Iridium Oxide Nanorods Supported on Sb-Doped SnO2 As Highly Active Oxygen Evolution Catalysts for PEM Water Electrolysis
Authors: Shi Guoyu , Tano Tetsuro , Tryk Donald A. , Iiyama Akihiro , Uchida Makoto , Yamaguchi Miho , Kakinuma Katsuyoshi 
Published: February 2024

With the increasing installation of renewable energy generation systems such as solar and wind power, efficient energy storage devices are required to overcome the problem of fluctuations in the availability of electric energy. In particular, the splitting of water by electrolysis to produce storable hydrogen and oxygen appears to be one of the most promising approaches for large-scale energy storage. Proton exchange membrane water electrolysis (PEMWE) has received a great deal of attention due to its ability to respond quickly to renewable energy fluctuations and to operate at high current densities. However, a key limitation of PEMWE is the high cost associated with the use of high loadings of noble metal Ir catalysts at the anode electrode, which is necessary due to the slow kinetics of the oxygen evolution reaction (OER). Therefore, reducing the Ir loading at the OER electrode is essential to realize large-scale applications of PEMWE. This requires the development of highly active OER catalysts to accelerate the reaction or reduce the overpotential. Herein, we report a remarkably active OER catalyst of Ir oxide with nanorod-like structure supported on antimony-doped tin oxide (Sb-SnO2), showing an order of magnitude increase in Ir mass-specific activity than a commercial IrOx catalyst at 1.5 V vs. RHE. We also investigated the temperature dependence of the OER activity, as a way to elucidate the mechanism of enhanced catalysis, from both experimental and theoretical perspectives.
The Sb-SnO2 support material (Sb dopant content 4 at.%) with fused-aggregate network structure was prepared by flame pyrolysis method.1 The as-prepared support powder was annealed at 700 oC for 2 h in air using a rotary kiln furnace. Sb-SnO2 supported IrOx nanorods (NRs) catalyst was synthesized by a colloidal method.2 The obtained IrOx NRs/Sb-SnO2 powder was heat-treated at 350 °C in N2 atmosphere for 2 h and at 150 °C in 1% H2 (N2 balance) for 2 h. The Ir loading was determined to be 49.3 wt.% by inductively coupled plasma optical emission spectrometry (ICP-OES). The OER activity was evaluated in 0.1 M HClO4 at 25 to 80 oC using the rotating disk electrode (RDE) technique.2,3

From Figure 1a, it can be seen that the Sb-SnO2 support particles present an interconnected network structure, which is considered to be beneficial to enhance the electron conduction and gas diffusion in the electrocatalytic reaction. On the support, the majority of IrOx nanoparticles are shown to have coalesced, forming rodlike structures. Figure 1b shows OER polarization curves (iR-corrected and normalized to the Ir mass) of the IrOx NRs/Sb-SnO2 catalyst compared to commercial IrOx catalyst (TANAKA Precious Metals). It is clear that the IrOx NRs/Sb-SnO2 catalyst significantly outperforms the IrOx reference catalyst over the entire potential range, and the OER onset potential of the IrOx NRs/Sb-SnO2 catalyst is lower. At 1.5 V (Figure 1c), the IrOx NRs/Sb-SnO2 catalyst exhibits a mass activity (MA) of 0.40 A mg-1
Ir, which is about 10 times higher than that of the IrOx reference catalyst. This dramatically enhanced activity makes it possible to significantly reduce the Ir loading on the anode of PEMWE. Experimental observations and density functional theory (DFT) calculations suggest that the nanorod geometry and strong metal-support interactions may play an important role in lowering the energy barrier for the crucial first step of the OER, thereby enhancing the OER activity.

Acknowledgement

This work was partly supported by the JSPS KAKENHI (23H02059) and by the project from the New Energy and Industrial Technology Development Organization (NEDO) of Japan.

References

[1] Kakinuma, K.; Uchida, M.; Kamino, T.; Uchida, H.; Watanabe, M. Electrochim.
Acta
2011, 56, 2881-2887.
[2] Shi, G.; Tano, T.; Tryk, D. A.; Iiyama, A.; Uchida, M.; Kakinuma, K. ACS Catal.
2021, 11, 5222-5230.
[3] Shi, G.; Tano, T.; Tryk, D. A.; Yamaguchi, M.; Iiyama, A.; Uchida, M.; Iida, K.; Arata, C.; Watanabe, S.; Kakinuma, K. ACS Catal.
2022, 12, 14209-14219.

Figure 1