Mechanism of Oxygen Evolution Catalyzed by Cobalt Oxyhydroxide: Cobalt Superoxide Species as a Key Intermediate and Dioxygen Release as a Rate-Determining Step

Journal of the American Chemical Society
Aliki MoysiadouXile Hu

Abstract

The oxygen evolution reaction (OER) is the performance-limiting half reaction of water splitting, which can be used to produce hydrogen fuel using renewable energies. Whereas a number of transition metal oxides and oxyhydroxides have been developed as promising OER catalysts in alkaline medium, the mechanisms of OER on these catalysts are not well understood. Here we combine electrochemical and in situ spectroscopic methods, particularly operando X-ray absorption and Raman spectroscopy, to study the mechanism of OER on cobalt oxyhydroxide (CoOOH), an archetypical unary OER catalyst. We find the dominating resting state of the catalyst as a Co(IV) species CoO2. Through oxygen isotope exchange experiments, we discover a cobalt superoxide species as an active intermediate in the OER. This intermediate is formed concurrently to the oxidation of CoOOH to CoO2. Combing spectroscopic and electrokinetic data, we identify the rate-determining step of the OER as the release of dioxygen from the superoxide intermediate. The work provides important experimental fingerprints and new mechanistic perspectives for OER catalysts.

References

Oct 18, 2006·Proceedings of the National Academy of Sciences of the United States of America·Nathan S Lewis, Daniel G Nocera
Jun 26, 2009·Journal of the American Chemical Society·Javier J ConcepcionThomas J Meyer
May 4, 2010·Journal of the American Chemical Society·J Gregory McAlpinR David Britt
Sep 16, 2010·Journal of the American Chemical Society·Matthew W KananDaniel G Nocera
Oct 28, 2010·Journal of the American Chemical Society·Yogesh SurendranathDaniel G Nocera
Oct 28, 2010·Journal of the American Chemical Society·Derek J WasylenkoCurtis P Berlinguette
Mar 19, 2011·Journal of the American Chemical Society·Boon Siang Yeo, Alexis T Bell
Nov 10, 2011·Physical Chemistry Chemical Physics : PCCP·Michael E G LyonsMichael P Brandon
Aug 17, 2012·Nature·Steven Chu, Arun Majumdar
May 9, 2013·Physical Chemistry Chemical Physics : PCCP·Richard L DoyleMichael E G Lyons
Jul 16, 2013·Nature Materials·M SathiyaJ-M Tarascon
Aug 16, 2013·Journal of the American Chemical Society·Michal BajdichAlexis T Bell
Aug 24, 2013·Journal of the American Chemical Society·Xichen Li, Per E M Siegbahn
Sep 13, 2013·Physical Chemistry Chemical Physics : PCCP·Daniel FriebelAnders Nilsson
Sep 21, 2013·Journal of the American Chemical Society·Giuseppe MattioliLeonardo Guidoni
Nov 1, 2013·Journal of the American Chemical Society·Charles C L McCroryThomas F Jaramillo
May 2, 2014·Journal of the American Chemical Society·Lena TrotochaudShannon W Boettcher
Dec 2, 2014·Nature Materials·M SathiyaJ-M Tarascon
Oct 20, 2015·Journal of the American Chemical Society·Craig P Plaisance, Rutger A van Santen
Dec 29, 2015·Journal of the American Chemical Society·Hsin-Yi WangBin Liu
Jan 23, 2016·Nature Materials·A GrimaudJ-M Tarascon
Feb 2, 2016·Journal of the American Chemical Society·Rodney D L Smith, Curtis P Berlinguette
Jun 28, 2016·Journal of the American Chemical Society·Carlos G Morales-GuioXile Hu
Sep 7, 2016·Journal of Colloid and Interface Science·Tshifhiwa M MasikhwaNcholu Manyala
Nov 1, 2016·Chemical Reviews·Bryan M HunterAstrid M Müller
Dec 10, 2016·The Journal of Physical Chemistry Letters·Hsin-Yi WangBin Liu
Jan 14, 2017·Chemical Society Reviews·Nian-Tzu SuenHao Ming Chen
Apr 22, 2017·Nature Chemistry·Alexis GrimaudYang Shao-Horn
Sep 7, 2017·Proceedings of the National Academy of Sciences of the United States of America·Cyrille Costentin, Daniel G Nocera
Sep 26, 2017·Nano Letters·Alaina L StricklerThomas F Jaramillo
Jan 18, 2019·Journal of the American Chemical Society·Chiara PasquiniHolger Dau
Aug 27, 2019·Science Advances·Xiang LiJohn B Goodenough

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Citations

Nov 21, 2020·Chemical Communications : Chem Comm·Shengqi ZhangXuanwen Liu
Jul 29, 2021·Journal of the American Chemical Society·Jaruwan AmtawongT Don Tilley
Dec 2, 2020·Journal of the American Chemical Society·Biswajit MondalAbhishek Dey
Sep 2, 2021·Proceedings of the National Academy of Sciences of the United States of America·Xueli ZhengYi Cui
Sep 14, 2021·Inorganic Chemistry·Malaya K SahooJ N Behera
Oct 26, 2021·ACS Applied Materials & Interfaces·Ching Thian MoiMohammad Qureshi
Dec 9, 2021·Journal of the American Chemical Society·Xiao LinLinjuan Zhang
Dec 17, 2021·ACS Applied Materials & Interfaces·Ji QiWeiming Lü
Dec 10, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Amirreza ValizadehMohammad Mahdi Najafpour
Jan 21, 2022·Dalton Transactions : an International Journal of Inorganic Chemistry·Ivy GhoshTapan Kanti Paine

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