Electrochemical Synthesis of Cauliflower-Like PtPd@PVF Nanocatalyst for Electrooxidation of Methanol

Year 2021, Volume: 49 Issue: 1, 79 - 91, 01.01.2021

Mutlu Sönmez Çelebi , Kübra Öztürk Mehmet Dumangöz

https://doi.org/10.15671/hjbc.704959

Abstract

In this study, a bimetallic catalyst consisting of Pt and Pd nanoparticles supported on poly(vinylferrocene), i.e., PtPd@PVF was electrochemically prepared on pencil graphite electrode to improve the catalytic properties of previously developed Pt@PVF catalyst. K2PtCl4 and K2PdCl4 were used as the metal precursors in order to disperse the Pt and Pd onto the conducting polymer support by cyclic voltammetry technique. Electrochemical and chemical reduction methods were compared for the reduction of Pt and Pd complexes. The prepared catalyst system was electrochemically characterized by cyclic voltammetry. Physical characterization of the catalyst was performed by recording scanning electron microscopy images and energy dispersive X-ray spectrum. The PtPd@PVF catalyst showed superior catalytic activity towards electrooxidation of methanol compared to the monometallic Pt/PVF catalyst.

Keywords

Poli(vinilferrosen), Bimetallic catalyst, Methanol oxidation, Pt Pd nanoparticles

Supporting Institution

Scientific Research Projects Coordination Department of Ordu University (ODUBAP)

Project Number

AR-1403

References

• [1] O. Z. Sharaf and M. F. Orhan, “An overview of fuel cell technology: Fundamentals and applications,” Renew. Sustain. Energy Rev., vol. 32, pp. 810–853, 2014.
• [2] M. S. Çelebi, “Energy Applications : Fuel Cells,” 2016, pp. 397–434.
• [3] X. Li and A. Faghri, “Review and advances of direct methanol fuel cells (DMFCs) part I: Design, fabrication, and testing with high concentration methanol solutions,” J. Power Sources, vol. 226, pp. 223–240, 2013.
• [4] B. C. Ong, S. K. Kamarudin, and S. Basri, “Direct liquid fuel cells: A review,” Int. J. Hydrogen Energy, vol. 42, no. 15, pp. 10142–10157, 2017.
• [5] H. Liu, C. Song, L. Zhang, J. Zhang, H. Wang, and D. P. Wilkinson, “A review of anode catalysis in the direct methanol fuel cell,” J. Power Sources, vol. 155, no. 2, pp. 95–110, 2006.
• [6] S. Sharma and B. G. Pollet, “Support materials for PEMFC and DMFC electrocatalysts - A review,” J. Power Sources, vol. 208, pp. 96–119, 2012.
• [7] S. K. Kamarudin, F. Achmad, and W. R. W. Daud, “Overview on the application of direct methanol fuel cell (DMFC) for portable electronic devices,” Int. J. Hydrogen Energy, vol. 34, no. 16, pp. 6902–6916, 2009.
• [8] A. M. Zainoodin, S. K. Kamarudin, and W. R. W. Daud, “Electrode in direct methanol fuel cells,” Int. J. Hydrogen Energy, vol. 35, no. 10, pp. 4606–4621, 2010.
• [9] S. Basri, S. K. Kamarudin, W. R. W. Daud, and Z. Yaakub, “Nanocatalyst for direct methanol fuel cell (DMFC),” Int. J. Hydrogen Energy, vol. 35, no. 15, pp. 7957–7970, 2010.
• [10] H. Wu et al., “Facile synthesis of Pt/Pd nanodendrites for the direct oxidation of methanol,” Nanotechnology, vol. 25, no. 19, 2014.
• [11] N. Toshima, H. Yan, and Y. Shiraishi, “Recent Progress in Bimetallic Nanoparticles: Their Preparation, Structures and Functions,” Met. Nanoclusters Catal. Mater. Sci. Issue Size Control, pp. 49–75, 2008.
• [12] M. Xiao, X. Liang, W. Li, Y. Yang, and Y. Miao, “Synthesis of Ultrafine Pt/Pd Bimetallic Nanoparticles and Their Decoration on MWCNTs for Hydrogen Evolution,” J. Electrochem. Soc., vol. 162, no. 6, pp. H415–H418, 2015.
• [13] K. An and G. A. Somorjai, “Nanocatalysis I: Synthesis of Metal and Bimetallic Nanoparticles and Porous Oxides and Their Catalytic Reaction Studies,” Catal. Letters, vol. 145, no. 1, pp. 233–248, 2015.
• [14] H. R. Cho and J. R. Regalbuto, “The rational synthesis of Pt-Pd bimetallic catalysts by electrostatic adsorption,” Catal. Today, vol. 246, pp. 143–153, 2015.
• [15] M. Wang, Z. Zheng, J. Liu, and C. Wang, “Pt-Pd Bimetallic Nanoparticles Decorated Nanoporous Graphene as a Catalytic Amplification Platform for Electrochemical Detection of Xanthine,” Electroanalysis, vol. 29, no. 5, pp. 1258–1266, 2017.
• [16] X. Chen, Z. Cai, M. Oyama, and X. Chen, “Synthesis of bimetallic PtPd nanocubes on graphene with N,N-dimethylformamide and their direct use for methanol electrocatalytic oxidation,” Carbon N. Y., vol. 66, pp. 387–394, 2014.
• [17] N. V. Long, M. Ohtaki, T. D. Hien, J. Randy, and M. Nogami, “A comparative study of Pt and Pt-Pd core-shell nanocatalysts,” Electrochim. Acta, vol. 56, no. 25, pp. 9133–9143, 2011.
• [18] E. Kim, H. S. Jeong, and B. M. Kim, “Efficient chemoselective reduction of nitro compounds and olefins using Pd-Pt bimetallic nanoparticles on functionalized multi-wall-carbon nanotubes,” Catal. Commun., vol. 45, pp. 25–29, 2014.
• [19] Z. X. Cai, C. C. Liu, G. H. Wu, X. M. Chen, and X. Chen, “Green synthesis of Pt-on-Pd bimetallic nanodendrites on graphene via in situ reduction, and their enhanced electrocatalytic activity for methanol oxidation,” Electrochim. Acta, vol. 127, pp. 377–383, 2014.
• [20] Y. Zhang, G. Chang, H. Shu, M. Oyama, X. Liu, and Y. He, “Synthesis of Pt-Pd bimetallic nanoparticles anchored on graphene for highly active methanol electro-oxidation,” J. Power Sources, vol. 262, pp. 279–285, 2014.
• [21] O. Akyıldırım, G. Kotan, M. L. Yola, T. Eren, and N. Atar, “Fabrication of bimetallic Pt/Pd nanoparticles on 2-thiolbenzimidazole functionalized reduced graphene oxide for methanol oxidation,” Ionics (Kiel)., vol. 22, no. 4, pp. 593–600, 2016.
• [22] Y. Y. Chu, Z. B. Wang, Z. Z. Jiang, D. M. Gu, and G. P. Yin, “Facile synthesis of hollow spherical sandwich PtPd/C catalyst by electrostatic self-assembly in polyol solution for methanol electrooxidation,” J. Power Sources, vol. 203, pp. 17–25, 2012.
• [23] Y. Lim et al., “One-step synthesis of carbon-supported Pd@Pt/C core-shell nanoparticles as oxygen reduction electrocatalysts and their enhanced activity and stability,” Nanoscale, vol. 6, no. 8, pp. 4038–4042, 2014.
• [24] J. J. Lv et al., “Facile synthesis of bimetallic alloyed Pt-Pd nanocubes on reduced graphene oxide with enhanced eletrocatalytic properties,” Electrochim. Acta, vol. 143, pp. 36–43, 2014.
• [25] X. Chen, X. Tian, L. Zhao, Z. Huang, and M. Oyama, “Nonenzymatic sensing of glucose at neutral pH values using a glassy carbon electrode modified with graphene nanosheets and Pt-Pd bimetallic nanocubes,” Microchim. Acta, vol. 181, no. 7–8, pp. 783–789, 2014.
• [26] S. Dutta, C. Ray, S. Sarkar, A. Roy, R. Sahoo, and T. Pal, “Facile Synthesis of Bimetallic Au-Pt, Pd-Pt, and Au-Pd Nanostructures: Enhanced Catalytic Performance of Pd-Pt Analogue towards Fuel Cell Application and Electrochemical Sensing,” Electrochim. Acta, vol. 180, pp. 1075–1084, 2015.
• [27] C. X. Yuan et al., “A new electrochemical sensor of nitro aromatic compound based on three-dimensional porous Pt-Pd nanoparticles supported by graphene-multiwalled carbon nanotube composite,” Biosens. Bioelectron., vol. 58, pp. 85–91, 2014.
• [28] B. Neppolian, V. Sáez, J. González-García, F. Grieser, R. Gómez, and M. Ashokkumar, “Sonochemical synthesis of graphene oxide supported Pt–Pd alloy nanocrystals as efficient electrocatalysts for methanol oxidation,” J. Solid State Electrochem., vol. 18, no. 11, pp. 3163–3171, 2014.
• [29] F. Kadirgan et al., “Carbon supported nano-sized Pt-Pd and Pt-Co electrocatalysts for proton exchange membrane fuel cells,” Int. J. Hydrogen Energy, vol. 34, no. 23, pp. 9450–9460, 2009.
• [30] R. Kortlever, I. Peters, S. Koper, and M. T. M. Koper, “Electrochemical CO2Reduction to Formic Acid at Low Overpotential and with High Faradaic Efficiency on Carbon-Supported Bimetallic Pd-Pt Nanoparticles,” ACS Catal., vol. 5, no. 7, pp. 3916–3923, 2015.
• [31] J. Zhang, X. Hu, B. Yang, N. Su, and H. Huang, “Novel synthesis of PtPd nanoparticles with good electrocatalytic activity and durability,” vol. 709, pp. 588–595, 2017.
• [32] K. Wu et al., “Graphene-supported Pd-Pt alloy nanoflowers: In situ growth and their enhanced electrocatalysis towards methanol oxidation,” Int. J. Hydrogen Energy, vol. 40, no. 20, pp. 6530–6537, 2015.
• [33] Y. Yang et al., “In situ synthesis of PtPd bimetallic nanocatalysts supported on graphene nanosheets for methanol oxidation using triblock copolymer as reducer and stabilizer,” J. Electroanal. Chem., vol. 783, pp. 132–139, 2016.
• [34] S. Ghosh, S. Mondal, and C. Retna Raj, “Carbon nanotube-supported dendritic Pt-on-Pd nanostructures: growth mechanism and electrocatalytic activity towards oxygen reduction reaction,” J. Mater. Chem. A, vol. 2, no. 7, pp. 2233–2239, 2014.
• [35] A. Zielińska-Jurek and J. Hupka, “Preparation and characterization of Pt/Pd-modified titanium dioxide nanoparticles for visible light irradiation,” Catal. Today, vol. 230, pp. 181–187, 2014.
• [36] K. Hassan, A. S. M. Iftekhar Uddin, and G. S. Chung, “Fast-response hydrogen sensors based on discrete Pt/Pd bimetallic ultra-thin films,” Sensors Actuators, B Chem., vol. 234, pp. 435–445, 2016.
• [37] J. Datta, A. Dutta, and M. Biswas, “Enhancement of functional properties of PtPd nano catalyst in metal-polymer composite matrix: Application in direct ethanol fuel cell,” Electrochem. commun., vol. 20, no. 1, pp. 56–59, 2012.
• [38] P. Boomi, H. G. Prabu, and J. Mathiyarasu, “Synthesis, characterization and antibacterial activity of polyaniline/Pt-Pd nanocomposite,” Eur. J. Med. Chem., vol. 72, pp. 18–25, 2014.
• [39] M. Lin, X. Hu, Z. Ma, and L. Chen, "Functionalized polypyrrole nanotube arrays as electrochemical biosensor for the determination of copper ions", Analytica Chimica Acta, vol. 746, pp. 63-69, 2012.
• [40] S. Y. Huang, P. Ganesan, and B.N. Popov, "Development of conducting polypyrrole as corrosion-resistant catalyst support for polymer electrolyte membrane fuel cell (PEMFC) application", Appl Catal B-Environ, vol. 93, pp. 75-81, 2009.
• [41] G. Wu, L. Li, J. H. Li, and B. Q. Xu, "Methanol electrooxidation on Pt particles dispersed into PANI/SWNT composite films", J Power Sources, vol. 155, pp. 118-127, 2006.
• [42] M. S. Çelebi, and K. Pekmez, "Electrooxidation of Formic Acid Using Pt Nanoparticles Supported on Conducting Poly(Vinylferrocene) Polymer Support," Hacettepe J. Biol. & Chem., vol. 45, no. 3, pp. 351–358, 2017.
• [43] M. S. Çelebi, K. Pekmez, H. Özyörük, and A. Yildiz, “Preparation and physical/electrochemical characterization of Pt/poly(vinylferrocenium) electrocatalyst for methanol oxidation,” J. Power Sources, vol. 183, no. 1, pp. 8–13, 2008.
• [44] M. S. Çelebi, K. Pekmez, H. Özyörük, and A. Yildiz, “Electrochemical synthesis of Pd particles on poly(vinylferrocenium),” Catal. Commun., vol. 9, no. 13, pp. 2175–2178, 2008.
• [45] W. Ye, H. Kou, Q. Liu, J. Yan, F. Zhou, and C. Wang, “Electrochemical deposition of Au-Pt alloy particles with cauliflower-like microstructures for electrocatalytic methanol oxidation,” Int. J. Hydrogen Energy, vol. 37, no. 5, pp. 4088–4097, 2012.
• [46] M. F. Hossain and J. Y. Park, “Amperometric glucose biosensor based on Pt-Pd nanoparticles supported by reduced graphene oxide and integrated with glucose oxidase,” Electroanalysis, vol. 26, no. 5, pp. 940–951, 2014.
• [47] X. Quan, Y. Mei, H. Xu, B. Sun, and X. Zhang, “Optimization of Pt-Pd alloy catalyst and supporting materials for oxygen reduction in air-cathode microbial fuel cells,” Electrochim. Acta, vol. 165, pp. 72–77, 2015.
• [48] X. Yan, T. Liu, J. Jin, S. Devaramani, D. Qin, and X. Lu, “Well dispersed Pt-Pd bimetallic nanoparticles on functionalized graphene as excellent electro-catalyst towards electro-oxidation of methanol,” J. Electroanal. Chem., vol. 770, pp. 33–38, 2016.
• [49] A. Pinithchaisakula, K. Ounnunkad, S. Themsirimongkon, N. Promsawan, P. Waenkaew, and S. Saipanya, “Efficiency of bimetallic PtPd on polydopamine modified on various carbon supports for alcohol oxidations,” Chem. Phys., vol. 483–484, pp. 56–67, 2017.
• [50] C. Aso, T. Kunitake, and T. Nakashima, “Cationic polymerization and copolymerization of vinylferrocene,” Die Makromol. …, vol. 124, no. 166, pp. 232–240, 1969.
• [51] P. J. Peerce and A. J. Bard, “Polymer films on electrodes. Part II. Film structure and mechanism of electron transfer with electrodeposited poly(vinylferrocene),” J. Electroanal. Chem., vol. 112, no. 1, pp. 97–115, 1980.
• [52] M. S. Çelebi, H. Özyörük, A. Yıldız, and S. Abacı, "Determination of Hg2+ on poly (vinylferrocenium)(PVF+)-modified platinum electrode", Talanta, vol. 78, no. 2, pp. 405-409, 2009.