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

Title: Acid–base catalysis over perovskites: a review

Abstract

We present that perovskite catalysts have been extensively studied for reduction–oxidation (redox) reactions; however, their acid–base catalytic properties are still under-explored. This review collects work aiming to study the acid–base catalytic properties of perovskites. Reports regarding combined acid–base/redox catalysis over perovskites lie beyond the scope of the present review. For the characterization of acid–base properties, researchers have studied the interaction of probe molecules with perovskite surfaces by means of multiple techniques that provide information about the density, strength and type of adsorption sites. The top-surface composition of perovskites, which relates to the abundance of the acid–base sites, has been studied by means of low energy ion scattering (LEIS), and, the less surface sensitive, conventional X-ray photoelectron spectroscopy (XPS). Probe reactions, with the conversion of 2-propanol as the common choice, have also been employed for characterizing the acid–base catalytic properties of perovskites. The complex nature of perovskite surfaces, which explains the still absent fundamental relations between the structure of the catalyst and reaction rates/selectivity, encounters a great challenge due to the surface reconstruction of these materials. In this review, we devote a special section to highlight recent publications that report the impact of surface reconstruction and particle shape on acid–base catalysismore » over perovskites. In addition, we review promising catalytic performances of perovskite catalysts for other reactions of interest. Challenges in acid–base catalysis over perovskites focus on the development of time-resolved monolayer-sensitive characterization of surfaces under operando conditions and the discernment of combined acid–base/redox reaction mechanisms. Finally, opportunities lay on tuning the acid–base characteristics of perovskites with computation-based catalytic descriptors to achieve desired selectivities and enhanced rates.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division and Center for Nanophase Materials Sciences
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). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1426559
Alternate Identifier(s):
OSTI ID: 1458369
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Polo-Garzon, Felipe, and Wu, Zili. Acid–base catalysis over perovskites: a review. United States: N. p., 2018. Web. doi:10.1039/c7ta10591f.
Polo-Garzon, Felipe, & Wu, Zili. Acid–base catalysis over perovskites: a review. United States. doi:10.1039/c7ta10591f.
Polo-Garzon, Felipe, and Wu, Zili. Mon . "Acid–base catalysis over perovskites: a review". United States. doi:10.1039/c7ta10591f. https://www.osti.gov/servlets/purl/1426559.
@article{osti_1426559,
title = {Acid–base catalysis over perovskites: a review},
author = {Polo-Garzon, Felipe and Wu, Zili},
abstractNote = {We present that perovskite catalysts have been extensively studied for reduction–oxidation (redox) reactions; however, their acid–base catalytic properties are still under-explored. This review collects work aiming to study the acid–base catalytic properties of perovskites. Reports regarding combined acid–base/redox catalysis over perovskites lie beyond the scope of the present review. For the characterization of acid–base properties, researchers have studied the interaction of probe molecules with perovskite surfaces by means of multiple techniques that provide information about the density, strength and type of adsorption sites. The top-surface composition of perovskites, which relates to the abundance of the acid–base sites, has been studied by means of low energy ion scattering (LEIS), and, the less surface sensitive, conventional X-ray photoelectron spectroscopy (XPS). Probe reactions, with the conversion of 2-propanol as the common choice, have also been employed for characterizing the acid–base catalytic properties of perovskites. The complex nature of perovskite surfaces, which explains the still absent fundamental relations between the structure of the catalyst and reaction rates/selectivity, encounters a great challenge due to the surface reconstruction of these materials. In this review, we devote a special section to highlight recent publications that report the impact of surface reconstruction and particle shape on acid–base catalysis over perovskites. In addition, we review promising catalytic performances of perovskite catalysts for other reactions of interest. Challenges in acid–base catalysis over perovskites focus on the development of time-resolved monolayer-sensitive characterization of surfaces under operando conditions and the discernment of combined acid–base/redox reaction mechanisms. Finally, opportunities lay on tuning the acid–base characteristics of perovskites with computation-based catalytic descriptors to achieve desired selectivities and enhanced rates.},
doi = {10.1039/c7ta10591f},
journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 7,
volume = 6,
place = {United States},
year = {2018},
month = {1}
}

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

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Perovskite bulk structure (a). Top view of the (001) (b), (011) (c) and (111) (d) terminated surfaces.

Save / Share:

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

Solid base catalysts: generation of basic sites and application to organic synthesis
journal, December 2001


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


Surface properties of Sr- and Co-doped LaFeO3
journal, January 2008


Perovskite Oxides: Preparation, Characterizations, and Applications in Heterogeneous Catalysis
journal, August 2014

  • Zhu, Junjiang; Li, Hailong; Zhong, Linyun
  • ACS Catalysis, Vol. 4, Issue 9
  • DOI: 10.1021/cs500606g

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

Influence of surface composition of perovskite-type complex oxides on methane oxidative coupling
journal, October 1993


Acid-base properties and catalytic activity of ABO3 (perovskite-type) oxides consisting of rare earth and 3d transition metals
journal, November 1997

  • Sugunan, S.; Meera, V.
  • Reaction Kinetics and Catalysis Letters, Vol. 62, Issue 2
  • DOI: 10.1007/BF02475471

Effect of synthesis method of LSCF perovskite on its catalytic properties for phenol methylation
journal, August 2010

  • Zawadzki, Mirosław; Grabowska, Hanna; Trawczyński, Janusz
  • Solid State Ionics, Vol. 181, Issue 23-24
  • DOI: 10.1016/j.ssi.2010.06.009

Catalytic conversion of C12–C14 primary alcohols mixture into long-chain ketones
journal, August 2010

  • Klimkiewicz, Roman; Morawski, Ireneusz; Trawczyński, Janusz
  • Catalysis Communications, Vol. 11, Issue 14
  • DOI: 10.1016/j.catcom.2010.05.024

Surface acidity and basicity of γ-Al2O3 doped with K+ and La3+ and calcined at elevated temperatures
journal, February 2003


Absolute Molecular Orientation of Isopropanol at Ceria (100) Surfaces: Insight into Catalytic Selectivity from the Interfacial Structure
journal, June 2017

  • Doughty, Benjamin; Goverapet Srinivasan, Sriram; Bryantsev, Vyacheslav S.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 26
  • DOI: 10.1021/acs.jpcc.7b03272

Synthesis-Dependent Surface Acidity and Structure of SrTiO 3 Nanoparticles
journal, May 2010

  • Rabuffetti, Federico A.; Stair, Peter C.; Poeppelmeier, Kenneth R.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 25
  • DOI: 10.1021/jp101727c

X-ray photoelectron spectroscopy and heterogeneous catalysis, with elimination reactions as an example
journal, January 1977

  • Vinek, Hannelore; Noller, H.; Ebel, Maria
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 73, Issue 0
  • DOI: 10.1039/f19777300734

Structures and Acid−Base Properties of La/Al 2 O 3 Role of La Addition to Enhance Thermal Stability of γ-Al 2 O 3
journal, December 2003

  • Yamamoto, Takashi; Hatsui, Takaki; Matsuyama, Takahiro
  • Chemistry of Materials, Vol. 15, Issue 25
  • DOI: 10.1021/cm034732c

Secondary ketonization of primary alcohol over LaMn-based mixed oxides with perovskite-like structure
journal, June 2009


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


Comprehensive IR study on acid/base properties of metal oxides
journal, August 2012


Structure Sensitivity of Sol-Gel Alkali Tantalates, ATaO<sub>3</sub> (A= Li, Na and K): Acetone Gas Phase Condensation
journal, August 2010


Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting
journal, July 2017

  • Fabbri, Emiliana; Nachtegaal, Maarten; Binninger, Tobias
  • Nature Materials, Vol. 16, Issue 9
  • DOI: 10.1038/nmat4938

Catalysis Science of Bulk Mixed Oxides
journal, April 2012

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

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


Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts
journal, July 2017

  • Polo‐Garzon, Felipe; Yang, Shi‐Ze; Fung, Victor
  • Angewandte Chemie, Vol. 129, Issue 33
  • DOI: 10.1002/ange.201704656

Alumina-Supported Rare-Earth Oxides Characterized by Acid-Catalyzed Reactions and Spectroscopic Methods
journal, March 2001

  • Yamamoto, Takashi; Tanaka, Tsunehiro; Matsuyama, Takahiro
  • The Journal of Physical Chemistry B, Vol. 105, Issue 9
  • DOI: 10.1021/jp003589x

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

Solid-State and Surface Spectroscopic Characterization of BaTiO3 Fine Powders
journal, July 1994

  • Busca, Guido; Buscaglia, Vincenzo; Leoni, Marcello
  • Chemistry of Materials, Vol. 6, Issue 7
  • DOI: 10.1021/cm00043a016

New mesoporous perovskite ZnTiO3 and its excellent catalytic activity in liquid phase organic transformations
journal, February 2011


Exploring perovskites for methane activation from first principles
journal, January 2018

  • Fung, Victor; Polo-Garzon, Felipe; Wu, Zili
  • Catalysis Science & Technology, Vol. 8, Issue 3
  • DOI: 10.1039/c7cy01791j

Double perovskite Pr2−xBixSr2O6 (x=0.533) in ketonization of 1-butanol: Effect of water vapor addition
journal, November 2009


Cubic Perovskite ZnTiO 3 Nanopowder as a Recyclable Heterogeneous Catalyst for the Synthesis of 1,6-Naphthyridines in Water
journal, January 2015


Hybrid catalyst containing nano-sized LaMnO3 and carbon black for high yield and selective ketonization of n-butanol
journal, March 2011


Perovskite type oxide-supported Ni catalysts for the production of 2,5-dimethylfuran from biomass-derived 5-hydroxymethylfurfural
journal, January 2016

  • Chen, Meng-Yuan; Chen, Chu-Bai; Zada, Bakht
  • Green Chemistry, Vol. 18, Issue 13
  • DOI: 10.1039/C6GC00432F

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


Preparation and characterisation of SrTi1−x−yZrxMnyO3 solid solution powders in relation to their use in combustion catalysis
journal, July 1997


Acid–base characterization of heterogeneous catalysts: an up-to-date overview
journal, March 2015


Electron donor sites and acid-base properties of oxide surfaces, as studied by electron spin resonance spectroscopy
journal, January 1976

  • Cordischi, Dante; Indovina, Valerio
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 72, Issue 0
  • DOI: 10.1039/f19767202341

Catalytic activity and selectivity of perovskites La1−xSrxV1−x3+Vx4+O3 for the transformation of isopropanol
journal, October 1995


Recent Approaches in Mechanistic and Kinetic Studies of Catalytic Reactions Using SSITKA Technique
journal, November 2014

  • Ledesma, Cristian; Yang, Jia; Chen, De
  • ACS Catalysis, Vol. 4, Issue 12
  • DOI: 10.1021/cs501264f

Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study
journal, October 2017


Enhanced CO catalytic oxidation by Sr reconstruction on the surface of La x Sr 1− x CoO 3− δ
journal, May 2017


Theoretical Model of Oxidative Adsorption of Water on a Highly Reduced Reconstructed Oxide Surface
journal, September 2014

  • Koocher, Nathan Z.; Martirez, John Mark P.; Rappe, Andrew M.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 19
  • DOI: 10.1021/jz501635f

Perovskites and metal nitrides as catalysts in the base-catalysed aldol addition of isobutyraldehyde to formaldehyde
journal, January 2016

  • Kleineberg, Henrike; Eisenacher, Matthias; Lange, Horst
  • Catalysis Science & Technology, Vol. 6, Issue 15
  • DOI: 10.1039/C5CY01479D

Catalytic behavior of AMoOx (A=Ba, Sr) in oxidation of 2-propanol
journal, April 2009


Dehydrogenation of Isobutane over Zinc Titanate Thin Film Catalysts
journal, July 1996


Crystal facet tailoring arts in perovskite oxides
journal, January 2015

  • Huang, Keke; Yuan, Long; Feng, Shouhua
  • Inorganic Chemistry Frontiers, Vol. 2, Issue 11
  • DOI: 10.1039/C5QI00168D

Shape Effect Undermined by Surface Reconstruction: Ethanol Dehydrogenation over Shape-Controlled SrTiO 3 Nanocrystals
journal, December 2017


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

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


Surface and structure characterization of some perovskite-type powders to be used as combustion catalysts
journal, November 1995

  • Daturi, Marco; Busca, Guido; Willey, Ronald J.
  • Chemistry of Materials, Vol. 7, Issue 11
  • DOI: 10.1021/cm00059a020

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

Understanding trends in C–H bond activation in heterogeneous catalysis
journal, October 2016

  • Latimer, Allegra A.; Kulkarni, Ambarish R.; Aljama, Hassan
  • Nature Materials, Vol. 16, Issue 2
  • DOI: 10.1038/nmat4760

Low energy ion scattering (LEIS). A practical introduction to its theory, instrumentation, and applications
journal, January 2016

  • Cushman, Cody V.; Brüner, Philipp; Zakel, Julia
  • Anal. Methods, Vol. 8, Issue 17
  • DOI: 10.1039/C6AY00765A

Extending the applicability of the Goldschmidt tolerance factor to arbitrary ionic compounds
journal, April 2016

  • Sato, Toyoto; Takagi, Shigeyuki; Deledda, Stefano
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep23592