Research ArticleMgFe2O4 decoration of g-C3N4 nanosheets to enhance CIP oxidation in visible-light photocatalysis
Introduction
Organics and especially pharmaceuticals remediation is becoming a pressing matter due the increased industrialization and the extensive use of antibiotics in societies [1]. Fluoroquinolone, an antibiotic known as Ciprofloxacin (CIP) is an example of widely used antibacterial agent which is frequently released into the environment after use [2]. Because CIP is weakly metabolized in the body it is secreted as pharmacologically active compound and enters natural sources of water [3]. It has been shown that CIP is present in aquatic environments in appreciable amounts [4,5]. Conventional wastewater treatment plants have very little effect on the pharmacologically active compounds which may result in the presence of these compounds in freshwater resources. Photocatalytic degradation of the pharmacologically active compounds and other organics into CO2 and H2O utilizing semiconductor-based catalysts could be essential to prevent accumulation of these pollutants in water resources [6,7]. Research in this area is expanding and search for suitable low-cost materials has produced numerous data and papers [[8], [9], [10], [11], [12]].
One of the interesting materials that gained growing recognition is g-C3N4, a graphene-like structure that is easy to synthesize through various routs hic allow to a certain extent morphological and characteristic manipulation. g-C3N4 possesses a polymeric 2-dimensional layered structure with adjacent layers attached by van der Waals forces. Its organic and inorganic characteristics enable g-C3N4 to retain chemical components in aqueous media while the relatively small band gap of 2.7 eV allow photocatalysis which creates an ideal basis for a pollutant remediation process. Along with these essential properties g-C3N4 is thermally and chemically stable and nontoxic [[13], [14], [15], [16]]. Indeed, these characteristics resulted in applications of g-C3N4 that include organic pollutants remediation, CO2 reduction, catalysis, hydrogen production through water splitting, membrane water purification and many others [[17], [18], [19], [20], [21], [22], [23], [24]]. Three major shortcomings hamper g-C3N4 ability to be of high efficiency in these applications namely, a relatively small surface area, low electrical conductivity, and instantaneous combination of photogenerated charge carriers [16,[25], [26], [27], [28]]. In recent years, research has concentrated on overcoming these shortcomings through many aspects such as efforts to increase the surface area through various synthesis routs [21], bandgap narrowing through introduction of semiconductors and other material [18]. Minimization of charge carrier recombination via heterojunction creation between g-C3N4 and a guest material in the mesostructure [29]. Examples of incorporated nanoparticles in the mesostructure include ZnO, Pt, Fe3O4, TiO2, SnO2, Ag, AgO2 and BiPO4 and others [[30], [31], [32], [33], [34], [35], [36], [37], [38]].
One important required technical aspect in remediation of pollutants in aqueous media is the capability to separate the photocatalyst from the waste solution, this can be achieved via incorporation of magnetic material into the mesostructure [39]. In addition to magnetic separability, ferrites can also be incorporated as nanoparticles that promote band structure and morphological fine tuning. In this regard, enhancement of the photocatalytic ability of g-C3N4 by incorporation of CoFe2O4 and CuFe2O4 through synergetic impact on the heterostructures have been reported [[40], [41], [42]]. Magnetic ferrite materials can be synthesized in many ways such as electrospray [43], co-precipitation [44], hydrothermal synthesis [45], microwave pyrolysis [46] and sol-gel synthesis [47]. Most of these approaches involve complicated procedures and extended synthesis times.
mesoporous MgFe2O4 nanoparticles possess spinel structure and magnetic properties that can be fine-tuned through shape and size manipulation to produce high saturation magnetization for the application in treatment of industrial wastewaters. The self-assembly procedure in the presence of templates is a simple method to synthesize nanocomposite-materials that possess high surface areas, within the nanoparticle scale, inexpensive, and favorable pores structure, the method allows the overcome of complications in the aforementioned methods of synthesis [48,49].
In this work, we synthesized mesoporous MgFe2O4/porous g-C3N4 heterostructures and applied these structures in the CIP photooxidation from aqueous media. This research provides a first example of production of a mesoporous MgFe2O4/g-C3N4 heterostructure with a high surface-area of 120 m2g-1 and a 2.57 eV bandgap for fast CIP photooxidation with high photocatalytic efficiency. Furthermore, MgFe2O4/g-C3N4 photocatalyst show substantially superior efficacy when compared to either pure MgFe2O4 or g-C3N4, it also exhibits stability upon multiple reuses, and a charge separation ability that allows smooth photocatalysis. A five recycling trials of the MgFe2O4/g-C3N4 nanocomposite demonstrate that this novel photocatalyst can easily be separated by magnetic means and reused without significant loss of its photocatalytic efficiency.
Section snippets
Materials
Dicyandiamide, Urea, Poly (propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol), this is a triblock copolymer with surfactant properties commercially known as Pluronic 31R1 with a molecular weight of 3,300 g/mol, Fe(NO3)2·9H2O, Mg(NO3)2·6H2O, C2H5OH, C₆H₁₄, CH3COOH, HCl, C2H5OH, and HCOOH.
MgFe2O4-g-C3N4 heterostructures synthesis
MgFe2O4-g-C3N4 heterostructures were synthesized in a three-stage procedure, Mesoporous MgFe2O4 synthesis, mesostructured g-C3N4, and finally combination of the two to produce MgFe2O4-g-C3
Characterization of synthesized photocatalysts
Physical and chemical characteristics of the crystalline phases of pure g-C3N4 and MgFe2O4 nanoparticles and MgFe2O4/g-C3N4 nanocomposite with various MgFe2O4 content were thoroughly investigated employing various techniques. Crystalline structure examined by XRD data (Fig. 1) show a major diffraction peak at 2Ө = 27.3° showing interplanar graphitic stacking (JCPDS 87–1526) and the interplanar structural packing identified by 2Ө = 13.1° [16,17]. In the MgFe2O4 NXRD pattern (Fig. 1) peaks
Conclusions
A template assisted approach was utilized for the synthesis of mesoporous MgFe2O4/g-C3N4 heterostructures. This approach yields a high surface area product with a suitable bandgap that was utilized for CIP photooxidation. A cubic structure 10–15 nm MgFe2O4 nanoparticles were evenly distributed on g-C3N4 to form the MgFe2O4/g-C3N4 heterostructure. The 3% MgFe2O4/g-C3N4 showed enhanced ability for CIP photooxidation efficiency which was 8 and 4 times better than that of pure g-C3N4 or MgFe2O4.
CRediT authorship contribution statement
Mohammad W. Kadi: Validation, Formal analysis, Visualization, Writing – original draft. Reda M. Mohamed: Conceptualization, Project administration, Formal analysis, Supervision. Detlef W. Bahnemann: Formal analysis, Visualization, Project administration.
Declaration of competing interest
The authors declare that they have no known competing for financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgment
This project was funded by the Deanship of Scientific Research (DSR) at King Abdulaziz University, Jeddah, under grant no. RG-4-130-41. The authors, therefore, acknowledge with thanks DSR for technical and financial support.
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