Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Single-Facet Dominant Anatase TiO2 (101) and (001) Model Catalysts to Elucidate the Active Sites for Alkanol Dehydration

Abstract

Alkanol dehydration on Lewis acid-base pairs of transition metal oxide catalysts is a reaction of importance in oxygen removal from biomass-derived feedstocks and their conversion to chemicals in general. However, catalysts with a high degree of structural heterogeneity, such as commercial TiO2 powders, are not well-suited to establish rigorous structure-function relationships at an atomic level. Here, we provide compelling evidence for the effects of surface orientation of TiO2 catalyst on elimination reactions of alcohols. Two anatase titania model catalysts, with preferential exposure of (101) and (001) facets, were synthesized and studied for 2-propanol dehydration using kinetic, isotopic, microscopic, and spectroscopic measurements, coupled with DFT calculations. Surface Lewis acid sites were found to be active for 2-propanol dehydration and (101) facets are more reactive than (001) facets under the reaction conditions studied. On both anatase surfaces, 2-propanol was found to dehydrate via concerted E2 elimination pathways, but with different initial states and thus also different intrinsic activation barriers. Molecular 2-propanol dehydration dominates on TiO2 (101) while on TiO2 (001), 2-propanol simultaneously converts to more stable 2-propoxide before dehydration, which then requires higher activation energies for E2 elimination.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Washington State Univ., Pullman, WA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1634996
Report Number(s):
PNNL-SA-150163
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 10; Journal Issue: 7; 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

Citation Formats

Lin, Fan, Chen, Yuan, Zhang, Lu, Mei, Donghai, Kovarik, Libor, Sudduth, Berlin, Wang, Huamin, Gao, Feng, and Wang, Yong. Single-Facet Dominant Anatase TiO2 (101) and (001) Model Catalysts to Elucidate the Active Sites for Alkanol Dehydration. United States: N. p., 2020. Web. doi:10.1021/acscatal.9b04654.
Copy to clipboard
Lin, Fan, Chen, Yuan, Zhang, Lu, Mei, Donghai, Kovarik, Libor, Sudduth, Berlin, Wang, Huamin, Gao, Feng, & Wang, Yong. Single-Facet Dominant Anatase TiO2 (101) and (001) Model Catalysts to Elucidate the Active Sites for Alkanol Dehydration. United States. https://doi.org/10.1021/acscatal.9b04654
Copy to clipboard
Lin, Fan, Chen, Yuan, Zhang, Lu, Mei, Donghai, Kovarik, Libor, Sudduth, Berlin, Wang, Huamin, Gao, Feng, and Wang, Yong. Thu . "Single-Facet Dominant Anatase TiO2 (101) and (001) Model Catalysts to Elucidate the Active Sites for Alkanol Dehydration". United States. https://doi.org/10.1021/acscatal.9b04654. https://www.osti.gov/servlets/purl/1634996.
Copy to clipboard
@article{osti_1634996,
title = {Single-Facet Dominant Anatase TiO2 (101) and (001) Model Catalysts to Elucidate the Active Sites for Alkanol Dehydration},
author = {Lin, Fan and Chen, Yuan and Zhang, Lu and Mei, Donghai and Kovarik, Libor and Sudduth, Berlin and Wang, Huamin and Gao, Feng and Wang, Yong},
abstractNote = {Alkanol dehydration on Lewis acid-base pairs of transition metal oxide catalysts is a reaction of importance in oxygen removal from biomass-derived feedstocks and their conversion to chemicals in general. However, catalysts with a high degree of structural heterogeneity, such as commercial TiO2 powders, are not well-suited to establish rigorous structure-function relationships at an atomic level. Here, we provide compelling evidence for the effects of surface orientation of TiO2 catalyst on elimination reactions of alcohols. Two anatase titania model catalysts, with preferential exposure of (101) and (001) facets, were synthesized and studied for 2-propanol dehydration using kinetic, isotopic, microscopic, and spectroscopic measurements, coupled with DFT calculations. Surface Lewis acid sites were found to be active for 2-propanol dehydration and (101) facets are more reactive than (001) facets under the reaction conditions studied. On both anatase surfaces, 2-propanol was found to dehydrate via concerted E2 elimination pathways, but with different initial states and thus also different intrinsic activation barriers. Molecular 2-propanol dehydration dominates on TiO2 (101) while on TiO2 (001), 2-propanol simultaneously converts to more stable 2-propoxide before dehydration, which then requires higher activation energies for E2 elimination.},
doi = {10.1021/acscatal.9b04654},
journal = {ACS Catalysis},
number = 7,
volume = 10,
place = {United States},
year = {Thu Feb 20 00:00:00 EST 2020},
month = {Thu Feb 20 00:00:00 EST 2020}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acscatal.9b04654
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Dehydration Pathways of 1-Propanol on HZSM-5 in the Presence and Absence of Water
journal, December 2015

  • Zhi, Yuchun; Shi, Hui; Mu, Linyu
  • Journal of the American Chemical Society, Vol. 137, Issue 50
  • DOI: 10.1021/jacs.5b09107

Catalytic dehydration of ethanol using transition metal oxide catalysts
journal, April 2005

Structure–activity relationships on metal-oxides: alcohol dehydration
journal, January 2014

  • Kostestkyy, Pavlo; Yu, Jingye; Gorte, Raymond J.
  • Catal. Sci. Technol., Vol. 4, Issue 11
  • DOI: 10.1039/C4CY00632A

Erratum: Structure and energetics of stoichiometric TiO 2 anatase surfaces [Phys. Rev. B 63 , 155409 (2001)]
journal, February 2002

Anatase TiO2 single crystals with a large percentage of reactive facets
journal, May 2008

  • Yang, Hua Gui; Sun, Cheng Hua; Qiao, Shi Zhang
  • Nature, Vol. 453, Issue 7195
  • DOI: 10.1038/nature06964

On the Unusual Properties of Anatase TiO 2 Exposed by Highly Reactive Facets
journal, March 2011

  • Fang, Wen Qi; Gong, Xue-Qing; Yang, Hua Gui
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 7
  • DOI: 10.1021/jz200117r

Anatase TiO 2 with Dominant High-Energy {001} Facets: Synthesis, Properties, and Applications
journal, September 2011

  • Liu, Shengwei; Yu, Jiaguo; Jaroniec, Mietek
  • Chemistry of Materials, Vol. 23, Issue 18
  • DOI: 10.1021/cm200597m

Nonaqueous Synthesis of TiO 2 Nanocrystals Using TiF 4 to Engineer Morphology, Oxygen Vacancy Concentration, and Photocatalytic Activity
journal, April 2012

  • Gordon, Thomas R.; Cargnello, Matteo; Paik, Taejong
  • Journal of the American Chemical Society, Vol. 134, Issue 15
  • DOI: 10.1021/ja300823a

Anatase TiO2 single crystals with exposed {001} and {110} facets: facile synthesis and enhanced photocatalysis
journal, January 2010

  • Liu, Min; Piao, Lingyu; Zhao, Lei
  • Chemical Communications, Vol. 46, Issue 10
  • DOI: 10.1039/b924172h

Synthesis of Titania Nanosheets with a High Percentage of Exposed (001) Facets and Related Photocatalytic Properties
journal, March 2009

  • Han, Xiguang; Kuang, Qin; Jin, Mingshang
  • Journal of the American Chemical Society, Vol. 131, Issue 9
  • DOI: 10.1021/ja8092373

Enhanced Photocatalytic CO 2 -Reduction Activity of Anatase TiO 2 by Coexposed {001} and {101} Facets
journal, June 2014

  • Yu, Jiaguo; Low, Jingxiang; Xiao, Wei
  • Journal of the American Chemical Society, Vol. 136, Issue 25
  • DOI: 10.1021/ja5044787

Anatase TiO2 single crystals with dominant {0 0 1} facets: Synthesis, shape-control mechanism and photocatalytic activity
journal, June 2018

Oxidative dehydrogenation of isobutane over vanadia catalysts supported by titania nanoshapes
journal, April 2016

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

Nonaqueous Production of Nanostructured Anatase with High-Energy Facets
journal, December 2008

  • Wu, Binghui; Guo, Changyou; Zheng, Nanfeng
  • Journal of the American Chemical Society, Vol. 130, Issue 51
  • DOI: 10.1021/ja8069715

Synthesis of Anatase TiO 2 Nanocrystals with Exposed {001} Facets
journal, June 2009

  • Dai, Yunqian; Cobley, Claire M.; Zeng, Jie
  • Nano Letters, Vol. 9, Issue 6
  • DOI: 10.1021/nl901181n

Effect of Additives on the Structure and Reactivity of the Surface Vanadium Oxide Phase in V2O5/TiO2 Catalysts
journal, April 1994

Mechanistic Investigation of Isopropanol Conversion on Alumina Catalysts: Location of Active Sites for Alkene/Ether Production
journal, June 2015

Surface Properties and Catalytic Activity of TiO 2 –ZrO 2 Mixed Oxides in Dehydration of Methanol to Dimethyl Ether
journal, July 2004

Preparation of TiO2–ZrO2 mixed oxides with controlled acid–basic properties
journal, October 2004

Kinetic and Theoretical Insights into the Mechanism of Alkanol Dehydration on Solid Brønsted Acid Catalysts
journal, February 2016

  • Knaeble, William; Iglesia, Enrique
  • The Journal of Physical Chemistry C, Vol. 120, Issue 6
  • DOI: 10.1021/acs.jpcc.5b11127

Mechanistic Consequences of Composition in Acid Catalysis by Polyoxometalate Keggin Clusters
journal, August 2008

  • Macht, Josef; Janik, Michael J.; Neurock, Matthew
  • Journal of the American Chemical Society, Vol. 130, Issue 31
  • DOI: 10.1021/ja803114r

Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

Separable dual-space Gaussian pseudopotentials
journal, July 1996

Relativistic separable dual-space Gaussian pseudopotentials from H to Rn
journal, August 1998

All-electron ab-initio molecular dynamics
journal, January 2000

  • Krack, Matthias; Parrinello, Michele
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 10
  • DOI: 10.1039/b001167n

Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007

  • VandeVondele, Joost; Hutter, Jürg
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2770708

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

OH Group Dynamics of 1,3-Propanediol on TiO 2 (110)
journal, October 2012

  • Zhang, Zhenrong; Yoon, Yeohoon; Lin, Xiao
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 22
  • DOI: 10.1021/jz301412m

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

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

Reversible work transition state theory: application to dissociative adsorption of hydrogen
journal, February 1995

Effects of morphology on surface hydroxyl concentration: a DFT comparison of anatase–TiO2 and γ-alumina catalytic supports
journal, February 2004

Mechanistic insights into aqueous phase propanol dehydration in H-ZSM-5 zeolite
journal, October 2016

  • Mei, Donghai; Lercher, Johannes A.
  • AIChE Journal, Vol. 63, Issue 1
  • DOI: 10.1002/aic.15517

Dehydration of 1-Octadecanol over H-BEA: A Combined Experimental and Computational Study
journal, January 2016

Solvothermal Synthesis and Photoreactivity of Anatase TiO 2 Nanosheets with Dominant {001} Facets
journal, March 2009

  • Yang, Hua Gui; Liu, Gang; Qiao, Shi Zhang
  • Journal of the American Chemical Society, Vol. 131, Issue 11
  • DOI: 10.1021/ja808790p

Transient Studies of 2-Propanol Photocatalytic Oxidation on Titania
journal, December 1995

  • Larson, S. A.; Widegren, J. A.; Falconer, J. L.
  • Journal of Catalysis, Vol. 157, Issue 2
  • DOI: 10.1006/jcat.1995.1326

Kinetics and Selectivity of 2-Propanol Conversion on Oxidized Anatase TiO2
journal, January 1997

Site Titration with Organic Bases During Catalysis: Selectivity Modifier and Structural Probe in Methanol Oxidation on Keggin Clusters
journal, October 2003

  • Liu, Haichao; Bayat, Nader; Iglesia, Enrique
  • Angewandte Chemie International Edition, Vol. 42, Issue 41
  • DOI: 10.1002/anie.200352393

IR Spectroscopy of Surface Water and Hydroxyl Species on Nanocrystalline TiO 2 Films
journal, February 2001

  • Finnie, Kim S.; Cassidy, David J.; Bartlett, John R.
  • Langmuir, Vol. 17, Issue 3
  • DOI: 10.1021/la0009240

XPS and FTIR Surface Characterization of TiO 2 Particles Used in Polymer Encapsulation
journal, May 2001

  • Erdem, Bedri; Hunsicker, Robert A.; Simmons, Gary W.
  • Langmuir, Vol. 17, Issue 9
  • DOI: 10.1021/la0015213

In Situ FTIR Spectroscopic Study of 2-Propanol Adsorptive and Catalytic Interactions on Metal-Modified Aluminas
journal, June 2001

  • Zaki, Mohamed I.; Hasan, Muhammad A.; Pasupulety, Lata
  • Langmuir, Vol. 17, Issue 13
  • DOI: 10.1021/la001810r

Structure Determination of the Two-Domain ( 1 × 4 ) Anatase TiO 2 ( 001 ) Surface
journal, April 2000

Surface structure of anatase TiO 2 ( 001 ) : Reconstruction, atomic steps, and domains
journal, May 2001

Role of point defects on the reactivity of reconstructed anatase titanium dioxide (001) surface
journal, July 2013

  • Wang, Yang; Sun, Huijuan; Tan, Shijing
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3214

Visualizing H 2 O molecules reacting at TiO 2 active sites with transmission electron microscopy
journal, January 2020

Structure and stability of the anatase TiO2 (101) and (001) surfaces
journal, July 2000

Dehydration of ethanol over heteropoly acid catalysts in the gas phase
journal, November 2014

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: