Advertisement

Journal of Materials Science

, Volume 54, Issue 7, pp 5294–5310 | Cite as

Highly sensitive, stable g-CN decorated with AgNPs for SERS sensing of toluidine blue and catalytic reduction of crystal violet

  • E. MuruganEmail author
  • S. Santhosh Kumar
  • K. M. Reshna
  • S. Govindaraju
Chemical routes to materials
  • 65 Downloads

Abstract

SERS substrates with high sensitivity, SERS enhancement and stability are essential for fabrication of SERS sensors to detect dyes at low concentration. Such substrates generally have a versatile support bonded to metal nanoparticles of optimum size. Simple methodology that yields SERS substrates with reproducible results is mostly desired for sensor fabrication. In this study, silver ions were reduced with safe reducing agent NaBH4 to Ag metal nanoparticles (AgNPs) in the presence of previously prepared g-CN to obtain g-CN decorated with silver nanoparticles (AgNPs@g-CN) of average diameter 22 nm. The results of XPS and UV–Vis spectroscopy unambiguously establish significant interaction between the nitrogen sites of g-CN and AgNPs. The AgNPs@g-CN yielded very high SERS enhancement for toluidine blue at very low concentration (2.5 × 10−09 M), and the SERS results are reproducible. The surface enhancement factor (EF) is one of the important criteria to evaluate and compare SERS materials, and it was equal to 9.13 × 106 toward toluidine blue. The catalytic activity of the substrate for the reduction of crystal violet (CV) to its leuco-form was tested with NABH4. The reaction was monitored by UV Vis spectroscopy. There was a rapid fall in intensity of CV. The reduction of CV mainly occurred via electron transfer from AgNPs, and the product did not interfere with the absorbance of CV. Hence, AgNPs@g-CN could be a convenient choice for fabrication of commercial SERS sensors for detection of dyes at low concentrations. It is also useful as a catalyst for the reduction of organic dyes.

Notes

Acknowledgements

The authors greatly acknowledge financial supports from the UGC-UPE-Phase-II New Materials Research and DST-SERB/SB/EMEQ/456/2014.

Compliance with ethical standards

Conflicts of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2018_3184_MOESM1_ESM.docx (1.9 mb)
Supplementary material 1 (DOCX 1976 kb)

References

  1. 1.
    Georgakilas V, Otyepka M, Bourlinos AB, Chandra V, Kim N, Kemp KC, Hobza P, Zboril R, Kim KS (2012) Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. Chem Rev 112:6156–6214CrossRefGoogle Scholar
  2. 2.
    Li X, Zhu J, Wei B (2016) Hybrid nanostructures of metal/two-dimensional nanomaterials for plasmon-enhanced applications. Chem Soc Rev 45:3145–3187CrossRefGoogle Scholar
  3. 3.
    Kim J, Byun S, Smith AJ, Yu J, Huang J (2013) Enhanced electrocatalytic properties of transition-metal dichalcogenides sheets by spontaneous gold nanoparticle decoration. J Phys Chem Lett 4:1227–1232CrossRefGoogle Scholar
  4. 4.
    Wang X, Liu D, Song S, Zhang H (2013) Pt@CeO2 multicore@ shell self-assembled nanospheres: clean synthesis, structure optimization, and catalytic applications. J Am Chem Soc 135:15864–15872CrossRefGoogle Scholar
  5. 5.
    Wang F, Zeng X, Yao Y, Sun R, Xu J, Wong C-P (2016) Silver nanoparticle-deposited boron nitride nanosheets as fillers for polymeric composites with high thermal conductivity. Sci Rep 6:19394CrossRefGoogle Scholar
  6. 6.
    Satheeshkumar E, Makaryan T, Melikyan A, Minassian H, Gogotsi Y, Yoshimura M (2016) One-step solution processing of Ag, Au and Pd@ MXene hybrids for SERS. Sci Rep 6:32049CrossRefGoogle Scholar
  7. 7.
    Chen C, Gunawan P, Lou XW, Xu R (2012) Silver nanoparticles deposited layered double hydroxide nanoporous coatings with excellent antimicrobial activities. Adv Funct Mater 22:780–787CrossRefGoogle Scholar
  8. 8.
    Tian J, Liu Q, Asiri AM, Al-Youbi AO, Sun X (2013) Ultrathin graphitic carbon nitride nanosheet: a highly efficient fluorosensor for rapid, ultrasensitive detection of Cu2+. Anal Chem 85:5595–5599CrossRefGoogle Scholar
  9. 9.
    Wang Y, Wang X, Antonietti M (2012) Polymeric graphitic carbon nitride as a heterogeneous organocatalyst: from photochemistry to multipurpose catalysis to sustainable chemistry. Angew Chem Int Ed 51:68–89CrossRefGoogle Scholar
  10. 10.
    Han Q, Wang B, Gao J, Cheng ZH, Zhao Y, Zhang ZP, Qu LT (2016) Atomically thin mesoporous nanomesh of graphitic C3N4 for high-efficiency photocatalytic hydrogen evolution. ACS Nano 10:2745–2751CrossRefGoogle Scholar
  11. 11.
    Deng Q, Li Q (2018) Facile preparation of Mg-doped graphitic carbon nitride composites as a solid base catalyst for Knoevenagel condensations. J Mater Sci 53:506–515CrossRefGoogle Scholar
  12. 12.
    Yang J, Cao B, Li H, Liu B (2014) Investigation of the catalysis and SERS properties of flower-like and hierarchical silver microcrystals. J Nanopart Res 16:2651CrossRefGoogle Scholar
  13. 13.
    Anantharaj S, Ede R, Nithiyanantham U, Kundu S (2014) Osmium organosol on DNA: application in catalytic hydrogenation reaction and in SERS studies. Ind Eng Chem Res 53(49):19228–19238CrossRefGoogle Scholar
  14. 14.
    Chen H, Wei G, Ispas A, Hickey SG, Eychmüller A (2010) Synthesis of palladium nanoparticles and their applications for surface-enhanced Raman scattering and electrocatalysis. J Phys Chem C 114:21976–21981CrossRefGoogle Scholar
  15. 15.
    Yin AX, Liu WC, Ke J, Zhu W, Gu J, Zhang YW, Yan C-H (2012) Ru nanocrystals with Shape-dependent surface-enhanced Raman spectra and catalytic properties: controlled synthesis and DFT calculations. J Am Chem Soc 134:20479–20489CrossRefGoogle Scholar
  16. 16.
    Li JF, Huang YF, Duan S, Pang R, Wu DY, Ren B, Xu X, Tian ZQ (2010) SERS and DFT study of water on metal cathodes of silver, gold and platinum nanoparticles. Phys Chem Chem Phys 12:2493–2502CrossRefGoogle Scholar
  17. 17.
    Sakthikumar K, Anantharaj S, Ede SR, Karthick K, Kundu S (2016) A highly stable rhenium organosol on a DNA Scaffold for catalytic and SERS applications. J Mater Chem C 4:6309–6320CrossRefGoogle Scholar
  18. 18.
    Li D-W, Zhai W-L, Li Y-T, Long Y-T (2014) Recent progress in surface enhanced Raman spectroscopy for the detection of environmental pollutants. Microchim Acta 181:23–43CrossRefGoogle Scholar
  19. 19.
    Ma P, Liang F, Sun Y, Jin Y, Chen Y, Wang X, Zhang H, Gao D, Song D (2013) Rapid determination of melamine in milk and milk powder by surface-enhanced Raman spectroscopy and using cyclodextrin-decorated silver nanoparticles. Microchim Acta 180:1173–1180CrossRefGoogle Scholar
  20. 20.
    Murugan E, Santhosh Kumar S, Raman A (2018) Synthesis of Ag nanoparticles decorated CeO2 nanocomposite material for effective SERS analysis. AMP 3:112–117CrossRefGoogle Scholar
  21. 21.
    Sharma B, Frontiera RR, Henry AI, Ringe E, Van Duyne RP (2012) SERS: materials, applications, and the future. Mater Today 15:16–25CrossRefGoogle Scholar
  22. 22.
    Jiang J, Zhu L, Zou J, Ou-yang L, Zheng A, Tang H (2015) Micro/nano-structured graphitic carbon nitride-ag nanoparticle hybrids as surface-enhanced Raman scattering substrates with much improved long-term stability. Carbon 87:193–205CrossRefGoogle Scholar
  23. 23.
    Jiang J (2016) Improving the surface-enhanced Raman scattering activity of carbon nitride by two-step calcining. RSC Adv 6:47368–47372CrossRefGoogle Scholar
  24. 24.
    Jiang J, Zou J, Wee ATS, Zhang W (2016) Use of single-layer g-C3N4/Ag hybrids for surface-enhanced Raman scattering (SERS). Sci Rep 6:34599CrossRefGoogle Scholar
  25. 25.
    Gokul S, Akhil AS (2012) Toluidine blue: A review of its chemistry and clinical utility. J Oral Maxillofac Pathol 16:251–255CrossRefGoogle Scholar
  26. 26.
    He Y, Wang Y, Yang X, Xie S, Yuan R, Chai Y (2016) Metal organic frameworks combining CoFe2O4 magnetic nanoparticles as highly efficient SERS sensing platform for ultrasensitive detection of N-terminal pro-brain natriuretic peptide. ACS Appl Mater Interfaces 8:7683–7690CrossRefGoogle Scholar
  27. 27.
    Veerakumar P, Muthuselvam P, Pounraj T, Lin K (2018) Low-cost palladium decorated on m-aminophenol-formaldehyde derived porous carbon spheres for enhanced catalytic reduction of organic dyes. Inorg Chem Front 5:354–363CrossRefGoogle Scholar
  28. 28.
    Su X, Vinu A, Aldeyab SS, Zhong L (2015) Highly uniform Pd nanoparticles supported on g-C3N4 for efficiently catalytic Suzuki–Miyaura reactions. Catal Lett 145:1388–1395CrossRefGoogle Scholar
  29. 29.
    Wen Y, Fan H, Ning L, Wang C, Hu B, Ma J, Wang W, Cui K (2019) Graphitic carbon nitride nanosheets prepared by gaseous molecules assembling for enhanced photocatalytic performance. J Mater Sci 54:1462–1474.  https://doi.org/10.1007/s10853-018-2937-5 CrossRefGoogle Scholar
  30. 30.
    Yan J, Han X, Qian J, Liu J, Dong X, Xi F (2017) Preparation of 2D graphitic carbon nitride nanosheets by a green exfoliation approach and the enhanced photocatalytic performance. J Mater Sci 52:13091–13102CrossRefGoogle Scholar
  31. 31.
    Jia X, Dai R, Sun Y, Song H, Wu X (2016) One-step hydrothermal synthesis of Fe3O4/g-C3N4 nanocomposites with improved photocatalytic activities. J Mater Sci Mater Electron 27:3791–3798CrossRefGoogle Scholar
  32. 32.
    Leong KH, Liu SL, Sim LC, Saravanan P, Jang M, Ibrahim S (2015) Surface reconstruction of titania with g-C3N4 and Ag for promoting efficient electrons migration and enhanced visible light photocatalysis. Appl Surf Sci 358:370–376CrossRefGoogle Scholar
  33. 33.
    Yu M-E, Cheong B-S, Cho H-G (2017) SERS spectroscopy and DFT studies of thionine and its derivatives adsorbed on silver colloids: which N atom is used for coordination of a phenothiazine-based natural dye to electron-deficient metal surface? Bull Korean Chem Soc 38:928–934CrossRefGoogle Scholar
  34. 34.
    Maher RC (2012) SERS hot spots. In: Kumar CSSR (ed) Raman spectroscopy for nanomaterials characterization. Springer, Berlin, pp 215–260CrossRefGoogle Scholar
  35. 35.
    Mazˇeikiene R, Niaura G, Eicher-Lorka O, Malinauskas A (2008) Raman spectroelectrochemical study of toluidine Blue, adsorbed and electropolymerized at a gold electrode. Vib Spectrosc 47:105–112CrossRefGoogle Scholar
  36. 36.
    Zhao Y, Pan X, Zhang L, Xu Y, Li C, Wang J, Ou J, Xiu X, Man B, Yang C (2017) Dense AuNP/MoS2 hybrid fabrication on fiber membranes for molecule separation and SERS detection. RSC Adv 7:36516–36524CrossRefGoogle Scholar
  37. 37.
    Murugan E, Jebaranjitham N (2012) Synthesis and characterization of silver nanoparticles supported on surface-modified poly (N-vinylimidazale) as catalysts for the reduction of 4-nitrophenol. J Mol Catal A Chem 365:128–135CrossRefGoogle Scholar
  38. 38.
    Murugan E, Jebaranjitham JN (2015) Dendrimer grafted core-shell Fe3O4-polymer magnetic nanocomposites stabilized with AuNPs for enhanced catalytic degradation of Rhodamine B—a kinetic study. Chem Eng J 259:266–276CrossRefGoogle Scholar
  39. 39.
    Murugan E, Rangasamy R (2010) Synthesis, Characterization, and heterogeneous catalysis of polymer-supported poly(propyleneimine) dendrimer stabilized gold nanoparticle catalyst. J Polym Sci Part A Polym Chem 48:2525–2532CrossRefGoogle Scholar
  40. 40.
    Murugan E, Shanmugam P (2015) Efficient functionalization of poly(styrene) beads immobilized metal nanoparticle catalysts for the reduction of crystal violet. Bull Mater Sci 38:1–9CrossRefGoogle Scholar
  41. 41.
    Veerakumar P, Dhenadhayalan N, Lin K, Liu S (2015) Highly stable ruthenium nanoparticles on 3D mesoporous carbon: an excellent opportunity for reduction reactions. J Mater Chem A 3:23448–23457CrossRefGoogle Scholar
  42. 42.
    Guo Y, Tang D, Zhang L, Li B, Iqbal A, Liu W, Qin W (2017) Synthesis of ultrathin carbon dots-coated iron oxide nanocubes decorated with silver nanoparticles and their excellent catalytic properties. Ceram Int 43:7311–7320CrossRefGoogle Scholar
  43. 43.
    Sivaranjan K, Vanitha P, Sathiyaseelan A, Kalaichelvan PT, Sathuvan M, Rengasamy R, Santhanalakshmi J (2017) Insights into the catalytic reduction of organic dyes and antibacterial activity of graphene oxide supported mono and bimetallic nanocomposites. New J Chem 41:4348–4359CrossRefGoogle Scholar
  44. 44.
    Murugan E, Nimita Jebaranjitham J, Janaki Raman K, Mandal A, Geethalakshmi D, Dharmendira Kumar M, Saravanakumar A (2017) Insoluble dendrimer-grafted poly(vinylimidazole) microbeads stabilized with mono/bimetallic nanoparticle catalysts for effective degradation of malachite green. New J Chem 41:10860–10871CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Physical Chemistry, School of Chemical SciencesUniversity of MadrasChennaiIndia

Personalised recommendations