First principles calculations on oxygen vacant hydrated α-MnO2 for activating water oxidation and its self-healing mechanism.

Understanding the mechanism behind water oxidation is the prime requirement for designing better catalysts for electrochemical energy devices. In this work, we demonstrate by employing first principles calculations that an initial step of water oxidation is observed to be associated with the dissociation of water dimers into hydronium and hydroxide ions, in the tunnel of a hydrated α-MnO2 compound with an oxygen vacancy. The former ion is intercalated within the network, while the latter ion occupies the oxygen vacant site and interacts strongly with the Mn atoms.