In situ atomic-scale observation of inhomogeneous oxide reduction

Chen, Xiaobo; Wu, Dongxiang; Zou, Lianfeng; Yin, Qiyue; Zhang, Hanlei; Zakharov, Dmitri N.; Stach, Eric A.; Zhou, Guangwen

doi:10.1039/C8CC03822H

Title: In situ atomic-scale observation of inhomogeneous oxide reduction

Abstract

Here, we report in situ atomic-scale transmission electron microscopy observations of the surface dynamics during Cu₂O reduction. We show inhomogeneous oxide reduction caused by the preferential adsorption of hydrogen at step edges that induces oxygen loss and destabilizes Cu atoms within the step edge, thereby resulting in the retraction motion of atomic steps at the oxide surface.

Authors:

^[1]; Wu, Dongxiang ^[1]; Zou, Lianfeng ^[1];

^[1]; Zhang, Hanlei ^[1];

^[2];

^[3];

^[1]

State Univ. of New York at Binghamton, Binghamton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)

Publication Date:: Mon Jun 11 00:00:00 EDT 2018

Research Org.:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1476762

Alternate Identifier(s):: OSTI ID: 1454633

Report Number(s):: BNL-209150-2018-JAAM
Journal ID: ISSN 1359-7345; CHCOFS

Grant/Contract Number:: SC0012704; SC0001135

Resource Type:: Accepted Manuscript

Journal Name:: ChemComm

Additional Journal Information:: Journal Volume: 54; Journal Issue: 53; Journal ID: ISSN 1359-7345

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; oxide; reduction; transmission electron microscopy; high resolution transmission electron microscopy

Citation Formats


                    Chen, Xiaobo, Wu, Dongxiang, Zou, Lianfeng, Yin, Qiyue, Zhang, Hanlei, Zakharov, Dmitri N., Stach, Eric A., and Zhou, Guangwen. In situ atomic-scale observation of inhomogeneous oxide reduction.  United States: N. p., 2018. 
Web.  doi:10.1039/C8CC03822H.

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                    Chen, Xiaobo, Wu, Dongxiang, Zou, Lianfeng, Yin, Qiyue, Zhang, Hanlei, Zakharov, Dmitri N., Stach, Eric A., & Zhou, Guangwen. In situ atomic-scale observation of inhomogeneous oxide reduction.  United States.  https://doi.org/10.1039/C8CC03822H

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                    Chen, Xiaobo, Wu, Dongxiang, Zou, Lianfeng, Yin, Qiyue, Zhang, Hanlei, Zakharov, Dmitri N., Stach, Eric A., and Zhou, Guangwen. Mon .  
"In situ atomic-scale observation of inhomogeneous oxide reduction".  United States.  https://doi.org/10.1039/C8CC03822H.  https://www.osti.gov/servlets/purl/1476762.

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@article{osti_1476762,

  title        = {In situ atomic-scale observation of inhomogeneous oxide reduction},

  author       = {Chen, Xiaobo and Wu, Dongxiang and Zou, Lianfeng and Yin, Qiyue and Zhang, Hanlei and Zakharov, Dmitri N. and Stach, Eric A. and Zhou, Guangwen},

  abstractNote = {Here, we report in situ atomic-scale transmission electron microscopy observations of the surface dynamics during Cu2O reduction. We show inhomogeneous oxide reduction caused by the preferential adsorption of hydrogen at step edges that induces oxygen loss and destabilizes Cu atoms within the step edge, thereby resulting in the retraction motion of atomic steps at the oxide surface.},

  doi          = {10.1039/C8CC03822H},

  journal      = {ChemComm},

  number       = 53,

  volume       = 54,

  place        = {United States},

  year         = {Mon Jun 11 00:00:00 EDT 2018},

  month        = {Mon Jun 11 00:00:00 EDT 2018}

}

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https://doi.org/10.1039/C8CC03822H

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Cited by: 8 works

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Figures / Tables:

Fig. 1: (a–h) Time-resolved HRTEM images showing oxide reduction in the local region, resulting in the formation of a nanoscale hole during the reduction of a Cu₂O(100) thin film at T = 350 °C and pH₂ = 1.2 10^-2 Torr. Scale bar, 2 nm (a–h). (i) Schematic illustrating the inhomogeneousmore »

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Works referenced in this record:

Design and Applications of Environmental Cell Transmission Electron Microscope for In Situ Observations of Gas–Solid Reactions
journal, November 2001

Sharma, Renu
Microscopy and Microanalysis, Vol. 7, Issue 6
DOI: 10.1007/S10005-001-0015-1

Surface hydride formation on a metal oxide surface: the interaction of atomic hydrogen with Cu2O(100)
journal, November 1992

Schulz, Kirk H.; Cox, David F.
Surface Science, Vol. 278, Issue 1-2
DOI: 10.1016/0039-6028(92)90579-U

Transmission Electron Microscopy
book, January 2009

Williams, David B.; Carter, C. Barry
DOI: 10.1007/978-0-387-76501-3

Visualizing the Cu/Cu ₂ O Interface Transition in Nanoparticles with Environmental Scanning Transmission Electron Microscopy
journal, December 2016

LaGrow, Alec P.; Ward, Michael R.; Lloyd, David C.
Journal of the American Chemical Society, Vol. 139, Issue 1
DOI: 10.1021/jacs.6b08842

Atomic-Step-Induced Local Nonequilibrium Effects on Surface Oxidation
journal, October 2017

Qin, Hailang; Chen, Xidong; Li, Jonathan
The Journal of Physical Chemistry C, Vol. 121, Issue 41
DOI: 10.1021/acs.jpcc.7b07321

Theoretical study of CO oxidation on Au nanoparticles supported by MgO(100)
journal, April 2004

Molina, L. M.; Hammer, B.
Physical Review B, Vol. 69, Issue 15
DOI: 10.1103/PhysRevB.69.155424

Reduction of the Phillips catalyst by various olefins: Stoichiometry, thermochemistry, reaction products and polymerization activity
journal, December 2016

Potter, Kelsey C.; Beckerle, Connor W.; Jentoft, Friederike C.
Journal of Catalysis, Vol. 344
DOI: 10.1016/j.jcat.2016.10.031

Experimental and Theoretical Studies on the Reaction of H ₂ with NiO: Role of O Vacancies and Mechanism for Oxide Reduction
journal, January 2002

Rodriguez, José A.; Hanson, Jonathan C.; Frenkel, Anatoly I.
Journal of the American Chemical Society, Vol. 124, Issue 2
DOI: 10.1021/ja0121080

Time-resolved Studies for the Mechanism of Reduction of Copper Oxides with Carbon Monoxide: Complex Behavior of Lattice Oxygen and the Formation of Suboxides
journal, September 2004

Wang, Xianqin; Hanson, Jonathan C.; Frenkel, Anatoly I.
The Journal of Physical Chemistry B, Vol. 108, Issue 36
DOI: 10.1021/jp040366o

In situ atomic-scale imaging of the metal/oxide interfacial transformation
journal, August 2017

Zou, Lianfeng; Li, Jonathan; Zakharov, Dmitri
Nature Communications, Vol. 8, Issue 1
DOI: 10.1038/s41467-017-00371-4

Steps on surfaces: experiment and theory
journal, September 1999

Jeong, Hyeong-Chai; Williams, Ellen D.
Surface Science Reports, Vol. 34, Issue 6-8
DOI: 10.1016/S0167-5729(98)00010-7

In Situ Atomic-Scale Probing of the Reduction Dynamics of Two-Dimensional Fe ₂ O ₃ Nanostructures
journal, December 2016

Zhu, Wenhui; Winterstein, Jonathan P.; Yang, Wei-Chang David
ACS Nano, Vol. 11, Issue 1
DOI: 10.1021/acsnano.6b06950

First principles calculations of solid–solid interfaces: an application to conversion materials for lithium-ion batteries
journal, January 2012

Martin, L.; Vallverdu, G.; Martinez, H.
Journal of Materials Chemistry, Vol. 22, Issue 41
DOI: 10.1039/c2jm35078e

Atom-Resolved Imaging of Dynamic Shape Changes in Supported Copper Nanocrystals
journal, March 2002

Hansen, P. L.
Science, Vol. 295, Issue 5562
DOI: 10.1126/science.1069325

Visualizing Redox Dynamics of a Single Ag/AgCl Heterogeneous Nanocatalyst at Atomic Resolution
journal, February 2016

Wu, Yimin A.; Li, Liang; Li, Zheng
ACS Nano, Vol. 10, Issue 3
DOI: 10.1021/acsnano.6b00355

CuO reduction induced formation of CuO/Cu2O hybrid oxides
journal, December 2013

Yuan, Lu; Yin, Qiyue; Wang, Yiqian
Chemical Physics Letters, Vol. 590
DOI: 10.1016/j.cplett.2013.10.040

Autocatalytic Reduction of a Cu ₂ O/Cu(111) Surface by CO: STM, XPS, and DFT Studies
journal, July 2010

Yang, Fan; Choi, YongMan; Liu, Ping
The Journal of Physical Chemistry C, Vol. 114, Issue 40
DOI: 10.1021/jp1029079

THERMOGRAVIMETRIC STUDY OF THE KINETICS OF THE REDUCTION OF CUPRIC OXIDE BY HYDROGEN ¹
journal, September 1962

Bond, W. D.
The Journal of Physical Chemistry, Vol. 66, Issue 9
DOI: 10.1021/j100815a002

Formation of stable Cu₂O from reduction of CuO nanoparticles
journal, April 2006

Pike, Jenna; Chan, Siu-Wai; Zhang, Feng
Applied Catalysis A: General, Vol. 303, Issue 2, p. 273-277
DOI: 10.1016/j.apcata.2006.02.008

Hydrogen-induced atomic structure evolution of the oxygen-chemisorbed Cu(110) surface
journal, December 2016

Shan, Weitao; Liu, Qianqian; Li, Jonathan
The Journal of Chemical Physics, Vol. 145, Issue 23
DOI: 10.1063/1.4972070

Atomic origins of the high catalytic activity of nanoporous gold
journal, August 2012

Fujita, Takeshi; Guan, Pengfei; McKenna, Keith
Nature Materials, Vol. 11, Issue 9
DOI: 10.1038/nmat3391

Works referencing / citing this record:

Laser Synthesis of Iridium Nanospheres for Overall Water Splitting
journal, September 2019

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Materials, Vol. 12, Issue 18
DOI: 10.3390/ma12183028

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journal, January 2020

Sun, Xianhu; Zhu, Wenhui; Wu, Dongxiang
Nature Communications, Vol. 11, Issue 1
DOI: 10.1038/s41467-019-14167-1

Figures / Tables found in this record:

Fig. 1 (p. 4)

Fig. 2 (p. 5)

Fig. 3 (p. 5)

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Title: In situ atomic-scale observation of inhomogeneous oxide reduction

Abstract

Citation Formats

Figures / Tables:

Design and Applications of Environmental Cell Transmission Electron Microscope for In Situ Observations of Gas–Solid Reactions journal, November 2001

Surface hydride formation on a metal oxide surface: the interaction of atomic hydrogen with Cu2O(100) journal, November 1992

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Time-resolved Studies for the Mechanism of Reduction of Copper Oxides with Carbon Monoxide: Complex Behavior of Lattice Oxygen and the Formation of Suboxides journal, September 2004

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Steps on surfaces: experiment and theory journal, September 1999

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THERMOGRAVIMETRIC STUDY OF THE KINETICS OF THE REDUCTION OF CUPRIC OXIDE BY HYDROGEN 1 journal, September 1962

Formation of stable Cu2O from reduction of CuO nanoparticles journal, April 2006

Hydrogen-induced atomic structure evolution of the oxygen-chemisorbed Cu(110) surface journal, December 2016

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Surface hydride formation on a metal oxide surface: the interaction of atomic hydrogen with Cu2O(100)
journal, November 1992

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book, January 2009

Visualizing the Cu/Cu ₂ O Interface Transition in Nanoparticles with Environmental Scanning Transmission Electron Microscopy
journal, December 2016

Atomic-Step-Induced Local Nonequilibrium Effects on Surface Oxidation
journal, October 2017

Theoretical study of CO oxidation on Au nanoparticles supported by MgO(100)
journal, April 2004

Reduction of the Phillips catalyst by various olefins: Stoichiometry, thermochemistry, reaction products and polymerization activity
journal, December 2016

Experimental and Theoretical Studies on the Reaction of H ₂ with NiO: Role of O Vacancies and Mechanism for Oxide Reduction
journal, January 2002

Time-resolved Studies for the Mechanism of Reduction of Copper Oxides with Carbon Monoxide: Complex Behavior of Lattice Oxygen and the Formation of Suboxides
journal, September 2004

In situ atomic-scale imaging of the metal/oxide interfacial transformation
journal, August 2017

Steps on surfaces: experiment and theory
journal, September 1999

In Situ Atomic-Scale Probing of the Reduction Dynamics of Two-Dimensional Fe ₂ O ₃ Nanostructures
journal, December 2016

First principles calculations of solid–solid interfaces: an application to conversion materials for lithium-ion batteries
journal, January 2012

Atom-Resolved Imaging of Dynamic Shape Changes in Supported Copper Nanocrystals
journal, March 2002

Visualizing Redox Dynamics of a Single Ag/AgCl Heterogeneous Nanocatalyst at Atomic Resolution
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CuO reduction induced formation of CuO/Cu2O hybrid oxides
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