Effect of ZrO2 Additive for IrO2-Ta2O5/Ti on Activity of Oer in Sulfuric Acid with Toluene Contamination
Authors: Nagai Kohei , Matsumae Kenji , Kohno Yuji , Matsuzawa Koichi , Kato Akihiro , Awaludin Zaenal , Nishiki Yoshinori , Mitsushima Shigenori 
Published: February 2020

Introduction
In order to promote the introduction of renewable energy, large-scale energy storage and transportation systems are required. Hydrogen is expected to apply for the energy storage and transportation. Organic chemical hydride materials are prospective energy carriers to solve the issue of hydrogen’s low volumetric energy density. Among them, toluene (TL)/methylcyclohexane (MCH) system has been focused due to the easy handling and the low toxicity. Recently, researches of one-step electrolytic hydrogenation of TL have just been started[1].
DSA® type anodes composed of IrO2-based electrocatalyst coated on Ti which have excellent activity and extremely high durability for oxygen evolution reaction (OER)[2] is required as a counter electrode of electrolytic process. It is well known that some organic additive lead serious degradation of the anodes[3]. IrO2-Ta2O5/Ti would be a good candidate, because the overpotential of IrO2-Ta2O5/Ti in sulfuric acid with organic compound contamination is lower than that of IrO2/Ti [3]. However, the OER activity of IrO2-Ta2O5/Ti would not still be enough and the effect of TL and MCH on the activity and durability have not been clarified.
In this study, activity of IrO2-Ta2O5 based Ti electrodes whose Ta is replaced by Zr was investigated in sulfuric acid with TL contamination.
Experimental
The precursor of the electrocatalyst was n-butanol solution of H2IrCl6・6H2O, Ta(C4H9O)5 and Zr(C4H9O)4 with nominal composition of Ir: Ta: Zr= 50: (50-X): X (0 ≦X < 50) in mole fraction. A pretreated Ti plate was dipped in the precursor, and dried at 100 oC for 10 min. Then it was thermally decomposed at 500 oC for 10 min. The process of the dipping, drying, and decomposition were repeated several times to get around 10 g m-2 of IrO2 loading. Finally, it was baked at 500 oC for 1h. The loading was evaluated by a X-ray fluorescent analysis.
Polarization of the OER was evaluated with 5 mV s-1 of potential sweep between 1.2 and 2.0 V vs. RHE in 1 M H2SO4 with and without saturated TL at 60oC. A counter electrode and a reference electrode were platinum wire and reversible hydrogen electrode, respectively. Resistance of the electrolyte and double layer capacitance was evaluated with AC impedance method.
Results and discussion
Double layer capacitance (C
dl) of IrO2/Ti, Ir50Ta50-Oxide/Ti and Ir50Ta20Zr30-Oxide/Ti anodes in 1 M H2SO4 at 60 oC were 2.1, 25, and 75 mF cm-2, respectively. The C
dl of the Ir50Ta20Zr30-Oxide/Ti was three times larger than that of Ir50Ta50-Oxide/Ti which was ten times larger than the IrO2/Ti. The C
dl corresponds to the real surface area for precious metal oxide coated electrode [4]. Therefore, Ta and Zr additives increase the real surface area of the IrO2 based coating, and the ternary system would increase real surface area compared to the binary system.
The polarization curves for OER current density on IrO2/Ti, Ir50Ta50-Oxide/Ti and Ir50Ta20Zr30-Oxide/Ti in 1 M H2SO4 with and without saturated TL were shown in Fig. 1. The current densities in Tafel region were 0.9, 13, and 115 mA cm-2 at 1.55 V vs. RHE in 1 M H2SO4 at 60 oC for IrO2/Ti, Ir50Ta50-Oxide/Ti and Ir50Ta20Zr30-Oxide/Ti, respectively. The large potential reduction more than 100mV at 100 mA cm-2 was obtained with Ir50Ta20Zr30-Oxide/Ti compared to the others, reflecting their C
dl values. While the current density of IrO2/Ti decreased by 43% with TL contamination, the others decreased by 10% or less with TL contamination.
The current densities based on C
dl on Ir50Ta(50-X)Zr
X
-Oxide/Ti at 1.55 V vs. RHE in 1 M H2SO4 with and without saturated TL were shown in Fig. 2. They increased with Zr content, and the decrement of current density by TL contamination was kept constant in spite of change in Zr content.
TL would decrease the current density of OER with the adsorption onto IrO2. However, the addition of Ta might prevent the adsorption of TL onto IrO2 due to the catalytic contribution on Ir and the addition of Zr might mainly increase the real surface area without changing the Ta effect.
Acknowledgments
This work was supported by Council for Science, Technology and Innovation (CSTI), Cross-ministerial Strategic Innovation Promotion Program (SIP), “energy carrier” (Funding agency: JST). We applicate the person concerned them.
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Figure 1