The Oxygen Evolution Reaction at Transition Metal Oxide (TMO) Films in Alkaline Media
Authors: Browne Michelle Phillippa , Stafford Shelley , O'Brien Maria , Nolan Hugo , Berner Nina , Duesberg Georg S. , Colavita Paula E , Lyons Micheal E.G 
Published: February 2020

Alkaline water electrolysis produces H2 gas, which can be used as a fuel in H2/O2 fuel cells to generate power. The most energy intensive step in water electrolysis is the evolution of O2 due to the large anodic overpotential of the Oxygen Evolution Reaction (OER).1 Thus, understanding and optimizing electrocatalysts for OER remains one of the grand challenges for both physical electrochemistry and energy science. For the OER in alkaline media, the best performing electrocatalysts are thermally prepared RuO2 and IrO2, which exhibit the lowest OER overpotentials to date, but these oxides are expensive and somewhat unstable in alkaline media, rendering them impractical and uneconomical.1 First row Transition Metal Oxides (TMO), e.g. Mn, Ni, Co or Fe, show great promise as alternative materials for OER, as they exhibit low overpotentials and high stability at lower costs than those of RuO2 or IrO2. However, mechanistic studies of OER at TMO electrodes in alkaline media have been sparse and the nature of catalytic sites and the mechanism leading to O2 evolution are not well understood.2

In this work, pure and mixed Ni/Fe materials were electrochemically deposited on Ti supports to fabricate inexpensive electrocatalysts. Their potential as OER catalysts was elucidated in NaOH electrolyte with different amounts of Fe impurities; 1 ppb, 5 ppb and 102 ppb, as determined by Inductive Coupled Plasma (ICP) spectroscopy. The results indicate that the electrocatalytic activity of the materials depends on the ratio of Ni/Fe and the concentration of Fe impurities in the electrolyte. Most of the mixed catalysts show improved OER performances compared to the pure Ni and Fe oxide materials with respect to overpotential at 10 mA cm-2, Figure 1(a), Tafel slope values and Turnover Frequencies (TOF) numbers. Interestingly, the pure and mixed Ni/Fe materials in the NaOH electrolyte containing 5 ppb Fe impurities exhibited lower overpotentials at 10mA cm-2 compared to the same material in the NaOH containing 1 ppb and 100 ppb, Figure 1(a). This is thought to be due to the substitution of the Fe ions in the electrolyte for the Ni atoms in the material lattice, improving the OER performance.3

Pure and mixed manganese and ruthenium oxides were also examined in this work. The OER catalytic activity of pure manganese oxide compounds displaying overpotentials between 0.74 - 0.49 V at a current density of 10 mA cm-2. Furthermore, when combined with other compounds this overpotential value further decreases.4 However, mechanistic studies of the OER at thermally prepared DSA® type MnxOy electrodes in alkaline media have been sparse.2 Several of the mixed Mn/Ru electrode materials in this study were found to exhibit significantly improved OER activity and stability when compared with pure RuO2films, Figure 1(b), while lowering the cost of producing the catalyst.5 These Mn/Ru materials could therefore offer a competitive low-cost alternative to the already commercially available OER catalysts.
The composition, morphology and structure of all the aforementioned materials are thoroughly characterised by X-Ray Photoelectron Spectroscopy (XPS), Raman spectroscopy and Scanning Electron Microscopy–Energy Dispersive X-Ray (SEM-EDX). Finally, the Ni/Fe and Mn/Ru oxides will be a compared under cost and OER performance, to help identify the most economic and practical OER catalyst in this work.

Acknowledgements

We would like to thank Science Foundation Ireland (SFI) under the Grant Number SFI/10/IN.1/I2969.

References

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(2) Fernández, J. L.; Gennero De Chialvo, M. R.; Chialvo, A. C. J. Appl. Electrochem.
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(3) Klaus, S.; Louie, M. W.; Trotochaud, L.; Bell, A. T. The Journal of Physical Chemistry C
2015, 119, 18303-18316.
(4) Gao, M.-R.; Xu, Y.-F.; Jiang, J.; Zheng, Y.-R.; Yu, S.-H. J. Am. Chem. Soc.
2012, 134, 2930-2933.
(5) Browne, M. P.; Nolan, H.; Duesberg, G. S.; Colavita, P. E.; Lyons, M. E. G. ACS Catalysis 2016.

Figure 1