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

Title: Understanding the Impact of Surface Reconstruction of Perovskite Catalysts on CH4 Activation and Combustion

Abstract

Methane conversion has received renewed interest due to the rapid growth in production of shale gas. Methane combustion for power generation and transportation is one of the alternatives for methane utilization. However, complete conversion of methane is critical to minimize negative environmental effects from unburned methane, whose noxious effect is 25 times greater than that of CO2. Although perovskite catalysts have high thermal stability, their low activities for methane combustion prevent them from being utilized on a commercial basis. In this work, we show the impact from reconstruction of surface and subsurface monolayers of perovskite catalysts on methane combustion, using SrTiO3 (STO) as a model perovskite. Several STO samples obtained through different synthetic methods and subjected to different postsynthetic treatments were tested for methane combustion. Through top surface characterization, kinetic experiments (including isotope labeling experiments) and density functional theory calculations, it is shown that both surface segregation of Sr and creation of step surfaces of STO can impact the rate of methane combustion over an order of magnitude. Here, this work highlights the role of surface reconstruction in tuning perovskite catalysts for methane activation.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [3];  [4];  [5];  [6];  [7]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of California, Riverside, CA (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  4. Tennessee Technological Univ., Cookeville, TN (United States); Purdue Univ., West Lafayette, IN (United States)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); West Virginia Univ., Morgantown, WV (United States)
  6. West Virginia Univ., Morgantown, WV (United States)
  7. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); W. L. Gore and Assoc., Newark, DE (United States)
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)
OSTI Identifier:
1486951
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 11; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; methane activation; methane combustion; perovskite catalysts; step-sites; surface reconstruction

Citation Formats

Polo-Garzon, Felipe, Fung, Victor, Liu, Xiaoming, Hood, Zachary D., Bickel, Elizabeth E., Bai, Lei, Tian, Hanjing, Foo, Guo Shiou, Chi, Miaofang, Jiang, De-en, and Wu, Zili. Understanding the Impact of Surface Reconstruction of Perovskite Catalysts on CH4 Activation and Combustion. United States: N. p., 2018. Web. https://doi.org/10.1021/acscatal.8b02307.
Polo-Garzon, Felipe, Fung, Victor, Liu, Xiaoming, Hood, Zachary D., Bickel, Elizabeth E., Bai, Lei, Tian, Hanjing, Foo, Guo Shiou, Chi, Miaofang, Jiang, De-en, & Wu, Zili. Understanding the Impact of Surface Reconstruction of Perovskite Catalysts on CH4 Activation and Combustion. United States. https://doi.org/10.1021/acscatal.8b02307
Polo-Garzon, Felipe, Fung, Victor, Liu, Xiaoming, Hood, Zachary D., Bickel, Elizabeth E., Bai, Lei, Tian, Hanjing, Foo, Guo Shiou, Chi, Miaofang, Jiang, De-en, and Wu, Zili. Mon . "Understanding the Impact of Surface Reconstruction of Perovskite Catalysts on CH4 Activation and Combustion". United States. https://doi.org/10.1021/acscatal.8b02307. https://www.osti.gov/servlets/purl/1486951.
@article{osti_1486951,
title = {Understanding the Impact of Surface Reconstruction of Perovskite Catalysts on CH4 Activation and Combustion},
author = {Polo-Garzon, Felipe and Fung, Victor and Liu, Xiaoming and Hood, Zachary D. and Bickel, Elizabeth E. and Bai, Lei and Tian, Hanjing and Foo, Guo Shiou and Chi, Miaofang and Jiang, De-en and Wu, Zili},
abstractNote = {Methane conversion has received renewed interest due to the rapid growth in production of shale gas. Methane combustion for power generation and transportation is one of the alternatives for methane utilization. However, complete conversion of methane is critical to minimize negative environmental effects from unburned methane, whose noxious effect is 25 times greater than that of CO2. Although perovskite catalysts have high thermal stability, their low activities for methane combustion prevent them from being utilized on a commercial basis. In this work, we show the impact from reconstruction of surface and subsurface monolayers of perovskite catalysts on methane combustion, using SrTiO3 (STO) as a model perovskite. Several STO samples obtained through different synthetic methods and subjected to different postsynthetic treatments were tested for methane combustion. Through top surface characterization, kinetic experiments (including isotope labeling experiments) and density functional theory calculations, it is shown that both surface segregation of Sr and creation of step surfaces of STO can impact the rate of methane combustion over an order of magnitude. Here, this work highlights the role of surface reconstruction in tuning perovskite catalysts for methane activation.},
doi = {10.1021/acscatal.8b02307},
journal = {ACS Catalysis},
number = 11,
volume = 8,
place = {United States},
year = {2018},
month = {9}
}

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

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Surface Sr/(Sr+Ti) cation intensity ratio as a function of probing depth using LEIS analysis for a) commercial STO, commercial STO impregnated with Sr and dried at 110 °C overnight (Sr/STO), and Sr/STO calcined at 750 °C; b) chemically etched STO (STO(HNO3)), STO(HNO3) impregnated with Sr and dried atmore » 110 °C overnight (Sr/STO(HNO3)), and Sr/STO(HNO3) calcined at 750 °C. $c$) Correlation between the concentration of Sr at the top surface of the catalyst and the concentration of the subsurface at different probing depths for all STO catalysts studied in this work. Refer to Supporting Information for detailed information about these samples.« less

Save / Share:

Works referenced in this record:

Recent Advances in Catalysts for Methane Combustion
journal, August 2015

  • Chen, Jinghuan; Arandiyan, Hamidreza; Gao, Xiang
  • Catalysis Surveys from Asia, Vol. 19, Issue 3
  • DOI: 10.1007/s10563-015-9191-5

Complete oxidation of methane at low temperature over noble metal based catalysts: a review
journal, November 2002


Catalysts for combustion of methane and lower alkanes
journal, August 2002


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

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

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

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


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

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

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

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


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

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

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

Interaction of nanostructured metal overlayers with oxide surfaces
journal, November 2007


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


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


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


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

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

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


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


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


Sites for Methane Activation on Lithium-Doped Magnesium Oxide Surfaces
journal, April 2014

  • Kwapien, Karolina; Paier, Joachim; Sauer, Joachim
  • Angewandte Chemie International Edition, Vol. 53, Issue 33
  • DOI: 10.1002/anie.201310632

Oxidative Coupling of Methane over SrO Deposited on Different Commercial Supports Precoated with La 2 O 3
journal, June 1998

  • Choudhary, V. R.; Mulla, S. A. R.; Uphade, B. S.
  • Industrial & Engineering Chemistry Research, Vol. 37, Issue 6
  • DOI: 10.1021/ie9706018

Basicities of alumina-supported alkaline earth metal oxides
journal, September 1998

  • Chen, Yu-Wen; Chen, Hsueh-Ying; Lin, Wen-Fa
  • Reaction Kinetics and Catalysis Letters, Vol. 65, Issue 1
  • DOI: 10.1007/BF02475319

Shape-controlled growth of SrTiO3 polyhedral submicro/nanocrystals
journal, August 2014


Enhancing charge separation on high symmetry SrTiO 3 exposed with anisotropic facets for photocatalytic water splitting
journal, January 2016

  • Mu, Linchao; Zhao, Yue; Li, Ailong
  • Energy & Environmental Science, Vol. 9, Issue 7
  • DOI: 10.1039/C6EE00526H

Facet-Specific Assembly of Proteins on SrTiO3 Polyhedral Nanocrystals
journal, May 2014

  • Dong, Lingqing; Luo, Qi; Cheng, Kui
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep05084

Adsorption of Gases in Multimolecular Layers
journal, February 1938

  • Brunauer, Stephen; Emmett, P. H.; Teller, Edward
  • Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319
  • DOI: 10.1021/ja01269a023

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Projector augmented-wave method
journal, December 1994


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects
journal, March 2017


FT-IR Spectroscopic Studies of Methane Adsorption on Magnesium Oxide
journal, February 1994

  • Li, Can; Li, Guoqiang; Xin, Qin
  • The Journal of Physical Chemistry, Vol. 98, Issue 7
  • DOI: 10.1021/j100058a036

Interaction of methane with surface of alumina studied by FT-IR spectroscopy
journal, January 1994

  • Li, Can; Yan, Weihong; Xin, Qin
  • Catalysis Letters, Vol. 24, Issue 3-4
  • DOI: 10.1007/BF00811797

Characterisation of the basicity of modified MgO-catalysts
journal, May 1999


    Works referencing / citing this record:

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


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


    Redox oxidative cracking of n -hexane with Fe-substituted barium hexaaluminates as redox catalysts
    journal, January 2019

    • Tian, Xin; Dudek, Ryan B.; Gao, Yunfei
    • Catalysis Science & Technology, Vol. 9, Issue 9
    • DOI: 10.1039/c8cy02530d

    Surface phase diagrams of La-based perovskites towards the O-rich limit from first principles
    journal, January 2019

    • Li, Yang; Yang, Jie; Zhu, Yi-An
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 24
    • DOI: 10.1039/c9cp02288k

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.