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Title: High Activity of Au/K/TiO2(110) for CO Oxidation: Alkali-Metal-Enhanced Dispersion of Au and Bonding of CO

Abstract

In this paper, images from scanning tunneling microscopy show high mobility for potassium (K) on an oxidized TiO2(110) surface. At low coverages, the alkali metal occupies mainly terrace sites of the o-TiO2(110) system. The results of X-ray photoelectron spectroscopy indicate that K is fully ionized. The electron transferred from K to the titania affects the reactivity of this oxide, favoring the dispersion of Au particles on the terraces of the o-TiO2(110) surface. When small coverages of K and Au are present on the o-TiO2(110) system, only a few K–Au pairs are formed and the alkali metal affects Au chemisorption mainly through the oxide interactions. Addition of K to Au/o-TiO2(110) enhances the reactivity of the system, opening new reaction paths for the adsorption and oxidation of carbon monoxide. CO can undergo disproportionation (2CO → Cads + CO2,ads) on K/o-TiO2(110) and Au/K/o-TiO2(110) surfaces. The Au–KOx interface binds CO much better than plain Au–TiO2, increasing the surface coverage of CO and facilitating its oxidation. Kinetic tests show that K promotes CO oxidation on Au/TiO2. Finally, turnover frequencies of 2.1 and 10.8 molecules (Au site)-1 s–1 were calculated for oxidation of CO on Au/o-TiO2(110) and Au/K/o-TiO2(110) catalysts, respectively.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
  2. Central Univ. of Venezuela, Caracas (Venezuela)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1430849
Report Number(s):
BNL-203369-2018-JAAM
Journal ID: ISSN 1932-7447; TRN: US1802626
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 8; 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

Rodriguez, Jose A., Grinter, David C., Ramirez, Pedro J., Stacchiola, Dario J., and Senanayake, Sanjaya. High Activity of Au/K/TiO2(110) for CO Oxidation: Alkali-Metal-Enhanced Dispersion of Au and Bonding of CO. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.7b11771.
Rodriguez, Jose A., Grinter, David C., Ramirez, Pedro J., Stacchiola, Dario J., & Senanayake, Sanjaya. High Activity of Au/K/TiO2(110) for CO Oxidation: Alkali-Metal-Enhanced Dispersion of Au and Bonding of CO. United States. https://doi.org/10.1021/acs.jpcc.7b11771
Rodriguez, Jose A., Grinter, David C., Ramirez, Pedro J., Stacchiola, Dario J., and Senanayake, Sanjaya. Wed . "High Activity of Au/K/TiO2(110) for CO Oxidation: Alkali-Metal-Enhanced Dispersion of Au and Bonding of CO". United States. https://doi.org/10.1021/acs.jpcc.7b11771. https://www.osti.gov/servlets/purl/1430849.
@article{osti_1430849,
title = {High Activity of Au/K/TiO2(110) for CO Oxidation: Alkali-Metal-Enhanced Dispersion of Au and Bonding of CO},
author = {Rodriguez, Jose A. and Grinter, David C. and Ramirez, Pedro J. and Stacchiola, Dario J. and Senanayake, Sanjaya},
abstractNote = {In this paper, images from scanning tunneling microscopy show high mobility for potassium (K) on an oxidized TiO2(110) surface. At low coverages, the alkali metal occupies mainly terrace sites of the o-TiO2(110) system. The results of X-ray photoelectron spectroscopy indicate that K is fully ionized. The electron transferred from K to the titania affects the reactivity of this oxide, favoring the dispersion of Au particles on the terraces of the o-TiO2(110) surface. When small coverages of K and Au are present on the o-TiO2(110) system, only a few K–Au pairs are formed and the alkali metal affects Au chemisorption mainly through the oxide interactions. Addition of K to Au/o-TiO2(110) enhances the reactivity of the system, opening new reaction paths for the adsorption and oxidation of carbon monoxide. CO can undergo disproportionation (2CO → Cads + CO2,ads) on K/o-TiO2(110) and Au/K/o-TiO2(110) surfaces. The Au–KOx interface binds CO much better than plain Au–TiO2, increasing the surface coverage of CO and facilitating its oxidation. Kinetic tests show that K promotes CO oxidation on Au/TiO2. Finally, turnover frequencies of 2.1 and 10.8 molecules (Au site)-1 s–1 were calculated for oxidation of CO on Au/o-TiO2(110) and Au/K/o-TiO2(110) catalysts, respectively.},
doi = {10.1021/acs.jpcc.7b11771},
journal = {Journal of Physical Chemistry. C},
number = 8,
volume = 122,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Figure 1 Figure 1: STM images of (a) as-prepared h-TiO2(110) and (b) oxidised o-TiO2(110). (20 × 10 nm2, V = +1.74 V, I = 0.1 nA)

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Works referenced in this record:

Alkali-metal-affected adsorption of molecules on metal surfaces
journal, January 1988


The Mechanism of Potassium Promoter: Enhancing the Stability of Active Surfaces
journal, June 2011

  • Huo, Chun-Fang; Wu, Bao-Shan; Gao, Peng
  • Angewandte Chemie International Edition, Vol. 50, Issue 32
  • DOI: 10.1002/anie.201007484

Hydrogen Chemisorption on Potassium Promoted Supported Ruthenium Catalysts
journal, April 1994

  • Uner, D. O.; Pruski, M.; Gerstein, B. C.
  • Journal of Catalysis, Vol. 146, Issue 2
  • DOI: 10.1006/jcat.1994.1091

Low-coverage condensation of K on TiO2(110) 1×1
journal, June 2005


The reactivity of CO2 with K atoms adsorbed on MgO powders
journal, January 2009

  • Preda, Gloria; Pacchioni, Gianfranco; Chiesa, Mario
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 37
  • DOI: 10.1039/b906192d

Modeling Alkali Atoms Deposition on TiO 2 (110) Surface
journal, March 2001

  • San Miguel, M. A.; Calzado, C. J.; Sanz, J. F.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 9
  • DOI: 10.1021/jp002288k

The effect of preadsorbed K on the size distribution of Au nanoparticles on TiO2(110) surface
journal, August 2006


Theoretical Analysis of K Adsorption on TiO2(110) Rutile Surface
journal, January 1999

  • Calzado, C. J.; San Miguel, M. A.; Sanz, J. F.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 3
  • DOI: 10.1021/jp982994+

Potassium and Water Coadsorption on TiO 2 (110): OH-Induced Anchoring of Potassium and the Generation of Single-Site Catalysts
journal, September 2016

  • Grinter, David C.; R. Remesal, Elena; Luo, Si
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 19
  • DOI: 10.1021/acs.jpclett.6b01623

The effect of potassium on the adsorption of gold on the TiO 2 (110)-1 × 1 surface
journal, July 2006


Interaction of Molecular Oxygen with the Vacuum-Annealed TiO 2 (110) Surface:  Molecular and Dissociative Channels
journal, June 1999

  • Henderson, Michael A.; Epling, William S.; Perkins, Craig L.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 25
  • DOI: 10.1021/jp990655q

Chemical reactions on rutile TiO2(110)
journal, January 2008

  • Lun Pang, Chi; Lindsay, Robert; Thornton, Geoff
  • Chemical Society Reviews, Vol. 37, Issue 10
  • DOI: 10.1039/b719085a

Structure of Clean and Adsorbate-Covered Single-Crystal Rutile TiO 2 Surfaces
journal, December 2012

  • Pang, Chi Lun; Lindsay, Robert; Thornton, Geoff
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr300409r

Molecular Oxygen Adsorption Behaviors on the Rutile TiO 2 (110)-1×1 Surface: An in Situ Study with Low-Temperature Scanning Tunneling Microscopy
journal, February 2011

  • Tan, Shijing; Ji, Yongfei; Zhao, Yan
  • Journal of the American Chemical Society, Vol. 133, Issue 6
  • DOI: 10.1021/ja110375n

A new recipe for preparing oxidized TiO2(1 1 0) surfaces: An STM study
journal, December 2017


Insights into Catalytic Oxidation at the Au/TiO 2 Dual Perimeter Sites
journal, December 2013

  • Green, Isabel X.; Tang, Wenjie; Neurock, Matthew
  • Accounts of Chemical Research, Vol. 47, Issue 3
  • DOI: 10.1021/ar400196f

CO chemisorption on TiO 2 (110): Oxygen vacancy site influence on CO adsorption
journal, December 1995

  • Linsebigler, Amy; Lu, Guangquan; Yates, John T.
  • The Journal of Chemical Physics, Vol. 103, Issue 21
  • DOI: 10.1063/1.470005

Electronic structure effects of potassium adsorption on TiO2(100)
journal, May 1992


Adsorption of potassium on Cr 2 O 3 ( 0001 ) at ionic and metallic coverages and uv-laser-induced desorption
journal, May 1999


Water Dissociation and KOH Formation on Potassium-Covered MgO/Ru(001)
journal, December 1998

  • Huang, H. H.; Jiang, X.; Siew, H. L.
  • Langmuir, Vol. 14, Issue 25
  • DOI: 10.1021/la980616q

Importance of the Metal-Oxide Interface in Catalysis: In Situ Studies of the Water-Gas Shift Reaction by Ambient-Pressure X-ray Photoelectron Spectroscopy
journal, April 2013

  • Mudiyanselage, Kumudu; Senanayake, Sanjaya D.; Feria, Leticia
  • Angewandte Chemie International Edition, Vol. 52, Issue 19
  • DOI: 10.1002/anie.201210077

Activation and Reactions of CO 2 on a K-Promoted Au(111) Surface
journal, October 2009

  • Farkas, Arnold Péter; Solymosi, Frigyes
  • The Journal of Physical Chemistry C, Vol. 113, Issue 46
  • DOI: 10.1021/jp9061779

CO Oxidation on Au/TiO 2 : Condition-Dependent Active Sites and Mechanistic Pathways
journal, August 2016

  • Wang, Yang-Gang; Cantu, David C.; Lee, Mal-Soon
  • Journal of the American Chemical Society, Vol. 138, Issue 33
  • DOI: 10.1021/jacs.6b04187

Size- and support-dependency in the catalysis of gold
journal, April 1997


CO Oxidation over Supported Gold Catalysts—“Inert” and “Active” Support Materials and Their Role for the Oxygen Supply during Reaction
journal, January 2001

  • Schubert, Markus M.; Hackenberg, Stefan; van Veen, Andre C.
  • Journal of Catalysis, Vol. 197, Issue 1
  • DOI: 10.1006/jcat.2000.3069

Activation of Gold on Titania:  Adsorption and Reaction of SO 2 on Au/TiO 2 (110)
journal, May 2002

  • Rodriguez, José A.; Liu, Gang; Jirsak, Tomas
  • Journal of the American Chemical Society, Vol. 124, Issue 18
  • DOI: 10.1021/ja020115y

Catalytically active Au-O(OH) x - species stabilized by alkali ions on zeolites and mesoporous oxides
journal, November 2014


A Common Single-Site Pt(II)–O(OH) x – Species Stabilized by Sodium on “Active” and “Inert” Supports Catalyzes the Water-Gas Shift Reaction
journal, March 2015

  • Yang, Ming; Liu, Jilei; Lee, Sungsik
  • Journal of the American Chemical Society, Vol. 137, Issue 10
  • DOI: 10.1021/ja513292k

Works referencing / citing this record:

Morphology and chemical behavior of model CsO x /Cu 2 O/Cu(111) nanocatalysts for methanol synthesis: Reaction with CO 2 and H 2
journal, January 2020

  • Hamlyn, Rebecca; Mahapatra, Mausumi; Orozco, Ivan
  • The Journal of Chemical Physics, Vol. 152, Issue 4
  • DOI: 10.1063/1.5129152

Supported Gold Nanoparticles as Catalysts for the Oxidation of Alcohols and Alkanes
journal, November 2019