Structural Distortion in MnO2 Nanosheets and Its Suppression by Cobalt Substitution

Co-Mn oxide nanosheets with the chemical composition H0.23Co0.23Mn0.77O2 (C23M77NS) and MnO2 nanosheets (M100NS) were prepared by exfoliation of layer-structured oxides via chemical processing in an aqueous medium. The optical properties of C23M77NS and M100NS were compared using UV-Vis spectroscopy, and the valence states of Mn and Co and local structures around them were examined using X-ray absorption spectroscopy. M100NS with an average Mn valence of 3.6 exhibits large structural distortion, whereas C23M77NS with an average Mn valence of 4.0 does not exhibit structural distortion. Spontaneous oxidization of Mn occurs during ion-exchange and/or exfoliation into nanosheets. These results have originated the hypothesis that structural distortion determines the valence state of Mn in compounds with CdI2-type-structured MnO2 layers.