Gold nanoparticles decorated bimetallic CuNi-based hollow nanoarchitecture for the enhancement of electrochemical sensing performance of nitrite


Gold nanoparticles (AuNPs) decorated bimetallic CuNi-based hollow nanoarchitecture (CNHN) are reported for the first time as a nonenzymatic sensor for the quantification of nitrite in neutral solution . The CNHN was prepared via a convenient calcining routine using the bimetallic CuNi-MOFs as a coprecursor. The unique chemical structure of hollow CNHN with high specific surface area and abundant terminal amino groups effectively avoid the aggregation of AuNPs and facilitate the subsequent adsorption of nitrite. The Au/CNHN exhibited high electrocatalytic activity towards nitrite oxidation due to the synergetic catalytic effect of AuNPs and CNHN. Chronoamperometric detection of nitrite at the Au/CNHN/GCE achieved a lower linear calibration range of 0.05 to 1.15 mM, with an LOD of 0.017 μM compared with previous reports. The proposed method obtained satisfactory recoveries for nitrite determination in practical applications, which was verified by UV-Vis spectrophotometry. The prepared sensor based on Au/CNHN featured favorable selectivity and stability, which provides a promising approach for real sample analysis.

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  1. 1.

    Ding ZS, Johanningsmeier SD, Price R, Reynolds R, Truong VD, Payton SC, Breidt F (2018) Evaluation of nitrate and nitrite contents in pickled fruit and vegetable products. Food Control 190:304–311

    Article  CAS  Google Scholar 

  2. 2.

    Sudarvizhi A, Pandian K, Oluwafemi OS, Gopinath SC (2018) Amperometry detection of nitrite in food samples using tetrasulfonated copper phthalocyanine modified glassy carbon electrode. Sens Actuator B: Chem 272:151–159

    Article  CAS  Google Scholar 

  3. 3.

    Radhakrishnan S, Krishnamoorthy K, Sekar C, Wilson J, Kim SJ (2014) A highly sensitive electrochemical sensor for nitrite detection based on Fe2O3 nanoparticles decorated reduced graphene oxide nanosheets. Appl Catal B Environ 22:148–149

    Google Scholar 

  4. 4.

    Ma C, Qian YY, Zhang SP, Song HO, Gao JJ, Wang S, Liu MX, Xie KJ, Zhang XM (2018) Temperature–controlled ethanolamine and Ag–nanoparticle dual–functionalization of graphene oxide for enhanced electrochemical nitrite determination. Sens Actuator B: Chem 274:441–450

    Article  CAS  Google Scholar 

  5. 5.

    Khan MR, Wabaidur SM, Alothman ZA, Busquets R, Naushad M (2016) Method for the fast determination of bromate, nitrate and nitrite by ultraperformance liquid chromatographyemass spectrometry and their monitoring in saudi arabian drinking water with chemometric data treatment. Talanta 152:513–520

    PubMed  Article  CAS  Google Scholar 

  6. 6.

    Menon S, Vikraman AE, Jesny S, Kumar KG (2016) “Turn on” fluorescence determination of nitrite using green synthesized carbon nanoparticles. J Fluoresc 26:129–134

    PubMed  Article  CAS  Google Scholar 

  7. 7.

    Khanfar MF, Al-Faqheri W, Al-Halhouli AA (2017) Low cost lab on chip for the colorimetric detection of nitrate in mineral water products. Sensors 17:2345–2353

    Article  CAS  Google Scholar 

  8. 8.

    Wu J, Wang X, Lin Y, Zheng Y, Lin JM (2016) Peroxynitrous–acid–induced chemiluminescence detection of nitrite based on microfluidic chip. Talanta 154:73–79

    PubMed  Article  CAS  Google Scholar 

  9. 9.

    Mollarasouli F, Majidi MR, Asadpour-Zeynali K (2018) Amperometric sensor based on carbon dots decorated self–assembled 3D flower–like β–Ni(OH)2 nanosheet arrays for the determination of nitrite. Electrochim Acta 291:132–141

    Article  CAS  Google Scholar 

  10. 10.

    Rao HB, Liu YT, Zhong J, Zhang ZY, Zhao X, Liu X, Jiang YY, Zou P, Wang XX, Wang YY (2017) Gold nanoparticle/chitosan@N, S co–doped multiwalled carbon nanotubes sensor: fabrication, characterization, and electrochemical detection of catechol and nitrite. ACS Sustain Chem Eng 5:10926–10939

    Article  CAS  Google Scholar 

  11. 11.

    Wu H, Fan SH, Jin XY, Zhang H, Chen H, Dai Z, Zou XY (2014) Construction of a zinc porphyrin–fullerene–derivative based nonenzymatic electrochemical sensor for sensitive sensing of hydrogen peroxide and nitrite. Anal Chem 86:6285–6290

    PubMed  Article  CAS  Google Scholar 

  12. 12.

    Dagci K, Alanyalıoglu M (2016) Preparation of free–standing and flexible graphene/Ag nanoparticles/poly(pyronin Y) hybrid paper electrode for amperometric determination of nitrite. ACS Appl Mater Interfaces 8:2713–2722

    PubMed  Article  CAS  Google Scholar 

  13. 13.

    Ma Y, Wang YC, Xie DH, Gu Y, Zhang HM, Wang GZ, Zhang YX, Zhao HJ, Wong PK (2018) NiFe–layered double hydroxide nanosheet arrays supported on carbon cloth for highly sensitive detection of nitrite. ACS Appl Mater Interfaces 10:6541–6551

    PubMed  Article  CAS  Google Scholar 

  14. 14.

    Wang HG, Wen FF, Chen YJ, Sun T, Meng Y, Zhang Y (2016) Electrocatalytic determination of nitrite based on straw cellulose/molybdenum sulfide nanocomposite. Biosens Bioelectron 85:692–697

    PubMed  Article  CAS  Google Scholar 

  15. 15.

    Wang KD, Wu C, Wang F, Jiang GQ (2018) MOF–derived CoPx nanoparticles embedded in nitrogen–doped porous carbon polyhedrons for nanomolar sensing of p–nitrophenol. ACS Appl Nano Mater 1:5843–5853

    Article  CAS  Google Scholar 

  16. 16.

    Xiao PT, Bu FX, Zhao RR, Aly Aboud MF, Shakir I, Xu YX (2018) Sub–5 nm ultrasmall metal–organic framework nanocrystals for highly efficient electrochemical energy storage. ACS Nano 12:3947–3953

    PubMed  Article  CAS  Google Scholar 

  17. 17.

    Liu Y, Li G, Fu J, Chen Z, Peng X (2017) Strings of porous carbon polyhedrons as self–standing cathode host for high–energy–density lithium–sulfur batteries. Angew Chem 129:6272–6276

    Article  Google Scholar 

  18. 18.

    Han J, Zhang MF, Chen GJ, Zhang YQ, Wei Q, Zhuo Y, Xie G, Yuan R, Chen SP (2017) Ferrocene covalently confined in porous MOF as signal tag for highly sensitive electrochemical immunoassay of amyloid–β. J Mater Chem B 5:8330–8336

    PubMed  Article  CAS  Google Scholar 

  19. 19.

    Xie DH, Ma Y, Gu Y, Zhou HJ, Zhang HM, Wang GZ, Zhang YX, Zhao HJ (2017) Bifunctional NH2–MIL–88(Fe) metal–organic framework nanooctahedra for highly sensitive detection and efficient removal of arsenate in aqueous media. J Mater Chem A 5:23794–23804

    Article  CAS  Google Scholar 

  20. 20.

    Zhou XX, Guo SJ, Gao JX, Zhao JM, Xue SY, Xu WJ (2017) Glucose oxidase–initiated cascade catalysis for sensitive impedimetric aptasensor based on metal–organic frameworks functionalized with Pt nanoparticles and hemin/G–quadruplex as mimicking peroxidases. Biosens Bioelectron 98:83–90

    PubMed  Article  CAS  Google Scholar 

  21. 21.

    Hosseini H, Ahmar H, Dehghani A, Bagheri A, Tadjarodi A, Fakhari AR (2013) A novel electrochemical sensor based on metal–organic framework for electro–catalytic oxidation of L–cysteine. Biosens Bioelectron 42:26–429

    Article  CAS  Google Scholar 

  22. 22.

    Wang J, Xu H, Li SM, Yan B, Shi YT, Wang CQ, Du YK (2017) Plasmonic and photo–electrochemical enhancements of the AuAg@Au/RGO–C3N4 nanocomposite for the detection of DA. Analyst 142:4852–4861

    PubMed  Article  CAS  Google Scholar 

  23. 23.

    Peng BG, Cui JW, Wang Y, Liu JQ, Zheng HM, Jin L, Zhang XY, Zhang Y, Wu YC (2018) CeO2-x/C/rGO nanocomposites derived from Ce–MOF and graphene oxide as a robust platform for highly sensitive uric acid detection. Nanoscale 10:1939–1945

    PubMed  Article  CAS  Google Scholar 

  24. 24.

    Cioncoloni G, Roger I, Wheatley PS, Wilson C, Morris RE, Sproules S, Symes MD (2018) Proton–coupled electron transfer enhances the electrocatalytic reduction of nitrite to NO in a bioinspired copper complex. ACS Catal 8:5070–5084

    Article  CAS  Google Scholar 

  25. 25.

    Wen YY, Meng W, Li C, Dai L, He ZX, Wang L, Li M, Zhu J (2018) Enhanced glucose sensing based on a novel composite CoII–MOF/Acb modified electrode. Dalton Trans 47:3872–3879

    PubMed  Article  CAS  Google Scholar 

  26. 26.

    Zhang S, Tang YP, Chen YY, Zheng JB (2019) Synthesis of gold nanoparticles coated on flower–like MoS2 microsphere and their application for electrochemical nitrite sensing. J Electroanal Chem 839:195–201

    Article  CAS  Google Scholar 

  27. 27.

    Viswanathan P, Ramaraj R (2018) Bi–functional sensing capability of gold multi–pod network nanostructures towards nitrite and guanine. Sens Actuator B: Chem 270:56–63

    Article  CAS  Google Scholar 

  28. 28.

    Xiao XL, Peng SH, Wang C, Cheng D, Li N, Dong YL, Li QH, Wei DG, Liu P, Xie ZZ, Qu DY, Li X (2019) Metal/metal oxide@carbon composites derived from bimetallic Cu/Ni–based MOF and their electrocatalytic performance for glucose sensing. J Electroanal Chem 841:94–100

    Article  CAS  Google Scholar 

  29. 29.

    Dubé CE, Workie B, Kounaves SP, Robbat A, Aksu ML, Davies G (1995) Electrodeposition of metal alloy and mixed oxide films using a single–precursor tetranuclear copper–nickel complex. J Electrochem Soc 142:3357–3365

    Article  Google Scholar 

  30. 30.

    Zhu J, Yin H, Gong J, Al-Furjan MSH, Nie QL (2018) In situ growth of Ni/NiO on N–doped carbon spheres with excellent electrocatalytic performance for non–enzymatic glucose detection. J Alloys Compd 748:145–153

    Article  CAS  Google Scholar 

  31. 31.

    Han HJ, Chao SJ, Yang XL, Wang XB, Wang K, Bai ZY, Yang L (2017) Ni nanoparticles embedded in N doped carbon nanotubes derived from a metal organic framework with improved performance for oxygen evolution reaction. Int J Hydrog Energy 42:16149–16156

    Article  CAS  Google Scholar 

  32. 32.

    Nithyayini KN, Harish MNK, Nagashree KL (2019) Electrochemical detection of nitrite at NiFe2O4 nanoparticles synthesised by solvent deficient method. Electrochim Acta 317:701–710

    Article  CAS  Google Scholar 

  33. 33.

    Liang TT, Zou L, Guo XG, Ma XQ, Zhang CK, Zou Z, Zhang YH, Hu FX, Lu ZS, Tang KL, Li CM (2019) Rising mesopores to realize direct electrochemistry of glucose oxidase toward highly sensitive detection of glucose. Adv Funct Mater 29:1903026–1903036

    Article  CAS  Google Scholar 

  34. 34.

    Sakthivel M, Sukanya R, Chen SM, Dinesh B (2018) Synthesis of two–dimensional Sr–doped MoSe2 nanosheets and their application for efficient electrochemical reduction of metronidazole. J Phys Chem C 122:12474–12484

    Article  CAS  Google Scholar 

  35. 35.

    Li YG, Zhang L, Dang YY, Chen ZQ, Zhang RY, Li YC, Ye BC (2019) A robust electrochemical sensing of molecularly imprinted polymer prepared by using bifunctional monomer and its application in detection of cypermethrin. Biosens Bioelectron 127:204–214

    Google Scholar 

  36. 36.

    Kang SH, Zhang HM, Wang GZ, Zhang YX, Zhao HJ, Zhou HJ, Cai WP (2019) Highly sensitive detection of nitrite by using gold nanoparticle–decorated α–Fe2O3 nanorod arrays as self–supporting photo–electrodes. Inorg Chem Front 6:1432–1441

    Article  CAS  Google Scholar 

  37. 37.

    Sun CX, Pan WX, Zheng DY, Zheng YH, Zhu JH (2019) An electrochemical sensor for nitrite using a glassy carbon electrode modified with Cu/CBSA nanoflower networks. Anal Methods 11:4998–5006

    Article  CAS  Google Scholar 

  38. 38.

    Zhou YQ, Yan DP, Wei M (2015) A 2D quantum dot–based electrochemiluminescence film sensor towards reversible temperature–sensitive response and nitrite detection. J Mater Chem C 3:10099–10106

    Article  CAS  Google Scholar 

  39. 39.

    Manibalan G, Murugadoss G, Thangamuthu R, Ragupathy P, Kumar MR, Kumar RM, Jayavel R (2019) High electrochemical performance and enhanced electrocatalytic behavior of a hydrothermally synthesized highly crystalline heterostructure CeO2@NiO nanocomposite. Inorg Chem 58:13843–13861

    PubMed  Article  CAS  Google Scholar 

  40. 40.

    Jilani BS, Mounesh MP, Mruthyunjayachari CD, Reddy KRV (2020) Cobalt (II) tetra methyl–quinoline oxy bridged phthalocyanine carbon nano particles modified glassy carbon electrode for sensing nitrite: a voltammetric study. Mater Chem Phys 239:121920–121927

    Article  CAS  Google Scholar 

  41. 41.

    Lu L (2019) Highly sensitive detection of nitrite at a novel electrochemical sensor based on mutually stabilized Pt nanoclusters doped CoO nanohybrid. Sens Actuator B: Chem 281:182–190

    Article  CAS  Google Scholar 

  42. 42.

    Abdel Hameed RM, Medany SS (2019) Construction of core–shell structured nickel@platinum nanoparticles on graphene sheets for electrochemical determination of nitrite in drinking water samples. Microchem J 145:354–366

    Article  CAS  Google Scholar 

  43. 43.

    Madhuvilakku R, Alagar S, Mariappan R, Piraman S (2020) Glassy carbon electrodes modified with reduced graphene oxide–MoS2–poly (3, 4–ethylene dioxythiophene) nanocomposites for the nonenzymatic detection of nitrite in water and milk. Anal Chim Acta 1093:93–105

    PubMed  Article  CAS  Google Scholar 

  44. 44.

    Duan C, Wushuang B, Jianbin Z (2018) Non–enzymatic sensor based on a glassy carbon electrode modified with au nanoparticles/polyaniline/SnO2 fibrous nanocomposites for nitrite sensing. New J Chem 42:11516–11524

    Article  CAS  Google Scholar 

  45. 45.

    Lin P, Chai F, Zhang R, Xu G, Fan X, Luo X (2016) Electrochemical synthesis of poly(3,4–ethylenedioxythiophene) doped with gold nanoparticles, and its application to nitrite sensing. Microchim Acta 183:1235–1241

    Article  CAS  Google Scholar 

  46. 46.

    Jiao M, Li Z, Li Y, Cui M, Luo X (2018) Poly(3,4–ethylenedioxythiophene) doped with engineered carbon quantum dots for enhanced amperometric detection of nitrite. Microchim Acta 185:249

    Article  CAS  Google Scholar 

  47. 47.

    Zhao X, Li N, Jing M, Zhang Y, Wang W, Liu L, Xu Z, Liu L, Li F, Wu N (2019) Monodispersed and spherical silver nanoparticles/graphene nanocomposites from gamma-ray assisted in–situ synthesis for nitrite electrochemical sensing. Electrochim Acta 295:434–443

    Article  CAS  Google Scholar 

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The research was financially supported by the National Natural Science Foundation of China (No. 21874087), the Key R&D project of Shanxi Province (201803D421031), the Shanxi Scholarship Council of China (2017 Key1), the Shanxi Province Hundred Talents Project, the Queensland Government (WRAP052-2019RD1), and the James Cook University. The authors would like to thank Lijie Hou from Shiyanjia Lab for the support of XPS analysis.

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Correspondence to Ying Zhou or Yang Liu or Shaomin Shuang.

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Lei, P., Zhou, Y., Zhu, R. et al. Gold nanoparticles decorated bimetallic CuNi-based hollow nanoarchitecture for the enhancement of electrochemical sensing performance of nitrite. Microchim Acta 187, 572 (2020).

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  • Hollow nanoarchitecture
  • Au nanoparticles
  • Nitrite oxidation
  • Synergistic catalysis
  • Electrochemical sensor