Enhanced catalytic activity of ternary Pd-Ni-Ir nanoparticles supported on carbon toward formic acid electro-oxidation

Original Paper


Aiming to further promote the performance of PdNi for formic acid electro-oxidation (FAEO), ternary Pd-Ni-Ir/C nanocatalyst was synthesized via an ethylene glycol-assisted NaBH4 reduction process. The physical characterizations show that the PdNiIr nanoparticles with a small mean size are well dispersed on carbon support. The electrochemical measurements demonstrate that the PdNiIr/C catalyst exhibits the highest activity for FAEO. The onset and peak potential of FAEO on PdNiIr/C is about 70 mV more negative than that on the Pd/C and PdNi/C catalysts. The mass activity of Pd in PdNiIr/C at 0.14 V is 2830 mA mg−1Pd, which is about 1.65, 1.82, and 2.2 times as high as that of PdIr/C, PdNi/C, and Pd/C, respectively. The enhancement should be attributed to the electronic effect and bi-functional mechanism.


Formic acid Electro-oxidation Nanoparticles PdNiIr/C catalyst 



This work is supported by the Key Research and Development Projects in Sichuan Province (2017GZ0397), the Science and Technology Project of Chengdu (2015-HM01-00531-SF), the National Natural Science Foundation of China (21306119), and the Outstanding Young Scientist Foundation of Sichuan University (2013SCU04A23).


  1. 1.
    Yu X, Pickup PG (2008) Recent advances in direct formic acid fuel cells (DFAFC). J Power Sources 182(1):124–132.  https://doi.org/10.1016/j.jpowsour.2008.03.075 CrossRefGoogle Scholar
  2. 2.
    Rees NV, Compton RG (2011) Sustainable energy: a review of formic acid electrochemical fuel cells. J Solid State Electr 15(10):2095–2100.  https://doi.org/10.1007/s10008-011-1398-4 CrossRefGoogle Scholar
  3. 3.
    Zhang L, Choi S-I, Tao J, Peng H-C, Xie S, Zhu Y, Xie Z, Xia Y (2014) Pd-Cu bimetallic tripods: a mechanistic understanding of the synthesis and their enhanced electrocatalytic activity for formic acid oxidation. Adv Funct Mater 24(47):7520–7529.  https://doi.org/10.1002/adfm.201402350 CrossRefGoogle Scholar
  4. 4.
    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(1):122–126.  https://doi.org/10.1002/anie.201308620 CrossRefGoogle Scholar
  5. 5.
    Yang S, Chung DY, Tak Y-J, Kim J, Han H, Yu J-S, Soon A, Sung Y-E, Lee H (2015) Electronic structure modification of platinum on titanium nitride resulting in enhanced catalytic activity and durability for oxygen reduction and formic acid oxidation. Appl Catal Environ 174:35–42CrossRefGoogle Scholar
  6. 6.
    Chen J, Li Y, Gao Z, Wang G, Tian J, Jiang C, Zhu S, Wang R (2013) Ultrahigh activity of Pd decorated Ir/C catalyst for formic acid electro-oxidation. Electrochem Commun 37:24–27.  https://doi.org/10.1016/j.elecom.2013.10.001 CrossRefGoogle Scholar
  7. 7.
    Liang X, Liu B, Zhang J, Lu S, Zhuang Z (2016) Ternary Pd-Ni-P hybrid electrocatalysts derived from Pd-Ni core-shell nanoparticles with enhanced formic acid oxidation activity. Chem Commun 52(74):11143–11146.  https://doi.org/10.1039/C6CC04382H CrossRefGoogle Scholar
  8. 8.
    Gunji T, Noh SH, Tanabe T, Han B, Nien CY, Ohsaka T, Matsumoto F (2017) Enhanced electrocatalytic activity of carbon-supported ordered intermetallic palladium-lead (Pd3Pb) nanoparticles toward electrooxidation of formic acid. Chem Mater 29(7):2906–2913.  https://doi.org/10.1021/acs.chemmater.6b05191 CrossRefGoogle Scholar
  9. 9.
    Zhao R, Liu Z, Gong M, Zhang Q, Shi X, Hu Y, Qi W, Tang Y, Wang Y (2017) Ethylenediamine tetramethylene phosphonic acid assisted synthesis of palladium nanocubes and their electrocatalysis of formic acid oxidation. J Solid State Electr 21(5):1297–1303.  https://doi.org/10.1007/s10008-016-3470-6 CrossRefGoogle Scholar
  10. 10.
    Xi Z, Erdosy DP, Mendoza-Garcia A, Duchesne PN, Li J, Muzzio M, Li Q, Zhang P, Sun S (2017) Pd nanoparticles coupled to WO2.72 nanorods for enhanced electrochemical oxidation of formic acid. Nano Lett 17(4):2727–2731.  https://doi.org/10.1021/acs.nanolett.7b00870 CrossRefGoogle Scholar
  11. 11.
    Liu H, Yu Y, Yang W, Lei W, Gao M, Guo S (2017) High-density defects on PdAg nanowire networks as catalytic hot spots for efficient dehydrogenation of formic acid and reduction of nitrate. Nanoscale 9(27):9305–9309CrossRefGoogle Scholar
  12. 12.
    Maringa A, Mashazi P, Nyokong T (2015) Electrocatalytic activity of bimetallic Au-Pd nanoparticles in the presence of cobalt tetraaminophthalocyanine. J Colloid Interface Sci 440:151–161.  https://doi.org/10.1016/j.jcis.2014.10.056 CrossRefGoogle Scholar
  13. 13.
    Li X, Wei J, Chai Y, Zhang S (2015) Carbon nanotubes/tin oxide nanocomposite-supported Pt catalysts for methanol electro-oxidation. J Colloid Interface Sci 450:74–81.  https://doi.org/10.1016/j.jcis.2015.02.072 CrossRefGoogle Scholar
  14. 14.
    Ma J, Wang L, Mu X, Cao Y (2015) Enhanced electrocatalytic activity of Pt naonoparticles supported on functionalized graphene for methanol oxidation and oxygen reduction. J Colloid Interface Sci 457:102–107.  https://doi.org/10.1016/j.jcis.2015.06.031 CrossRefGoogle Scholar
  15. 15.
    Matos J, Borodzinski A, Zychora AM, Kedzierzawski P, Mierzwa B, Juchniewicz K, Mazurkiewicz M, Hernandez-Garrido JC (2015) Direct formic acid fuel cells on Pd catalysts supported on hybrid TiO2-C materials. Appl Catal Environ 163:167–178.  https://doi.org/10.1016/j.apcatb.2014.07.063 CrossRefGoogle Scholar
  16. 16.
    Huayu Q, Huajie H, Xin W (2015) Design and synthesis of palladium/graphitic carbon nitride/carbon black hybrids as high-performance catalysts for formic acid and methanol electrooxidation. J Power Sources 275:734–741CrossRefGoogle Scholar
  17. 17.
    Chen J, Wang G, Wang X, Yang X, Zhu S, Wang R (2013) Effect of NaBH4 concentration and synthesis temperature on the performance of Pd/C catalyst for formic acid electro-oxidation. Mater Express 3(2):176–180.  https://doi.org/10.1166/mex.2013.1109 CrossRefGoogle Scholar
  18. 18.
    Chen L, Guo H, Fujita T, Hirata A, Zhang W, Inoue A, Chen M (2011) Nanoporous PdNi bimetallic catalyst with enhanced electrocatalytic performances for electro-oxidation and oxygen reduction reactions. Adv Funct Mater 21(22):4364–4370.  https://doi.org/10.1002/adfm.201101227 CrossRefGoogle Scholar
  19. 19.
    She Y, Lu Z, Fan W, Jewell S, Leung MKH (2014) Facile preparation of PdNi/rGO and its electrocatalytic performance towards formic acid oxidation. J Mater Chem A 2(11):3894–3898.  https://doi.org/10.1039/c3ta14546h CrossRefGoogle Scholar
  20. 20.
    Hosseini H, Mahyari M, Bagheri A, Shaabani A (2014) Pd and PdCo alloy nanoparticles supported on polypropylenimine dendrimer-grafted graphene: a highly efficient anodic catalyst for direct formic acid fuel cells. J Power Sources 247:70–77.  https://doi.org/10.1016/j.jpowsour.2013.08.061 CrossRefGoogle Scholar
  21. 21.
    Feng A, Bai J, Shao W, Hong W, Tian Z-Q, Xiao Z (2017) Surfactant-free Pd-Fe nanoparticles supported on reduced graphene oxide as nanocatalyst for formic acid oxidation. Inter J Hydrogen Energy 42(22):15196–15202.  https://doi.org/10.1016/j.ijhydene.2017.04.278 CrossRefGoogle Scholar
  22. 22.
    Matin MA, Jang J-H, Kwon Y-U (2014) PdM nanoparticles (M = Ni, Co, Fe, Mn) with high activity and stability in formic acid oxidation synthesized by sonochemical reactions. J Power Sources 262:356–363.  https://doi.org/10.1016/j.jpowsour.2014.03.109 CrossRefGoogle Scholar
  23. 23.
    Zhang LY, Liu Z (2017) Graphene decorated with Pd4Ir nanocrystals: ultrasound-assisted synthesis, and application as a catalyst for oxidation of formic acid. J Colloid Interface Sci 505:783–788.  https://doi.org/10.1016/j.jcis.2017.06.084 CrossRefGoogle Scholar
  24. 24.
    Wang X, Tang Y, Gao Y, Lu T (2008) Carbon-supported Pd-Ir catalyst as anodic catalyst in direct formic acid fuel cell. J Power Sources 175(2):784–788.  https://doi.org/10.1016/j.jpowsour.2007.10.011 CrossRefGoogle Scholar
  25. 25.
    Cai J, Zeng Y, Guo Y (2014) Copper@palladium-copper core-shell nanospheres as a highly effective electrocatalyst for ethanol electro-oxidation in alkaline media. J Power Sources 270:257–261.  https://doi.org/10.1016/j.jpowsour.2014.07.131 CrossRefGoogle Scholar
  26. 26.
    Shen L, Li H, Lu L, Luo Y, Tang Y, Chen Y, Lu T (2013) Improvement and mechanism of electrocatalytic performance of Pd-Ni/C anodic catalyst in direct formic acid fuel cell. Electrochim Acta 89:497–502.  https://doi.org/10.1016/j.electacta.2012.10.077 CrossRefGoogle Scholar
  27. 27.
    Ding K, Liu L, Cao Y, Yan X, Wei H, Guo Z (2014) Formic acid oxidation reaction on a PdxNiy bimetallic nanoparticle catalyst prepared by a thermal decomposition process using ionic liquids as the solvent. Inter J Hydrogen Energy 39(14):7326–7337.  https://doi.org/10.1016/j.ijhydene.2014.03.026 CrossRefGoogle Scholar
  28. 28.
    Zhang J-M, Wang R-X, Nong R-J, Li Y, Zhang X-J, Zhang P-Y, Fan YJ (2017) Hydrogen co-reduction synthesis of PdPtNi alloy nanoparticles on carbon nanotubes as enhanced catalyst for formic acid electrooxidation. Inter J Hydrogen Energy 42(10):7226–7234.  https://doi.org/10.1016/j.ijhydene.2016.05.198 CrossRefGoogle Scholar
  29. 29.
    Chen J, Jiang C, Yang X, Feng L, Gallogly EB, Wang R (2011) Studies on how to obtain the best catalytic activity of Pt/C catalyst by three reduction routes for methanol electro-oxidation. Electrochem Commun 13(4):314–316.  https://doi.org/10.1016/j.elecom.2011.01.012 CrossRefGoogle Scholar
  30. 30.
    Chen J, Wang G, Wang X, Jiang C, Zhu S, Wang R (2013) Synthesis of highly dispersed Pd nanoparticles with high activity for formic acid electro-oxidation. J Mater Res 28(12):1553–1558.  https://doi.org/10.1557/jmr.2013.137 CrossRefGoogle Scholar
  31. 31.
    Antolini E, Cardellini F (2001) Formation of carbon supported PtRu alloys: an XRD analysis. J Alloys Compd 315(1–2):118–122.  https://doi.org/10.1016/S0925-8388(00)01260-3 CrossRefGoogle Scholar
  32. 32.
    Wang X-M, Xia Y-Y (2009) Synthesis, characterization and catalytic activity of an ultrafine Pd/C catalyst for formic acid electrooxidation. Electrochim Acta 54(28):7525–7530.  https://doi.org/10.1016/j.electacta.2009.08.007 CrossRefGoogle Scholar
  33. 33.
    Shen S, Zhao TS, Xu J, Li Y (2011) High performance of a carbon supported ternary PdIrNi catalyst for ethanol electro-oxidation in anion-exchange membrane direct ethanol fuel cells. Energy Environ Sci 4(4):1428–1433.  https://doi.org/10.1039/c0ee00579g CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Department of Integrated Traditional Chinese and Western Medicine, West China HospitalSichuan UniversityChengduPeople’s Republic of China
  2. 2.College of Materials Science and EngineeringSichuan UniversityChengduPeople’s Republic of China

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