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Title: Shape Effect Undermined by Surface Reconstruction: Ethanol Dehydrogenation over Shape-Controlled SrTiO3 Nanocrystals

Abstract

For this research, to gain an in-depth understanding of the surface properties relevant for catalysis using ternary oxides, we report the acid–base pair reactivity of shape-controlled SrTiO3 (STO) nanocrystals for the dehydrogenation of ethanol. Cubes, truncated cubes, dodecahedra, and etched cubes of STO with varying ratios of (001) and (110) crystal facets were synthesized using a hydrothermal method. Low-energy ion scattering (LEIS) analysis revealed that the (001) surface on cubes of STO is enriched with SrO due to surface reconstruction, resulting in a high ratio of strong base sites. Chemical treatment with dilute nitric acid to form etched cubes of STO resulted in a surface enriched with Ti cations and strong acidity. Furthermore, the strength and distribution of surface acidic sites increase with the ratio of (110) facet from cubes to truncated cubes to dodecahedra for STO. Kinetic, isotopic, and spectroscopy methods show that the dehydrogenation of ethanol proceeds through the facile dissociation of the alcohol group, followed by the cleavage of the Cα–H bond, which is the rate-determining step. Co-feeding of various probe molecules during catalysis, such as NH3, 2,6-di-tert-butylpyridine, CO2, and SO2, reveals that a pair of Lewis acid site and basic surface oxygen atom is involved inmore » the dehydrogenation reaction. The surface density of acid–base site pairs was measured using acetic acid as a probe molecule, allowing initial acetaldehyde formation turnover rates to be obtained. Comparison among various catalysts reveals no simple correlation between ethanol turnover rate and the percentage of either surface facet ((001) or (110)) of the STO nanocrystals. Instead, the reaction rate is found to increase with the strength of acid sites but reversely with the strength of base sites. The acid–base property is directly related to the surface composition as a result from different surface reconstruction behaviors of the shaped STO nanocrystals. Lastly, the finding in this work underscores the importance of characterizing the top surface compositions and sites properties when assessing the catalytic performance of shape-controlled complex oxides such as perovskites.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division and Center for Nanophase Materials Sciences
  2. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemistry and Biochemistry
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). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1422990
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; 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; 36 MATERIALS SCIENCE; (001) facet; (110) facet; dehydrogenation; ethanol; strontium titanate; surface termination

Citation Formats

Foo, Guo Shiou, Hood, Zachary D., and Wu, Zili. Shape Effect Undermined by Surface Reconstruction: Ethanol Dehydrogenation over Shape-Controlled SrTiO3 Nanocrystals. United States: N. p., 2017. Web. https://doi.org/10.1021/acscatal.7b03341.
Foo, Guo Shiou, Hood, Zachary D., & Wu, Zili. Shape Effect Undermined by Surface Reconstruction: Ethanol Dehydrogenation over Shape-Controlled SrTiO3 Nanocrystals. United States. https://doi.org/10.1021/acscatal.7b03341
Foo, Guo Shiou, Hood, Zachary D., and Wu, Zili. Tue . "Shape Effect Undermined by Surface Reconstruction: Ethanol Dehydrogenation over Shape-Controlled SrTiO3 Nanocrystals". United States. https://doi.org/10.1021/acscatal.7b03341. https://www.osti.gov/servlets/purl/1422990.
@article{osti_1422990,
title = {Shape Effect Undermined by Surface Reconstruction: Ethanol Dehydrogenation over Shape-Controlled SrTiO3 Nanocrystals},
author = {Foo, Guo Shiou and Hood, Zachary D. and Wu, Zili},
abstractNote = {For this research, to gain an in-depth understanding of the surface properties relevant for catalysis using ternary oxides, we report the acid–base pair reactivity of shape-controlled SrTiO3 (STO) nanocrystals for the dehydrogenation of ethanol. Cubes, truncated cubes, dodecahedra, and etched cubes of STO with varying ratios of (001) and (110) crystal facets were synthesized using a hydrothermal method. Low-energy ion scattering (LEIS) analysis revealed that the (001) surface on cubes of STO is enriched with SrO due to surface reconstruction, resulting in a high ratio of strong base sites. Chemical treatment with dilute nitric acid to form etched cubes of STO resulted in a surface enriched with Ti cations and strong acidity. Furthermore, the strength and distribution of surface acidic sites increase with the ratio of (110) facet from cubes to truncated cubes to dodecahedra for STO. Kinetic, isotopic, and spectroscopy methods show that the dehydrogenation of ethanol proceeds through the facile dissociation of the alcohol group, followed by the cleavage of the Cα–H bond, which is the rate-determining step. Co-feeding of various probe molecules during catalysis, such as NH3, 2,6-di-tert-butylpyridine, CO2, and SO2, reveals that a pair of Lewis acid site and basic surface oxygen atom is involved in the dehydrogenation reaction. The surface density of acid–base site pairs was measured using acetic acid as a probe molecule, allowing initial acetaldehyde formation turnover rates to be obtained. Comparison among various catalysts reveals no simple correlation between ethanol turnover rate and the percentage of either surface facet ((001) or (110)) of the STO nanocrystals. Instead, the reaction rate is found to increase with the strength of acid sites but reversely with the strength of base sites. The acid–base property is directly related to the surface composition as a result from different surface reconstruction behaviors of the shaped STO nanocrystals. Lastly, the finding in this work underscores the importance of characterizing the top surface compositions and sites properties when assessing the catalytic performance of shape-controlled complex oxides such as perovskites.},
doi = {10.1021/acscatal.7b03341},
journal = {ACS Catalysis},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {12}
}

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Works referenced in this record:

A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface
journal, January 2004


Anisotropic two-dimensional electron gas at SrTiO3(110)
journal, March 2014

  • Wang, Z.; Zhong, Z.; Hao, X.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 11
  • DOI: 10.1073/pnas.1318304111

Emergent phenomena at oxide interfaces
journal, January 2012

  • Hwang, H. Y.; Iwasa, Y.; Kawasaki, M.
  • Nature Materials, Vol. 11, Issue 2
  • DOI: 10.1038/nmat3223

Propane Oxidation over Pt/SrTiO 3 Nanocuboids
journal, May 2011

  • Enterkin, James A.; Setthapun, Worajit; Elam, Jeffrey W.
  • ACS Catalysis, Vol. 1, Issue 6
  • DOI: 10.1021/cs200092c

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

Recent Advances of Lanthanum-Based Perovskite Oxides for Catalysis
journal, September 2015


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

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

A homologous series of structures on the surface of SrTiO3(110)
journal, February 2010

  • Enterkin, James A.; Subramanian, Arun K.; Russell, Bruce C.
  • Nature Materials, Vol. 9, Issue 3
  • DOI: 10.1038/nmat2636

Transition from Order to Configurational Disorder for Surface Reconstructions on SrTiO 3 (111)
journal, June 2015


Complex surface structure of (110) terminated strontium titanate nanododecahedra
journal, January 2016

  • Crosby, Lawrence A.; Kennedy, Robert M.; Chen, Bor-Rong
  • Nanoscale, Vol. 8, Issue 37
  • DOI: 10.1039/C6NR05516H

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


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


Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts
journal, July 2017

  • Polo-Garzon, Felipe; Yang, Shi-Ze; Fung, Victor
  • Angewandte Chemie International Edition, Vol. 56, Issue 33
  • DOI: 10.1002/anie.201704656

Ab initio calculations of Ba Ti O 3 and Pb Ti O 3 (001) and (011) surface structures
journal, October 2007


Ab initio calculations of the atomic and electronic structure of CaTiO 3 (001) and (011) surfaces
journal, October 2008


Surface properties of atomically flat poly-crystalline SrTiO3
journal, March 2015

  • Woo, Sungmin; Jeong, Hoidong; Lee, Sang A.
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep08822

Acid–Base Reactivity of Perovskite Catalysts Probed via Conversion of 2-Propanol over Titanates and Zirconates
journal, June 2017


Sub-10 nm strontium titanate nanocubes highly dispersed in non-polar organic solvents
journal, January 2010

  • Fujinami, Kyoichi; Katagiri, Kiyofumi; Kamiya, Jumpei
  • Nanoscale, Vol. 2, Issue 10
  • DOI: 10.1039/c0nr00543f

Cubic Perovskite ZnTiO 3 Nanopowder as a Recyclable Heterogeneous Catalyst for the Synthesis of 1,6-Naphthyridines in Water
journal, January 2015


A General Approach to Porous Crystalline TiO 2 , SrTiO 3 , and BaTiO 3 Spheres
journal, July 2006

  • Wang, Yawen; Xu, Hua; Wang, Xiaobing
  • The Journal of Physical Chemistry B, Vol. 110, Issue 28
  • DOI: 10.1021/jp061597t

Template-Free Hydrothermal Synthesis of Single-Crystalline Barium Titanate and Strontium Titanate Nanowires
journal, December 2005


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

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

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

Applications of High Sensitivity-Low Energy Ion Scattering (HS-LEIS) in heterogeneous catalysis
journal, February 2009


Nature of Catalytic Active Sites Present on the Surface of Advanced Bulk Tantalum Mixed Oxide Photocatalysts
journal, November 2013

  • Phivilay, Somphonh P.; Puretzky, Alexander A.; Domen, Kazunari
  • ACS Catalysis, Vol. 3, Issue 12
  • DOI: 10.1021/cs400662m

Direct measurements of water adsorption enthalpy on hafnia and zirconia
journal, October 2005

  • Ushakov, Sergey V.; Navrotsky, Alexandra
  • Applied Physics Letters, Vol. 87, Issue 16
  • DOI: 10.1063/1.2108113

Energy Landscape of Water and Ethanol on Silica Surfaces
journal, June 2015


Changes in the surface topography and electronic structure of SrTiO3(110) single crystals heated under oxidizing and reducing conditions
journal, September 2004


Comprehensive IR study on acid/base properties of metal oxides
journal, August 2012


An FT-IR study of ammonia adsorption and oxidation over anatase-supported metal oxides
journal, September 1997

  • Amores, JosèManuel Gallardo; Escribano, Vicente Sanchez; Ramis, Gianguido
  • Applied Catalysis B: Environmental, Vol. 13, Issue 1
  • DOI: 10.1016/S0926-3373(96)00092-6

Acid–base properties of alumina–magnesia mixed oxides. Part 4.—Infrared study of adsorption of carbon dioxide
journal, January 1984

  • Lercher, Johannes A.; Colombier, Christian; Noller, Heinrich
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 80, Issue 4
  • DOI: 10.1039/f19848000949

Surface Interactions of Glycerol with Acidic and Basic Metal Oxides
journal, October 2013

  • Copeland, John R.; Santillan, Ivan A.; Schimming, Sarah McNew
  • The Journal of Physical Chemistry C, Vol. 117, Issue 41
  • DOI: 10.1021/jp4078695

Ethanol Dehydration and Dehydrogenation on γ-Al 2 O 3 : Mechanism of Acetaldehyde Formation
journal, November 2014

  • DeWilde, Joseph F.; Czopinski, Christopher J.; Bhan, Aditya
  • ACS Catalysis, Vol. 4, Issue 12
  • DOI: 10.1021/cs501239x

Mechanism of dehydrogenation of secondary alcohols on chromia
journal, October 1975


Influence of the Preparative Method on the Activity of Highly Acidic WOx/ZrO2and the Relative Acid Activity Compared with Zeolites
journal, June 1997

  • Santiesteban, J. G.; Vartuli, J. C.; Han, S.
  • Journal of Catalysis, Vol. 168, Issue 2
  • DOI: 10.1006/jcat.1997.1658

Comparison of the acidities of WO3/Al2O3 and ultrastable faujasite catalysts
journal, June 1988


Support effects on Brønsted acid site densities and alcohol dehydration turnover rates on tungsten oxide domains
journal, October 2004


Fourier-transform infrared study of the oxidation of ethene on MoO3/TiO2 catalysts doped with alkali metals
journal, January 1993

  • Martin, Cristina; Martin, Ines; Rives, Vicente
  • Journal of the Chemical Society, Faraday Transactions, Vol. 89, Issue 22
  • DOI: 10.1039/ft9938904131

A dems and FTir spectroscopic investigation of adsorbed ethanol on polycrystalline platinum
journal, March 1994


Isotopic transient analysis of the ethanol coupling reaction over magnesia
journal, February 2013


Multiproduct Steady-State Isotopic Transient Kinetic Analysis of the Ethanol Coupling Reaction over Hydroxyapatite and Magnesia
journal, February 2015

  • Hanspal, Sabra; Young, Zachary D.; Shou, Heng
  • ACS Catalysis, Vol. 5, Issue 3
  • DOI: 10.1021/cs502023g

IR spectral evidence of aldol condensation: Acetaldehyde adsorption over TiO2 surface
journal, December 2008


Competition between Acetaldehyde and Crotonaldehyde during Adsorption and Reaction on Anatase and Rutile Titanium Dioxide
journal, February 1999

  • Rekoske, James E.; Barteau, Mark A.
  • Langmuir, Vol. 15, Issue 6
  • DOI: 10.1021/la9805140

Adsorption and surface reactions of acetaldehyde on TiO2, CeO2 and Al2O3
journal, June 2005


Adsorption and Reaction of Acetaldehyde on Shape-Controlled CeO 2 Nanocrystals: Elucidation of Structure–Function Relationships
journal, June 2014

  • Mann, Amanda K. P.; Wu, Zili; Calaza, Florencia C.
  • ACS Catalysis, Vol. 4, Issue 8
  • DOI: 10.1021/cs500611g

Aldol Condensation of Acetaldehyde over Titania, Hydroxyapatite, and Magnesia
journal, April 2016


Structure and Surface and Catalytic Properties of Mg-Al Basic Oxides
journal, September 1998

  • Di Cosimo, J. I.; Dı́ez, V. K.; Xu, M.
  • Journal of Catalysis, Vol. 178, Issue 2
  • DOI: 10.1006/jcat.1998.2161

Adsorption and Photoinduced Decomposition of Acetone and Acetic Acid on Anatase, Brookite, and Rutile TiO 2 Nanoparticles
journal, July 2010

  • Mattsson, A.; Österlund, L.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 33
  • DOI: 10.1021/jp103263n

On the intermediates of the acetic acid reactions on oxides: an IR study
journal, October 1996


FTIR study of adsorption and photoreactions of acetic acid on TiO2
journal, January 2001

  • Liao, Li-Fen; Lien, Chen-Fu; Lin, Jong-Liang
  • Physical Chemistry Chemical Physics, Vol. 3, Issue 17
  • DOI: 10.1039/b103419g

Ketonization of Carboxylic Acids: Mechanisms, Catalysts, and Implications for Biomass Conversion
journal, October 2013

  • Pham, Tu N.; Sooknoi, Tawan; Crossley, Steven P.
  • ACS Catalysis, Vol. 3, Issue 11
  • DOI: 10.1021/cs400501h

Kinetics and Mechanism of Ethanol Dehydration on γ-Al 2 O 3 : The Critical Role of Dimer Inhibition
journal, February 2013

  • DeWilde, Joseph F.; Chiang, Hsu; Hickman, Daniel A.
  • ACS Catalysis, Vol. 3, Issue 4
  • DOI: 10.1021/cs400051k

Kinetics and Mechanism of Methanol Conversion over Anatase Titania Nanoshapes
journal, July 2017


Ceria Catalysts at Nanoscale: How Do Crystal Shapes Shape Catalysis?
journal, June 2017


    Works referencing / citing this record:

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


    Acid–base catalysis over perovskites: a review
    journal, January 2018

    • Polo-Garzon, Felipe; Wu, Zili
    • Journal of Materials Chemistry A, Vol. 6, Issue 7
    • DOI: 10.1039/c7ta10591f

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


    Capsule‐Structured Copper–Zinc Catalyst for Highly Efficient Hydrogenation of Carbon Dioxide to Methanol
    journal, November 2019


    Interstitial N-doped SrSnO 3 perovskite: structural design, modification and photocatalytic degradation of dyes
    journal, January 2019

    • Zhang, Xinhua; Liu, Anjie; Cao, Yali
    • New Journal of Chemistry, Vol. 43, Issue 27
    • DOI: 10.1039/c9nj02087j