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Title: Short O–O separation in layered oxide Na 0.67CoO 2 enables an ultrafast oxygen evolution reaction

Abstract

The layered oxide Na 0.67CoO 2with Na +occupying trigonal prismatic sites between CoO 2layers exhibits a remarkably high room temperature oxygen evolution reaction (OER) activity in alkaline solution. The high activity is attributed to an unusually short O–O separation that favors formation of peroxide ions by O -–O interactions followed by O 2evolution in preference to the conventional route through surface O–OH species. The dependence of the onset potential on the pH of the alkaline solution was found to be consistent with the loss of H +ions from the surface oxygen to provide surface O -that may either be attacked by solution OH -or react with another O -; a short O–O separation favors the latter route. The role of a strong hybridization of the O-2pand low-spin Co III/Co IVπ-bondingdstates is also important; the OER on other Co III/Co IVoxides is compared with that on Na 0.67CoO 2as well as that on IrO 2.

Authors:
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Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1576000
Resource Type:
Journal Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 116; Journal Issue: 47; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Wang, Hao, Wu, Jinpeng, Dolocan, Andrei, Li, Yutao, Lü, Xujie, Wu, Nan, Park, Kyusung, Xin, Sen, Lei, Ming, Yang, Wanli, and Goodenough, John B. Short O–O separation in layered oxide Na0.67CoO2 enables an ultrafast oxygen evolution reaction. United States: N. p., 2019. Web. doi:10.1073/pnas.1901046116.
Wang, Hao, Wu, Jinpeng, Dolocan, Andrei, Li, Yutao, Lü, Xujie, Wu, Nan, Park, Kyusung, Xin, Sen, Lei, Ming, Yang, Wanli, & Goodenough, John B. Short O–O separation in layered oxide Na0.67CoO2 enables an ultrafast oxygen evolution reaction. United States. doi:10.1073/pnas.1901046116.
Wang, Hao, Wu, Jinpeng, Dolocan, Andrei, Li, Yutao, Lü, Xujie, Wu, Nan, Park, Kyusung, Xin, Sen, Lei, Ming, Yang, Wanli, and Goodenough, John B. Mon . "Short O–O separation in layered oxide Na0.67CoO2 enables an ultrafast oxygen evolution reaction". United States. doi:10.1073/pnas.1901046116.
@article{osti_1576000,
title = {Short O–O separation in layered oxide Na0.67CoO2 enables an ultrafast oxygen evolution reaction},
author = {Wang, Hao and Wu, Jinpeng and Dolocan, Andrei and Li, Yutao and Lü, Xujie and Wu, Nan and Park, Kyusung and Xin, Sen and Lei, Ming and Yang, Wanli and Goodenough, John B.},
abstractNote = {The layered oxide Na0.67CoO2with Na+occupying trigonal prismatic sites between CoO2layers exhibits a remarkably high room temperature oxygen evolution reaction (OER) activity in alkaline solution. The high activity is attributed to an unusually short O–O separation that favors formation of peroxide ions by O-–O–interactions followed by O2evolution in preference to the conventional route through surface O–OH–species. The dependence of the onset potential on the pH of the alkaline solution was found to be consistent with the loss of H+ions from the surface oxygen to provide surface O-that may either be attacked by solution OH-or react with another O-; a short O–O separation favors the latter route. The role of a strong hybridization of the O-2pand low-spin CoIII/CoIVπ-bondingdstates is also important; the OER on other CoIII/CoIVoxides is compared with that on Na0.67CoO2as well as that on IrO2.},
doi = {10.1073/pnas.1901046116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 47,
volume = 116,
place = {United States},
year = {2019},
month = {11}
}