Effect of the morphology and composition of trimetallic PtCuAu/C catalysts on the activity and stability of the methanol oxidation reaction

Vldislav S. Menshikov; Sergey V. Belenov; Aleksey Y. Nikulin

doi:10.17308/kcmf.2022.24/9057

Vldislav S. Menshikov Southern Federal University, 105/42 Bolshaya Sadovaya str., Rostov-on-Don 344006, Russian Federation https://orcid.org/0000-0002-0531-2156
Sergey V. Belenov Southern Federal University, 105/42 Bolshaya Sadovaya str., Rostov-on-Don 344006, Russian Federation https://orcid.org/0000-0003-2980-7089
Aleksey Y. Nikulin Southern Federal University, 105/42 Bolshaya Sadovaya str., Rostov-on-Don 344006, Russian Federation

DOI: https://doi.org/10.17308/kcmf.2022.24/9057

Keywords: methanol fuel cells, catalysis, trimetallic catalysts, galvanic replacement

Abstract

A study on the influence of the method for obtaining trimetallic PtCuAu/C catalysts on their activity in the oxidation of methanol has been carried out.
The structural characteristics of the obtained trimetallic catalysts have been studied by X-ray diffraction and transmission electron microscopy. The nanoparticles of the material obtained by the galvanic synthesis method had a size twice as large (~ 6 nm) than the nanoparticles of the material obtained by the co-deposition of metal precursors. According to the results from the accelerated stress testing of catalysts, it was found that the material obtained by the galvanic method of substitution of copper atoms with gold had a higher residual activity in the oxidation of methanol than the commercial Pt/C analogue.
This study shows the potential of obtaining and using multicomponent platinum-containing nanoparticles deposited on a carbon carrier as effective catalysts for use in methanol fuel cells.

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Author Biographies

Vldislav S. Menshikov, Southern Federal University, 105/42 Bolshaya Sadovaya str., Rostov-on-Don 344006, Russian Federation

PhD student, Researcher at
the Department of Electrochemistry, Southern Federal
University (Rostov-on-Don, Russian Federation).

Sergey V. Belenov, Southern Federal University, 105/42 Bolshaya Sadovaya str., Rostov-on-Don 344006, Russian Federation

PhD in Chemistry, Research
Fellow at the Department of Electrochemistry,
Southern Federal University (Rostov-on-Don, Russian
Federation).

Aleksey Y. Nikulin, Southern Federal University, 105/42 Bolshaya Sadovaya str., Rostov-on-Don 344006, Russian Federation

Researcher at the Department
of Electrochemistry, Southern Federal University
(Rostov-on-Don, Russian Federation;).

References

Alias M. S., Kamarudin S. K., Zainoodin A. M., Masdar M. S. Active direct methanol fuel cell: An overview. International Journal of Hydrogen Energy. 2020;45(38): 19620–19641. https://doi.org/10.1016/j.ijhydene.2020.04.202

Gwak G., Kim D., Lee S. Ju H. Luo Y., Zhao J. Studies of the methanol crossover and cell performance behaviors of high temperature-direct methanol fuel cells (HT-DMFCs). International Journal of Hydrogen Energy. 2018;43(30): 13999–14011. https://doi.org/10.1016/j.ijhydene.2017.11.029

Hamnett A. Mechanism and electrocatalysis in the direct methanol fuel cell. Catalysis Today. 1997;38(4): 445–457. https://doi.org/10.1016/S0920-5861(97)00054-0

Wu M., Wu X., Zhang L., Abdelhafiz A., Chang I., Qu C., Jiang Y., Zeng J., Alamgir F. Cu@Pt catalysts prepared by galvanic replacement of polyhedral copper nanoparticles for polymer electrolyte membrane fuel cells. Electrochimica Acta. 2019;306: 167–174. https://doi.org/10.1016/j.electacta.2019.03.111

Qian J., Wei W., Huang X., Tao Y., Chen K., Tang X. A study of different polyphosphazene-coated carbon nanotubes as a Pt–Co catalyst support for methanol oxidation fuel cell. Journal of Power Sources. 2012;210: 345–349. https://doi.org/10.1016/j.jpowsour.2012.03.012

Fang B., Liu Z., Bao Y., Feng L. Unstable Ni leaching in MOF-derived PtNi-C catalyst with improved performance for alcohols fuel electrooxidation. Chinese Chemical Letters. 2020;31(9): 2259–2262. https://doi.org/10.1016/j.cclet.2020.02.045

Mansor M., Timmiati S, Lim K, Wong W, Kamarudin S. K., Kamarudin N. H. N. Recent progress of anode catalysts and their support materials for methanol electrooxidation reaction. International Journal of Hydrogen Energy. 2019;44: 14744-69. https://doi.org/10.1016/j.ijhydene.2019.04.100

An X.-S., Fan Y.-J., Chen D.-J., Wang Q., Zhou Z.‑Y., Sun S.-G. Enhanced activity of rare earth doped PtRu/C catalysts for methanol electrooxidation. Electrochimica Acta. 2011;56(24): 8912–8918. https://doi.org/10.1016/j.electacta.2011.07.106

Sulaiman J, Zhu S, Xing Z, Chang Q, Shao M. Pt-Ni octahedra as electrocatalysts for ethanol electrooxidation reaction. ACS Catalysis. 2017;7: 5134–5141. https://pubs.acs.org/doi/10.1021/acscatal.7b01435

Page T, Johnson R, Hormes J, Noding S, Rambabu B. A study of methanol electro-oxidation reactions in carbon membrane electrodes and structural properties of Pt alloy electrocatalysts by EXAFS. Journal of Electroanalytical Chemistry. 2000;485: 34–41. https://doi.org/10.1016/S0022-0728(00)00090-5

Baronia R, Goel J, Tiwari S, Singh P. Efficient electro-oxidation of methanol using PtCo nanocatalysts supported reduced graphene oxide matrix as anode for DMFC. International Journal of Hydrogen Energy. 2017;42:10238–10247. https://doi.org/10.1016/j.ijhydene.2017.03.011

Markovic N, Gasteiger H, Ross P, Jiang X, Villegas I., Weaver M.J. Electro-oxidation mechanisms of methanol and formic acid on Pt–Ru alloy surfaces. Electrochimica Acta. 1995;40: 91-8.

https://doi.org/10.1016/0013-4686(94)00241-R

Wang X., Zhang L., Wang F., Yu J., Zhu H. Nickel-introduced structurally ordered PtCuNi/C as high performance electrocatalyst for oxygen reduction reaction. Progress in Natural Science: Materials International. 2020;30(6): 905–911. https://doi.org/10.1016/j.pnsc.2020.10.017

Wang X., Zhang L., Gong H., Zhu Y., Zhao H., Fu Y. Dealloyed PtAuCu electrocatalyst to improve the activity and stability towards both oxygen reduction and methanol oxidation reactions. Electrochimica Acta. 2016;212: 277–285. https://doi.org/10.1016/j.electacta.2016.07.028

Sarkar A., Murugan A. V., Manthiram A. Rapid microwave-assisted solvothermal synthesis of methanol tolerant Pt-Pd-Co nanoalloy electrocatalysts. Fuel Cells. 2010;10(3): 375–383. https://doi.org/10.1002/fuce.200900139

Srivastava R., Mani P., Hanh N., Strasser P. Efficient oxygen reduction fuel cell electrocatalysis on voltammetrically dealloyed Pt-Cu-Co nanoparticles. Angewandte Chemie - International Edition. 2007;46(47): 8988–8991. https://doi.org/10.1002/anie.200703331

Khatib F. N., Wilberforce T., Ijaodola O., Ogungbemi E., El-Hassan Z., Durrant A., Thompson J., Olabi A.G., Material degradation of components in polymer electrolyte membrane (PEM) electrolytic cell and mitigation mechanisms: Renewable and Sustainable Energy Reviews. 2019;111: 1–14. https://doi.org/10.1016/j.rser.2019.05.007

Belenov S. V., Men’shchikov V. S., Nikulin A. Y., Novikovskii N. M. PtCu/C materials doped with different amounts of gold as the catalysts of oxygen electroreduction and methanol electrooxidation. Russian Journal of Electrochemistry. 2020;56(8): 660–668. https://doi.org/10.1134/S1023193520080029

Belenov S. V., Menschikov V. S., Nevelskaya A. K., Rezvan D. V. Influence of PtCuAu’s nanoparticle structure on its activity in methanol oxidation reaction. Nanotechnol Russia. 2019;14(11-12): 557– 564. https://doi.org/10.1134/S1995078019060028

Alekseenko A. A., Guterman V. E., Volochaev V. A., Belenov, S. V. Effect of wet synthesis conditions on the microstructure and active surface area of Pt/C catalysts. Russ. J. Inorganic Materials. 2015;51(12): 1258–1263. http://dx.doi.org/10.1134/S0020168515120018

Guterman V. E., Belenov S. V., Pakharev A. Yu., Min M., Tabachkova N. Yu., Mikheykina E. B., Vysochina L. L., Lastovina T. A. Pt-M/C (M = Cu, Ag) electrocatalysts with an inhomogeneous distribution of metals in the nanoparticles. International Journal of Hydrogen Energy. 2016;41(3): 1609–1626. https://doi.org/10.1016/j.ijhydene.2015.11.002

Brugeman S. A., Zekhtor M. Yu., Novikovskiy N. M. Universal Roentgen Spectra (UniveRS). Certificate of state registration of the computer program no. 2010615318 (Russia). 2010.

Langford J. I., Wilson A. J. C. Scherrer after Sixty Years: A Survey and Some New Results in the Determination of Crystallite Size. Journal of Applied Crystallography. 1978;11: 102–103. https://doi.org/10.1107/S0021889878012844

Guterman, V. E., Belenov, S. V., Lastovina, T. A., Fokina, E. P., Prutsakova, N. V., Konstantinova, Y. B. Microstructure and electrochemically active surface area of PtM/C electrocatalysts. Russian Journal of Electrochemistry. 2011;47(8) 997–1004. https://doi.org/10.1134/S1023193511080052

Groger O., Gasteiger H. A., Suchsland J. P. Review—Electromobility: Batteries or Fuel Cells? Journal of The Electrochemical Society. 2015;162(14): 2605–2623. http://dx.doi.org/10.1149/2.0211514jes

Garsany Y., Ge J., St-Pierre J., Rocheleau R., Swider-Lyons K. Analytical procedure for accurate comparison of rotating disk electrode results for the oxygen reduction activity of Pt/C. Journal of The Electrochemical Society. 2014;161(5): 628–640. http://dx.doi.org/10.1149/2.036405jes

Banham D., Ye S. Current status and future development of catalyst materials and catalyst layers for proton exchange membrane fuel cells: An industrial perspective. ACS Energy Letters. 2017;2(3): 629–638. https://doi.org/10.1021/acsenergylett.6b00644

Zhang C., Zhang Y., Xiao H., Zhang J., Li L., Wang L., Bai Q., Liu M., Wang Z, Sui N. Superior catalytic

performance and CO tolerance of PtCu/graphdiyne electrocatalyst toward methanol oxidation reaction. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2021;612: 125960. https://doi.org/10.1016/j.colsurfa.2020.125960

Menshikov V. S. , Novomlincky I. N. ,Belenov S. V., Alekseenko A. A., Safronenko O. I., Guterman V. E. ethanol, ethanol, and formic acid oxidation on new platinum-containing catalysts. Catalysts. 2021;11(2): 158–176. https://doi.org/10.3390/catal11020158

Guo J. W., Zhao T. S., Prabhuram J., Chen R., Wong C. W. Preparation and characterization of a PtRu/C canocatalysts for direct methanol fuel cell. Electrochimica Acta. 2005;51(4): 754–763. https://doi.org/10.1016/j.electacta.2005.05.056

Shao Y., Yin G., Gao Y. Understanding and approaches for the durability issues of Pt-based catalysts for PEM fuel cell. Journal of Power Sources. 2007;171(2): 558–566. https://doi.org/10.1016/j.jpowsour.2007.07.004

Pryadchenko V. V., Srabionyan V. V., Kurzin A. A., Bulat N. V., Shemet D. B., Avakyan L. A., Belenov S. V., Volochaev V. A., Zizak I., Guterman V. E., Bugaev L. A. Bimetallic Pt Cunan oparticlesin Pt Cu/Celectrocatalysts: structural and electrochemical characterization. Applied Catalysis A: General. 2016;525: 226–236. https://doi.org/10.1016/j.apcata.2016.08.008

Guterman V. E., Belenov S. V., Alekseenko A. A., Lin R., Tabachkova N. Y., Safronenko O. I. Activity and stability of Pt/C and Pt-Cu/C. Electrocatalysts. 2018;9(5): 550–562. https://doi.org/10.1007/s12678-017-0451-1

Guterman V. E., Belenov S. V., Alekseenko A. A., Volochaev V. A., Tabachkova N. Y. The relationship between activity and stability of deposited platinumcarbon electrocatalysts. Russian Journal of Electrochemistry. 2017;53(5): 531–539. https://doi.org/10.1134/S1023193517050081

Zhu H., Li X., Wang F. Synthesis and characterization of Cu@Pt/C core-shell structured catalysts for proton exchange membrane fuel cell. International Journal of Hydrogen Energy. 2011;36(15) 9151–9154. https://doi.org/10.1016/j.ijhydene.2011.04.224

Wang Y., Zhou H., Sun P., Chen T. Exceptional methanol electro-oxidation activity by bimetallic concave and dendritic Pt-Cu nanocrystals catalysts. Journal of Power Sources. 2014;245(1): 663–670. https://doi.org/10.1016/j.jpowsour.2013.07.015

Na H., Choi H., Oh J. W., Jung Y. S., Cho Y. S. Enhanced CO oxidation and cyclic activities in threedimensional platinum/indium tin oxide/carbon black electrocatalysts processed by cathodic arc deposition. ACS Applied Materials and Interfaces. 2019;11(28): 25179–25185. https://doi.org/10.1021/acsami.9b06159