, Volume 25, Issue 7, pp 3351–3362 | Cite as

Simple and cost-effective sonochemical preparation of ternary NZnO–Mn2O3@rGO nanohybrid: a potential electrode material for supercapacitor and ammonia sensing

  • Benjamin Raj
  • Ramesh Oraon
  • Arun Kumar PadhyEmail author
Original Paper


The present work deals with a simple and cost-effective sonochemical assisted synthesis of binary transition metal oxide (BTMOs) (NZnO–Mn2O3) and NZnO–Mn2O3@rGO ternary nanohybrid using a imidazole derivative as an organic precursor aimed at the application in supercapacitor and sensing of ammonia in aqueous medium. Morphological analysis using various physicochemical techniques, like FESEM, TEM, XRD, and BET, revealed surface enriched property (high surface area and porous nature) with uniform decoration of binary metal oxides (NZnO–Mn2O3) over reduced graphene oxide (rGO). Formation and synergistic interaction of nanohybrid materials were confirmed from FTIR and Raman analysis. Electrochemical measurements showed maximum capacitance performance via cyclic voltammetry (CV) achieved by ternary nanohybrid NZnO–Mn2O3@rGO (252.77 Fg−1 at scan rate 50 mV s−1) which is in good agreement with the charging–discharging (GCD) and electrochemical impedance spectroscopy (EIS) analysis. Further, the ternary nanohybrid material exhibited good sensing of ammonia in aqueous medium as indicated by continuous amperometric reponse with a lowest sensitivity of 0.47 ppm.


Nanohybrid Supercapacitor (SCs) Specific capacitance Sensor Porous 



Benjamin Raj is thankful to Central University of Jharkhand, Ranchi (India) for the University fellowship to carry out the research work. The author is also thankful to CoE-GEET (Centre of Excellence in Green and Efficient Energy and Technology) Central University of Jharkhand, Ranchi (India) for providing instrumentation facility.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Pathak A, Gangan S, Ratha S, Chakarborty B, Rout S (2017) Enhanced pseudocapacitance of MoO3-reduced graphene oxide hybrids with insight from density functional theory investigations. J Phys Chem C 121:18992–19001CrossRefGoogle Scholar
  2. 2.
    Zhao C, Ang JM, Liu Z, Luz X (2017) Alternately stacked metallic 1T-MoS2/polyaniline heterostructure for high performance supercapacitors. Chem Eng J 330:462–469CrossRefGoogle Scholar
  3. 3.
    Tiwari SK, Mishra RK, Ha SK, Huczko AJ (2018) Evolution of graphene oxide and graphene: from imagination to industrialization. Chem Nano Mat 4:598–620Google Scholar
  4. 4.
    Raccichini R, Varzi A, Passerini S, Scrosati B (2015) The role of graphene for electrochemical energy storage. Nat Mater 14:271–279CrossRefGoogle Scholar
  5. 5.
    Chiam SL, Lim HN, Hafiz SM, Pandikumar A, Huang M (2018) Electrochemical performance of supercapacitor with stacked copper foils coated with graphene nanoplatelets. Sci Rep 8:3093CrossRefGoogle Scholar
  6. 6.
    Yuan ZY, Ren TZ, Vantomme A, Su BL (2004) Facile and generalized preparation of hierarchically mesoporous macroporous binary metal oxide materials. Chem Mater 16:5096–5106CrossRefGoogle Scholar
  7. 7.
    Dhelipan M, Arunchander A, Sahu AK, Kalpana D (2016) Activated carbon from orange peels as supercapacitor electrode and catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell. J Saudi Chem Soc 4(21):487–494Google Scholar
  8. 8.
    Liu M, Shi M, Lu W, Zhu D, Li L, Gan L (2017) Core-shell reduced graphene oxide/MnOx@ carbon hollow nanospheres for high performance supercapacitor electrodes. Chem Eng J 313:518–526CrossRefGoogle Scholar
  9. 9.
    Shah A, Sultan X, Zahid A, Aftab S, Nisar J, Nayab S, Qureshi R, Khan GS, Hussain H, Ozkan SA (2017) Highly sensitive and selective electrochemical sensor for the trace level detection of mercury and cadmium. Electrochim Acta 258:1397–1403CrossRefGoogle Scholar
  10. 10.
    Dikin DA, Stankovich S, Zimney EJ, Piner RD, Dommett GHB, Evmenenko G, Nguyen ST, Ruoff RS (2007) Preparation and characterization of graphene oxide paper. Nature 448:457–460CrossRefGoogle Scholar
  11. 11.
    Salunkhe RR, Kaneti YV, Yamauchi Y (2017) Metal organic framework derived nanoporous metal oxides towards supercapacitor applications: progress and prospects. ACS Nano 11:5293–5308CrossRefGoogle Scholar
  12. 12.
    Jain S, Patrike A, Badahe SS, Bhardwaj M, Ogale SC (2018) Room temperature ammonia gas sensing using mixed-valent CuCo2O4 nanoplatelets: performance enhancement through stoichiometry control. ACS Omega 3:1977–1982CrossRefGoogle Scholar
  13. 13.
    Zhang Y, Li Y, Su H, Huang W, Dong X (2015) Binary metal oxide: advanced energy storage materials in supercapacitors. J Mater Chem A 3:43–59CrossRefGoogle Scholar
  14. 14.
    Mishra RK, Ha SK, Verma K, Tiwari SK (2018) Recent progress in selected bio-nanomaterials and their engineering applications: an overview. Journal of Science: Advanced Material and Devices 3:263–288Google Scholar
  15. 15.
    Wang C, Yin L, Zhang L, Xiang D, Gao R (2010) Metal oxide gas sensors: sensitivity and influencing factors. Sensors 10:2088–2016CrossRefGoogle Scholar
  16. 16.
    Li L, Gao P, Baumgarten M, Mullen K, Lu N, Fuchs H, Chi L (2013) High performance field effect ammonia sensors based on a structured ultrathin organic semiconductor film. Adv Mater 25:3419–3425CrossRefGoogle Scholar
  17. 17.
    Ashok AH, Rao V (2017) Synthesis of nanostructured metal oxide by microwave-assisted method and its humidity sensor application. Mater Today Proc 4:3816–3824CrossRefGoogle Scholar
  18. 18.
    Pinna N, Garnweitner G, Antonietti M, Niederberger M (2005) A general nonaqueous route to binary metal oxide nanocrystals involving a C-C bond cleavage. J Am Chem Soc 127:5608–5612CrossRefGoogle Scholar
  19. 19.
    Zhang L, Bai D, Zhou M, Pan C (2017) Surfactant free hydrothermal synthesis, growth mechanism and photocatalytic properties of PbMoO4 polyhedron microcrystals. J Saudi Chem Soc 1:S275–S282CrossRefGoogle Scholar
  20. 20.
    Moussaoui R, Elghniji K, Mosbah M, Elalouj F, Moussaoui Y (2017) Sol gel synthesis of highly TiO2 aerogel photocatalyst via high temperature supercritical drying. J Saudi Chem Soc 6:751–760CrossRefGoogle Scholar
  21. 21.
    Kumar RV, Damant Y, Fedanken A (2000) Sonochemical synthesis and characterized of nanometer-sized transition metal oxide from metal acetates. Chem Mater 12:2301–2305CrossRefGoogle Scholar
  22. 22.
    Xu H, Zeige BW, Suslick KS (2013) Sonochemical synthesis of nanomaterials. Chem Soc Rev 42:2555–2567CrossRefGoogle Scholar
  23. 23.
    Huang Y, Kershaw SV, Wang Z, Pei Z, Liu L, Huang Y, Li H, Zhu M, Rogach AL, Zhi C (2016) Highly integrated supercapacitor sensor systems via material and geometry design. Small 12:3393–3399CrossRefGoogle Scholar
  24. 24.
    Wei C, Sun Y, Zhan N, Liu M, Zhao L, Cheng C, Zhang D (2017) Preparation of hierarchical MnCo2S4 nanotubes for high performance supercapacitors and non-enzymatic glucose sensors. Chem Select 2:11154–11159Google Scholar
  25. 25.
    Dong XC, Xu H, Wang WX, Huang XW, Park MBC, Zhang H, Wang LH, Huang W, Chen P (2012) 3D graphene cobalt oxide electrode for high performance supercapacitor and enzymeless glucose detection. ACS Nano 6:3206–3213CrossRefGoogle Scholar
  26. 26.
    Khairy M, Ayoub A, Banks CE (2018) Large scale production of CdO/Cd(OH)2 nanocomposites for non-enzyme sensing and supercapacitor applications. RSC Adv 8:921–930CrossRefGoogle Scholar
  27. 27.
    Padhy AK, Chetia B, Mishra S, Pati A, Iyer PK (2010) Imidazole derivatives as the organic precursors of ZnO nanoparticles. Tetrahedron Lett 51:2751–2753CrossRefGoogle Scholar
  28. 28.
    Abuzalat O, Wong D, Elsaved M, Park S, Kim S (2018) Sonochemical fabrication of Cu(II) and Zn(II) metal-organic framework films on metal substrates. Ultrason Sonochem 45:180–188CrossRefGoogle Scholar
  29. 29.
    Wang C, Cheng H, Sun Y, Lin Q, Zhang C (2015) Rapid sonochemical synthesis of luminescent and paramagnetic copper nanoclusters for bimodal bioimaging. Chem Nano Mat 1:27–31Google Scholar
  30. 30.
    Oraon R, De Adhikari A, Tiwari SK, Nayak GC (2015) Nanoclay based graphene polyaniline hybrid nanocomposites: promising electrode materials for supercapacitors. RSC Adv 5:68334–68344CrossRefGoogle Scholar
  31. 31.
    Lu J, Zhang Q, Wang J, Saito F, Uchida M (2006) Synthesis of N-doped ZnO by grinding and subsequent heating ZnO-urea mixture. Powder Technol 162:33–37CrossRefGoogle Scholar
  32. 32.
    Manigandan R, Giribabul K, Munusamy S, Kumar SP, Muthamizh S, Dhanasekaran A, Suresh R, Stephen A, Narayan V (2015) Manganese sesquioxide to trimanganese tetraoxide hierarchical hollow nanostructures: effect of gadolinium on structural, optical and magnetic properties. CrystEngComm 17:2886–2895CrossRefGoogle Scholar
  33. 33.
    Ossonon BD, Belange D (2017) Synthesis and characterization of sulfophenyl-functionalized reduced graphene oxide sheets. RSC Adv 7:27224–27234CrossRefGoogle Scholar
  34. 34.
    Kumari R, Sahai A, Goswami N (2015) Effect of nitrogen doping on structural and optical properties of ZnO nanoparticles. Prog Nat Sci Mater Int 25:300–309CrossRefGoogle Scholar
  35. 35.
    Luo L, Deng Y, Mao W, Yang X, Zhu K, Xu J, Han Y (2012) Probing the surface structure of αMn2O3 nanocrystal during CO oxidation by operando Raman spectroscopy. J Phys Chem C 116:20975–20981CrossRefGoogle Scholar
  36. 36.
    Gao J, Liu F, Ma N, Wang Z, Zhang X (2010) Environment friendly method to produce graphene that employs vitamin C and amino acid. J Mater Chem 22:2213–2218CrossRefGoogle Scholar
  37. 37.
    Browne MP, Nolan H, Twamley B, Duesberg GS, Colavita PE, Lyons MEG (2016) Thermally prepared Mn2O3/RuO2/Ru thin films a highly active catalysts for the oxygen evaluation reaction in alkaline media. Chem Aust 3:1847–1855Google Scholar
  38. 38.
    Wu N, She X, Yang D, Su F, Chen Y (2012) Synthesis of network reduced graphene oxide in polystyrene matrix by a two-step reduction method for superior conductivity of the composite. J Mater Chem A 22:17254–17261CrossRefGoogle Scholar
  39. 39.
    Nazari Y, Salem S (2017) Magnetisation of TiO2/reduced graphene oxide nano photocatalyst. International Proceedings of Chemical, Biological and Environmental Engineering 102:50–56Google Scholar
  40. 40.
    Lavand AB, Malghe YS (2015) Synthesis, characterization and visible light photocatalytic activity of nitrogen doped zinc oxide nanospheres. J Asian Ceramic Soc 3:305–310CrossRefGoogle Scholar
  41. 41.
    Barai HR, Banerjee AN, Hamnabard N, Joo SW (2016) Synthesis of amorphous manganese oxide nanoparticles-to-crystalline nanorods through a simple wet-chemical technique using K+ ions as a growth director and their morphology-controlled high performance supercapacitors applications. RSC Adv 6:78887–78908CrossRefGoogle Scholar
  42. 42.
    Shahid MM, Rameshkumar P, Pandikumar A (2015) An electrochemical sensing platform based on a reduced graphene oxide–cobalt oxide nanocube@platinum nanocomposite for nitric acid detection. J Mater Chem 3:14458–14468CrossRefGoogle Scholar
  43. 43.
    Oraon R, De Adhikari A, Tiwari SK, Nayak GC (2015) Nanoclay based graphene polyaniline hybrid nanocomposite: promising electrode materials for supercapacitor. RSC Adv 5:68344–68344CrossRefGoogle Scholar
  44. 44.
    Oraon R, De Adhikari A, Tiwari SK, Nayak GC (2016) Nanoclay-based hierarchical interconnected mesoporous CNT/PPy electrode with improved specific capacitance for high performance supercapacitors. RSC Dalton Trans 45:9113–9126CrossRefGoogle Scholar
  45. 45.
    Saranya M, Ramachandran R, Wang F (2016) Graphene-zinc oxide (G-ZnO) nanocomposite for electrochemical supercapacitor applications. J Sci Adv Mater Devices 1:454–460CrossRefGoogle Scholar
  46. 46.
    Selvakumar M, Bhatt DK, Aggarwal AM, Iyer SP, Sravani G (2010) Nano ZnO-activated carbon composite electrodes for supercapacitors. Physica B 405:2286–2289CrossRefGoogle Scholar
  47. 47.
    Goikela E, Daffos B, Taberna PL, Simon P (2013) Synthesis of nanosized MnO2 prepared by the polyol method and its application in high power supercapacitors, mat. Renew Sustain Energ Rev 2:16Google Scholar
  48. 48.
    Dang TD, Hang TT, Hoang BT, Mai TT (2015) Synthesis of nanostructured manganese oxides based materials and application for supercapacitor. Adv Nat Sci Nanosci Nanotechnol 6:25011CrossRefGoogle Scholar
  49. 49.
    Zhang J, Liu F, Cheng JP, Zhang XB (2015) Binary nickel-cobalt oxides electrode materials for high performance supercapacitor: influence of its composition and porous nature. ACS Appl Mater Interfaces 7:17630–17640CrossRefGoogle Scholar
  50. 50.
    Yadav MS, Singh N, Kumar A (2018) Synthesis and characterization of zinc oxide nanoparticles and activated charcoal based nanocomposite for supercapacitor electrode application. J Mater Sci Mater Electron 29:6853–6869CrossRefGoogle Scholar
  51. 51.
    Yan Y, Wu B, Zheng C, Fang D (2012) Capacitive properties of mesoporous Mn-Co oxide derived from a mixed oxalate. Mater Sci Appl 3:377–383Google Scholar
  52. 52.
    Kong LB, Lu C, LuO YC, Kang L (2014) The specific capacitance of sol-gel synthesized spinel MnCo2O4 in an alkaline electrolyte. Electrochim Acta 111:22–27CrossRefGoogle Scholar
  53. 53.
    Sahoo S, Dhibar S, Hatui G, Bhattacharya P, Das CK (2013) Graphene/polypyrrole nanofiber nanocomposite as electrode materials for electrochemical supercapacitor. Polymer 54:1033–1042CrossRefGoogle Scholar
  54. 54.
    Saravanan R, Gupta VK, Narayan V, Stephen A (2014) Visible light degradation of textile effluent using novel catalyst ZnO/γ-Mn2O3. J Taiwan Inst Chem Eng 45:1910–1917CrossRefGoogle Scholar
  55. 55.
    Huixia L, Yong L, Yanni T, Lanlan L, Qing Z, Kun L, Hanchun T (2015) Room temperature gas sensing properties of tubular hydroxyapatite. New J Chem 39:3865–3874CrossRefGoogle Scholar
  56. 56.
    Poloju M, Jayababu N, Reddy MV (2018) Improved gas sensing performance of Al doped ZnO/CuO nanocomposite based ammonia gas sensor. Mater Sci Eng B 227:61–67CrossRefGoogle Scholar
  57. 57.
    Hazra SK, Basu S (2016) Graphene-oxide nano composite for chemical sensor applications. C 2:12Google Scholar
  58. 58.
    Oudenhovena JFM, Knobena W, van Schaijka R (2015) Electrochemical detection of ammonia using a thin ionic liquid film as the electrolyte. Procedia Eng 120:983–986CrossRefGoogle Scholar
  59. 59.
    Nikolina AT, Kavindra S, Enrique RC, Teresa JB (2015) Cu-BTC MOF/graphene-based hybrid materials as low concentration ammonia sensors. J Mater Chem A 3(21):11417–11429CrossRefGoogle Scholar
  60. 60.
    Ming ZD, Yi LL, Hung CL, Hsiao WZ, Kai TC, Hsin FM, Jiunn WL, May JT, Henrich C (2013) Highly sensitive ammonia sensor with organic vertical nanojunctions for non-invasive detection of hepatic injury. Anal Chem 85:3110–3117CrossRefGoogle Scholar
  61. 61.
    Samotaev NN, Podlepetsky BI, Vasiliev AA, Pisliakov AV, Sokolov AV (2013) Metal-oxide gas sensor high-selective to ammonia. Sens Syst 74:308–312Google Scholar
  62. 62.
    Sadanand P, Karuna KN (2015) An Au nanocomposite based chemiresistive ammonia sensor for health monitoring. ACS Sens 1:55–62Google Scholar
  63. 63.
    Qishu W, Yangong Z, Jiawen J, Jinxia W (2016) Gas sensing performance of ion-exchanged Y zeolites as an impedimetric ammonia sensor. Ionics 23(3):751–758Google Scholar
  64. 64.
    Mackin C, Vera S, Amaia Z, Cong S, Kong J, Timothy MS, Tomas P (2018) Chemiresistive graphene sensors for ammonia detection. ACS Appl Mater Interfaces 10:16169–16176CrossRefGoogle Scholar
  65. 65.
    Andre RS, Kwak D, Dong Q, Zhong W, Correa DS, Mattoso LH, Lei Y (2018) Sensitive and selective NH3 monitoring at room temperature using ZnO ceramic nanofibers decorated with poly (styrene sulfonate). Sensor 18:1058CrossRefGoogle Scholar
  66. 66.
    Arain M, Nafady A, Ibupoto ZH, Sherazi STH, Shaikh T, Khan H, Alsalme A, Niaz A, Wilander M (2016) Simpler and highly sensitive enzyme-free sensing of urea via NiO nanostructures modified electrode. RSC Adv 6:39001–39006CrossRefGoogle Scholar
  67. 67.
    Bandgar D, Navale S, Naushad M, Mane R, Stadler F, Patil VB (2015) Ultra-sensitive polyaniline–iron oxide nanocomposite room temperature flexible ammonia sensor. RSC Adv 5:68964–68971CrossRefGoogle Scholar
  68. 68.
    Mani V, Devasenathipathy R, Chen S-M, Kohilarani K, Ramachandran R (2015) A sensitive amperometric sensor for the determination of dopamine at graphene and bismuth nanocomposite film modified electrode. Int J Electrochem Sci 10:1199–1207Google Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Department of ChemistryCentral University of JharkhandRanchiIndia
  2. 2.Department of NanotechnologyCentral University of JharkhandRanchiIndia

Personalised recommendations