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AgO Nano Composite
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ScienceDirect Materials Today: Proceedings 5 (2018) 22663–22668
www.materialstoday.com/proceedings
ICASE_2017
Photo Decomposition of Acid Orang 8 from Aqueous Solution by Using rGO/CNT/AgO Nano Composite T. Venkatesha, D.M.K. Siddeswarab, M. Mylarappac, K. R. Vishnu Maheshd* H.P. Nagaswarupae, N. Raghavendraf a
Department of Chemistry, ACS College of Engineering, Bengaluru-560074, Karnataka, India Department of Chemistry, Jyothi Institute of technology, Bengaluru-560062, Karnataka, India c Research Centre, Department of Chemistry, AMCEC, Bengalureu-560083, Karnataka, India d National Assessment and Accreditation Council Bangalore-560072, Karnataka, India (An autonomous institution of the university Grants Commission) e Research Centre, Department of Chemistry, EWIT, Bengaluru-560091,India. f CMRTU, RV College of Engineering, Bengaluru-560059. India.
b
Abstract In present study rGO produced by modified hummer’s method, which is used for one pot synthesis of AgO incorporated rGO/AgO and rGO/CNT’s/AgO composite. As synthesized rGO composites were studied using X-ray Diffractometer (XRD), Scanning Electron Microscopy (SEM) andFourier-transform infrared spectroscopy (FTIR). After characterization and confirmation of these compounds were used as a Photo catalyst for the degradation of Acid Orange 8 dye. The catalytic degradation varied by the catalysts which we used in this study. © 2018 Elsevier Ltd. All rights reserved. Selection and/or Peer-review under responsibility ofInternational Conference on Advances in Science & Engineering ICASE - 2017. Keywords::rGO,CNT,Acid Orange 8, Nanoomposite,Water purification, Photocatalytic
1. Introduction Over the last decade, Nanotechnology has become a vital key tool to develop carbon primarily based Nanocomposite[1], composed of carbon nanostructures and metal nanoparticles has enchant multifaceted interests due to their giant prospective for the technologicalapplications like sensors, super capacitors[2], catalyst, biomedicine and medical care[3].
*Corresponding author, Tel: +919916009341 E-mail address: [email protected], [email protected] 2214-7853© 2018 Elsevier Ltd. All rights reserved. Selection and/or Peer-review under responsibility ofInternational Conference on Advances in Science & Engineering ICASE - 2017.
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The graphene oxide(GO) has received intensive attention due to the fascinating mechanical, electrical, thermal, opticalproperties yet as environmental and bio-medical applications[4]. Compared with alternative carbon materials, GO has the proper sp2 hybrid carbon nanostructure and varied O groups as well as epoxide, hydroxyl, carbonyl and carboxyl groups [5]. Due to its distinctive single atomic layer configuration it possesses high specific extent. The most advantage of GO derivatives is that they have ability to be spread in solution [6]. Nanotubes (CNT’s), viewed as rolled version of graphene sheets is another well-known element of carbon owns distinctive electrical, mechanical, chemical action and electro chemical action properties and dominated the whole material science analysis since its discovery in 1991[7]. Generally, CNTs tend to agglomerate in organic dispersion; thus, varied efforts were developed to disperse the CNT by using micelles, ionic liquids, surfactants, chemical compound wrapping and different chemical functionalization approaches [8-9]. It’s been well-tried that GO can be a more robust dispersant to create a stable dispersion of CNT and also the resulted dispersion may be a novel hybrid named as graphene oxide-CNT (GOCNT) [10-11]. Studies well-tried that GO-CNT and graphene-CNT hybrid nanomaterials exhibit higher electrical conductivities, giant specific space and chemical action properties compared with either pristine CNTs or GO/graphene [12-13].The hybrids were ready by many approaches together with straight forward sonication technique, CVD technique twenty two and static spray technique [14-15]. The strong π-π stacking interaction operational between graphene and CNT create a 3D network for the hybrid material and supply exceptional stability[16].The silver nanoparticles are dispersed on the surface of the GO and intercalated into the layers[17]. The silver doped GO may type a versatile free standing film with the addition of a chemical compound. Electrochemical properties of the samples were investigated and notice that the pseudo electrical phenomenon properties increase within the silver doped samples, leading to a rise of the capacitance [18-19]. Incurrent, nano-sized metal oxides have gotten ample attention thanks to its distinctive optical, magnetic and electrical properties that is influenced by its form and size of the nanomaterial. Silver compound may be a acquainted material that having large properties and applications like chemical reaction, chemical change, sensors, fuel cells, electrical phenomenon cells etc[20-21].Acid Orange 8 is a very important industrial textile dye. As a powerful solution, it is completely dissociated under the acid conditions employed in the colouring method. Its principalapplication is in animal skin colouring and paper coloration and also the second principal application is in wool colouring, that makes its waste byproducts a very important economic regional issue[22]. Acid Orange 8 possesses no outstanding coloristic properties among the acid monoazo dyes, but it isdistinguished by the brilliance of its shade and significantly low cost. Anionic monoazo dyes are still employed in larger quantities for affordable articles and consequently are unit long in wastewater [23]. AO8 belongs to the azo dye family, which are characterized by the presence of one or more azo groups (-N=N-) and represent up to 70% of the amount of dyestuffs consumed in industrial applications [24-26]. In this present research work the Graphene material is synthesized using modified Hummer’s method and was used for the further synthesis rGO/AgO and rGO/CNTs/AgO were synthesized by appropriate precursor materials were characterized by using XRD, SEM and FTIR. The photo catalytic activity of as prepared rGO/AgO and rGO/CNTs/AgOwere used and studied against the Acid orange 8 dye by the irradiation of UV light. 2. Experimental 2.1. Material Graphite and multiwalled carbon nanotube are procured from United Nanotech India Pvt. Ltd, Bengaluru, Hydrochloric acid (HCl), Sulphuric acid (H2SO4), Potassium permanganate (KMnO4), Hydrogen peroxide (H2O2),Sodium nitrate (NaNO3), and Sodium hydroxide (NaOH) were purchased from Merck, Bengaluru and Silver nitrate(AgNO3) is purchased from Sigma-Aldrich, Bengaluru. 2.2. Synthesis of GO by modified Hummer’s method GO was synthesized from natural graphite using a modified Hummers method. In a typical experiment, graphite (1.5 g), NaNO3 (1.5 g) and H2SO4 (70 mL) were mixed and stirred by keeping it in an ice bath. Consequently, 9 g of
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KMnO4 was added slowly. In a particular reaction condition water was slowly added, followed by the slow addition of 10 mL of 30% H2O2. The above mixture was centrifuged and purified, then it was mixed with demineralized water to get highly stacked rGO sheets. 2.3. Synthesis of rGO/AgO Nano Composite As prepared rGO from the modified Hummers method. The synthesis procedure for the rGO/AgO composite is using following method, 20.0 mg of rGO was dispersed in 40 mL of deionized water uniformly with the assistance of sonication process. Then 62 mg of AgNO3 powder and 80.0 mg of NaOH powder were consequently added under vigorously stirring. The mixture was constantly stirred for about 15 min and then refluxed at 100 °C for 2 hours in a flask which leads to get the binary composite. 2.4. Synthesis of rGO/CNTs/AgO Nano Composite To synthesis of rGO/CNTs/AgO ternary composite with the continuation of above mentioned process 140.0 mg of multiwalled carbon nanotube is dispersed in 40.0 mL of Distilled water and it was further added to the above mixture and agitated well for about 4 hrs. at room temperature. As prepared slurry was filtered, washed with DI water and dried. Figure.1 shows the flow chart for the synthesis of rGO/CNT/AgO 3. Results and Discussion 3.1. X-ray diffraction and SEM Analysis Figure.1 shows the phase purity of rGO/AgO and rGO/CNT/AgO were analyzed by X-ray diffraction studies. Xray peaks of both binary and ternary composite illustrates that the peaks with diffraction angles at 27°, 33° , 39° , 45° , 55° , 66° , 78° with corresponding planes (002), (101), (111), (200), (204), (220) were observed for both rGO/CNT/AgO and rGO/AgO composite11. As compared to rGO/AgO, intensity of peak increased in case of rGO/CNT/AgO, which is due to the presence of CNT on rGO/AgO composite. The particle size of nanoparticles was found to be 12nm and 10 nm for rGO/AgO and rGO/CNTs/AgO respectively, which was estimated by relative intensity of peaks and peak sharpness, indicates that particles are in crystalline structure. No obvious peaks related to impurities were observed. The average crystalline sizes (D) of the Nanoparticles were calculated by using Debye-Scherer equation34. D=
. C
………………. (1)
D = shape factor, λ = X-ray wavelength, β = FWHM of diffraction peak, θ = Bragg angle. 3.2. SEM Analysis From Figure.2 a) and b) it shows SEM images of rGO/AgO and rGO/CNTs/AgO. In Figure 3 a) the different shapes of AgO nanoparticles are dispersed on the surface of rGO sheet and in Figure.3 b) it shows both CNTs different shaped AgO nanoparticles are dispersed on the surface of rGO sheets. The typical superficial layer of graphene and the nanosheets layered together form a typical multi-layer structure. The geometric furrowing arising from π–bond interface between the sheets of graphene which increases tensile strength of the material due to this layer creating ability will be improved. Further to reduce the silver ions, AgO were dispersed on graphene sheets particles which showed a tough interface between graphene and CNTs composite. Moreover, due to crumpled surface and wide surface areas of graphene nanosheets the presence of AgO particles were observed on both sides of graphene sheets. AgNPs dispersed with Graphene sheets and multi walled carbon nanotube to improve the catalytic activity.
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Fig. 1. XRD of (a) rGO/AgO(b) rGO/CNT/AgO nanocomposite
b)
Fig. 2. SEM Image of (a) rGO/AgO (b) rGO/CNT/AgO.
3.3. FTIR Analysis The FT-IR spectroscopy was utilized to illustrate the typical spectra of rGO/AgO and rGO/CNT/AgO as shown in Fig. 3 a) and b).
Fig. 3. FTIR Spectra of (a) rGO/AgO (b) rGO/CNT/AgO nanocomposite
The peaks located at 1372.0 cm-1 and 1634.8 cm-1, 3398.33 cm-1 and 3229.59 cm-1 which correspond to the C– H , O-H stretching and vibration mode of intercalated water, could be observed; suggest that the oxidation of graphite by modified Hummers method took place and the formation of rGO/AgO was achieved successfully. As for the rGO/CNT/AgO hybrids, the band appearing at 3398.33cm-1 shifted to 3754.6 cm-1 and 3229.59 cm-1 shifted to 3438.11cm-1, which could be assigned to the O-H stretching mode of adsorbed water on the surface of AgO (Fig. 3
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b)). In addition, the appearance of sharp peaks located below at 700 cm-1 might be assigned to the AgO stretching and bending vibrations. 3.4. Photo catalytic Activity The catalytic activity of the prepared rGO/AgO and rGO/CNT/AgO composites are analysed by using Acid orange 8. This method is attained by exactly 0.06 g of rGO/AgO) and rGO/CNT/AgO were weighed and dispersed in 250 millilitre of Acid orange 8 dye (20ppm)with constant stirring.The mixture is irradiated to UltraVioletlight which is formed by a 400W Philips lamp of 254 nm wavelength. With specific interval of time (10 min), the 5 ml mixture is collected from the photo reactor and collected solution absorbance was analysed by UV-Vis spectrophotometer.
Fig. 4.UV- visible absorption of spectra of Acid orange 8 catalyzed by (a) rGO/AgO (b) rGO/CNT/AgO.
Fig. 5. Percentage decomposition of Acid orange 8 catalyzed byrGO/AgO and rGO/CNT/AgO
Normally once the catalyst and dye mixture is exposed to the ultra violet light, the prepared catalyst will absorbs and produce electron-hole pairs that results in the decomposition of dye. The rGO/AgO and rGO/CNT/AgO will take up ultraviolet light and produces electron-hole pairs, the resultant photo generated pairs of electrons and holes are transfer to the surface of the catalyst and react with surface adsorbed O2 to form O2-.Photo degradation of Acid orange 8 by rGO/AgO and rGO/CNTs/AgO Nanocomposite were studied reliably and influence of many parameters like catalyst loading, dye concentration etc., was also examined. In Fig.4 (a) and(b) shows UVvis absorption spectra of acid orange 8 dye with rGO/AgO and rGO/CNTs/AgONanocomposite as a operate of
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the chemical action time (0 to50 min). After 50 min, The Acid orange 8 dye solution turns colourless specifies that by utilisation the prepared catalysts wereshows the degradation of dye but rGO/CNTs/AgO compared to rGO/AgO show more degradation. It is observed that using the as-prepared composite material, the Acid orange 8 solution with 60 mg/L of catalyst can be degraded up to 45 % byrGO/CNTs/AgO andrGO/AgO degraded up to 35%. 4. Conclusion Graphene nano sheets were synthesised by chemical modified Hummer’s method and it was used as a precursor material for the preparation of rGO/AgO and rGO/CNTs/AgO composites were successfully confirmed through different characterization. The synthesised compounds were used for the applications of photo catalysis studies.The Photocatalytic studies was examined through UV-Visible spectra, from which, we can conclude that rGO/CNTs/AgO catalyst showed a good catalytic degradation of Acid orenge-8. This test showed that using the asprepared rGO/AgO composite material, the Acid orenge-8 solution taken with the concentration of 60 mg/L can be degraded up to 35 % and under the similar conditions rGO/CNTs/AgO composite degraded up to 45 %. From the above evidence it can be concluded that both rGO/Ago and rGO/CNTs/AgO catalysts which shows good catalytic degradation at room temperature. In the comparison between two catalysts, the rGO/CNTs/AgO shows high catalytic activity against the Acid orenge-8 dye compared to that of rGO/AgO composite material. References. [1] B.H. Nanjunda Reddy, V. Venkata Lakshmi, K.R. Vishnu Mahesh, M. Mylarappa, N. Raghavendra and T. Venkatesh, NANOSYSTEMS: PHYSICS, CHEMISTRY, MATHEMATICS, 2016, 7 (4), P. 667–674 [2] V. C. Sanchez, A. Jachak, R. H. Hurt and A. B. Kane, Chem. Res. Toxicol., 25(2012) 15-34. [3] H. Zhang, G. Gr¨uner and Y. Zhao, J. Mater. Chem. B, 1(2013) 2542– 2567. [4] S. Iijima, Nature, 354 (1991) 56.57. [5] T. Venkatesh, K. R. Vishnu Mahesh, M. Mylarappa, H. P. Nagaswarupa, D. M. K. Siddeswara et al., Int. J. Adv. Res. 4(9), 1956-1960. [6] S. Niogi, M.A. Hamon, H.Hu, B.Zhao, P. Bhowmik, R. Sen, M.E. Itkis, R.C. Haddon, Acc. Chem. Res., 35 (2002) 1105 [7] K-C. Lin, C.-P. Hong, S.-M. Chen, Int. J. Electrochem. Sci.7 (2012) 11426. [8] D.M.K Siddeswara, T.Venkatesh, K.R. Vishnu Maheshc, M. Mylarappa, K.S. Anantharaju c, K.N.Shravana Kumara, N.Raghavendraf, M.S.Shivakumar, Materials Today: Proceedings 4 (2017) 11799–11805 [9] T. Venkatesha, K. R. Vishnu Mahesh, M. Mylarappa, et al., Materials Today: Proceedings 4 (2017) 11915–11922. [10] B. Unnikrishnan, Y. Umasankar, S. -M. Chen, C.-C. Ti, Int. J. Electrochem. Sci., 7 (2012), 3047. [11] R. Martel, T. Schmidt, H.R. Shea, T. Hertel, P. Avouris, Appl. Phys. Lett., 73 (1998) 2447. [12] Y. Kang, T.A. Taton, J. Am. Chem. Soc., 125 (2003) 5650. [13] R.T. Kachoosangi, M.M. Musameh, I.A.-Yousef, J.M. Yousef, S.M.Kanan, L. Xiao, S.G.Davies, A. Russell, R.G. Compton, Anal. Chem., 81 (2009) 435. [14] J.L. Bahr, J. Yang, D.V. Kosynkin, M.J. Bronikowski, R.E. Smalley, J.M. Tour, J. Am. Chem.Soc., 123 (2001) 6536. [15] V. Mani, B. Devadas, S.-M. Chen, Biosens.Bioelectron. 41(2013) 309. [16] B. Devadas, V. Mani, S.-M. Chen, Int. J. Electrochem. Sci., 7 (2012) 8064. [17] M.-Y. Yen, M-C. Hsiao, S.-H. Liao, P.-I. Liu, H.-M. Tsai, C.-C. M. Ma, -W. Pu, M.-D. Ger, Carbon, 49 (2011) 3597. [18] C. Lee, X. Wei, J.W. Kysar, J. Hone, Sci. 321 (2008) 385-388. [19] C. Zhang, L. Ren, X. Wang, T. Liu, J. Phys. Chem. C, 114 (2010) 1435. [20] F. Derikvand, F. Bigi, R. Maggi, C.G. Piscopo, G. Sartori, Journal of Catalysis 271 (2010)99. [21] W. Wang, Q. Zhao, J. Dong, J. Li, International Journal of Hydrogen Energy 36 (2011) 7374. [22] V.V. Petrov, T.N. Nazarova, A.N. Korolev, N.F. Kopilova, Sensors and Actuators B: Chemical 133 (2008) 291. [23] E. Sanli, B.Z. Uysal, M.L. Aksu, International Journal of Hydrogen Energy 33 (2008) 2097. [24] Hunger K., Industrial dyes: Chemistry, Properties, Applications, Wiley-VCH, Germany, 2003. [25] Stolz A., Basic and applied aspects in the microbial degradation of azo dyes, Microbiol.Biotechnol. 56, 69 (2001). [26] Carina P. Magdalena1, Denise A. Fungaro2, International Journal of Advanced Research in Chemical Science (IJARCS) Volume 1, Issue 7, September 2014, PP 23-33.
ScienceDirect Materials Today: Proceedings 5 (2018) 22663–22668
www.materialstoday.com/proceedings
ICASE_2017
Photo Decomposition of Acid Orang 8 from Aqueous Solution by Using rGO/CNT/AgO Nano Composite T. Venkatesha, D.M.K. Siddeswarab, M. Mylarappac, K. R. Vishnu Maheshd* H.P. Nagaswarupae, N. Raghavendraf a
Department of Chemistry, ACS College of Engineering, Bengaluru-560074, Karnataka, India Department of Chemistry, Jyothi Institute of technology, Bengaluru-560062, Karnataka, India c Research Centre, Department of Chemistry, AMCEC, Bengalureu-560083, Karnataka, India d National Assessment and Accreditation Council Bangalore-560072, Karnataka, India (An autonomous institution of the university Grants Commission) e Research Centre, Department of Chemistry, EWIT, Bengaluru-560091,India. f CMRTU, RV College of Engineering, Bengaluru-560059. India.
b
Abstract In present study rGO produced by modified hummer’s method, which is used for one pot synthesis of AgO incorporated rGO/AgO and rGO/CNT’s/AgO composite. As synthesized rGO composites were studied using X-ray Diffractometer (XRD), Scanning Electron Microscopy (SEM) andFourier-transform infrared spectroscopy (FTIR). After characterization and confirmation of these compounds were used as a Photo catalyst for the degradation of Acid Orange 8 dye. The catalytic degradation varied by the catalysts which we used in this study. © 2018 Elsevier Ltd. All rights reserved. Selection and/or Peer-review under responsibility ofInternational Conference on Advances in Science & Engineering ICASE - 2017. Keywords::rGO,CNT,Acid Orange 8, Nanoomposite,Water purification, Photocatalytic
1. Introduction Over the last decade, Nanotechnology has become a vital key tool to develop carbon primarily based Nanocomposite[1], composed of carbon nanostructures and metal nanoparticles has enchant multifaceted interests due to their giant prospective for the technologicalapplications like sensors, super capacitors[2], catalyst, biomedicine and medical care[3].
*Corresponding author, Tel: +919916009341 E-mail address: [email protected], [email protected] 2214-7853© 2018 Elsevier Ltd. All rights reserved. Selection and/or Peer-review under responsibility ofInternational Conference on Advances in Science & Engineering ICASE - 2017.
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T. Venkatesh et al. / Materials Today: Proceedings 5 (2018) 22663–22668
The graphene oxide(GO) has received intensive attention due to the fascinating mechanical, electrical, thermal, opticalproperties yet as environmental and bio-medical applications[4]. Compared with alternative carbon materials, GO has the proper sp2 hybrid carbon nanostructure and varied O groups as well as epoxide, hydroxyl, carbonyl and carboxyl groups [5]. Due to its distinctive single atomic layer configuration it possesses high specific extent. The most advantage of GO derivatives is that they have ability to be spread in solution [6]. Nanotubes (CNT’s), viewed as rolled version of graphene sheets is another well-known element of carbon owns distinctive electrical, mechanical, chemical action and electro chemical action properties and dominated the whole material science analysis since its discovery in 1991[7]. Generally, CNTs tend to agglomerate in organic dispersion; thus, varied efforts were developed to disperse the CNT by using micelles, ionic liquids, surfactants, chemical compound wrapping and different chemical functionalization approaches [8-9]. It’s been well-tried that GO can be a more robust dispersant to create a stable dispersion of CNT and also the resulted dispersion may be a novel hybrid named as graphene oxide-CNT (GOCNT) [10-11]. Studies well-tried that GO-CNT and graphene-CNT hybrid nanomaterials exhibit higher electrical conductivities, giant specific space and chemical action properties compared with either pristine CNTs or GO/graphene [12-13].The hybrids were ready by many approaches together with straight forward sonication technique, CVD technique twenty two and static spray technique [14-15]. The strong π-π stacking interaction operational between graphene and CNT create a 3D network for the hybrid material and supply exceptional stability[16].The silver nanoparticles are dispersed on the surface of the GO and intercalated into the layers[17]. The silver doped GO may type a versatile free standing film with the addition of a chemical compound. Electrochemical properties of the samples were investigated and notice that the pseudo electrical phenomenon properties increase within the silver doped samples, leading to a rise of the capacitance [18-19]. Incurrent, nano-sized metal oxides have gotten ample attention thanks to its distinctive optical, magnetic and electrical properties that is influenced by its form and size of the nanomaterial. Silver compound may be a acquainted material that having large properties and applications like chemical reaction, chemical change, sensors, fuel cells, electrical phenomenon cells etc[20-21].Acid Orange 8 is a very important industrial textile dye. As a powerful solution, it is completely dissociated under the acid conditions employed in the colouring method. Its principalapplication is in animal skin colouring and paper coloration and also the second principal application is in wool colouring, that makes its waste byproducts a very important economic regional issue[22]. Acid Orange 8 possesses no outstanding coloristic properties among the acid monoazo dyes, but it isdistinguished by the brilliance of its shade and significantly low cost. Anionic monoazo dyes are still employed in larger quantities for affordable articles and consequently are unit long in wastewater [23]. AO8 belongs to the azo dye family, which are characterized by the presence of one or more azo groups (-N=N-) and represent up to 70% of the amount of dyestuffs consumed in industrial applications [24-26]. In this present research work the Graphene material is synthesized using modified Hummer’s method and was used for the further synthesis rGO/AgO and rGO/CNTs/AgO were synthesized by appropriate precursor materials were characterized by using XRD, SEM and FTIR. The photo catalytic activity of as prepared rGO/AgO and rGO/CNTs/AgOwere used and studied against the Acid orange 8 dye by the irradiation of UV light. 2. Experimental 2.1. Material Graphite and multiwalled carbon nanotube are procured from United Nanotech India Pvt. Ltd, Bengaluru, Hydrochloric acid (HCl), Sulphuric acid (H2SO4), Potassium permanganate (KMnO4), Hydrogen peroxide (H2O2),Sodium nitrate (NaNO3), and Sodium hydroxide (NaOH) were purchased from Merck, Bengaluru and Silver nitrate(AgNO3) is purchased from Sigma-Aldrich, Bengaluru. 2.2. Synthesis of GO by modified Hummer’s method GO was synthesized from natural graphite using a modified Hummers method. In a typical experiment, graphite (1.5 g), NaNO3 (1.5 g) and H2SO4 (70 mL) were mixed and stirred by keeping it in an ice bath. Consequently, 9 g of
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KMnO4 was added slowly. In a particular reaction condition water was slowly added, followed by the slow addition of 10 mL of 30% H2O2. The above mixture was centrifuged and purified, then it was mixed with demineralized water to get highly stacked rGO sheets. 2.3. Synthesis of rGO/AgO Nano Composite As prepared rGO from the modified Hummers method. The synthesis procedure for the rGO/AgO composite is using following method, 20.0 mg of rGO was dispersed in 40 mL of deionized water uniformly with the assistance of sonication process. Then 62 mg of AgNO3 powder and 80.0 mg of NaOH powder were consequently added under vigorously stirring. The mixture was constantly stirred for about 15 min and then refluxed at 100 °C for 2 hours in a flask which leads to get the binary composite. 2.4. Synthesis of rGO/CNTs/AgO Nano Composite To synthesis of rGO/CNTs/AgO ternary composite with the continuation of above mentioned process 140.0 mg of multiwalled carbon nanotube is dispersed in 40.0 mL of Distilled water and it was further added to the above mixture and agitated well for about 4 hrs. at room temperature. As prepared slurry was filtered, washed with DI water and dried. Figure.1 shows the flow chart for the synthesis of rGO/CNT/AgO 3. Results and Discussion 3.1. X-ray diffraction and SEM Analysis Figure.1 shows the phase purity of rGO/AgO and rGO/CNT/AgO were analyzed by X-ray diffraction studies. Xray peaks of both binary and ternary composite illustrates that the peaks with diffraction angles at 27°, 33° , 39° , 45° , 55° , 66° , 78° with corresponding planes (002), (101), (111), (200), (204), (220) were observed for both rGO/CNT/AgO and rGO/AgO composite11. As compared to rGO/AgO, intensity of peak increased in case of rGO/CNT/AgO, which is due to the presence of CNT on rGO/AgO composite. The particle size of nanoparticles was found to be 12nm and 10 nm for rGO/AgO and rGO/CNTs/AgO respectively, which was estimated by relative intensity of peaks and peak sharpness, indicates that particles are in crystalline structure. No obvious peaks related to impurities were observed. The average crystalline sizes (D) of the Nanoparticles were calculated by using Debye-Scherer equation34. D=
. C
………………. (1)
D = shape factor, λ = X-ray wavelength, β = FWHM of diffraction peak, θ = Bragg angle. 3.2. SEM Analysis From Figure.2 a) and b) it shows SEM images of rGO/AgO and rGO/CNTs/AgO. In Figure 3 a) the different shapes of AgO nanoparticles are dispersed on the surface of rGO sheet and in Figure.3 b) it shows both CNTs different shaped AgO nanoparticles are dispersed on the surface of rGO sheets. The typical superficial layer of graphene and the nanosheets layered together form a typical multi-layer structure. The geometric furrowing arising from π–bond interface between the sheets of graphene which increases tensile strength of the material due to this layer creating ability will be improved. Further to reduce the silver ions, AgO were dispersed on graphene sheets particles which showed a tough interface between graphene and CNTs composite. Moreover, due to crumpled surface and wide surface areas of graphene nanosheets the presence of AgO particles were observed on both sides of graphene sheets. AgNPs dispersed with Graphene sheets and multi walled carbon nanotube to improve the catalytic activity.
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Fig. 1. XRD of (a) rGO/AgO(b) rGO/CNT/AgO nanocomposite
b)
Fig. 2. SEM Image of (a) rGO/AgO (b) rGO/CNT/AgO.
3.3. FTIR Analysis The FT-IR spectroscopy was utilized to illustrate the typical spectra of rGO/AgO and rGO/CNT/AgO as shown in Fig. 3 a) and b).
Fig. 3. FTIR Spectra of (a) rGO/AgO (b) rGO/CNT/AgO nanocomposite
The peaks located at 1372.0 cm-1 and 1634.8 cm-1, 3398.33 cm-1 and 3229.59 cm-1 which correspond to the C– H , O-H stretching and vibration mode of intercalated water, could be observed; suggest that the oxidation of graphite by modified Hummers method took place and the formation of rGO/AgO was achieved successfully. As for the rGO/CNT/AgO hybrids, the band appearing at 3398.33cm-1 shifted to 3754.6 cm-1 and 3229.59 cm-1 shifted to 3438.11cm-1, which could be assigned to the O-H stretching mode of adsorbed water on the surface of AgO (Fig. 3
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b)). In addition, the appearance of sharp peaks located below at 700 cm-1 might be assigned to the AgO stretching and bending vibrations. 3.4. Photo catalytic Activity The catalytic activity of the prepared rGO/AgO and rGO/CNT/AgO composites are analysed by using Acid orange 8. This method is attained by exactly 0.06 g of rGO/AgO) and rGO/CNT/AgO were weighed and dispersed in 250 millilitre of Acid orange 8 dye (20ppm)with constant stirring.The mixture is irradiated to UltraVioletlight which is formed by a 400W Philips lamp of 254 nm wavelength. With specific interval of time (10 min), the 5 ml mixture is collected from the photo reactor and collected solution absorbance was analysed by UV-Vis spectrophotometer.
Fig. 4.UV- visible absorption of spectra of Acid orange 8 catalyzed by (a) rGO/AgO (b) rGO/CNT/AgO.
Fig. 5. Percentage decomposition of Acid orange 8 catalyzed byrGO/AgO and rGO/CNT/AgO
Normally once the catalyst and dye mixture is exposed to the ultra violet light, the prepared catalyst will absorbs and produce electron-hole pairs that results in the decomposition of dye. The rGO/AgO and rGO/CNT/AgO will take up ultraviolet light and produces electron-hole pairs, the resultant photo generated pairs of electrons and holes are transfer to the surface of the catalyst and react with surface adsorbed O2 to form O2-.Photo degradation of Acid orange 8 by rGO/AgO and rGO/CNTs/AgO Nanocomposite were studied reliably and influence of many parameters like catalyst loading, dye concentration etc., was also examined. In Fig.4 (a) and(b) shows UVvis absorption spectra of acid orange 8 dye with rGO/AgO and rGO/CNTs/AgONanocomposite as a operate of
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the chemical action time (0 to50 min). After 50 min, The Acid orange 8 dye solution turns colourless specifies that by utilisation the prepared catalysts wereshows the degradation of dye but rGO/CNTs/AgO compared to rGO/AgO show more degradation. It is observed that using the as-prepared composite material, the Acid orange 8 solution with 60 mg/L of catalyst can be degraded up to 45 % byrGO/CNTs/AgO andrGO/AgO degraded up to 35%. 4. Conclusion Graphene nano sheets were synthesised by chemical modified Hummer’s method and it was used as a precursor material for the preparation of rGO/AgO and rGO/CNTs/AgO composites were successfully confirmed through different characterization. The synthesised compounds were used for the applications of photo catalysis studies.The Photocatalytic studies was examined through UV-Visible spectra, from which, we can conclude that rGO/CNTs/AgO catalyst showed a good catalytic degradation of Acid orenge-8. This test showed that using the asprepared rGO/AgO composite material, the Acid orenge-8 solution taken with the concentration of 60 mg/L can be degraded up to 35 % and under the similar conditions rGO/CNTs/AgO composite degraded up to 45 %. From the above evidence it can be concluded that both rGO/Ago and rGO/CNTs/AgO catalysts which shows good catalytic degradation at room temperature. In the comparison between two catalysts, the rGO/CNTs/AgO shows high catalytic activity against the Acid orenge-8 dye compared to that of rGO/AgO composite material. References. [1] B.H. Nanjunda Reddy, V. Venkata Lakshmi, K.R. Vishnu Mahesh, M. Mylarappa, N. Raghavendra and T. Venkatesh, NANOSYSTEMS: PHYSICS, CHEMISTRY, MATHEMATICS, 2016, 7 (4), P. 667–674 [2] V. C. Sanchez, A. Jachak, R. H. Hurt and A. B. Kane, Chem. Res. Toxicol., 25(2012) 15-34. [3] H. Zhang, G. Gr¨uner and Y. Zhao, J. Mater. Chem. B, 1(2013) 2542– 2567. [4] S. Iijima, Nature, 354 (1991) 56.57. [5] T. Venkatesh, K. R. Vishnu Mahesh, M. Mylarappa, H. P. Nagaswarupa, D. M. K. Siddeswara et al., Int. J. Adv. Res. 4(9), 1956-1960. [6] S. Niogi, M.A. Hamon, H.Hu, B.Zhao, P. Bhowmik, R. Sen, M.E. Itkis, R.C. Haddon, Acc. Chem. Res., 35 (2002) 1105 [7] K-C. Lin, C.-P. Hong, S.-M. Chen, Int. J. Electrochem. Sci.7 (2012) 11426. [8] D.M.K Siddeswara, T.Venkatesh, K.R. Vishnu Maheshc, M. Mylarappa, K.S. Anantharaju c, K.N.Shravana Kumara, N.Raghavendraf, M.S.Shivakumar, Materials Today: Proceedings 4 (2017) 11799–11805 [9] T. Venkatesha, K. R. Vishnu Mahesh, M. Mylarappa, et al., Materials Today: Proceedings 4 (2017) 11915–11922. [10] B. Unnikrishnan, Y. Umasankar, S. -M. Chen, C.-C. Ti, Int. J. Electrochem. Sci., 7 (2012), 3047. [11] R. Martel, T. Schmidt, H.R. Shea, T. Hertel, P. Avouris, Appl. Phys. Lett., 73 (1998) 2447. [12] Y. Kang, T.A. Taton, J. Am. Chem. Soc., 125 (2003) 5650. [13] R.T. Kachoosangi, M.M. Musameh, I.A.-Yousef, J.M. Yousef, S.M.Kanan, L. Xiao, S.G.Davies, A. Russell, R.G. Compton, Anal. Chem., 81 (2009) 435. [14] J.L. Bahr, J. Yang, D.V. Kosynkin, M.J. Bronikowski, R.E. Smalley, J.M. Tour, J. Am. Chem.Soc., 123 (2001) 6536. [15] V. Mani, B. Devadas, S.-M. Chen, Biosens.Bioelectron. 41(2013) 309. [16] B. Devadas, V. Mani, S.-M. Chen, Int. J. Electrochem. Sci., 7 (2012) 8064. [17] M.-Y. Yen, M-C. Hsiao, S.-H. Liao, P.-I. Liu, H.-M. Tsai, C.-C. M. Ma, -W. Pu, M.-D. Ger, Carbon, 49 (2011) 3597. [18] C. Lee, X. Wei, J.W. Kysar, J. Hone, Sci. 321 (2008) 385-388. [19] C. Zhang, L. Ren, X. Wang, T. Liu, J. Phys. Chem. C, 114 (2010) 1435. [20] F. Derikvand, F. Bigi, R. Maggi, C.G. Piscopo, G. Sartori, Journal of Catalysis 271 (2010)99. [21] W. Wang, Q. Zhao, J. Dong, J. Li, International Journal of Hydrogen Energy 36 (2011) 7374. [22] V.V. Petrov, T.N. Nazarova, A.N. Korolev, N.F. Kopilova, Sensors and Actuators B: Chemical 133 (2008) 291. [23] E. Sanli, B.Z. Uysal, M.L. Aksu, International Journal of Hydrogen Energy 33 (2008) 2097. [24] Hunger K., Industrial dyes: Chemistry, Properties, Applications, Wiley-VCH, Germany, 2003. [25] Stolz A., Basic and applied aspects in the microbial degradation of azo dyes, Microbiol.Biotechnol. 56, 69 (2001). [26] Carina P. Magdalena1, Denise A. Fungaro2, International Journal of Advanced Research in Chemical Science (IJARCS) Volume 1, Issue 7, September 2014, PP 23-33.