Operando X-Ray Absorption Spectroscopic Study of Pt-Based Nanowire Catalysts Under Oxygen Reduction Reaction

Polymer electrolyte fuel cells (PEFCs) are attracting attention as an environmentally friendly electrochemical device that uses hydrogen as a fuel. The application of PEFC has been limited by the consumption of platinum due to the sluggish kinetics of the cathode reaction and limiting platinum reserves. It has been noted that the interaction between the cathode catalyst and the oxygen intermediate species results in an overpotential in the ORR process. Therefore, it is very important to evaluate the interaction between the oxygen species and the catalyst based on the electronic structure. Pt nanowires are known to be highly active as ORR catalysts because they tend to expose more active planes for ORR, such as (111) planes1. Pt oxides formed on Pt nanowires with such 1D anisotropy are different from conventional nanoparticle catalysts in terms of structure and electronic structure2. However, this has not been fully clarified yet under oxygen reduction conditions. In this study, we analyzed the oxidation state of Pt nanowire catalysts in the ORR by operando analysis and analyzed the electronic and local structures. Synthesis of Pt nanowire catalyst : Oleylamine (5 mL) was used as a solvent and Pt(acac)2, Ni(acac)2, W(CO)6 and CTAC (hexadecyltrimethylammonium chloride) were added and sonicated for 1 hour. The product was dissolved and allowed to react in an oil bath at 160°C for 2 hours. The product particles were collected by centrifugation, and the washing and centrifugation were repeated three times with a mixture of cyclohexane: ethanol = 1:9. The nanowires were then loaded on Vulcan XC-72. ORR activity evaluation and XAS measurement: The rotating disk electrode (RDE) method was used for electrochemical measurements. A tripolar cell was used for the measurements. catalyst ink containing Pt nanowires was prepared and applied to a glassy carbon electrode for the RDE to prepare the electrode. A catalyst-coated electrode was used as the working electrode, a platinum mesh as the counter electrode, and a reversible hydrogen electrode (RHE) as the reference electrode. The electrolyte was 0.1 M HClO4. The cell temperature was controlled at 25 oC. XAS measurements were performed using a home-made measuring cell and the same electrochemical measurement conditions as for the RDE. The morphology and structure of the prepared Pt nanowires were observed by electron microscopy. As shown in Figure 1, the nanowires were uniformly distributed on the carbon and no significant aggregation was observed. The average diameter of the nanowires was 2.0 nm.To analyze the local structure of the Pt nanowire catalyst, the Pt-Pt bond length was estimated from EXAFS. Figure 2 shows the fitting results of the Pt-Pt bond lengths of Pt nanowire and Pt nanoparticle (TEC10V30E, TKK) catalysts in the range 0.5-1.1 V vs. RHE. With increasing potential, the Pt-Pt bond lengths of both catalysts gradually increased, but the Pt nanowire catalyst maintained a short Pt-Pt bond, and this nanowire characteristic structure may be the reason for its higher ORR activity than the nanoparticle. Acknowledgements: This work was supported by the project (JPNP20003) and a NEDO FC-Platform project commissioned by the New Energy and Industrial Technology Development Organization (NEDO). References [1] Kim J. M. et al., Science Advances 2021, 7, (30), e1601705. [2] Zhaoyu Y. et al., Nano Letters 2021 21 (21), 9354-9360. Figure 1