Atomic Origin of the Autocatalytic Reduction of Monoclinic CuO in a Hydrogen Atmosphere

Sun, Xianhu; Wu, Dongxiang; Zhu, Wenhui; Chen, Xiaobo; Sharma, Renu; Yang, Judith C.; Zhou, Guangwen

doi:10.1021/acs.jpclett.1c02369

Title: Atomic Origin of the Autocatalytic Reduction of Monoclinic CuO in a Hydrogen Atmosphere

Abstract

Reducibility is key for the use of bulk metal oxides in chemical transformation involving redox reactions but probing microscopic processes of oxide reduction is challenging. This is because the insulating nature of bulk oxides restricts ion and electron spectroscopic measurements of oxide surfaces. Herein, using a combination of environmental transmission electron microscopy and atomistic modeling, we report direct in-situ atomic-scale observations of the surface and subsurface dynamics and show that the hydrogen induced CuO reduction occurs via the surface decay of Cu-O/Cu bilayer atomic steps, formation of partially reduced CuO superstructure by the self-ordering of O vacancies in the subsurface, and collapse of Cu-O layers in the bulk. In this work, all these substeps can be traced back to the progressively increased concentration and activity of O vacancies in the surface and subsurface of the oxide, thereby leading to the self-accelerated oxide reduction. These results demonstrate the microscopic details that may have broader applicability in modulating various redox processes.

Authors:

Sun, Xianhu ^[1]; Wu, Dongxiang ^[1]; Zhu, Wenhui ^[1]; Chen, Xiaobo ^[1]; Sharma, Renu ^[2]; Yang, Judith C. ^[3];

^[1]

State Univ. of New York (SUNY), Binghamton, NY (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Univ. of Pittsburgh, PA (United States)

Publication Date:: Mon Sep 27 00:00:00 EDT 2021

Research Org.:: State Univ. of New York (SUNY), Binghamton, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)

OSTI Identifier:: 1864760

Grant/Contract Number:: SC0001135; SC0012704; OCI-1053575

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry Letters

Additional Journal Information:: Journal Volume: 12; Journal Issue: 39; Journal ID: ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; CuO; Reduction; TEM; Transmission electron microscopy; Defects in solids; Redox reactions; Oxides; Lattices

Citation Formats


                    Sun, Xianhu, Wu, Dongxiang, Zhu, Wenhui, Chen, Xiaobo, Sharma, Renu, Yang, Judith C., and Zhou, Guangwen. Atomic Origin of the Autocatalytic Reduction of Monoclinic CuO in a Hydrogen Atmosphere.  United States: N. p., 2021. 
Web.  doi:10.1021/acs.jpclett.1c02369.

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                    Sun, Xianhu, Wu, Dongxiang, Zhu, Wenhui, Chen, Xiaobo, Sharma, Renu, Yang, Judith C., & Zhou, Guangwen. Atomic Origin of the Autocatalytic Reduction of Monoclinic CuO in a Hydrogen Atmosphere.  United States.  https://doi.org/10.1021/acs.jpclett.1c02369

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                    Sun, Xianhu, Wu, Dongxiang, Zhu, Wenhui, Chen, Xiaobo, Sharma, Renu, Yang, Judith C., and Zhou, Guangwen. Mon .  
"Atomic Origin of the Autocatalytic Reduction of Monoclinic CuO in a Hydrogen Atmosphere".  United States.  https://doi.org/10.1021/acs.jpclett.1c02369.  https://www.osti.gov/servlets/purl/1864760.

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@article{osti_1864760,

  title        = {Atomic Origin of the Autocatalytic Reduction of Monoclinic CuO in a Hydrogen Atmosphere},

  author       = {Sun, Xianhu and Wu, Dongxiang and Zhu, Wenhui and Chen, Xiaobo and Sharma, Renu and Yang, Judith C. and Zhou, Guangwen},

  abstractNote = {Reducibility is key for the use of bulk metal oxides in chemical transformation involving redox reactions but probing microscopic processes of oxide reduction is challenging. This is because the insulating nature of bulk oxides restricts ion and electron spectroscopic measurements of oxide surfaces. Herein, using a combination of environmental transmission electron microscopy and atomistic modeling, we report direct in-situ atomic-scale observations of the surface and subsurface dynamics and show that the hydrogen induced CuO reduction occurs via the surface decay of Cu-O/Cu bilayer atomic steps, formation of partially reduced CuO superstructure by the self-ordering of O vacancies in the subsurface, and collapse of Cu-O layers in the bulk. In this work, all these substeps can be traced back to the progressively increased concentration and activity of O vacancies in the surface and subsurface of the oxide, thereby leading to the self-accelerated oxide reduction. These results demonstrate the microscopic details that may have broader applicability in modulating various redox processes.},

  doi          = {10.1021/acs.jpclett.1c02369},

  journal      = {Journal of Physical Chemistry Letters},

  number       = 39,

  volume       = 12,

  place        = {United States},

  year         = {Mon Sep 27 00:00:00 EDT 2021},

  month        = {Mon Sep 27 00:00:00 EDT 2021}

}

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Title: Atomic Origin of the Autocatalytic Reduction of Monoclinic CuO in a Hydrogen Atmosphere

Abstract

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Hydrogen-Induced Clustering of Metal Atoms in Oxygenated Metal Surfaces
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Redox-Mediated Reconstruction of Copper during Carbon Monoxide Oxidation
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