Microchimica Acta

, 186:226 | Cite as

Reduced graphene oxide nanosheets modified with plasmonic gold-based hybrid nanostructures and with magnetite (Fe3O4) nanoparticles for cyclic voltammetric determination of arsenic(III)

  • Zhenlu ZhaoEmail author
  • Chuanping Li
  • Haoxi Wu
Original Paper


The authors have fabricated reduced graphene oxide nanosheets (rGO) supported with Fe3O4 nanoparticles and Ag/Au hollow nanoshells. The material was placed on a glassy carbon electrode which is shown to enable highly sensitive determination of As(III) which is first preconcentrated from solution at a potential of −0.35 V (versus Ag/AgCl) for 100 s. The electrode, typically operated at a working potential as low as 0.06 V, has a linear response in the 0.1 to 20 ppb As(III) concentration range and a 0.01 ppb detection limit. The electrochemical sensitivity is 52 μA ppb−1. The high sensitivity is assumed to be the result of various synergistic effects. The method was applied to ultratrace (0.1 ppt) determination of As(III) in real water samples.

Graphical abstract

The hybrid displays a wide linear response in the 0.1 to 20 ppb As(III) concentration range and a 0.01 ppb detection limit. The high sensitivity is attributed to various synergistic effects. The method was applied to ultratrace determination of As(III) in real water samples.


Electrochemical analysis Arsenic Ultratrace detection Synergistic effect Plasmonic Ag/Au hollow nanoshells 



Financial supports from National Natural Science Foundation (Grant No. 21605057, No. 21705056), Natural Science Foundation of Shandong Province (No. ZR2016BQ07), Foundation of State Key Laboratory of Electroanaytical Chemistry (SKLEAC201907), and Study Abroad Fund were acknowledged.

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2019_3328_MOESM1_ESM.doc (894 kb)
ESM 1 (DOC 893 kb)


  1. 1.
    Gao C, Yu X-Y, Xiong S-Q, Liu J-H, Huang X-J (2013) Electrochemical detection of arsenic(III) completely free from Noble metal: Fe3O4 microspheres-room temperature ionic liquid composite showing better performance than gold. Anal Chem 85:2673–2680CrossRefGoogle Scholar
  2. 2.
    Pungjunun K, Chaiyo S, Jantrahong I, Nantaphol S, Siangproh W, Chailapakul O (2018) Anodic stripping Voltammetric determination of Total arsenic using a gold nanoparticle-modified boron-doped diamond electrode on a paper-based device. Microchim Acta 185:324CrossRefGoogle Scholar
  3. 3.
    Bralatei E, Nekrosiute K, Ronan J, Raab A, McGovern E, Stengel DB, Feldmann J (2017) A field deployable method for a rapid screening analysis of inorganic arsenic in seaweed. Microchim Acta 184:1701–1709CrossRefGoogle Scholar
  4. 4.
    Su CK, Chen WC (2018) 3D-printed, TiO2 NP-incorporated minicolumn coupled with ICP-MS for speciation of inorganic arsenic and selenium in high-salt-content samples. Microchim Acta 185:268CrossRefGoogle Scholar
  5. 5.
    Yang M, Chen X, Jiang T-J, Guo Z, Liu J-H, Huang X-J (2016) Electrochemical detection of trace arsenic(III) by nanocomposite of nanorod-like α-MnO2 decorated with ∼5 nm Au nanoparticles: considering the change of arsenic speciation. Anal Chem 88:9720–9728CrossRefGoogle Scholar
  6. 6.
    Kempahanumakkagari S, Deep A, Kim K-H, Kumar Kailasa S, Yoon H-O (2017) Nanomaterial-based electrochemical sensors for arsenic - a review. Biosens Bioelectron 95:106–116CrossRefGoogle Scholar
  7. 7.
    Zaib M, Athar MM, Saeed A, Farooq U (2015) Electrochemical determination of inorganic mercury and arsenic-a review. Biosens Bioelectron 74:895–908CrossRefGoogle Scholar
  8. 8.
    Jia Z, Simm AO, Dai X, Compton RG (2006) The electrochemical reaction mechanism of arsenic deposition on an Au(111) electrode. J Electroanal Chem 587:247–253CrossRefGoogle Scholar
  9. 9.
    Zhou S, Han X, Fan H, Liu Y (2016) Electrochemical sensing toward trace as(III) based on mesoporous MnFe2O4/Au hybrid nanospheres modified glass carbon electrode. Sensors 16:935CrossRefGoogle Scholar
  10. 10.
    Innocenti M, Forni F, Pezzatini G, Raiteri R, Loglio F, Foresti ML (2001) Electrochemical behavior of as on silver single crystals and experimental conditions for InAs growth by ECALE. J Electroanal Chem 514:75–82CrossRefGoogle Scholar
  11. 11.
    Podešva P, Gablech I, Neužil P (2018) Nanostructured gold microelectrode array for ultrasensitive detection of heavy metal contamination. Anal Chem 90:1161–1167CrossRefGoogle Scholar
  12. 12.
    Seeber R, Terzi F, Zanardi C (2014) Functional materials in amperometric sensing, functional materials in Amperometric sensing. Springer, Berlin, HeidelbergGoogle Scholar
  13. 13.
    Feeney R, Kounaves SP (2000) On-site analysis of arsenic in groundwater using a microfabricated gold ultramicroelectrode array. Anal Chem 72:2222–2228CrossRefGoogle Scholar
  14. 14.
    Rahman MR, Okajima T, Ohsaka T (2010) Selective detection of As(III) at the au(111)-like polycrystalline gold electrode. Anal Chem 82:9169–9176CrossRefGoogle Scholar
  15. 15.
    Zhao Z, Wang P, Xu X, Sheves M, Jin Y (2015) Bacteriorhodopsin/Ag nanoparticle-based hybrid nano-bio electrocatalyst for efficient and robust H2 evolution from water. J Am Chem Soc 137:2840–2843CrossRefGoogle Scholar
  16. 16.
    Jin Y, Gao X (2009) Plasmonic fluorescent quantum dots. Nat Nanothch 4:571–576CrossRefGoogle Scholar
  17. 17.
    Zhao Z, Wu H, He H, Xu X, Jin Y (2014) A high-performance binary Ni–Co hydroxide-based water oxidation electrode with three-dimensional coaxial nanotube Array structure. Adv Funct Mater 24:4698–4705CrossRefGoogle Scholar
  18. 18.
    Jin Y (2013) Multifunctional compact hybrid au Nanoshells: a new generation of nanoplasmonic probes for biosensing, imaging, and controlled release. Acc Chem Res 47:138–148CrossRefGoogle Scholar
  19. 19.
    Brina R, Pons S, Fleischmann M (1988) Ultramicroelectrode sensors and detectors: considerations of the stability, sensitivity, reproducibility, and mechanism of ion transport in gas phase chromatography and in high performance liquid phase chromatography. J Electroanal Chem Interfacial Electrochem 244:81–90Google Scholar
  20. 20.
    Halas NJ, Lal S, Chang W-S, Link S, Nordlander P (2011) Plasmons in strongly coupled metallic nanostructures. Chem Rev 111:3913–3961CrossRefGoogle Scholar
  21. 21.
    Wu H, Wang P, He H, Jin Y (2012) Controlled synthesis of porous Ag/Au bimetallic hollow nanoshells with tunable Plasmonic and catalytic properties. Nano Res 5:135–144CrossRefGoogle Scholar
  22. 22.
    Liu M, Zhang R, Chen W (2014) Graphene-supported nanoelectrocatalysts for fuel cells: synthesis, properties, and applications. Chem Rev 114:5117–5160CrossRefGoogle Scholar
  23. 23.
    Ramesha GK, Sampath S (2011) In-situ formation of graphene–lead oxide composite and its use in trace arsenic detection. Sensors Actuators B Chem 160:306–311CrossRefGoogle Scholar
  24. 24.
    Andjelkovic I, Tran DN, Kabiri S, Azari S, Markovic M, Losic D (2015) Graphene aerogels decorated with α-FeOOH nanoparticles for efficient adsorption of arsenic from contaminated waters. ACS Appl Mater Interfaces 7:9758–9766CrossRefGoogle Scholar
  25. 25.
    Chandra V, Park J, Chun Y, Lee JW, Hwang I-C, Kim KS (2010) Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. ACS Nano 4:3979–3986CrossRefGoogle Scholar
  26. 26.
    Kumar S, Nair RR, Pillai PB, Gupta SN, Iyengar MA, Sood AK (2014) Graphene oxide–MnFe2O4 magnetic nanohybrids for efficient removal of lead and arsenic from water. ACS Appl Mater Interfaces 6:17426–17436CrossRefGoogle Scholar
  27. 27.
    Chimezie AB, Hajian R, Yusof NA, Woi PM, Shams N (2017) Fabrication of reduced graphene oxide-magnetic nanocomposite (rGO-Fe3O4) as an electrochemical sensor for trace determination of as(III) in water resources. J Electroanal Chem 796:33–42CrossRefGoogle Scholar
  28. 28.
    Lee PC, Meisel D (1982) Adsorption and surface-enhanced raman of dyes on silver and aold sols. J Phys Chem C 86:3391–3395CrossRefGoogle Scholar
  29. 29.
    Jin Y, Dong S (2002) Diffusion-limited, aggregation-based, mesoscopic assembly of roughened Core–Shell bimetallic nanoparticles into fractal networks at the air–water Interface. Angew Chem Int Ed 41:1040–1044CrossRefGoogle Scholar
  30. 30.
    McCrory CCL, Jung S, Peters JC, Jaramillo TF (2013) Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J Am Chem Soc 135:16977–16987CrossRefGoogle Scholar
  31. 31.
    Wouda PT, Schmid M, Nieuwenhuys BE, Varga P (1998) STM study of the (111) and (100) surfaces of PdAg. Surf Sci 417:292–300CrossRefGoogle Scholar
  32. 32.
    Amandusson H, Ekedahl LG, Dannetun H (2001) Hydrogen permeation through surface modified Pd and PdAg membranes. J Membr Sci 193:35–47CrossRefGoogle Scholar
  33. 33.
    Cong H-P, He J-J, Lu Y, Yu S-H (2010) Water-soluble magnetic-functionalized reduced graphene oxide sheets: in situ synthesis and magnetic resonance imaging applications. Small 6:169–173CrossRefGoogle Scholar
  34. 34.
    Zhao Z, Zhang G, Sun L, Gao Y, Yang X, Li Y (2012) Synthesis of a hierarchical three-component nanocomposite structure system with enhanced electrocatalytic and photoelectrical properties. Chem–Eur J 18:5248–5255CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.School of Material Science and EngineeringUniversity of JinanJinanChina
  2. 2.Department of Bionano EngineeringHanyang UniversityAnsanSouth Korea
  3. 3.State Key Lab of Electroanalytical Chemistry, Changchun Institute of Applied ChemistryChinese Academy of SciencesJilinChina
  4. 4.Institute of Materials, China Academy of Engineering PhysicsMianyangChina

Personalised recommendations