Proceedings of nanoGe Fall Meeting 2018 (NFM18)
DOI: https://doi.org/10.29363/nanoge.nfm.2018.147
Publication date: 6th July 2018
Finding electro-catalysts for driving the oxygen evolution reaction (OER) at the minimum overpotential remains the bottle neck in water splitting. Birnessite is a promising earth-abundant electrode material, since its layered calcium manganese oxide structure with intercalated crystal water possibly allows bulk OER activity [1,2].
We study a nanocrystalline type of highly active electrode, prepared by dropping ink solutions on top of a substrate. The structure of the highly porous electrodes with a grain size down to a few nanometres are analysed with High Resolution Transmission Electron Microscopy (HRTEM) and Selected Area Electron Diffraction (SAED). To gain more information about the mechanism of water oxidation we investigated the interaction of the electrode with the electrolyte. Electron Energy Loss Spectroscopy (EELS) and Energy Dispersive X-Ray Spectroscopy (EDX) indicate an intercalation of the electrolyte cation phosphorous while calcium was depleted from the electrode. The exchange mainly happens at the surface and at grain boundaries.
To further explore the active centres of water oxidation with Birnessite we took steps towards in-situ TEM studies in water vapour. The Environmental TEM (ETEM) offers to investigate Birnessite active states in electric potentials close to operando conditions. Based on our studies we present conclusions on the involved OER mechanism and design strategies for highly active and stable electro-catalysts.
[1] S. Y. Lee, D. González-Flores, J. Ohms, T. Trost, H. Dau, I. Zaharieva and P. Kurz, ChemSusChem, 2014, 7, 3442-3451
[2] C. E. Frey and P. Kurz, Dalton Trans. , 2014, 43, 4370-4379
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