Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

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

doi:10.1002/anie.201704656

Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

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

Surface Chemistry & Catalysis Group

Research output: Contribution to journal › Article › peer-review

53 Scopus citations

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 SrTiO₃ (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 TiO₂. 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 BaZrO₃, thus highlighting the generality of the findings of this study.

Original language	English
Pages (from-to)	9820-9824
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	33
DOIs	https://doi.org/10.1002/anie.201704656
State	Published - Aug 7 2017

Funding

This research was sponsored by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. Part of the research, including FTIR, BET, and kinetic measurements, was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. Electron microscopy at Oak Ridge National Laboratory (S.-Z.Y. and M.F.C.) was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. We thank Henry Luftman (Lehigh University) for performing the LEIS analysis and Zach Hood (graduate student at Georgia Institute of Technology) for performing XPS measurements.

Funders	Funder number
BET
U.S. Department of Energy
Office of Science	DE-AC02-05CH11231
Basic Energy Sciences
Oak Ridge National Laboratory
Division of Materials Sciences and Engineering
Chemical Sciences, Geosciences, and Biosciences Division

Keywords

acid/base catalysis
dehydration/dehydrogenation
heterogeneous catalysis
perovskites
surface termination

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10.1002/anie.201704656

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title = "Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts",

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 SrTiO3 (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 TiO2. 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 BaZrO3, thus highlighting the generality of the findings of this study.",

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author = "Felipe Polo-Garzon and Yang, {Shi Ze} and Victor Fung and Foo, {Guo Shiou} and Bickel, {Elizabeth E.} and Chisholm, {Matthew F.} and Jiang, {De En} and Zili Wu",

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AU - Fung, Victor

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AU - Bickel, Elizabeth E.

AU - Chisholm, Matthew F.

AU - Jiang, De En

AU - Wu, Zili

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N2 - 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 SrTiO3 (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 TiO2. 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 BaZrO3, thus highlighting the generality of the findings of this study.

AB - 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 SrTiO3 (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 TiO2. 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 BaZrO3, thus highlighting the generality of the findings of this study.

KW - acid/base catalysis

KW - dehydration/dehydrogenation

KW - heterogeneous catalysis

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Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

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