There has been a tremendous surge in research on the synthesis of various metal compounds aimed at simulating the water-oxidizing complex (WOC) of photosystem II (PSII). This is crucial because the water oxidation half reaction is overwhelmingly rate-limiting and needs high over-voltage (approx. 1 V), which results in low conversion efficiencies when working at current densities required for hydrogen production via water splitting. Particular attention has been given to the manganese compounds not only because manganese has been used by nature to oxidize water but also because manganese is cheap and environmentally friendly. The manganese-calcium cluster in PSII has a dimension of about approximately 0.5 nm. Thus, nano-sized manganese compounds might be good structural and functional models for the cluster. As in the nanometre-size of the synthetic models, most of the active sites are at the surface, these compounds could be more efficient catalysts than micrometre (or bigger) particles. In this paper, we focus on nano-sized manganese oxides as functional and structural models of the WOC of PSII for hydrogen production via water splitting and review nano-sized manganese oxides used in water oxidation by some research groups.

Nano-sized particles of manganese oxides have been prepared by a very simple and cheap process using a decomposing aqueous solution of manganese nitrate at 100 °C. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction spectrometry have been used to characterize the phase and the morphology of the manganese oxide. The nano-sized manganese oxide shows efficient catalytic activity toward water oxidation and the epoxidation of olefins in the presence of cerium(IV) ammonium nitrate and hydrogen peroxide, respectively.

In this report, gold or silver deposited on layered manganese oxide has been synthesized by a simple method and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction spectrometry, atomic absorption spectroscopy, and energy-dispersive X-ray mapping. The gold deposited on layered manganese oxide showed efficient catalytic activity toward water oxidation in the presence of cerium(IV) ammonium nitrate. The properties associated with this compound suggest it is a functional model for the water-oxidizing complex in photosystem II.

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