Water-oxidation catalysis by manganese in a geochemical-like cycle


Water oxidation in all oxygenic photosynthetic organisms is catalysed by the Mn4CaO4 cluster of Photosystem II. This cluster has inspired the development of synthetic manganese catalysts for solar energy production. A photoelectrochemical device, made by impregnating a synthetic tetranuclear-manganese cluster into a Nafion matrix, has been shown to achieve efficient water oxidation catalysis. We report here in situ X-ray absorption spectroscopy and transmission electron microscopy studies that demonstrate that this cluster dissociates into Mn(II) compounds in the Nafion, which are then reoxidized to form dispersed nanoparticles of a disordered Mn(III/IV)-oxide phase. Cycling between the photoreduced product and this mineral-like solid is responsible for the observed photochemical water-oxidation catalysis. The original manganese cluster serves only as a precursor to the catalytically active material. The behaviour of Mn in Nafion therefore parallels its broader biogeochemistry, which is also dominated by cycles of oxidation into solid Mn(III/IV) oxides followed by photoreduction to Mn2+.

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Figure 1: Comparison of Mn K-edge XAS spectra.
Figure 2: Comparison of electro-oxidized products in Nafion and those of natural and synthetic birnessites.
Figure 3: Comparison of the EXAFS spectra of the electro-oxidized product of [Mn4O4L6]+ in Nafion (black) to a series of standards (grey).
Figure 4: High-resolution transmission electron microscopy images.
Figure 5: Comparison of XANES spectra during various states of catalytic cycling.


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M. Belousoff and K. Morgan are thanked for their assistance with the collection of the XAS data, D. Desbois and P. Nichols for assistance with the NMR experiments, B. Johannessen, G. Foran, S. P. Best, R. D. Britt, G. C. Dismukes and G. F. Swiegers for helpful discussions, and M. Ma for proof reading the manuscript. We acknowledge the operational support of the High Energy Accelerator Research Organisation (KEK) in Tsukuba, Japan and access to the Australian National Beam-line Facility. We acknowledge financial support from the Australian Research Council through the Australian Centre of Excellence for Electromaterials Science as well as the Linkage Infrastructure, Equipment and Facilities and Discovery Programs (L.S. and R.K.H.), the US DOE (W.H.C.) and US NSF (W.H.C.). B. Birch and the staff at the Melbourne Museum are thanked for the gift of mineral samples M38218 and 6512 from their collection.

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R.K.H. and L.S. proposed the research. R.K.H. participated in the development of the concept of this research, performed the XAS experiments, the NMR experiments, generated samples, analysed the data and co-wrote the manuscript. R.B. participated in the development of the concept of this research, generated samples for analysis and performed some of the XAS experiments. S.L.Y.C. participated in the development of TEM methodology, and performed the TEM experiments. A.S. prepared samples for TEM measurements and measured the photo-current data on catalytic systems. M.H.C and C.G. provided critical advice and assistance with the design of the XAS experiments. W.H.C and L.S. participated in the development of the concept of this research and co-wrote the manuscript.

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Correspondence to Rosalie K. Hocking or Leone Spiccia.

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Hocking, R., Brimblecombe, R., Chang, LY. et al. Water-oxidation catalysis by manganese in a geochemical-like cycle. Nature Chem 3, 461–466 (2011). https://doi.org/10.1038/nchem.1049

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