Skip to main content
Log in

Process engineering studies on gold nanoparticle formation via dynamic spectroscopic approach

  • Original Paper
  • Published:
Gold Bulletin Aims and scope Submit manuscript

Abstract

The present paper reports a systematic study on kinetics of formation of metal nanoparticles from their precursors. Synthesis of gold nanoparticles (AuNPs) from chloroauric acid by the Turkevich method was selected as a model reaction where trisodium citrate acted as a reducing agent and stabilizer. Time-variant concentration of chloroauric acid was measured directly by monitoring UV spectroscopic absorbance at 212.5 nm and cross-checked by iodometric titration method. The reaction was suitably modeled by pseudo-first-order kinetics, and rate constant value [k = (7.93 ± 0.67) × 10−3 s−1] at a fixed baseline condition was reported. Morphological studies on particle growth mechanism were done by atomic force microscopy (AFM). Effects of process variables—initial molar ratio of reactants (0.37–5.21), temperature (333–373 K), and pH (3.6–6.5)—on kinetic parameters were investigated. Fastest reaction rate and spherical particle symmetry were observed at an optimal reductant to precursor ratio of 1.33. From an Arrhenius plot of rate constant data, preexponential factor (A = 8.013 ± 0.896 mM s−1) and activation energy (E a = 21.69 ± 2.3 kJ mol−1) were calculated. A global kinetic equation for AuNP synthesis has been determined. Process conditions for synthesis of mature AuNPs with optical and morphological characteristics suitable for biomedical applications were identified.

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

Access this article

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

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13

Similar content being viewed by others

Abbreviations

C A :

Concentration of chloroauric acid at time t (mM)

C A0 :

Initial concentration of chloroauric acid (mM)

C B :

Concentration of trisodium citrate at time t (mM)

C B0 :

Initial concentration of trisodium citrate (mM)

k 0 :

Reaction rate constant defined by Eq. 2

k :

Pseudo-first-order reaction rate constant (s−1) defined by Eq. 3

M:

Initial molar ratio (C B0/C A0)

R :

Universal gas constant (J mol−1 K−1)

t :

Time (s)

T :

Temperature (K)

References

  1. Link S, El-Sayed MA (1999) Size and temperature dependence of the plasmon absorption of colloidal gold nanoparticles. J Phys Chem B 103:4212

    Article  Google Scholar 

  2. Haiss W, Thanh NT, Aveyard J, Fernig DG (2007) Determination of size and concentration of gold nanoparticles from Uv−Vis spectra. Anal Chem 79:4215

    Article  Google Scholar 

  3. Sinha AK, Seelan S, Tsubota S, Haruta M (2004) Catalysis by gold nanoparticles: epoxidation of propene. Top Catal 29:95

    Article  Google Scholar 

  4. Mertens P, Corthals S, Ye X, Poelman H, Jacobs P, Sels B, Vankelecom I, De Vos D (2009) Selective alcohol oxidation to aldehydes and ketones over base-promoted gold–palladium clusters as recyclable quasihomogeneous and heterogeneous metal catalysts. J Mol Catal A Chem 313:14

    Article  Google Scholar 

  5. Lin CAJ, Yang TY, Lee CH, Huang SH, Sperling RA, Zanella M, Li JK, Shen JL, Wang HH, Yeh HI (2009) Synthesis, characterization, and bioconjugation of fluorescent gold nanoclusters toward biological labeling applications. ACS Nano 3:395

    Article  Google Scholar 

  6. Basu M, Seggerson S, Henshaw J, Jiang J, Cordona RA, Lefave C, Boyle PJ, Miller A, Pugia M, Basu S (2004) Nano-biosensor development for bacterial detection during human kidney infection: use of glycoconjugate-specific antibody-bound gold nanowire arrays. Glycoconj J 21:487

    Article  Google Scholar 

  7. Daniel MC, Astruc D (2004) Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. Chem Rev 104:293

    Article  Google Scholar 

  8. Baptista P, Pereira E, Eaton P, Doria G, Miranda A, Gomes I, Quaresma P, Franco R (2008) Gold nanoparticles for the development of clinical diagnosis methods. Anal Bioanal Chem 391:943

    Article  Google Scholar 

  9. Turkevich J, Stevenson PC, Hillier J (1951) A study of nucleation and growth processes in the synthesis of colloidal gold. Discus Faraday Soc 11:55

    Article  Google Scholar 

  10. Frens G (1973) Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions. Nature 241:20

    Google Scholar 

  11. Sivaraman SK, Kumar S, Santhanam V (2010) Room-temperature synthesis of gold nanoparticles-size-control by slow addition. Gold Bull 43:275

  12. Sivaraman SK, Kumar S, Santhanam V (2011) Monodisperse sub-10 nm gold nanoparticles by reversing the order of addition in Turkevich method—the role of chloroauric acid. J Colloid Interface Sci 361:543

    Article  Google Scholar 

  13. Kimling J, Maier M, Okenve B, Kotaidis V, Ballot H, Plech A (2006) Turkevich method for gold nanoparticle synthesis revisited. J Phys Chem B 110:15700

    Article  Google Scholar 

  14. Ji X, Song X, Li J, Bai Y, Yang W, Peng X (2007) Size control of gold nanocrystals in citrate reduction: the third role of citrate. J Am Chem Soc 129:13939

    Article  Google Scholar 

  15. Paclawski K, Streszewski B, Jaworski W, Luty-Blocho M, Fitzner K (2012) Gold nanoparticles formation via gold(III) chloride complex ions reduction with glucose in the batch and in the flow microreactor systems. Colloids Surf A Physicochem Eng Asp 413:208

    Article  Google Scholar 

  16. Bastus NG, Comenge J, Puntes V (2011) Kinetically controlled seeded growth synthesis of citrate-stabilized gold nanoparticles of up to 200 nm: size focussing versus Ostwald ripening. Langmuir 27:11098

    Article  Google Scholar 

  17. Watzky MA, Finke RG (1997) Transition metal nanocluster formation kinetic and mechanistic studies: a new mechanism when hydrogen is the reductant: slow, continuous nucleation and fast autocatalytic surface growth. J Am Chem Soc 119:10382

  18. Patakfalvi R, Papp S, Dekany I (2007) The kinetics of homogeneous nucleation of silver nanoparticles stabilized by polymer. J Nanopart Res 9:353

    Article  Google Scholar 

  19. Chakraborty A, Chakraborty S, Chaudhuri B, Bhanacharjee S (2012) Spectroscopic estimation of chloroauric acid during synthesis of gold nanoparticles by citrate reduction method. Adv Sci Eng Med 4:128

  20. Ojea-Jimenez I, Bastus NG, Puntes V (2011) Small gold nanoparticles synthesized with sodium citrate and heavy water: insights into the reaction mechanism. J Phys Chem C 115:15752

    Article  Google Scholar 

  21. Polte JR, Aimer TT, Delissen F, Sokolov S, Emmerling F, Thunemann AF, Kraehnert R (2010) Mechanism of gold nanoparticle formation in the classical citrate synthesis method derived from coupled in-situ XANES and SAXS evaluation. J Am Chem Soc 132:1296

    Article  Google Scholar 

  22. Kumar S, Gandhi K, Kumar R (2007) Modeling of formation of gold nanoparticles by citrate method. Ind Eng Chem Res 46:3128

    Article  Google Scholar 

  23. Chow M, Zukoski C (1994) Gold sol formation mechanism: role of colloidal stability. J Colloid Interface Sci 165:97

    Article  Google Scholar 

  24. Okitsu K, Ashokkumar M, Grieser F (2005) Sonochemical synthesis of gold nanoparticles: effects of ultrasound frequency. Phys Chem B 109:20673

  25. Peck JA, Tait CD, Swanson BI, Brown GE (1991) Speciation of aqueous gold(III) chlorides from ultraviolet/visible absorption and Raman/resonance Raman spectroscopies. Geochim Cosmochim Acta 55:671

    Article  Google Scholar 

  26. Chow A, Beamish F (1963) Studies of titrimetric and spectrophotometric methods for the determination of gold. Talanta 10:883

    Article  Google Scholar 

  27. Itoh H, Naka K, Chujo Y (2004) Synthesis of gold nanoparticles modified with ionic liquid based on the imidazolium cation. J Am Chem Soc 126:3026

  28. Zhou J, Ralston J, Sedev R, Beattie DA (2009) Functionalized gold nanoparticles: synthesis, structure and colloid stability. J Colloid Interface Sci 331:251

    Article  Google Scholar 

  29. Suman T, Rajasree SR, Ramkumar R, Rajthilak C, Perumal P (2014) The Green synthesis of gold nanoparticles using an aqueous root extract of Morinda citrifolia. Spectrochim Acta, Part A 118:11

    Article  Google Scholar 

  30. Turkevich J (1985) Colloidal gold. Part I: historical and preparative aspects, morphology and structure. Gold Bull 18:86

  31. Zabetakis K, Ghann WE, Kumar S, Daniel MC (2012) Effect of high gold salt concentrations on the size and polydispersity of gold nanoparticles prepared by an extended Turkevich-Frens method. Gold Bull 45:203

    Article  Google Scholar 

  32. Pong BK, Elim HI, Chong JX, Ji W, Trout BL, Lee JY (2007) New insights on the nanoparticle growth mechanism in the citrate reduction of gold(III) salt: formation of the Au nanowire intermediate and its nonlinear optical properties. J Phys Chem C 111:6281

    Article  Google Scholar 

  33. Zhang G, Jasinski JB, Howell JL, Patel D, Stephens DP, Gobin AM (2012) Tunability and stability of gold nanoparticles obtained from chloroauric acid and sodium thiosulfate reaction. Nanoscale Res Lett 7:1

    Article  Google Scholar 

  34. Freund PL, Spiro M (1985) Colloidal catalysis: the effect of sol size and concentration. J Phys Chem 89:1074

    Article  Google Scholar 

  35. Liu Z, Zu Y, Guo S (2009) Synthesis of micron-scale gold nanochains by a modified citrate reduction method. Appl Surf Sci 255:5827

  36. Wager K, Chui T, Adem S (2014) Effect of pH on the stability of gold nanoparticles and their application for melamine detection in infant formula. IOSR-JAC 7:8

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Sekhar Bhattacharjee.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chakraborty, A., Chakraborty, S., Chaudhuri, B. et al. Process engineering studies on gold nanoparticle formation via dynamic spectroscopic approach. Gold Bull 49, 75–85 (2016). https://doi.org/10.1007/s13404-016-0183-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13404-016-0183-7

Keywords

Navigation