Multi-Modal Structure and Distribution Analysis of Functional Groups on Carbon Supports for Polymer-Electrolyte Fuel Cells

Abstract

Although structures of the functional groups formed on the surface of the carbon supports and their distribution on/inside supports have crucial impacts on determining performance of the catalyst electrodes, understanding of the relationship between them remains unclear, because of limitation of experimental methods for quantitative analysis of them with high spatial resolution. It is well-known that functional groups of the catalyst supports affect chemical properties of the supports, such as, redox- and acid-base properties, hydrophobicity, and electronic interaction. Thus, they should have a great influence on various aspects those related to the performance of polymer electrolyte fuel cell (PEFC), such as the activity, mass transportability, and durability of the catalysts and catalyst layers, and manufacturing process of catalysts and catalyst layer. 1,2). Furthermore, recently, in addition to various conventional high-surface area carbon supports, such as, Vulcan and Ketjen black, accessible carbon supports with mesopores which can host Pt particles protects them from direct ionomer adsorption and allow proton and O2 to have reasonable access to Pt particles, have been attracting great attention for improving catalyst utilization, activity, mass transportability, and suppression of Pt dissolution 3-5). The relationship between structure variation of functional groups on various supports and electrode performances should be of interest. The major difficulty for analyzing the functional groups on carbon supports come from the structure complexity of carbon surface (as well as inner part of the carbon particles), inhomogeneous distribution of various functional groups produced in various chemical processes, and multi-component structure of catalyst electrodes with catalysts and ionomers. Against such background, in this study, we have developed a new experimental approach utilizing multi-modal analysis method with x-ray photoelectron spectroscopy (XPS), x-ray absorption spectroscopy (XAS), temperature-programmed-desorption mass spectroscopy (TPD-MS), vibrational spectroscopy, electron tomography (3D-TEM), and cryo transmission electron microscopy (cryo-TEM). By combining suitable experimental probes for each structural feature and each component in multi-component structures, and by analyzing in integrated manner, we are able to understand the complex structure of functional groups on and inside carbon supports. Here, we demonstrate an example of the analysis for Vulcan (VULCAN® XC72, Cabot Corporation) and Pt-supported Vulcan (TEC10V30E, Tanaka Kikinnzoku Kogyo K. K. ). Vulcan is a solid carbon support used for polymer electrolyte fuel cell catalysts. The sample was reduced for about 30 minutes in a 100% hydrogen atmosphere at room temperature. Hard x-ray photoelectron spectroscopy (HAXPES) using synchrotron radiation x-rays with x-ray energy of 8 keV (BL46XU at SPring-8) . Also soft X-ray XAS were performed on BL1N2 at Aichi SR . Figure 1 shows the C1s HAXPES spectrum and the C K-edge XANES spectrum acquired by total electron yield (TEY) method. HAXPES was normalized by the signal intensity of the C-C substrate components (sp2, sp3) of the support at 284.5 eV 6), whereas the C K-edge XANES is normalized by the signal intensity of the 2pz (π*) orbital extending perpendicular to the carbon hexagonal network plane of the C–C substrate component of the support at 285.2 eV 7, 8). The functional groups are clearly observed in both spectra and the signal intensity of the functional group of the Pt catalyst increased with respect to the support alone, indicating that the amount of functional group on the support increased due to the Pt loading process. By combining other experimental results and theoretical simulations, the relationship between structure properties and electrode performance can be discussed. Acknowledgement This work was conducted in FC-Platform project supported by the New Energy and Industrial Technology Development Organization (NEDO). References :1) E. Antolini, Applied Catalysis B: Environmental 88, 1 (2009)2) Y.-J. Wang, N. Zhao, B. Fang, H. Li, X. T. Bi, and H. Wang, Chem Rev 115, 3433 (2015)3)V. Yarlagadda, M. K. Carpenter, T. E. Moylan, R. S. Kukreja, R. Koestner, W. Gu, L. Thompson, and A. Kongkanand, ACS Energy Letters 3, 618 (2018)4)S. Ott, A. Orfanidi, H. Schmies, B. Anke, H. N. Nong, J. Hübner, U. Gernert, M. Gliech, M. Lerch and P. Strasser , Nature Mater., 19, 77 (2020)5)A. Kobayash, T. Fujii, C. Harada, E. Yasumoto, K. Takeda, K. Kakinuma, and M. Uchida, Acs Appl. Energy Mater. 4 2307 (2021)6) S. Kundu, Y. Wang, W. Xia, and M. Muhler, J. Phys. Chem. C, 112, 16869 (2008)7) Y. Murakami, Y. Ota, and T. Okada, Anal. Sci., 39, 67 (2023)8) C. L. Guillou, S. Bernard. F. de la Pena, and Y. L. Brech, Anal. Chem., 90, 8379 (2018) Figure 1