Preparation and activity evaluation of n-p CuO/CeO2ZrO2 heterojunction photocatalyst for degradation of organic azo dye in wastewater under visible light irradiation

Document Type : Research Paper


1 Department of Environmental Science, Yuvaraja's College,University of Mysore, Mysore, Karnataka, India.

2 Department of Agricultural Research and Extension Authority, Ministry of Agriculture, Yemen.


In this work, the auto solution combustion method was used to prepare p-CuO/n-CeO2ZrO2 with different concentrations of p-CuO, which was found to be an effective photocatalyst for degrading azo dye under visible light irradiation. To investigate the photocatalytic activity of p-CuO/n-CeO2ZrO2, nonbiodegradable azo dyes such as acid orange 7 (AO7) were chosen as the modal target. The catalyst was characterised using X-ray diffraction (XRD), EDS, SEM, XPS, BET, and UV-vis DRS. Under visible light irradiation, AO7 solution easily mineralized with existing p-CuO/n-CeO2ZrO2. Experiments were carried out to determine the adsorption potential of acid orange 7 on p-CuO/n-CeO2ZrO2 at different pH values. Using some radical scavengers to evaluate intermediates, a potential degradation pathway for photocatalytic degradations has been proposed. Under similar visible light conditions, the photodegradation rate of this azo dye catalysed by p-CuO/n-CeO2ZrO2 is much faster than that of n-type CeO2ZrO2. The photocatalytic activity of the sample with a p-n CuO/ CeO2-ZrO2 molar ratio of 0.021 was 35% higher than that of n-type CeO2ZrO2. The impact of pH on photocatalytic activity of the photocatalyst was also studied. At a pH of 3, acid orange 7 showed the most degradation.


Main Subjects

[1] Shiping, Xu., Jiawei, Ng., Xiwang, Z., Hongwei, B., Darren, S. (2011). Adsorption and photocatalytic degradation of Acid Orange 7 over hydrothermally synthesized mesoporous TiO2 nanotube. Colloids and surfaces A: physicochemical and engineering aspects, 379 (1–3), 169-175.
 [2] Sergi, G., Sergi, D.b., Josep, M., Guilemany, b., Enric, B. (2013). Solar photoelectrocatalytic degradation of Acid Orange 7 azo dye using a highly stable TiO2 photoanode synthesized by atmospheric plasma spray. Applied catalysis                         B: environmental, 133(27), 142-150.
[3] Nematollah, J., Sahand, J., Farshid, G., Mehdi, A., Gelavizh, B. (2018). The performance study on ultrasonic/Fe3O4/H2O2 for degradation of azo dye and real textile wastewater treatment. Journal of molecular liquids, 256(15), 462-470.
 [4] Esther, F., Tibor C., Gyula, O. (2004). Removal of synthetic dyes from wastewaters. Environment international, 30(7), 953-971.
 [5] Gupta, V. K., Mittal, A., Gajbe, V., Mittal, J. (2006). Removal and recovery of the hazardous azo dye acid orange 7 through adsorption over waste materials: bottom ash and de-oiled soya. Industrial and engineering chemistry research, 45(4), 1446-1453.
[6] Aber, S., Daneshvar, N., Soroureddin, S. M., Chabok, A., Asadpour-Zeynali, K. (2007). Study of acid orange 7 removal from aqueous solutions by powdered activated carbon and modeling of experimental results by artificial neural network. Desalination, 211(1-3), 87-95.
[7] Özcan, A., Oturan, M. A., Oturan, N., ┼×ahin, Y. (2009). Removal of Acid Orange 7 from water by electrochemically generated Fenton's reagent. Journal of hazardous materials, 163(2-3), 1213-1220.
[8] Greluk, M., Hubicki, Z. (2011). Efficient removal of Acid Orange 7 dye from water using the strongly basic anion exchange resin Amberlite IRA-958. Desalination, 278(1-3), 219-226.
[9] Ji, P., Zhang, J., Chen, F., Anpo, M. (2009). Study of adsorption and degradation of acid orange 7 on the surface of CeO2 under visible light irradiation. Applied catalysis B: environmental, 85(3-4), 148-154.
[10] Muhd Julkapli, N., Bagheri, S., Bee Abd Hamid, S. (2014). Recent advances in heterogeneous photocatalytic decolorization of synthetic dyes. The scientific world journal, 2014.
[11] Antonopoulou, M., Kosma, C., Albanis, T., & Konstantinou, I. (2020). An overview of homogeneous and heterogeneous photocatalysis applications for the removal of pharmaceutical compounds from real or synthetic hospital wastewaters under lab or pilot scale. Science of the total environment,765, 144163.
[12] Zhao, J., Gea, S., Pana, D., Shao, Q., Linb, J., Wangc, Z., Hud, Z., Wue, T., Guo, Z. (2018). Solvothermal synthesis, characterization and photocatalytic property of zirconium dioxide doped titanium dioxide spinous hollow microsphereswith sunflower pollen as bio-templates. Journal of colloid and interface science, 529,111-121.
[13] Pirzada, B. M., Mir, N. A., Qutub, N., Mehraj, O., Sabir, S., Muneer, M. (2015). Synthesis, characterization and optimization of photocatalytic activity of TiO2/ZrO2 nanocomposite heterostructures. Materials Science and engineering: B, 193, 137-145.
[14] Kusmierek, E. (2020). A CeO2 Semiconductor as a Photocatalytic and photoelectrocatalytic material for the remediation of pollutants in industrial wastewater: A review. Catalysts, 10(12), 1-54.
[15] Bakkiyaraj, R., Bharath, G., Ramsait, K. H., Abdel-Wahab, A., Alsharaeh, E. H., Chen, S. M., Balakrishnan, M. (2016). Solution combustion synthesis and physico-chemical properties of ultrafine CeO2 nanoparticles and their photocatalytic activity. RSC advances, 6(56), 51238-51245.
[16] Prabhu, S., Viswanathan, T., Jothivenkatachalam, K., Jeganathan, K. (2014). Visible light photocatalytic activity of CeO2-ZnO-TiO2 composites for the degradation of rhodamine B. Indian journal of materials science, 2014, 1-10.
[17] Ahmad, U.R., Kumar, M.S., Akhtar, G., Kumar, S.H., Kim. (2015). Growth and properties of well-crystalline cerium oxide (CeO2) nanoflakes for environmental and sensor applications. Journal of colloid and interface science, 454(15), 61-68.
[18] Hu, S., Zhou, F., Wang, L., Zhang, J., (2011). Preparation of Cu2O/CeO2 heterojunction photocatalyst for the degradation of Acid Orange 7 under visible light irradiation. Catalysis communications, 12(9),794–797.
[19] SILVA, W. J. D., SILVA, M. R., Takashima, K. (2015). Preparation and characterization of Zno/CuO semiconductor and photocatalytic activity on the decolorization of direct red 80 azodye. Journal of the chilean chemical society, 60(4), 2749-2751.
[20] Asl, I.M., Ghazi, M.M., Jahangiri M. (2016). Synthesis, characterization and degradation activity of Methyl orange Azo dye using synthesized CuO/α-Fe2O3 nanocomposite. Advances in environmental technology, 4, 169-177.
[21] Zoolfakar, A. S., Rani, R. A., Morfa, A. J., O'Mullane, A. P., Kalantar-Zadeh, K. (2014). Nanostructured copper oxide semiconductors: a perspective on materials, synthesis methods and applications. journal of materials chemistry c, 2(27), 5247-5270.
[22] Liu W.Chen S., Zhang S., Zhao W., Zhang H., Yu X. (2010). Preparation and characterization of p–n heterojunction photocatalyst p-CuBi2O4/n-TiO2 with high photocatalytic activity under visible and UV light irradiation. Journal of nanoparticle research, 12, 1355–1366.
[23] Wen, W., and Wu, J. (2014). Nanomaterials via solution combustion synthesis: a step nearer to controllability. RSC advances, 4, 580–8100.
[24] Deganello, F., and Tyagi, A. (2018). Solution combustion synthesis, energy and environment: Best parameters for better materials. Progress in crystal growth and characterization of materials, 64(2), 23-61.
[25] Hu, S., Zhou, F., Wang, L., Zhang, J., (2011). Preparation of Cu2O/CeO2 heterojunction photocatalyst for the degradation of Acid Orange 7 under visible light irradiation. Catalysis communications,12(9),794–797.
[26] Chan, Y. N., Hsu, R. S., Lin, J. J. (2010). Mechanism of silicate platelet self-organization during clay-initiated epoxy polymerization. The journal of physical chemistry C, 114(23), 10373-10378.
[27] Mageshwari, K., Nataraj, D., Pal, T., Sathyamoorthy, R., Park, J. (2015). Improved photocatalytic activity of ZnO coupled CuO nanocomposites synthesized by reflux condensation method. Journal of alloys and compounds, 625, 362-370.
[28] Yang, L., Chu, D., Wang, L. (2016). CuO core–shell nanostructures: precursor-mediated fabrication and visible-light induced photocatalytic degradation of organic pollutants. Powder technology, 287, 346-354.
[29] Shifu, C., Sujuan, Z., Wei, L., Wei, Z. (2008). Preparation and activity evaluation of p–n junction photocatalyst NiO/TiO2. Journal of hazardous materials, 155(1-2), 320-326.
[30] Chen, S., Zhao, W., Liu, W., & Zhang, S. (2008). Preparation, characterization and activity evaluation of p–n junction photocatalyst p-ZnO/n-TiO2. Applied surface science, 255(5), 2478-2484.