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Title: Self-healing catalysis in water

Abstract

Principles for designing self-healing water-splitting catalysts are presented together with a formal kinetics model to account for the key chemical steps needed for self-healing. Self-healing may be realized if the catalysts are able to self-assemble at applied potentials less than that needed for catalyst turnover. Solution pH provides a convenient handle for controlling the potential of these two processes, as demonstrated for the cobalt phosphate (CoP i) water-splitting catalyst. For Co 2+ ion that appears in solution due to leaching from the catalyst during turnover, a quantitative description for the kinetics of the redeposition of the ion during the self-healing process has been derived. In this work, the model reveals that OER activity of CoP i occurs with negligible film dissolution in neutral pH for typical cell geometries and buffer concentrations.

Authors:
ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1378779
Alternate Identifier(s):
OSTI ID: 1529224
Grant/Contract Number:  
SC0017619
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: 51; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solar energy; water splitting; renewable energy storage; self-healing catalysis; cobalt phosphate

Citation Formats

Costentin, Cyrille, and Nocera, Daniel G. Self-healing catalysis in water. United States: N. p., 2017. Web. doi:10.1073/pnas.1711836114.
Costentin, Cyrille, & Nocera, Daniel G. Self-healing catalysis in water. United States. doi:10.1073/pnas.1711836114.
Costentin, Cyrille, and Nocera, Daniel G. Tue . "Self-healing catalysis in water". United States. doi:10.1073/pnas.1711836114.
@article{osti_1378779,
title = {Self-healing catalysis in water},
author = {Costentin, Cyrille and Nocera, Daniel G.},
abstractNote = {Principles for designing self-healing water-splitting catalysts are presented together with a formal kinetics model to account for the key chemical steps needed for self-healing. Self-healing may be realized if the catalysts are able to self-assemble at applied potentials less than that needed for catalyst turnover. Solution pH provides a convenient handle for controlling the potential of these two processes, as demonstrated for the cobalt phosphate (CoPi) water-splitting catalyst. For Co2+ ion that appears in solution due to leaching from the catalyst during turnover, a quantitative description for the kinetics of the redeposition of the ion during the self-healing process has been derived. In this work, the model reveals that OER activity of CoPi occurs with negligible film dissolution in neutral pH for typical cell geometries and buffer concentrations.},
doi = {10.1073/pnas.1711836114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 51,
volume = 114,
place = {United States},
year = {2017},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1711836114

Figures / Tables:

Fig. 1 Fig. 1: Frost diagram for H2O at pH 7. The apparent standard potential for redox couple is given by the slope of the line connecting the two species on a Frost diagram.

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.