Copper-and-Nitrogen-Codoped Zirconium Titanate (Cu-N-ZrTiO4) as a Photocatalyst for Photo-Degradation of Methylene Blue under Visible-Light Irradiation

Lenny Rahmawati(1), Rian Kurniawan(2), Niko Prasetyo(3), Sri Sudiono(4), Akhmad Syoufian(5*)

(1) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(2) Institute of Chemical Technology, Universität Leipzig, Linnéstr. 3, 04103 Leipzig, Germany
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(4) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(5) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(*) Corresponding Author


Synthesis and characterization of copper-and-nitrogen-codoped zirconium titanate (Cu-N-ZrTiO4) as a photocatalyst for the degradation of methylene blue (MB) have been conducted. The main purpose of this research was to investigate the co-doping effect of copper and nitrogen dopants in ZrTiO4 as a photocatalyst for the photodegradation of MB. Titanium-(IV) tetraisopropoxide (TTIP) was dissolved into ethanol and mixed with aqueous zirconia (ZrO2) suspension containing 10% nitrogen (N) (w/w to Ti) from urea and various amount of copper as dopants. The calcination was performed at temperatures of 500, 700, and 900 °C. The composites were characterized using Fourier transform infrared spectrophotometer (FTIR), X-ray diffractometer (XRD), scanning electron microscopy with energy dispersive X-ray (SEM-EDX) mapping, and specular reflectance UV-Visible spectrophotometer (SRUV-Vis). The degradation of 4 mg L1 MB solution was conducted for various irradiation times. Characterization shows a significant decrease of the ZrTiO4 band gap from 3.09 to 2.65 eV, which was given by the composite with the addition of 4% Cu and calcination of 900 °C. Cu-N-ZrTiO4 composite can degrade MB solution up to 83% after 120 min under the irradiation of visible light.


bandgap; degradation; methylene blue; Cu-N-codoped ZrTiO4

Full Text:

Full Text PDF


[1] Al-Mamun, M.R., Kader, S., Islam, M.S., and Khan, M.Z.H., 2019, Photocatalytic activity improvement and application of UV-TiO2 photocatalysis in textile wastewater treatment: A review, J. Environ. Chem. Eng., 7 (5), 103248.

[2] Hamdy, M.S., Saputera, W.H., Groenen, E.J., and Mul, G., 2014, A novel TiO2 composite for photocatalytic wastewater treatment, J. Catal., 310, 75–83.

[3] Zhang, T., Xiang, Y., Su, Y., Zhang, Y., Huang, X., and Qian, X., 2022, Anchoring of copper sulfide on cellulose fibers with polydopamine for efficient and recyclable photocatalytic degradation of organic dyes, Ind. Crops Prod., 187, 115357.

[4] Yan, K., Wu, G., Jarvis, C., Wen, J., and Chen, A., 2014, Facile synthesis of porous microspheres composed of TiO2 nanorods with high photocatalytic activity for hydrogen production, Appl. Catal. Environ., 148-149, 281–287.

[5] Yaacob, N., Sean, G.P., Nazri, N.A.M., Ismail, A.F., Zainol Abidin, M.N., and Subramaniam, M.N., 2021, Simultaneous oily wastewater adsorption and photo-degradation by ZrO2–TiO2 heterojunction photocatalysts, J. Water Process Eng., 39, 101644.

[6] El-Sharkawy, E., Soliman, A.Y., and Al-Amer, K.M., 2007, Comparative study for the removal of methylene blue via adsorption and photocatalytic degradation, J. Colloid Interface Sci., 310 (2), 498–508.

[7] Chen, D., Jiang, Z., Geng, J., Wang, Q., and Yang, D., 2017, Carbon and nitrogen co-doped TiO2 with enhanced visible-light photocatalytic activity, Ind. Eng. Chem. Res., 46 (9), 2741–2746.

[8] Liu, W.J., Zeng, F.X., Jiang, H., Zhang, X.S., and Li, W.W., 2012, Composite Fe2O3 and ZrO2/Al2O3 photocatalyst: Preparation, characterization, and studies on the photocatalytic and chemical stability, Chem. Eng. J., 180, 9–18.

[9] Sharma, A., and Dutta, R.K., 2010, Studies on drastic improvement of photocatalytic degradation of acid orange-74 dye by TPPO capped CuO nanoparticles with suitable electron capturing agents, RSC Adv., 5 (54), 43815–43823.

[10] Jing, Y., Yin, H., Li, C., Chen, J., Wu, S., Liu, H., Xie, L., Lei, Q., Sun, M., and Yu, S., 2022, Fabrication of Pt doped TiO2-ZnO@ZIF-8 core@shell photocatalyst with enhanced activity for phenol degradation, Environ. Res., 203, 111819.

[11] Verma, S., Rani, S., Kumar, S., dan Khan, M.A.M., 2018, Rietveld refinement, micro-structural, optical and thermal parameters of zirconium titanate composites, Ceram. Int., 44 (2), 1653–1661.

[12] Liang, Q., Liu, X., Zeng, G., Liu, Z., Tang, L., Shao, B., Zeng, Z., Zhang, W., Liu, Y., Cheng, M., Tang, W., and Gong, S., 2019, Surfactant-assisted synthesis of photocatalysts: Mechanism, synthesis, Chem. Eng. J., 372, 429–451.

[13] Mogal, S.I., Mishra, M., Gandhi, V.G., and Tayade, R.J., 2012, Metal doped titanium dioxide: Synthesis and effect of metal ions on physico-chemical and photocatalytic properties, Mater. Sci. Forum, 734, 364–378.

[14] Wang, J., Zhao, Y.F., Wang, T., Li, H., and Li, C., 2015, Photonic, and photocatalytic behavior of TiO2 mediated by Fe, CO, Ni, N doping and co-doping, Phys. B, 478, 6–11.

[15] Allen, N.S., Mahdjoub, N., Vishnyakov, V., Kelly, P.J., and Kriek, R.J., 2018, The effect of crystalline phase (anatase, brookite and rutile) and size on the photocatalytic activity of calcined polymorphic titanium dioxide (TiO2), Polym. Degrad. Stab., 150, 31–36.

[16] Zhang, J., Zhou, P., Liu, J., and Yu, J., 2014, New understanding of the difference of photocatalytic activity among anatase, rutile and brookite TiO2, Phys. Chem. Chem. Phys., 16 (38), 20382–20386.

[17] Gnanaprakasam, A., Sivakumar, V.M., and Thirumarimurugan, M., 2015, Influencing parameters in the photocatalytic degradation of organic effluent via nanometal oxide catalyst: A review, Indian J. Mater. Sci., 2015, 601827.

[18] Barkul, R.P., Koli, V.B., Shewale, V.B., Patil, M.K., and Delekar, S.D., 2016, Visible active nanocrystalline N-doped anatase TiO2 particles for photocatalytic mineralization studies, Mater. Chem. Phys., 173, 42–51.

[19] Shao, G.N., Imran, S.M., Jeon, S.J., Engole, M., Abbas, N., Salman Haider, M., Kang, S.J., and Kim, H.T., 2014, Sol-gel synthesis of photoactive zirconia-titania from metal salts and investigation of their photocatalytic properties in the photo-degradation of methylene blue, Powder Technol., 258, 99–109.

[20] Zheng, J., Sun, L., Jiao, C., Shao, Q., Lin, J., Pan, D., Naik, N., and Guo, Z., 2021, Hydrothermally synthesized Ti/Zr bimetallic MOFs derived N self-doped TiO2/ZrO2 composite catalysts with enhanced photocatalytic degradation of methylene blue, Colloids Surf., A, 623, 126629.

[21] Sherly, E.D., Vijaya, J.J., Selvam, N.C.S., and Kennedy, L.J., 2014, Microwave assisted combustion synthesis of coupled ZnO-ZrO2 nanoparticles and their role in the photocatalytic degradation of 2,4-dichlorophenol, Ceram. Int., 40 (4), 5681–5691.

[22] French, R.H., Glass, S.J., Ohuchi, F.S., Xu, Y.N., and Ching, W.Y., 1994, Experimental and theoretical determination of the electronic structure and optical properties of three phases of ZrO2, Phys. Rev. B: Condens. Matter Mater. Phys., 49 (8), 5133–5142.

[23] Piątkowska, A., Janus, M., Szymański, K., and Mozia, S., 2021, C-,N- and S-doped TiO2 photocatalysts: A review, Catalysts, 11 (1), 144.

[24] Kumaresan, L., Prabhu, A., Palanichamy, M., Arumugam, E., and Murugesan, V., 2014, Synthesis and characterization of Zr4+, La3+ and Ce3+ doped mesoporous TiO2: Evaluation of their photocatalytic activity, J. Hazard. Mater., 186 (2-3), 1183–1192.

[25] Dutta, H., Nandy, A., and Pradhan, S.K., 2016, Microstructure and optical characterizations of mechanosynthesized nanocrystalline semiconducting ZrTiO4 compound, J. Phys. Chem. Solids, 95, 56–64.

[26] Hayati, R., Kurniawan, R., Prasetyo, N., Sudiono, S., and Syoufian, A., 2022, Codoping effect of nitrogen (N) to iron (Fe) doped zirconium titanate (ZrTiO4) composite toward its visible light responsiveness as photocatalysts, Indones. J. Chem., 22 (3), 692–702.

[27] Muslim, M.I., Kurniawan, R., Pradipta, M.F., Trisunaryanti, W., and Syoufian, A., 2021, The effects of manganese dopant content and calcination temperature on properties of titania-zirconia composite, Indones. J. Chem., 21 (4), 882–890.

[28] Alifi, A., Kurniawan, R., and Syoufian, A., 2020, Zinc-doped titania embedded on the surface of Zirconia: A potential visible-responsive photocatalyst material, Indones, J. Chem., 20 (6), 1374–1381.

[29] Kim, J.Y., Kim, C.S., Chang, H.K., and Kim, T.O., 2011, Synthesis and characterization of N doped TiO2/ZrO2 visible light photocatalysts, Adv. Powder Technol., 22 (3), 443–448.

[30] Venkatesan, A., Al-onazi, W.A., Elshikh, M.S., Pham, T.H., Suganya, S., Boobas, S., and Priyadharsan, A., 2022, Study of synergistic effect of cobalt and carbon codoped TiO2 photocatalyst for visible light induced degradation of phenol, Chemosphere, 305, 135333.

[31] Kim, C.S., Shin, J.W., Cho, Y.H., Jang, H.D., Byun, H.S., and Kim, T.O., 2013, Synthesis and characterization of Cu/N-doped mesoporous TiO2 visible light photocatalysts, Appl. Catal., A, 455, 211–218.

[32] Li, D., Qin, Q., Duan, X., Yang, J., Guo, W., and Zheng, W., 2013, General one-pot template-free hydrothermal method to metal oxide hollow spheres and their photocatalytic activities and lithium storage properties, ACS Appl. Mater. Interfaces, 5 (18), 9095–9100.

[33] Khan, S., Kim, J., Sotto, A., and Van der Bruggen, B., 2015, Humic acid fouling in a submerged photocatalytic membrane reactor with binary TiO2-ZrO2 particles, J. Ind. Eng. Chem., 21, 779–786.

[34] Singh, H., Sunaina, S., Yadav, K.K., Bajpai, V.K., and Jha, M., 2020, Tuning the bandgap of m-ZrO2 by incorporation of copper nanoparticles into visible region for the treatment of organic pollutants, Mater. Res. Bull., 123, 110698.

[35] Kurniawan, R., Sudiono, S., Trisunaryanti, W., and Syoufian, A., 2019, Synthesis of iron-doped zirconium titanate as a potential visible-light responsive photocatalyst, Indones. J. Chem., 19 (2), 454–460.

[36] Syoufian, A., and Nakashima, K., 2008, Degradation of methylene blue in aqueous dispersion of hollow titania photocatalyst: Study of reaction enhancement by various electron scavengers, J. Colloid Interface Sci., 317 (2), 507–512.


Article Metrics

Abstract views : 994 | views : 751

Copyright (c) 2023 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.


Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Analytics View The Statistics of Indones. J. Chem.