Synthesis and Application of Granulated Cellulose/CuBDC/Fe3O4 in Elimination of Direct Blue 71 by Heterogeneous Fenton Process

Document Type : Research Paper


1 PhD. Student, Dept. of Chemical Engineering, Faculty of Chemical and Petroleum Engineering, University of Tabriz, Tabriz, Iran

2 Assoc. Prof., Dept. of Chemical Engineering, Faculty of Chemical and Petroleum Engineering, University of Tabriz, Tabriz, Iran

3 Prof., Organic and Nano Group (ONG), Dept. of Chemistry, Iran University of Science and Technology (IUST), Tehran, Iran


Plenty of methods have been introduced to treat the consumed water where the advantages and disadvantages of each method define their applications. Advanced oxidation processes have become a scientific trend due to high removal efficiency. As one of the AOP methods, heterogeneous Fenton method has received plenty of interest because of its high operational capability. In this study, cellulose/CuBDC/Fe3O4 nanocomposite was utilized as heterogeneous Fenton catalyst to remove Direct Blue 71 toxic dye from aqueous media. The catalyst was synthesized as granulated beads to eliminate the operational limitations of utilizing powdered catalysts. The catalysts were characterized by SEM, EDX, FTIR and XRD analysis to validate the successful synthesis procedure. The effects of each component of the nanocomposite on the removal efficiency were investigated. The effective operation of independent parameters such as the initial dye concentration, H2O2 concentration and catalyst dosage were modeled and optimized by RSM design of experiments method. At the optimum point, the removal efficiency of 86.93% was achieved. In addition, the COD of the wastewater was decreased by 73.52%, which demonstrated the high potential of granulated cellulose/CuBDC/Fe3O4 nanocomposite in decomposing organic matter to H2O, CO2, NO2 and SO2. The prepared granulated catalysts retain their removal characteristics over 8-cycle operation.


Aghdasinia, H., Bagheri, R., Vahid, B. & Khataee, A. 2016. Central composite design optimization of pilot plant fluidized-bed heterogeneous Fenton process for degradation of an azo dye. Environmental Technology, 37(21), 2703-2712.
Alamgholiloo, H., Pesyan, N. N., Mohammadi, R., Rostamnia, S. & Shokouhimehr, M. 2021. Synergistic advanced oxidation process for the fast degradation of ciprofloxacin antibiotics using a GO/CuMOF-magnetic ternary nanocomposite. Journal of Environmental Chemical Engineering, 9, 105486.
Bazer-Bachi, D., Assié, L., Lecocq, V., Harbuzaru, B. & Falk, V. 2014. Towards industrial use of metal-organic framework: impact of shaping on the MOF properties. Powder Technology, 255, 52-59.
Crini, G. & Lichtfouse, E. 2019. Advantages and disadvantages of techniques used for wastewater treatment. Environmental Chemistry Letters, 17, 145-155.
Dichiara, A. B., Weinstein, S. J. & Rogers, R. E. 2015. On the choice of batch or fixed bed adsorption processes for wastewater treatment. Industrial and Engineering Chemistry Research, 54, 8579-8586.
Emady, H., Hapgood, K. & Smith, R. 2016. Granulation and Tabletting. Production, Handling and Characterization of Particulate Materials. In: Kersbergen, A. 2016. Particle Technology Series. Springer, Cham. 107-136.
Ertugay, N. & Acar, F. N. 2017. Removal of COD and color from Direct Blue 71 azo dye wastewater by Fenton’s oxidation: kinetic study. Arabian Journal of Chemistry, 10, S1158-S1163.
Farshchi, M. E., Aghdasinia, H. & Khataee, A. 2018. Modeling of heterogeneous Fenton process for dye degradation in a fluidized-bed reactor: kinetics and mass transfer. Journal of Cleaner Production, 182, 644-653.
Farshchi, M. E., Aghdasinia, H. & Khataee, A. 2019. Heterogeneous Fenton reaction for elimination of Acid Yellow 36 in both fluidized-bed and stirred-tank reactors: computational fluid dynamics versus experiments. Water Research, 151, 203-214.
Fu, Q., Wen, L., Zhang, L., Chen, X., Pun, D., Ahmed, A., et al. 2017. Preparation of ice-templated MOF–polymer composite monoliths and their application for wastewater treatment with high capacity and easy recycling. ACS Applied Materials and Interfaces, 9, 33979-33988.
Hinkelmann, K. & Kempthorne, O. 2012. Design and Analysis of Experiments, Special Designs and Applications, John Wiley & Sons. New Jersey, USA.
Khataee, A., Gholami, P. & Sheydaei, M. 2016. Heterogeneous Fenton process by natural pyrite for removal of a textile dye from water: effect of parameters and intermediate identification. Journal of the Taiwan Institute of Chemical Engineers, 58, 366-373.
Kirchon, A., Zhang, P., Li, J., Joseph, E. A., Chen, W. & Zhou, H. C. 2020. Effect of isomorphic metal substitution on the Fenton and Photo-Fenton degradation of methylene blue using Fe-based metal–organic frameworks. ACS Applied Materials and Interfaces, 12, 9292-9299.
Li, J., Tao, T., Li, X. B., Zuo, J. L., Li, T., Lu, J., et al. 2009. A spectrophotometric method for determination of chemical Oxygen demand using home-made reagents. Desalination, 239, 139-145.
Liu, X., Wang, X. & Kapteijn, F. 2020. Water and metal–organic frameworks: from interaction toward utilization. Chemical Reviews, 120, 8303-8377.
Ma, Y., Wang, L., Ma, J., Wang, H., Zhang, C., Deng, H., et al. 2021. Investigation into the enhanced catalytic oxidation of O-Xylene over MOF-derived Co3O4 with different shapes: the role of surface twofold-coordinate lattice oxygen (O2f). ACS Catalysis, 11, 6614-6625.
Moradi, M., Eslami, A. & Ghanbari, F. 2016. Direct Blue 71 removal by electrocoagulation sludge recycling in photo-Fenton process: response surface modeling and optimization. Desalination and Water Treatment, 57, 4659-4670.
Myers, R. H., Montgomery, D. C. & Anderson-Cook, C. M. 2009. Response Surface Methodology: Process and Product Optimization Using Designed Experiments, John Wiley & Sons. New Jersey, USA.
Peng, D., Zhang, Y., Xu, G., Tian, Y., Ma, D., Zhang, Y., et al. 2020. Synthesis of multilevel structured MoS2@Cu/Cu2O@C visible-light-driven photocatalyst derived from MOF–guest polyhedra for cyclohexane oxidation. ACS Sustainable Chemistry and Engineering, 8, 6622-6633.
Pronk, W., Ding, A., Morgenroth, E., Derlon, N., Desmond, P., Burkhardt, M., et al. 2019. Gravity-driven membrane filtration for water and wastewater treatment: a review. Water Research, 149, 553-565.
Sasieekhumar, A., Somanathan, T., Abilarasu, A. & Shanmugam, M. 2017. Visible light induced heterogeneous photo-fenton oxidation of direct blue 71 using mesoporous Fe/KIT-6. Research Journal of Pharmacy and Technology, 10, 1455.
Sjöblom, J., Papadakis, K., Creaser, D. & Odenbrand, C. I. 2005. Use of experimental design in development of a catalyst system. Catalysis Today, 100, 243-248.
Tunç, S., Gürkan, T. & Duman, O. 2012. On-line spectrophotometric method for the determination of optimum operation parameters on the decolorization of Acid Red 66 and Direct Blue 71 from aqueous solution by Fenton process. Chemical Engineering Journal, 181, 431-442.
Wang, Z., Yin, Q., Gu, M., He, K. & Wu, G. 2018. Enhanced azo dye Reactive Red 2 degradation in anaerobic reactors by dosing conductive material of ferroferric oxide. Journal of Hazardous Materials, 357, 226-234.
Wardrop, D. M. & Myers, R. H. 1990. Some response surface designs for finding optimal conditions. Journal of Statistical Planning and Inference, 25, 7-28.
Yu, M., Wang, J., Tang, L., Feng, C., Liu, H., Zhang, H., et al. 2020. Intimate coupling of photocatalysis and biodegradation for wastewater treatment: mechanisms, recent advances and environmental applications. Water Research, 175, 115673.