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Title: Establishing structure-sensitivity of ceria reducibility: real-time observations of surface-hydrogen interactions

Abstract

The first layer of atoms on an oxide catalyst provides the first sites for adsorption of reactants and the last sites before products or oxygen are desorbed. We employ a unique combination of morphological, structural, and chemical analyses of a model ceria catalyst with different surface terminations under an H 2 environment to unequivocally establish the effect of the last layer of atoms on surface reduction. (111) and (100) terminated epitaxial islands of ceria are simultaneously studied in situ allowing for a direct investigation of the structure–reducibility relationship under identical conditions. Kinetic rate constants of Ce 4+ to Ce 3+ transformation and equilibrium concentrations are extracted for both surface terminations. Unlike the kinetic rate constants, which are practically the same for both types of islands, more pronounced oxygen release, and overall higher reducibility were observed for (100) islands compared to (111) ones. The findings are in agreement with coordination-limited oxygen vacancy formation energies calculated by density functional theory. The results point out the important aspect of surface terminations in redox processes, with particular impact on the catalytic reactions of a variety of catalysts.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [4];  [5];  [2];  [2];  [2];  [6];  [6]; ORCiD logo [7];  [8]
  1. Peter-Grünberg-Inst. (Germany); Charles Univ., Prague (Czech Republic)
  2. Peter-Grünberg-Inst. (Germany)
  3. Uppsala Univ. (Sweden)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Lab. Nacional de Luz Síncrotron (Brazil)
  6. Charles Univ., Prague (Czech Republic)
  7. Peter-Grünberg-Inst. (Germany); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  8. Peter-Grünberg-Inst. (Germany) ; Univ. of California, Davis, CA (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1603285
Alternate Identifier(s):
OSTI ID: 1598714
Report Number(s):
[BNL-213669-2020-JAAM]
[Journal ID: ISSN 2050-7488; JMCAET]
Grant/Contract Number:  
[SC0012704]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
[ Journal Volume: 8; Journal Issue: 11]; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Duchoň, Tomáš, Hackl, Johanna, Mueller, David N., Kullgren, Jolla, Du, Dou, Senanayake, Sanjaya D., Mouls, Caroline, Gottlob, Daniel M., Khan, Muhammad I., Cramm, Stefan, Veltruská, Kateřina, Matolín, Vladimír, Nemšák, Slavomír, and Schneider, Claus M. Establishing structure-sensitivity of ceria reducibility: real-time observations of surface-hydrogen interactions. United States: N. p., 2020. Web. doi:10.1039/C9TA11784A.
Duchoň, Tomáš, Hackl, Johanna, Mueller, David N., Kullgren, Jolla, Du, Dou, Senanayake, Sanjaya D., Mouls, Caroline, Gottlob, Daniel M., Khan, Muhammad I., Cramm, Stefan, Veltruská, Kateřina, Matolín, Vladimír, Nemšák, Slavomír, & Schneider, Claus M. Establishing structure-sensitivity of ceria reducibility: real-time observations of surface-hydrogen interactions. United States. doi:10.1039/C9TA11784A.
Duchoň, Tomáš, Hackl, Johanna, Mueller, David N., Kullgren, Jolla, Du, Dou, Senanayake, Sanjaya D., Mouls, Caroline, Gottlob, Daniel M., Khan, Muhammad I., Cramm, Stefan, Veltruská, Kateřina, Matolín, Vladimír, Nemšák, Slavomír, and Schneider, Claus M. Sat . "Establishing structure-sensitivity of ceria reducibility: real-time observations of surface-hydrogen interactions". United States. doi:10.1039/C9TA11784A.
@article{osti_1603285,
title = {Establishing structure-sensitivity of ceria reducibility: real-time observations of surface-hydrogen interactions},
author = {Duchoň, Tomáš and Hackl, Johanna and Mueller, David N. and Kullgren, Jolla and Du, Dou and Senanayake, Sanjaya D. and Mouls, Caroline and Gottlob, Daniel M. and Khan, Muhammad I. and Cramm, Stefan and Veltruská, Kateřina and Matolín, Vladimír and Nemšák, Slavomír and Schneider, Claus M.},
abstractNote = {The first layer of atoms on an oxide catalyst provides the first sites for adsorption of reactants and the last sites before products or oxygen are desorbed. We employ a unique combination of morphological, structural, and chemical analyses of a model ceria catalyst with different surface terminations under an H2 environment to unequivocally establish the effect of the last layer of atoms on surface reduction. (111) and (100) terminated epitaxial islands of ceria are simultaneously studied in situ allowing for a direct investigation of the structure–reducibility relationship under identical conditions. Kinetic rate constants of Ce4+ to Ce3+ transformation and equilibrium concentrations are extracted for both surface terminations. Unlike the kinetic rate constants, which are practically the same for both types of islands, more pronounced oxygen release, and overall higher reducibility were observed for (100) islands compared to (111) ones. The findings are in agreement with coordination-limited oxygen vacancy formation energies calculated by density functional theory. The results point out the important aspect of surface terminations in redox processes, with particular impact on the catalytic reactions of a variety of catalysts.},
doi = {10.1039/C9TA11784A},
journal = {Journal of Materials Chemistry. A},
number = [11],
volume = [8],
place = {United States},
year = {2020},
month = {2}
}

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