Mechanics, Materials Science & Engineering, May 2017
ISSN 2412-5954
Electrocatalytic and Photocatalytic Application of Carbon Nitride Nanocomposite6
Ag Hybrid
S. Munusamy1, R. Suresh1, K. Giribabu1, R. Manigandan1, S. Preenkumar1, S. Muthamizh1, T. Dhanasekaran1, A. Padmanapan1, G. Ganamoorthy1, A. Stephen2, V. Narayanan1, a 1
Department of Inorganic Chemistry, Guindy Campus, University of Madras, Chennai, India
2
Department of Nuclear Physics, Guindy Campus, University of Madras, Chennai, India
a
vnnara@yahoo.co.in DOI 10.2412/mmse.14.20.385 provided by Seo4U.link
Keywords: carbon nitride
Ag, hydroquinone, methylene blue.
ABSTRACT. In this paper, a carbon nitride Ag hybrid nanocomposite is synthesized. Carbon nitride Ag hybrid nanocomposite was synthesized by chemical oxidative polymerization method. The hybrid was characterized by UVVisible spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). The electrochemical oxidation of hydroquinone was inspected by cyclic voltammetry (CV). The Carbon nitride Ag hybrid modified GCE (hybrid nanocomposite /GCE) showed enhanced electrocatalytic oxidation of hydroquinone than GCE. The hybrid showed better photoccatalytic degradation of methylene blue within 180 mins.
Introduction. Diverse polymeric carbon nitrides, which differ in their atomic sizes, have been reported by thermal condensation of organic monomers. One of the most applicable is the polymeric form melon, H3C6N9, a major architecture which is a significance of an incomplete condensation of carbon nitride precursors. [1] Bojdys et al. reduce the hydrogen contented to a sensible C3N4 formulation by condensation of dicyandiamide in a salt melt of lithium and potassium chloride [2]. The results designate that graphitic allotropes are the most stable phases under ambient situations for the C3N4 composition. Carbon nitrides and connected compounds are of great engineering attention as possible materials for microelectronic devices, optical, magnetic and tri bological applications [3, [4], [5], [6]. Graphitic carbon nitrides container also be an energetic support, Lewis-base character, for the dispersal of metal particles in heterogeneous catalysis. [10] Recently, Wang et al. have measured g-C3N4 as a plentiful photocatalyst for hydrogen construction from water [11]. In adding to mentioned perspectives, in the past decades, studies on the most stable polymorphs of C3 N4 were interested by a special attention for the synthesis of new low-compressible materials [12], [13]. Synthesis of carbon nitride-Ag hybrid nanocomposite. The graphitic C3N4-silver hybrid nanocomposites were synthesized using urea-silver acetate poly-condensation methods. In 95:5% amounts of urea- silver acetate were taken in alumina crucibles with covered and calcined at 550 o C for 5 h at a heating rate of 50 C min -1. Result and Dissuasion UV-Visible spectroscopy. The UV-Visible absorption spectrum of the silver- carbon nitride nanocomposite is showed in Fig. 1. The broad peaks in the range of 600 nm were corresponding to -Visible absorption spectrum of the silver nanoparticles is one broad peak in the range of 410 nm. The result 6
d by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license http://creativecommons.org/licenses/by-nc-nd/4.0/
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Mechanics, Materials Science & Engineering, May 2017
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hybrid was confirm the absorption peak at 600, 410 nm of carbon nitride-silver nanocomposite. In the carbon nitride silver hybrid composite there is a small shift in the band edge position to a higher wavelength its suggesting that the recombination rate of the electron hole pair was successfully reduced in the hetero structured carbon nitride- silver composite hybrid nanocomposite. FT-IR spectroscopy. The FT-IR spectrum of the carbon nitride-silver hybrid nanocomposite is showed in Fig. 2. The fourier transform infrared spectroscopic measurement, which implies the existence of condensed aromatic carbon nitride hetrocycles. The stretching vibration near at 1546 and 1620 cm-1are attributed to C=N stretching, while the three bands at 1217, 1304 and 1409 cm-1 to aromatic C-N stretching [15] . The peak at 808 cm-1 belongs to triazine ring mode, which correspond to condensed CN heterocyclic. A broad band near at 3150-3500cm-1 correspond to the stretching modes of NH2 or =NH groups, are mostly due to typical vibrations of C-N that contain C-N hetrocycles and are generally associated with skeletal stretching vibration of these aromatic ring, which are uncondensed amine groups in agreement with the result. The FTIR a spectrum of the silver nanoparticles was confirm as expected at stretching vibration modes at 573 cm-1. In the result was confirming in the strong interaction between Ag-carbon nitride stretching vibration position to a lower wavenumber.
Fig. 1. UV-Visible spectroscopy of carbon nitride-silver nanocomposite.
Fig. 2. FTIR spectroscopy of carbon nitride-silver nanocomposite. Raman Spectroscopy. The Raman spectrum of the carbon nitride-silver nanocomposite is showed in Fig. 3. The Raman peaks observed at 786 and 1016 cm-1 are attributed to the different types of ring breathing modes of s-triazine unit, was confirm carbon nitride structure [16]. The above result is in
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Mechanics, Materials Science & Engineering, May 2017
ISSN 2412-5954
good agreement with the FTIR result. The Raman spectra of the silver were confirming nanoparticles as expected peak at 1650 nm. All the characteristic bands were observed in the hybrid nanocomposite. XRD: The X-ray diffraction pattern of carbon nitride-silver nanocomposite is shown in Fig. 4. The 0 corresponds to the in-plane structural packing motif of tristriazine units is corresponding to (002) plane. These plane (002) corresponding to the hole-to-hole interaction of carbon nitride and the presence of uncondensed amino groups [17]. The silver nanoparticle was confirm to the 2 = value (JCPDS-25-922). All the characteristic peaks were observed hybrid nanocomposite.
Fig. 3. Raman spectroscopy of carbon nitride-silver nanocomposite.
Fig. 4. XRD of carbon nitride-silver hybrid nanocomposite. FE-SEM. The surface of morphology of the hybrid was investigated by FE-SEM. The FE-SEM images of carbon nitride are shown in Fig. 5 (a-b). The grain size of g-C3N4 was distributed from 300 agglomerated sheet like morphology of carbon nitride-Ag. The nanoparticles calcined at 5500c for 4h at this temperature the nanoparticles walls were converted to nanosheets. The dispersed Nano spheres will have potential applications in photo catalysis due to larger available surface areas. The energy dispersive spectroscopy (EDS) shows that they consist of C, N and Ag only Fig. 2 (c) is consistent with good agreement with XRD results.
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Mechanics, Materials Science & Engineering, May 2017
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Fig. 5. FE-SEM and EDAX image of carbon nitride-silver nanocomposite.
Fig. 6. CV analysis of nitride/GCE/Hydroquinone.
(a)
bare
pH=4,
(b)
Hydroquinone/GCE,
(c)
Ag-carbon
Electrochemical sensing of mebendazole by Carbon nitride-Ag hybrid nanocomposite. Cyclic voltammetry. Fig. 6 shows CV of bare/GCE (a) and GaN/carbon nitride-Ag/GCE in the presence of 1 mM hydroquinone in 0.1 M PBS buffer (pH 4) at the scan rate of 50 mV/s. It shows an reversible behaviour at bare GCE with the anodic peak potential (Epa) at 0.6961mV, with an anodic peaks current (Ipa) of 1.1685 A and cathode peak potential (Epc) at -0.1373mV, with an cathode peaks current (Ipc) of -1.1378 A. The modified GaN/carbon nitride-Ag/GCE exhibits well-known redox hydroquinone anodic peak potential (Epa) at 0.4005mV, with anodic peak current (Ipa) of 1.6564 A and cathode peak potential (Epc) at -0.1544mV, with an cathode peaks current (Ipc) of -1.1452 A. The redox peak current is enhanced compared to bare GCE with negative shift of 0.45 mV. The result MMSE Journal. Open Access www.mmse.xyz
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Mechanics, Materials Science & Engineering, May 2017
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suggests that the GaN/carbon nitride-Ag/GCE has improved the electron transfer kinetics due to enhanced conducting nature.
Fig. 7. CV analysis hydroquinone of scan rate 50-150mVs-1 using Ag-carbon nitride/GCE.
Fig. 8. DPV analysis of hydroquinone concentration of 0.01nitride/GCE/Hydroquinone and calibrate plate.
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-carbon
Mechanics, Materials Science & Engineering, May 2017
ISSN 2412-5954
Fig. 9. Calibration plot. Fig. 7 shows the cyclic voltammograms of 1 mM hydroquinone at Ag-carbon nitride/GCE in the scan rate effective range of 50 to 150mVs-1. At scan rate were increasing, were corresponding to the current response increasing is good catalytic ability of the hydroquinone. The differential pulse voltammetry. The Fig. 8 shows the differential pulse voltammograms of hydroquinone at carbon nitride-Ag/GCE in different concentration. A successive addition of hydroquinoneto 0.1 M PBS (pH 4) produces a significant increase in the current with slight shift in peak potential. The calibration plots were found to be linear and the correlation equation of I ( ) = -1 ) (r 2= 0.9937). The calibration plot of carbon nitride-Ag/GCE is shown as inset in Fig. 9. The linear response is in the range from 0.4x10-6 ~ 1x10-7 M corresponding with a e-Ag/GCE is sensitive towards the 10-7 M. On the basis of our results, we expect that it is possible to use the hybrid have incredible advantages for constructing electrochemical sensor towards such other analytes. Photocatalytic degradation of MethyleBlue. Photocatalytic activity of the carbon nitride-silver hybrid was examined by using degradation of methylene blue (MB) as the model organic pollutant. -5 Fig.10 shows the absorption spectrum of M MB solution during different time intervals in presence of carbon nitride-silver nanocomposite respectively. The visible light irradiation of aqueous dye solution in presence of carbon nitride-silver nanocomposite nanoparticles showed decrease in absorption maximum with shift in absorption maximum ( = 663 nm). It suggests that the complete decolourization of MB solution was purely due to the photocatalytic degradation ability of carbon nitride-silver nanocomposite. Further, absorbance of carbon nitride-silver nanocomposite showed a maximum value of 0.45before irradiation and decreased to a value of 0.045 after 180 min. It should be mentioned that the continued irradiation of visible light for another 35min did not give any decrease in absorbance at 663 n values were calculated with that carbon nitride-silver value of absorbance and the degradation time of 180 min respectively. It can be seen that the carbon nitride-silver hybrid nanocomposite exhibits maximum efficiency towards the photocatalytic degradation of MB.
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Mechanics, Materials Science & Engineering, May 2017
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Fig. 10. Photocatalytic degradation of methylene blue. C3N4/Ag +h C3N4/Ag+
c3N4 /Ag+ + e CBC3N4/Ag +h B+
e CB-+ O2 h B++ H2O Dye+OH.
O2.-
(H++OH-) H+ +OH. oxidation products.
Summary. The synthesized of silver-carbon nitride hybrid nanocomposite was characterized by UVvisible, FT-IR spectroscopy, Raman, XRD. The particle size and morphology were observed by FESEM. The above characterization methods show strong evidence for the formation of Ag-carbon nitride nanocomposite and the interaction happened between Ag and carbon nitride. TheFE- SEM images show the nanosphere like morphology of the Ag-carbon nitride. The electrochemical sensing properties of hybride nanpcomosite were investigated by using hydroquinone as an analyte. The detection limit and sensitivity of Ag-carbon nitride/GCE is found to be 1.1 10-7 respectively. References [1] B. V. Lotsch, M. Doblinger, J. Sehnert, L. Seyfarth, J. Senker, O. Oeckler and W. Schnick, Unmasking Melon by a Complementary Approach Employing Electron Diffraction, Solid-State NMR Spectroscopy, and Theoretical Calculations Structural Characterization of a Carbon Nitride Polymer, Chem. Eur. J., 2007, Vol. 13, Iss. 17, 4969-4980, DOI: 10.1002/chem.200601759 [2] M. J. Bojdys, J.-O. Muller, M. Antonietti and A. Thomas, Ionothermal Synthesis of Crystalline, Condensed, Graphitic Carbon Nitride, Chem. Eur. J., 2008, Vol. 14, 8177-8182. DOI: 10.1002/chem.200800190 [3] T. W. Scharf, R. D. Ott, D. Yang and J. A. Barnard, Structural and tribological characterization of protective amorphous diamond-like carbon and amorphous CNxCNx overcoats for next generation hard disks J. Appl. Phys., 1999, 85, 3142, DOI: 10.1063/1.369654 [4] C. Donnet and A. Erdemir, Surf. Coat. Technol., 2004, 180, 76. [5] X. Li, J. Zhang, L. Shen, Y. Ma, W. Lei, Q. Cui and G. Zou, Appl. Phys. A, 2009, 94, 387. MMSE Journal. Open Access www.mmse.xyz
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