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Title: In-situ and theoretical studies for the dissociation of water on an active Ni/CeO₂ catalyst: Importance of strong metal-support interactions for the cleavage of O-H bonds

Abstract

Water dissociation is crucial in many catalytic reactions on oxide-supported transition-metal catalysts. Here, supported by experimental and density-functional theory results, we elucidate the effect of the support on O-H bond cleavage activity for nickel/ceria systems. Ambient-pressure O1s photoemission spectra at low Ni loadings on CeO₂(111) reveal a substantially larger amount of OH groups as compared to the bare support. Our computed activation energy barriers for water dissociation show an enhanced reactivity of Ni adatoms on CeO₂(111) compared with pyramidal Ni₄ particles with one Ni atom not in contact with the support, and extended Ni(111) surfaces. At the origin of this support effect is the ability of ceria to stabilize oxidized Ni²⁺ species by accommodating electrons in localized f-states. The fast dissociation of water on Ni/CeO₂ has a dramatic effect on the activity and stability of this system as a catalyst for the water-gas shift and ethanol steam reforming reactions.

Authors:
 [1];  [2];  [1];  [2];  [3];  [4];  [5];  [6];  [3];  [7]
  1. Inst. de Catalisis y Petroleoquimica, CSIC, Madrid (Spain); CIC Energigune, Minana, Alava (Spain)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
  3. Charles Univ., Praha (Czech Republic)
  4. Univ. Central de Venezuela, Caracas (Venezuela)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  7. Inst. de Catalisis y Petroleoquimica, CSIC, Madrid (Spain)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1183857
Report Number(s):
BNL-107982-2015-JA
Journal ID: ISSN 1433-7851; R&D Project: CO-040; KC0302010
Grant/Contract Number:  
SC00112704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 54; Journal Issue: 13; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; national synchrotron light source

Citation Formats

Carrasco, Javier, Rodriguez, Jose A., Lopez-Duran, David, Liu, Zongyuan, Duchon, Tomas, Evans, Jaime, Senanayake, Sanjaya D., Crumlin, Ethan J., Matolin, Vladimir, and Ganduglia-Pirovano, M. Veronica. In-situ and theoretical studies for the dissociation of water on an active Ni/CeO₂ catalyst: Importance of strong metal-support interactions for the cleavage of O-H bonds. United States: N. p., 2015. Web. doi:10.1002/anie.201410697.
Carrasco, Javier, Rodriguez, Jose A., Lopez-Duran, David, Liu, Zongyuan, Duchon, Tomas, Evans, Jaime, Senanayake, Sanjaya D., Crumlin, Ethan J., Matolin, Vladimir, & Ganduglia-Pirovano, M. Veronica. In-situ and theoretical studies for the dissociation of water on an active Ni/CeO₂ catalyst: Importance of strong metal-support interactions for the cleavage of O-H bonds. United States. doi:10.1002/anie.201410697.
Carrasco, Javier, Rodriguez, Jose A., Lopez-Duran, David, Liu, Zongyuan, Duchon, Tomas, Evans, Jaime, Senanayake, Sanjaya D., Crumlin, Ethan J., Matolin, Vladimir, and Ganduglia-Pirovano, M. Veronica. Mon . "In-situ and theoretical studies for the dissociation of water on an active Ni/CeO₂ catalyst: Importance of strong metal-support interactions for the cleavage of O-H bonds". United States. doi:10.1002/anie.201410697. https://www.osti.gov/servlets/purl/1183857.
@article{osti_1183857,
title = {In-situ and theoretical studies for the dissociation of water on an active Ni/CeO₂ catalyst: Importance of strong metal-support interactions for the cleavage of O-H bonds},
author = {Carrasco, Javier and Rodriguez, Jose A. and Lopez-Duran, David and Liu, Zongyuan and Duchon, Tomas and Evans, Jaime and Senanayake, Sanjaya D. and Crumlin, Ethan J. and Matolin, Vladimir and Ganduglia-Pirovano, M. Veronica},
abstractNote = {Water dissociation is crucial in many catalytic reactions on oxide-supported transition-metal catalysts. Here, supported by experimental and density-functional theory results, we elucidate the effect of the support on O-H bond cleavage activity for nickel/ceria systems. Ambient-pressure O1s photoemission spectra at low Ni loadings on CeO₂(111) reveal a substantially larger amount of OH groups as compared to the bare support. Our computed activation energy barriers for water dissociation show an enhanced reactivity of Ni adatoms on CeO₂(111) compared with pyramidal Ni₄ particles with one Ni atom not in contact with the support, and extended Ni(111) surfaces. At the origin of this support effect is the ability of ceria to stabilize oxidized Ni²⁺ species by accommodating electrons in localized f-states. The fast dissociation of water on Ni/CeO₂ has a dramatic effect on the activity and stability of this system as a catalyst for the water-gas shift and ethanol steam reforming reactions.},
doi = {10.1002/anie.201410697},
journal = {Angewandte Chemie (International Edition)},
number = 13,
volume = 54,
place = {United States},
year = {Mon Mar 23 00:00:00 EDT 2015},
month = {Mon Mar 23 00:00:00 EDT 2015}
}

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