Journal of Solid State Electrochemistry

, Volume 20, Issue 6, pp 1539–1550 | Cite as

Oxygen reduction reaction features in neutral media on glassy carbon electrode functionalized by chemically prepared gold nanoparticles

  • Guillaume Gotti
  • David EvrardEmail author
  • Katia Fajerwerg
  • Pierre Gros
Original Paper


Gold nanoparticles (AuNPs) were prepared by chemical route using four different protocols by varying reducer, stabilizing agent, and solvent mixture. The obtained AuNPs were characterized by transmission electronic microscopy (TEM), UV-visible, and zeta potential measurements. From these latter, surface charge densities σ were calculated to evidence the effect of the solvent mixture on AuNP stability. The AuNPs were then deposited onto glassy carbon (GC) electrodes by drop casting, and the resulting deposits were characterized by cyclic voltammetry (CV) in H2SO4 and field emission gun scanning electron microscopy (FEG-SEM). The electrochemical kinetic parameters of the four different modified electrodes toward oxygen reduction reaction (ORR) in neutral NaCl-NaHCO3 media (0.15 M/0.028 M, pH 7.4) were evaluated by rotating disk electrode voltammetry and subsequent Koutecky-Levich treatment. Contrary to what we previously obtained with electrodeposited AuNPs [Gotti et al., Electrochim. Acta 2014], the highest cathodic transfer coefficients β were not obtained on the smallest particles, highlighting the influence of the stabilizing ligand together with the deposit morphology on the ORR kinetics.


Chemically prepared gold nanoparticles Modified glassy carbon electrode Oxygen reduction reaction Neutral media Koutecky-Levich analysis Electrochemical kinetics Cathodic transfer coefficient Stabilizing ligand influence 



The authors thank the Pôle de Recherche et de l’Enseignement Supérieur (PRES) Toulouse and the Région Midi-Pyrénées for financial support, Dr. Teddy Hezard for his help in MATLAB programming, and Sandrine Desclaux for ζ potential measurements. DE thanks Dr. Martine Meireles and Dr. Yannick Hallez for helpful discussion.


  1. 1.
    Song C, Zhang J (2008) Electrocatalytic oxygen reduction reaction. In: Zhang J (ed) PEM fuel cell electrocatalysts and catalyst layers. Springer, LondonGoogle Scholar
  2. 2.
    Keith JA, Jacob T (2010) Computational simulations on the oxygen reduction reaction in electrochemical systems. Mod Aspect Electroc 50:89–132Google Scholar
  3. 3.
    Koper MTM, Heering HA (2010) Comparison of electrocatalysis and bioelectrocatalysis of hydrogen and oxygen redox reactions. In: Wieckowski A, Norskov JK (eds) Fuel cell science. Theory, fundamentals and biocatalysis. Wiley, HobokenGoogle Scholar
  4. 4.
    Adzic R (1998) Recent advances in the kinetics of oxygen reduction. Wiley VCH, New YorkGoogle Scholar
  5. 5.
    Kazeman I, Hasanzadeh M, Jafarian M, Shadjou N, Khalilzadeh B (2010) Oxygen reduction reaction on a rotating Ag-GC disk electrode in acidic solution. Chin J Chem 28:504–508CrossRefGoogle Scholar
  6. 6.
    Appleby AJ (1993) Electrocatalysis of aqueous dioxygen reduction. J Electroanal Chem 357:117–179CrossRefGoogle Scholar
  7. 7.
    Damjanovic A, Brusic V, Bockris JOM (1967) Mechanism of oxygen reduction related to electronic structure of gold-palladium alloy. J Phys Chem 71:2741–2742CrossRefGoogle Scholar
  8. 8.
    Sawyer DT, Chiericato G Jr, Angelis CT, Nanni EJ Jr, Tsuchiya T (1982) Effects of media and electrode materials on the electrochemical reduction of dioxygen. Anal Chem 54:1720–1724CrossRefGoogle Scholar
  9. 9.
    Yeager E (1984) Electrocatalysts for molecular oxygen reduction. Electrochim Acta 29:1527–1537CrossRefGoogle Scholar
  10. 10.
    Yeager E (1986) Dioxygen electrocatalysis. Mechanisms in relation to catalyst structure. J Mol Catal 38:5–25CrossRefGoogle Scholar
  11. 11.
    Gnanamuthu DS, Petrocelli JV (1967) A generalized expression for the Tafel slope and the kinetics of oxygen reduction on noble metals and alloys. J Electrochem Soc 114:1036–1041CrossRefGoogle Scholar
  12. 12.
    Sardar R, Funston AM, Mulvaney P, Murray RW (2009) Gold nanoparticles: past, present, and future. Langmuir 25:13840–13851CrossRefGoogle Scholar
  13. 13.
    Sarapuu A, Nurmik M, Mändar H, Rosental A, Laaksonen T, Kontturi K, Schiffrin DJ, Tammeveski K (2008) Electrochemical reduction of oxygen on nanostructured gold electrodes. J Electroanal Chem 612:78–86CrossRefGoogle Scholar
  14. 14.
    Dai X, Nekrassova O, Hyde ME, Compton RG (2004) Anodic stripping voltammetry of arsenic(III) using gold nanoparticle-modified electrodes. Anal Chem 76:5924–5929CrossRefGoogle Scholar
  15. 15.
    Campbell FW, Compton RG (2010) The use of nanoparticles in electroanalysis: an updated review. Anal Bioanal Chem 396:241–259CrossRefGoogle Scholar
  16. 16.
    Mohanty US (2011) Electrodeposition: a versatile and inexpensive tool for the synthesis of nanoparticles, nanorods, nanowires, and nanoclusters of metals. J Appl Electrochem 41:257–270CrossRefGoogle Scholar
  17. 17.
    Alexeyeva N, Tammeveski K (2008) Electroreduction of oxygen on gold nanoparticle/PDDA-MWCNT nanocomposites in acid solution. Anal Chim Acta 618:140–146CrossRefGoogle Scholar
  18. 18.
    Zhao P, Li N, Astruc D (2013) State of the art in gold nanoparticle synthesis. Coord Chem Rev 257:638–665CrossRefGoogle Scholar
  19. 19.
    El-Deab MS, Sotomura T, Ohsaka T (2005) Morphological selection of gold nanoparticles electrodeposited on various substrates. J Electrochem Soc 152:C730–C737CrossRefGoogle Scholar
  20. 20.
    Erikson H, Sarapuu A, Tammeveski K, Solla-Gullon J, Feliu JM (2014) Shape-dependent electrocatalysis: oxygen reduction on carbon-supported gold nanoparticles. Chem Electro Chem 1:1338–1347Google Scholar
  21. 21.
    Kuai L, Geng B, Wang S, Zhao Y, Luo Y, Jiang H (2011) Silver and gold icosahedra: one-pot water-based synthesis and their superior performance in the electrocatalysis for oxygen reduction reaction in alkaline media. Chemistry–A European J 17:3482–3489CrossRefGoogle Scholar
  22. 22.
    Hernández J, Solla-Gullón J, Herrero E, Aldaz A, Feliu JM (2007) Electrochemistry of shape-controlled catalysts: oxygen reduction reaction on cubic gold nanoparticles. J Phys Chem C 111:14078–14083CrossRefGoogle Scholar
  23. 23.
    Inasaki T, Kobayashi S (2009) Particle size effects of gold on the kinetics of the oxygen reduction at chemically prepared Au/C catalysts. Electrochim Acta 54:4893–4897CrossRefGoogle Scholar
  24. 24.
    Schmidt TJ, Stamenkovic V, Arenz M, Markovic NM, Ross PN Jr (2002) Oxygen electrocatalysis in alkaline electrolyte: Pt(hkl), Au(hkl) and the effect of Pd-modification. Electrochim Acta 47:3765–3776CrossRefGoogle Scholar
  25. 25.
    Hernández J, Solla-Gullón J, Herrero E, Feliu JM, Aldaz A (2009) In situ surface characterization and oxygen reduction reaction on shape-controlled gold nanoparticles. J Nanosci Nanotechnol 9:2256–2273CrossRefGoogle Scholar
  26. 26.
    El-Deab MS, Sotomura T, Ohsaka T (2005) Oxygen reduction at electrochemically deposited crystallographically oriented Au(100)-like gold nanoparticles. Electrochem Commun 7:29–34CrossRefGoogle Scholar
  27. 27.
    Wain AJ (2013) Imaging size effects on the electrocatalytic activity of gold nanoparticles using scanning electrochemical microscopy. Electrochim Acta 92:383–391CrossRefGoogle Scholar
  28. 28.
    Štrbac S, Adžic RR (1996) The influence of pH on reaction pathways for O2 reduction on the Au(100) face. Electrochim Acta 41:2903–2908CrossRefGoogle Scholar
  29. 29.
    Blizanac BB, Lucas CA, Gallagher ME, Arenz M, Ross PN, Markovic NM (2004) Anion adsorption, CO oxidation, and oxygen reduction reaction on a Au(100) surface: the pH effect. J Phys Chem B 108:625–634CrossRefGoogle Scholar
  30. 30.
    Mohammad AM, Awad MI, El-Deab MS, Okajima T, Ohsaka T (2008) Electrocatalysis by nanoparticles: optimization of the loading level and operating pH for the oxygen evolution at crystallographically oriented manganese oxide nanorods modified electrodes. Electrochim Acta 53:4351–4358CrossRefGoogle Scholar
  31. 31.
    Rodriguez P, Koper MTM (2014) Electrocatalysis on gold. Phys Chem Chem Phys 16:13583–13594CrossRefGoogle Scholar
  32. 32.
    Quaino P, Luque NB, Nazmutdinov R, Santos E, Schmickler W (2012) Why is gold such a good catalyst for oxygen reduction in alkaline media? Angew Chem, Int Ed Engl 51:12997–13000CrossRefGoogle Scholar
  33. 33.
    Wang Y, Laborda E, Plowman BJ, Tschulik K, Ward KR, Palgrave RG, Dammd C, Compton RG (2014) The strong catalytic effect of Pb(II) on the oxygen reduction reaction on 5 nm gold nanoparticles. Phys Chem Chem Phys 16:3200–3208Google Scholar
  34. 34.
    El-Deab MS, Sotomura T, Ohsaka T (2006) Oxygen reduction at Au nanoparticles electrodeposited on different carbon substrates. Electrochim Acta 52:1792–1798CrossRefGoogle Scholar
  35. 35.
    Vázquez-Huerta G, Ramos-Sánchez G, Antaño-López R, Solorza-Feria O (2009) Electrocatalysis of oxygen reduction on Au nanoparticles. ECS Trans 20:259–265CrossRefGoogle Scholar
  36. 36.
    Vázquez-Huerta G, Ramos-Sánchez G, Rodríguez-Castellanos A, Meza-Calderón D, Antaño-López R, Solorza-Feria O (2010) Electrochemical analysis of the kinetics and mechanism of the oxygen reduction reaction on Au nanoparticles. J Electroanal Chem 645:35–40CrossRefGoogle Scholar
  37. 37.
    Tang W, Lin H, Kleiman-Shwarsctein A, Stucky GD, McFarland EW (2008) Size-dependent activity of gold nanoparticles for oxygen electroreduction in alkaline electrolyte. J Phys Chem C 112:10515–10519CrossRefGoogle Scholar
  38. 38.
    Jirkovsky JS, Halasa M, Schiffrin DJ (2010) Kinetics of electrocatalytic reduction of oxygen and hydrogen peroxide on dispersed gold nanoparticles. Phys Chem Chem Phys 12:8042–8052CrossRefGoogle Scholar
  39. 39.
    El-Deab MS, Okajima T, Ohsaka T (2003) Electrochemical reduction of oxygen on gold nanoparticle-electrodeposited glassy carbon electrodes. J Electrochem Soc 150:A851–A857CrossRefGoogle Scholar
  40. 40.
    Raj CR, Abdelrahman AI, Ohsaka T (2005) Gold nanoparticle-assisted electroreduction of oxygen. Electrochem Commun 7:888–893CrossRefGoogle Scholar
  41. 41.
    Shim JH, Kim J, Lee C, Lee Y (2011) Electrocatalytic activity of gold and gold nanoparticles improved by electrochemical pretreatment. J Phys Chem C 115:305–309CrossRefGoogle Scholar
  42. 42.
    Skwierawski A (2013) The use of the integrated trophic state index in evaluation of the restored shallow water bodies. Ecol Chem Eng A 20:1275–1283Google Scholar
  43. 43.
    Hahn CEW (1998) Electrochemical analysis of clinical blood-gases, gases and vapors. Analyst 123:57R–86RCrossRefGoogle Scholar
  44. 44.
    Gotti G, Fajerwerg K, Evrard D, Gros P (2014) Electrodeposited gold nanoparticles on glassy carbon: correlation between nanoparticles characteristics and oxygen reduction kinetics in neutral media. Electrochim Acta 128:412–419CrossRefGoogle Scholar
  45. 45.
    Gotti G, Fajerwerg K, Evrard D, Gros P (2013) Kinetics of dioxygen reduction on gold and glassy carbon electrodes in neutral media. Int J Electrochem Sci 8:12643–12657Google Scholar
  46. 46.
    Turkevich J, Stevenson PC, Hillier J (1951) A study of the nucleation and growth processes in the synthesis of colloidal gold. Discuss Faraday Soc 11:55–75CrossRefGoogle Scholar
  47. 47.
    Frens G (1973) Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions. Nature (London). Physical Science 241:20–22CrossRefGoogle Scholar
  48. 48.
    Smoluchowski MV (1903) Contribution to the theory of electro-osmosis and related phenomena. Bull Int Acad Sci Cracovie 3:184–199Google Scholar
  49. 49.
    Wiersema PH, Loeb AL, Overbeek JTG (1966) calculation of the electrophoretic mobility of a spherical colloidal particle. J Colloid Interface Sci 22:78–99CrossRefGoogle Scholar
  50. 50.
    Turkevich J (1985) Colloidal gold. Part I. Historical and preparative aspects, morphology and structure. Gold Bull 18:86–91CrossRefGoogle Scholar
  51. 51.
    Su H, Zheng Q, Li H (2012) Colorimetric detection and separation of chiral tyrosine based on N-acetyl-L-cysteine modified gold nanoparticles. J Mater Chem 22:6546–6548CrossRefGoogle Scholar
  52. 52.
    Farrag M, Tschurl M, Heiz U (2013) Chiral gold and silver nanoclusters: preparation, size selection, and chiroptical properties. Chem Mater 25:862–870CrossRefGoogle Scholar
  53. 53.
    Link S, El-Sayed MA (1999) Size and temperature dependence of the plasmon absorption of colloidal gold nanoparticles. J Phys Chem B 103:4212–4217CrossRefGoogle Scholar
  54. 54.
    Majzik A, Patakfalvi R, Hornok V, Dékány I (2009) Growing and stability of gold nanoparticles and their functionalization by cysteine. Gold Bull 42:113–123CrossRefGoogle Scholar
  55. 55.
    Brewer SH, Glomm WR, Johnson MC, Knag MK, Franzen S (2005) Probing BSA binding to citrate-coated gold nanoparticles and surfaces. Langmuir 21:9303–9307CrossRefGoogle Scholar
  56. 56.
    Jin R, Zhu Y, Qian H (2011) Quantum-sized gold nanoclusters: bridging the gap between organometallics and nanocrystals. Chemistry–A European J 17:6584–6593CrossRefGoogle Scholar
  57. 57.
    Mocanu A, Cernica I, Tomoaia G, Bobos L-D, Horovitz O, Tomoaia-Cotisel M (2009) Self-assembly characteristics of gold nanoparticles in the presence of cysteine. Colloids Surf A Physicochem Eng Asp 338:93–101CrossRefGoogle Scholar
  58. 58.
    Hunter RJ (1981) Zeta potential in colloid science: principles and applications. Academic Press, London, UKGoogle Scholar
  59. 59.
    Jungers JC, Sajus L, de Aguirre I, Decroocq D (1968) L’analyse cinétique de la transformation chimique, Tome 2. Publications de l’Institut Français du Pétrole, Technip, ParisGoogle Scholar
  60. 60.
    Steven JT, Golovko VB, Johannessen B, Marshall AT (2016) Electrochemical stability of carbon-supported gold nanoparticles in acidic electrolyte during cyclic voltammetry. Electrochim Acta 187:593–604CrossRefGoogle Scholar
  61. 61.
    Cruickshank AC, Downard AJ (2009) Electrochemical stability of citrate-capped gold nanoparticles electrostatically assembled on amine-modified glassy carbon. Electrochim Acta 54:5566–5570CrossRefGoogle Scholar
  62. 62.
    Hendry EB (1962) The osmotic pressure and chemical composition of human body fluids. Human Body Fluids 8:246–265Google Scholar
  63. 63.
    Koutecky J (1953) Kinetics of electrode processes. XI The polarographic current due to an electrode process preceded by a chemical reaction in solution between reactants differing in their diffusion coefficients. Chemicke Listy pro Vedu a Prumysl 47:1758–1761Google Scholar
  64. 64.
    Benson BB, Krause DJ (1984) The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol Oceanogr 29:620–632CrossRefGoogle Scholar
  65. 65.
    van Stroe AJ, Janssen LJJ (1993) Determination of the diffusion coefficient of oxygen in sodium chloride solutions with a transient pulse technique. Anal Chim Acta 279:213–219CrossRefGoogle Scholar
  66. 66.
    Jamnongwong M, Loubiere K, Dietrich N, Hebrard G (2010) Experimental study of oxygen diffusion coefficients in clean water containing salt, glucose or surfactant: consequences on the liquid-side mass transfer coefficients. Chem Eng J 165:758–768CrossRefGoogle Scholar
  67. 67.
    Millero FJ, Huang F, Laferiere AL (2002) Solubility of oxygen in the major sea salts as a function of concentration and temperature. Mar Chem 78:217–230CrossRefGoogle Scholar
  68. 68.
    Mirkhalaf F, Schiffrin DJ (2010) Electrocatalytic oxygen reduction on functionalized gold nanoparticles incorporated in a hydrophobic environment. Langmuir 26:14995–15001CrossRefGoogle Scholar
  69. 69.
    Pietron JJ, Garsany Y, Baturina O, Swider-Lyons KE, Schull TL (2007) Electrochemical observation of ligand effects on oxygen reduction at ligand-stabilized Pt nanoparticle electrocatalysts. ECS Trans 11:217–226CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • Guillaume Gotti
    • 1
    • 2
    • 3
    • 4
  • David Evrard
    • 1
    • 2
    Email author
  • Katia Fajerwerg
    • 3
    • 4
  • Pierre Gros
    • 1
    • 2
  1. 1.Université de Toulouse, UPS, INPT, Laboratoire de Génie ChimiqueToulouseFrance
  2. 2.CNRS, Laboratoire de Génie ChimiqueToulouseFrance
  3. 3.CNRS, LCC (Laboratoire de Chimie de Coordination)ToulouseFrance
  4. 4.Université de Toulouse, UPS, INPT, LCCToulouseFrance

Personalised recommendations