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Title: Effects of TiO2 in Low Temperature Propylene Epoxidation Using Gold Catalysts

Abstract

Propylene epoxidation with molecular oxygen has been proposed as a green and alternative process to produce propylene oxide (PO). In order to develop catalysts with high selectivity, high conversion, and long stability for the direct propylene epoxidation with molecular oxygen, understanding of catalyst structure and reactivity relationships is needed. Here in this study, we combined atomic layer deposition and deposition precipitation to synthesize series of well-defined Au-based catalysts to study the catalyst structure and reactivity relationships for propylene epoxidation at 373 K. We showed that by decorating TiO2 on gold surface the inverse TiO2/Au/SiO2 catalysts maintained ~90% selectivity to PO regardless of the weight loading of the TiO2. The inverse TiO2/Au/SiO2 catalysts exhibited improved regeneration compared to Au/TiO2/SiO2. The inverse TiO2/Au/SiO2 catalysts can be regenerated in 10% oxygen at 373 K, while the Au/TiO2/SiO2 catalysts failed to regenerate at as high as 473 K. Combined characterizations of the Au-based catalysts by X-ray absorption spectroscopy, scanning transmission electron microscopy, and UV–vis spectroscopy suggested that the unique selectivity and regeneration of TiO2/Au/SiO2 are derived from the site-isolated Ti sites on Au surface and Au–SiO2 interfaces which are critical to achieve high PO selectivity and generate only coke-like species with high oxygen content.more » The high oxygen content coke-like species can therefore be easily removed. Lastly, these results indicate that inverse TiO2/Au/SiO2 catalyst represents a system capable of realizing sustainable gas phase propylene epoxidation with molecular oxygen at low temperature.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. University of Alabama, Huntsville, AL (United States). Department of Chemical and Materials Engineering
  2. University of Alabama, Tuscaloosa, AL (United States). Department of Chemical and Biological Engineering
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Science Division and Center for Nanophase Materials Sciences
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:
1468076
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 3; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lu, Zheng, Piernavieja-Hermida, Mar, Turner, C. Heath, Wu, Zili, and Lei, Yu. Effects of TiO2 in Low Temperature Propylene Epoxidation Using Gold Catalysts. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpcc.7b10902.
Lu, Zheng, Piernavieja-Hermida, Mar, Turner, C. Heath, Wu, Zili, & Lei, Yu. Effects of TiO2 in Low Temperature Propylene Epoxidation Using Gold Catalysts. United States. https://doi.org/10.1021/acs.jpcc.7b10902
Lu, Zheng, Piernavieja-Hermida, Mar, Turner, C. Heath, Wu, Zili, and Lei, Yu. Thu . "Effects of TiO2 in Low Temperature Propylene Epoxidation Using Gold Catalysts". United States. https://doi.org/10.1021/acs.jpcc.7b10902. https://www.osti.gov/servlets/purl/1468076.
@article{osti_1468076,
title = {Effects of TiO2 in Low Temperature Propylene Epoxidation Using Gold Catalysts},
author = {Lu, Zheng and Piernavieja-Hermida, Mar and Turner, C. Heath and Wu, Zili and Lei, Yu},
abstractNote = {Propylene epoxidation with molecular oxygen has been proposed as a green and alternative process to produce propylene oxide (PO). In order to develop catalysts with high selectivity, high conversion, and long stability for the direct propylene epoxidation with molecular oxygen, understanding of catalyst structure and reactivity relationships is needed. Here in this study, we combined atomic layer deposition and deposition precipitation to synthesize series of well-defined Au-based catalysts to study the catalyst structure and reactivity relationships for propylene epoxidation at 373 K. We showed that by decorating TiO2 on gold surface the inverse TiO2/Au/SiO2 catalysts maintained ~90% selectivity to PO regardless of the weight loading of the TiO2. The inverse TiO2/Au/SiO2 catalysts exhibited improved regeneration compared to Au/TiO2/SiO2. The inverse TiO2/Au/SiO2 catalysts can be regenerated in 10% oxygen at 373 K, while the Au/TiO2/SiO2 catalysts failed to regenerate at as high as 473 K. Combined characterizations of the Au-based catalysts by X-ray absorption spectroscopy, scanning transmission electron microscopy, and UV–vis spectroscopy suggested that the unique selectivity and regeneration of TiO2/Au/SiO2 are derived from the site-isolated Ti sites on Au surface and Au–SiO2 interfaces which are critical to achieve high PO selectivity and generate only coke-like species with high oxygen content. The high oxygen content coke-like species can therefore be easily removed. Lastly, these results indicate that inverse TiO2/Au/SiO2 catalyst represents a system capable of realizing sustainable gas phase propylene epoxidation with molecular oxygen at low temperature.},
doi = {10.1021/acs.jpcc.7b10902},
journal = {Journal of Physical Chemistry. C},
number = 3,
volume = 122,
place = {United States},
year = {2017},
month = {12}
}

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Cited by: 8 works
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Works referenced in this record:

Selective Vapor-Phase Epoxidation of Propylene over Au/TiO2Catalysts in the Presence of Oxygen and Hydrogen
journal, September 1998

  • Hayashi, Toshio; Tanaka, Koji; Haruta, Masatake
  • Journal of Catalysis, Vol. 178, Issue 2
  • DOI: 10.1006/jcat.1998.2157

Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects
journal, April 2010


Tuning Selectivity in Propylene Epoxidation by Plasmon Mediated Photo-Switching of Cu Oxidation State
journal, March 2013


Direct Oxidation of Propylene to Propylene Oxide with Molecular Oxygen: A Review
journal, June 2015


The Production of Propene Oxide:  Catalytic Processes and Recent Developments
journal, May 2006

  • Nijhuis, T. Alexander; Makkee, Michiel; Moulijn, Jacob A.
  • Industrial & Engineering Chemistry Research, Vol. 45, Issue 10
  • DOI: 10.1021/ie0513090

Gas-phase epoxidation of propylene in the presence of H2 and O2 over small gold ensembles in uncalcined TS-1
journal, May 2014


Synthesis and characterization of Ti-MCM-41 and vapor-phase epoxidation of propylene using H2 and O2 over Au/Ti-MCM-41
journal, July 2001


Effect of gold oxidation state on the epoxidation and hydrogenation of propylene on Au/TS-1
journal, May 2011


Propene epoxidation with O2 and H2: Identification of the most active gold clusters
journal, February 2011


Kinetic study of the selective oxidation of propene with O2 over Au–Ti catalysts in the presence of water
journal, October 2015

  • Perez Ferrandez, Dulce M.; Herguedas Fernandez, Iranzu; Teley, Martin P. G.
  • Journal of Catalysis, Vol. 330
  • DOI: 10.1016/j.jcat.2015.07.024

Monolayer iron oxide film on platinum promotes low temperature CO oxidation
journal, September 2009


Interface-Confined Ferrous Centers for Catalytic Oxidation
journal, May 2010


Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction
journal, December 2007


Charging of Metal Adatoms on Ultrathin Oxide Films: Au and Pd on FeO / Pt ( 111 )
journal, July 2008


Atomic Structure of Antiphase Domain Boundaries of a Thin A l 2 O 3 Film on NiAl(110)
journal, December 2003


Control of the Charge State of Metal Atoms on Thin MgO Films
journal, March 2007


Unique Properties of Ceria Nanoparticles Supported on Metals: Novel Inverse Ceria/Copper Catalysts for CO Oxidation and the Water-Gas Shift Reaction
journal, January 2013

  • Senanayake, Sanjaya D.; Stacchiola, Dario; Rodriguez, Jose A.
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300231p

Theory of the oxidation of metals
journal, January 1949


Atomic Layer Deposition: An Overview
journal, January 2010

  • George, Steven M.
  • Chemical Reviews, Vol. 110, Issue 1, p. 111-131
  • DOI: 10.1021/cr900056b

The Surface Chemistry of Atomic Layer Depositions of Solid Thin Films
journal, May 2012

  • Zaera, Francisco
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 10
  • DOI: 10.1021/jz300125f

Nanoengineering Heterogeneous Catalysts by Atomic Layer Deposition
journal, June 2017


Atomic layer deposition—Sequential self-limiting surface reactions for advanced catalyst “bottom-up” synthesis
journal, June 2016


Atomic Layer Deposition for Lithium-Based Batteries
journal, September 2016

  • Ma, Lu; Nuwayhid, Ramsay B.; Wu, Tianpin
  • Advanced Materials Interfaces, Vol. 3, Issue 21
  • DOI: 10.1002/admi.201600564

Catalyst Design with Atomic Layer Deposition
journal, February 2015

  • O’Neill, Brandon J.; Jackson, David H. K.; Lee, Jechan
  • ACS Catalysis, Vol. 5, Issue 3
  • DOI: 10.1021/cs501862h

Towards ALD thin film stabilized single-atom Pd 1 catalysts
journal, January 2016

  • Piernavieja-Hermida, Mar; Lu, Zheng; White, Anderson
  • Nanoscale, Vol. 8, Issue 33
  • DOI: 10.1039/C6NR04403D

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition
journal, May 2013

  • Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep01775

Combining Electronic and Geometric Effects of ZnO-Promoted Pt Nanocatalysts for Aqueous Phase Reforming of 1-Propanol
journal, April 2016


Coking- and Sintering-Resistant Palladium Catalysts Achieved Through Atomic Layer Deposition
journal, March 2012


Improved Thermal Stability and Methane-Oxidation Activity of Pd/Al 2 O 3 Catalysts by Atomic Layer Deposition of ZrO 2
journal, August 2015


Controlling Nanoscale Properties of Supported Platinum Catalysts through Atomic Layer Deposition
journal, January 2015

  • Gould, Troy D.; Lubers, Alia M.; Corpuz, April R.
  • ACS Catalysis, Vol. 5, Issue 2
  • DOI: 10.1021/cs501265b

Synthesis of Pt–Pd Core–Shell Nanostructures by Atomic Layer Deposition: Application in Propane Oxidative Dehydrogenation to Propylene
journal, September 2012

  • Lei, Yu; Liu, Bin; Lu, Junling
  • Chemistry of Materials, Vol. 24, Issue 18
  • DOI: 10.1021/cm300080w

Synthesis of Highly Dispersed and Highly Stable Supported Au–Pt Bimetallic Catalysts by a Two-Step Method
journal, November 2016


Controllable deposition of Pt nanoparticles into a KL zeolite by atomic layer deposition for highly efficient reforming of n-heptane to aromatics
journal, January 2017

  • Xu, Dan; Wu, Baoshan; Ren, Pengju
  • Catalysis Science & Technology, Vol. 7, Issue 6
  • DOI: 10.1039/C6CY02652D

Titanium isopropoxide as a precursor in atomic layer epitaxy of titanium dioxide thin films
journal, August 1993

  • Ritala, Mikko; Leskela, Markku; Niinisto, Lauri
  • Chemistry of Materials, Vol. 5, Issue 8
  • DOI: 10.1021/cm00032a023

DRIFTS-QMS Study of Room Temperature CO Oxidation on Au/SiO 2 Catalyst: Nature and Role of Different Au Species
journal, February 2009

  • Wu, Zili; Zhou, Shenghu; Zhu, Haoguo
  • The Journal of Physical Chemistry C, Vol. 113, Issue 9
  • DOI: 10.1021/jp809220z

Effects of Chlorine in Titanium Oxide on Palladium Atomic Layer Deposition
journal, September 2014

  • Lei, Yu; Liu, Bin; Lu, Junling
  • The Journal of Physical Chemistry C, Vol. 118, Issue 39
  • DOI: 10.1021/jp5067567

Structural investigation of silica gel films by infrared spectroscopy
journal, October 1990

  • Almeida, Rui M.; Pantano, Carlo G.
  • Journal of Applied Physics, Vol. 68, Issue 8
  • DOI: 10.1063/1.346213

Infrared spectroscopy study of low-dielectric-constant fluorine-incorporated and carbon-incorporated silicon oxide films
journal, October 2001

  • Kim, Yoon-Hae; Hwang, Moo Sung; Kim, Hyeong Joon
  • Journal of Applied Physics, Vol. 90, Issue 7
  • DOI: 10.1063/1.1402152

Adsorbate-Induced Structural Changes in 1–3 nm Platinum Nanoparticles
journal, June 2014

  • Lei, Yu; Zhao, Haiyan; Rivas, Rosa Diaz
  • Journal of the American Chemical Society, Vol. 136, Issue 26
  • DOI: 10.1021/ja4126998

Effect of Particle Size and Adsorbates on the L3, L2 and L1 X-ray Absorption Near Edge Structure of Supported Pt Nanoparticles
journal, February 2011


The effect of gold particle size on AuAu bond length and reactivity toward oxygen in supported catalysts
journal, June 2006


The role of support oxygen in the epoxidation of propene over gold–titania catalysts investigated by isotopic transient kinetics
journal, July 2009

  • Nijhuis, T. A.; Sacaliuc-Parvulescu, E.; Govender, N. S.
  • Journal of Catalysis, Vol. 265, Issue 2
  • DOI: 10.1016/j.jcat.2009.04.023

Synthesis of TiO2 nanoparticles on the Au(111) surface
journal, September 2005

  • Biener, Jürgen; Farfan-Arribas, Enrique; Biener, Monika
  • The Journal of Chemical Physics, Vol. 123, Issue 9
  • DOI: 10.1063/1.1999607

Oxidation of Au by Surface OH: Nucleation and Electronic Structure of Gold on Hydroxylated MgO(001)
journal, July 2011

  • Brown, Matthew A.; Fujimori, Yuichi; Ringleb, Franziska
  • Journal of the American Chemical Society, Vol. 133, Issue 27
  • DOI: 10.1021/ja204798z

Vapor phase propylene epoxidation over Au/Ti-MCM-41 catalysts prepared by different Ti incorporation modes
journal, February 2003


Three-Dimensional Mesoporous Titanosilicates Prepared by Modified Sol−Gel Method:  Ideal Gold Catalyst Supports for Enhanced Propene Epoxidation
journal, March 2005

  • Sinha, A. K.; Seelan, S.; Okumura, M.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 9
  • DOI: 10.1021/jp0465229

Reactivity and stability of Au in and on TS-1 for epoxidation of propylene with H2 and O2
journal, August 2004


Gold Nanoparticles Located at the Interface of Anatase/Rutile TiO 2 Particles as Active Plasmonic Photocatalysts for Aerobic Oxidation
journal, April 2012

  • Tsukamoto, Daijiro; Shiraishi, Yasuhiro; Sugano, Yoshitsune
  • Journal of the American Chemical Society, Vol. 134, Issue 14
  • DOI: 10.1021/ja2120647

Mechanistic Study into the Direct Epoxidation of Propene over Gold/Titania Catalysts
journal, October 2005

  • Nijhuis, T. Alexander; Visser, Tom; Weckhuysen, Bert M.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 41
  • DOI: 10.1021/jp053173p

Stability and Selectivity of Au/TiO2 and Au/TiO2/SiO2 Catalysts in Propene Epoxidation: An in Situ FT-IR Study
journal, July 2001

  • Mul, Guido; Zwijnenburg, Aalbert; van der Linden, Bart
  • Journal of Catalysis, Vol. 201, Issue 1
  • DOI: 10.1006/jcat.2001.3239

Direct Epoxidation of Propene Using Gold Dispersed on TS-1 and Other Titanium-Containing Supports
journal, March 1999

  • Nijhuis, T. Alexander; Huizinga, Bart J.; Makkee, Michiel
  • Industrial & Engineering Chemistry Research, Vol. 38, Issue 3
  • DOI: 10.1021/ie980494x

Reaction kinetic analysis of the gas-phase epoxidation of propylene over Au/TS-1
journal, August 2006


Catalysis by Gold Nanoparticles: Epoxidation of Propene
journal, June 2004


Gas-phase epoxidation of propylene over small gold ensembles on TS-1
journal, September 2005


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    journal, June 2019

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    • ChemCatChem, Vol. 11, Issue 13
    • DOI: 10.1002/cctc.201900512

    Diamine-Decorated Graphene Oxide with Immobilized Gold Nanoparticles of Small Size for Alkenes Epoxidation with H2O2
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