Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

Polo-Garzon, Felipe; Yang, Shi-Ze; Fung, Victor; Foo, Guo Shiou; Bickel, Elizabeth E.; Chisholm, Matthew F.; Jiang, De-en; Wu, Zili

doi:10.1002/anie.201704656

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

Abstract

Abstract Although perovskites have been widely used in catalysis, tuning of their surface termination to control reaction selectivity has not been well established. In this study, we employed multiple surface‐sensitive techniques to characterize the surface termination (one aspect of surface reconstruction) of SrTiO ₃ (STO) after thermal pretreatment (Sr enrichment) and chemical etching (Ti enrichment). We show, by using the conversion of 2‐propanol as a probe reaction, that the surface termination of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivity over a wide range, which is not possible with single‐metal oxides, either SrO or TiO ₂ . Density functional theory (DFT) calculations explain well the selectivity tuning and reaction mechanism on STO with different surface termination. Similar catalytic tunability was also observed on BaZrO ₃ , thus highlighting the generality of the findings of this study.

Authors:

^[1]; Yang, Shi-Ze ^[1]; Fung, Victor ^[2]; Foo, Guo Shiou ^[1]; Bickel, Elizabeth E. ^[3]; Chisholm, Matthew F. ^[1]; Jiang, De-en ^[2];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of California, Riverside, CA (United States)
Tennessee Technological Univ., Cookeville, TN (United States)

Publication Date:: Wed Jul 19 00:00:00 EDT 2017

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1399923

Alternate Identifier(s):: OSTI ID: 1378301

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Angewandte Chemie (International Edition)

Additional Journal Information:: Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 33; Journal ID: ISSN 1433-7851

Publisher:: Wiley

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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.

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                    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.  https://doi.org/10.1002/anie.201704656

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                    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.  https://doi.org/10.1002/anie.201704656.  https://www.osti.gov/servlets/purl/1399923.

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@article{osti_1399923,

  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 = {Abstract Although perovskites have been widely used in catalysis, tuning of their surface termination to control reaction selectivity has not been well established. In this study, we employed multiple surface‐sensitive techniques to characterize the surface termination (one aspect of surface reconstruction) of SrTiO 3 (STO) after thermal pretreatment (Sr enrichment) and chemical etching (Ti enrichment). We show, by using the conversion of 2‐propanol as a probe reaction, that the surface termination of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivity over a wide range, which is not possible with single‐metal oxides, either SrO or TiO 2 . Density functional theory (DFT) calculations explain well the selectivity tuning and reaction mechanism on STO with different surface termination. Similar catalytic tunability was also observed on BaZrO 3 , thus highlighting the generality of the findings of this study.},

  doi          = {10.1002/anie.201704656},

  journal      = {Angewandte Chemie (International Edition)},

  number       = 33,

  volume       = 56,

  place        = {United States},

  year         = {Wed Jul 19 00:00:00 EDT 2017},

  month        = {Wed Jul 19 00:00:00 EDT 2017}

}

Copy to clipboard

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

Abstract

Citation Formats

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

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

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

Anomale Oberflächenzusammensetzung stöchiometrischer Mischoxid-Verbindungen journal, September 2010

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

The Facet Structure and Photochemical Reactivity of Arbitrarily Oriented Strontium Titanate Surfaces journal, July 2019

Impact of Surface Composition of SrTiO 3 Catalysts for Oxidative Coupling of Methane journal, April 2019

Insights into Crystal Facets of Perovskite SrSnO 3 as High‐Performance Photocatalysts toward Environmental Remediation journal, August 2018

Enhancement of the SrTiO 3 Surface Reactivity by Exposure to Electric Fields journal, May 2019

Perovskite-Derived Pt–Ni/Zn(Ni)TiO3/SiO2 Catalyst for Propane Dehydrogenation to Propene journal, June 2019

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

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

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

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

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

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

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

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

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

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

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

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

Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO ₂ Nanocrystals and Its Implication on Photocatalytic Activity
journal, June 2017

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

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

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

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

Catalysis Science of Bulk Mixed Oxides
journal, April 2012

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

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

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

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

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

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

Anomale Oberflächenzusammensetzung stöchiometrischer Mischoxid-Verbindungen
journal, September 2010

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

The Facet Structure and Photochemical Reactivity of Arbitrarily Oriented Strontium Titanate Surfaces
journal, July 2019

Impact of Surface Composition of SrTiO ₃ Catalysts for Oxidative Coupling of Methane
journal, April 2019

Insights into Crystal Facets of Perovskite SrSnO ₃ as High‐Performance Photocatalysts toward Environmental Remediation
journal, August 2018

Enhancement of the SrTiO ₃ Surface Reactivity by Exposure to Electric Fields
journal, May 2019

Perovskite-Derived Pt–Ni/Zn(Ni)TiO3/SiO2 Catalyst for Propane Dehydrogenation to Propene
journal, June 2019