Skip to main content
SpringerLink
Log in

Uniformly dispersed carbon-supported bimetallic ruthenium–platinum electrocatalysts for the methanol oxidation reaction

  • Original Paper
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Reducing the Pt-based electrocatalysts to sub-nanometer sizes is an effective way to achieve high utilization of noble metals. Herein, we report a successive route to synthesize carbon-supported bimetallic ruthenium–platinum electrocatalysts (Ru–Pt/C) with uniform dispersion and fine sizes. In this strategy, carbon-supported Ru nanoparticles (Ru/C) with a mean size of 1.4 nm are firstly prepared in a mixture of ethylene glycol and water, and the Pt precursors are then reduced in the presence of pre-formed Ru/C. The average diameter of the bimetallic Ru–Pt particles on carbon supports is 1.9 nm, which corresponds to one to two Pt layers deposited on the surface of Ru seeds. The as-prepared bimetallic Ru–Pt/C electrocatalysts are analyzed by the CO stripping voltammetry, a diagnostic electrochemical tool. Compared with the commercial PtRu/C catalyst and the control PtRu/C prepared by a conventional co-reduction method, the bimetallic Ru–Pt/C has higher electrochemical surface area (92.5 m2 g−1) and mass activity (483 A g−1) for methanol oxidation reaction. The strategy reported in this study is effective to produce fine bimetallic Ru–Pt particles (less than 2.0 nm) with uniform dispersion and high activity.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6

Similar content being viewed by others

References

  1. Ehteshami SMM, Chan SH (2013) A review of electrocatalysts with enhanced CO tolerance and stability for polymer electrolyte membarane fuel cells. Electrochim Acta 93:334–345

    Article  Google Scholar 

  2. Cao M, Wu D, Cao R (2014) Recent advances in the stabilization of platinum electrocatalysts for fuel–cell reactions. ChemCatChem 6:26–45

    Article  Google Scholar 

  3. Zeng J, Su F, Lee JY et al (2007) Method for preparing highly dispersed Pt catalysts on mesoporous carbon support. J Mater Sci 42:7197. doi:10.1007/s10853-007-1571-4

    Google Scholar 

  4. Rabis A, Rodriguez P, Schmidt TJ (2012) Electrocatalysis for polymer electrolyte fuel cells: recent achievements and future challenges. ACS Catal 2:864–890

    Article  Google Scholar 

  5. Fu G-T, Ma R-G, Gao X-Q et al (2014) Hydrothermal synthesis of Pt–Ag alloy nano-octahedra and their enhanced electrocatalytic activity for the methanol oxidation reaction. Nanoscale 6:12310–12314

    Article  Google Scholar 

  6. Xiao M, Feng L, Zhu J et al (2015) Rapid synthesis of a PtRu nano-sponge with different surface compositions and performance evaluation for methanol electrooxidation. Nanoscale 7:9467−9471

    Article  Google Scholar 

  7. Cheng Q, Wang L, Jiang Z et al (2015) Shape-controlled porous heterogeneous PtRu/C/Nafion microspheres enabling high performance direct methanol fuel cells. J Mater Chem A 3:15177–15183

    Article  Google Scholar 

  8. Zeng JH, Han XY, Lu D et al (2013) Highly ordered and surfactant-free PtxRuy bimetallic nanocomposites synthesized by electrostatic self assembly for methanol oxidation reaction. Electrochim Acta 112:431–438

    Article  Google Scholar 

  9. Sun Y, Hsieh YC, Chang LC et al (2015) Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes. J Power Sources 277:116–123

    Article  Google Scholar 

  10. Cai Y, Vukmirovic MB, Zhou WP et al (2010) Enhancing oxygen reduction reaction activity via Pd–Au alloy sublayer mediation of Pt monolayer electrocatalysts. J Phys Chem Lett 1:3238–3242

    Article  Google Scholar 

  11. Wang W, Zhao Y, Ding Y (2015) 2D ultrathin core–shell Pd@Pt monolayer nanosheets: defect-mediated thin film growth and enhanced oxygen reduction performance. Nanoscale 7:11934–11939

    Article  Google Scholar 

  12. Koenigsmann C, Santulli AC, Gong K et al (2011) Enhanced electrocatalytic performance of processed, ultrathin, supported Pd–Pt core–shell nanowire catalysts for the oxygen reduction reaction. J Am Chem Soc 133:9783–9795

    Article  Google Scholar 

  13. Zeng JH, Yang J, Lee JY, Zhou WJ (2006) Preparation of carbon-supported core-shell Au–Pt nanoparticles for methanol oxidation reaction: the promotional effect of the Au core. J Phys Chem B 110:24606–24611

    Article  Google Scholar 

  14. Alia SM, Jensen KO, Pivovar BS, Yan Y (2012) Platinum-coated palladium nanotubes as oxygen reduction reaction electrocatalysts. ACS Catal 2:858–863

    Article  Google Scholar 

  15. Chu YY, Wang ZB, Jiang ZZ et al (2012) Facile synthesis of hollow spherical sandwich PtPd/C catalyst by electrostatic self-assembly in polyol solution for methanol electrooxidation. J Power Sources 203:17–25

    Article  Google Scholar 

  16. Nishanth KG, Sridhar P, Pitchumani S (2013) Carbon-supported Pt encapsulated Pd nanostructure as methanol-tolerant oxygen reduction electro-catalyst. Int J Hydrog Energy 38:612–619

    Article  Google Scholar 

  17. Cochell T, Manthiram A (2012) Pt@PdxCuy/C core–shell electrocatalysts for oxygen reduction reaction in fuel cells. Langmuir 28:1579–1587

    Article  Google Scholar 

  18. Sarkar A, Manthiram A (2010) Synthesis of Pt@Cu core-shell nanoparticles by galvanic displacement of Cu by Pt4+ ions and their application as electrocatalysts for oxygen reduction reaction in fuel cells. J Phys Chem C 114:4725–4732

    Article  Google Scholar 

  19. Zhou W, Lee JY (2007) Highly active core–shell Au@Pd catalyst for formic acid electrooxidation. Electrochem Commun 9:1725–1729

    Article  Google Scholar 

  20. Dang D, Liao S, Luo F et al (2014) A pulse electrochemical deposition method to prepare membrane electrode assemblies with ultra-low anode Pt loadings through in situ construction of active core-shell nanoparticles on an electrode. J Power Sources 260:27–33

    Article  Google Scholar 

  21. Dang D, Zou H, Xiong Z et al (2015) High-performance, ultralow platinum membrane electrode assembly fabricated by in situ deposition of a Pt shell layer on carbon-supported Pd nanoparticles in the catalyst layer using a facile pulse electrodeposition approach. ACS Catal 5:4318–4324

    Article  Google Scholar 

  22. Chen D, Li Y, Liao S et al (2015) Ultra-high-performance core-shell structured Ru@Pt/C catalyst prepared by a facile pulse electrochemical deposition method. Sci Rep 5:11604–11612

    Article  Google Scholar 

  23. Hsieh Y-C, Chang L-C, Wu P et al (2011) Displacement reaction of Pt on carbon-supported Ru nanoparticles in hexachloroplatinic acids. Appl Catal B 103:116–127

    Article  Google Scholar 

  24. Alayoglu S, Zavalij P, Eichhorn B et al (2009) Structural and architectural evaluation of bimetallic nanoparticles: acase study of Pt–Ru core–shell and alloy nanoparticles. ACS Nano 3:3127–3137

    Article  Google Scholar 

  25. Zheng Y, Dou Z, Fang Y et al (2016) Platinum nanoparticles on carbon-nanotube support prepared by room-temperature reduction with H2 in ethylene glycol/water mixed solvent as catalysts for polymer electrolyte membrane fuel cells. J Power Sources 306:448–453

    Article  Google Scholar 

  26. Zeng JH, Lee JY (2007) More active PtRu/C catalyst for methanol electrooxidation by reversal of mixing sequence in catalyst preparation. Mater Chem Phys 104:336–341

    Article  Google Scholar 

  27. Zeng JH, Lee JY (2005) Effects of preparation conditions on performance of carbon-supported nanosize Pt–Co catalysts for methanol electro-oxidation under acidic conditions. J Power Sources 140:268–273

    Article  Google Scholar 

  28. de la Ochal P, Fuente JLG, Tsypkin M et al (2011) CO stripping as an electrochemical tool for characterization of Ru@Pt core–shell catalysts. J Electroanal Chem 655:140–146

    Article  Google Scholar 

  29. Muthuswamy N, de la Fuente JLG, Tran D et al (2013) Ru@Pt core–shell nanoparticles for methanol fuel cell catalyst: control and effects of shell composition. Int J Hydrog Energy 38:16631–16641

    Article  Google Scholar 

  30. Li Y, Zheng L, Liao S, Zeng JH (2011) PtRu/C catalysts synthesized by a two-stage polyol reduction process for methanol oxidation reaction. J Power Sources 196:10570–10575

    Article  Google Scholar 

  31. Lee Y-W, Lee J-Y, Kwak D-H et al (2015) Pd@Pt core–shell nanostructures for improved electrocatalytic activity in methanol oxidation reaction. Appl Catal B 179:178–184

    Article  Google Scholar 

  32. Zhang L, Kim J, Zhang J et al (2013) Ti4O7 supported Ru@Pt core–shell catalyst for CO-tolerance in PEM fuel cell hydrogen oxidation reaction. Appl Energy 103:507–513

    Article  Google Scholar 

  33. Che CS, Pan FM (2012) Effects of the PdO nanoflake support on electrocatalytic activity of Pt nanoparticles toward methanol oxidation in acidic solutions. J Power Sources 208:9–17

    Article  Google Scholar 

  34. Chang SH, Su WN, Yeh MH et al (2010) Structural and electronic effects of carbon-supported PtxPd1 − x nanoparticles on the electrocatalytic activity of the oxygen–reduction reaction and on methanol tolerance. Chem Eur J 16:11064–11071

    Article  Google Scholar 

Download references

Acknowledgements

Financial supports from the Key Project on the National Natural Science Foundation-Guangdong Joint Foundation (No.: U1301245), National Natural Science Foundation of China (Nos.: 51572090, 21376247, 21506225, 21573240), Natural Science Foundation of Guangdong Province (No.: 2016A030313484), and Science and Technology Planning Project of Guangdong Province (Nos.: 2014A010105041, 2016A010103028) are gratefully acknowledged.

Author information

Authors and Affiliations

  1. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, 510006, China

    Yuying Zheng, Hengtong Zhan & Yanxiong Fang

  2. Guangdong Key Lab for Fuel Cell Technology, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510641, China

    Jianhuang Zeng & Shijun Liao

  3. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, China

    Hui Liu & Jun Yang

Authors
  1. Yuying Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hengtong Zhan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yanxiong Fang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jianhuang Zeng
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Hui Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jun Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Shijun Liao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Jianhuang Zeng or Jun Yang.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 106 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zheng, Y., Zhan, H., Fang, Y. et al. Uniformly dispersed carbon-supported bimetallic ruthenium–platinum electrocatalysts for the methanol oxidation reaction. J Mater Sci 52, 3457–3466 (2017). https://doi.org/10.1007/s10853-016-0635-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-016-0635-8

Keywords

Search

Navigation