Nano Research

, Volume 11, Issue 6, pp 3222–3232 | Cite as

One-pot synthesis of Au@Pt star-like nanocrystals and their enhanced electrocatalytic performance for formic acid and ethanol oxidation

  • Yi Peng
  • Lidong LiEmail author
  • Ran Tao
  • Lingyu Tan
  • Mengna Qiu
  • Lin GuoEmail author
Research Article


The current bottleneck facing further developments in fuel cells is the lack of durable electrocatalysts with satisfactory activity. In this study, a simple and fast one-pot wet-chemical method is proposed to synthesize novel Au@Pt star-like bimetallic nanocrystals (Au@Pt SLNCs) with a low Pt/Au ratio of 1:4, which show great electrocatalytic properties and outstanding stability toward the electro-oxidation reactions commonly found in fuel cells. The star-like Au core (90 ± 20 nm) is partially coated with 5 nm Pt nanocluster shells, a morphology which creates a large amount of boundaries and edges, thus tuning the surface electronic structure as demonstrated by X-ray photoelectron spectroscopy and CO-stripping measurements. This promotes excellent electrocatalytic performance towards the formic acid oxidation reaction in acidic media and the ethanol oxidation reaction in alkaline media, compared to commercial Pt or Au@Pt triangular nanoprisms, in which the Au core is fully coated by a Pt shell. Au@Pt SLNCs have the highest current density within the dehydrogenation potential range, needing the least potential to achieve a certain current density as well as the highest long-term stability. Because of the small amount of Pt usage, very fast synthesis, excellent electrocatalytic activity and durability, the proposed Au@Pt SLNCs have a promising practical application in fuel cells.


Au@Pt core–shell nanocrystals electrocatalyst formic acid ethanol oxidation 


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This work was financially supported by the National Natural Science Foundation of China (No. 21273001) and the National Basic Research Program of China (No. 2014CB931802).

Supplementary material

12274_2017_1851_MOESM1_ESM.pdf (1.7 mb)
One-pot synthesis of Au@Pt star-like nanocrystals and their enhanced electrocatalytic performance for formic acid and ethanol oxidation


  1. [1]
    Sharaf, O. Z.; Orhan, M. F. An overview of fuel cell technology: Fundamentals and applications. Renew. Sust. Energ. Rev. 2014, 32, 810–853.CrossRefGoogle Scholar
  2. [2]
    Peng, Y.; Lu, B. Z.; Wang, N.; Li, L. G.; Chen, S. W. Impacts of interfacial charge transfer on nanoparticle electrocatalytic activity towards oxygen reduction. Phys. Chem. Chem. Phys. 2017, 19, 9336–9348.CrossRefGoogle Scholar
  3. [3]
    Stamenkovic, V. R.; Strmcnik, D.; Lopes, P. P.; Markovic, N. M. Energy and fuels from electrochemical interfaces. Nat. Mater. 2017, 16, 57–69.CrossRefGoogle Scholar
  4. [4]
    Sui, S.; Wang, X. Y.; Zhou, X. T.; Su, Y. H.; Riffatc, S.; Liu, C. J. A comprehensive review of Pt electrocatalysts for the oxygen reduction reaction: Nanostructure, activity, mechanism and carbon support in PEM fuel cells. J. Mater. Chem. A 2017, 5, 1808–1825.CrossRefGoogle Scholar
  5. [5]
    Sheng, T.; Xu, Y. F.; Jiang, Y. X.; Huang, L.; Tian, N.; Zhou, Z. Y.; Broadwell, I.; Sun, S. G. Structure design and performance tuning of nanomaterials for electrochemical energy conversion and storage. Acc. Chem. Res. 2016, 49, 2569–2577.CrossRefGoogle Scholar
  6. [6]
    Zhu, C. Z.; Du, D.; Eychmuller, A.; Lin, Y. H. Engineering ordered and nonordered porous noble metal nanostructures: Synthesis, assembly, and their applications in electrochemistry. Chem. Rev. 2015, 115, 8896–8943.CrossRefGoogle Scholar
  7. [7]
    Chen, Y. X.; Heinen, M.; Jusys, Z.; Behm, R. J. Bridgebonded formate: Active intermediate or spectator species in formic acid oxidation on a Pt film electrode? Langmuir 2006, 22, 10399–10408.CrossRefGoogle Scholar
  8. [8]
    Cuesta, A. At least three contiguous atoms are necessary for CO formation during methanol electrooxidation on platinum. J. Am. Chem. Soc. 2006, 128, 13332–13333.CrossRefGoogle Scholar
  9. [9]
    Cuesta, A.; Cabello, G.; Gutiérrez, C.; Osawa, M. Adsorbed formate: The key intermediate in the oxidation of formic acid on platinum electrodes. Phys. Chem. Chem. Phys. 2011, 13, 20091–20095.CrossRefGoogle Scholar
  10. [10]
    Herrero, E.; Fernández-Vega, A.; Feliu, J. M.; Aldaz, A. Poison formation reaction from formic acid and methanol on Pt(111) electrodes modified by irreversibly adsorbed Bi and As. J. Electroanal. Chem. 1993, 350, 73–88.CrossRefGoogle Scholar
  11. [11]
    Sun, S. G.; Clavilier, J. Electrochemical study on the poisoning intermediate formed from methanol dissociation at low index and stepped platinum surfaces. J. Electroanal. Chem. 1987, 236, 95–112.CrossRefGoogle Scholar
  12. [12]
    Wang, S. Y.; Kristian, N.; Jiang, S. P.; Wang, X. Controlled deposition of Pt on Au nanorods and their catalytic activity towards formic acid oxidation. Electrochem. Commun. 2008, 10, 961–964.CrossRefGoogle Scholar
  13. [13]
    Zhang, S.; Shao, Y. Y.; Liao, H. G.; Liu, J.; Aksay, I. A.; Yin, G. P.; Lin, Y. H. Graphene decorated with PtAu alloy nanoparticles: Facile synthesis and promising application for formic acid oxidation. Chem. Mater. 2011, 23, 1079–1081.CrossRefGoogle Scholar
  14. [14]
    Zhang, S.; Shao, Y. Y.; Yin, G. P.; Lin, Y. H. Electrostatic self-assembly of a Pt-around-Au nanocomposite with high activity towards formic acid oxidation. Angew. Chem., Int. Ed. 2010, 49, 2211–2214.CrossRefGoogle Scholar
  15. [15]
    Tian, N.; Zhou, Z. Y.; Sun, S. G.; Ding, Y.; Wang, Z. L. Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electro-oxidation activity. Science 2007, 316, 732–735.CrossRefGoogle Scholar
  16. [16]
    Zhou, Z. Y.; Huang, Z. Z.; Chen, D. J.; Wang, Q.; Tian, N.; Sun, S. G. High-index faceted platinum nanocrystals supported on carbon black as highly efficient catalysts for ethanol electrooxidation. Angew. Chem., Int. Ed. 2010, 49, 411–414.CrossRefGoogle Scholar
  17. [17]
    Colmati, F.; Antolini, E.; Gonzalez, E. R. Effect of temperature on the mechanism of ethanol oxidation on carbon supported Pt, PtRu and Pt3Sn electrocatalysts. J. Power Sources 2006, 157, 98–103.CrossRefGoogle Scholar
  18. [18]
    Dong, L. F.; Gari, R. R. S.; Li, Z.; Craig, M. M.; Hou, S. F. Graphene-supported platinum and platinum-ruthenium nanoparticles with high electrocatalytic activity for methanol and ethanol oxidation. Carbon 2010, 48, 781–787.CrossRefGoogle Scholar
  19. [19]
    Dutta, A.; Mahapatra, S. S.; Datta, J. High performance PtPdAu nano-catalyst for ethanol oxidation in alkaline media for fuel cell applications. Int. J. Hydrogen Energ. 2011, 36, 14898–14906.CrossRefGoogle Scholar
  20. [20]
    Ren, F. F.; Wang, H. W.; Zhai, C. Y.; Zhu, M. S.; Yue, R. R.; Du, Y. K.; Yang, P.; Xu, J. K.; Lu, W. S. Clean method for the synthesis of reduced graphene oxide-supported PtPd alloys with high electrocatalytic activity for ethanol oxidation in alkaline medium. ACS Appl. Mater. Interfaces 2014, 6, 3607–3614.CrossRefGoogle Scholar
  21. [21]
    Shao, M. H.; Peles, A.; Shoemaker, K. Electrocatalysis on platinum nanoparticles: Particle size effect on oxygen reduction reaction activity. Nano Lett. 2011, 11, 3714–3719.CrossRefGoogle Scholar
  22. [22]
    Yang, X. F.; Wang, A. Q.; Qiao, B. T.; Li, J.; Liu, J. Y.; Zhang, T. Single-atom catalysts: A new frontier in heterogeneous catalysis. Acc. Chem. Res. 2013, 46, 1740–1748.CrossRefGoogle Scholar
  23. [23]
    Gan, L.; Rudi, S.; Cui, C. H.; Heggen, M.; Strasser, P. Sizecontrolled synthesis of sub-10 nm PtNi3 alloy nanoparticles and their unusual volcano-shaped size effect on ORR electrocatalysis. Small 2016, 12, 3189–3196.CrossRefGoogle Scholar
  24. [24]
    Valden, M.; Lai, X.; Goodman, D. W. Onset of catalytic activity of gold clusters on titania with the appearance of nonmetallic properties. Science 1998, 281, 1647–1650.CrossRefGoogle Scholar
  25. [25]
    Li, J.; Li, X.; Zhai, H. J.; Wang, L. S. Au20: A tetrahedral cluster. Science 2003, 299, 864–867.CrossRefGoogle Scholar
  26. [26]
    Xia, Y. N.; Xiong, Y. J.; Lim, B.; Skrabalak, S. E. Shapecontrolled synthesis of metal nanocrystals: Simple chemistry meets complex physics? Angew. Chem., Int. Ed. 2009, 48, 60–103.CrossRefGoogle Scholar
  27. [27]
    Chen, M.; Wu, B. H.; Yang, J.; Zheng, N. F. Small adsorbateassisted shape control of Pd and Pt nanocrystals. Adv. Mater. 2012, 24, 862–879.CrossRefGoogle Scholar
  28. [28]
    Wu, J. B.; Yang, H. Platinum-based oxygen reduction electrocatalysts. Acc. Chem. Res. 2013, 46, 1848–1857.CrossRefGoogle Scholar
  29. [29]
    Bai, J.; Fang, C. L.; Liu, Z. H.; Chen, Y. A one-pot gold seed-assisted synthesis of gold/platinum wire nanoassemblies and their enhanced electrocatalytic activity for the oxidation of oxalic acid. Nanoscale 2016, 8, 2875–2880.CrossRefGoogle Scholar
  30. [30]
    Fu, G. T.; Xia, B. Y.; Ma, R. G.; Chen, Y.; Tang, Y. W.; Lee, J. M. Trimetallic PtAgCu@PtCu core@shell concave nanooctahedrons with enhanced activity for formic acid oxidation reaction. Nano Energy 2015, 12, 824–832.CrossRefGoogle Scholar
  31. [31]
    Gong, M. X.; Li, F. M.; Yao, Z. G.; Zhang, S. Q.; Dong, J. W.; Chen, Y.; Tang, Y. W. Highly active and durable platinum-lead bimetallic alloy nanoflowers for formic acid electrooxidation. Nanoscale 2015, 7, 4894–4899.CrossRefGoogle Scholar
  32. [32]
    Li, F. M.; Kang, Y. Q.; Peng, R. L.; Li, S. N.; Xia, B. Y.; Liu, Z. H.; Chen, Y. Sandwich-structured Au@polyallylamine@Pd nanostructures: Tuning the electronic properties of the Pd shell for electrocatalysis. J. Mater. Chem. A 2016, 4, 12020–12024.CrossRefGoogle Scholar
  33. [33]
    Chen, C.; Kang, Y. J.; Huo, Z. Y.; Zhu, Z. W.; Huang, W. Y.; Xin, H. L. L.; Snyder, J. D.; Li, D. G.; Herron, J. A.; Mavrikakis, M. et al. Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces. Science 2014, 343, 1339–1343.CrossRefGoogle Scholar
  34. [34]
    Liu, X. W.; Wang, D. S.; Li, Y. D. Synthesis and catalytic properties of bimetallic nanomaterials with various architectures. Nanotoday 2012, 7, 448–466.CrossRefGoogle Scholar
  35. [35]
    Porter, N. S.; Wu, H.; Quan, Z. W.; Fang, J. Y. Shapecontrol and electrocatalytic activity-enhancement of Pt-based bimetallic nanocrystals. Acc. Chem. Res. 2013, 46, 1867–1877.CrossRefGoogle Scholar
  36. [36]
    Zhang, H.; Jin, M. S.; Xia, Y. N. Enhancing the catalytic and electrocatalytic properties of Pt-based catalysts by forming bimetallic nanocrystals with Pd. Chem. Soc. Rev. 2012, 41, 8035–8049.CrossRefGoogle Scholar
  37. [37]
    Tan, L. Y.; Li, L. D.; Peng, Y.; Guo, L. Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction. Nanotechnology 2015, 26, 505401.CrossRefGoogle Scholar
  38. [38]
    Huang, X. Q.; Zhao, Z. P.; Fan, J. M.; Tan, Y. M.; Zheng, N. F. Amine-assisted synthesis of concave polyhedral platinum nanocrystals having {411} high-index facets. J. Am. Chem. Soc. 2011, 133, 4718–4721.CrossRefGoogle Scholar
  39. [39]
    Xia, B. Y.; Wu, H. B.; Yan, Y.; Lou, X. W.; Wang, X. Ultrathin and ultralong single-crystal platinum nanowire assemblies with highly stable electrocatalytic activity. J. Am. Chem. Soc. 2013, 135, 9480–9485.CrossRefGoogle Scholar
  40. [40]
    Iyyamperumal, R.; Zhang, L.; Henkelman, G.; Crooks, R. M. Efficient electrocatalytic oxidation of formic acid using Au@Pt dendrimer-encapsulated nanoparticles. J. Am. Chem. Soc. 2013, 135, 5521–5524.CrossRefGoogle Scholar
  41. [41]
    Devivaraprasad, R.; Ramesh, R.; Naresh, N.; Kar, T.; Singh, R. K.; Neergat, M. Oxygen reduction reaction and peroxide generation on shape-controlled and polycrystalline platinum nanoparticles in acidic and alkaline electrolytes. Langmuir 2014, 30, 8995–9006.CrossRefGoogle Scholar
  42. [42]
    Higgins, D. C.; Wang, R. Y.; Hoque, M. A.; Zamani, P.; Abureden, S.; Chen, Z. W. Morphology and composition controlled platinum-cobalt alloy nanowires prepared by electrospinning as oxygen reduction catalyst. Nano Energy 2014, 10, 135–143.CrossRefGoogle Scholar
  43. [43]
    Nogami, M.; Koike, R.; Jalem, R.; Kawamura, G.; Yang, Y.; Sasaki, Y. Synthesis of porous single-crystalline platinum nanocubes composed of nanoparticles. J. Phys. Chem. Lett. 2010, 1, 568–571.CrossRefGoogle Scholar
  44. [44]
    Yin, J.; Wang, J. H.; Li, M. R.; Jin, C. Z.; Zhang, T. Iodine ions mediated formation of monomorphic single-crystalline platinum nanoflowers. Chem. Mater. 2012, 24, 2645–2654.CrossRefGoogle Scholar
  45. [45]
    Eustis, S.; El-Sayed, M. A. Why gold nanoparticles are more precious than pretty gold: Noble metal surface plasmon resonance and its enhancement of the radiative and nonradiative properties of nanocrystals of different shapes. Chem. Soc. Rev. 2006, 35, 209–217.CrossRefGoogle Scholar
  46. [46]
    Schrinner, M.; Ballauff, M.; Talmon, Y.; Kauffmann, Y.; Thun, J.; Möller, M.; Breu, J. Single nanocrystals of platinum prepared by partial dissolution of Au-Pt nanoalloys. Science 2009, 323, 617–620.CrossRefGoogle Scholar
  47. [47]
    García-Negrete, C. A.; Rojas, T. C.; Knappett, B. R.; Jefferson, D. A.; Wheatley, A. E. H.; Fernandez, A. Shapedefined nanodimers by tailored heterometallic epitaxy. Nanoscale 2014, 6, 11090–11097.CrossRefGoogle Scholar
  48. [48]
    Wang, D. S.; Li, Y. D. One-pot protocol for Au-based hybrid magnetic nanostructures via a noble-metal-induced reduction process. J. Am. Chem. Soc. 2010, 132, 6280–6281.CrossRefGoogle Scholar
  49. [49]
    Lee, J.; Oh, I.; Hwang, S.; Kwak, J. Scanning tunneling microscopy investigation of silver deposition upon Au(111) in the presence of chloride. Langmuir 2002, 18, 8025–8032.CrossRefGoogle Scholar
  50. [50]
    Li, L. D.; Peng, Y.; Yue, Y. H.; Hu, Y.; Liang, X.; Yin, P. G.; Guo, L. Synthesis of concave gold nanocuboids with high-index facets and their enhanced catalytic activity. Chem. Commun. 2015, 51, 11591–11594.CrossRefGoogle Scholar
  51. [51]
    Wang, L.; Yamauchi, Y. Autoprogrammed synthesis of triple-layered Au@Pd@Pt core–shell nanoparticles consisting of a Au@Pd bimetallic core and nanoporous Pt shell. J. Am. Chem. Soc. 2010, 132, 13636–13638.CrossRefGoogle Scholar
  52. [52]
    Personick, M. L.; Langille, M. R.; Zhang, J.; Mirkin, C. A. Shape control of gold nanoparticles by silver underpotential deposition. Nano Lett. 2011, 11, 3394–3398.CrossRefGoogle Scholar
  53. [53]
    Wanjala, B. N.; Luo, J.; Loukrakpam, R.; Fang, B.; Mott, D.; Njoki, P. N.; Engelhard, M.; Naslund, H. R.; Wu, J. K.; Wang, L. C. et al. Nanoscale alloying, phase-segregation, and core–shell evolution of gold-platinum nanoparticles and their electrocatalytic effect on oxygen reduction reaction. Chem. Mater. 2010, 22, 4282–4294.CrossRefGoogle Scholar
  54. [54]
    Chen, S. G.; Wei, Z. D.; Qi, X. Q.; Dong, L. C.; Guo, Y. G.; Wan, L. J.; Shao, Z. G.; Li, L. Nanostructured polyanilinedecorated Pt/C@PANI core–shell catalyst with enhanced durability and activity. J. Am. Chem. Soc. 2012, 134, 13252–13255.CrossRefGoogle Scholar
  55. [55]
    Yang, J.; Ying, J. Y. Nanocomposites of Ag2S and noble metals. Angew. Chem., Int. Ed. 2011, 50, 4637–4643.CrossRefGoogle Scholar
  56. [56]
    Wu, Y.; Wang, D. S.; Chen, X. B.; Zhou, G.; Yu, R.; Li, Y. D. Defect-dominated shape recovery of nanocrystals: A new strategy for trimetallic catalysts. J. Am. Chem. Soc. 2013, 135, 12220–12223.CrossRefGoogle Scholar
  57. [57]
    Wu, J. B.; Qi, L.; You, H. J.; Gross, A.; Li, J.; Yang, H. Icosahedral platinum alloy nanocrystals with enhanced electrocatalytic activities. J. Am. Chem. Soc. 2012, 134, 11880–11883.CrossRefGoogle Scholar
  58. [58]
    Ilayaraja, N.; Prabu, N.; Lakshminarasimhan, N.; Murugan, P.; Jeyakumar, D. Au-Pt graded nano-alloy formation and its manifestation in small organics oxidation reaction. J. Mater. Chem. A 2013, 1, 4048–4056.CrossRefGoogle Scholar
  59. [59]
    Fennell, J.; He, D. S.; Tanyi, A. M.; Logsdail, A. J.; Johnston, R. L.; Li, Z. Y.; Horswell, S. L. A selective blocking method to control the overgrowth of Pt on Au nanorods. J. Am. Chem. Soc. 2013, 135, 6554–6561.CrossRefGoogle Scholar
  60. [60]
    Peng, Z. M.; Yang, H. PtAu bimetallic heteronanostructures made by post-synthesis modification of Pt-on-Au nanoparticles. Nano Res. 2009, 2, 406–415.CrossRefGoogle Scholar
  61. [61]
    Chen, Y. X.; Heinen, M.; Jusys, Z.; Behm, R. J. Kinetics and mechanism of the electrooxidation of formic acid— Spectroelectrochemical studies in a flow cell. Angew. Chem., Int. Ed. 2006, 45, 981–985.CrossRefGoogle Scholar
  62. [62]
    Ge, X. B.; Yan, X. L.; Wang, R. Y.; Tian, F.; Ding, Y. Tailoring the structure and property of Pt-decorated nanoporous gold by thermal annealing. J. Phys. Chem. C 2009, 113, 7379–7384.CrossRefGoogle Scholar
  63. [63]
    Kristian, N.; Yan, Y. S.; Wang, X. Highly efficient submonolayer Pt-decorated Au nano-catalysts for formic acid oxidation. Chem. Commun. 2008, 353–355.Google Scholar
  64. [64]
    Zhang, D. F.; Li, J.; Kang, J. X.; Chen, T. W.; Zhang, Y.; Wang, L. L.; Guo, L. From Pt-rich dendrites to Ni-rich cuboctahedrons: Structural evolution and electrocatalytic property studies. CrystEngComm 2014, 16, 5331–5337.CrossRefGoogle Scholar
  65. [65]
    Xu, J. F.; Liu, X. Y.; Chen, Y.; Zhou, Y. M.; Lu, T. H.; Tang, Y. W. Platinum-cobalt alloy networks for methanol oxidation electrocatalysis. J. Mater. Chem. 2012, 22, 23659–23667.CrossRefGoogle Scholar
  66. [66]
    Zhang, B. W.; Zhang, Z. C.; Liao, H. G.; Gong, Y.; Gu, L.; Qu, X. M.; You, L. X.; Liu, S.; Huang, L.; Tian, X. C. et al. Tuning Pt-skin to Ni-rich surface of Pt3Ni catalysts supported on porous carbon for enhanced oxygen reduction reaction and formic electro-oxidation. Nano Energy 2016, 19, 198–209.CrossRefGoogle Scholar
  67. [67]
    Kim, B. J.; Kwon, K.; Rhee, C. K.; Han, J.; Lim, T. H. Modification of Pt nanoelectrodes dispersed on carbon support using irreversible adsorption of Bi to enhance formic acid oxidation. Electrochim. Acta 2008, 53, 7744–7750.CrossRefGoogle Scholar

Copyright information

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2017

Authors and Affiliations

  1. 1.Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry and EnvironmentBeihang UniversityBeijingChina
  2. 2.Department of Chemistry and BiochemistryUniversity of CaliforniaSanta CruzUSA

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