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Title: The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals

Abstract

Strontium titanate (SrTiO3) is an extensively investigated perovskite for various applications due to its optical, electrical and chemical properties. To gain an in-depth understanding of the active sites involved in heterogeneous catalysis over the broadly used SrTiO3 (STO), we studied a model reaction, isopropanol conversion, on three differently shape-controlled nanocrystals: cube, truncated cube and dodecahedra. SEM, XRD and XPS confirmed the morphology, phase and composition of STO shapes. Low energy ion scattering (LEIS) revealed the occurrence of surface reconstruction over STO shapes during O2 pretreatment at different temperatures. Based on the catalytic activities, scanning transmission electron microscopy images and density functional theory calculations, the step sites on STO derived from surface reconstruction were proposed to be the active sites for isopropanol conversion. This was further confirmed by steady state isotopic kinetic analysis (SSITKA) which demonstrated similar intrinsic turnover frequencies (TOFs) for the differently reconstructed STO shapes. It is concluded that the crystal facets impose an indirect effect on the catalysis of STO via controlling the degrees of surface reconstruction: the less stable STO (1 1 0) facet (dodecahedra) leads to more step sites after reconstruction and hence higher overall reaction rate than the more stable (1 0 0) facet (cube).more » This work highlights the important interplay between the crystal facet and surface reconstruction in controlling the nature and density of active sties and thus catalysis over complex oxides.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [3]; ORCiD logo [1]; ORCiD logo [1];  [4];  [5]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of California, Riverside, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); West Virginia Univ., Morgantown, WV (United States)
  5. Univ. of California, Riverside, CA (United States)
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)
OSTI Identifier:
1606883
Alternate Identifier(s):
OSTI ID: 1601912
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 384; Journal Issue: C; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Surface reconstruction; SrTiO3; Isopropyl alcohol; Nanoshapes; Facet; SSITKA

Citation Formats

Bao, Zhenghong, Fung, Victor, Polo Garzon, Felipe, Hood, Zachary, Cao, Shaohong, Chi, Miaofang, Bai, Lei, Jiang, De-en, and Wu, Zili. The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals. United States: N. p., 2020. Web. https://doi.org/10.1016/j.jcat.2020.02.014.
Bao, Zhenghong, Fung, Victor, Polo Garzon, Felipe, Hood, Zachary, Cao, Shaohong, Chi, Miaofang, Bai, Lei, Jiang, De-en, & Wu, Zili. The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals. United States. https://doi.org/10.1016/j.jcat.2020.02.014
Bao, Zhenghong, Fung, Victor, Polo Garzon, Felipe, Hood, Zachary, Cao, Shaohong, Chi, Miaofang, Bai, Lei, Jiang, De-en, and Wu, Zili. Thu . "The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals". United States. https://doi.org/10.1016/j.jcat.2020.02.014. https://www.osti.gov/servlets/purl/1606883.
@article{osti_1606883,
title = {The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals},
author = {Bao, Zhenghong and Fung, Victor and Polo Garzon, Felipe and Hood, Zachary and Cao, Shaohong and Chi, Miaofang and Bai, Lei and Jiang, De-en and Wu, Zili},
abstractNote = {Strontium titanate (SrTiO3) is an extensively investigated perovskite for various applications due to its optical, electrical and chemical properties. To gain an in-depth understanding of the active sites involved in heterogeneous catalysis over the broadly used SrTiO3 (STO), we studied a model reaction, isopropanol conversion, on three differently shape-controlled nanocrystals: cube, truncated cube and dodecahedra. SEM, XRD and XPS confirmed the morphology, phase and composition of STO shapes. Low energy ion scattering (LEIS) revealed the occurrence of surface reconstruction over STO shapes during O2 pretreatment at different temperatures. Based on the catalytic activities, scanning transmission electron microscopy images and density functional theory calculations, the step sites on STO derived from surface reconstruction were proposed to be the active sites for isopropanol conversion. This was further confirmed by steady state isotopic kinetic analysis (SSITKA) which demonstrated similar intrinsic turnover frequencies (TOFs) for the differently reconstructed STO shapes. It is concluded that the crystal facets impose an indirect effect on the catalysis of STO via controlling the degrees of surface reconstruction: the less stable STO (1 1 0) facet (dodecahedra) leads to more step sites after reconstruction and hence higher overall reaction rate than the more stable (1 0 0) facet (cube). This work highlights the important interplay between the crystal facet and surface reconstruction in controlling the nature and density of active sties and thus catalysis over complex oxides.},
doi = {10.1016/j.jcat.2020.02.014},
journal = {Journal of Catalysis},
number = C,
volume = 384,
place = {United States},
year = {2020},
month = {2}
}

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Works referenced in this record:

Physics of SrTiO 3 -based heterostructures and nanostructures: a review
journal, February 2018

  • Pai, Yun-Yi; Tylan-Tyler, Anthony; Irvin, Patrick
  • Reports on Progress in Physics, Vol. 81, Issue 3
  • DOI: 10.1088/1361-6633/aa892d

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

Review of photoresponsive properties at SrTiO 3 -based heterointerfaces
journal, November 2018


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

Morphology and CO Oxidation Activity of Pd Nanoparticles on SrTiO 3 Nanopolyhedra
journal, April 2018


Transient Behavior of Ni@NiO x Functionalized SrTiO 3 in Overall Water Splitting
journal, January 2017


Kinetic Coupling of Water Splitting and Photoreforming on SrTiO 3 -Based Photocatalysts
journal, February 2018


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


Strong evidence for d-electron spin transport at room temperature at a LaAlO3/SrTiO3 interface
journal, February 2017

  • Ohshima, Ryo; Ando, Yuichiro; Matsuzaki, Kosuke
  • Nature Materials, Vol. 16, Issue 6
  • DOI: 10.1038/nmat4857

Observation of inverse Edelstein effect in Rashba-split 2DEG between SrTiO 3 and LaAlO 3 at room temperature
journal, March 2017


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

Shape Effect Undermined by Surface Reconstruction: Ethanol Dehydrogenation over Shape-Controlled SrTiO 3 Nanocrystals
journal, December 2017


Understanding the Impact of Surface Reconstruction of Perovskite Catalysts on CH 4 Activation and Combustion
journal, September 2018


Recent Approaches in Mechanistic and Kinetic Studies of Catalytic Reactions Using SSITKA Technique
journal, November 2014

  • Ledesma, Cristian; Yang, Jia; Chen, De
  • ACS Catalysis, Vol. 4, Issue 12
  • DOI: 10.1021/cs501264f

Turnover rates on complex heterogeneous catalysts
journal, September 2018


Reduction of Propionic Acid over a Pd-Promoted ReO x /SiO 2 Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis
journal, July 2018


Characterization of Catalytic Surfaces by Isotopic-Transient Kinetics during Steady-State Reaction
journal, May 1995

  • Shannon, Schohn L.; Goodwin, James G.
  • Chemical Reviews, Vol. 95, Issue 3
  • DOI: 10.1021/cr00035a011

The mechanism of the CH4/O2 reaction on the Pd–Pt/γ-Al2O3 catalyst: A SSITKA study
journal, November 2014


Dry Reforming of Methane on Rh-Doped Pyrochlore Catalysts: A Steady-State Isotopic Transient Kinetic Study
journal, May 2016


Investigation of Alumina-Supported Au Catalyst for CO Oxidation by Isotopic Transient Analysis and X-ray Absorption Spectroscopy
journal, February 2005

  • Calla, Jason T.; Davis, Robert J.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 6
  • DOI: 10.1021/jp0488719

Effect of alumina and titania on the oxidation of CO over Au nanoparticles evaluated by 13C isotopic transient analysis
journal, March 2006


DRIFTS/MS Studies during Chemical Transients and SSITKA of the CO/H 2 Reaction over Co-MgO Catalysts
journal, January 2010

  • Schweicher, Julien; Bundhoo, Adam; Frennet, Alfred
  • The Journal of Physical Chemistry C, Vol. 114, Issue 5
  • DOI: 10.1021/jp909754w

Elucidation of deactivation phenomena in cobalt catalyst for Fischer-Tropsch synthesis using SSITKA
journal, December 2016


Synthesis-Dependent First-Order Raman Scattering in SrTiO 3 Nanocubes at Room Temperature
journal, September 2008

  • Rabuffetti, Federico A.; Kim, Hack-Sung; Enterkin, James A.
  • Chemistry of Materials, Vol. 20, Issue 17
  • DOI: 10.1021/cm801192t

Elucidation of the Reaction Mechanism for High-Temperature Water Gas Shift over an Industrial-Type Copper–Chromium–Iron Oxide Catalyst
journal, April 2019

  • Polo-Garzon, Felipe; Fung, Victor; Nguyen, Luan
  • Journal of the American Chemical Society, Vol. 141, Issue 19
  • DOI: 10.1021/jacs.9b03516

Controlling selectivities in CO2 reduction through mechanistic understanding
journal, September 2017


Steady State Isotopic Transient Kinetic Analysis (SSITKA) Investigation of NO Reduction with CO over Perovskite Catalysts
journal, December 1994

  • Ocal, Meltem; Oukaci, Rachid; Marcelin, George
  • Industrial & Engineering Chemistry Research, Vol. 33, Issue 12
  • DOI: 10.1021/ie00036a006

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

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Projector augmented-wave method
journal, December 1994


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 111, Issue 15
  • DOI: 10.1063/1.480097

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

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


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


Acid–base properties of silica–alumina samples derived from NaX zeolites. Part 1.—Physical characterization and an infrared study of the adsorption of acetone
journal, January 1984

  • Lercher, Johannes A.; Vinek, Hannelore; Noller, Heinrich
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 80, Issue 5
  • DOI: 10.1039/f19848001239

Combustion-synthesis of SrTiO 3 Part II. Sintering behaviour and surface characterization
journal, May 2000


Adsorption of 2-propanol on MgO surface: A combined experimental and theoretical study
journal, February 2015


FT-IR Spectroscopy Study of Surface Acidity and 2-Propanol Decomposition on Mixed Oxides Obtained upon Calcination of Layered Double Hydroxides
journal, April 1997

  • Kooli, Fathi; Martín, Cristina; Rives, Vicente
  • Langmuir, Vol. 13, Issue 8, p. 2303-2306
  • DOI: 10.1021/la960583j

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


Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study
journal, October 2017


Dehydrogenation of isopropyl alcohol on carbon-supported Pt and Cu–Pt catalysts
journal, July 2005


Strong Effect of B-Site Substitution on the Reactivity of Layered Perovskite Oxides Probed via Isopropanol Conversion
journal, July 2019


Revisiting CO Activation on Co Catalysts: Impact of Step and Kink Sites from DFT
journal, February 2017

  • Petersen, Melissa A.; van den Berg, Jan-Albert; Ciobîcă, Ionel M.
  • ACS Catalysis, Vol. 7, Issue 3
  • DOI: 10.1021/acscatal.6b02843

Role of Lattice Strain and Defects in Copper Particles on the Activity of Cu/ZnO/Al2O3 Catalysts for Methanol Synthesis
journal, September 2007

  • Kasatkin, Igor; Kurr, Patrick; Kniep, Benjamin
  • Angewandte Chemie International Edition, Vol. 46, Issue 38
  • DOI: 10.1002/anie.200702600

Structure sensitivity of the methanation reaction: H2-induced CO dissociation on nickel surfaces
journal, April 2008


Crystal facet tailoring arts in perovskite oxides
journal, January 2015

  • Huang, Keke; Yuan, Long; Feng, Shouhua
  • Inorganic Chemistry Frontiers, Vol. 2, Issue 11
  • DOI: 10.1039/C5QI00168D

Surface Reconstructions of Metal Oxides and the Consequences on Catalytic Chemistry
journal, May 2019


Shape-dependence of the thermal and photochemical reactions of methanol on nanocrystalline anatase TiO2
journal, December 2016