Significant role of Mn(III) sites in eg1 configuration in manganese oxide catalysts for efficient artificial water oxidation

• Chemical and photochemical water oxidation with manganese oxide.
• Stepwise oxidation of low valent manganese monooxide to active catalyst.
• Efficient water oxidation with higher amount of MnIII species.
• Degeneracy in eg orbital facilitates structural flexibility in manganese oxide.

Development of efficient bio-inspired water oxidation system with transition metal oxide catalyst has been considered as the one of the most challenging task in the recent years. As the oxygen evolving center of photosystem II consists of Mn4CaO5 cluster, most of the water oxidation study was converged to build up manganese oxide based catalysts. Here we report the synthesis of efficient artificial water oxidation catalysts by transferring the inactive manganese monooxide (MnO) under highly oxidizing conditions with ceric ammonium nitrate (CAN) and ozone (O3). MnO was partially oxidized to form mixed-valent manganese oxide (MnOx) with CAN whereas completely oxidized to mineral phase of ε-MnO2 (Akhtenskite) upon treatment of O3 in acidic solution, which we explore first time as a water oxidation catalyst. Chemical water oxidation, as well as the photochemical water oxidation in the presence of sacrificial electron acceptor and photosensitizer with the presented catalysts were carried out that followed the trends: MnOx > MnO2 > MnO. Structural and activity correlation reveals that the presence of larger extent of Mn(III) in MnOx is the responsible factor for higher activity compared to MnO2. Mn(III) species in octahedral system with eg1 configuration furnishes and facilitates the Mn–O and Mn–Mn bond enlargement with required structural flexibility and disorder in the manganese oxide structure which indeed facilitates water oxidation.

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