International Journal of Industrial Engineering


                                                                              ISSN 2456-8449
ISSN 2456-8449

International Journal of Industrial Engineering, Vol. 1, No. 2, 2017, Pages 67-77.


Effect of Ni on graphene supported Pt–Ru binary catalyst for borohydride electro-oxidation
M. Elumalai¹, S. Kiruthika², B. Muthukumaran¹,*     

​¹Department of Chemistry, Presidency College, Chennai – 600 005, India.
²Department of Chemical Engineering, SRM University, Chennai – 603 203, India.     
*Corresponding author’s e-mail:
Catalysts of Pt–Ni, Pt–Ru and Pt–Ru–Ni supported on graphene are prepared using Bonnemann reduction method to study the electro-oxidation of sodium borohydride in membraneless fuel cell. The prepared electrocatalysts were characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) analyses. The synthesized catalysts had similar particle morphology, and their particle sizes were 3-5 nm. The electrocatalytic activities were examined by cyclic voltammetry (CV) and chronoamperometry (CA). The electrochemical results obtained at room temperature indicated that the ternary Pt–Ru–Ni/G (60:30:10) catalyst displayed better catalytic activity for sodium borohydride oxidation compared with the other prepared catalysts. During the experiments performed on single membraneless fuel cell, Pt–Ru–Ni/G (60:30:10) performed better among all the catalysts prepared with power density of 35.61 mWcm─2. The better performance of ternary Pt–Ru–Ni/G catalysts may be due to the formation of a ternary alloy and the smaller particle size.

​​​​Keywords: Sodium borohydride; Graphene support; Power density; Ternary alloy catalyst; Membraneless borohydride fuel cell.  


  1. Duteanu N, Vlachogiannopoulos G, Shivhare MR, Yu EH, Keith S, A parametric study of a platinum ruthenium anode in a direct borohydride fuel cell, J Appl Electrochem. 2007; 37(9): 1085–1091.
  2. Tegou A, Papadimitriou S, Mintsouli I, Armyanov S, Valova E, Kokkinidis G, Rotating disc electrode studies of borohydride oxidation at Pt and bimetallic Pt‒Ni and Pt-Co electrodes. Catal Today, 2011; 170(1): 126-33.
  3. Yi LH, Liu L, Liu X, Wang XY, Yi W, He PY, Carbon supported Pt‒Co nanoparticles as anode catalyst for direct borohydride-hydrogen peroxide fuel cell: electrocatalysts and fuel cell performance. Int. J. Hydrogen Energy, 2012; 37(17): 12650-12658.
  4. Gowdhamamoorthi M, Arun A, Kiruthika S and Muthukumaran B. Percarbonate as novel fuel for enhanced performance of membraneless fuel cells. Int. J. of Ionics 2014; 20(12): 1723-1728.
  5. Arun A, Gowdhamamoorthi M, Kiruthika S and Muthukumaran B. Analysis of membraneless methanol fuel cell using percarbonate as an oxidant. J. of the Electrochemical Society, 2013; 161: F1-F7.
  6. Yi LH, Liu L, Wang XY, Liu X, Yi W, Wang XY. Carbon supported Pt‒Sn nanoparticles as anode catalyst for direct borohydride-hydrogen peroxide fuel cell: electrocatalysis and fuel cell performance. J Power Sources, 2013; 224: 6-12.
  7. Yi LH, Hu B, Song YF, Wang XY, Zou GS, Yi W, Studies of electrochemical performance of carbon supported Pt‒Cu nanoparticles as anode catalysts for direct borohydride hydrogen peroxide fuel cell, J Power Sources 2011; 196(23): 9924-30.
  8. Elumalai M, Priya M, Kiruthika S, Muthukumaran B, Effect of acid and alkaline media on membraneless fuel cell using sodium borohydride as a fuel, J. Afinidad 2015; 72: 572.
  9. Yang H, Coutanceau C, Leger JM, Alonso-Vante N, Lamy C, Methanol tolerant oxygen reduction on carbon-supported Pt-Ni alloy nanoparticles, J. Electroanal. Chem. 2005; 576(2): 305–313.
  10. Lobato J, Ca nizares P, Rodrigo MA, Linares JJ, Lopez-Vizcaino R, Performance of a Vapor-Fed Polybenzimidazole (PBI)-Based Direct Methanol Fuel Cell, J. of Energy Fuels, 2008; 22(5):3335–3345.
  11. Hsieh CT, Lin JY, Fabrication of bimetallic Pt–M (M= Fe, Co, and Ni) nanoparticle/carbon nanotubes electrocatalysts for direct methanol fuel cells, J. Power Sources 2009; 188(2): 347–352.
  12. Lobato C J, Ca nizares P, Ubeda D, Pinar FJ, Rodrigo MA, Testing PtRu/CNF catalysts for a high temperature polybenzimidazole-based direct ethanol fuel cell. Effect of metal content, Appl. Catal. B: Environ. 2011; 106(2): 174–180.
  13. Yaojuan H, Ping W, Yajing Y, Hui Z, Chenxin C, Effects of structure, composition, and carbon support properties on the electrocatalytic activity of Pt-Ni-graphene nanocatalysts for the methanol oxidation, Applied Catalysis B: Environmental, 2012; 111: 208– 217.
  14. John S.St, Dutta I, Angelopoulos A.P, Enhanced Electrocatalytic Oxygen Reduction through Electrostatic Assembly of Pt Nanoparticles onto Porous Carbon Supports from SnCl2-Stabilized Suspensions, Langmuir, 2011; 27(10): 5781–5791.
  15. Qi J, Jiang L, Wang S, Sun G, Synthesis of graphitic mesoporous carbons with high surface areas and their applications in direct methanol fuel cells, Appl. Catal. B: Environ. 2011; 107(2): 95–103.
  16. Yang H, Li F, Shan C, Han D, Zhang Q, Niu L, Ivaska A, Covalent functionalization of chemically converted graphene sheets via silane and its reinforcement, J. Mater. Chem. 2009; 19(26): 4632–4638.
  17. Kou R, Shao Y, Mei D, Nie Z, Wang D, Wang C, Viswanathan VV, Park S, Aksay IA, Lin Y, Wang Y, Liu J, Stabilization of Electrocatalytic Metal Nanoparticles at Metal-Metal Oxide-Graphene Triple Junction Points, J. Am. Chem. Soc. 2011; 133(8): 2541–2547.
  18. Yang F, Liu Y, Gao L, Sun J, pH-Sensitive Highly Dispersed Reduced Graphene Oxide Solution Using Lysozyme via an in Situ Reduction Method, J. Phys. Chem. C,  2010; 114(50): 22085–22091.
  19. Ermete A, Effect of the Structural Characteristics of Binary Pt–Ru and Ternary Pt–Ru–M Fuel Cell Catalysts on the Activity of Ethanol Electro-oxidation in Acid Medium. ChemSusChem. 2013; 6(6): 966-973.
  20. Lam VW S, AlfantaziA, Gyenge EL, The effect of catalyst support on the performance of PtRu in direct borohydride fuel cell anodes, J Appl Electrochem. 2009; 39:1763–1770.
  21. Martinez-Huerta MV, Rojas S, Fuente JLG, Terreros P, Pena MA, Fierro JLG, Effect of Ni addition over PtRu/C based electrocatalysts for fuel cell applications, Appl. Catal. B: Environ. 2006; 69(2): 75–84.
  22. Moreno B, Chinarro E, Perez JC, Jurado JR, Combustion synthesis and electrochemical characterization of Pt–Ru–Ni anode electrocatalyst for PEMFC, Appl. Catal. B: Environ. 2007; 76(3): 368–374.
  23. Gotz M, Wendt H, Binary and ternary anode catalyst formulations including the elements W, Sn and Mo for PEMFCs operated on methanol or reformate gas. Electrochemica Acta, 1998; 43(24): 3637-3644.
  24. Radmilovic V, Gasteiger HA, Ross Jr. PN, Structure and chemical composition of a supported Pt-Ru electrocatalyst for methanol oxidation, J. Catal. 1995; 154(1): 98-106.
  25. Beyhan S, Leger J-M, Kadırgan F, Pronounced synergetic effect of the nano-sized PtSnNi/C catalyst for methanol oxidation in direct methanol fuel cell, Applied Catalysis B: Environmental 2013; 130: 305–313.
  26. Giorgi L, Pozio A, Bracchini C, Giorgi R, Turtu S, H2 and H2/CO oxidation mechanism on Pt/C, Ru/C and Pt–Ru/C electrocatalysts, J. Appl. Electrochem. 2001: 31(3) 325-334.
  27. Wang ZB, Yin GP, Shi PF, Sun YC, Novel Pt–Ru–Ni/C Catalysts for Methanol Electro-oxidation in Acid Medium, Electrochem. Solid-State Lett. 2006; 9(1): A13.