Bimetallic Pt/Pd nanoparticles in sol–gel-derived silica films and xerogels

  • N. N. GubanovaEmail author
  • V. A. Matveev
  • O. A. Shilova
Original Paper: Functional coatings, thin films and membranes (including deposition techniques)


This work is devoted to the study of the composition and structure of thin “spin-on glass” films and xerogels prepared from silica sols containing platinum and palladium compounds, both separately and together. The thickness and concentration distribution of Pt/Pd nanoparticles (NPs) in silica films depending on the concentration of precursors of platinum and palladium in silica sols were determined using the method of X-ray reflectometry. The composition and size of Pt/Pd nanoparticles formed in xerogels and thin films were determined in the nanometer and submicron ranges by means of atomic force and transmission electron microscopy of high resolution as well as by means of X-ray diffraction analysis. It was also determined that bimetallic Pt/Pd nanoparticles possess a common crystal lattice forming clusters with the structure of a mixed alloy type.


  • Pt/Pd NPs with bimetallic crystal lattices form from TEOS-derived sols doped with Pt and Pd.

  • The size of Pt/Pd bimetallic NPs formed in films is 5–6 nm and of the ones formed in xerogels–10–18 nm.

  • A Pt and Pd concentration gradient is detected in 30–40 nm-thick doped silica films.

  • Pt/Pd crystallites up to 70 nm in size form at the meso level as well.


TEOS-derived sols Doped silica spin-on glass films Pt/Pd bimetallic nanoparticles Mixed alloy structure Xerogel 



This work was supported by the Russian State Program (No. AAAA-А19-119022290091-8). The authors are grateful to the National Research Centre “Kurchatov Institute,” (Moscow, Russia) for the time granted and experimental equipment, namely to M. Yu Presnyakov for the help in the TEM measurements.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Sharma G, Kumar A, Sharma S, Naushad Mu, Dwivedi RP, ALOthman ZA, Mola GT (2017) Novel development of nanoparticles to bimetallic nanoparticles and their composites: a review. J King Saud Univ Sci (in press, Corrected Proof).
  2. 2.
    Medynska AZ, Marchelek M, Diak M, Grabowska E (2016) Noble metal-based bimetallic nanoparticles: the effect of the structure on the optical, catalytic and photocatalytic properties. Adv Colloid Interface Sci 229:80–107. CrossRefGoogle Scholar
  3. 3.
    Bukhtiyarov VI, Slinko MG (2001) Metallic nanosystems in catalysis, Russian. Chem Rev 70:147–159. Google Scholar
  4. 4.
    Ghosh Chaudhuri R, Paria S (2011) Core/shell nanoparticles: classes, properties, synthesis mechanisms, characterization, and applications. Chem Rev 112(4):2373–2433. CrossRefGoogle Scholar
  5. 5.
    Gawande MB, Goswami A, Asefa T, Guo H, Biradar AV, Peng D-L, Zboril R, Varma RS (2015) Core–shell nanoparticles: synthesis and applications in catalysis and electrocatalysis. Chem Soc Rev 44:7540–7590. CrossRefGoogle Scholar
  6. 6.
    Major KJ, De C, Obare SO (2009) Recent advances in the synthesis of plasmonic bimetallic nanoparticles. Plasmonics 4:61–78. CrossRefGoogle Scholar
  7. 7.
    Ferrando R, Jellinek J, Johnston RL (2008) Nanoalloys: from theory to applications of alloy clusters and nanoparticles. Chem Rev 108:845–910. CrossRefGoogle Scholar
  8. 8.
    Chen Y-H, Tseng Y-H, Yeh C-S (2002) Laser-induced alloying Au–Pd and Ag–Pd colloidal mixtures: the formation of dispersed Au/Pd and Ag/Pd. J Mater Chem 12:1419–1422. CrossRefGoogle Scholar
  9. 9.
    Liu J, Zou S, Xiao L, Fan J (2014) Well-dispersed bimetallic nanoparticles confined in mesoporous metal oxides and their optimized catalytic activity for nitrobenzene hydrogenation. Catal Sci Technol 4:441–446. CrossRefGoogle Scholar
  10. 10.
    Suyal G (2003) Bimetallic colloids of silver and copper in thin films: sol–gel synthesis and characterization. Thin Solid Films 426:53–61. CrossRefGoogle Scholar
  11. 11.
    Dauthal P, Mukhopadhyay M (2016) AuPd bimetallic nanoparticles: single step biofabrication, structural characterization and catalytic activity. J Ind Eng Chem 35:45–53. CrossRefGoogle Scholar
  12. 12.
    Benito P, Gregori M, Andreoli S, Fornasari G, Millefanti S, Ospitali F, Albonetti S (2014) Role of the preparation method on properties of Pd/Cu-MCM-41 hydrodechlorinating catalysts. Catal Today 235:134–143. CrossRefGoogle Scholar
  13. 13.
    De G, Rao CNR (2005) Au–Pt alloy nanocrystals incorporated in silica films. J Mater Chem 15:891–894. CrossRefGoogle Scholar
  14. 14.
    Croy JR, Mostafa S, Hickman L, Heinrich H, Cuenya BR (2008) Bimetallic Pt–metal catalysts for the decomposition of methanol: effect of secondary metal on the oxidation state, activity, and selectivity of Pt. Appl Catal A 350:207–216. CrossRefGoogle Scholar
  15. 15.
    Bogdanovskaya VA, Tarasevich MR, Kuznetsova LN, Radina MV (2009) The structure and characteristics of a PtCoCr nanosized polymetallic cathode catalyst on a carbon carrier. Russ J Phys Chem A 83:2045–2049. CrossRefGoogle Scholar
  16. 16.
    Gutierrez FA, Giordana IS, Fuertes VC, Montemerlo AE, Sieben JM, Alvarez AE, Rubianes MD, Rivas GA (2018) Analytical applications of Cu@PtPd/C nanoparticles for the quantification of hydrogen peroxide. Microchem J 141:240–246. CrossRefGoogle Scholar
  17. 17.
    Zhou WJ, Li WZ, Song SQ, Zhou ZH, Jiang LH, Sun GQ, Xin Q, Poulianitis K, Kontou S, Tsiakaras P (2004) Bi- and tri-metallic Pt-based anode catalysts for direct ethanol fuel cells. J Power Sources 131:217–223. CrossRefGoogle Scholar
  18. 18.
    Liu C, Tan R, Yu N, Yin D (2010) Pt–Pd bi-metal nanoparticles captured and stabilized by imine groups in a periodic mesoporous organosilica of SBA-15 for hydrogenation of nitrobenzene. Microporous Mesoporous Mater 131:162–169. CrossRefGoogle Scholar
  19. 19.
    Wei Y, Wu Q, Xiong J, Li J, Liu J, Zhao Z, Hao S (2018) Efficient catalysts of supported PtPd nanoparticles on 3D ordered macroporous TiO2 for soot combustion: synergic effect of Pt-Pd binary components. Catal Today (in press, Corrected Proof).
  20. 20.
    Lebedeva MV, Yashtulov NA, Flid VR (2016) Сatalysts with platinum–palladium nanoparticles on polymer matrix supports. Kinet Catal 57:847–852. CrossRefGoogle Scholar
  21. 21.
    Zhang Y, Zhao L, Walton J, Liu Z, Tang Z (2017) Facile fabrication of PtPd alloyed worm-like nanoparticles for electrocatalytic reduction of oxygen. Int J Hydrogen Energy 42:17112–17121. CrossRefGoogle Scholar
  22. 22.
    Zhang J, Hu X, Yang B, Su N, Huang H, Cheng J, Yang H, Saito N (2017) Novel synthesis of PtPd nanoparticles with good electrocatalytic activity and durability. J Alloys Compd 709:588–595. CrossRefGoogle Scholar
  23. 23.
    Zheng Y, Qiao J, Yuan J, Shen J, Wang A, Huang S (2018) Controllable synthesis of PtPd nanocubes on graphene as advanced catalysts for ethanol oxidation. Int J Hydrogen Energy 43:4902–4911. CrossRefGoogle Scholar
  24. 24.
    Shilova O, Gubanova N, Matveev V, Ivanova A, Arsentev M, Pugachev K, Ivankova E, Kruchinina (2019) Processes of film-formation and crystallization in catalytically active ‘spin-on glass’ silica films containing Pt and Pd nanoparticles. J Mol Liquids (in press)Google Scholar
  25. 25.
    Nie Q, Zhang W, Wang L, Guo Z, Li C, Yao J, Li M, Wu D, Zhoua L (2018) Sensitivity enhanced, stability improved ethanol gas sensor based on multi-wall carbon nanotubes functionalized with Pt-Pd nanoparticles. Sens Actuators B 270:140–148. CrossRefGoogle Scholar
  26. 26.
    Peng Y, Ye J, Zheng L, Zou K (2016) The hydrogen sensing properties of Pt–Pd/reduced graphene oxide based sensor under different operating conditions. RSC Adv 6:24880–24888. CrossRefGoogle Scholar
  27. 27.
    Jiao J, Zuo J, Pang H, Tan L, Chen T, Ma H (2018) A dopamine electrochemical sensor based on Pd-Pt alloy nanoparticles decorated polyoxometalate and multiwalled carbon nanotubes. J Electroanal Chem 827:103–111. CrossRefGoogle Scholar
  28. 28.
    Shilova OA (2005) Silicate nanosized films prepared by the sol-gel method for use in planar technology for fabricating semiconductor gas sensors. Glass Phys Chem 31:201–218. CrossRefGoogle Scholar
  29. 29.
    Shilova OA (2013) Synthesis and structure features of composite silicate and hybrid TEOS-derived thin films doped by inorganic and organic additives. J Sol Gel Sci Technol 68:387–410. CrossRefGoogle Scholar
  30. 30.
    Negishi E, Choueiry D (2002) Pd(0) and Pd(II) complexes containing phosphorus and other group 15 atom ligands, in: Handbook of organopalladium chemistry for organic synthesis, vol 1. John Wiley & Sons, Inc., New York.
  31. 31.
    Shilova OA, Gubanova NN, Ivanova AG, Arsentyev MY, Ukleev VA (2017) Composition and structure of platinum-containing thin composite films prepared from silica sol. Russ J Inorg Chem 62:650–657. CrossRefGoogle Scholar
  32. 32.
    Mitchell DRG (2008) DiffTools: electron diffraction software tools for digital micrograph. Microsc Res Tech 71:588–593. CrossRefGoogle Scholar
  33. 33.
    Heavens OS (1955) Optical properties of thin films. Butterworth, London. ISBN 1621986489Google Scholar
  34. 34.
    Shilova OA, Gubanova NN, Matveev VA, Bayramukov VY, Kobzev AP (2016) Composition, structure, and morphology of the surface of nanodimensional platinum-containing films obtained from sols. Glass Phys Chem 42:78–86. CrossRefGoogle Scholar
  35. 35.
    Taylor A, Sinclair H (1945) On the determination of lattice parameters by the Debye-Scherrer method. Proc Phys Soc 57:126–135CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Petersburg Nuclear Physics Institute of National Research Centre “Kurchatov Institute”GatchinaRussia
  2. 2.Institute of Silicate Chemistry of the Russian Academy of SciencesSaint-PetersburgRussia
  3. 3.Saint Petersburg Electrotechnical University “LETI”Saint-PetersburgRussia

Personalised recommendations