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Electroless deposition of silver on poly(3, 4-ethylenedioxythiophene): role of the organic ions used in the course of electrochemical synthesis

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Abstract

The electroless deposition of silver is studied on poly(3, 4-ethylenedioxythiophene) (PEDOT) layers synthesized in the presence of excess of perchlorate ions with and without the addition of two organic dopants: dodecylsulfate (DDS) or polystyrenesulfonate (PSS). Silver deposition is carried out at the expense of oxidation of the pre-reduced PEDOT layers using either Ag+ cation or [AgEDTA]3− complex anion solutions. The amount of deposited silver is monitored by voltammetric stripping. The type of the metal deposit is imaged by SEM. It is found that there are marked differences between the three types of PEDOT with respect to the amount of deposited silver and size distribution of the metallic species. In both silver plating solutions, the largest amount of silver is deposited on PEDOT/DDS, followed by PEDOT/PSS and PEDOT/ClO4 . These results are discussed in the context of possible structural difference of the three types of PEDOT layers. The comparison between the silver deposits obtained in the two silver plating solutions shows finer dispersion and larger amount of the metallic phase obtained in the presence of the silver complex anions. This solution presents a better opportunity to obtain homogeneous distribution of silver crystalline species on the PEDOT surface.

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References

  • Abrantes LM, Correia JP (1995) Polymer Films Containing Metal Particles-Noble Metals in Polyaniline. Mater Sci Forum 191:235–340

    Article  CAS  Google Scholar 

  • Balamurugan A, Chen SM (2009) Silver nanograins incorporated PEDOT modified electrode for electrocatalytic sensing of hydrogen peroxide. Electroanalysis 21:1419–1423

    Article  CAS  Google Scholar 

  • Dallas P, Sharma VK, Zboril R (2011) Silver polymeric nanocomposites as advanced antimicrobial agents: classification, synthetic paths, applications, and perspectives. Adv Colloid Interface Sci 166:119–135

    Article  CAS  Google Scholar 

  • Dogan Ü, Kaya M, Cihaner A, Volkan M (2012) Ag nanostructures on a poly(3,4-ethylenedioxythiophene) film prepared with electrochemical route: A controllable roughened SERS substrate with high repeatability and stability. Electrochim Acta 85:220–227

    Article  CAS  Google Scholar 

  • Eliseeva SN, Malev VV, Kondratiev VV (2009) Electrochemical properties of composite films based on poly-3,4-ethylenedioxythiophene with inclusions of metallic palladium. Russ J Electrochem 45:1045–1051

    Article  CAS  Google Scholar 

  • Fedorczyk A, Ratajczak J, Czerwinski A, Skompska M (2014) Selective deposition of gold nanoparticles on the top or inside a thin conducting polymer film, by combination of electroless deposition and electrochemical reduction. Electrochim Acta 122:267–274

    Article  CAS  Google Scholar 

  • Filjova DG, Ilieva GP, Tsakova VT (2013) Electropolymerization of poly(3, 4-ethylenedioxythiophene) layers in the presence of different dopants and their effect on the polymer electrocatalytic properties. Oxidation of ascorbic acid and dopamine. Bulg Chem Commun 45:196–201

    Google Scholar 

  • Girard J, Brunetto PS, Braissant O, Rajacic Z, Khanna N, Landmann R, Daniels AU, Fromm KM (2013) Development of a polystyrene sulfonate/silver nanocomposite with self-healing properties for biomaterial applications. C R Chim 16:550–556

    Article  CAS  Google Scholar 

  • Huang SW, Neoh KG, Shih CW, Lim DS, Kang ET, Han HS, Tan KL (1998) Synthesis, characterization and catalytic properties of palladium-containing electroactive polymers. Synth Metals 96:117–122

    Article  CAS  Google Scholar 

  • Ignatova M, Labaye D, Lenoir S, Strivay D, Jerome R, Jerome C (2003) Immobilization of silver in polypyrrole/polyanion composite coatings: preparation, characterization, and antibacterial activity. Langmuir 19:8971–8979

    Article  CAS  Google Scholar 

  • Ilieva M, Tsakova V, Erfurth W (2006) Electrochemical formation of bi-metal (copper–palladium) electrocatalyst supported on poly-3,4-ethylenedioxythiophene. Electrochim Acta 52:816–824

    Article  CAS  Google Scholar 

  • Ivanov S, Tsakova V (2005) Electroless versus electrodriven deposition of silver crystals in polyaniline: Role of silver anion complexes. Electrochim Acta 50:5616–5623

    Article  CAS  Google Scholar 

  • Iwan A, Boharewicz B, Tazbir I, Sikora A, Zboromirska-Wnukiewicz B (2015) Silver nanoparticles in PEDOT: PSS layer for polymer solar cell application. Int J Photoenergy 764938:1–9

    Article  Google Scholar 

  • Kim H, Veerappan G, Wang DH, Park JH (2016) Large area platinum and fluorine-doped tin oxide-free dye sensitized solar cells with silver-nanoplate embedded poly(3,4-ethylenedioxythiophene) counter electrode. Electrochim Acta 187:218–223

    Article  CAS  Google Scholar 

  • Kondratiev VV, Pogulaichenko NA, Tolstopjatova EG, Malev VV (2011) Hydrogen peroxide electroreduction on composite PEDOT films with included gold nanoparticles. J Solid State Electrochem 15:2383–2393

    Article  CAS  Google Scholar 

  • Kucekova Z, Kasparkova V, Humpolicek P, Sevcikova P, Stejskal J (2013) Antibacterial properties of polyaniline–silver films. Chem Pap 67:1103–1108

    Article  CAS  Google Scholar 

  • Lim VWL, Kang ET, Neoh KG (2001) Electroless plating of palladium and copper on polypyrrole films. Synth Metals 123:107–115

    Article  CAS  Google Scholar 

  • Mack NH, Bailey JA, Doorn SK, Chen CA, Gau HM, Xu P, Williams DJ, Akhadov EA, Wang HL (2011) Mechanistic study of silver nanoparticle formation on conducting polymer surfaces. Langmuir 27:4979–4985

    Article  CAS  Google Scholar 

  • Mourato A, Viana AS, Correia JP, Siegenthaler H, Abrantes LM (2004) Polyaniline films containing electrolessly precipitated palladium. Electrochim Acta 49:2249–2257

    Article  CAS  Google Scholar 

  • Mourato A, Wong SM, Siegenthaler H, Abrantes LM (2006) Polyaniline films containing palladium microparticles for electrocatalytic purposes. J Solid State Electrochem 10:140–147

    Article  CAS  Google Scholar 

  • Namboothiry MAG, Zimmerman T, Coldren FM, Liu J, Kim K, Carrol DL (2007) Electrochromic properties of conducting polymer metal nanoparticles composites. Synth Metals 157:580–584

    Article  CAS  Google Scholar 

  • Ocypa M, Ptasinska M, Michalska A, Maksymiuk K, Hall EAH (2006) Electroless silver deposition on polypyrrole and poly(3,4-ethylenedioxythiophene): The reaction/diffusion balance. J Electroanal Chem 596:157–168

    Article  CAS  Google Scholar 

  • Park E, Kwon OS, Park SJ, Lee JS, You S, Jang J (2012) One-pot synthesis of silver nanoparticles decorated poly(3,4-ethylenedioxythiophene) nanotubes for chemical sensor application. J Mater Chem 22:1521–1526

    Article  CAS  Google Scholar 

  • Scheffer M, Martina V, Seeber R, Mandler D (2008) Deposition of gold nanoparticles on thin polyaniline films. Isr J Chem 48:349–357

    Article  Google Scholar 

  • Sheffer M, Mandler D (2009) Control of locally deposited gold nanoparticle on polyaniline films. Electrochim Acta 54:2951–2956

    Article  CAS  Google Scholar 

  • Smith JA, Josowicz M, Janata J (2003) Polyaniline-gold nanocomposite system. J Electrochem Soc 150:384–388

    Article  Google Scholar 

  • Song FY, Shiu KK (2001) Preconcentration and electroanalysis of silver species at polypyrrole film modified glassy carbon electrodes. J Electroanal Chem 498:161–170

    Article  CAS  Google Scholar 

  • Stejskal J (2013) Conducting polymer-silver composites. Chem Pap 67:814–848

    Article  CAS  Google Scholar 

  • Stejskal J, Trchová M, Brožová L, Prokeš J (2009) Reduction of silver nitrate by polyaniline nanotubes to produce silver–polyaniline composites. Chem Pap 63:77–83

    Article  CAS  Google Scholar 

  • Tolstopyatova EG, Pogulyaichenko NA, Kondratiev VV (2014) Synthesis and electrochemical properties of composite films based on poly-3,4-ethylenedioxythiophene with inclusions of silver particles. Russ J Electrochem 50:510–516

    Article  CAS  Google Scholar 

  • Tsakova V (2010) Metallic-Based Nanocomposites of Conductive Polymers. In: Eftekhari A (ed) Nanostructured conductive polymers. Wiley, New York, pp 289–340

    Chapter  Google Scholar 

  • Tsakova V, Ilieva G, Filjova D (2015) Role of the anionic dopant of poly(3,4-ethylenedioxythiophene) for the electroanalytical performance: electrooxidation of acetaminophen. Electrochim Acta 179:343–349

    Article  CAS  Google Scholar 

  • Vaslow F, Boyd GE (1966) Thermodynamic properties in the exchange of silver with sodium ions in cross-linked polystyrene sulfonate cation exchangers. J Phys Chem 70:2295–2299

    Article  CAS  Google Scholar 

  • Wang HL, Li W, Jia QX, Akhadov E (2007) Tailoring conducting polymer chemistry for the chemical deposition of metal particles and clusters. Chem Mater 19:520–525

    Article  Google Scholar 

  • Zhang AQ, Cui CQ, Lee JY, Loh FC (1995) Interactions between polyaniline and silver cations. J Electrochem Soc 142:1097–1104

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge the financial support of Bulgarian Academy of Sciences under Program for career development of young scientists (Project DFNP-18/20.04.2016). The SEM pictures are obtained with the kind assistance of Dr. S. Piroeva (Laboratory for Electron Microscopy at Institute of Physical Chemistry, Sofia).

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Correspondence to Vessela Tsakova.

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Karabozhikova, V., Tsakova, V. Electroless deposition of silver on poly(3, 4-ethylenedioxythiophene): role of the organic ions used in the course of electrochemical synthesis. Chem. Pap. 71, 339–346 (2017). https://doi.org/10.1007/s11696-016-0076-5

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  • DOI: https://doi.org/10.1007/s11696-016-0076-5

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