Journal of Applied Electrochemistry

, Volume 46, Issue 11, pp 1109–1118 | Cite as

Core–shell Pd–P@Pt nanoparticles as efficient catalysts for electrooxidation of formic acid

  • Jing Xu
  • Ming Zhao
  • Shin-ichi Yamaura
  • Tienan Jin
  • Naoki Asao
Research Article
Part of the following topical collections:
  1. Fuel cells


Tailoring the composition and structure is an effective approach for improving the properties of electrocatalysts in fuel cells. In this study, the core–shell Pd–P@Pt nanoparticles were synthesized using a seed-mediated growth method and applied to the formic acid oxidation reaction like electrocatalysts. The core–shell structure was confirmed by transmission electron microscopy, elemental mapping analyses, energy-dispersive X-ray spectroscopy line scan, inductively coupled plasma mass spectrometry, and X-ray photoelectron spectroscopy. The catalytic activity and durability were evaluated by cyclic voltammetry, electrochemically active surface area loss, and chronoamperometry. The obtained particles exhibit higher catalytic activity and durability compared to those of Pt/C and Pt black commercial reference catalysts due to the synergistic effect between the Pd–P core and the Pt shell. In addition, the Pt shell inhibits the corrosion of Pd in the acidic solution, resulting in good stability.

Graphical Abstract


Electrochemistry Nanoparticles Phosphorus Formic acid Fuel cells 

Supplementary material

10800_2016_997_MOESM1_ESM.doc (1.2 mb)
Supplementary material 1 (DOC 1275 kb)


  1. 1.
    Chang J, Feng L, Liu C, Xing W, Hu X (2014) An effective Pd-Ni2P/C anode catalyst for direct formic acid fuel cells. Angew Chem Int Ed 53:122–126CrossRefGoogle Scholar
  2. 2.
    Kim Y, Kim HJ, Kim YS, Choi SM, Seo MH, Kim WB (2012) Shape- and composition-sensitive activities of Pt and PtAu catalysts for formic acid electrooxidation. J Phys Chem C 116:18093–18100CrossRefGoogle Scholar
  3. 3.
    Rao CV, Cabrera CR, Ishikawa Y (2011) Graphene-supported Pt–Au alloy nanoparticles: a highly efficient anode for direct formic acid fuel cells. J Phys Chem C 115:21963–21970CrossRefGoogle Scholar
  4. 4.
    Rice C, Ha S, Masel RI, Waszczuk P, Wieckowski A, Barnard T (2002) Direct formic acid fuel cells. J Power Sources 111:83–89CrossRefGoogle Scholar
  5. 5.
    Winter M, Brodd RJ (2004) What are batteries, fuel cells, and supercapacitors? Chem Rev 104:4245–4269CrossRefGoogle Scholar
  6. 6.
    Yu X, Pickup PG (2008) Recent advances in direct formic acid fuel cells (DFAFC). J Power Sources 182:124–132CrossRefGoogle Scholar
  7. 7.
    Okamoto H, Kon W, Mukouyama Y (2005) Five current peaks in voltammograms for oxidations of formic acid, formaldehyde, and methanol on platinum. J Phys Chem B 109:15659–15666CrossRefGoogle Scholar
  8. 8.
    Zhang LJ, Wang ZY, Xia DG (2006) Bimetallic PtPb for formic acid electro-oxidation. J Alloys Compd 426:268–271CrossRefGoogle Scholar
  9. 9.
    Xu H, Ding L-X, Liang C-L, Tong Y-X, Li G-R (2013) High-performance polypyrrole functionalized PtPd electrocatalysts based on PtPd/PPy/PtPd three-layered nanotube arrays for the electrooxidation of small organic molecules. NPG Asia Mater 5:e69CrossRefGoogle Scholar
  10. 10.
    Chen S, Su H, Wang Y, Wu W, Zeng J (2015) Size-controlled synthesis of platinum-copper hierarchical trigonal bipyramid nanoframes. Angew Chem Int Ed 54:108–113CrossRefGoogle Scholar
  11. 11.
    Xiao M, Li S, Zhu J, Li K, Liu C, Xing W (2014) Highly active PtAu nanowire networks for formic acid oxidation. ChemPlusChem 79:1123–1128CrossRefGoogle Scholar
  12. 12.
    Ji X, Lee KT, Holden R, Zhang L, Zhang J, Botton GA, Couillard M, Nazar LF (2010) Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes. Nat Chem 2:286–293CrossRefGoogle Scholar
  13. 13.
    Jiang K, Zhang H-X, Zou S, Cai W-B (2014) Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications. Phys Chem Chem Phys 16:20360–20376CrossRefGoogle Scholar
  14. 14.
    Capon A, Parsons R (1973) The oxiation of formic acid at noble metal electrodes part III. Intermediates and mechanism on platinum electrodes. J Electroanal Chem 45:205–231CrossRefGoogle Scholar
  15. 15.
    Park S, Xie Y, Weaver MJ (2002) Electrocatalytic pathways on carbon-supported platinum nanoparticles: comparison of particle-size-dependent rates of methanol, formic acid, and formaldehyde electrooxidation. Langmuir 18:5792–5798CrossRefGoogle Scholar
  16. 16.
    Godínez-Salomón F, Arce-Estrada E, Hallen-López M (2012) Electrochemical study of the Pt nanoparticles size effect in the formic acid oxidation. Int J Electrochem Sci 7:2566–2576Google Scholar
  17. 17.
    Kang Y, Murray CB (2010) Synthesis and electrocatalytic properties of cubic Mn–Pt nanocrystals (nanocubes). J Am Chem Soc 132:7568–7569CrossRefGoogle Scholar
  18. 18.
    Lee H, Habas SE, Somorjai GA, Yang P (2008) Localized Pd overgrowth on cubic Pt nanocrystals for enhanced electrocatalytic oxidation of formic acid. J Am Chem Soc 130:5406–5407CrossRefGoogle Scholar
  19. 19.
    Alden LR, Han DK, Matsumoto F, Abruña HD, DiSalvo FJ (2006) Intermetallic PtPb nanoparticles prepared by sodium naphthalide reduction of metal-organic precursors: electrocatalytic oxidation of formic acid. Chem Mater 18:5591–5596CrossRefGoogle Scholar
  20. 20.
    Xu Y, Hou S, Liu Y, Zhang Y, Wang H, Zhang B (2012) Facile one-step room-temperature synthesis of Pt3Ni nanoparticle networks with improved electro-catalytic properties. Chem Commun 48:2665–2667CrossRefGoogle Scholar
  21. 21.
    Yao Z, Zhu M, Jiang F, Du Y, Wang C, Yang P (2012) Highly efficient electrocatalytic performance based on Pt nanoflowers modified reduced graphene oxide/carbon cloth electrode. J Mater Chem 22:13707–13713CrossRefGoogle Scholar
  22. 22.
    Yuan Q, Huang D-B, Wang H-H, Zhou Z-Y, Wang Q (2014) One-pot synthesis of Pd-Pt@Pd core-shell nanocrystals with enhanced electrocatalytic activity for formic acid oxidation. CrystEngComm 16:2560–2564CrossRefGoogle Scholar
  23. 23.
    Xu Y, Yuan Y, Ma A, Wu X, Liu Y, Zhang B (2012) Composition-tunable Pt–Co alloy nanoparticle networks: facile room-temperature synthesis and supportless electrocatalytic applications. ChemPhysChem 13:2601–2609CrossRefGoogle Scholar
  24. 24.
    Guo J, Sun Y, Zhang X, Tang L, Liu H (2014) FePt nanoalloys anchored reduced graphene oxide as high-performance electrocatalysts for formic acid and methanol oxidation. J Alloys Compd 604:286–291CrossRefGoogle Scholar
  25. 25.
    Xie R, Chen M, Wang J, Mei S, Pan Y, Gu H (2015) Facile synthesis of Au–Pt bimetallic nanocomplexes for direct oxidation of methanol and formic acid. RSC Adv 5:650–653CrossRefGoogle Scholar
  26. 26.
    Guo Z, Zhang X, Sun H, Dai X, Yang Y, Li X, Meng T (2014) Novel honeycomb nanosphere Au@Pt bimetallic nanostructure as a high performance electrocatalyst for methanol and formic acid oxidation. Electrochim Acta 134:411–417CrossRefGoogle Scholar
  27. 27.
    Zhang S, Guo S, Zhu H, Su D, Sun S (2012) Structure-induced enhancement in electrooxidation of trimetallic FePtAu nanoparticles. J Am Chem Soc 134:5060–5063CrossRefGoogle Scholar
  28. 28.
    Kang Y, Qi L, Li M, Diaz RE, Su D, Adzic RR, Stach E, Li J, Murray CB (2012) Highly active Pt3Pb and core–shell Pt3Pb-Pt electrocatalysts for formic acid oxidation. ACS Nano 6:2818–2825CrossRefGoogle Scholar
  29. 29.
    Xu C, Hao Q, Duan H (2014) Nanoporous PdPt alloy as a highly active electrocatalyst for formic acid oxidation. J Mater Chem A 2:8875–8880CrossRefGoogle Scholar
  30. 30.
    Ye Y, Joo J, Lee S, Lee J (2014) A direct one-step synthetic route to Pd–Pt nanostructures with controllable shape, size, and composition for electrocatalytic applications. J Mater Chem A 2:19239–19246CrossRefGoogle Scholar
  31. 31.
    Gong M, Li F, Yao Z, Zhang S, Dong J, Chen Y, Tang Y (2015) Highly active and durable platinum–lead bimetallic alloy nanoflowers for formic acid electrooxidation. Nanoscale 7:4894–4899CrossRefGoogle Scholar
  32. 32.
    Chaudhuri RG, Paria S (2012) Core/shell nanoparticles: classes, properties, synthesis mechanisms, characterization, and applications. Chem Rev 112:2373–2433CrossRefGoogle Scholar
  33. 33.
    Zhang S, Hao Y, Su D, Doan-Nguyen VVT, Wu Y, Li J, Sun S, Murray CB (2014) Monodisperse core/shell Ni/FePt nanoparticles and their conversion to Ni/Pt to catalyze oxygen reduction. J Am Chem Soc 136:15921–15924CrossRefGoogle Scholar
  34. 34.
    Mazumder V, Chi M, More KL, Sun S (2010) Core/shell Pd/FePt nanoparticles as an active and durable catalyst for the oxygen reduction reaction. J Am Chem Soc 132:7848–7849CrossRefGoogle Scholar
  35. 35.
    Sun X, Li D, Ding Y, Zhu W, Guo S, Wang ZL, Sun S (2014) Core/shell Au/CuPt nanoparticles and their dual electrocatalysis for both reduction and oxidation reactions. J Am Chem Soc 136:5745–5749CrossRefGoogle Scholar
  36. 36.
    Ding L-X, Wang A-L, Li G-R, Liu Z-Q, Zhao W-X, Su C-Y, Tong Y-X (2012) Porous Pt–Ni–P composite nanotube arrays: highly electroactive and durable catalysts for methanol electrooxidation. J Am Chem Soc 134:5730–5733CrossRefGoogle Scholar
  37. 37.
    Zhao M, Abe K, Yamaura S, Yamamoto Y, Asao N (2014) Fabrication of Pd–Ni–P metallic glass nanoparticle and their application as highly durable catalysts in methanol electro-oxidation. Chem Mater 26:1056–1061CrossRefGoogle Scholar
  38. 38.
    Zhang J, Xu Y, Zhang B (2014) Facile synthesis of 3D Pd–P nanoparticle networks with enhanced electrocatalytic performance towards formic acid electrooxidation. Chem Commun 50:13451–13453CrossRefGoogle Scholar
  39. 39.
    Narayanamoorthy B, Datta KKR, Eswaramoorthy M, Balaji S (2014) Highly active and stable Pt3Rh nanoclusters as supportless electrocatalyst for methanol oxidation in direct methanol fuel cells. ACS Catal 4:3621–3629CrossRefGoogle Scholar
  40. 40.
    Yang G, Chen Y, Zhou Y, Tang Y, Lu T (2010) Preparation of carbon supported Pd–P catalyst with high content of element phosphorous and its electrocatalytic performance for formic acid oxidation. Electrochem Commun 12:492–495CrossRefGoogle Scholar
  41. 41.
    Xia BY, Wu HB, Li N, Yan Y, Lou XW, Wang X (2015) One-pot synthesis of Pt–Co alloy nanowire assemblies with tunable composition and enhanced electrocatalytic properties. Angew Chem Int Ed 54:3797–3801CrossRefGoogle Scholar
  42. 42.
    Serpell CJ, Cookson J, Ozkaya D, Beer PD (2011) Core@shell bimetallic nanoparticle synthesis via anion coordination. Nat Chem 3:478–483Google Scholar
  43. 43.
    Lim B, Jiang M, Camargo PHC, Cho EC, Tao J, Lu X, Zhu Y, Xia Y (2009) Pd–Pt bimetallic nanodendrites with high activity for oxygen reduction. Science 324:1302–1305CrossRefGoogle Scholar
  44. 44.
    Zhang H, Yin Y, Hu Y, Li C, Wu P, Wei S, Cai C (2010) Pd@Pt core–shell nanostructures with controllable composition synthesized by a microwave method and their enhanced electrocatalytic activity toward oxygen reduction and methanol oxidation. J Phys Chem C 114:11861–11867CrossRefGoogle Scholar
  45. 45.
    Cui Z, Chen H, Zhao M, Marshall D, Yu Y, Abruña H, DiSalvo FJ (2014) Synthesis of structurally ordered Pt3Ti and Pt3V nanoparticles as methanol oxidation catalysts. J Am Chem Soc 136:10206–10209CrossRefGoogle Scholar
  46. 46.
    Samjeské G, Miki A, Ye S, Osawa M (2006) Mechanistic study of electrocatalytic oxidation of formic acid at platinum in acidic solution by time-resolved surface-enhanced infrared absorption spectroscopy. J Phys Chem B 110:16559–16566CrossRefGoogle Scholar
  47. 47.
    Burke GM, Wurster DE, Berg MJ, Veng-Pedersen P, Schottelius DD (1992) Surface characterization of activated charcoal by X-ray photoelectron spectroscopy (XPS): correlation with phenobarbital adsorption data. Pharm Res 9:126–130CrossRefGoogle Scholar
  48. 48.
    Brun M, Berthet A, Bertolini JC (1999) XPS, AES and auger parameter of Pd and PdO. J Electron Spectrosc Relat Phenom 104:55–60CrossRefGoogle Scholar
  49. 49.
    Lee S-P, Chen Y-W (1999) Selective hydrogenation of furfural on Ni–P, Ni–B, and Ni–P–B ultrafine materials. Ind Eng Chem Res 38:2548–2556CrossRefGoogle Scholar
  50. 50.
    Liang C, Ding L, Li C, Pang M, Su D, Li W, Wang Y (2010) Nanostructured WCx/CNTs as highly efficient support of electrocatalysts with low Pt loading for oxygen reduction reaction. Energy Environ Sci 3:1121–1127CrossRefGoogle Scholar
  51. 51.
    Aricò AS, Shukla AK, Kim H, Park S, Min M, Antonucci V (2001) An XPS study on oxidation states of Pt and its alloys with Co and Cr and its relevance to electroreduction of oxygen. Appl Surf Sci 172:33–40CrossRefGoogle Scholar
  52. 52.
    Eberhardt WE, Fayet P, Cox DM, Fu Z, Kalder A, Sherwood R, Sondericker D (1990) Photoemission from mass-selected monodispersed Pt clusters. Phys Rev Lett 64:780CrossRefGoogle Scholar
  53. 53.
    Igarashi H, Fujino T, Zhu Y, Uchida H, Watanabe M (2001) CO tolerance of Pt alloy electrocatalysts for polymer electrolyte fuel cells and the detoxification mechanism. Phys Chem Chem Phys 3:306–314CrossRefGoogle Scholar
  54. 54.
    Poh CK, Tian Z, Gao J, Liu Z, Lin J, Feng YP, Su F (2012) Nanostructured trimetallic Pt/FeRuC, Pt/NiRuC, and Pt/CoRuC catalysts for methanol electrooxidation. J Mater Chem 22:13643–13652CrossRefGoogle Scholar
  55. 55.
    Chen S, Wei Z, Qi XQ, Dong L, Guo Y-G, Wan L, Shao Z, Li L (2012) Nanostructured polyaniline-decorated Pt/C@PANI core–shell catalyst with enhanced durability and activity. J Am Chem Soc 134:13252–13255CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  1. 1.WPI-Advanced Institute for Materials ResearchTohoku UniversitySendaiJapan
  2. 2.School of Chemical EngineeringChina University of Mining and TechnologyXuzhouChina
  3. 3.Institute for Materials ResearchTohoku UniversitySendaiJapan
  4. 4.Faculty of Textile Science and TechnologyShinshu UniversityUedaJapan

Personalised recommendations