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

Title: Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

Abstract

Although well known in the material science field, surface reconstruction of perovskites has not been implemented in heterogeneous catalysis. In this work, we employ multiple surface sensitive techniques to characterize the surface reconstruction of SrTiO3 (STO) after thermal pretreatment (Sr-enrichment) and chemical etching (Ti-enrichment). We show, using the conversion of 2-propanol as a probe reaction, that the surface reconstruction of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivities in a wide range, which are inaccessible using single metal oxides, either SrO or TiO2. Density functional theory (DFT) calculations well explain the selectivity tuning and reaction mechanism on differently reconstructed surfaces of STO. Similar catalytic tunability is also observed on BaZrO3, highlighting the generality of the finding from this work.

Authors:
ORCiD logo [1];  [2];  [3];  [1];  [4];  [2];  [3]; ORCiD logo [1]
  1. Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA
  2. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA
  3. Department of Chemistry, University of California, Riverside CA 92521 USA
  4. Department of Chemical Engineering, Tennessee Technological University, Cookeville TN 38505 USA
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1400188
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 56; Journal Issue: 33; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English

Citation Formats

Polo-Garzon, Felipe, Yang, Shi-Ze, Fung, Victor, Foo, Guo Shiou, Bickel, Elizabeth E., Chisholm, Matthew F., Jiang, De-en, and Wu, Zili. Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts. United States: N. p., 2017. Web. doi:10.1002/anie.201704656.
Polo-Garzon, Felipe, Yang, Shi-Ze, Fung, Victor, Foo, Guo Shiou, Bickel, Elizabeth E., Chisholm, Matthew F., Jiang, De-en, & Wu, Zili. Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts. United States. doi:10.1002/anie.201704656.
Polo-Garzon, Felipe, Yang, Shi-Ze, Fung, Victor, Foo, Guo Shiou, Bickel, Elizabeth E., Chisholm, Matthew F., Jiang, De-en, and Wu, Zili. Wed . "Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts". United States. doi:10.1002/anie.201704656.
@article{osti_1400188,
title = {Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts},
author = {Polo-Garzon, Felipe and Yang, Shi-Ze and Fung, Victor and Foo, Guo Shiou and Bickel, Elizabeth E. and Chisholm, Matthew F. and Jiang, De-en and Wu, Zili},
abstractNote = {Although well known in the material science field, surface reconstruction of perovskites has not been implemented in heterogeneous catalysis. In this work, we employ multiple surface sensitive techniques to characterize the surface reconstruction of SrTiO3 (STO) after thermal pretreatment (Sr-enrichment) and chemical etching (Ti-enrichment). We show, using the conversion of 2-propanol as a probe reaction, that the surface reconstruction of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivities in a wide range, which are inaccessible using single metal oxides, either SrO or TiO2. Density functional theory (DFT) calculations well explain the selectivity tuning and reaction mechanism on differently reconstructed surfaces of STO. Similar catalytic tunability is also observed on BaZrO3, highlighting the generality of the finding from this work.},
doi = {10.1002/anie.201704656},
journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 33,
volume = 56,
place = {United States},
year = {2017},
month = {7}
}

Works referenced in this record:

Perovskites as Substitutes of Noble Metals for Heterogeneous Catalysis: Dream or Reality
journal, September 2014

  • Royer, Sébastien; Duprez, Daniel; Can, Fabien
  • Chemical Reviews, Vol. 114, Issue 20
  • DOI: 10.1021/cr500032a

Hybrid HF–DFT modeling of monolayer water adsorption on (001) surface of cubic BaHfO3 and BaZrO3 crystals
journal, September 2010


Applications of High Sensitivity-Low Energy Ion Scattering (HS-LEIS) in heterogeneous catalysis
journal, February 2009


Structure of Superconducting [BaCuOx]2/[CaCuO2]n Superlattices on SrTiO3(001) Investigated by X-ray Scattering
journal, February 2001


Structure change of TiO2-terminated SrTiO3(001) surfaces by annealing in O2 atmosphere and ultrahigh vacuum
journal, February 1999


Recent Advances of Lanthanum-Based Perovskite Oxides for Catalysis
journal, September 2015


Photocatalytic Activities of Noble Metal Ion Doped SrTiO 3 under Visible Light Irradiation
journal, July 2004

  • Konta, Ryoko; Ishii, Tatsuya; Kato, Hideki
  • The Journal of Physical Chemistry B, Vol. 108, Issue 26
  • DOI: 10.1021/jp049556p

Surface Structures of SrTiO 3 (001):  A TiO 2 -rich Reconstruction with a c(4 × 2) Unit Cell
journal, August 2003

  • Erdman, Natasha; Warschkow, Oliver; Asta, Mark
  • Journal of the American Chemical Society, Vol. 125, Issue 33
  • DOI: 10.1021/ja034933h

Synthesis-Dependent Atomic Surface Structures of Oxide Nanoparticles
journal, October 2013


Surface termination and subsurface restructuring of perovskite-based solid oxide electrode materials
journal, January 2014

  • Druce, J.; Téllez, H.; Burriel, M.
  • Energy Environ. Sci., Vol. 7, Issue 11
  • DOI: 10.1039/C4EE01497A

Water Reactivity on the LaCoO 3 (001) Surface: An Ambient Pressure X-ray Photoelectron Spectroscopy Study
journal, August 2014

  • Stoerzinger, Kelsey A.; Hong, Wesley T.; Crumlin, Ethan J.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 34
  • DOI: 10.1021/jp502970r

c(6×2) and c(4×2) reconstruction of SrTiO 3 (001)
journal, April 1999


Acid–Base Reactivity of Perovskite Catalysts Probed via Conversion of 2-Propanol over Titanates and Zirconates
journal, June 2017


Achieving A-Site Termination on La0.18Sr0.82Al0.59Ta0.41O3 Substrates
journal, April 2010

  • Ngai, Joseph H.; Schwendemann, Todd C.; Walker, Anna E.
  • Advanced Materials, Vol. 22, Issue 26-27
  • DOI: 10.1002/adma.200904328

Adsorption and Reaction of CO and CO 2 on Oxidized and Reduced SrTiO 3 (100) Surfaces
journal, May 2005

  • Azad, Samina; Engelhard, Mark H.; Wang, Li-Qiong
  • The Journal of Physical Chemistry B, Vol. 109, Issue 20
  • DOI: 10.1021/jp045864b

The water adsorption on the surfaces of SrMO 3 (M= Ti, Zr, and Hf) crystalline oxides: quantum and classical modelling
journal, December 2007


DFT-GGA study of NO adsorption on the LaO (001) surface of LaFeO3
journal, February 2012


Anomalous Surface Compositions of Stoichiometric Mixed Oxide Compounds
journal, September 2010

  • Merzlikin, Sergiy V.; Tolkachev, Nikolay N.; Briand, Laura E.
  • Angewandte Chemie International Edition, Vol. 49, Issue 43
  • DOI: 10.1002/anie.201001804

First principle study of SrTiO3 (001) surface and adsorption of NO on SrTiO3 (001)
journal, August 2007


Electronic and chemical properties of mixed-metal oxides: Adsorption and reaction of NO on SrTiO3(100)
journal, April 2003

  • Rodriguez, J. A.; Azad, S.; Wang, L. -Q.
  • The Journal of Chemical Physics, Vol. 118, Issue 14
  • DOI: 10.1063/1.1539864

A DFT+U investigation of hydrogen adsorption on the LaFeO 3 (010) surface
journal, January 2017

  • Boateng, Isaac W.; Tia, Richard; Adei, Evans
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 10
  • DOI: 10.1039/C6CP08698E

Electronic structure and visible light photocatalysis water splitting property of chromium-doped SrTiO3
journal, December 2006


Transition from Reconstruction toward Thin Film on the (110) Surface of Strontium Titanate
journal, March 2016


Influence of LaFeO 3 Surface Termination on Water Reactivity
journal, February 2017

  • Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 5
  • DOI: 10.1021/acs.jpclett.7b00195

Adsorption of atomic oxygen on cubic PbTiO3 and LaMnO3 (001) surfaces: A density functional theory study
journal, October 2010


Electronic structure and thermodynamic stability of double-layered Sr Ti O 3 ( 001 ) surfaces: Ab initio simulations
journal, March 2007


Photoelectrolysis of water in cells with SrTiO 3 anodes
journal, March 1976

  • Mavroides, J. G.; Kafalas, J. A.; Kolesar, D. F.
  • Applied Physics Letters, Vol. 28, Issue 5
  • DOI: 10.1063/1.88723

Water Adsorption at the Tetrahedral Titania Surface Layer of SrTiO 3 (110)-(4 × 1)
journal, December 2013

  • Wang, Zhiming; Hao, Xianfeng; Gerhold, Stefan
  • The Journal of Physical Chemistry C, Vol. 117, Issue 49
  • DOI: 10.1021/jp407889h

The structure and chemistry of the TiO2-rich surface of SrTiO3 (001)
journal, September 2002

  • Erdman, Natasha; Poeppelmeier, Kenneth R.; Asta, Mark
  • Nature, Vol. 419, Issue 6902
  • DOI: 10.1038/nature01010

Adsorption of water on (001) surface of SrTiO3 and SrZrO3 cubic perovskites: Hybrid HF-DFT LCAO calculations
journal, April 2007


A highly active and stable IrO x /SrIrO 3 catalyst for the oxygen evolution reaction
journal, September 2016


High Chemical Activity of a Perovskite Surface: Reaction of CO with Sr 3 Ru 2 O 7
journal, September 2014


Development of high dielectric constant epitaxial oxides on silicon by molecular beam epitaxy
journal, December 2001


Synergistic Oxygen Evolving Activity of a TiO 2 -Rich Reconstructed SrTiO 3 (001) Surface
journal, February 2015

  • Martirez, John Mark P.; Kim, Seungchul; Morales, Erie H.
  • Journal of the American Chemical Society, Vol. 137, Issue 8
  • DOI: 10.1021/ja511332y

Catalysis Science of Bulk Mixed Oxides
journal, April 2012

  • Wachs, Israel E.; Routray, Kamalakanta
  • ACS Catalysis, Vol. 2, Issue 6
  • DOI: 10.1021/cs2005482

Atomically flat SrO-terminated SrTiO3(001) substrate
journal, October 2009

  • Bachelet, R.; Sánchez, F.; Palomares, F. J.
  • Applied Physics Letters, Vol. 95, Issue 14
  • DOI: 10.1063/1.3240869

Rh-Doped SrTiO 3 Photocatalyst Electrode Showing Cathodic Photocurrent for Water Splitting under Visible-Light Irradiation
journal, August 2011

  • Iwashina, Katsuya; Kudo, Akihiko
  • Journal of the American Chemical Society, Vol. 133, Issue 34
  • DOI: 10.1021/ja2050315

Ethanol reactivity over La1+x FeO3+δ perovskites
journal, February 2016


Combined experimental and theoretical investigation of the CO2 adsorption on LaMnO3+y perovskite oxide
journal, October 2009


Surface Tuning of La 0.5 Sr 0.5 CoO 3 Perovskite Catalysts by Acetic Acid for NO x Storage and Reduction
journal, June 2016

  • Peng, Yue; Si, Wenzhe; Luo, Jinming
  • Environmental Science & Technology, Vol. 50, Issue 12
  • DOI: 10.1021/acs.est.6b00110

Electric field effect in high T c superconducting ultrathin YBa 2 Cu 3 O 7− x films
journal, December 1991

  • Xi, X. X.; Li, Q.; Doughty, C.
  • Applied Physics Letters, Vol. 59, Issue 26
  • DOI: 10.1063/1.105656

A review of dry (CO 2 ) reforming of methane over noble metal catalysts
journal, January 2014

  • Pakhare, Devendra; Spivey, James
  • Chem. Soc. Rev., Vol. 43, Issue 22
  • DOI: 10.1039/C3CS60395D

Nature of Catalytic Active Sites Present on the Surface of Advanced Bulk Tantalum Mixed Oxide Photocatalysts
journal, November 2013

  • Phivilay, Somphonh P.; Puretzky, Alexander A.; Domen, Kazunari
  • ACS Catalysis, Vol. 3, Issue 12
  • DOI: 10.1021/cs400662m

Anomale Oberflächenzusammensetzung stöchiometrischer Mischoxid-Verbindungen
journal, September 2010

  • Merzlikin, Sergiy V.; Tolkachev, Nikolay N.; Briand, Laura E.
  • Angewandte Chemie, Vol. 122, Issue 43
  • DOI: 10.1002/ange.201001804

Surface phase, morphology, and charge distribution transitions on vacuum and ambient annealed SrTi O 3 (100)
journal, May 2016