Issue 29, 2017

Electrocatalytic water oxidation at low energy cost by a highly active and robust calcium–manganese oxide thin film sintered on an FTO electrode with ethyl methyl imidazolium triflate ionic liquid

Abstract

We report a simple and novel method involving an ethyl methyl imidazolium triflate ionic liquid (EMI OTf) to prepare highly mechanically stable crystalline α-Mn2O3 and calcium-incorporated manganese oxide (CaMn-oxide) thin film water oxidation electrocatalysts (WOCs) on a fluorine-doped tin oxide (FTO) electrode (FTO/EMI α-Mn2O3 and FTO/EMI CaMn-oxide). Electrochemical measurements showed that the incorporation of calcium into manganese oxide promotes water oxidation at a very low energy cost, similar to that observed in natural photosystem II (PSII). The low energy cost is due to the involvement of the MnIV[double bond, length as m-dash]O species in the catalysis as compared to the MnV[double bond, length as m-dash]O species that has been previously detected in calcium-free α-Mn2O3. Moreover, the FTO/EMI CaMn-oxide electro-catalyst showed unprecedentedly high activity (TOF ≈ 29.8 s−1 at η = 0.57 V) and robustness (tested for 40 h) for water oxidation in a neutral potassium phosphate (KPi) buffer solution (0.1 M, pH 7.0). The mechanism of water oxidation by FTO/EMI CaMn-oxide was discussed and applied for water oxidation by the μ-oxido-CaMn4O5 cluster of photosystem II (PS II).

Graphical abstract: Electrocatalytic water oxidation at low energy cost by a highly active and robust calcium–manganese oxide thin film sintered on an FTO electrode with ethyl methyl imidazolium triflate ionic liquid

Supplementary files

Article information

Article type
Paper
Submitted
28 Apr 2017
Accepted
26 Jun 2017
First published
26 Jun 2017

J. Mater. Chem. A, 2017,5, 15167-15174

Electrocatalytic water oxidation at low energy cost by a highly active and robust calcium–manganese oxide thin film sintered on an FTO electrode with ethyl methyl imidazolium triflate ionic liquid

Z. N. Zahran, E. A. Mohamed and Y. Naruta, J. Mater. Chem. A, 2017, 5, 15167 DOI: 10.1039/C7TA03665E

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