Microsystem Technologies

, Volume 24, Issue 9, pp 3623–3630 | Cite as

Self-assembled graphene and copper nanoparticles composite sensor for nitrate determination

  • Li Wang
  • Jungyoon Kim
  • Tianhong Cui
Technical Paper


A new sensor based on decorated copper nanoparticles and self-assembled graphene was fabricated and exemplified with the determination of nitrate solutions. Traditionally, graphene is coated on the sensor by drop-casting, leading to poor adhesion between graphene and the sensor. The self-assembled graphene proposed in this paper not only have a firm connection with the substrate, but also provide a three-dimensional network structure for copper nanoparticles. Copper was found as an effective catalyst for nitrate reduction. The combination of copper nanoparticles and self-assembled graphene can greatly enhance the sensitivity. Thus, low detection limit of 7.89 µM is obtained for nitrate, which to our knowledge, is among the lowest reported in the literatures. This method was employed for the determination of nitrate in lake water and the results were in good agreement with those obtained from a standard analytical procedure.



One of the authors acknowledges the support from China Scholarship Council. The devices are fabricated at Minnesota Nano Center, Minneapolis, MN, USA.


  1. Bard AJ, Faulkner LR (1980) Electrochemical methods: fundamentals and applications. Wiley, New YorkGoogle Scholar
  2. Bockris J, Kim J (1996) Electrochemical reductions of Hg(II), ruthenium-nitrosyl complex, chromate, and nitrate in a strong alkaline solution. J Electrochem Soc 143:3801–3808CrossRefGoogle Scholar
  3. Camargo JA, Alonso A, Salamanca A (2005) Nitrate toxicity to aquatic animals: a review with new data for freshwater invertebrates. Chemosphere 58:1255–1267. CrossRefGoogle Scholar
  4. Campanella L, Colapicchioni C, Crescentini G et al (1995) Sensitive membrane ISFETs for nitrate analysis in waters. Sens Actuators B Chem 27:329–335. CrossRefGoogle Scholar
  5. Carpenter NG, Pletcher D (1995) Amperometric method for the determination of nitrate in water. Anal Chim Acta 317:287–293CrossRefGoogle Scholar
  6. Chandrasekaran S, Seidel C, Schulte K (2013) Preparation and characterization of graphite nano-platelet (GNP)/epoxy nano-composite: mechanical, electrical and thermal properties. Eur Polym J 49:3878–3888. CrossRefGoogle Scholar
  7. Crawford NM (1995) Nitrate: nutrient and signal for plant growth. Plant Cell Online 7:859–868. CrossRefGoogle Scholar
  8. Genders JD, Hartsough D, Hobbs DT (1996) Electrochemical reduction of nitrates and nitrites in alkaline nuclear waste solutions. J Appl Electrochem 26:1–9. CrossRefGoogle Scholar
  9. World Health Organization (2008) Guidelines for drinking water quality, 3rd edn. World Health Organization, GenevaGoogle Scholar
  10. Gulis G, Czompolyova M, Cerhan JR (2002) An ecologic study of nitrate in municipal drinking water and cancer incidence in Trnava District, Slovakia. Environ Res 88:182–187. CrossRefGoogle Scholar
  11. Hu J, Sun J, Bian C et al (2013) 3D dendritic nanostructure of silver-array: preparation, growth mechanism and application in nitrate sensor. Electroanalysis 25:546–556. CrossRefGoogle Scholar
  12. Huang H, Tao L, Liu F et al (2016) Chemical-sensitive graphene modulator with a memory effect for internet-of-things applications. Microsyst Nanoeng 2:1–9. Google Scholar
  13. Kazemzadeh A, Ensafi AA (2001) Simultaneous determination of nitrite and nitrate in various samples using flow-injection spectrophotometric detection. Microchem J 69:61–68. CrossRefGoogle Scholar
  14. Keawkim K, Chuanuwatanakul S, Chailapakul O, Motomizu S (2013) Determination of lead and cadmium in rice samples by sequential injection/anodic stripping voltammetry using a bismuth film/crown ether/Nafion modified screen-printed carbon electrode. Food Control 31:14–21. CrossRefGoogle Scholar
  15. Knobeloch L, Salna B, Hogan A et al (2000) Blue babies and nitrate-contaminated well water. Environ Health Perspect 108:675–678. CrossRefGoogle Scholar
  16. Lee YS (2006) Factors affecting outbreaks of high-density Cochlodinium polykrikoides red tides in the coastal seawaters around Yeosu and Tongyeong, Korea. Mar Pollut Bull 52:1249–1259. CrossRefGoogle Scholar
  17. Liu S, Tian J, Wang L et al (2011) Self-assembled graphene platelet-glucose oxidase nanostructures for glucose biosensing. Biosens Bioelectron 26:4491–4496. CrossRefGoogle Scholar
  18. Lopez-Moreno C, Perez IV, Urbano AM (2016) Development and validation of an ionic chromatography method for the determination of nitrate, nitrite and chloride in meat. Food Chem 194:687–694. CrossRefGoogle Scholar
  19. Luo Y, Kong D, Jia Y et al (2013) Self-assembled graphene@PANI nanoworm composites with enhanced supercapacitor performance. RSC Adv 3:5851. CrossRefGoogle Scholar
  20. Masserini RT, Fanning KA (2000) A sensor package for the simultaneous determination of nanomolar concentrations of nitrite, nitrate, and ammonia in seawater by fluorescence detection. Mar Chem 68:323–333. CrossRefGoogle Scholar
  21. Nazoa P, Vidmar JJ, Tranbarger TJ et al (2003) Regulation of the nitrate transporter gene AtNRT2.1 in Arabidopsis thaliana: responses to nitrate, amino acids and developmental stage. Plant Mol Biol 52:689–703. CrossRefGoogle Scholar
  22. Pletcher D, Poorabedi Z (1979) The reduction of nitrate at a copper cathode in aqueous acid. Electrochim Acta 24:1253–1256. CrossRefGoogle Scholar
  23. Sayer RM, Gatherer RDB, Gilham RJJ, Reid JP (2003) Determination and validation of water droplet size distributions probed by cavity enhanced Raman scattering. Phys Chem Chem Phys 5:3732. CrossRefGoogle Scholar
  24. Shen J, Hu Y, Li C et al (2009) Layer-by-layer self-assembly of graphene nanoplatelets. Langmuir 25:6122–6128. CrossRefGoogle Scholar
  25. Solak AO, Pi Gülser, Gökm E, Gökmesşe F (2000) A new differential pulse voltammetric method for the determination of nitrate at a copper plated glassy carbon electrode. Microchim Acta 134:77–82. CrossRefGoogle Scholar
  26. Stortini AM, Moretto LM, Mardegan A et al (2015) Arrays of copper nanowire electrodes: preparation, characterization and application as nitrate sensor. Sens Actuators B Chem 207:186–192. CrossRefGoogle Scholar
  27. Ward-Jones S, Banks CE, Simm AO et al (2005) An in situ copper plated boron-doped diamond microelectrode array for the sensitive electrochemical detection of nitrate. Electroanalysis 17:1806–1815. CrossRefGoogle Scholar
  28. Zeng Q, Cheng J, Tang L et al (2010) Self-assembled graphene-enzyme hierarchical nanostructures for electrochemical biosensing. Adv Funct Mater 20:3366–3372. CrossRefGoogle Scholar
  29. Zhang B, Cui T (2012) High-perfermance and low-cost ion sensitive sensor array based on self-assembled graphene. Sens Actuators A Phys 177:110–114. CrossRefGoogle Scholar
  30. Zhang D, Wang K, Tong J, Xia B (2014) Characterization of layer-by-layer nano self-assembled carbon nanotube/polymer film sensor for ethanol gas sensing properties. Microsyst Technol 20:379–385. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.State Key Laboratory of Precision Measurement Technology and Instruments, Department of Precision InstrumentTsinghua UniversityBeijingChina
  2. 2.Department of Mechanical EngineeringUniversity of MinnesotaMinneapolisUSA

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