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Title: Acid–Base Reactivity of Perovskite Catalysts Probed via Conversion of 2-Propanol over Titanates and Zirconates

Abstract

Although perovskite catalysts are well-known for their excellent redox property, their acid–base reactivity remains largely unknown. To explore the potential of perovskites in acid–base catalysis, we made a comprehensive investigation in this work on the acid–base properties and reactivity of a series of selected perovskites, SrTiO3, BaTiO3, SrZrO3, and BaZrO3, via a combination of various approaches including adsorption microcalorimetry, in situ FTIR spectroscopy, steady state kinetic measurements, and density functional theory (DFT) modeling. The perovskite surfaces are shown to be dominated with intermediate and strong basic sites with the presence of some weak Lewis acid sites, due to the preferred exposure of SrO/BaO on the perovskite surfaces as evidenced by low energy ion scattering (LEIS) measurements. Using the conversion of 2-propanol as a probe reaction, we found that the reaction is more selective to dehydrogenation over dehydration due to the dominant surface basicity of the perovskites. Furthermore, the adsorption energy of 2-propanol (ΔHads,2–propanol) is found to be related to both a bulk property (tolerance factor) and the synergy between surface acid and base sites. The results from in situ FTIR and DFT calculations suggest that both dehydration and dehydrogenation reactions occur mainly through the E1cB pathway, which involves the deprotonationmore » of the alcohol group to form a common alkoxy intermediate on the perovskite surfaces. The results obtained in this work pave a path for further exploration and understanding of acid–base catalysis over perovskite catalysts.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  2. Department of Chemistry, University of California, Riverside, California 92521, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1485294
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2155-5435
Country of Publication:
United States
Language:
English

Citation Formats

Foo, Guo Shiou, Polo-Garzon, Felipe, Fung, Victor, Jiang, De-en, Overbury, Steven H., and Wu, Zili. Acid–Base Reactivity of Perovskite Catalysts Probed via Conversion of 2-Propanol over Titanates and Zirconates. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b00783.
Foo, Guo Shiou, Polo-Garzon, Felipe, Fung, Victor, Jiang, De-en, Overbury, Steven H., & Wu, Zili. Acid–Base Reactivity of Perovskite Catalysts Probed via Conversion of 2-Propanol over Titanates and Zirconates. United States. doi:10.1021/acscatal.7b00783.
Foo, Guo Shiou, Polo-Garzon, Felipe, Fung, Victor, Jiang, De-en, Overbury, Steven H., and Wu, Zili. Fri . "Acid–Base Reactivity of Perovskite Catalysts Probed via Conversion of 2-Propanol over Titanates and Zirconates". United States. doi:10.1021/acscatal.7b00783.
@article{osti_1485294,
title = {Acid–Base Reactivity of Perovskite Catalysts Probed via Conversion of 2-Propanol over Titanates and Zirconates},
author = {Foo, Guo Shiou and Polo-Garzon, Felipe and Fung, Victor and Jiang, De-en and Overbury, Steven H. and Wu, Zili},
abstractNote = {Although perovskite catalysts are well-known for their excellent redox property, their acid–base reactivity remains largely unknown. To explore the potential of perovskites in acid–base catalysis, we made a comprehensive investigation in this work on the acid–base properties and reactivity of a series of selected perovskites, SrTiO3, BaTiO3, SrZrO3, and BaZrO3, via a combination of various approaches including adsorption microcalorimetry, in situ FTIR spectroscopy, steady state kinetic measurements, and density functional theory (DFT) modeling. The perovskite surfaces are shown to be dominated with intermediate and strong basic sites with the presence of some weak Lewis acid sites, due to the preferred exposure of SrO/BaO on the perovskite surfaces as evidenced by low energy ion scattering (LEIS) measurements. Using the conversion of 2-propanol as a probe reaction, we found that the reaction is more selective to dehydrogenation over dehydration due to the dominant surface basicity of the perovskites. Furthermore, the adsorption energy of 2-propanol (ΔHads,2–propanol) is found to be related to both a bulk property (tolerance factor) and the synergy between surface acid and base sites. The results from in situ FTIR and DFT calculations suggest that both dehydration and dehydrogenation reactions occur mainly through the E1cB pathway, which involves the deprotonation of the alcohol group to form a common alkoxy intermediate on the perovskite surfaces. The results obtained in this work pave a path for further exploration and understanding of acid–base catalysis over perovskite catalysts.},
doi = {10.1021/acscatal.7b00783},
journal = {ACS Catalysis},
issn = {2155-5435},
number = 7,
volume = 7,
place = {United States},
year = {2017},
month = {6}
}