Skip to main content
SpringerLink
Log in

Preparation of Copper (I) Chelated Strip Catalysts Based on PEI Immobilized on Graphene-Coated Bacterial Cellulose for ATRP Reaction

  • Research Article-Chemistry
  • Published:
Arabian Journal for Science and Engineering Aims and scope Submit manuscript

Abstract

Achieving an efficient catalyst in the ATRP system with a simple preparation method and high recyclability is an important challenging issue. In this study, a dip-catalyst based on functional graphene oxide-coated bacterial cellulose as a green support was prepared. Graphene oxide (GO) nanosheets were first conjugated with ethylated-branched-polyethyleneimine (E-bPEI), showing as an effective ATRP ligand. Then, the ligand-modified GO was coated on the surface of bacterial cellulose (BC/GO-E-bPEI). In the next step, copper (I) was incorporated into the BC/GO-E-bPEI through strong chelation by E-bPEI (Cu@BC/GO-E-bPEI). The synthesized dip-catalyst, in the form of the strips, was used for the first time in the ATRP reaction of methyl methacrylate to investigate catalytic activity. The prepared dip catalysts showed high catalytic activity, reasonable control over molecular weight, and narrow molecular weight distribution. Importantly, the reaction was simply turned on/off at any time by insertion/removal of the strips. The recyclability of the catalyst was studied for 7 runs. Also, the amount of residual copper in the polymer was very low (1.5 ppm).

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Pramounmat, N.; Asaei, S.; Hostert, J.D.; Young, K.; von Recum, H.A.; Renner, J.N.: Grafting of short elastin-like peptides using an electric field. Sci. Rep. 12(1), 18682 (2022)

    Google Scholar 

  2. Ouchi, M.; Terashima, T.; Sawamoto, M.: Transition metal-catalyzed living radical polymerization: toward perfection in catalysis and precision polymer synthesis. Chem. Rev. 109(11), 4963–5050 (2009)

    Google Scholar 

  3. Le Droumaguet, B.; Nicolas, J.: Recent advances in the design of bioconjugates from controlled/living radical polymerization. Polym. Chem. 1(5), 563–598 (2010)

    Google Scholar 

  4. Matyjaszewski, K.; Tsarevsky, N.V.: Macromolecular engineering by atom transfer radical polymerization. J. Am. Chem. Soc. 136(18), 6513–6533 (2014)

    Google Scholar 

  5. Tang, W., et al.: Understanding atom transfer radical polymerization: effect of ligand and initiator structures on the equilibrium constants. J. Am. Chem. Soc. 130(32), 10702–10713 (2008)

    Google Scholar 

  6. Ding, M., et al.: Recent progress on transition metal catalyst separation and recycling in ATRP. Macromol. Rapid Commun. 36(19), 1702–1721 (2015)

    Google Scholar 

  7. Lorandi, F.; Matyjaszewski, K.: Why do we need more active ATRP catalysts? Isr. J. Chem. 60(1–2), 108–123 (2020)

    Google Scholar 

  8. Shen, Y.; Tang, H.; Ding, S.: Catalyst separation in atom transfer radical polymerization. Prog. Polym. Sci. 29(10), 1053–1078 (2004)

    Google Scholar 

  9. Feiz, E.; Mahyari, M.; Ghaieni, H.R.; Tavangar, S.: Copper on chitosan-modified cellulose filter paper as an efficient dip catalyst for ATRP of MMA. Sci. Rep. 11(1), 8257 (2021)

    Google Scholar 

  10. Zheng, G., et al.: Gold nanoparticle-loaded filter paper: a recyclable dip-catalyst for real-time reaction monitoring by surface enhanced Raman scattering. Chem. Commun. 51(22), 4572–4575 (2015)

    Google Scholar 

  11. Porel, S., et al.: Polymer thin film with in situ synthesized silver nanoparticles as a potent reusable bactericide. Curr. Sci. (Bangalore) 101(7), 927–934 (2011)

    Google Scholar 

  12. Karthikeyan, B.; Anija, M.; Philip, R.: In situ synthesis and nonlinear optical properties of Au: Ag nanocomposite polymer films. Appl. Phys. Lett. 88(5), 053104 (2006)

    Google Scholar 

  13. Ramesh, G.; Radhakrishnan, T.: A universal sensor for mercury (Hg, HgI, HgII) based on silver nanoparticle-embedded polymer thin film. ACS Appl. Mater. Interfaces. 3(4), 988–994 (2011)

    Google Scholar 

  14. Ramesh, G., et al.: Microwave absorber based on silver nanoparticle-embedded polymer thin film. J. Nanosci. Nanotechnol. 9(1), 261–266 (2009)

    Google Scholar 

  15. Golabdar, A., et al.: Anti-bacterial poly (vinyl alcohol) nanocomposite hydrogels reinforced with in situ synthesized silver nanoparticles. Polym. Compos. 40(4), 1322–1328 (2019)

    Google Scholar 

  16. Hariprasad, E.; Radhakrishnan, T.: A highly efficient and extensively reusable “dip catalyst” based on a silver-nanoparticle-embedded polymer thin film. Chem. A Eur. J. 16(48), 14378–14384 (2010)

    Google Scholar 

  17. Choosakoonkriang, S., et al.: Biophysical characterization of PEI/DNA complexes. J. Pharm. Sci. 92(8), 1710–1722 (2003)

    Google Scholar 

  18. Godbey, W.; Wu, K.K.; Mikos, A.G.: Poly (ethylenimine)-mediated gene delivery affects endothelial cell function and viability. Biomaterials 22(5), 471–480 (2001)

    Google Scholar 

  19. Corti, M., et al.: Magnetic and relaxometric properties of polyethylenimine-coated superparamagnetic MRI contrast agents. J. Magn. Magn. Mater. 320(14), e316–e319 (2008)

    Google Scholar 

  20. Einafshar, E.; Khodadadipoor, Z.; Nejabat, M.; Ramezani, M.: Synthesis, characterization and application of α, β, and γ cyclodextrin-conjugated graphene oxide for removing cadmium ions from aqueous media. J. Polym. Environ. 29, 3161–3173 (2021)

    Google Scholar 

  21. Si, Y.; Samulski, E.T.: Synthesis of water soluble graphene. Nano Lett. 8(6), 1679–1682 (2008)

    Google Scholar 

  22. Pumera, M.: Graphene-based nanomaterials for energy storage. Energy Environ. Sci. 4(3), 668–674 (2011)

    Google Scholar 

  23. Hosseini, S.G.; Khodadadipoor, Z.; Mahyari, M.; Zinab, J.M.: Copper chromite decorated on nitrogen-doped graphene aerogel as an efficient catalyst for thermal decomposition of ammonium perchlorate particles. J. Therm. Anal. Calorim. 138, 963–972 (2019)

    Google Scholar 

  24. Kamal, T.; Khan, S.B.; Asiri, A.M.: Nickel nanoparticles-chitosan composite coated cellulose filter paper: an efficient and easily recoverable dip-catalyst for pollutants degradation. Environ. Pollut. 218, 625–633 (2016)

    Google Scholar 

  25. Molnár, Á.; Papp, A.: The use of polysaccharides and derivatives in palladium-catalyzed coupling reactions. Catal. Sci. Technol. 4(2), 295–310 (2014)

    Google Scholar 

  26. Hosseini, H., et al.: Pd and PdCo alloy nanoparticles supported on polypropylenimine dendrimer-grafted graphene: a highly efficient anodic catalyst for direct formic acid fuel cells. J. Power Sources 247, 70–77 (2014)

    Google Scholar 

  27. Einafshar, E.; Khodadadipoor, Z.; Fazli, M.; Einafshar, N.; Mohebbi Zinab, J.; Asaei, S.: Preparation of Ag-Al2O3 nano structures by combustion method and investigation of photocatalytic activity. Int. J. Appl. Ceram. Technol. 18(6), 2064–2074 (2021)

    Google Scholar 

  28. Mahyari, M.; Shaabani, A.: Nickel nanoparticles immobilized on three-dimensional nitrogen-doped graphene as a superb catalyst for the generation of hydrogen from the hydrolysis of ammonia borane. J. Mater. Chem. A 2(39), 16652–16659 (2014)

    Google Scholar 

  29. Torres, F.G., et al.: Enhanced conductivity of bacterial cellulose films reinforced with NH4I-doped graphene oxide. Polym. Plast. Technol. Mater. 58(14), 1585–1595 (2019)

    Google Scholar 

  30. Hosseini, S.G.; Khodadadipoor, Z.; Mahyari, M.: CuO nanoparticles supported on three-dimensional nitrogen-doped graphene as a promising catalyst for thermal decomposition of ammonium perchlorate. Appl. Organomet. Chem. 32(1), e3959 (2018)

    Google Scholar 

  31. Matyjaszewski, K., et al.: Tridentate nitrogen-based ligands in Cu-based ATRP: a structure–activity study. Macromolecules 34(3), 430–440 (2001)

    Google Scholar 

  32. Ren, Q., et al.: A highly sensitive competitive immunosensor based on branched polyethyleneimine functionalized reduced graphene oxide and gold nanoparticles modified electrode for detection of melamine. Food Chem. 304, 125397 (2020)

    Google Scholar 

  33. Shao, W., et al.: Anti-bacterial performances and biocompatibility of bacterial cellulose/graphene oxide composites. RSC Adv. 5(7), 4795–4803 (2015)

    Google Scholar 

  34. Liu, J.; Cui, L.; Losic, D.: Graphene and graphene oxide as new nanocarriers for drug delivery applications. Acta Biomater. 9(12), 9243–9257 (2013)

    Google Scholar 

  35. Adelnia, H.; Gavgani, J.N.; Soheilmoghaddam, M.: Fabrication of composite polymer particles by stabilizer-free seeded polymerization. Colloid Polym. Sci. 293(8), 2445–2450 (2015)

    Google Scholar 

  36. Madhuri, U.D.; Saha, J.; Radhakrishnan, T.: ‘Dip catalysts’ based on polymer-metal nanocomposite thin films: combining soft-chemical fabrication with efficient application and monitoring. ChemNanoMat 4(12), 1191–1201 (2018)

    Google Scholar 

  37. Liu, Y., et al.: Facile synthesis of bacterial cellulose fibres covalently intercalated with graphene oxide by one-step cross-linking for robust supercapacitors. J. Mater. Chem. C 3(5), 1011–1017 (2015)

    Google Scholar 

  38. Chang, Y., et al.: Embedding reduced graphene oxide in bacterial cellulose-derived carbon nanofibril networks for supercapacitors. ChemElectroChem 4(10), 2448–2452 (2017)

    Google Scholar 

  39. Zhou, P., et al.: Bacteria cellulose nanofibers supported palladium (0) nanocomposite and its catalysis evaluation in Heck reaction. Ind. Eng. Chem. Res. 51(16), 5743–5748 (2012)

    Google Scholar 

  40. Czaja, W., et al.: Microbial cellulose—the natural power to heal wounds. Biomaterials 27(2), 145–151 (2006)

    Google Scholar 

  41. Adhikari, B.; Biswas, A.; Banerjee, A.: Graphene oxide-based supramolecular hydrogels for making nanohybrid systems with Au nanoparticles. Langmuir 28(2), 1460–1469 (2012)

    Google Scholar 

  42. Aladejana, J.T., et al.: Key advances in development of straw fibre bio-composite boards: an overview. Mater. Res. Express 7(1), 012005 (2020)

    Google Scholar 

  43. Nabid, M.R.; Bide, Y.; Ghalavand, N.: Copper (I) ion stabilized on fe3o4‐core ethylated branched polyethyleneimine‐shell as magnetically recyclable catalyst for ATRP reaction. J. Appl. Polym. Sci. 132(33), 42337–42345 (2015)

    Google Scholar 

  44. Wang, Y.; Clay, A.; Nguyen, M.: ATRP by continuous feeding of activators: limiting the end-group loss in the polymerizations of methyl methacrylate and styrene. Polymer 188, 122097 (2020)

    Google Scholar 

  45. Mittal, A.; Baskaran, D.; Sivaram, S.: Copper catalyzed ATRP of methyl methacrylate using aliphatic α‐bromo ketone initiator. In: Macromolecular symposia. Wiley Online Library (2006)

  46. Xu, Q., et al.: Atom transfer radical polymerization of methyl acrylate, methyl methacrylate and styrene in the presence of trolamine as a highly effective promoter. Chin. Chem. Lett. 26(6), 773–778 (2015)

    Google Scholar 

  47. Wang, L., et al.: Corn starch-based graft copolymers prepared via ATRP at the molecular level. Polym. Chem. 6(18), 3480–3488 (2015)

    Google Scholar 

  48. Jones, C.W.: On the stability and recyclability of supported metal–ligand complex catalysts: myths, misconceptions and critical research needs. Top. Catal. 53(13–14), 942–952 (2010)

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Faculty of Chemistry and Chemical Engineering, Malek Ashtar University of Technology, Tehran, Iran

    Mojtaba Mahyari, Zahra Khodadadipoor, Elham Feiz & Mohammad Ali Zarei

  2. Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, P.O.Box-15875-4413, Tehran, Iran

    Jaber Nasrollah Gavgani

Authors
  1. Mojtaba Mahyari
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zahra Khodadadipoor
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Elham Feiz
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mohammad Ali Zarei
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jaber Nasrollah Gavgani
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mojtaba Mahyari.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mahyari, M., Khodadadipoor, Z., Feiz, E. et al. Preparation of Copper (I) Chelated Strip Catalysts Based on PEI Immobilized on Graphene-Coated Bacterial Cellulose for ATRP Reaction. Arab J Sci Eng 49, 565–575 (2024). https://doi.org/10.1007/s13369-023-08161-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13369-023-08161-5

Keywords

Search

Navigation