Analytical and Bioanalytical Chemistry

, Volume 411, Issue 13, pp 2781–2791 | Cite as

Plasmonic MoO2 nanospheres assembled on graphene oxide for highly sensitive SERS detection of organic pollutants

  • Jianli Chen
  • Kai Sun
  • Yi Zhang
  • Di Wu
  • Zhen Jin
  • Fazhi Xie
  • Xiaoli ZhaoEmail author
  • Xiufang WangEmail author
Paper in Forefront


The molybdenum oxide and graphene oxide (MoO2/GO) nanocomposite has been fabricated via simple hydrothermal assisted synthesis using Mo and MoO3 as precursors. The MoO2 nanospheres with porous hollow structure are assembled onto GO nanosheets. Profiting from the plasmonic effects of MoO2 and synergistic effect of MoO2 and GO, this hybrid nanomaterial exhibits significantly enhanced surface enhanced Raman scattering (SERS) activity for organic pollutants. The detection limit for rhodamine 6G (R6G) is 1.0 × 10−9 M, and the maximum enhancement factor (EF) reaches up to 1.05 × 107, which is the best among the semiconductor-based SERS materials. For practical application, the MoO2/GO SERS substrates are also applied to detect Methylene blue (MB) in river water, and the detection limit (1.0 × 10−8 M) can be acquired. Pyrene is also chosen as probe molecule, and quantitative determination is achieved with detection limit of 1.0 × 10−7 M. These demonstrate the well feasibility for multi-molecule detection. Furthermore, the nanocomposite displays high stability, reproducible stability, and acid and alkali resistance.

Graphical abstract


MoO2 Graphene oxide SERS Plasmonic effect Detection Organic pollutants 



This work was supported by the Anhui Provincial Natural Science Research Project (KJ2018A0512), the Initial Scientific Research Fund of Anhui Jianzhu University (2017QD14), and the Natural Science Foundation of China (41673131, 21777001).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

Supplementary material

216_2019_1751_MOESM1_ESM.pdf (181 kb)
ESM 1 (PDF 180 kb)


  1. 1.
    Sun YD, Peng P, Guo RY, Wang HH, Li T. Exonuclease III-boosted cascade reactions for ultrasensitive SERS detection of nucleic acids. Biosens Bioelectron. 2018;104:32–8.CrossRefGoogle Scholar
  2. 2.
    Sharma V, Krishnan V. Fabrication of highly sensitive biomimetic SERS substrates for detection of herbicides in trace concentration. Sensors Actuators B Chem. 2018;262:710–9.CrossRefGoogle Scholar
  3. 3.
    Qian XM, Nie SM. Single-molecule and single-nanoparticle SERS: from fundamental mechanisms to biomedical applications. Chem Soc Rev. 2008;37:912–20.CrossRefGoogle Scholar
  4. 4.
    Li DW, Zhai WL, Li YT, Long YT. Recent progress in surface enhanced Raman spectroscopy for the detection of environmental pollutants. Microchim Acta. 2014;181:23–43.CrossRefGoogle Scholar
  5. 5.
    Li DW, Sun JJ, Gan ZF, Chen HY, Guo D. Reaction-based SERS nanosensor for monitoring and imaging the endogenous hypochlorous acid in living cells. Anal Chim Acta. 2018;1018:104–10.CrossRefGoogle Scholar
  6. 6.
    Boltasseva A, Atwater HA. Low-loss plasmonic metamaterials. Science. 2011;331:290–1.CrossRefGoogle Scholar
  7. 7.
    Huang X, Tang S, Mu X, Dai Y, Chen G, Zhou Z, et al. Free standing palladium nanosheets with plasmonic and catalytic properties. Nat Nano Technol. 2011;6:28–32.CrossRefGoogle Scholar
  8. 8.
    Quang GCP, Lee HK, Phang IY, Ling XY. Plasmonic colloidosomes as three-dimensional SERS platforms with enhanced surface area for multiphase sub-microliter toxin sensing. Angew Chem Int Ed. 2015;127:9827–31.CrossRefGoogle Scholar
  9. 9.
    Alessandri I. Enhancing Raman scattering without plasmons: unprecedented sensitivity achieved by TiO2 shell-based resonators. J Am Chem Soc. 2013;135:5541–4.CrossRefGoogle Scholar
  10. 10.
    Hsu SW, Bryks W, Tao AR. Effects of carrier density and shape on the localized surface plasmon resonances of Cu2–xS nanodisks. Chem Mater. 2012;24:3765–71.CrossRefGoogle Scholar
  11. 11.
    Wang Y, Hu H, Jing S, Wang Y, Sun Z, Zhao B, et al. Enhanced Raman scattering as a probe for 4-mercaptopyridine surface-modified copper oxide nanocrystals. Anal Sci. 2007;23:787–91.CrossRefGoogle Scholar
  12. 12.
    Li WH, Zamani R, Gil PR, Pelaz B, Ibanez M, Cadavid D, et al. CuTe nanocrystals: shape and size control, plasmonic properties, and use as SERS probes and phototherma agent. J Am Chem Soc. 2013;135:7098–101.CrossRefGoogle Scholar
  13. 13.
    Livingstone R, Zhou XC, Tamargo MC, Lombardi JR. Surface enhanced Raman spectroscopy of pyridine on CdSe/ZnBeSe quantum dots grown by molecular beam epitaxy. J Phys Chem C. 2010;114:17460–4.CrossRefGoogle Scholar
  14. 14.
    Cong S, Yuan YY, Chen ZG, Hou JY, Yang M, Su YL, et al. Noble metal-comparable SERS enhancement from semiconducting metal oxides by making oxygen vacancies. Nat Commun. 2015;6:7800–6.CrossRefGoogle Scholar
  15. 15.
    Lin J, Shang Y, Li XX, Yu J, Wang XT, Guo L. Ultrasensitive SERS detection by defect engineering on single Cu2O superstructure particle. Adv Mater. 2017;29:1604797–803.CrossRefGoogle Scholar
  16. 16.
    Guo BK, Fang XP, Li B, Shi YF, Ouyang CY, Hu YS, et al. Synthesis and lithium storage mechanism of ultrafine MoO2 nanorods. Chem Mater. 2012;24:457–63.CrossRefGoogle Scholar
  17. 17.
    Jin YS, Wang HT, Li JJ, Yue X, Han YJ, Shen PK, et al. Porous MoO2 nanosheets as non-noble bifunctional electrocatalysts for overall water splitting. Adv Mater. 2016;28:3785–90.CrossRefGoogle Scholar
  18. 18.
    Sun YM, Hu XL, Luo W, Huang YH. Self-assembled hierarchical MoO2/graphene nanoarchitectures and their application as a high-performance anode material for lithium-ion batteries. ACS Nano. 2011;5:7100–7.CrossRefGoogle Scholar
  19. 19.
    Zhang Q, Li X, Ma Q, Zhang Q, Bai H, Yi W, et al. A metallic molybdenum dioxide with high stability for surface enhanced Raman spectroscopy. Nat Commun. 2017;8:14903–4.CrossRefGoogle Scholar
  20. 20.
    Zhang QQ, Li XS, Yi WC, Li WT, Bai H, Liu JY, et al. Plasmonic MoO2 nanospheres as a highly sensitive and stable non-noble metal substrate for multi-component surface-enhanced Raman analysis. Anal Chem. 2017;89:11765–71.CrossRefGoogle Scholar
  21. 21.
    Zhan Y, Liu YL, Zu HG, Guo YX, Wu SS, Yang HY, et al. Phase-controlled synthesis of molybdenum oxide nanoparticles for surface enhanced Raman scattering and photothermal therapy. Nanoscale. 2018;10:5997–6004.CrossRefGoogle Scholar
  22. 22.
    Sun YM, Hu XL, Luo W, Huang YH. Electrospinning of carbon-coated MoO2 nanofibers with enhanced lithium-storage properties. J Mater Chem. 2012;22:425–31.CrossRefGoogle Scholar
  23. 23.
    Xiang ZC, Zhang Q, Zhang Z, Xu XJ, Wang QB. Preparation and photoelectric properties of semiconductor MoO2 micro/nanospheres with wide band gap. Ceram Int. 2015;41:977–81.CrossRefGoogle Scholar
  24. 24.
    Wu V, Wang X, Sun Y, Liu Y, Li J. Flawed MoO2 belts transformed from MoO3 on a graphene template for the hydrogen evolution reaction. Nanoscale. 2015;7:7040–4.CrossRefGoogle Scholar
  25. 25.
    Jin YS, Shen PK. Nanoflower-like metallic conductive MoO2 as a high-performance non-precious metal electrocatalyst for hydrogen evolution reaction. J Mater Chem A. 2015;3:20080–5.CrossRefGoogle Scholar
  26. 26.
    Sun ST, Wu PY. Competitive surface-enhanced Raman scattering effects in noble metal nanoparticle-decorated graphene sheets. Phys Chem. 2011;13:21116–20.Google Scholar
  27. 27.
    Ling X, Zhang J. First-layer effect in graphene-enhanced Raman scattering. Small. 2010;6:2020–5.CrossRefGoogle Scholar
  28. 28.
    Hummers WS, Offeman RE. Preparation of graphitic oxide. J Am Chem Soc. 1958;80:1339.CrossRefGoogle Scholar
  29. 29.
    Yu XX, Cai HB, Zhang WH, Li XJ, Pan N, Luo Y, et al. Tuning chemical enhancement of SERS by controlling the chemical reduction of graphene oxide nanosheets. ACS Nano. 2011;5:952–8.CrossRefGoogle Scholar
  30. 30.
    Itoh T, Yamamoto YS. Recent topics on single-molecule fluctuation analysis using blinking in surface-enhanced resonance Raman scattering: clarification by electromagnetic mechanism. Analyst. 2016;141:5000–9.CrossRefGoogle Scholar
  31. 31.
    Nguyen AH, Ma XY, Park HG, Sim SJ. Low-blinking SERS substrate for switchable detection of kanamycin. Sensors Actuators B Chem. 2019;282:765–73.CrossRefGoogle Scholar
  32. 32.
    Itoh T, Yamamoto YS, Biju V, Tamaru H, Wakida S. Fluctuating single sp2 carbon clusters at single hotspots of silver nanoparticle dimers investigated by surface-enhanced resonance Raman scattering. AIP Adv. 2015;5:127113–23.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Materials and Chemical EngineeringAnhui Jianzhu UniversityHefeiChina
  2. 2.State Key Laboratory of Environmental Criteria and Risk AssessmentChinese Research Academy of Environmental SciencesBeijingChina

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