Enhanced Methanol Fuel Cell Performance Using Copper-doped Carbon-supported Platinum Catalysts

doi:10.1007/s40242-025-4260-4

Abstract

Abstract: Platinum is a crucial anode catalyst in methanol oxidation reactions (MOR) due to its exceptional electrochemical performance, which has led to its widespread application. However, to enhance its catalytic activity and stability, platinum is typically supported on carrier materials, such as carbon-based substrates. Current commercial platinum-carbon catalysts exhibit limited activity, low utilization efficiency of metallic platinum, and a tendency to bind with intermediate species, leading to a decline in catalytic performance. To address these challenges, this study proposes the utilization of copper-doped carbon for the development of a composite support (Cu₂C₇). Compared with the pure carbon supported platinum catalyst (Pt@Cu₀C₇), the electrochemical activity of Cu₂C₇ supported platinum catalyst (Pt@Cu₂C₇) was significantly enhanced, as evidenced by a current density of 412 mA/cm² and an onset potential of -0.8 V. In chronoamperometry experiments, after 2 h of electrochemical testing, the activity of Pt@Cu₂C₇ decreased by only 4.24%, whereas Pt@Cu₀C₇ experienced a significant reduction of 55% in activity. The incorporation of copper is hypothesized to provide additional active sites for the deposition of metallic platinum on the carrier, thereby enhancing the platinum loading capacity. According to inductively coupled plasma (ICP) analysis, when the copper-to-carbon ratio is 2:7, the platinum loading amount increases by 25.78%. Furthermore, some platinum forms an alloy with the copper embedded in the carbon, a phenomenon corroborated by X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. The literature suggests that the formation of such alloys can significantly improve the catalyst's resistance to poisoning. The incorporation of copper not only enhances the platinum loading capacity but may also induce a synergistic effect among the active platinum components, thereby further improving catalytic performance. In summary, the findings of this study offer critical theoretical insights and practical guidelines for the design of high-performance MOR electrocatalysts, laying a robust foundation for future advancements in catalyst development.

Key words: Fuel cell, Carbon material, Doped metal, Pt-Cu alloy, Methanol oxidation

WANG Haozhe, BAI Xueli, LI Jiamei, LI Hao, ZHANG Xiaoping, WANG Feng. Enhanced Methanol Fuel Cell Performance Using Copper-doped Carbon-supported Platinum Catalysts[J]. Chemical Research in Chinese Universities, 2025, 41(3): 573-582.

References

[1] de Sá M. H., Moreira C. S., Pinto A. M. F. R., Oliveira V. B., Energies, 2022, 15, 17.
[2] Mansor M., Timmiati S. N., Lim K. L.,Wong W. Y., Kamarudin S. K., Kamarudin N. H. N., International Journal of Hydrogen Energy, 2019, 44, 14744.
[3] Chen F., Sun Y. X., Li H. Y., Li C. J., Energy Technology, 2022, 10, 6.
[4] Zhu H., Luo M. C., Wang F. H., Wang Z. M., Han K. F., Abstracts of Papers of the American Chemical Society, 2014, 247, 146.
[5] Duan S. B., Du Z., Fan H. S., Wang R. M., Nanomaterials, 2018, 8, 11.
[6] Wu Z. P., Hopkinz E., Park K., Yan S., Wang J., Wen J. G., Luo J., Wang L. C., Zhong C. J., Abstracts of Papers of the American Chemical Society, 2018, 256.
[7] Joglekar M., Gray T. S., Gunnoe T. B., Trewyn B. G., Abstracts of Papers of the American Chemical Society, 2014, 247, 909.
[8] Shi X. Y., Chen S. S., Chempluschem, 2023, 88, 5.
[9] Han F., Lu A. H., Li W. C., Progress in Chemistry, 2012, 24, 2443.
[10] Zhu Y. Y., Wang Y. H., Wang Y. T., Xu T. J., Chang P., Carbon Energy, 2022, 4, 1182.
[11] Tolbin A. Y., Spitsyn B. V., Serdan A. A., Averin A. A., Malakho A. P., Kepman A. V., Sorokina N. E., Avdeev V. V., Inorganic Materials, 2013, 49.
[12] Fan Q. Y., Zhao Y. B., Yu X. H., Song Y. X., Zhang W., Yun S. N., Diamond and Related Materials, 2020, 106.
[13] Wang H. L., Gao Q. M., Chem. J. Chinese Universities, 2011, 32, 462.
[14] Borchardt L., Oschatz M., Kaskel S., Materials Horizons, 2014, 1, 157.
[15] Li D. G., Gong Y. L., Li G., Lyu X., Dai Z. Q., Wang Q., New Journal of Chemistry, 2021, 45, 13088.
[16] Shih K. Y., Wei J. J., Tsai M. C., Nanomaterials, 2021, 11, 9.
[17] Chen Y. J., Ji S. F., Chen C., Peng Q., Wang D. S., Li Y. D., Joule, 2018, 2, 1242.
[18] Chang Y. N., Yang J. Y., Zhang M., Yue M., Wang W., Li J. W., Wang J. D., Song K. F., Liu Y., Zuo Y. X., Xing R., Journal of Alloys and Compounds, 2024, 1005.
[19] Liang C. X., Wang M., Liu W., Liu H. Y., Huang D. W., Zhang Y. Z., Zhang K. H., Jiang L. S., Jia Y. Y., Niu C. G., Chemical Engineering Journal, 2023, 466.
[20] Chen W. M., Luo M., Yang K., Zhang D. T., Zhou X. Y., Journal of Cleaner Production, 2021, 282.
[21] Guy F., Runtti H., Duclaux L., Ondarts M., Reinert L., Outin J., Gonze E., Bonnamy S., Soneda Y., Microporous and Mesoporous Materials, 2021, 322.
[22] Joseph S. R., Sebastian L., Mythili U., Biomass Conversion and Biorefinery, 2023, 10, 1007.
[23] Palomero-Gallagher N., Bidmon H. J., Cremer M., Schleicher A., Kircheis G., Reifenberger G., Kostopoulos G., Häussinger D., Zilles K., Cellular Physiology and Biochemistry, 2009, 24, 291.
[24] Pavlets A. S., Alekseenko A. A., Nikolskiy A. V., Kozakov A. T., Safronenko O. I., Pankov I. V., Guterman V. E., International Journal of Hydrogen Energy, 2022, 47, 30460.
[25] Lin R. H., Fang L., Li X. P., Zhang S. F., Polymer-Plastics Technology and Engineering, 2006, 45, 1243.
[26] Ren Q. G., Xue Y. H., Cui Z. J., Lu Y. H., Li W. M., Zhang W. J., Ye T., Diamond and Related Materials, 2022, 125, 25.
[27] Wei J. J., Ge L., Wang W. L., Hong P. D., Li Y. L., Li Y. H., Xie C., Wu Z. J., He J. Y., Kong L. T., Journal of Environmental Chemical Engineering, 2024, 12, 2.
[28] Shimbori YY., Shiroishi H., Ono R., Kosaka S., Saito M., Yoshida T., Katagiri H., Miyazawa K., Tanaka Y., Materials Science and Engineering B: Advanced Functional Solid-State Materials, 2018, 228, 190.
[29] Zhou P., Erning J. W., Ogle K., Electrochimica Acta, 2019, 293, 290.
[30] Wei Z., Zhao H. X., Niu Y. B., Zhang S. Y., Wu Y. B., Yan H. J., Xin S., Yin Y. X., GuoY. G., Materials Chemistry Frontiers, 2021, 5, 3911.
[31] Yi L. H., Liu L., Liu X., Wang X. Y., Yi W., He P. Y., Wang X. Y., International Journal of Hydrogen Energy, 2012, 37, 12650.
[32] Belenov S. V., Guterman V. E., Tabachkova N. Y., Moguchikh E. A., Alekseenko A. A., Russian Journal of Electrochemistry, 2018, 54, 1209.
[33] Liu D., Cui W., Yao M. G., Li Q. J., Cui T., Liu B. B., Liu D. P., Sundqvist B., Optical Materials, 2013, 36, 449.
[34] Yoshio M., Nakamura H., Wang H. Y., Electrochemical and Solid State Letters, 2006, 9, 12.
[35] Sankar S., Ahmed A. T. A., Inamdar A. I., Im H., Im Y. Bin, Lee Y., Kim D. Y., Lee S., Materials & Design, 2019, 169, 107688.
[36] Wu MM. X., Wu X., Zhang L., Abdelhafiz A., Chang I., Qu C., Jiang Y. C., Zeng J. H., Alamgir F., Electrochimica Acta, 2019, 306, 167.
[37] Tate G. L., Mehrabadi B. A. T., Xiong W., Kenvin A., Monnier J. R., Nanomaterials, 2021, 11, 793.
[38] Mintsouli I., Georgieva J., Armyanov S., Valova E., Avdeev G., Hubin A., Steenhaut O., Dille J., Tsiplakides D., Balomenou S., Sotiropoulos S., Applied Catalysis B: Environmental, 2013, 136, 160.
[39] Biesinger M. C., Surface and Interface Analysis, 2017, 49, 1325.
[40] Wang C., Kuai L., Cao W., Singh H., Zakharov A., Niu Y. R., Sun H. X., Geng B. Y., Chemical Engineering Journal, 2021, 426.
[41] Douk A. S., Saravani H., American Chemical Society, 2023, 8, 45245.
[42] Oezaslan M., Hasche F., Strasser P., Journal of The Electrochemical Society, 2012, 159, 4.
[43] Shen S., Xu S., Zhao S., ACS Sustainable Chemistry and Engineering, 2022, 10, 2.
[44] You H., Zhang F., Liu Z., ACS Catalysis, 2014, 4, 9.
[45] Moulijn J. A., Van Diepen A. E., Kapteijn F., Applied Catalysis A: General, 2001, 212, 1.
[46] Nassr A. B. A. A., Sinev I., Grünert W., Applied Catalysis B: Environmental, 2013, 142, 849.