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

Abstract

The layered oxide Na 0.67 CoO 2 with Na + occupying trigonal prismatic sites between CoO 2 layers 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 2 evolution 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–2 p and low-spin Co III /Co IV π-bonding d states is also important; the OER on other Co III /Co IV oxides is compared with that on Na 0.67 CoO 2 as well as that on IrO 2 .

Authors:
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Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1573105
Grant/Contract Number:  
EE000762
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: 116 Journal Issue: 47; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the 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 Na 0.67 CoO 2 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 Na 0.67 CoO 2 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 Na 0.67 CoO 2 enables an ultrafast oxygen evolution reaction". United States. doi:10.1073/pnas.1901046116.
@article{osti_1573105,
title = {Short O–O separation in layered oxide Na 0.67 CoO 2 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 Na 0.67 CoO 2 with Na + occupying trigonal prismatic sites between CoO 2 layers 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 2 evolution 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–2 p and low-spin Co III /Co IV π-bonding d states is also important; the OER on other Co III /Co IV oxides is compared with that on Na 0.67 CoO 2 as well as that on IrO 2 .},
doi = {10.1073/pnas.1901046116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 47,
volume = 116,
place = {United States},
year = {2019},
month = {11}
}

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