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J Am Chem Soc. 2017 Feb 15;139(6):2277-2285. doi: 10.1021/jacs.6b10657. Epub 2017 Feb 1.

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

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Department of Materials Science and Engineering, Seoul National University , Seoul 151-742, Korea.
Department of Applied Chemistry, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Biofunctional Catalyst Research Team, RIKEN Center for Sustainable Resource Science (CSRS) , 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Western Seoul Center, Korea Basic Science Institute (KBSI) , 150, Bukahyeon-ro, Seodaemun-gu, Seoul 120-140, Korea.
Pohang Accelerator Laboratory, Pohang University of Science and Technology (POSTECH) , Pohang 790-784, Korea.


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.


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