Journal
CHEMSUSCHEM
Volume 6, Issue 4, Pages 643-651Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cssc.201200849
Keywords
electrochemistry; manganese oxides; thin films; water splitting; x-ray absorption spectroscopy
Funding
- Australian Research Council (ARC)
- ARC Centre of Excellence for Electromaterials Science (ACES)
- Federation Fellowship Scheme
- Laureate Fellowship Scheme
- Monash University
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Manganese oxides (MnOx) are considered to be promising catalysts for water oxidation. Electrodeposited MnOx films from aqueous electrolytes have previously been shown to exhibit a lower catalytic action than films deposited from ionic liquids when tested in strongly alkaline conditions. In this study, we describe a thermal treatment that converts the MnOx films deposited from aqueous electrolytes to highly catalytic films with comparable activity to ionic-liquid-deposited films. The films deposited from aqueous electrolytes show a remarkable improvement in the catalysis of water oxidation after heat treatment at a low temperature (120 degrees C) for 30min. The films were characterised by using XRD and SEM, and energy-dispersive X-ray (EDX), FTIR and Raman spectroscopy, which indicate that dehydration occurs during the heat treatment without significant change to the microstructure or bulk composition. The X-ray absorption spectroscopy (XAS) results show the growth of small amounts (ca. 310%) of reduced Mn species (MnII or MnIII) after heat treatment. The dehydration process removes structural water and hydroxyl species to result in a conductivity improvement and a more active catalyst, thereby contributing to the enhancement in water oxidation performance.
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