Importance of trivalency and the eg1 configuration in the photocatalytic oxidation of water by Mn and Co oxides

Prompted by the early results on the catalytic activity of LiMn2O4 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, Mn2O3, LaMnO3, and MgMn2O4 are found to be very good catalysts with turnover frequencies of 5 x 10(-4) s(-1), 4.8 x 10(-4) s(-1), and 0.8 x 10(-4) s(-1), respectively. Among the cobalt oxides, Li2Co2O4 and LaCoO3-especially the latter-exhibit excellent catalytic activity, with the turnover frequencies being 9 x 10(-4) s(-1) and 1.4 x 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 t(2g) (5)e(g)(1) state whereas Mn3+ is in the t(2g) (3)e(g)(1) state. The presence of the e(g)(1) electron in these Mn and Co oxides is considered to play a crucial role in the photocatalytic properties of the oxides.