Synthesis and characterization of cobalt nanocomposite using aniline-formaldehyde resin

Journal Pre-proof Synthesis and Characterization of Cobalt Nanocomposite Using AnilineFormaldehyde Resin Jyoti Chaudhary, Giriraj Tailor, Deepshikha Verma, Ravi Verma PII:

S2452-2139(20)30014-0

DOI:

https://doi.org/10.1016/j.coco.2020.01.005

Reference:

COCO 302

To appear in:

Composites Communications

Received Date: 10 July 2019 Revised Date:

3 December 2019

Accepted Date: 5 January 2020

Please cite this article as: J. Chaudhary, G. Tailor, D. Verma, R. Verma, Synthesis and Characterization of Cobalt Nanocomposite Using Aniline-Formaldehyde Resin, Composites Communications, https:// doi.org/10.1016/j.coco.2020.01.005. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2020 Published by Elsevier Ltd.

Synthesis and Characterization of Cobalt Nanocomposite Using AnilineFormaldehyde Resin Jyoti Chaudhary, Giriraj Tailor, Deepshikha Verma, Ravi Verma Department of Polymer Science, M.L.S. University, Udaipur, Rajasthan, India,313001 Department of Chemistry, Mewar University, Gangrar, Chittorgarh, Rajasthan, India, Abstract In this work, cobalt doped aniline-formaldehyde nanocomposite with average particles size of 32.16 nm were prepared by simple chemical method. The concentrations of such nanocomposites were investigated by Scanning electron microscope (SEM), Transmission electron microscope (TEM), Atomic electron microscopy (AFM) and X-ray diffraction. XRD. The synthesized nanocomposite was formed in cubes and spherical shaped. The roughness and average maximum height of cobalt nanocomposite is 141 nm and 106 nm respectively. The X-RD confirms that the cobalt doped aniline formaldehyde nanocomposite was formed in crystalline in nature. Keywords- Cobalt, XRD, TEM, SEM, Aniline. 1. Introduction The Nano-object attracts great attention of scientists and technologists due to their unique magnetic, thermal, magnetic, catalytic and other properties that differ from those of bulk material [1,2 15-18] This determines the high potential of their practical use. Metal-polymer nanomaterial based on polymer with conjugation system are candidates for organic electronic as well as the creation of microelectromechanical systems, supper condenser, sensors, solar batteries, display etc. [3-5]. Due to their small size nanoparticles exhibit novel material properties that are significantly different from those of their bulk counterparts. Cobalt nanoparticles have been synthesized by various methods like thermal decomposition, sol-gel, surfactant-mediated synthesis, polymer-matrix assisted synthesis and spry pyrolysis [6-7]. Some of the above method suffer from the difficulty in size- homogeneity as well as dispersion of cobalt nanoparticles. Several methods have been reported to prepare fine cobalt powder, including low pressure spray pyrolysis, optical gas sensors, solar thermal absorbers, etc. [8] In this study we have reported the synthesis of cobalt nanoparticles using thermal decomposition method and characterized its structural and morphological properties. 2. Experimental 2.1 Chemicals Inorganic salt (Cobalt chloride, CoCl2), and organic salt Aniline (C6H5NH2), Formaldehyde (HCHO), Hydrochloride acid (HCl) and sodium hydroxide (NaOH)- all are of AR grade and supplied by Central Drug House Ltd. India. Distilled water was used in all experiments carried out.

2.2 Method Cobalt nanocomposites were synthesized in two stepsIn first step - 9.5 mL of aniline in dilute hydrochloric acid was taken in a 250 mL beaker. 10 ml of formaldehyde solution (40%) was added slowly in this aniline solution with constant stirring. The mixture was stirred well for another 15 minutes to form an orange red solution. Then this solution was fed into aqueous sodium hydroxides solution (1%) and refluxed for 30-45 minutes. The precipitate of aniline formaldehyde was formed. 15 mL of 1.5 N cobalt ion solution was added drop by drop and the reaction mixture was stirred continuously for 30 minutes followed by the heating at 450Cfor one hour on heating mental. After the heating polymer metal complex was formed. The excess metal ion and impurities were washed out by multiple washing with distilled water. Second Step- formation of cobalt nanocomposite by decomposition of polymer metal complex, at 8000C in muffle furnace for 35 minutes. [9] Purification of polymer metal nanocomposite was done in following steps: (i) Volatile impurities were separated during the decomposition period. (ii) Metallic ions were removed by keeping the nanocomposite in 12N hydrochloric acid solution for 24 hours. The nanocomposites were centrifuged and washed multiple times with distilled water to remove the hydrochloric acid completely. [10] Reaction SchemeNH2

NH2 H+

+

H 2C

ad R

O

NH

R

NaOH -H2O

n

OH aniline

R1

f o r m a ld e h y d e

Aniline Formaldehyde

(4 - aminophenyl)methanol

R1

NH

R1 NH

+ H2C

R1

∆

O

Co2+ R1 Salts

NH

R1

2+

Co

+

R1 R1

NH

NH

R1 R1

NH

R1 n

R1

Cobalt polymer Complex

Characterization Techniques – Scanning Electron Microscopy

Samples were investigated by Nova Nano FE-SEM 450 (FEI) scanning electron microscope to obtain topological, morphological and compositional information. Lens mounted DBS and LVD offer best selection of information and image optimization. Beam landing energy cam go down from 30 KeV to 50ev and resolution of 1.4 nm at 1 kV (TLD-SE) and 1 nm at 15 kV (TLD-SE). The entire sample was coated with gold before SEM analysis.

Transmission Electron Microscopy Transmission electron microscopy (TEM) was performed for characterizing size and shape of synthesized zinc nanoparticles. It was performed on a Tecnai G2 20 (FEI) S- Twin electron microscope at accelerating voltage of 20 kV. Specimens for TEM measurement were prepared by depositing a drop of colloid solution on a 400 mesh copper grid coated by an amorphous carbon film and evaporating the solvent in air at room temperature.

Atomic Force Microscopy Atomic force microscopy is used to measure the nanoscale surface roughness, study the surface morphology, grain size analysis. In this study AFM of make CSM Instrument (ANTON PARR Tritec) with Specifications of Probe radius: > 10 nm and Scan area limits: 1 µm x 1 µm to 40 µm x 40 µm with Maximum in Z axis: 4 µm was used.

X- Ray Diffraction (XRD) analysis XRD patterns were recorded on Philips PW 3050/10 model. The sample was recorded on a Philips X-Pert MMP diffractometer. The diffractometer was controlled and operated by a PC computer with the programs P Rofit and used a MoK (source with wavelength0.70930 A°, operating with Mo-tube radiation at 50 kV and 40 mA.

Results and discussion Cobalt nanoparticles were obtained by chemical method. The method utilised in this study is cost-effective and facile one compared to other methods reported earlier. By the procedure described above the SEM studies were conducted in order to examine the morphology of the prepared nanocomposite. SEM images of the obtained zinc nanocomposite are shown in figure 1 and 2 at 30000X and 20000X magnification. The morphology of the nanocomposite indicates cubic, spherical and cluster shape of various sizes. (. In an earlier work of synthesis of Cobalt doped Manganese Oxide Nanoparticles by Chemical route, the nanoclusters have been found to possess special shapes and particle size decreased with increase in concentration [12]. Salman et al has reported the synthesis of dendritic large particles at 353 K by employing the liquid-phase reduction method and hydrazine [13]. Figure .3 shows that the TEM images and size of histogram clearly reveals the aggregated nature of the final products, which of smaller units. Cobalt clusters formed by the reaction with aniline – formaldehyde resin and forming lager aggregates. These clusters tend to sinter together into a spherical shape in order to minimize the surface energy. This morphology is different from nanoparticles synthesized by similar method [11, 14].

NANO CUBES

NANO CUBES

(A) (B) Figure-1 SEM images of cobalt doped Aniline-formaldehyde nanocomposite at (A) 30000 and (B) 20000 magnification

Cluster Cluster

(A) (B) Figure-2 SEM images of cobalt doped Aniline-formaldehyde nanocomposite at (A) 30000 and (B) 20000 magnification

(A)

(B)

(C)

Figure- 3 TEM images of cobalt doped nanocomposite at (A) 500 nm (B) 100 nm (C) 50 nm

X-ray diffraction Diffraction (XRD) studies carried using X-ray diffractometer with Cu Kα radiation (λ = 1.5418 A) in the range of 10–80° to determine their crystal structure and phase. Figures 4 illustrates a typical XRD spectrum of Co nanocomposite prepared by the chemical precipitation method. X-ray diffraction patterns indicate that the obtained ultra-fine particles are in good crystallinity. Diffraction peaks related to impurities were observed in the XRD pattern in the sample. The particles size can be evaluated by Scherrer formula: D = Kλ/ (β cos ϴ) Where D is the mean size of crystallites (nm). K is crystallite shape factor a good approximation is 0.9, λ is X- ray wave length B is full the maximum (FWHM) in radius of the X-ray diffraction peak and ϴ is the Bragg’s angle. The peak values are listed below in the “Peak List”The particles size predicted is 32.56 nm.

Figure- 4 XRD image of cobalt doped aniline- formaldehyde nanocomposite Peak List Pos.[°2Th.] 16.4900 32.0382 39.5195 45.7766 56.8048 66.5049 75.5318

Height [cts] FWHMLeft[°2Th.] d-spacing [Å] Rel. Int. [%] 113.07 0.1771 5.37589 32.93 343.35 0.2066 2.79368 100.00 56.24 0.4723 2.28036 16.38 199.48 0.1181 1.98217 58.10 43.53 0.1771 1.62077 12.68 17.28 0.3542 1.40598 5.03 13.54 0.4723 1.25880 3.94

Figure -5 are the images of the atomic force microscopy of cobalt doped anilineformaldehyde resin. Surface imaging studies were preformed using AFM for estimating surface morphology and particles size distribution by investigating the spherical shape of metal ion at the surface of aniline formaldehyde resin is identified. The result of AFM is shown in figure – 6 .

(A)

(B)

Figure – 5 (A) 3D (B) 2D AFM topography of cobalt doped aniline – formaldehyde nanocomposite.

Figure-6 Result of AFM cobalt doped Aniline- formaldehyde resin

ConclusionThe cobalt nanocomposite was successfully prepared by chemical precipitation methods using cobalt chloride as a source. The cobalt nanocomposite surface morphologies were analysed by using SEM, TEM and AFM. The XRD confirms the size of cobalt doped anilineformaldehyde cobalt nanocomposite is 32.16 nm. The mean particle determined by TEM in close agreement with the XRD. The present synthesis method is very simple and cheap can be applied for large scale industrial production of cobalt nanocomposite thus protecting our environment from the use of harmful chemicals.

AcknowledgementAuthors are grateful to departments of Polymer Science, Mohan Lal Sukhadia University Udaipur, Rajasthan, and Mewar University, Chittorgarh, Rajasthan for fruitful discussions and support during the preparation of this manuscript. Authors also acknowledge the technicians of the instrumental lab, University of Rajasthan Jaipur and MNIT Jaipur Rajasthan for the experimental assistance in this work. References 1. A. Henglein, Chem. Rev. 89, 1861 (1989). 2. B. Corain and M. Kralik, J. Mol. Catal. A.: Chem. 159, 153 (2000). 3. S. Zh. Ozkana, E. L. Dzidzigur, P. A. Chernavskiic, G. P. Karpachevaa,M. N. Efimova, and G. N. Bondarenkoa Nanotechnologies in Russia, 8,7–8, (2013). 4 M. I. Shiloms, A. F. Pshenichnikov, K. I. Morozov, I. Yu. Shurubor, J Magn Magn Mater., 85, (1990). 5. C. Bergemann, D. Muller-Schulte, J. Oster, L.A. Brassard, A. S. Lubbe, J Magn Magn Mater., 194, (1999). 6. C. Gruttner, J. Teller, J Magn Magn Mater.,194, (1999) 7. L Guo, J Huang, X Y Li, S. H. Yang, Phys Chem Chem Phys., 3, (2001). 8. R. Manigandan, K. Giribabu, R. Suresh, L. Vijayalakshmi, A. Stephen and V. Narayanan, Chem Sci Trans. 2, S1, (2013). 9. J. Chaudhary, G. Tailor, D. kumar, Res. J. Chem. Environ, 23,3, (2018). 10. J. Chaudhary, G. Tailor, D. Kumar, A. Joshi, Asian J. Chem. 29, 7, (2017). 11. V. S. Maceira, M. A. C. Duarte, M. Farle, M. A. L. pez-Quintela, K. Sieradzki, R. Diaz, Langmuir, 22, (2006). 12. K.S.Pugazhvadivua, K.Ramachandranb and K.Tamilarasana,Synthesis and Characterization of Cobalt doped Manganese Oxide Nanoparticles by Chemical Route, Physics Procedia 49 ( 2013 ) 205 – 216 13. S. A. Salman, T. Usami, K. Kuroda,1 and M. Okido,Synthesis and Characterization of Cobalt Nanoparticles Using Hydrazine and Citric Acid, Journal of Nanotechnology, http://dx.doi.org/10.1155/2014/525193. 14. Igor Luisetto Æ Franco Pepe Æ Edoardo Bemporad, Preparation and characterization of nano cobalt oxide, J Nanopart Res (2008) 10:59–67.

15. Kousar Parveen and Uzaira Rafique, Development of cobalt-doped alumina hybrids for adsorption of textile effluents, Adsorption Science & Technology,2018, Vol. 36(1–2) 182– 197 16. Nur Oktri Mulya Dewi , Green synthesis of Co3O4 nanoparticles using Euphorbia heterophylla L. leaves extract: characterization and photocatalytic activity, IOP Conf. Series: Materials Science and Engineering 509 (2019) 012105, IOP Publishing doi:10.1088/1757-899X/509/1/012105. 17. V. Usai, T. Mugadza, F. Chigondo, M. Shumba, T. Nharingo, M. Moyo, P. Tshuma, Synthesis and Characterisation of cobalt oxide nanoparticles decorated graphene oxide and its electrocatalytic behaviour, Polyhedron (2018), doi: https://doi.org/10.1016/j.poly.2018.10.002. 18. Tahir Rasheed, Faran Nabeel, Muhammad Bilal, Hafiz M.N. Iqbalc Biogenic synthesis and characterization of cobalt oxide nanoparticles for catalytic reduction of direct yellow-142 and methyl orange dyes Biocatalysis and Agricultural Biotechnology 19 (2019) 101154

Details of proposed highlight article: 1. Provisional title: Synthesis and Characterization of Cobalt Nanocomposite Using Aniline-Formaldehyde Resin 2. Author(s): Jyoti Chaudhary, Giriraj Tailor, Deepshikha Verma and Ravi Verma 3. Number of expected pages (note: not more than 2 printed pages, including a maximum of 2 figures): 06 4. Date of submission: 10 july 2019 5. Short description of scope/content of proposed highlight (200 words max) : In this paper we were synthesized cobalt nanocomposite by very effective, simple and cheap method. The synthesized nanocomposite microscopic study done by SEM, TEM and AFM and also calculated roughness of the composite.

6. Inviting Editor: L. Ye The University of Sydney, Sydney, Australia.

Author contributions Jyoti Chaudhary: Contributed reagents, materials, analysis tools or data. Giriraj Tailor: Conceived and designed the experiments; Analyzed and interpreted the data; Wrote the paper. Deepshikha Verma: Performed the experiments. Ravi Verma: Analysed and interpreted the data.

Author has been no conflict of interest.