Preparation, characterization and dielectric properties of GO based ZnO embedded mixed metal oxides ternary nanostructured composites

https://doi.org/10.1016/j.jallcom.2021.159274Get rights and content

Highlights

  • GO/ZnO@MOs composite designed via sol-gel technique.

  • Dielectric gradients of composite observed with both temperature and frequency parameters.

  • A very high ε′ observed between 5 × 102 - 3.1 × 104 with the minimal ε′′ of ≤ 4.

  • At 1 kHz and 2 MHz, σac conductivities are found to be 2.25 × 10−4 S/m and 2.5 × 10−2 S/m respectively.

  • All the designed composites can be used for designing various electronic devices.

Abstract

The present work aims to highlight the enhanced dielectric permittivity and electronic properties of GO-based ZnO, CuO and Ag2O mixed ternary nanostructured composite developed by simple sol-gel based hetero-selection synthesis approach. The significant dielectric properties is observed for GO/ZnO@Ag2O nanostructured composite with the dielectric constant ε′ between 5 × 102 up to 3.1 × 104 with the minimal dielectric loss ε′′ of ≤ 4 at all ranges of given frequency and temperature. At the lower and higher frequency of 1 kHz and 2 MHz, σac conductivities value is found to 2.25 × 10−4 S/m and 2.5 × 10−2 S/m at 200 °C respectively. This value is found to be dependent on frequency and increases linearly with the increase in frequency. The other physio-chemical characterization techniques are done to study the properties of nanostructured composite via TEM, FESEM, FTIR, XRD, Zeta and BET. The present work involves the remarkable dielectric and charge storage uses.

Introduction

The present world is mainly dependent on several types of electronic devices and equipment to lead a comfortable life [1], [2]. There are reports associated to avoid the charge storage problem to run such equipment in need. The introduction of mixed nanostructured composites has been very much useful for several purposes including sensor, microelectronics, optical devices and other electronic applications. The nanostructured composites have been used with their remarkable properties in industry, academia and medical technology [3], [4]. The outstanding mechanical strength, magnificent electrical barrier properties and good thermal stability of such nanostructured composites have enhanced its use in electronic applications including energy storage devices, sensors and capacitors. Among such nanostructured composites graphene oxide (GO) based nanostructured composites [5] are showing a remarkable electronic property from RT to 200 °C. Being inexpensive, possessing an excellent mechanical property, low density-based transparent structure, and highly thermal conductive nature, GO has been extensively used for the efficient electronic packaging, device and sensor purpose [6], [7]. GO nanosheets possess a giant dielectric permittivity (ε′) of 106 and a very low loss of (tan δ) at 1 kHz, at room temperature (RT) due to its high surface area [8]. The smart and flexible structure of GO is mainly dependent on the synthesis route from the precursor graphite. The formation of hydrophilic groups like ‒OH‒, ‒COOH‒ on GO surface can be designed by a few experimental parameters. It is also reported that possessing a more number of hydrophilic groups on its surface, GO is easily dispersible in aqueous medium proving the development of its based composites in a green and sustainable manner. The creation of new bulk composites based on GO has a great scope in the designing of various nanoelectronics.

The other precursors of this work are metal oxide (MOs) nanoparticles (NPs). The chemical stability, low toxicity, thermal stability are the prime components to choose metal NPs for our research. Zinc oxide (ZnO) NPs an n-type semiconductor which possesses a wide bandgap of 3.37 eV and more numbers of active sites with a large surface area. The factors like size quantization effect and surface state of such NPs on the nanometer scale encourages its use for the development of electronic and optical properties of materials [9]. ZnO NPs are extensively used in gas sensor, photo detectors and solar cells. It is reported that without capping agents, ZnO NPs may easily form aggregations in the medium causing the property loss. But the hydrophilic groups along with the aromaticity associated on GO sheet hindered the agglomeration process of ZnO NPs protecting the NPs for the further applicative purpose [8]. ZnO NPs possess a very low ε′ of< 3.5 which mostly used for microwave absorption and satellite communication purposes [10]. Arunpandian et al. in his work have mentioned about GO/ZnO nanostructured composites showing en effective photocatalytic [11] properties bearing a suitable bandgap. Such composites also showed a very good activity towards antifouling and antibacterial nature caused by microorganisms [12]. CuO NPs are p-type semiconductor material with a bandgap of 1.2 eV, very good catalyst and environment-friendly in nature [13], [14], [15]. It also has a strong optical and electrical property like ZnO NPs and very much useful for Li-ion battery, organic compound detector [16]. The possibility of formation of higher reactive sites only occurred with the interaction of some other semiconducting material (ZnO/Ag2O) promoting electron/mass transfer in the system [17]. Ag2O NPs are one of the stable form of Ag NPs and slightly soluble in water. This also acts as conducting material due to activation of charge at the interface region which helps the enhancement of its optical, dielectric and electric properties [18]. The Ag2O based nanostructured composites mainly show a good dielectric behaviour due to the generation of photoelectrons and the occurrence of a transfer of such electrons to the GO sheets enhance the dielectric properties [19], [20].

From the detailed literature survey, the scope of GO based MO NPs and their application in the field of permittivity study are much demanding. There are no reports available with the development of GO/ZnO/MOs (Cu/Ag) via single-step green synthetic way and its detailed dielectric study at different frequency and temperature ranges. In this present work, we designed GO as the primary precursor as the previous study suggested that GO helps the improvement of the functionality of MO NPs including ZnO, CuO and Ag2O via simple sol-gel technique and hetero synthetic route. The development of such ternary GO/ZnO@MO nanostructured composites aimed with the target to enhance the dielectric permittivity and the charge storage capacity. The mechanism associated with the excellent chemical functionality of di MOs on the surface of graphene layers. The unique morphology, high thermal stability, presence of oxygen moieties, possibility of electron transfer and conducting nature of MOs attributed to the development of dielectric behaviour at RT as well as high-temperature zone. This work has been synthesized in a single step green synthetic route with a higher yield. The synthesized ternary mixed nanostructured composites are successfully characterised by TEM, FESEM, EDAX, FTIR, XRD, DLS and BET. The factors like the interaction between the oxygen moieties of MO NPs and GO, the higher surface area of GO, morphology, high ε′ value, a very low tan δ and ε′′ which enabled the composite to enhance the dielectric permittivity and charge storage capacity.

Section snippets

Materials

Graphite powder (synthetic powder, Sigma Aldrich), Sulphuric acid (Conc.H2SO4, 98.0%, ACS reagent, Sigma Aldrich), Sigma Aldrich), Phosphorous pentoxide (P2O5,99.9%, Sigma Aldrich), Hydrogen peroxide (H2O2, Sigma Aldrich), Potassium Persulfate (K2S2O8,> 99%, ACS reagent, Hydrochloric acid (dil. HCl solution, 37%, ACS reagent, Sigma Aldrich)), Potassium permanganate (KMnO4,99.9%)), Zinc Oxide (ZnO NPs, 95%), Copper Oxide (CuO NPs, 95%) and Silver Oxide (Ag2O NPs, 95%,) of Sigma Aldrich make.,

Results and discussion

The chemical functionality of mixed nanostructured composites is performed by FTIR spectra and corresponding spectra of GO/ZnO, GO/ZnO@CuO and GO/ZnO@Ag2O mixed hybrid nanostructured composites are shown in Fig. 1. The prominent peaks are assigned to be found at 3690 cm−1 and 3517 cm−1 by the O‒H stretching caused due to free and substituted OH groups present in the layer of GO sheets and the GO-MOs components. GO also shows few other characteristic vibrational peaks of C─O, C─OH and C═O

Conclusion

Summarizing to this work, an one step hetero synthetic Sol-gel pathway has been introduced for the development of GO/ZnO@CuO and GO/ZnO@Ag2O mixed nanocomposites. The interesting morphology and the interaction of emedded MOs NPs on the GO sheet help the enhancement of dielectric properties. The CV experiment resulted with good reduction behaviour of ternary composites at both the N2 and O2 environment with the proof of active charge/ionic transfer effect. The dielectric constant, Tanδ, σac

CRediT authorship contribution statement

Debasrita Bharatiya: Methodology, Investigation, Data representation; Biswajit Parhi: Formal analysis; Sarat K. Swain: Supervision, Conceptualization and Scientific analysis of data.

Declaration of Competing Interest

The authors declare there is no conflict of interest in publishing this article.

Acknowledgements

The authors also acknowledge the research support grants awarded by UGC India (No.F.4-2/2006(BSR)/CH/19-20/0002) for awarding DSK Kothari Post-Doctoral fellowship to Dr. Biswajit Parhi. Special acknowledgement to Dr. MPK Sahoo, Department of Physics, VSSUT, Burla for his help during the analysis of dielectric properties.

References (45)

  • R. Muduli et al.

    Dielectric, ferroelectric and impedance spectroscopic study of Ta2O5, Sb2O5, and V2O5-doped AgNbO3 ceramic

    J. Alloy. Compd.

    (2016)
  • Y. Lu et al.

    ZnO nanoparticles-tailored GO dispersion toward flexible dielectric composites with high relative permittivity, low dielectric loss and high breakdown strength

    Compos. Part A Appl. Sci. Manuf.

    (2019)
  • Y.L. Chen et al.

    Preparation of ZnO/GO composite material with highly photocatalytic performance via an improved two-step method

    Chin. Chem. Lett.

    (2013)
  • A.A. Menazea et al.

    Synthesis and antibacterial activity of graphene oxide decorated by silver and copper oxide nanoparticles

    J. Mol. Struct.

    (2020)
  • P. Mujeeb Rahman et al.

    Chitosan/nano ZnO composite films: enhanced mechanical, antimicrobial and dielectric properties

    Arab. J. Chem.

    (2018)
  • N. Senthil Kumar et al.

    ZnO/Ni(OH)2 core-shell nanoparticles: synthesis, optical, electrical and photoacoustic property analysis

    J. Alloy. Compd.

    (2017)
  • M.D. Parvez Ahmad et al.

    Particle size effect on the dielectric properties of ZnO nanoparticles

    Mater. Chem. Phys.

    (2019)
  • Z. Li et al.

    High-performance solid-state supercapacitors based on graphene-ZnO hybrid nanocomposites

    Nanoscale Res. Lett.

    (2013)
  • W. Wu et al.

    Significantly improved dielectric properties of polylactide nanocomposites via TiO2 decorated carbon nanotubes

    Compos. Part A Appl. Sci. Manuf.

    (2019)
  • R.K. Jammula et al.

    Cupric oxide decked few-layered graphene: synthesis and dielectric behaviour

    Carbon N. Y.

    (2014)
  • L. Ren et al.

    Silver nanoparticle-modified alumina microsphere hybrid composites for enhanced energy density and thermal conductivity

    Compos. Part A Appl. Sci. Manuf.

    (2019)
  • J.W. Lee et al.

    Enhanced dielectric properties of Ag-doped CCTO ceramics for energy storage devices

    Ceram. Int.

    (2017)
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