Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

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

doi:10.1002/ange.201704656

Title: Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

Journal Article · Wed Jul 19 00:00:00 EDT 2017 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201704656· OSTI ID:1378295

^[1]; Yang, Shi‐Ze ^[2]; Fung, Victor ^[3]; Foo, Guo Shiou ^[1]; Bickel, Elizabeth E. ^[4]; Chisholm, Matthew F. ^[2]; Jiang, De‐en ^[3];

^[1]

Chemical Sciences Division and Center for Nanophase Materials Sciences Oak Ridge National Laboratory Oak Ridge TN 37831 USA
Materials Science and Technology Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA
Department of Chemistry University of California Riverside CA 92521 USA
Department of Chemical Engineering Tennessee Technological University Cookeville TN 38505 USA

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 SrTiO ₃ (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 TiO ₂ . 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 BaZrO ₃ , thus highlighting the generality of the findings of this study.

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Sponsoring Organization:: USDOE

OSTI ID:: 1378295

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 129 Journal Issue: 33; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (46)

Perovskites as Substitutes of Noble Metals for Heterogeneous Catalysis: Dream or Reality Royer, Sébastien; Duprez, Daniel; Can, Fabien Chemical Reviews, Vol. 114, Issue 20 https://doi.org/10.1021/cr500032a	journal	September 2014
Hybrid HF–DFT modeling of monolayer water adsorption on (001) surface of cubic BaHfO3 and BaZrO3 crystals Bandura, A. V.; Evarestov, R. A.; Kuruch, D. D. Surface Science, Vol. 604, Issue 19-20 https://doi.org/10.1016/j.susc.2010.05.030	journal	September 2010
Applications of High Sensitivity-Low Energy Ion Scattering (HS-LEIS) in heterogeneous catalysis ter Veen, H. R. J.; Kim, T.; Wachs, I. E. Catalysis Today, Vol. 140, Issue 3-4 https://doi.org/10.1016/j.cattod.2008.10.012	journal	February 2009
Structure of Superconducting [BaCuOx]2/[CaCuO2]n Superlattices on SrTiO3(001) Investigated by X-ray Scattering Aruta, C.; Zegenhagen, J.; Cowie, B. physica status solidi (a), Vol. 183, Issue 2 https://doi.org/10.1002/1521-396X(200102)183:2<353::AID-PSSA353>3.0.CO;2-V	journal	February 2001
Structure change of TiO2-terminated SrTiO3(001) surfaces by annealing in O2 atmosphere and ultrahigh vacuum Nishimura, T.; Ikeda, A.; Namba, H. Surface Science, Vol. 421, Issue 3 https://doi.org/10.1016/S0039-6028(98)00840-1	journal	February 1999
Recent Advances of Lanthanum-Based Perovskite Oxides for Catalysis Zhu, Huiyuan; Zhang, Pengfei; Dai, Sheng ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01667	journal	September 2015
Photocatalytic Activities of Noble Metal Ion Doped SrTiO ₃ under Visible Light Irradiation Konta, Ryoko; Ishii, Tatsuya; Kato, Hideki The Journal of Physical Chemistry B, Vol. 108, Issue 26 https://doi.org/10.1021/jp049556p	journal	July 2004
Surface Structures of SrTiO ₃ (001): A TiO ₂ -rich Reconstruction with a c(4 × 2) Unit Cell Erdman, Natasha; Warschkow, Oliver; Asta, Mark Journal of the American Chemical Society, Vol. 125, Issue 33 https://doi.org/10.1021/ja034933h	journal	August 2003
Synthesis-Dependent Atomic Surface Structures of Oxide Nanoparticles Lin, Yuyuan; Wen, Jianguo; Hu, Linhua Physical Review Letters, Vol. 111, Issue 15 https://doi.org/10.1103/PhysRevLett.111.156101	journal	October 2013
Surface termination and subsurface restructuring of perovskite-based solid oxide electrode materials Druce, J.; Téllez, H.; Burriel, M. Energy Environ. Sci., Vol. 7, Issue 11 https://doi.org/10.1039/C4EE01497A	journal	January 2014
Water Reactivity on the LaCoO ₃ (001) Surface: An Ambient Pressure X-ray Photoelectron Spectroscopy Study Stoerzinger, Kelsey A.; Hong, Wesley T.; Crumlin, Ethan J. The Journal of Physical Chemistry C, Vol. 118, Issue 34 https://doi.org/10.1021/jp502970r	journal	August 2014
c(6×2) and c(4×2) reconstruction of SrTiO 3 (001) Jiang, Q. D.; Zegenhagen, J. Surface Science, Vol. 425, Issue 2-3 https://doi.org/10.1016/S0039-6028(99)00223-X	journal	April 1999
Acid–Base Reactivity of Perovskite Catalysts Probed via Conversion of 2-Propanol over Titanates and Zirconates Foo, Guo Shiou; Polo-Garzon, Felipe; Fung, Victor ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.7b00783	journal	June 2017
Achieving A-Site Termination on La0.18Sr0.82Al0.59Ta0.41O3 Substrates Ngai, Joseph H.; Schwendemann, Todd C.; Walker, Anna E. Advanced Materials, Vol. 22, Issue 26-27 https://doi.org/10.1002/adma.200904328	journal	April 2010
Adsorption and Reaction of CO and CO ₂ on Oxidized and Reduced SrTiO ₃ (100) Surfaces Azad, Samina; Engelhard, Mark H.; Wang, Li-Qiong The Journal of Physical Chemistry B, Vol. 109, Issue 20 https://doi.org/10.1021/jp045864b	journal	May 2005
The water adsorption on the surfaces of SrMO ₃ (M= Ti, Zr, and Hf) crystalline oxides: quantum and classical modelling Evarestov, R. A.; Bandura, A. V.; Blokhin, E. N. Journal of Physics: Conference Series, Vol. 93 https://doi.org/10.1088/1742-6596/93/1/012001	journal	December 2007
DFT-GGA study of NO adsorption on the LaO (001) surface of LaFeO3 Kizaki, Hidetoshi; Kusakabe, Koichi Surface Science, Vol. 606, Issue 3-4 https://doi.org/10.1016/j.susc.2011.10.016	journal	February 2012
Anomalous Surface Compositions of Stoichiometric Mixed Oxide Compounds Merzlikin, Sergiy V.; Tolkachev, Nikolay N.; Briand, Laura E. Angewandte Chemie International Edition, Vol. 49, Issue 43 https://doi.org/10.1002/anie.201001804	journal	September 2010
First principle study of SrTiO3 (001) surface and adsorption of NO on SrTiO3 (001) Zhang, H. J.; Chen, G.; Li, Z. H. Applied Surface Science, Vol. 253, Issue 20 https://doi.org/10.1016/j.apsusc.2007.03.051	journal	August 2007
Electronic and chemical properties of mixed-metal oxides: Adsorption and reaction of NO on SrTiO3(100) Rodriguez, J. A.; Azad, S.; Wang, L. -Q. The Journal of Chemical Physics, Vol. 118, Issue 14 https://doi.org/10.1063/1.1539864	journal	April 2003
A DFT+U investigation of hydrogen adsorption on the LaFeO ₃ (010) surface Boateng, Isaac W.; Tia, Richard; Adei, Evans Physical Chemistry Chemical Physics, Vol. 19, Issue 10 https://doi.org/10.1039/C6CP08698E	journal	January 2017
Electronic structure and visible light photocatalysis water splitting property of chromium-doped SrTiO3 Liu, J. W.; Chen, G.; Li, Z. H. Journal of Solid State Chemistry, Vol. 179, Issue 12 https://doi.org/10.1016/j.jssc.2006.08.014	journal	December 2006
Transition from Reconstruction toward Thin Film on the (110) Surface of Strontium Titanate Wang, Z.; Loon, A.; Subramanian, A. Nano Letters, Vol. 16, Issue 4 https://doi.org/10.1021/acs.nanolett.5b05211	journal	March 2016
Influence of LaFeO ₃ Surface Termination on Water Reactivity Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R. The Journal of Physical Chemistry Letters, Vol. 8, Issue 5 https://doi.org/10.1021/acs.jpclett.7b00195	journal	February 2017
Adsorption of atomic oxygen on cubic PbTiO3 and LaMnO3 (001) surfaces: A density functional theory study Pilania, G.; Ramprasad, R. Surface Science, Vol. 604, Issue 21-22 https://doi.org/10.1016/j.susc.2010.07.021	journal	October 2010
Electronic structure and thermodynamic stability of double-layered $Sr Ti O_{3} (001)$ surfaces: Ab initio simulations Heifets, Eugene; Piskunov, Sergei; Kotomin, Eugene A. Physical Review B, Vol. 75, Issue 11 https://doi.org/10.1103/PhysRevB.75.115417	journal	March 2007
Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO ₂ Nanocrystals and Its Implication on Photocatalytic Activity Liu, Jue; Olds, Daniel; Peng, Rui Chemistry of Materials, Vol. 29, Issue 13 https://doi.org/10.1021/acs.chemmater.7b01172	journal	June 2017
Photoelectrolysis of water in cells with SrTiO ₃ anodes Mavroides, J. G.; Kafalas, J. A.; Kolesar, D. F. Applied Physics Letters, Vol. 28, Issue 5 https://doi.org/10.1063/1.88723	journal	March 1976
Water Adsorption at the Tetrahedral Titania Surface Layer of SrTiO ₃ (110)-(4 × 1) Wang, Zhiming; Hao, Xianfeng; Gerhold, Stefan The Journal of Physical Chemistry C, Vol. 117, Issue 49 https://doi.org/10.1021/jp407889h	journal	December 2013
The structure and chemistry of the TiO2-rich surface of SrTiO3 (001) Erdman, Natasha; Poeppelmeier, Kenneth R.; Asta, Mark Nature, Vol. 419, Issue 6902 https://doi.org/10.1038/nature01010	journal	September 2002
Adsorption of water on (001) surface of SrTiO3 and SrZrO3 cubic perovskites: Hybrid HF-DFT LCAO calculations Evarestov, R. A.; Bandura, A. V.; Alexandrov, V. E. Surface Science, Vol. 601, Issue 8 https://doi.org/10.1016/j.susc.2007.02.010	journal	April 2007
A highly active and stable IrO _x /SrIrO ₃ catalyst for the oxygen evolution reaction Seitz, Linsey C.; Dickens, Colin F.; Nishio, Kazunori Science, Vol. 353, Issue 6303 https://doi.org/10.1126/science.aaf5050	journal	September 2016
High Chemical Activity of a Perovskite Surface: Reaction of CO with ${Sr}_{3} {Ru}_{2} O_{7}$ Stöger, Bernhard; Hieckel, Marcel; Mittendorfer, Florian Physical Review Letters, Vol. 113, Issue 11 https://doi.org/10.1103/PhysRevLett.113.116101	journal	September 2014
Development of high dielectric constant epitaxial oxides on silicon by molecular beam epitaxy Droopad, R.; Yu, Z.; Ramdani, J. Materials Science and Engineering: B, Vol. 87, Issue 3 https://doi.org/10.1016/S0921-5107(01)00727-9	journal	December 2001
Synergistic Oxygen Evolving Activity of a TiO ₂ -Rich Reconstructed SrTiO ₃ (001) Surface Martirez, John Mark P.; Kim, Seungchul; Morales, Erie H. Journal of the American Chemical Society, Vol. 137, Issue 8 https://doi.org/10.1021/ja511332y	journal	February 2015
Catalysis Science of Bulk Mixed Oxides Wachs, Israel E.; Routray, Kamalakanta ACS Catalysis, Vol. 2, Issue 6 https://doi.org/10.1021/cs2005482	journal	April 2012
Atomically flat SrO-terminated SrTiO3(001) substrate Bachelet, R.; Sánchez, F.; Palomares, F. J. Applied Physics Letters, Vol. 95, Issue 14 https://doi.org/10.1063/1.3240869	journal	October 2009
Rh-Doped SrTiO ₃ Photocatalyst Electrode Showing Cathodic Photocurrent for Water Splitting under Visible-Light Irradiation Iwashina, Katsuya; Kudo, Akihiko Journal of the American Chemical Society, Vol. 133, Issue 34 https://doi.org/10.1021/ja2050315	journal	August 2011
Ethanol reactivity over La1+x FeO3+δ perovskites Tesquet, Guillaume; Faye, Jérémy; Hosoglu, Fadime Applied Catalysis A: General, Vol. 511 https://doi.org/10.1016/j.apcata.2015.12.005	journal	February 2016
Combined experimental and theoretical investigation of the CO2 adsorption on LaMnO3+y perovskite oxide Hammami, Ramzi; Batis, Habib; Minot, Christian Surface Science, Vol. 603, Issue 20 https://doi.org/10.1016/j.susc.2009.08.016	journal	October 2009
Surface Tuning of La _0.5 Sr _0.5 CoO ₃ Perovskite Catalysts by Acetic Acid for NO _x Storage and Reduction Peng, Yue; Si, Wenzhe; Luo, Jinming Environmental Science & Technology, Vol. 50, Issue 12 https://doi.org/10.1021/acs.est.6b00110	journal	June 2016
Electric field effect in high T _c superconducting ultrathin YBa ₂ Cu ₃ O _{7− x} films Xi, X. X.; Li, Q.; Doughty, C. Applied Physics Letters, Vol. 59, Issue 26 https://doi.org/10.1063/1.105656	journal	December 1991
A review of dry (CO ₂ ) reforming of methane over noble metal catalysts Pakhare, Devendra; Spivey, James Chem. Soc. Rev., Vol. 43, Issue 22 https://doi.org/10.1039/C3CS60395D	journal	January 2014
Nature of Catalytic Active Sites Present on the Surface of Advanced Bulk Tantalum Mixed Oxide Photocatalysts Phivilay, Somphonh P.; Puretzky, Alexander A.; Domen, Kazunari ACS Catalysis, Vol. 3, Issue 12 https://doi.org/10.1021/cs400662m	journal	November 2013
Anomale Oberflächenzusammensetzung stöchiometrischer Mischoxid-Verbindungen Merzlikin, Sergiy V.; Tolkachev, Nikolay N.; Briand, Laura E. Angewandte Chemie, Vol. 122, Issue 43 https://doi.org/10.1002/ange.201001804	journal	September 2010
Surface phase, morphology, and charge distribution transitions on vacuum and ambient annealed $SrTi O_{3}$ (100) Dagdeviren, Omur E.; Simon, Georg H.; Zou, Ke Physical Review B, Vol. 93, Issue 19 https://doi.org/10.1103/PhysRevB.93.195303	journal	May 2016

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