Synthesis and Evaluation of Novel Iridium Ruthenium Oxide Catalysts Supported on Reduced Graphene Oxide for Oxygen Evolution Reaction
Authors: Hara Masanori , Joshi Prerna , Huang Hsin-Hui , Yoshimura Masamichi 
Published: February 2020

Recently, environmental issues such as global warming and depletion of fossil fuels have become important topic, and progress toward sustainable societies with renewable energies such as solar and wind energy is a critical issue to overcome the social problems. Conversion of surplus energies to hydrogen via water electrolysis has attracted attention as energy storage method to utilize renewable energies effectively. However, activity, durability, and cost of catalysts are insufficient for practical application in water electrolysis systems due to high over-potential and low kinetics of electrode reactions, especially, oxygen evolution reaction (OER) on the anode [1-2] for polymer electrolyte water electrolyzer (PEWE). Iridium oxide (IrO2) particles have been used as anode catalysts, because of its high activity and durability for OER. However, decreasing iridium loading amount is required to reduce catalyst cost. In a previous study, we have successfully synthesized novel IrO2 nanoparticle catalyst supported on carbon nanotubes with large surface area of IrO2 catalyst to improved OER activity [3]. For further improvement of OER activity, increasing the specific activity of the catalyst for OER is required. One of the approaches to improve catalytic activity is formation of alloy of iridium with other metals with high activity, such as ruthenium.
In the present study, we have synthesized novel alloy nanoparticle catalysts, IrRuOx, supported on the reduced graphene oxide (rGO), as active catalysts for OER. The IrRuOx / rGO catalyst was characterized and evaluated in catalytic activity for OER in sulfuric acid solution.
The IrRuOx / rGO catalyst was synthesized by hydrothermal method. Briefly, required amount of metal complexes, H2IrCl6 and RuCl3, and graphene oxide (GO) prepared by modified Hummers’ method were dispersed in ethanol/water mixture and the mixture was heated at 80˚C for 6 h. Then, the mixture was heated at 150˚C in hydrothermal autoclave for 4 h to form IrRuOx nanoparticles. The IrRuOx / rGO catalysts were characterized by transmission electron microscopy (TEM), energy dispersed X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electrochemical methods. The OER activity of the IrRuOx / rGO was examined in 0.5 M H2SO4 solution by linear sweep voltammetry (LSV) using a rotating disk electrode (RDE) system.
A TEM image of the Ir0.7Ru0.3Ox / rGO catalyst is shown in Figure 1. The Ir0.7Ru0.3Ox nanoparticles with wide particle size distribution were dispersed on the surface of rGO substrate. An average size of the nanoparticles was 1.9 ± 0.8 nm. The loading amount of the Ir0.7Ru0.3Ox catalyst is estimated to be approximately 23.9 wt% by EDX measurements. In addition, the EDX analysis reveals that the ratio of Ir to Ru of the IrRuOx nanoparticles is proportional to the ratio of starting materials, H2IrCl6 and RuCl3.
The XRD patterns of the IrRuOx / rGO catalysts with different Ir/Ru ratio are shown in Figure 2. The XRD data shows the (200) peak of IrRuOx is shifted to small angle and became broader with increasing Ir ratio of the catalysts. Furthermore, the XPS results of the IrRuOx / rGO catalysts showed binding energy of Ir 4f peak was shifted to a lower energy state with increasing the ratio of Ru. The XRD and XPS data suggest that nanoparticles of the catalyst form alloy of RuO2 and IrO2. In addition, the shift of the binding energy of Ir 4f peak reflects the modification of the electronic state of Ir, which affects the catalytic activity for OER, by alloy formation with Ru atom.
Figure 3 shows linear sweep voltammogram of the IrRuOx / rGO catalyst obtained in 0.5 M H2SO4 solution. Electrochemical measurement reveals activity of the IrRuOx / rGO catalyst for OER is higher than that of the IrO2 / rGO catalyst, especially, onset potential of the reaction is 68 mV lower than that on the IrO2 / rGO catalyst. High activity of the IrRuOx / rGO catalyst indicates that alloying IrO2 with RuO2 improves the catalytic activity for OER. In summary, we successfully prepared the alloy catalysts of IrO2 and RuO2 supported on rGO substrate, and the IrRuOx / rGO catalysts can be a promising candidate as anode for water electrolysis.

Acknowledgements

This work was supported by JSPS KAKENHI Grant number 17K05969.

References
[1] M. Carmo, D. L. Fritz, J. Mergel, D. Stolten, Int. J. Hydrogen Energy 38 (2013) 4901.
[2] J. Cheng, H. Zhang, H. Ma, H. Zhong, Y. Zou, Electrochim. Acta 55 (2010) 1855.
[3] R. Badam, M. Hara, H.-H. Huang, M. Yoshimura, Int. J. Hydrogen. Energy, 43 (2018) 18095.

Figure 1