Chemical Papers

, Volume 74, Issue 2, pp 471–483 | Cite as

A novel colloidal deposition method to prepare copper nanoparticles/polystyrene nanocomposite with antibacterial activity and its comparison to the liquid-phase in situ reduction method

  • Yu Ma
  • Yongheng Chen
  • Jing Huang
  • Zhixin Zhang
  • Dongyu ZhaoEmail author
  • Xiwen Zhang
  • Bin Zhang
Original Paper


Here, we study a simple and effective colloidal deposition method (D) to synthesize a type of core–shell structure composed of copper nanoparticles/polystyrene (CuNPs/PS) microsphere nanocomposite. CuNPs/PS nanocomposite can effectively avoid the agglomeration and oxidation of CuNPs, while retaining its original antibacterial ability, prolonging the service life of antibacterial materials and improving the practical value of Copper in the antibacterial field. The CuNPs with controllable size and excellent stability are successfully synthesized by the double-template method using polyvinylpyrrolidone–sodium dodecylbenzene sulfonate (PVP–SDBS) as template. Compared to the traditional in situ reduction method (R), the novel colloidal deposition method (D) does not involve any surface pretreatment of the PS microspheres, and the size of the CuNPs loaded on the surface of the support PS microspheres can be conveniently controlled. Therefore, we believe that this method is relatively simple and easy to operate, and it is more practical. In addition, the CuNPs/PS (D) nanocomposite has better antibacterial activity and oxidation resistance than the CuNPs/PS (R) nanocomposite, the symbols D and R mean the CuNPs/PS prepared by the novel colloidal deposition method and the liquid-phase in situ reduction method, respectively. Moreover, both the synthesis mechanism of the double-template method and the mechanism for the superiority of colloidal deposition method are examined. The findings of this study provide new ideas for controllably loading metal nanoparticles on polymeric microspheres.


Colloidal deposition method Core–shell structure Nanocomposite Antibacterial activity Resistance to oxidation 



This work was supported by Harbin Scientific and Technological Special Fund for Innovative Talents (Grant No. 2012RFXXG093).


  1. Akhavan O, Ghaderi E (2010) Cu and CuO nanoparticles immobilized by silica thin films as antibacterial materials and photocatalysts. Surf Coat Tech 205:219–223. CrossRefGoogle Scholar
  2. Al-Saleh MH, Gelves GA, Sundararaj U (2011) Copper nanowire/polystyrene nanocomposites: lower percolation threshold and higher EMI shielding. Compos Part A Appl Sci Manuf 42:92–97. CrossRefGoogle Scholar
  3. Bi Y, Ren H, Chen B (2012) Synthesis monolithic copper-based aerogel with polyacrylic acid as template. J Sol-Gel Sci Technol 63(1):140–145. CrossRefGoogle Scholar
  4. Chen CW, Chen MQ (1998) In situ synthesis and the catalytic properties of platinum colloids on polystyrene microspheres with surface-grafted poly (N-isopropylacrylamide). Chem Commun 7:831–832. CrossRefGoogle Scholar
  5. Chen CW, Chen MQ, Serizawa T, Akashi M (1998) In-Situ formation of silver nanoparticles on poly(N-isopropylacrylamide)-coated polystyrene microspheres. Adv Mater 10:1122–1126.;2-N CrossRefGoogle Scholar
  6. Chou TM, Chan SW, Lin YJ (2019) A highly efficient Au-MoS2 nanocatalyst for tunable piezocatalytic and photocatalytic water disinfection. Nano Energy 57:14–21. CrossRefGoogle Scholar
  7. Cu TS, Cao VD, Nguyen CK, Tran NQ (2014) Preparation of silver core-chitosan shell nanoparticles using catechol-functionalized chitosan and antibacterial studies. Macromol Res 22:418–423. CrossRefGoogle Scholar
  8. Dokoutchaev A, James JT, Koene SC, Pathak S, Prakash GS, Thompson ME (1999) Colloidal metal deposition onto functionalized polystyrene microspheres. Chem Mater 11:2389–2399. CrossRefGoogle Scholar
  9. Ghodselahi T, Vesaghi MA, Shafiekhani A, Baghizadeh A, Lameii M (2008) XPS study of the Cu@Cu2O core-shell nanoparticles. Appl Surf Sci 255:2730–2734. CrossRefGoogle Scholar
  10. Gholinejad M, Saadati F, Shaybanizadeh S, Pullithadathil B (2016) Copper nanoparticles supported on starch micro particles as a degradable heterogeneous catalyst for three-component coupling synthesis of propargylamines. RSC Adv 6:4983–4991. CrossRefGoogle Scholar
  11. Gurav KV, Patil UM, Shin SW, Agawane GL, Suryawanshi MP, Pawar SM, Kim JH (2013) Room temperature chemical synthesis of Cu(OH)2 thin films for supercapacitor application. J Alloy Compd 573:27–31. CrossRefGoogle Scholar
  12. Hong SC, Shin KE, Noh SK, Lyoo WS (2005) Cu catalyst system with phosphorous containing bidendate ligand for living radical polymerization of MMA. Macromol Res 13:391–396. CrossRefGoogle Scholar
  13. Hüfner S, Wertheim GK, Smith NV, Traum MM (1972) XPS density of states of copper, silver, and nickel. Solid State Commun 11:323–326. CrossRefGoogle Scholar
  14. Ithurria S, Talapin DV (2012) Colloidal atomic layer deposition (c-ALD) using self-limiting reactions at nanocrystal surface coupled to phase transfer between polar and nonpolar media. J Am Chem Soc 134:18585–18590. CrossRefPubMedGoogle Scholar
  15. Jung DR, King DE, Czanderna AW (1993) Metal overlayers on organic functional groups of self-organized molecular assemblies. II. X-ray photoelectron spectroscopy of interactions of Cu/CN on 12-mercaptododecanenitrile. J Vac Sci Technol A 11:2382–2386. CrossRefGoogle Scholar
  16. Kamrupi IR, Dolui SK (2011) Synthesis of copper–polystyrene nanocomposite particles using water in supercritical carbon dioxide medium and its antimicrobial activity. J Appl Polym Sci 120:1027–1033. CrossRefGoogle Scholar
  17. Kang YM, Park MS, Lee JY, Liu HK (2007) Si–Cu/carbon composites with a core–shell structure for Li-ion secondary battery. Carbon 45:1928–1933. CrossRefGoogle Scholar
  18. Kim C, Kim SY, Yong TL, Lee TS (2017) Synthesis of conjugated polymer nanoparticles with core–shell structure for cell imaging and photodynamic cancer therapy. Macromol Res 25:1–6. CrossRefGoogle Scholar
  19. Li CM, Lei H, Tang YJ, Luo JS, Liu W, Chen ZM (2004) Production of copper nanoparticles by the flow-levitation method. Nanotechnology 15:1866. CrossRefGoogle Scholar
  20. Li H, Kang W, Xi B, Yan Y, Bi H, Zhu Y, Qian Y (2010) Thermal synthesis of Cu@ carbon spherical core–shell structures from carbonaceous matrices containing embedded copper particles. Carbon 48:464–469. CrossRefGoogle Scholar
  21. Li H, Li C, Bai J, Zhang C, Sun W (2014a) Carbon nanofiber supported copper nanoparticles catalyzed Ullmann-type coupling reactions under ligand-free conditions. RSC Adv 4:48362–48367. CrossRefGoogle Scholar
  22. Li Y, Tang X, Zhang Y, Li J, Lv C, Meng X, Wang C (2014b) Cu nanoparticles of low polydispersity synthesized by a double-template method and their stability. Colloid Polym Sci 292:715–722. CrossRefGoogle Scholar
  23. Li B, Li Y, Wu Y, Zhao Y (2014c) Synthesis of water-soluble Cu/PAA composite flowers and their antibacterial activities. Mat Sci Eng C Mater 35:205–211. CrossRefGoogle Scholar
  24. Li Y, Wu Z, Ye S (2015) Highly facile and efficient assembly of palladium nanoparticles on polystyrene microspheres and their application in catalysis. New J Chem 39:8108–8113. CrossRefGoogle Scholar
  25. Lin JH, Tsao YH, Wu MH (2017) Single-and few-layers MoS2 nanocomposite as piezo-catalyst in dark and self-powered active sensor. Nano Energy 31:575–581. CrossRefGoogle Scholar
  26. Lin YJ, Chou TM, Lin ZH (2018) Multifunctional MoS2 nanocatalysts for water disinfection. ECS Trans 85(9):47–51. CrossRefGoogle Scholar
  27. Macomber L, Imlay JA (2009) The iron-sulfur clusters of dehydratases are primary intracellular targets of copper toxicity. Proc Natl Acad Sci 106(20):8344–8349. CrossRefPubMedGoogle Scholar
  28. Mahmoud MA, Snyder B, Elsayed MA (2009) Polystyrene microspheres: inactive supporting material for recycling and recovering colloidal nanocatalysts in solution. J Phys Chem Lett 1:28–31. CrossRefGoogle Scholar
  29. Mani S, Weiss RA, Williams CE, Hahn SF (1999) Microstructure of ionomers based on sulfonated block copolymers of polystyrene and poly(ethylene-alt-propylene). Macromolecules 32:3663–3670. CrossRefGoogle Scholar
  30. Martins CR, Ruggeri G, Paoli MAD (2003) Synthesis in pilot plant scale and physical properties of sulfonated polystyrene. J Braz Chem Soc 14:797–802. CrossRefGoogle Scholar
  31. Nador F, Volpe MA, Alonso F, Feldhoff A, Krischning A, Radivoy G (2013) Copper nanoparticles supported on silica coated maghemite as versatile, magnetically recoverable and reusable catalyst for alkyne coupling and cycloaddition reactions. Appl Catal A Gen 455:39–45. CrossRefGoogle Scholar
  32. Ni Z, Wang Z, Sun L, Li B, Zhao Y (2014) Synthesis of poly acrylic acid modified silver nanoparticles and their antimicrobial activities. Mat Sci Eng C Mater 41:249–254. CrossRefGoogle Scholar
  33. Nirmala R, Kim HY, Kalpana D, Navamathavan R, Lee YS (2013) Multipurpose polyurethane antimicrobial metal composite films via wet; cast technology. Macromol Res 21:843–851. CrossRefGoogle Scholar
  34. Paladini F, Pollini M, Sannino A, Ambrosio L (2015) Metal-based antibacterial substrates for biomedical applications. Biomacromolecules 16:1873–1885. CrossRefPubMedGoogle Scholar
  35. Palza H (2015) Antimicrobial polymers with metal nanoparticles. Int J Mol Sci 16:2099–2116. CrossRefPubMedPubMedCentralGoogle Scholar
  36. Park H, Han TH (2014) Facile hybridization of graphene oxide and Cu2O for high-performance electrochemical supercapacitors. Macromol Res 22:809–812. CrossRefGoogle Scholar
  37. Patterson AL (1939) The Scherrer formula for X-ray particle size determination. Phys Rev 56:978–982. CrossRefGoogle Scholar
  38. Peceros KE, Xu X, Bulcock SR (2005) Dipole-dipole plasmon interactions in gold-on-polystyrene composites. J Phys Chem B 109(46):21516–21520. CrossRefPubMedGoogle Scholar
  39. Potara M, Jakab E, Damert A, Popescu O, Canpean V, Astilean S (2011) Synergistic antibacterial activity of chitosan–silver nanocomposites on Staphylococcus aureus. Nanotechnology 22:135101. CrossRefPubMedGoogle Scholar
  40. Qi C, Ye J, Zeng W, Jiang H (2010) Polystyrene-supported amino acids as efficient catalyst for chemical fixation of carbon dioxide. Adv Synth Catal 352:1925–1933. CrossRefGoogle Scholar
  41. Quaranta D, Krans T, Santo CE (2011) Mechanisms of contact-mediated killing of yeast cells on dry metallic copper surfaces. Appl Environ Microbiol 77(2):416–426. CrossRefPubMedGoogle Scholar
  42. Rubinger CPL, Martins CR, Paoli MAD, Rubinger MA (2007) Sulfonated polystyrene polymer humidity sensor: synthesis and characterization. Sens Actuators B Chem 123:42–49. CrossRefGoogle Scholar
  43. Santo CE, Lam EW, Elowsky CG (2011) Bacterial killing by dry metallic copper surfaces. Appl Environ Microbiol 77(3):794–802. CrossRefGoogle Scholar
  44. Sugawa K, Yamaguchi D, Tsunenari N (2016) Efficient photocurrent enhancement from porphyrin molecules on plasmonic copper arrays: beneficial utilization of copper nanoantennae on plasmonic photoelectric conversion systems. ACS Appl Mater Interfaces 9(1):750–762. CrossRefPubMedGoogle Scholar
  45. Tian K, Liu C, Yang H, Ren X (2012) In situ synthesis of copper nanoparticles/polystyrene composite. Colloid Surface A 397:12–15. CrossRefGoogle Scholar
  46. Veerakumar P, Velayudham M, Lu KL, Rajagopal S (2011) Highly dispersed silica-supported nanocopper as an efficient heterogeneous catalyst: application in the synthesis of 1, 2, 3-triazoles and thioethers. Catal Sci Technol 1:1512–1525. CrossRefGoogle Scholar
  47. Wang P, Chen D, Tang FQ (2006) Preparation of titania-coated polystyrene particles in mixed solvents by ammonia catalysis. Langmuir 22:4832–4835. CrossRefPubMedGoogle Scholar
  48. Wang J, Zhu H, Chen JD, Zhang B, Zhang M, Wang LN, Du ML (2016) Small and well-dispersed Cu nanoparticles on carbon nanofibers: self-supported electrode materials for efficient hydrogen evolution reaction. Int J Hydrogen Energy 41:18044–18049. CrossRefGoogle Scholar
  49. Warnes SL, Keevil CW (2011) Mechanism of copper surface toxicity in vancomycin-resistant enterococci following wet or dry surface contact. Appl Environ Microbiol 77(17):6049–6059. CrossRefPubMedPubMedCentralGoogle Scholar
  50. Warnes SL, Caves V, Keevil CW (2012) Mechanism of copper surface toxicity in Escherichia coli O157: H7 and Salmonella involves immediate membrane depolarization followed by slower rate of DNA destruction which differs from that observed for Gram-positive bacteria. Environ Microbiol 14(7):1730–1743. CrossRefPubMedGoogle Scholar
  51. Yang J, Chen J, Zhou Y, Wu K (2011) a nano-copper electrochemical sensor for sensitive detection of chemical oxygen demand. Sens Actuators B Chem 153:78–82. CrossRefGoogle Scholar
  52. Yu HL, Xu BS, Xu Y, Wang XL, Qi Liu (2005) Design of wear-out-failure in situ repair parts by environment-friendly nanocopper additive. J Cent South Univ Technol 12:215–220. CrossRefGoogle Scholar
  53. Yu S, Park K, Lee JW, Hong SM, Park C, Han TH (2017a) Enhanced thermal conductivity of epoxy/Cu-plated carbon fiber fabric composites. Macromol Res 25:559–564. CrossRefGoogle Scholar
  54. Yu Q, Li M, Zeng Q, Wu X (2017b) Highly porous copper with hollow microsphere structure from polystyrene templates via electroless plating. J Electrochem Soc 164:D135–D142. CrossRefGoogle Scholar
  55. Yu Y, Luan D, Bi C, Ma Y, Chen Y, Zhao D (2018) Synthesis of polystyrene microsphere-supported Ag–Ni-alloyed catalysts with core–shell structures for electrocatalytic performance. Polym Plast Technol Eng 57:875–883. CrossRefGoogle Scholar
  56. Zhang H, Zhong X, Xu JJ, Chen HY (2008) Fe3O4/Polypyrrole/Au nanocomposites with core/shell/shell structure: synthesis, characterization, and their electrochemical properties. Langmuir 24:13748–13752. CrossRefPubMedGoogle Scholar
  57. Zhao Y, Feng J, Hong L, Li Y, Wang C, Ye S (2018) Simple surface-assisted formation of palladium nanoparticles on polystyrene microspheres and their application in catalysis. Inorg Chem Front 5:1133–1138. CrossRefGoogle Scholar
  58. Zhong Z, Yin Y, Gates B, Xia Y (2000) Preparation of mesoscale hollow spheres of TiO2 and SnO2 by templating against crystalline arrays of polystyrene beads. Adv Mater 12:206–209.;2-5 CrossRefGoogle Scholar
  59. Zhou S, Varughese B, Eichhorn B, Jackson G, McIlwrath K (2005) Pt–Cu core–shell and alloy nanoparticles for heterogeneous NOx reduction: anomalous stability and reactivity of a core–shell nanostructure. Angew Chem Int Edit 117:4615–4619. CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2019

Authors and Affiliations

  1. 1.Department of Macromolecular Science and Engineering, School of Chemistry and Materials ScienceHeilongjiang UniversityHarbinChina
  2. 2.Key Laboratory of Chemical Engineering Process and Technology for High-efficiency ConversionCollege of Heilongjiang ProvinceHarbinChina
  3. 3.Institute of PetrochemistryHeilongjiang Academy of SciencesHarbinChina

Personalised recommendations