Porous palladium-poly(3,4-ethylenedioxythiophene)–coated carbon microspheres/graphene nanoplatelet–modified electrode for flow-based-amperometric hydrazine sensor


A highly stable flow-injection amperometric hydrazine sensor was developed based on a glassy carbon electrode modified with palladium-poly(3,4-ethylene dioxythiophene) coated on carbon microspheres/graphene nanoplatelets (Pd-PEDOT@CM/GNP/GCE). The Pd-PEDOT@CM/GNP composite was characterized by scanning electron microscopy and energy-dispersive x-ray analysis (SEM/EDX). The modified GCE was electrochemically characterized using cyclic voltammetry and chronoamperometry. The electrocatalytic activity of the Pd-PEDOT@CM/GNP/GCE toward hydrazine oxidation was significantly better than the activity of a bare GCE, a CM/GCE, a GNP/GCE, a Pd-PEDOT/GCE, and a Pd-PEDOT@CM/GCE. The sensor operated best at a low working potential of + 0.10 V (vs. Ag/AgCl). Under optimal conditions, sensitivity toward hydrazine detection and operational stability (601 injections/one electrode preparation) were excellent. The response was linear from 1.0 to 100 μmol L−1 and from 100 to 5000 μmol L−1 with a detection limit of 0.28 ± 0.02 μmol L−1 and high sensitivity of 0.200 μA μM−1 cm−2. The sensor showed good repeatability (relative standard deviation (RSD) < 1.4%, n = 15), reproducibility (RSD < 2.7%, n = 6), and anti-interference characteristics toward hydrazine detection. The feasibility of the electrochemical sensor was proved by the successful determination of hydrazine in water samples, and the results were in good agreement with those obtained from spectrophotometric analysis.

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  1. 1.

    Zhang X, Zheng J (2020) Amperometric hydrazine sensor based on the use of a gold nanoparticle- modified nanocomposite consisting of porous polydopamine, multiwalled carbon nanotubes and reduced graphene oxide. Microchim Acta 187(1):89

    CAS  Article  Google Scholar 

  2. 2.

    Avanes A, Hasanzadeh-Karamjavan M, Shokri-Jarcheloo G (2019) Electrocatalytic oxidation and amperometric determination of hydrazine using a carbon paste electrode modified with β-nickel hydroxide nanoplatelets. Microchim Acta 186(7):441

    Article  Google Scholar 

  3. 3.

    Deroco PB, Melo IG, Silva LSR, Eguiluz KIB, Salazar-Banda GR, Fatibello-Filho O (2018) Carbon black supported Au–Pd core-shell nanoparticles within a dihexadecylphosphate film for the development of hydrazine electrochemical sensor. Sensors Actuators B 256:535–542

    CAS  Article  Google Scholar 

  4. 4.

    Huang H, Li T, Sun Y, Yu L, Wang C, Shen R, Ye W, Wang D, Li Y (2019) Amperometric sensing of hydrazine in environmental and biological samples by using CeO2-encapsulated gold nanoparticles on reduced graphene oxide. Microchim Acta 186(1):46

    Article  Google Scholar 

  5. 5.

    Zheng X, Zhang Z, Guo Z, Wang Q (2002) Flow-injection electrogenerated chemiluminescence detection of hydrazine based on its in-situ electrochemical modification at a pre-anodized platinum electrode. Analyst 127(10):1375–1379

    CAS  Article  Google Scholar 

  6. 6.

    Watt GW, Chrisp JD (1952) Spectrophotometric method for determination of hydrazine. Anal Chem 24(12):2006–2008

    CAS  Article  Google Scholar 

  7. 7.

    Oh JA, Park JH, Shin HS (2013) Sensitive determination of hydrazine in water by gas chromatography-mass spectrometry after derivatization with ortho-phthalaldehyde. Anal Chim Acta 769:79–83

    CAS  Article  Google Scholar 

  8. 8.

    Chen W, Wang H, Tang H, Yang C, Guan X, Li Y (2019) Amperometric sensing of hydrazine by using single gold nanopore electrodes filled with Prussian Blue and coated with polypyrrole and carbon dots. Microchim Acta 186(6):350

    Article  Google Scholar 

  9. 9.

    Promsuwan K, Thavarungkul P, Kanatharana P, Limbut W (2017) Flow injection amperometric nitrite sensor based on silver microcubics-poly (acrylic acid)/poly (vinyl alcohol) modified screen printed carbon electrode. Electrochim Acta 232:357–369

    CAS  Article  Google Scholar 

  10. 10.

    Promsuwan K, Kachatong N, Limbut W (2019) Simple flow injection system for non-enzymatic glucose sensing based on an electrode modified with palladium nanoparticles-graphene nanoplatelets/mullti-walled carbon nanotubes. Electrochim Acta 320:134621

    CAS  Article  Google Scholar 

  11. 11.

    Promsuwan K, Thavarungkul P, Kanatharana P, Limbut W (2019) Nitrite amperometric sensor for gunshot residue screening. Electrochim Acta 331:135309

    Article  Google Scholar 

  12. 12.

    Sirisaeng T, Thavarungkul P, Kanatharana P, Limbut W (2018) Flow injection non-enzymatic amperometric detection of hydrogen peroxide based on a glassy carbon electrode modified with silver particles on glassy carbon spherical powder. J Electrochem Soc 165(3):74–82

    Article  Google Scholar 

  13. 13.

    Ghasemi S, Hosseini SR, Hasanpoor F, Nabipour S (2019) Amperometric hydrazine sensor based on the use of Pt-Pd nanoparticles placed on reduced graphene oxide nanosheets. Microchim Acta 186(9):601

    Article  Google Scholar 

  14. 14.

    Belaidi FS, Civélas A, Castagnola V, Tsopela A, Mazenq L, Gros P, Launay J, Temple-Boyer P (2015) PEDOT-modified integrated microelectrodes for the detection of ascorbic acid, dopamine and uric acid. Sensors Actuators B 214:1–9

    CAS  Article  Google Scholar 

  15. 15.

    Kongkaew S, Kanatharana P, Thavarungkul P, Limbut W (2017) A preparation of homogeneous distribution of palladium nanoparticle on poly (acrylic acid)-functionalized graphene oxide modified electrode for formalin oxidation. Electrochim Acta 247:229–240

    CAS  Article  Google Scholar 

  16. 16.

    Ilieva M, Nakova A, Tsakova V (2016) Pd-modified PEDOT layers obtained through electroless metal deposition—electrooxidation of glycerol. J Solid State Electrochem 20(11):3015–3023

    CAS  Article  Google Scholar 

  17. 17.

    Jiang F, Yue R, Du Y, Xu J, Yang P (2013) A one-pot ‘green’ synthesis of Pd-decorated PEDOT nanospheres for nonenzymatic hydrogen peroxide sensing. Biosens Bioelectron 44:127–131

    CAS  Article  Google Scholar 

  18. 18.

    Sivakumar M, Veeramani V, Chen S-M, Madhu R, Liu S-B (2019) Porous carbon-NiO nanocomposites for amperometric detection of hydrazine and hydrogen peroxide. Microchimi Acta 186(2):59

    Article  Google Scholar 

  19. 19.

    Bard AJ, Faulkner LR (2001) Fundamentals and applications. Electrochemical methods, 2nd edn. Wiley, N Y

    Google Scholar 

  20. 20.

    Kim SK, Jeong YN, Ahmed MS, You J-M, Choi HC, Jeon S (2011) Electrocatalytic determination of hydrazine by a glassy carbon electrode modified with PEDOP/MWCNTs–Pd nanoparticles. Sensors Actuators B 153(1):246–251

    CAS  Article  Google Scholar 

  21. 21.

    Harraz FA, Ismail AA, Al-Sayari SA, Al-Hajry A, Al-Assiri MS (2016) Highly sensitive amperometric hydrazine sensor based on novel α-Fe2O3/crosslinked polyaniline nanocomposite modified glassy carbon electrode. Sensors Actuators B 234:573–582

    CAS  Article  Google Scholar 

  22. 22.

    Mejri A, Mars A, Elfil H, Hamzaoui AH (2019) Voltammetric simultaneous quantification of p-nitrophenol and hydrazine by using magnetic spinel FeCo2O4 nanosheets on reduced graphene oxide layers modified with curcumin-stabilized silver nanoparticles. Microchim Acta 186(8):561

    Article  Google Scholar 

  23. 23.

    Zhang C, Wang G, Ji Y, Liu M, Feng Y, Zhang Z, Fang B (2010) Enhancement in analytical hydrazine based on gold nanoparticles deposited on ZnO-MWCNTs films. Sensors Actuators B 150(1):247–253

    CAS  Article  Google Scholar 

  24. 24.

    Da X, Wildgoose GG, Compton RG (2006) Designer electrode interfaces simultaneously comprising three different metal nanoparticle (Au, Ag, Pd)/carbon microsphere/carbon nanotube composites: progress towards combinatorial electrochemistry. Analyst 131(11):1241–1247

    Article  Google Scholar 

  25. 25.

    Zhao J, Zhu M, Zheng M, Tang Y, Chen Y, Lu T (2011) Electrocatalytic oxidation and detection of hydrazine at carbon nanotube-supported palladium nanoparticles in strong acidic solution conditions. Electrochim Acta 56(13):4930–4936

    CAS  Article  Google Scholar 

  26. 26.

    Zhang H, Huang J, Hou H, You T (2009) Electrochemical detection of hydrazine based on electrospun palladium nanoparticle/carbon nanofibers. Electroanalysis 21(16):1869–1874

    Article  Google Scholar 

  27. 27.

    Panchompoo J, Aldous L, Downing C, Crossley A, Compton RG (2011) Facile synthesis of Pd nanoparticle modified carbon black for electroanalysis: application to the detection of hydrazine. Electroanalysis 23(7):1568–1578

    CAS  Article  Google Scholar 

  28. 28.

    Abdul Aziz M, Kawde A-N (2013) Gold nanoparticle-modified graphite pencil electrode for the high-sensitivity detection of hydrazine. Talanta 115:214–221

    CAS  Article  Google Scholar 

  29. 29.

    Zhao Z, Sun Y, Li P, Zhang W, Lian K, Hu J, Chen Y (2016) Preparation and characterization of AuNPs/CNTs-ErGO electrochemical sensors for highly sensitive detection of hydrazine. Talanta 158:283–291

    CAS  Article  Google Scholar 

  30. 30.

    Zhao S, Wang L, Wang T, Han Q, Xu S (2016) A high-performance hydrazine electrochemical sensor based on gold nanoparticles/single-walled carbon nanohorns composite film. Appl Surf Sci 369:36–42

    CAS  Article  Google Scholar 

  31. 31.

    Zhou T, Lu P, Zhang Z, Wang Q, Umar (2016) A perforated CO3O4 nanoneedles assembled in chrysanthemum-like CO3O4 structures for ultra-high sensitive hydrazine chemical sensor. Sensors Actuators B 235:457–465

    CAS  Article  Google Scholar 

  32. 32.

    Feng F, Ma Z (2016) Sensitive electrochemical detection of hydrazine based on hollow core-satellite hZnS@Au nanoparticles. Sensors Actuators B 232:9–15

    CAS  Article  Google Scholar 

  33. 33.

    Mutyala S, Mathiyarasu J (2015) Preparation of graphene nanoflakes and its application for detection of hydrazine. Sensors Actuators B 210:692–699

    CAS  Article  Google Scholar 

  34. 34.

    Duan C, Dong Y, Sheng Q, Zheng J (2019) A high-performance non-enzymatic electrochemical hydrazine sensor based on NiCo2S4 porous sphere. Talanta 198:23–29

    CAS  Article  Google Scholar 

  35. 35.

    Wang Y, Yang X, Bai J, Jiang X, Fan G (2013) High sensitivity hydrogen peroxide and hydrazine sensor based on silver nanocubes with rich {100} facets as an enhanced electrochemical sensing platform. Biosens Bioelectron 43:180–185

    CAS  Article  Google Scholar 

  36. 36.

    Luan F, Zhang S, Chen D, Zheng K, Zhuang X (2018) CoS2-decorated ionic liquid-functionalized graphene as a novel hydrazine electrochemical sensor. Talanta 182:529–535

    CAS  Article  Google Scholar 

  37. 37.

    Wang L, Meng T, Jia H, Feng Y, Gong T, Wang H, Zhang Y (2019) Electrochemical study of hydrazine oxidation by leaf-shaped copper oxide loaded on highly ordered mesoporous carbon composite. J Colloid Interface Sci 549:98–104

    CAS  Article  Google Scholar 

  38. 38.

    AOAC (2016) Appendix F: guidelines for standard method performance requirements. Official methods of analysis of AOAC INTERNATIONAL, 20th edition

  39. 39.

    Gholamian F, Sheikh-Mohseni MA, Naeimi H (2012) Simultaneous determination of phenylhydrazine and hydrazine by a nanostructured electrochemical sensor. Mater Sci Eng C 32(8):2344–2348

    CAS  Article  Google Scholar 

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Thanks to Mr. Thomas Duncan Coyne, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla, Thailand, for assistance with the English.


The authors received grants from the Royal Golden Jubilee Ph.D-program (RGJ) supported by the Thailand Research Fund (PHD/0212/2559); the Thailand Research Fund (TRF) and Prince of Songkla University (grant no. RSA 6280081); the Center of Excellence for Innovation in Chemistry (PERCH-CIC), Ministry of Higher Education, Science, Research and Innovation; the Center of Excellence for Trace Analysis and Biosensor (TAB-CoE), and the Graduate School, Prince of Songkla University, Hat Yai, Thailand.

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Correspondence to Warakorn Limbut.

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Promsuwan, K., Thongtawat, J. & Limbut, W. Porous palladium-poly(3,4-ethylenedioxythiophene)–coated carbon microspheres/graphene nanoplatelet–modified electrode for flow-based-amperometric hydrazine sensor. Microchim Acta 187, 539 (2020). https://doi.org/10.1007/s00604-020-04470-w

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  • Palladium-poly(3,4-ethylenedioxythiophene)
  • Carbon microspheres (CMs)
  • Graphene nanoplatelets (GNPs)
  • Hydrazine
  • Flow injection amperometry