of reactivities and determined accordingly. In particular, we distinguish two calculation methods based on the availability and reliability of reactant and product data. The theoretical results are illustrated using a reverse example with given parameters as well as an experimental example of CO oxidation over a supported Au/SiO2 catalyst. The procedure presented here provides an efficient tool for kinetic characterization of many complex chemical reactions.},
doi = {10.1016/j.cattod.2017.04.036},
journal = {Catalysis Today},
number = ,
volume = 298,
place = {United States},
year = {2017},
month = {4}
}