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Title: Reversible oxidation and reduction of gold-supported iron oxide islands at room temperature

Abstract

Monolayer iron oxides grown on metal substrates have widely been used as model systems in heterogeneous catalysis. By means of ambient-pressure scanning tunneling microscopy (AP-STM), we studied the in situ oxidation and reduction of FeO(111) grown on Au(111) by oxygen (O2) and carbon monoxide (CO), respectively. Oxygen dislocation lines present on FeO islands are highly active for O2 dissociation. X-ray photoelectron spectroscopy measurements distinctly reveal the reversible oxidation and reduction of FeO islands after sequential exposure to O2 and CO. Here, our AP-STM results show that excess O atoms can be further incorporated on dislocation lines and react with CO, whereas the CO is not strong enough to reduce the FeO supported on Au(111) that is essential to retain the activity of oxygen dislocation lines.

Authors:
 [1];  [2];  [1];  [3];  [1]; ORCiD logo [4]; ORCiD logo [1]
  1. Nanjing Univ. of Science and Technology, Xiaolingwei (China)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); State Univ. of New York, Binghamton, NY (United States)
  3. Xi’an Jiaotong Univ. (China)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation of Jiangsu Province
OSTI Identifier:
1614693
Alternate Identifier(s):
OSTI ID: 1600585
Report Number(s):
BNL-213814-2020-JAAM
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
SC0012704; SC0012573; BK20181297
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; carbon monoxide; catalyst; scanning tunneling microscopy; catalysis; density functional theory; temperature programmed desorption; X-ray photoelectron spectroscopy; oxidation; surface science

Citation Formats

Jiang, Yixuan, Zhu, Yaguang, Zhou, Dechun, Jiang, Zhao, Si, Nan, Stacchiola, Dario, and Niu, Tianchao. Reversible oxidation and reduction of gold-supported iron oxide islands at room temperature. United States: N. p., 2020. Web. doi:10.1063/1.5136279.
Jiang, Yixuan, Zhu, Yaguang, Zhou, Dechun, Jiang, Zhao, Si, Nan, Stacchiola, Dario, & Niu, Tianchao. Reversible oxidation and reduction of gold-supported iron oxide islands at room temperature. United States. doi:https://doi.org/10.1063/1.5136279
Jiang, Yixuan, Zhu, Yaguang, Zhou, Dechun, Jiang, Zhao, Si, Nan, Stacchiola, Dario, and Niu, Tianchao. Wed . "Reversible oxidation and reduction of gold-supported iron oxide islands at room temperature". United States. doi:https://doi.org/10.1063/1.5136279. https://www.osti.gov/servlets/purl/1614693.
@article{osti_1614693,
title = {Reversible oxidation and reduction of gold-supported iron oxide islands at room temperature},
author = {Jiang, Yixuan and Zhu, Yaguang and Zhou, Dechun and Jiang, Zhao and Si, Nan and Stacchiola, Dario and Niu, Tianchao},
abstractNote = {Monolayer iron oxides grown on metal substrates have widely been used as model systems in heterogeneous catalysis. By means of ambient-pressure scanning tunneling microscopy (AP-STM), we studied the in situ oxidation and reduction of FeO(111) grown on Au(111) by oxygen (O2) and carbon monoxide (CO), respectively. Oxygen dislocation lines present on FeO islands are highly active for O2 dissociation. X-ray photoelectron spectroscopy measurements distinctly reveal the reversible oxidation and reduction of FeO islands after sequential exposure to O2 and CO. Here, our AP-STM results show that excess O atoms can be further incorporated on dislocation lines and react with CO, whereas the CO is not strong enough to reduce the FeO supported on Au(111) that is essential to retain the activity of oxygen dislocation lines.},
doi = {10.1063/1.5136279},
journal = {Journal of Chemical Physics},
number = 7,
volume = 152,
place = {United States},
year = {2020},
month = {2}
}

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Works referenced in this record:

Reactive metal–oxide interfaces: A microscopic view
journal, March 2016


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


A liquid metal reaction environment for the room-temperature synthesis of atomically thin metal oxides
journal, October 2017


Inverse Oxide/Metal Catalysts in Fundamental Studies and Practical Applications: A Perspective of Recent Developments
journal, June 2016

  • Rodriguez, José A.; Liu, Ping; Graciani, Jesús
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 13
  • DOI: 10.1021/acs.jpclett.6b00499

Wet-Chemistry Strong Metal–Support Interactions in Titania-Supported Au Catalysts
journal, January 2019

  • Zhang, Jian; Wang, Hai; Wang, Liang
  • Journal of the American Chemical Society, Vol. 141, Issue 7
  • DOI: 10.1021/jacs.8b10864

Iron oxide surfaces
journal, March 2016


Interface-Confined Oxide Nanostructures for Catalytic Oxidation Reactions
journal, March 2013

  • Fu, Qiang; Yang, Fan; Bao, Xinhe
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300249b

Growth of ultrathin cobalt oxide films on Pt(111)
journal, September 2011


Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands
journal, January 2017

  • Fester, J.; García-Melchor, M.; Walton, A. S.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14169

The promotion of CO dissociation by molybdenum oxide overlayers on rhodium
journal, March 2017


Interfacing with silica boosts the catalysis of copper
journal, August 2018


Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2
journal, July 2014


In situ studies of oxide nucleation, growth, and transformation using slow electrons
journal, May 2018


Water Gas Shift Catalysis
journal, September 2009


Promotion Mechanisms of Iron Oxide-Based High Temperature Water–Gas Shift Catalysts by Chromium and Copper
journal, June 2016


The role of Pt-FexOy interfacial sites for CO oxidation
journal, February 2018


Active Phase of FeO x /Pt Catalysts in Low-Temperature CO Oxidation and Preferential Oxidation of CO Reaction
journal, May 2017


Oxygen activation on oxide surfaces: A perspective at the atomic level
journal, December 2014


CO Oxidation on Rutile-Supported Au Nanoparticles
journal, February 2005

  • Remediakis, Ioannis N.; Lopez, Nuria; Nørskov, Jens K.
  • Angewandte Chemie International Edition, Vol. 44, Issue 12
  • DOI: 10.1002/anie.200461699

Water-Enhanced Low-Temperature CO Oxidation and Isotope Effects on Atomic Oxygen-Covered Au(111)
journal, May 2008

  • Ojifinni, Rotimi A.; Froemming, Nathan S.; Gong, Jinlong
  • Journal of the American Chemical Society, Vol. 130, Issue 21
  • DOI: 10.1021/ja800351j

Enhanced CO Oxidation on the Oxide/Metal Interface: From Ultra-High Vacuum to Near-Atmospheric Pressures
journal, August 2015


In Situ Photoemission Observation of Catalytic CO Oxidation Reaction on Pd(110) under Near-Ambient Pressure Conditions: Evidence for the Langmuir–Hinshelwood Mechanism
journal, September 2013

  • Toyoshima, Ryo; Yoshida, Masaaki; Monya, Yuji
  • The Journal of Physical Chemistry C, Vol. 117, Issue 40
  • DOI: 10.1021/jp4054132

Activation of Molecular Oxygen and the Nature of the Active Oxygen Species for CO Oxidation on Oxide Supported Au Catalysts
journal, December 2013

  • Widmann, D.; Behm, R. J.
  • Accounts of Chemical Research, Vol. 47, Issue 3
  • DOI: 10.1021/ar400203e

Dynamic surface composition in a Mars-van Krevelen type reaction: CO oxidation on Au/TiO2
journal, January 2018


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


Unraveling the Edge Structures of Platinum(111)-Supported Ultrathin FeO Islands: The Influence of Oxidation State
journal, January 2015

  • Zeuthen, Helene; Kudernatsch, Wilhelmine; Merte, Lindsay R.
  • ACS Nano, Vol. 9, Issue 1
  • DOI: 10.1021/nn505890v

Direct Visualization of Catalytically Active Sites at the FeO–Pt(111) Interface
journal, June 2015


Reversible structural transformation of FeOx nanostructures on Pt under cycling redox conditions and its effect on oxidation catalysis
journal, January 2013

  • Fu, Qiang; Yao, Yunxi; Guo, Xiaoguang
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 35
  • DOI: 10.1039/c3cp52587b

Adsorption of O2 and oxidation of CO at Au nanoparticles supported by TiO2(110)
journal, April 2004

  • Molina, L. M.; Rasmussen, M. D.; Hammer, B.
  • The Journal of Chemical Physics, Vol. 120, Issue 16
  • DOI: 10.1063/1.1687337

Increasing Oxide Reducibility: The Role of Metal/Oxide Interfaces in the Formation of Oxygen Vacancies
journal, August 2017

  • Ruiz Puigdollers, Antonio; Schlexer, Philomena; Tosoni, Sergio
  • ACS Catalysis, Vol. 7, Issue 10
  • DOI: 10.1021/acscatal.7b01913

Electron Localization Determines Defect Formation on Ceria Substrates
journal, July 2005


Water-Activated Lattice Oxygen in FeO(111) Islands for Low-Temperature Oxidation of CO at Pt–FeO Interface
journal, May 2016

  • Jin, Yuekang; Sun, Guanghui; Xiong, Feng
  • The Journal of Physical Chemistry C, Vol. 120, Issue 18
  • DOI: 10.1021/acs.jpcc.6b02256

The critical role of water at the gold-titania interface in catalytic CO oxidation
journal, September 2014


A Comparison of CO Oxidation by Hydroxyl and Atomic Oxygen from Water on Low-Coordinated Au Atoms
journal, September 2016

  • van Spronsen, Matthijs A.; Weststrate, Kees-Jan; Juurlink, Ludo B. F.
  • ACS Catalysis, Vol. 6, Issue 10
  • DOI: 10.1021/acscatal.6b01720

Promoting Effects of Hydrothermal Treatment on the Activity and Durability of Pd/CeO 2 Catalysts for CO Oxidation
journal, September 2017


The Interplay between Structure and CO Oxidation Catalysis on Metal-Supported Ultrathin Oxide Films
journal, June 2010

  • Sun, Ying-Na; Giordano, Livia; Goniakowski, Jacek
  • Angewandte Chemie, Vol. 122, Issue 26
  • DOI: 10.1002/ange.201000437

Carbon Monoxide Oxidation on Metal-Supported Monolayer Oxide Films: Establishing Which Interface is Active
journal, January 2018

  • Zhang, Ke; Li, Linfei; Shaikhutdinov, Shamil
  • Angewandte Chemie International Edition, Vol. 57, Issue 5
  • DOI: 10.1002/anie.201710934

CO oxidation over Au/TiO2 catalyst: Pretreatment effects, catalyst deactivation, and carbonates production
journal, November 2013


CO Oxidation on Gold-Supported Iron Oxides: New Insights into Strong Oxide–Metal Interactions
journal, July 2015


Surface chemistry and catalysis on well-defined epitaxial iron-oxide layers
journal, March 2002


Single-atom catalysis of CO oxidation using Pt1/FeOx
journal, July 2011

  • Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng
  • Nature Chemistry, Vol. 3, Issue 8
  • DOI: 10.1038/nchem.1095

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

Break-Up of Stepped Platinum Catalyst Surfaces by High CO Coverage
journal, February 2010


Surface Structures of Model Metal Catalysts in Reactant Gases
journal, October 2017

  • Tao, Franklin Feng; Ralston, Walter T.; Liu, Huimin
  • The Journal of Physical Chemistry B, Vol. 122, Issue 2
  • DOI: 10.1021/acs.jpcb.7b06950

Observing the oxidation of platinum
journal, September 2017

  • van Spronsen, Matthijs A.; Frenken, Joost W. M.; Groot, Irene M. N.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-00643-z

A new scanning tunneling microscope reactor used for high-pressure and high-temperature catalysis studies
journal, August 2008

  • Tao, Feng; Tang, David; Salmeron, Miquel
  • Review of Scientific Instruments, Vol. 79, Issue 8
  • DOI: 10.1063/1.2960569

The structure and reactivity of surfaces revealed by scanning tunneling microscopy
journal, July 2012

  • Besenbacher, Flemming; Thostrup, Peter; Salmeron, Miquel
  • MRS Bulletin, Vol. 37, Issue 7
  • DOI: 10.1557/mrs.2012.142

Ambient pressure photoelectron spectroscopy: A new tool for surface science and nanotechnology
journal, April 2008


In Situ Observation of Competitive CO and O 2 Adsorption on the Pt(111) Surface Using Near-Ambient Pressure Scanning Tunneling Microscopy
journal, February 2018

  • Kim, Jeongjin; Noh, Myung Cheol; Doh, Won Hui
  • The Journal of Physical Chemistry C, Vol. 122, Issue 11
  • DOI: 10.1021/acs.jpcc.8b01672

In situ observation of self-assembled hydrocarbon Fischer–Tropsch products on a cobalt catalyst
journal, September 2016

  • Navarro, Violeta; van Spronsen, Matthijs A.; Frenken, Joost W. M.
  • Nature Chemistry, Vol. 8, Issue 10
  • DOI: 10.1038/nchem.2613

Oxygen-Promoted Methane Activation on Copper
journal, November 2017

  • Niu, Tianchao; Jiang, Zhao; Zhu, Yaguang
  • The Journal of Physical Chemistry B, Vol. 122, Issue 2
  • DOI: 10.1021/acs.jpcb.7b06956

Iterative minimization techniques for ab initio total-energy calculations: molecular dynamics and conjugate gradients
journal, October 1992


Generalized gradient approximation for the exchange-correlation hole of a many-electron system
journal, December 1996


Transition-metal dioxides: A case for the intersite term in Hubbard-model functionals
journal, March 2011

  • Kulik, Heather J.; Marzari, Nicola
  • The Journal of Chemical Physics, Vol. 134, Issue 9
  • DOI: 10.1063/1.3559452

The synchronous-transit method for determining reaction pathways and locating molecular transition states
journal, July 1977


Atomic-Scale View of the Oxidation and Reduction of Supported Ultrathin FeO Islands
journal, September 2019


Identification of O-rich structures on platinum(111)-supported ultrathin iron oxide films
journal, October 2016


Interface Controlled Oxidation States in Layered Cobalt Oxide Nanoislands on Gold
journal, February 2015


Phase Transitions of Cobalt Oxide Bilayers on Au(111) and Pt(111): The Role of Edge Sites and Substrate Interactions
journal, August 2017

  • Fester, Jakob; Sun, Zhaozong; Rodríguez-Fernández, Jonathan
  • The Journal of Physical Chemistry B, Vol. 122, Issue 2
  • DOI: 10.1021/acs.jpcb.7b04944

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


Cobalt-Oxide-Based Materials as Water Oxidation Catalyst: Recent Progress and Challenges
journal, September 2014

  • Deng, Xiaohui; Tüysüz, Harun
  • ACS Catalysis, Vol. 4, Issue 10
  • DOI: 10.1021/cs500713d

Comparative Analysis of Cobalt Oxide Nanoisland Stability and Edge Structures on Three Related Noble Metal Surfaces: Au(111), Pt(111) and Ag(111)
journal, September 2016


Enhanced oxidation resistance of active nanostructures via dynamic size effect
journal, February 2017

  • Liu, Yun; Yang, Fan; Zhang, Yi
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14459

An Atomic-Scale View of CO and H 2 Oxidation on a Pt/Fe 3 O 4 Model Catalyst
journal, September 2015

  • Bliem, Roland; van der Hoeven, Jessi; Zavodny, Adam
  • Angewandte Chemie International Edition, Vol. 54, Issue 47
  • DOI: 10.1002/anie.201507368

In situ XPS analysis of various iron oxide films grown by NO 2 -assisted molecular-beam epitaxy
journal, January 1999


On the Surface Chemistry of Iron Oxides in Reactive Gas Atmospheres
journal, January 2011

  • de Smit, Emiel; van Schooneveld, Matti M.; Cinquini, Fabrizio
  • Angewandte Chemie International Edition, Vol. 50, Issue 7
  • DOI: 10.1002/anie.201005282

The adsorption behaviors of CO and H 2 on FeO surface: A density functional theory study
journal, December 2016


Role of Lattice Oxygen Participation in Understanding Trends in the Oxygen Evolution Reaction on Perovskites
journal, April 2018


Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution
journal, January 2017

  • Grimaud, Alexis; Diaz-Morales, Oscar; Han, Binghong
  • Nature Chemistry, Vol. 9, Issue 5
  • DOI: 10.1038/nchem.2695

Chemisorption of CO and Mechanism of CO Oxidation on Supported Platinum Nanoclusters
journal, March 2011

  • Allian, Ayman D.; Takanabe, Kazuhiro; Fujdala, Kyle L.
  • Journal of the American Chemical Society, Vol. 133, Issue 12
  • DOI: 10.1021/ja110073u

CO Oxidation at the Interface of Au Nanoclusters and the Stepped-CeO 2 (111) Surface by the Mars–van Krevelen Mechanism
journal, December 2012

  • Kim, Hyun You; Henkelman, Graeme
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 1
  • DOI: 10.1021/jz301778b