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Ionics

, Volume 25, Issue 11, pp 5141–5152 | Cite as

Synthesis and electrocatalytic performance of a P-Mo-V Keggin heteropolyacid modified Ag@Pt/MWCNTs catalyst for oxygen reduction in proton exchange membrane fuel cell

  • Shuping YuEmail author
  • Xiaohong Zhao
  • Guiyang Su
  • Yan Wang
  • Zhongming Wang
  • Kefei Han
  • Hong ZhuEmail author
Original Paper

Abstract

In this study, the Keggin type molybdovanadophosphoric acid (PMo12-xVxO40 (x = 1,2,3), abbreviated as PMoV) modified on Ag@Pt/MWCNTs composite catalysts were successfully prepared by a chemical impregnation method. The results of physical characterization revealed that PMoV molecules were incorporated into the Ag@Pt/MWCNTs structure. The effect of the composite catalyst on oxygen reduction was studied by electrochemical analysis. The catalytic performance of the composite catalyst changed with the change of the number of the substituted vanadium atoms in the heteropolyacid. The PMo10V2 catalyst shows the best activity and stability among the three heteropolyacid-modified catalysts evaluated. When the optimum doping ratio is 20%, the electrochemically active surface area (ECSA) of the composite catalyst is 99.69 m2/gPt, and it is increased by 49.11% compared with commercial Pt/C catalysts (65.63 m2/gPt). The initial reduction potential of the composite catalyst is 0.968 V, which is shifted by 73 mV compared with the 20% Pt/C catalyst. Additionally, the mechanism of catalytic reaction is also investigated.

Keywords

Heteropolyacid PMoV Platinum catalyst Oxygen reduction reaction PEMFC 

Notes

Acknowledgments

The authors gratefully acknowledge the financial supports from the National Natural Science Foundation of China (Nos. 21176022, 21176023, 21276021, and 21376022), the International S&T Cooperation Program of China (No.2013DFA51860), the National High Technology Research and Development Program of China (No. 2011AA11A273), the Program for Changjiang Scholars and Innovative Research Team in University (IRT1205), and the Fundamental Research Funds for the Central Universities (YS1406).

References

  1. 1.
    Shao M, Chang Q, Dodelet JP, Chenitz R (2016) Recent advances in electrocatalysts for oxygen reduction reaction. Chem Rev 116:3594–3657.  https://doi.org/10.1021/acs.chemrev.5b00462 CrossRefPubMedGoogle Scholar
  2. 2.
    Hasnat MA, Ben Aoun S, Nizam Uddin SM, Alam MM, Koay PP, Amertharaj S, Rashed MA, Rahman MM, Mohamed N (2014) Copper-immobilized platinum electrocatalyst for the effective reduction of nitrate in a low conductive medium: mechanism, adsorption thermodynamics and stability. Appl Catal A Gen 478:259–266.  https://doi.org/10.1016/j.apcata.2014.04.017 CrossRefGoogle Scholar
  3. 3.
    Li B, Higgins DC, Xiao Q, Yang D, Zhng C, Cai M, Chen Z, Ma J (2015) The durability of carbon supported Pt nanowire as novel cathode catalyst for a 1.5 kW PEMFC stack. Appl Catal B Environ 162:133–140.  https://doi.org/10.1016/j.apcatb.2014.06.040 CrossRefGoogle Scholar
  4. 4.
    Pech-Pech IE, Gervasio DF, Godínez-Garcia A, Solorza-Feria O, Pérez-Robles JF (2015) Nanoparticles of ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: part 1. J Power Sources 276:365–373.  https://doi.org/10.1016/j.jpowsour.2014.09.112 CrossRefGoogle Scholar
  5. 5.
    Wang R, Higgins DC, Prabhudev S, Lee DU, Choi JY, Hoque MA, Botton GA, Chen Z (2015) Synthesis and structural evolution of Pt nanotubular skeletons: revealing the source of the instability of nanostructured electrocatalysts. J Mater Chem A 3:12663–12671.  https://doi.org/10.1039/c5ta01503k CrossRefGoogle Scholar
  6. 6.
    Yu S, Liu R, Yang W, Han K, Wang Z, Zhu H (2014) Synthesis and electrocatalytic performance of MnO2-promoted ag@Pt/MWCNT electrocatalysts for oxygen reduction reaction. J Mater Chem A 2:5371–5378.  https://doi.org/10.1039/c3ta14564f CrossRefGoogle Scholar
  7. 7.
    Bhorodwaj SK, Dutta DK (2011) Activated clay supported heteropoly acid catalysts for esterification of acetic acid with butanol. Appl Clay Sci 53:347–352.  https://doi.org/10.1016/j.clay.2011.01.019 CrossRefGoogle Scholar
  8. 8.
    Han X-X, Chen KK, Yan W, Hung CT, Liu LL, Wu PH, Lin KC, Liu SB (2016) Amino acid-functionalized heteropolyacids as efficient and recyclable catalysts for esterification of palmitic acid to biodiesel. Fuel 165:115–122.  https://doi.org/10.1016/j.fuel.2015.10.027 CrossRefGoogle Scholar
  9. 9.
    Sun Z, Wang S, Wang X, Jiang Z (2016) Lysine functional heteropolyacid nanospheres as bifunctional acid–base catalysts for cascade conversion of glucose to levulinic acid. Fuel 164:262–266.  https://doi.org/10.1016/j.fuel.2015.10.014 CrossRefGoogle Scholar
  10. 10.
    Yuan B, Li Y, Wang Z, Yu F, Xie C, Yu S (2017) A novel Brønsted-Lewis acidic catalyst based on heteropoly phosphotungstates: synthesis and catalysis in benzylation of p-xylene with benzyl alcohol. Mol Catal 443:110–116.  https://doi.org/10.1016/j.mcat.2017.10.003 CrossRefGoogle Scholar
  11. 11.
    Han X, Chen K, du H, Tang XJ, Hung CT, Lin KC, Liu SB (2016) Novel Keggin-type H4PVMo11O40 -based ionic liquid catalysts for n-caprylic acid esterification. J Taiwan Inst Chem Eng 58:203–209.  https://doi.org/10.1016/j.jtice.2015.07.005 CrossRefGoogle Scholar
  12. 12.
    Feyzi M, Nourozi L, Zakarianezhad M (2014) Preparation and characterization of magnetic CsH2PW12O40/Fe–SiO2 nanocatalysts for biodiesel production. Mater Res Bull 60:412–420.  https://doi.org/10.1016/j.materresbull.2014.09.005 CrossRefGoogle Scholar
  13. 13.
    Tang S, She J, Fu Z, Zhang S, Tang Z, Zhang C, Liu Y, Yin D, Li J (2017) Study on the formation of photoactive species in XPMo12-n Vn O40 - HCl system and its effect on photocatalysis oxidation of cyclohexane by dioxygens under visible light irradiation. Appl Catal B Environ 214:89–99.  https://doi.org/10.1016/j.apcatb.2017.05.027 CrossRefGoogle Scholar
  14. 14.
    Fakhri H, Mahjoub AR, Aghayan H (2017) Effective removal of methylene blue and cerium by a novel pair set of heteropoly acids based functionalized graphene oxide: adsorption and photocatalytic study. Chem Eng Res Des 120:303–315.  https://doi.org/10.1016/j.cherd.2017.02.030 CrossRefGoogle Scholar
  15. 15.
    Li Y, Huang T, Wu Q, Xu L (2015) Synthesis and conductive performance of quaternary molybdotungstovanadophosphoric heteropoly acid with Keggin structure. Mater Lett 157:109–111.  https://doi.org/10.1016/j.matlet.2015.05.026 CrossRefGoogle Scholar
  16. 16.
    Fernandes DM, Freire C (2015) Carbon nanomaterial-phosphomolybdate composites for oxidative electrocatalysis. ChemElectroChem 2:269–279.  https://doi.org/10.1002/celc.201402271 CrossRefGoogle Scholar
  17. 17.
    Vijayalekshmi V, Khastgir D (2018) Fabrication and comprehensive investigation of physicochemical and electrochemical properties of chitosan-silica supported silicotungstic acid nanocomposite membranes for fuel cell applications. Energy 142:313–330.  https://doi.org/10.1016/j.energy.2017.10.019 CrossRefGoogle Scholar
  18. 18.
    Li Y, Wang H, Wu Q, Xu X, Lu S, Xiang Y (2017) A poly(vinyl alcohol)-based composite membrane with immobilized phosphotungstic acid molecules for direct methanol fuel cells. Electrochim Acta 224:369–377.  https://doi.org/10.1016/j.electacta.2016.12.076 CrossRefGoogle Scholar
  19. 19.
    Oh SY, Yoshida T, Kawamura G, Muto H, Sakai M, Matsuda A (2010) Proton conductivity and fuel cell property of composite electrolyte consisting of Cs-substituted heteropoly acids and sulfonated poly(ether–ether ketone). J Power Sources 195:5822–5828.  https://doi.org/10.1016/j.jpowsour.2010.01.063 CrossRefGoogle Scholar
  20. 20.
    Lu S, Wu C, Liang D, Tan Q, Xiang Y (2014) Layer-by-layer self-assembly of Nafion–[CS–PWA] composite membranes with suppressed vanadium ion crossover for vanadium redox flow battery applications. RSC Adv 4:24831–24837.  https://doi.org/10.1039/c4ra01775g CrossRefGoogle Scholar
  21. 21.
    Tang H, Pan M, Lu S, Lu J, Jiang SP (2010) One-step synthesized HPW/meso-silica inorganic proton exchange membranes for fuel cells. Chem Commun (Camb) 46:4351–4353.  https://doi.org/10.1039/c003129a CrossRefGoogle Scholar
  22. 22.
    Qian W, Shang Y, Wang S, Xie X, Mao Z (2013) Phosphoric acid doped composite membranes from poly (2,5-benzimidazole) (ABPBI) and CsxH3−xPW12O40/CeO2 for the high temperature PEMFC. Int J Hydrog Energy 38:11053–11059.  https://doi.org/10.1016/j.ijhydene.2013.03.039 CrossRefGoogle Scholar
  23. 23.
    Zhang B, Cao Y, Li Z, Wu H, Yin Y, Cao L, He X, Jiang Z (2017) Proton exchange nanohybrid membranes with high phosphotungstic acid loading within metal-organic frameworks for PEMFC applications. Electrochim Acta 240:186–194.  https://doi.org/10.1016/j.electacta.2017.04.087 CrossRefGoogle Scholar
  24. 24.
    Malers JL, Sweikart M-A, Horan JL, Turner JA, Herring AM (2007) Studies of heteropoly acid/polyvinylidenedifluoride–hexafluoroproylene composite membranes and implication for the use of heteropoly acids as the proton conducting component in a fuel cell membrane. J Power Sources 172:83–88.  https://doi.org/10.1016/j.jpowsour.2007.02.009 CrossRefGoogle Scholar
  25. 25.
    Amirinejad M, Madaeni SS, Lee KS, Ko U, Rafiee E, Lee JS (2012) Sulfonated poly(arylene ether)/heteropolyacids nanocomposite membranes for proton exchange membrane fuel cells. Electrochim Acta 62:227–233.  https://doi.org/10.1016/j.electacta.2011.12.025 CrossRefGoogle Scholar
  26. 26.
    Kim K, Han J-I (2015) Heteropolyacids as anode catalysts in direct alkaline sulfide fuel cell. Int J Hydrog Energy 40:2979–2983.  https://doi.org/10.1016/j.ijhydene.2015.01.011 CrossRefGoogle Scholar
  27. 27.
    Wang D, Lu S, Jiang SP (2010) Pd/HPW-PDDA-MWCNTs as effective non-Pt electrocatalysts for oxygen reduction reaction of fuel cells. Chem Commun (Camb) 46:2058–2060.  https://doi.org/10.1039/b927375a CrossRefGoogle Scholar
  28. 28.
    Ensafi AA, Heydari-Soureshjani E, Jafari-Asl M, Rezaei B (2016) Polyoxometalate-decorated graphene nanosheets and carbon nanotubes, powerful electrocatalysts for hydrogen evolution reaction. Carbon 99:398–406.  https://doi.org/10.1016/j.carbon.2015.12.045 CrossRefGoogle Scholar
  29. 29.
    Guo ZP, Han DM, Wexler D, Zeng R, Liu HK (2008) Polyoxometallate-stabilized platinum catalysts on multi-walled carbon nanotubes for fuel cell applications. Electrochim Acta 53:6410–6416.  https://doi.org/10.1016/j.electacta.2008.04.050 CrossRefGoogle Scholar
  30. 30.
    Kourasi M, Wills RGA, Shah AA, Walsh FC (2014) Heteropolyacids for fuel cell applications. Electrochim Acta 127:454–466.  https://doi.org/10.1016/j.electacta.2014.02.006 CrossRefGoogle Scholar
  31. 31.
    Matsui T, Morikawa E, Nakada S, Okanishi T, Muroyama H, Hirao Y, Takahashi T, Eguchi K (2016) Polymer electrolyte fuel cells employing heteropolyacids as redox mediators for oxygen reduction reactions: Pt-free cathode systems. ACS Appl Mater Interfaces 8:18119–18125.  https://doi.org/10.1021/acsami.6b05202 CrossRefPubMedGoogle Scholar
  32. 32.
    Feng L, Lv Q, Sun X, Yao S, Liu C, Xing W (2012) Enhanced activity of molybdovanadophosphoric acid modified Pt electrode for the electrooxidation of methanol. J Electroanal Chem 664:14–19.  https://doi.org/10.1016/j.jelechem.2011.10.006 CrossRefGoogle Scholar
  33. 33.
    Cui Z, Xing W, Liu C, Tian D, Zhang H (2010) Synthesis and characterization of H5PMo10V2O40 deposited Pt/C nanocatalysts for methanol electrooxidation. J Power Sources 195:1619–1623.  https://doi.org/10.1016/j.jpowsour.2009.09.040 CrossRefGoogle Scholar
  34. 34.
    Arichi J, Pereira MM, Esteves PM, Louis B (2010) Synthesis of Keggin-type polyoxometalate crystals. Solid State Sci 12:1866–1869.  https://doi.org/10.1016/j.solidstatesciences.2010.01.022 CrossRefGoogle Scholar
  35. 35.
    Yu S, Lou Q, Han K, Wang Z, Zhu H (2012) Synthesis and electrocatalytic performance of MWCNT-supported Ag@Pt core–shell nanoparticles for ORR. Int J Hydrog Energy 37:13365–13370.  https://doi.org/10.1016/j.ijhydene.2012.06.109 CrossRefGoogle Scholar
  36. 36.
    Yu S, Wang Y, Zhu H, Wang Z, Han K (2016) Synthesis and electrocatalytic performance of phosphotungstic acid-modified ag@Pt/MWCNTs catalysts for oxygen reduction reaction. J Appl Electrochem 46:917–928.  https://doi.org/10.1007/s10800-016-0976-7 CrossRefGoogle Scholar
  37. 37.
    Cai Y, Gao P, Wang F, Zhu H (2017) Surface tuning of carbon supported chemically ordered nanoparticles for promoting their catalysis toward the oxygen reduction reaction. Electrochim Acta 246:671–679.  https://doi.org/10.1016/j.electacta.2017.05.068 CrossRefGoogle Scholar
  38. 38.
    Wang D, Lu S, Xiang Y, Jiang SP (2011) Self-assembly of HPW on Pt/C nanoparticles with enhanced electrocatalysis activity for fuel cell applications. Appl Catal B Environ 103:311–317.  https://doi.org/10.1016/j.apcatb.2011.01.037 CrossRefGoogle Scholar
  39. 39.
    Song J, Bazant MZ (2013) Effects of nanoparticle geometry and size distribution on diffusion impedance of battery electrodes. J Electrochem Soc 160:A15–A24.  https://doi.org/10.1149/2.023301jes CrossRefGoogle Scholar
  40. 40.
    Bassam El Ali AMEG, Fettouhi M (2001) H3+nPMo12-nVnO40-catalyzed selective oxidation of benzoins to benzils or aldehydes and esters by dioxygen. J Mol Catal A Chem 165:283–290CrossRefGoogle Scholar
  41. 41.
    Yan Z, Zhang M, Xie J, Zhu J, Shen PK (2015) A bimetallic carbide Fe2MoC promoted Pd electrocatalyst with performance superior to Pt/C towards the oxygen reduction reaction in acidic media. Appl Catal B Environ 165:636–641.  https://doi.org/10.1016/j.apcatb.2014.10.070 CrossRefGoogle Scholar
  42. 42.
    Yeager E (1986) Dioxygen electrocatalysis: mechanisms in relation to catalyst structure. J Mol Catal 38:5–25.  https://doi.org/10.1016/0304-5102(86)87045-6 CrossRefGoogle Scholar
  43. 43.
    Adzic R (1996) Recent advances in the kinetics of oxygen reduction. N Y J Math 17:683–697.  https://doi.org/10.2172/259357 CrossRefGoogle Scholar
  44. 44.
    Yang F, Hou Y, Niu M, Lu T, Wu W, Liu Z (2017) Catalytic oxidation of lignite to carboxylic acids in aqueous H5PV2Mo10O40/H2SO4 solution with molecular oxygen. Energy Fuel 31:3830–3837.  https://doi.org/10.1021/acs.energyfuels.6b03479 CrossRefGoogle Scholar
  45. 45.
    Gunn NLO, Ward DB, Menelaou C, Herbert MA, Davies TJ (2017) Investigation of a chemically regenerative redox cathode polymer electrolyte fuel cell using a phosphomolybdovanadate polyoxoanion catholyte. J Power Sources 348:107–117.  https://doi.org/10.1016/j.jpowsour.2017.02.048 CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.State Key Laboratory of Chemical Resource EngineeringBeijing University of Chemical TechnologyBeijingChina

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