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Title: Redox properties of birnessite from a defect perspective

Abstract

Birnessite, a layered-structure MnO 2 , is an earth-abundant functional material with potential for various energy and environmental applications, such as water oxidation. An important feature of birnessite is the existence of Mn(III) within the MnO 2 layers, accompanied by interlayer charge-neutralizing cations. Using first-principles calculations, we reveal the nature of Mn(III) in birnessite with the concept of the small polaron, a special kind of point defect. Further taking into account the effect of the spatial distribution of Mn(III), we propose a theoretical model to explain the structure–performance dependence of birnessite as an oxygen evolution catalyst. We find an internal potential step which leads to the easy switching of the oxidation state between Mn(III) and Mn(IV) that is critical for enhancing the catalytic activity of birnessite. Finally, we conduct a series of comparative experiments which support our model.

Authors:
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Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for the Computational Design of Functional Layered Materials (CCDM)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1375816
Alternate Identifier(s):
OSTI ID: 1469910
Grant/Contract Number:  
SC0012575; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 114 Journal Issue: 36; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; catalysis (heterogeneous); solar (photovoltaic); energy storage (including batteries and capacitors); hydrogen and fuel cells; defects; mechanical behavior; materials and chemistry by design; synthesis (novel materials); birnessite MnO2; small polaron; catalysis; water oxidation

Citation Formats

Peng, Haowei, McKendry, Ian G., Ding, Ran, Thenuwara, Akila C., Kang, Qing, Shumlas, Samantha L., Strongin, Daniel R., Zdilla, Michael J., and Perdew, John P. Redox properties of birnessite from a defect perspective. United States: N. p., 2017. Web. doi:10.1073/pnas.1706836114.
Peng, Haowei, McKendry, Ian G., Ding, Ran, Thenuwara, Akila C., Kang, Qing, Shumlas, Samantha L., Strongin, Daniel R., Zdilla, Michael J., & Perdew, John P. Redox properties of birnessite from a defect perspective. United States. doi:10.1073/pnas.1706836114.
Peng, Haowei, McKendry, Ian G., Ding, Ran, Thenuwara, Akila C., Kang, Qing, Shumlas, Samantha L., Strongin, Daniel R., Zdilla, Michael J., and Perdew, John P. Mon . "Redox properties of birnessite from a defect perspective". United States. doi:10.1073/pnas.1706836114.
@article{osti_1375816,
title = {Redox properties of birnessite from a defect perspective},
author = {Peng, Haowei and McKendry, Ian G. and Ding, Ran and Thenuwara, Akila C. and Kang, Qing and Shumlas, Samantha L. and Strongin, Daniel R. and Zdilla, Michael J. and Perdew, John P.},
abstractNote = {Birnessite, a layered-structure MnO 2 , is an earth-abundant functional material with potential for various energy and environmental applications, such as water oxidation. An important feature of birnessite is the existence of Mn(III) within the MnO 2 layers, accompanied by interlayer charge-neutralizing cations. Using first-principles calculations, we reveal the nature of Mn(III) in birnessite with the concept of the small polaron, a special kind of point defect. Further taking into account the effect of the spatial distribution of Mn(III), we propose a theoretical model to explain the structure–performance dependence of birnessite as an oxygen evolution catalyst. We find an internal potential step which leads to the easy switching of the oxidation state between Mn(III) and Mn(IV) that is critical for enhancing the catalytic activity of birnessite. Finally, we conduct a series of comparative experiments which support our model.},
doi = {10.1073/pnas.1706836114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 36,
volume = 114,
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1073/pnas.1706836114

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Cited by: 4 works
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