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Prompted by the early results on the catalytic activity of LiMn2 O4 and related oxides in the photochemical oxidation of water, our detailed study of several manganese oxides has shown that trivalency of Mn is an important factor in determining the catalytic activity. Thus, Mn2 O3 , LaMnO3 , and MgMn2 O4 are found to be very good catalysts with turnover frequencies of 5 × 10−4 s−1 , 4.8 × 10−4 s−1 , and 0.8 ×10−4 s−1 , respectively. Among the cobalt oxides, Li2 Co2 O4 and LaCoO3 —especially the latter—exhibit excellent catalytic activity, with the turnover frequencies being 9 × 10−4 s−1 and 1.4 × 10−3 s−1 , respectively. The common feature among the catalytic Mn and Co oxides is not only that Mn and Co are in the trivalent state, but Co3+ in the Co oxides is in the intermediate t2g 5 eg 1 state whereas Mn3+ is in the t2g 3 eg 1 state. The presence of the eg 1 electron in these Mn and Co oxides is considered to play a crucial role in the photocatalytic properties of the oxides.

Importance of trivalency and the e g 1 configuration in the photocatalytic oxidation of water by Mn and Co oxides

Importance of trivalency and the e _g ¹ configuration in the photocatalytic oxidation of water by Mn and Co oxides