Mechanistic Investigation of Water Oxidation Catalyzed by Uniform, Assembled MnO Nanoparticles

Kyoungsuk Jin, Hongmin Seo, Toru Hayashi, Mani Balamurugan, Donghyuk Jeong, Yoo Kyung Go, Jung Sug Hong, Kang Hee Cho, Hirotaka Kakizaki, Nadège Bonnet-Mercier, Min Gyu Kim, Sun Hee Kim, Ryuhei Nakamura, Ki Tae Nam

Research output: Contribution to journalArticlepeer-review

124 Citations (Scopus)


The development of active water oxidation catalysts is critical to achieve high efficiency in overall water splitting. Recently, sub-10 nm-sized monodispersed partially oxidized manganese oxide nanoparticles were shown to exhibit not only superior catalytic performance for oxygen evolution, but also unique electrokinetics, as compared to their bulk counterparts. In the present work, the water-oxidizing mechanism of partially oxidized MnO nanoparticles was investigated using integrated in situ spectroscopic and electrokinetic analyses. We successfully demonstrated that, in contrast to previously reported manganese (Mn)-based catalysts, Mn(III) species are stably generated on the surface of MnO nanoparticles via a proton-coupled electron transfer pathway. Furthermore, we confirmed as to MnO nanoparticles that the one-electron oxidation step from Mn(II) to Mn(III) is no longer the rate-determining step for water oxidation and that Mn(IV)O species are generated as reaction intermediates during catalysis.

Original languageEnglish
Pages (from-to)2277-2285
Number of pages9
JournalJournal of the American Chemical Society
Issue number6
Publication statusPublished - 2017 Feb 15
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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