Photocatalysts Capability of Bentonite-ZnO Nanocomposite Synthesized by Solution Combustion in Ciprofloxacin Degradation

Document Type : Research Paper


1 Department of Materials Engineering, Faculty of Mechanic and Materials Engineering, Birjand University of Technology, Birjand, Iran.

2 Department of Chemical Engineering, Birjand University of Technology, Birjand, Iran

3 Department of Industrial Engineering, Quchan University of Technology, Quchan, Iran



The increasing industries and population growth, make various new needs for water. So, scientists and researchers try to invent new methods for processing and synthesizing new materials to recycle used water sources. In this research, Zn (NO3)2.6H2O (zinc nitrate) and C2H5NO2 (glycine) were used as raw materials in Solution Combustion Synthesis technique (SCS) to synthesize ZnO nanoparticles. Also, the bentonite is added to the reaction container during the synthesis to act as substrate for nanoparticles to produce Bentonite-ZnO nanocomposite in-situ in less than 10 min at the air atmosphere. The successful synthesis was confirmed by X-ray diffraction analysis and the reason of that was explained by DSC-TGA of raw materials. It proved the same thermal behaviors of zinc nitrate as oxidizer and glycine as fuel could carry out the reaction. The SEM and TEM images demonstrated the decoration of ZnO on bentonite. Finally, the photodegradtaion of an antibiotic (ciprofloxacin) in presence of synthesized nanocomposite was examined under direct sunlight. The results showed about 97% degradation efficiency and 81% for total organic carbon removal after 3h reaction at the rate constants of 1.04 h-1. The blank test from just bentonite shows less than 10% degradation efficiency that proves the presence of ZnO increases this value more than 87%.


1.Manikandan S, Subbaiya R, Saravanan M, Ponraj M, Selvam M, Pugazhendhi A. A critical review of advanced nanotechnology and hybrid membrane based water recycling, reuse, and wastewater treatment processes. Chemosphere. 2022;289:132867.
2.Rabbani Y, Shariaty-Niassar M, Ebrahimi SS. The effect of superhydrophobicity of prickly shape carbonyl iron particles on the oil-water adsorption. Ceramics International. 2021;47(20):28400-10.
3.Baruah A, Chaudhary V, Malik R, Tomer VK. Nanotechnology based solutions for wastewater treatment.  Nanotechnology in Water and wastewater treatment: Elsevier; 2019. p. 337-68.
4.Al-Ghouti MA, Al-Kaabi MA, Ashfaq MY, Da’na DA. Produced water characteristics, treatment and reuse: A review. Journal of Water Process Engineering. 2019;28:222-39.
5.Honarmand M, Golmohammadi M, Hafezi-Bakhtiari J. Synthesis and characterization of SnO2 NPs for photodegradation of eriochrome black-T using response surface methodology. Environmental Science and Pollution Research. 2021;28(6):7123-33.
6.Wang F, Gao J, Zhai W, Cui J, Liu D, Zhou Z, et al. Effects of antibiotic norfloxacin on the degradation and enantioselectivity of the herbicides in aquatic environment. Ecotoxicology and Environmental Safety. 2021;208:111717.
7.Ramesh M, Sujitha M, Anila PA, Ren Z, Poopal RK. Responses of Cirrhinus mrigala to secondā€generation fluoroquinolone (ciprofloxacin) toxicity: Assessment of antioxidants, tissue morphology, and inorganic ions. Environmental Toxicology. 2021;36(5):887-902.
8.Malakootian M, Nasiri A, Asadipour A, Kargar E. Facile and green synthesis of ZnFe2O4@ CMC as a new magnetic nanophotocatalyst for ciprofloxacin degradation from aqueous media. Process Safety and Environmental Protection. 2019;129:138-51.
9.Wei R, Ge F, Huang S, Chen M, Wang R. Occurrence of veterinary antibiotics in animal wastewater and surface water around farms in Jiangsu Province, China. Chemosphere. 2011;82(10):1408-14.
10.Zare EN, Iftekhar S, Park Y, Joseph J, Srivastava V, Khan MA, et al. An overview on non-spherical semiconductors for heterogeneous photocatalytic degradation of organic water contaminants. Chemosphere. 2021;280:130907.
11.Golmohammadi M, Honarmand M, Esmaeili A. Biosynthesis of ZnO nanoparticles supported on bentonite and the evaluation of its photocatalytic activity. Materials Research Bulletin. 2021:111714.
12.Golmohammadi M, Hassankiadeh MN, Zhang L. Facile biosynthesis of SnO2/ZnO nanocomposite using Acroptilon repens flower extract and evaluation of their photocatalytic activity. Ceramics International. 2021;47(20):29303-8.
13.Nikitin PY, Matveev A, Zhukov I. Energy-effective AlMgB14 production by self-propagating high-temperature synthesis (SHS) using the chemical furnace as a source of heat energy. Ceramics International. 2021;47(15):21698-704.
14.Argolo MIS, Silva LS, Siqueira Jr JM, Miranda FdS, Medeiros ME, Garrido FM. Structural and optical properties of Ni/NiO composites synthesized by eco-friendly self-propagation synthesis (SHS): Effects of NH4OH addition. Ceramics International. 2019;45(17):21640-6.
15.Sharifitabar M. On the formation of Al2O3 nanofibers during self-propagating high-temperature synthesis of TiO2–Al–C system in various environments. Ceramics International. 2020;46(10):17053-61.
16.Roslyakov S, Yermekova Z, Trusov G, Khort A, Evdokimenko N, Bindiug D, et al. One-step solution combustion synthesis of nanostructured transition metal antiperovskite nitride and alloy. Nano-Structures & Nano-Objects. 2021;28:100796.
17.Potanin AY, Vorotilo S, Pogozhev YS, Rupasov S, Lobova T, Levashov E. Influence of mechanical activation of reactive mixtures on the microstructure and properties of SHS-ceramics MoSi2–HfB2–MoB. Ceramics International. 2019;45(16):20354-61.
18.Nasiri H, Motlagh EB, Khaki JV, Zebarjad SM. Role of fuel/oxidizer ratio on the synthesis conditions of Cu–Al2O3 nanocomposite prepared through solution combustion synthesis. Materials Research Bulletin. 2012;47(11):3676-80.
19.Mohammadi E, Nasiri H, Khaki JV, Zebarjad S. Copper-alumina nanocomposite coating on copper substrate through solution combustion. Ceramics International. 2018;44(3):3226-30.
20.Nasiri H, Khaki JV, Sabzevar MH. Fast prepared Ni-Al2O3 nanocomposite through solution combustion synthesis. Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry. 2015;45(8):1241-4.
21.Nasiri H, Khaki JV, Zebarjad SM. One-step fabrication of Cu–Al2O3 nanocomposite via solution combustion synthesis route. Journal of alloys and compounds. 2011;509(17):5305-8.
22.Singh J, Kumar D, Kumar P, Aguilar CH, Vo D-V, Sharma A, et al. Magnetically active Ag–Zn nanoferrites synthesized by solution combustion route: physical chemical studies and density functional theory analysis. Materials Today Chemistry. 2021;22:100588.
23.Khaliullin SM, Koshkina A. Influence of fuel on phase formation, morphology, electric and dielectric properties of iron oxides obtained by SCS method. Ceramics International. 2021;47(9):11942-50.
24.Deshpande K, Mukasyan A, Varma A. Direct synthesis of iron oxide nanopowders by the combustion approach: reaction mechanism and properties. Chemistry of materials. 2004;16(24):4896-904.
25.Biamino S, Badini C. Combustion synthesis of lanthanum chromite starting from water solutions: investigation of process mechanism by DTA–TGA–MS. Journal of the European Ceramic Society. 2004;24(10-11):3021-34.
26.Biswas M, Ojha PK, Prasad CD, Gokhale NM, Sharma SC. Synthesis of fluorite-type nanopowders by citrate-nitrate auto-combustion process: a systematic approach. 2012.
27.Huang M, Lv S, Zhou C. Thermal decomposition kinetics of glycine in nitrogen atmosphere. Thermochimica acta. 2013;552:60-4.
28.Tauc J. Optical properties of amorphous semiconductors.  Amorphous and liquid semiconductors: Springer; 1974. p. 159-220.
29.Chakraborty T, Chakraborty A, Shukla M, Chattopadhyay T. ZnO–Bentonite nanocomposite: an efficient catalyst for discharge of dyes, phenol and Cr (VI) from water. Journal of Coordination Chemistry. 2019;72(1):53-68.
30.Selvakumar K, Raja A, Arunpandian M, Stalindurai K, Rajasekaran P, Sami P, et al. Efficient photocatalytic degradation of ciprofloxacin and bisphenol A under visible light using Gd2WO6 loaded ZnO/bentonite nanocomposite. Applied Surface Science. 2019;481:1109-19.
31.Toor M, Jin B, Dai S, Vimonses V. Activating natural bentonite as a cost-effective adsorbent for removal of Congo-red in wastewater. Journal of Industrial and Engineering Chemistry. 2015;21:653-61.
32.Wang H, Li J, Huo P, Yan Y, Guan Q. Preparation of Ag2O/Ag2CO3/MWNTs composite photocatalysts for enhancement of ciprofloxacin degradation. Applied surface science. 2016;366:1-8.
33.Yu X, Zhang J, Zhang J, Niu J, Zhao J, Wei Y, et al. Photocatalytic degradation of ciprofloxacin using Zn-doped Cu2O particles: analysis of degradation pathways and intermediates. Chemical Engineering Journal. 2019;374:316-27.
34.Behera A, Kandi D, Mansingh S, Martha S, Parida K. Facile synthesis of ZnFe2O4@ RGO nanocomposites towards photocatalytic ciprofloxacin degradation and H2 energy production. Journal of colloid and interface science. 2019;556:667-79.
35.Wen X-J, Niu C-G, Zhang L, Liang C, Guo H, Zeng G-M. Photocatalytic degradation of ciprofloxacin by a novel Z-scheme CeO2–Ag/AgBr photocatalyst: influencing factors, possible degradation pathways, and mechanism insight. Journal of catalysis. 2018;358:141-54.
36.Das KK, Patnaik S, Mansingh S, Behera A, Mohanty A, Acharya C, et al. Enhanced photocatalytic activities of polypyrrole sensitized zinc ferrite/graphitic carbon nitride nn heterojunction towards ciprofloxacin degradation, hydrogen evolution and antibacterial studies. Journal of colloid and interface science. 2020;561:551-67.
37.Ahamad T, Naushad M, Alshehri SM. Analysis of degradation pathways and intermediates products for ciprofloxacin using a highly porous photocatalyst. Chemical Engineering Journal. 2021;417:127969.
38.Kumar M, Mehta A,  Mishra A,  Singh J, Rawat M, Basu S. Biosynthesis of tin oxide nanoparticles using Psidium Guajava leave extract for photocatalytic dye degradation under sunlight. Materials Letters. 2018, 215: 121-124.
39.Saravanan R, Karthikeyan S, Gupta V, Sekaran G, Narayanan V, Stephen A. Enhanced photocatalytic activity of ZnO/CuO nanocomposite for the degradation of textile dye on visible light illumination. Materials Science and Engineering: C. 2013. 33: 91-98.