A Simple Study on the Photocatalytic Efficiency of Copper Magnesium Ferrite

 

A. Saravanan^1*, A. Abilarasu², T. Somanathan²

¹Department of Chemistry, Saveetha Engineering College, Chennai-602105, Tamilnadu, India

²Department of Chemistry, School of Basic Sciences, VISTAS, Chennai-600117

 

ABSTRACT:

Nanostructured Materials have great scope in research due to their broad range of applications. Here in this study we have prepared copper doped magnesium ferrite (CuMgFe₂O₄)through Solution Combustion technique at very low temperature. The synthesized samples were analyzed by powder X-ray Diffraction (XRD) and Scanning Electron Microscope(SEM). The flake like morphology of CuMgFe₂O₄ catalyst could be clearly identified from the SEM images. The efficiency of CuMgFe₂O₄catalyst over Congo Red dye degradation under sunlight were studied and were found to be better than commercial photocatalyst. To further improve the degradation efficiency of the catalyst various parameters was optimized such as H₂O₂, pH and Catalyst weight. From our studies we confirm that the CuMgFe₂O₄ catalyst could be a promising material for practical application.

 

 

 

INTRODUCTION:

In common industries are looking for the refabrication of utilized water, as the huge amount of investment over steady fresh water is creating problem for developing industries. Under these circumstances purification of contaminated water had also become tedious work¹. When looking for materials with economic mode two major shortcomings were observed, very low efficiency under visible light irradiation and reusability mechanism. Henceforth development of effective photocatalyst is still under broad research race. Recent studies have provoked iron oxides Fe₃O₄ and γ-Fe₂O₃ to be a promising fentoncatalyst^2,3due to its overwhelming abilities such as low conductivity range, thermal stability and reusability. Still ferrite has a major disadvantage that a very high rate of electron hole pair recombination affecting the efficiency of photocatalyst⁴. To overcome this drawbacktransition elements like Cr,

 

Mn, Co, Ni and Cu etc.,⁵were replaced for Fe into the  crystal lattice proved which had effectively improve efficiency of the ferrite based heterogeneous fenton catalysts. But still the property of ferrite can be controlled by synthesis method such as hydrothermal, co-precipitation, sol-gel and combustion methods⁶.In this study we have synthesized the Cu doped Magnesium ferrite CuMgFe₂O₄  bysolution combustion method  to study its photocatalytic efficiency againtcongo red dye^7,8.

 

MATERIALS AND METHOD:

Analytical grade iron nitrate [Fe(NO₃)₃•9H₂O], magnesium nitrate [Mg(NO₃)₂•6H₂O], cobalt nitrate [Cu(NO₃)₂•3H₂O], Citric Acid, H₂O₂ and Congo Red Dye were purchased from Merck and used as such without any purification.

 

Synthesis method of CuMgFe₂O₄:

The CuMgFe₂O₄ were prepared by solution combustion method using citric acid as combustion fuel. Iron nitrate [Fe(NO₃)₃•9H₂O], magnesium nitrate Mg(NO₃)₂•6H₂O] and cobalt nitrate [Cu(NO₃)₂•3H₂O] solutions were prepared separately and mixed in definite stoichiometric proportions. To this stoichiometric solution citric acid were added and stirred for about 5 min to attain homogenous solution. The resultant solution was kept in muffle furnace for 5 min at 450°C and allowed to attain room temperature.The obtained product were crushed into powder and used for further analysis⁹.

 

Photodegradation Experiment:

The degradation efficiency of the above synthesized catalyst was examined using congo red dye under direct sunlight. In each study, 0.03mg of CuMgFe₂O₄ catalyst was added into 50ml of congo red dye solution with concentration of 0.2g/L. The resultant mixture was kept in dark room to attain adsorption equilibrium between dye and the photocatalyst for about 30min, and then the solution was illuminated by natural sunlight. The color removal of dye were monitored from 2ml sample collected from reaction mixtures at regular periods^10,11. The suspended catalyst was removed by centrifugation. The supernatant solution were analysed using Shimadzu UV-3600 Model at λmax=499 nm¹².

 

RESULT AND DISCUSSION:

XRD pattern of MNF catalyst:

XRD technique is used identify the crystal phase of the synthesized sample13. Figure 1 IllustratesXRD pattern of the prepared CuMgFe₂O₄catalyst. The crystalline peaks at 29.96° and 35.27° are corresponding to reflection planes (220) and (311) of Fe₂O₄JCPDS card no 65-3107. The peaks at 36.81°, 42.83° and 62.13° are indexed to (111), (200) and (220) planes of MgO¹⁴. Also the peaks at 48.43°, 56.96° and 60.04° were attributed to (202), (202) and (113) planes of CuO. From the peaks observed we are able to confer that the synthesized material has spinel ferrite strucuture.

 

 

Figure 1 XRD of synthesized Cu/MgFe₂O₄

 

SEM image of NMF photocatalyst:

The surface morphology of the catalyst was determined by Scanning Electron Microscope (SEM)^15,16 and the images were illustrated in Figure 2(a,b). The SEM images show clear resemblance of flake like morphology. Figure 2a shows agglomeration of many small particles which is due to the magnetic dipole-dipole interaction¹⁷. Figure 2b shows HRSEM image at high magnification inferring clear homogeneous flake surfaces.

 

Figure 2 SEM image of synthesized CuMgFe₂O₄

 

Comparative study of Photocatalayst:

The catalytic activity of the catalyst is examined by the degradation of congo red dye under ambient conditions and results are illustrated in Figure 3. From the experiments results we could find that degradation of CR dye is almost negligible under sunlight alone. Also without catalyst, from results we can observe that CR is very stable in presence of sun light.  It is also proved that a slight degradation was obtained with TiO₂ and MgFe₂O₄ alone. After inclusion of Cu into the MgFe₂O₄ the degradation efficiency is achieved to maximum. This result shows that the Cu could act as charge carrier and improve the catalytic efficiency^18,19.

 

 

Figure 3 Catalytic activity of CuMgFe₂O₄

 

Effect of H₂O₂:

The photocatalytic efficiency of the photocatalyst is significantly affected by the H₂O₂concentration²⁰. Photocatalytic degradation experiments were carried out to optimize the H₂O₂ concentration by varying the H₂O₂(1-4 ml/L) at constant pH (4), catalyst weight (30mg/L) and within the irradiation time of 90min and the results are shown in Figure 4 From the experiment we infer that initially the degradation efficiency is increased; however above certain concentration of H₂O₂ there is an decrease in degradation rate.  This is due to the reason that presence of excessive amount of H₂O₂ may react with hydroxyl radicals leading to formation of oxyhydroxy radicals which is less reactive than hydroxyl radicals ²¹.

 

 

Figure 4 Effect of H₂O₂ Concentration over Congo Red dye

 

Effect of pH:

Figure 5 illustrates the influence of pH on the degradation of CR using synthesized photocatalyst and results confirm that pH has significant role in degradation. The experiments were carried out at pH between 1 and 10. The degradation efficiency is very low at pH =1due to the dissolubility of ferrite materials.

 

 

Figure 5 Effect of pH on degradation studies

 

By increasing the pH from 1 to 4 we achieved a maximum degradation for the synthesized materials. At pH 7 and above the degradation efficiency is reduced because of  formationFe(OH)₂⁺ and Fe(OH)²⁺ions on the surface of the catalyst^22,23.

 

 

Effect of catalyst weight:

The degradation efficiency of the catalyst is increased when the catalyst weight is increased from 0.020g/L to 0.030g/L, due to the formation of more active radicals the degradation efficiency is enhanced and the results are presented in Figure 6.  The decomposition rate of H₂O₂ is high when more active site present in the sample which increase the degradation of congo red dye.  Above 0.030g/L the degradation efficiency is slightly decreased because of aggolomeration of catalyst reduced the active radials and inhibit the light penetration into the solution. Therefore, 0.030 g/L of the catalyst was used as the optimal dosage for the subsequent experiments^24,25.

 

 

Figure 6 Study of catalyst concentration

 

CONCLUSION:

A new CuMgFe₂O₄ was synthesized by solution–combustion method. The synthesized catalyst was characterized by different techniques. XRD results reveals that the prepared catalyst having spinel structure in nature revealing the presence of Mg, Fe and Co in the catalyst. CuMgFe₂O₄ is found to be more efficient than commercial catalysts for degradation of CR under sun light. The optimum pH and catalyst loading for efficient removal of dye are found to be 4 and 2 g L^-1, respectively. Hence when compared to other catalyst CuMgFe₂O₄ was foundto be better and efficient in terms of method of preparation, photocatalytic activity and reusability so it can be considered as potential candidate in industrial application point of view.

 

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Accepted on 04.07.2018          © RJPT All right reserved

Research J. Pharm. and Tech 2018; 11(9): 4029-4032.