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Title: Impact of Surface Composition of SrTiO 3 Catalysts for Oxidative Coupling of Methane

Abstract

Abstract Oxidative coupling of methane (OCM) to C 2 hydrocarbons (C 2 H 6 and C 2 H 4 ) have regained much attention due to the shale gas revolution. Perovskite catalysts have shown promising activity and selectivity to C 2 hydrocarbons. Here, we investigate the effect of surface reconstruction (leading to different surface compositions) of perovskites on the OCM by using SrTiO 3 (STO) as a model catalyst. Different surface densities of Sr (25–96 %) were attained via various treatments of STO. Low energy ion scattering (LEIS) and UV‐Raman results are in good agreement on the surface and subsurface composition of the reconstructed STO. From H 2 ‐TPR, the same H 2 consumption of STO samples allows relating their catalytic performances with surface acid‐base properties (quantified by NH 3 ‐/CO 2 ‐TPD). At 600–800 °C, the surface Sr enrichment was found to enhance CH 4 conversion, C 2 selectivity and the ratio C 2 H 4 /C 2 H 6 up to Sr/(Sr+Ti) of 0.66 and then levels off. Furthermore, the relative concentration of basic sites, base/(base+acid), is found as a better descriptor for STO catalytic performances. This work shows the clear correlation between surface reconstruction, relative basicity/acidity and OCM catalyticmore » performance over perovskite catalysts. The trends here are similar to those for CH 4 combustion over the reconstructed STO in our recent work. Overall, we suggest that tuning surface reconstruction/composition of perovskites can be an effective approach to control CH 4 activation and conversions.« less

Authors:
 [1];  [2];  [2];  [2];  [3];  [4]; ORCiD logo [2]
+ Show Author Affiliations
  1. Department of Chemical &, Biomedical Engineering West Virginia University Morgantown West Virginia 26506 USA, Center for Nanophase Materials Sciences Oak Ridge National Laboratory Oak Ridge Tennessee 37830 USA, Chemical Science Division Oak Ridge National Laboratory Oak Ridge Tennessee 37830 USA
  2. Center for Nanophase Materials Sciences Oak Ridge National Laboratory Oak Ridge Tennessee 37830 USA, Chemical Science Division Oak Ridge National Laboratory Oak Ridge Tennessee 37830 USA
  3. Operando Molecular Spectroscopy &, Catalysis Laboratory Department of Chemical and Biomolecular Engineering Lehigh University Bethlehem Pennsylvania 18015 USA
  4. Department of Chemical &, Biomedical Engineering West Virginia University Morgantown West Virginia 26506 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1504505
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Name: ChemCatChem Journal Volume: 11 Journal Issue: 8; Journal ID: ISSN 1867-3880
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Bai, Lei, Polo‐Garzon, Felipe, Bao, Zhenghong, Luo, Si, Moskowitz, Benjamin M., Tian, Hanjing, and Wu, Zili. Impact of Surface Composition of SrTiO 3 Catalysts for Oxidative Coupling of Methane. Germany: N. p., 2019. Web. doi:10.1002/cctc.201900159.
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Bai, Lei, Polo‐Garzon, Felipe, Bao, Zhenghong, Luo, Si, Moskowitz, Benjamin M., Tian, Hanjing, & Wu, Zili. Impact of Surface Composition of SrTiO 3 Catalysts for Oxidative Coupling of Methane. Germany. https://doi.org/10.1002/cctc.201900159
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Bai, Lei, Polo‐Garzon, Felipe, Bao, Zhenghong, Luo, Si, Moskowitz, Benjamin M., Tian, Hanjing, and Wu, Zili. Tue . "Impact of Surface Composition of SrTiO 3 Catalysts for Oxidative Coupling of Methane". Germany. https://doi.org/10.1002/cctc.201900159.
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@article{osti_1504505,
title = {Impact of Surface Composition of SrTiO 3 Catalysts for Oxidative Coupling of Methane},
author = {Bai, Lei and Polo‐Garzon, Felipe and Bao, Zhenghong and Luo, Si and Moskowitz, Benjamin M. and Tian, Hanjing and Wu, Zili},
abstractNote = {Abstract Oxidative coupling of methane (OCM) to C 2 hydrocarbons (C 2 H 6 and C 2 H 4 ) have regained much attention due to the shale gas revolution. Perovskite catalysts have shown promising activity and selectivity to C 2 hydrocarbons. Here, we investigate the effect of surface reconstruction (leading to different surface compositions) of perovskites on the OCM by using SrTiO 3 (STO) as a model catalyst. Different surface densities of Sr (25–96 %) were attained via various treatments of STO. Low energy ion scattering (LEIS) and UV‐Raman results are in good agreement on the surface and subsurface composition of the reconstructed STO. From H 2 ‐TPR, the same H 2 consumption of STO samples allows relating their catalytic performances with surface acid‐base properties (quantified by NH 3 ‐/CO 2 ‐TPD). At 600–800 °C, the surface Sr enrichment was found to enhance CH 4 conversion, C 2 selectivity and the ratio C 2 H 4 /C 2 H 6 up to Sr/(Sr+Ti) of 0.66 and then levels off. Furthermore, the relative concentration of basic sites, base/(base+acid), is found as a better descriptor for STO catalytic performances. This work shows the clear correlation between surface reconstruction, relative basicity/acidity and OCM catalytic performance over perovskite catalysts. The trends here are similar to those for CH 4 combustion over the reconstructed STO in our recent work. Overall, we suggest that tuning surface reconstruction/composition of perovskites can be an effective approach to control CH 4 activation and conversions.},
doi = {10.1002/cctc.201900159},
journal = {ChemCatChem},
number = 8,
volume = 11,
place = {Germany},
year = {Tue Apr 02 00:00:00 EDT 2019},
month = {Tue Apr 02 00:00:00 EDT 2019}
}
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