skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Importance of Low Dimensional CeO x Nanostructures in Pt/CeO x –TiO 2 Catalysts for the Water–Gas Shift Reaction

Abstract

CO2 and H2 production from the water–gas shift (WGS) reaction was studied over Pt/CeOx–TiO2 catalysts with incremental loadings of CeOx, which adopts variations in the local morphology. The lowest loading of CeOx (1 wt % to 0.5 at. %) that is configured in its smallest dimensions exhibited the best WGS activity over larger dimensional structures. We attribute this to several factors including the ultrafine dispersed one-dimensional nanocluster geometry, a large concentration of Ce3+ and enhanced reducibility of the low loadings. We utilized several in situ experiments to monitor the active state of the catalyst during the WGS reaction. X-ray diffraction (XRD) results showed lattice expansion that indicated reduced ceria was prevalent during the WGS reaction. On the surface, Ce3+ related hydroxyl groups were identified by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The enhanced reducibility of the catalyst with the introduction of ceria was further revealed by H2-temperature programed reduction (H2-TPR) and good thermal stability was confirmed by in situ environmental transmission electron microscopy (ETEM). Finally, we also investigated the formation of the low dimensional structures during catalyst preparation, through a two-stage crystal growth of ceria crystallite on TiO2 nanoparticle: fine crystallites ~1D formed at ~250 °C, followed by crystalmore » growth into 2D chain and 3D particle from 250–400 °C.« less

Authors:
; ; ; ORCiD logo; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1347370
Report Number(s):
BNL-113651-2017-JA
Journal ID: ISSN 1932-7447; R&D Project: CO009; KC0302010
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 12; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Luo, Si, Barrio, Laura, Nguyen-Phan, Thuy-Duong, Vovchok, Dimitriy, Johnston-Peck, Aaron C., Xu, Wenqian, Stach, Eric A., Rodriguez, José A., and Senanayake, Sanjaya D.. Importance of Low Dimensional CeO x Nanostructures in Pt/CeO x –TiO 2 Catalysts for the Water–Gas Shift Reaction. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpcc.6b12285.
Luo, Si, Barrio, Laura, Nguyen-Phan, Thuy-Duong, Vovchok, Dimitriy, Johnston-Peck, Aaron C., Xu, Wenqian, Stach, Eric A., Rodriguez, José A., & Senanayake, Sanjaya D.. Importance of Low Dimensional CeO x Nanostructures in Pt/CeO x –TiO 2 Catalysts for the Water–Gas Shift Reaction. United States. https://doi.org/10.1021/acs.jpcc.6b12285
Luo, Si, Barrio, Laura, Nguyen-Phan, Thuy-Duong, Vovchok, Dimitriy, Johnston-Peck, Aaron C., Xu, Wenqian, Stach, Eric A., Rodriguez, José A., and Senanayake, Sanjaya D.. Wed . "Importance of Low Dimensional CeO x Nanostructures in Pt/CeO x –TiO 2 Catalysts for the Water–Gas Shift Reaction". United States. https://doi.org/10.1021/acs.jpcc.6b12285. https://www.osti.gov/servlets/purl/1347370.
@article{osti_1347370,
title = {Importance of Low Dimensional CeO x Nanostructures in Pt/CeO x –TiO 2 Catalysts for the Water–Gas Shift Reaction},
author = {Luo, Si and Barrio, Laura and Nguyen-Phan, Thuy-Duong and Vovchok, Dimitriy and Johnston-Peck, Aaron C. and Xu, Wenqian and Stach, Eric A. and Rodriguez, José A. and Senanayake, Sanjaya D.},
abstractNote = {CO2 and H2 production from the water–gas shift (WGS) reaction was studied over Pt/CeOx–TiO2 catalysts with incremental loadings of CeOx, which adopts variations in the local morphology. The lowest loading of CeOx (1 wt % to 0.5 at. %) that is configured in its smallest dimensions exhibited the best WGS activity over larger dimensional structures. We attribute this to several factors including the ultrafine dispersed one-dimensional nanocluster geometry, a large concentration of Ce3+ and enhanced reducibility of the low loadings. We utilized several in situ experiments to monitor the active state of the catalyst during the WGS reaction. X-ray diffraction (XRD) results showed lattice expansion that indicated reduced ceria was prevalent during the WGS reaction. On the surface, Ce3+ related hydroxyl groups were identified by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The enhanced reducibility of the catalyst with the introduction of ceria was further revealed by H2-temperature programed reduction (H2-TPR) and good thermal stability was confirmed by in situ environmental transmission electron microscopy (ETEM). Finally, we also investigated the formation of the low dimensional structures during catalyst preparation, through a two-stage crystal growth of ceria crystallite on TiO2 nanoparticle: fine crystallites ~1D formed at ~250 °C, followed by crystal growth into 2D chain and 3D particle from 250–400 °C.},
doi = {10.1021/acs.jpcc.6b12285},
journal = {Journal of Physical Chemistry. C},
number = 12,
volume = 121,
place = {United States},
year = {2017},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction
journal, December 2007


New insights in reactivity of hydroxyl groups in water gas shift reaction on Pt/ZrO2
journal, March 2009


Gold-based catalysts for the water–gas shift reaction: Active sites and reaction mechanism☆
journal, February 2011


Mechanistic Studies of the Water–Gas Shift Reaction over Pt/Ce x Zr 1– x O 2 Catalysts: The Effect of Pt Particle Size and Zr Dopant
journal, November 2012

  • Kalamaras, C. M.; Dionysiou, D. D.; Efstathiou, A. M.
  • ACS Catalysis, Vol. 2, Issue 12
  • DOI: 10.1021/cs3006204

Morphological effects of the nanostructured ceria support on the activity and stability of CuO/CeO 2 catalysts for the water-gas shift reaction
journal, January 2014

  • Yao, S. Y.; Xu, W. Q.; Johnston-Peck, A. C.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 32
  • DOI: 10.1039/C4CP02276A

Iron-Based Catalysts for the High-Temperature Water–Gas Shift (HT-WGS) Reaction: A Review
journal, December 2015


Water Gas Shift Reaction on Cu and Au Nanoparticles Supported on CeO2(111) and ZnO(000): Intrinsic Activity and Importance of Support Interactions
journal, February 2007

  • Rodriguez, José A.; Liu, Ping; Hrbek, Jan
  • Angewandte Chemie International Edition, Vol. 46, Issue 8
  • DOI: 10.1002/anie.200603931

Catalytic and DRIFTS study of the WGS reaction on Pt-based catalysts
journal, July 2010


Unusual Physical and Chemical Properties of Ni in Ce 1− x Ni x O 2− y Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction
journal, June 2010

  • Barrio, Laura; Kubacka, Ania; Zhou, Gong
  • The Journal of Physical Chemistry C, Vol. 114, Issue 29
  • DOI: 10.1021/jp103958u

In situ characterization of Ptcatalysts supported on ceria modified TiO2 for the WGS reaction: influence of ceria loading
journal, January 2012

  • Barrio, L.; Zhou, G.; González, I. D.
  • Phys. Chem. Chem. Phys., Vol. 14, Issue 7
  • DOI: 10.1039/C1CP22509J

Water-Gas Shift Reaction on Ni–W–Ce Catalysts: Catalytic Activity and Structural Characterization
journal, January 2014

  • Zhao, Fuzhen; Liu, Zongyuan; Xu, Wenqian
  • The Journal of Physical Chemistry C, Vol. 118, Issue 5
  • DOI: 10.1021/jp410790z

Promotion of the Water-Gas-Shift Reaction by Nickel Hydroxyl Species in Partially Reduced Nickel-Containing Phyllosilicate Catalysts
journal, February 2016

  • Ashok, Jangam; Ang, Ming Li; Terence, Puar Zhi Liang
  • ChemCatChem, Vol. 8, Issue 7
  • DOI: 10.1002/cctc.201501284

PtMo Bimetallic Catalysts Synthesized by Controlled Surface Reactions for Water Gas Shift
journal, January 2016


Origin of Anomalous Lattice Expansion in Oxide Nanoparticles
journal, October 2000


Confinement effects in quasi-stoichiometric CeO 2 nanoparticles
journal, January 2004

  • Hernández-Alonso, María D.; Belén Hungría, Ana; Martínez-Arias, Arturo
  • Phys. Chem. Chem. Phys., Vol. 6, Issue 13
  • DOI: 10.1039/B403202K

Hierarchical Heterogeneity at the CeO x –TiO 2 Interface: Electronic and Geometric Structural Influence on the Photocatalytic Activity of Oxide on Oxide Nanostructures
journal, January 2015

  • Luo, Si; Nguyen-Phan, Thuy-Duong; Johnston-Peck, Aaron C.
  • The Journal of Physical Chemistry C
  • DOI: 10.1021/jp511986n

GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013


In situ diffuse reflectance IR spectroscopy and X-ray absorption spectroscopy for fast catalytic processes
journal, April 2011

  • Marinkovic, Nebojsa S.; Wang, Qi; Frenkel, Anatoly I.
  • Journal of Synchrotron Radiation, Vol. 18, Issue 3
  • DOI: 10.1107/S0909049511005802

Characterization of Structural and Surface Properties of Nanocrystalline TiO 2 −CeO 2 Mixed Oxides by XRD, XPS, TPR, and TPD
journal, July 2009

  • Watanabe, Shingo; Ma, Xiaoliang; Song, Chunshan
  • The Journal of Physical Chemistry C, Vol. 113, Issue 32
  • DOI: 10.1021/jp8110309

Complete Oxidation of CO, Ethanol, and Ethyl Acetate over Copper Oxide Supported on Titania and Ceria Modified Titania
journal, October 1998


Effect of catalyst preparation on Au/Ce1−xZrxO2 and Au–Cu/Ce1−xZrxO2 for steam reforming of methanol
journal, February 2013

  • Pojanavaraphan, Chinchanop; Luengnaruemitchai, Apanee; Gulari, Erdogan
  • International Journal of Hydrogen Energy, Vol. 38, Issue 3
  • DOI: 10.1016/j.ijhydene.2012.10.117

Ca Doping of Nanosize Ce−Zr and Ce−Tb Solid Solutions:  Structural and Electronic Effects
journal, August 2005

  • Fernández-García, Marcos; Wang, Xianqin; Belver, Carolina
  • Chemistry of Materials, Vol. 17, Issue 16
  • DOI: 10.1021/cm050265i

Properties of CeO 2 and Ce 1 - x Zr x O 2 Nanoparticles:  X-ray Absorption Near-Edge Spectroscopy, Density Functional, and Time-Resolved X-ray Diffraction Studies
journal, April 2003

  • Rodriguez, José A.; Hanson, Jonathan C.; Kim, Jae-Yong
  • The Journal of Physical Chemistry B, Vol. 107, Issue 15
  • DOI: 10.1021/jp022323i

The structural and electronic properties of nanostructured Ce1−x−yZrxTbyO2 ternary oxides: Unusual concentration of Tb3+ and metal↔oxygen↔metal interactions
journal, April 2005

  • Wang, Xianqin; Hanson, Jonathan C.; Rodriguez, José A.
  • The Journal of Chemical Physics, Vol. 122, Issue 15
  • DOI: 10.1063/1.1883631

A Model for the Temperature-Programmed Reduction of Low and High Surface Area Ceria
journal, July 2000

  • Giordano, Francesca; Trovarelli, Alessandro; de Leitenburg, Carla
  • Journal of Catalysis, Vol. 193, Issue 2
  • DOI: 10.1006/jcat.2000.2900

An FTIR study of surface ceria hydroxy groups during a redox process with H2
journal, January 1996

  • Badri, Ahmed; Binet, Claude; Lavalley, Jean-Claude
  • Journal of the Chemical Society, Faraday Transactions, Vol. 92, Issue 23
  • DOI: 10.1039/ft9969204669

On the reactivity of carbonate species on a Pt/CeO2 catalyst under various reaction atmospheres: Application of the isotopic exchange technique
journal, August 2005

  • Meunier, Frederic C.; Tibiletti, Daniele; Goguet, Alexandre
  • Applied Catalysis A: General, Vol. 289, Issue 1
  • DOI: 10.1016/j.apcata.2005.04.018

Effect of Support Particle Size in Steam Reforming of Ethanol over Co/CeO 2 Catalysts
journal, September 2012

  • Soykal, I. Ilgaz; Sohn, Hyuntae; Ozkan, Umit S.
  • ACS Catalysis, Vol. 2, Issue 11
  • DOI: 10.1021/cs3004159

Interactions of CO with Pt/ceria catalysts
journal, September 1999


On the structure dependence of CO oxidation over CeO2 nanocrystals with well-defined surface planes
journal, January 2012


CWO of phenol on two differently prepared CuO–CeO2 catalysts
journal, November 2000


Production of hydrogen by steam reforming of methanol over Cu/CeO2 catalysts derived from Ce1−Cu O2− precursors
journal, September 2001


A critical analysis of the experimental evidence for and against a formate mechanism for high activity water-gas shift catalysts
journal, December 2011


Low temperature CO oxidation and water gas shift reaction over Pt/Pd substituted in Fe/TiO2 catalysts
journal, December 2012


    Works referencing / citing this record:

    Hydrogen-Etched TiO2−x as Efficient Support of Gold Catalysts for Water–Gas Shift Reaction
    journal, January 2018


    Black TiO 2−x with stable surface oxygen vacancies as the support of efficient gold catalysts for water-gas shift reaction
    journal, January 2018

    • Li, Lei; Song, Li; Zhu, Longfeng
    • Catalysis Science & Technology, Vol. 8, Issue 5
    • DOI: 10.1039/c7cy02429k