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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 Na0.67CoO2 with Na+ occupying trigonal prismatic sites between CoO2 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 O2 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-2p and low-spin CoIII/CoIV π-bonding d states is also important; the OER on other CoIII/CoIV oxides is compared with that on Na0.67CoO2 as well as that on IrO2.

Authors:
; ; ; ; ; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3)
OSTI Identifier:
1573105
Alternate Identifier(s):
OSTI ID: 1597518; OSTI ID: 1601212
Grant/Contract Number:  
AC02-76SF00515; EE000762; F-1066; AC02-05CH11231; AC02-06CH11357
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:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; air electrodes; water electrolysis; catalytic mechanisms; structure−property relationship

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.
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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.
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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.
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@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 Na0.67CoO2 with Na+ occupying trigonal prismatic sites between CoO2 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 O2 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-2p and low-spin CoIII/CoIV π-bonding d states is also important; the OER on other CoIII/CoIV oxides is compared with that on Na0.67CoO2 as well as that on IrO2.},
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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DOI: 10.1073/pnas.1901046116
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