, Volume 24, Issue 10, pp 3085–3094 | Cite as

Palladium-ytterbium bimetallic electrocatalysts supported on carbon black, titanium suboxide, or poly(diallyldimethylammonium chloride)-functionalized titanium suboxide towards methanol oxidation in alkaline media

  • Yafeng Gong
  • Yinghua He
  • An Li
  • Yi WangEmail author
  • Jiehua LiuEmail author
  • Tao Qi
Original Paper


Palladium-ytterbium (Pd-Yb) bimetallic catalysts with different Pd/Yb ratios supported on carbon black (20%Pd-x%Yb/C, x = 0, 1, 5, 10, and 15) were prepared by a sodium borohydride reduction method. The 20%Pd-5%Yb/C catalyst exhibited the best electrocatalytic activity towards methanol oxidation in alkaline media. The improved electrocatalytic activity and stability of 20%Pd-5%Yb/C can be explained by a bi-functional mechanism. In addition, the higher content of metallic palladium caused by the addition of ytterbium also contributes to the better catalytic activity of the 20%Pd+5%Yb/C catalyst. In view of the good electrocatalytic performance of 20%Pd+5%Yb/C, the 20%Pd+5%Yb catalyst supported on titanium suboxide (20%Pd+5%Yb/Ti4O7) was prepared. However, the Pd-Yb particles supported on Ti4O7 were seriously agglomerated. To improve the dispersion status of alloy particles, the Ti4O7 was functionalized with poly(diallyldimethylammonium chloride) (Ti4O7-PDDA). Electrochemical characterizations showed that no matter Ti4O7 or Ti4O7-PDDA as supports, Pd-Yb catalysts exhibited better catalytic activity than 20%Pd-5%Yb/C. The improvement mainly results from the further increase of metallic Pd due to the presence of Ti4O7.


Pd-Yb/C Electrocatalysts Methanol oxidation Titanium suboxide Poly(diallyldimethylammonium chloride) 


Funding information

The authors are grateful for the financial support by the Key Research Program of Frontier Sciences of Chinese Academy of Sciences (Grant No. QYZDJ-SSW-JSC021), the Chinese National Programs for High Technology Research and Development (2014AA06A513), as well as by the 973 Program (Grant No. 2015CB251303).


  1. 1.
    Li J, Zhu Q-L, Xu Q (2015) Pd nanoparticles supported on hierarchically porous carbons derived from assembled nanoparticles of a zeolitic imidazolate framework (ZIF-8) for methanol electrooxidation. Chem Commun 51:10827–10830CrossRefGoogle Scholar
  2. 2.
    Lee Y-W, Ko AR, Han S-B, Kim H-S, Kim D-Y, Kim S-J, Park K-W (2010) Cuboctahedral Pd nanoparticles on WC for enhanced methanol electrooxidation in alkaline solution. Chem Commun 46:9241–9243CrossRefGoogle Scholar
  3. 3.
    Moon J-S, Lee Y-W, Han S-B, Park K-W (2014) Pd nanoparticles on mesoporous tungsten carbide as a non-Pt electrocatalyst for methanol electrooxidation reaction in alkaline solution. Int J Hydrog Energy 39:7798–7804CrossRefGoogle Scholar
  4. 4.
    Wang H, Xu C, Cheng F, Zhang M, Wang S, Jiang SP (2008) Pd/Pt core–shell nanowire arrays as highly effective electrocatalysts for methanol electrooxidation in direct methanol fuel cells. Electrochem Commun 10:1575–1578CrossRefGoogle Scholar
  5. 5.
    Alcaide F, Alvarez G, Cabot PL, Grande H-J, Miguel O, Querejeta A (2011) Testing of carbon supported Pd–Pt electrocatalysts for methanol electrooxidation in direct methanol fuel cells. Int J Hydrog Energy 36:4432–4439CrossRefGoogle Scholar
  6. 6.
    Lee Y-W, Han S-B, Park K-W (2009) Electrochemical properties of Pd nanostructures in alkaline solution. Electrochem Commun 11:1968–1971CrossRefGoogle Scholar
  7. 7.
    Tang W, Gan L, Wu B, Mao L, Yin D (2015) Carboxymethyl chitosan-assisted uniformly anchored Pd nanoparticles on carbon nanotubes for methanol electrooxidation in alkaline media. Micro Nano Lett 10:119–121CrossRefGoogle Scholar
  8. 8.
    Wang M, Liu W, Huang C (2009) Investigation of PdNiO/C catalyst for methanol electrooxidation. Int J Hydrog Energy 34:2758–2764CrossRefGoogle Scholar
  9. 9.
    Zhou L-N, Zhang X-T, Wang Z-H, Guo S, Li Y-J (2016) Cubic superstructures composed of PtPd alloy nanocubes and their enhanced electrocatalysis for methanol oxidation. Chem Commun 52:12737–12740CrossRefGoogle Scholar
  10. 10.
    Chu Y-Y, Wang Z-B, Jiang Z-Z, Gu D-M, Yin G-P (2012) Facile synthesis of hollow spherical sandwich PtPd/C catalyst by electrostatic self-assembly in polyol solution for methanol electrooxidation. J Power Sources 203:17–25CrossRefGoogle Scholar
  11. 11.
    Li S-S, Lv J-J, Hu Y-Y, Zheng J-N, Chen J-R, Wang A-J, Feng J-J (2014) Facile synthesis of porous Pt–Pd nanospheres supported on reduced graphene oxide nanosheets for enhanced methanol electrooxidation. J Power Sources 247:213–218CrossRefGoogle Scholar
  12. 12.
    Zhu C, Wen D, Oschatz M, Holzschuh M, Liu W, Herrmann A-K, Simon F, Kaskel S, Eychmueller A (2015) Kinetically controlled synthesis of PdNi bimetallic porous nanostructures with enhanced electrocatalytic activity. Small 11:1430–1434CrossRefGoogle Scholar
  13. 13.
    Miao F, Tao B, Chu PK (2012) Preparation and electrochemistry of Pd–Ni/Si nanowire nanocomposite catalytic anode for direct ethanol fuel cell. Dalton Trans 41:5055–5059CrossRefGoogle Scholar
  14. 14.
    Liu Z, Zhang X, Hong L (2009) Physical and electrochemical characterizations of nanostructured Pd/C and PdNi/C catalysts for methanol oxidation. Electrochem Commun 11:925–928CrossRefGoogle Scholar
  15. 15.
    Li R, Mao H, Zhang J, Huang T, Yu A (2013) Rapid synthesis of porous Pd and PdNi catalysts using hydrogen bubble dynamic template and their enhanced catalytic performance for methanol electrooxidation. J Power Sources 241:660–667CrossRefGoogle Scholar
  16. 16.
    Xu H, Yan B, Zhang K, Wang J, Li S, Wang C, Shiraishi Y, Du Y, Yang P (2017) Facile fabrication of novel PdRu nanoflowers as highly active catalysts for the electrooxidation of methanol. J Colloid Interface Sci 505:1–8CrossRefGoogle Scholar
  17. 17.
    Awasthi R, Singh RN (2013) Graphene-supported Pd–Ru nanoparticles with superior methanol electrooxidation activity. Carbon 51:282–289CrossRefGoogle Scholar
  18. 18.
    Awasthi R, Singh RN (2012) Optimization of the Pd–Sn–GNS nanocomposite for enhanced electrooxidation of methanol. Int J Hydrog Energy 37:2103–2110CrossRefGoogle Scholar
  19. 19.
    Li H-H, Zhao S, Gong M, Cui C-H, He D, Liang H-W, Wu L, Yu S-H (2013) Ultrathin PtPdTe nanowires as superior catalysts for methanol electrooxidation. Angew Chem Int Ed 52:7472–7476CrossRefGoogle Scholar
  20. 20.
    Yang Y, Wang L, Li A, Jia Z, Wang Y, Qi T (2015) Novel palladium–yttrium (Pd–Y/C) catalysts for methanol electrooxidation in alkaline media. J Solid State Electrochem 19:923–927CrossRefGoogle Scholar
  21. 21.
    Wang L, Wang Y, Li A, Yang Y, Tang Q, Cao H, Qi T, Li C (2014) Electrocatalysis of carbon black- or poly(diallyldimethylammonium chloride)-functionalized activated carbon nanotubes-supported Pd–Tb towards methanol oxidation in alkaline media. J Power Sources 257:138–146CrossRefGoogle Scholar
  22. 22.
    Nassr ABAA, Quetschke A, Koslowski E, Bron M (2013) Electrocatalytic oxidation of formic acid on Pd/MWCNTs nanocatalysts prepared by the polyol method. Electrochim Acta 102:202–211CrossRefGoogle Scholar
  23. 23.
    Zhao H, Tang Q, Wang Y, Qi T, Wang X (2014) Pd nanoparticles supported on PDDA-functionalized Ti4O7 as an effective catalyst for formic acid electrooxidation. ECS Solid State Lett 3:M37–M40CrossRefGoogle Scholar
  24. 24.
    Zhao H, Wang Y, Tang Q, Wang L, Zhang H, Quan C, Qi T (2014) Pt catalyst supported on titanium suboxide for formic acid electrooxidation reaction. Int J Hydrog Energy 39:9621–9627CrossRefGoogle Scholar
  25. 25.
    Senevirathne K, Hui R, Campbell S, Ye S, Zhang J (2012) Electrocatalytic activity and durability of Pt/NbO2 and Pt/Ti4O7 nanofibers for PEM fuel cell oxygen reduction reaction. Electrochim Acta 59:538–547Google Scholar
  26. 26.
    Li L-L, Liu K-P, Yang G-H, Wang C-M, Zhang J-R, Zhu J-J (2011) Fabrication of graphene-quantum dots composites for sensitive electrogenerated chemiluminescence immunosensing. Adv Funct Mater 21:869–878CrossRefGoogle Scholar
  27. 27.
    Wang Y, Liu H, Wang L, Wang H, Du X, Wang F, Qi T, Lee J-M, Wang X (2013) Pd catalyst supported on a chitosan-functionalized large-area 3D reduced graphene oxide for formic acid electrooxidation reaction. J Mater Chem 1:6839–6848CrossRefGoogle Scholar
  28. 28.
    Wang Y, Wang X, Li CM (2010) Electrocatalysis of Pd–Co supported on carbon black or ball-milled carbon nanotubes towards methanol oxidation in alkaline media. Appl Catal, B 99:229–234CrossRefGoogle Scholar
  29. 29.
    Huang J, Liu Z, He C, Gan LM (2005) Synthesis of PtRu nanoparticles from the hydrosilylation reaction and application as catalyst for direct methanol fuel cell. J Phys Chem B 109:16644–16649CrossRefGoogle Scholar
  30. 30.
    Xu M-W, Gao G-Y, Zhou W-J, Zhang K-F, Li H-L (2008) Novel Pd/β-MnO2 nanotubes composites as catalysts for methanol oxidation in alkaline solution. J Power Sources 175:217–220CrossRefGoogle Scholar
  31. 31.
    Liu J, Ye J, Xu C, Jiang SP, Tong Y (2008) Electro-oxidation of methanol, 1-propanol and 2-propanol on Pt and Pd in alkaline medium. J Power Sources 177:67–70CrossRefGoogle Scholar
  32. 32.
    Mancharan R, Goodenough JB (1992) Methanol oxidation in acid on ordered NiTi. J Mater Chem 2:875–887CrossRefGoogle Scholar
  33. 33.
    Cohen JL, Volpe DJ, Abruna HD (2007) Electrochemical determination of activation energies for methanol oxidation on polycrystalline platinum in acidic and alkaline electrolytes. Phys Chem Chem Phys 9:49–77CrossRefGoogle Scholar
  34. 34.
    Vigier F, Coutanceau C, Hahn F, Belgsir EM, Lamy C (2004) On the mechanism of ethanol electro-oxidation on Pt and PtSn catalysts: electrochemical and in situ IR reflectance spectroscopy studies. J Electroanal Chem 563:81–89CrossRefGoogle Scholar
  35. 35.
    Cui Z, Li CM, Jiang SP (2011) PtRu catalysts supported on heteropolyacid and chitosan functionalized carbon nanotubes for methanol oxidation reaction of fuel cells. Phys Chem Chem Phys 13:16349–16357CrossRefGoogle Scholar
  36. 36.
    Qu W-L, Wang Z-B, Jiang Z-Z, Gu D-M, Yin G-P (2012) Investigation on performance of Pd/Al2O3–C catalyst synthesized by microwave assisted polyol process for electrooxidation of formic acid. RSC Adv 2:344–350CrossRefGoogle Scholar
  37. 37.
    He N, Qin C, Wang R, Ma S, Wang Y, Qi T (2016) Electro-catalysis of carbon black or titanium sub-oxide supported Pd–Gd towards formic acid electro-oxidation. RSC Adv 6:68989–68996CrossRefGoogle Scholar
  38. 38.
    Leonov I, Yaresko AN, Antonov VN, Schwingenschlögl U, Eyert V, Anisimov VI (2006) Charge order and spin-singlet pair formation in Ti4O7. J Phys Condens Matter 18:10955–10964Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Materials Science and EngineeringHefei University of TechnologyHefeiChina
  2. 2.National Engineering Laboratory for Hydrometallurgical Cleaner Production TechnologyInstitute of Process Engineering, Chinese Academy of SciencesBeijingChina
  3. 3.The Experimental High School Attached to Beijing Normal UniversityBeijingChina
  4. 4.Department of Chemical Engineering, College of Petrochemical EngineeringLanzhou University of TechnologyLanzhouChina

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