Synthesis and characterization of organic–inorganic core–shell structure nanocomposite and application for Zn ions removal from aqueous solution in a fixed-bed column
Graphical abstract
Introduction
Heavy metal ion pollution is currently of great concern due to increasing awareness of the potentially hazardous effects of elevated levels of these materials in the environment [1]. Zinc is one of the most important pollutants in surface and ground water [2]. Although, Zinc is considered as an essential trace element for life, at high concentrations it could be damaging to human health. Zinc is widely used in many important industrial applications such as dry batteries, electroplating industry, insecticides, foundry, metallurgy, newsprint paper production and inorganic pigments industry [3], [4]. Since, Zn is not biodegradable and accumulates in living organisms causing diseases and other toxic effects, the recovery of Zn and other heavy metals from contaminated water is of environmental and agricultural importance [5]. Various treatment processes for the removal of metal ions including adsorption [6], [7], precipitation [8], ion exchange [9], membrane processes [10], [11], etc., have been proposed. Among them, adsorption is found to be cheap, effective and easy to adapt and has been confirmed as one of the most promising technologies for removing heavy metals from wastewaters [12]. Magnetic nanoparticles, especially maghemite as an efficient adsorbent have been receiving continuous attention because of their high adsorption capacity regarding their high surface area, low cost, environmental sustainability, easy separation and easy recovery via an external magnetic field [13], [14]. On the other hand, there are major limitations in the application of magnetic nanoparticles originating from the magnetically induced aggregation, surface oxidation, and deficiency of functional groups [15]. Aggregation reduces their high surface area to volume ratio and subsequently reduces effectiveness [16]. Inorganic nanoparticles coated with conducting polymer that form core/shell structured materials has been demonstrated to be an effective strategy to enhance the stability of composites and widen the applications because of the strong electronic interaction between the inorganic core and polymer shell [17]. The polymer shell provides a flexible functional group to magnetic nanoparticles and protects them from surface oxidation and aggregation, while increasing their stability [18]. The main idea in a composite is to integrate several component materials and their properties in a single material [19]. Conductive polymers have been the center of attention in the last several years, due to variety of their applications. Among the conductive polymers, polyrhodanine has attracted considerable attention in various application fields such as anticorrosion [20], antibacterial [21], and antihistaminic agents [22]. In addition, they can be used for detecting or adsorbing metal ions because the Rhodanine monomeric unit has metal-binding functional groups [23], [24]. Furthermore, the appropriate choice of polymer host with specific functional groups may even lead to enhancing the properties of nanoparticles [16]. Many polymerization methods have been applied to prepare magnetic polymer nanocomposites, for example, Pickering suspension polymerization [25], microemulsion polymerization [26], in situ polymerization and oxidative polymerization [27], [28].
The two main methods of synthesis of the polymer supported nanoparticles are ex situ and in situ method. In this work, the ex situ method is applied for synthesis of the polymer supported nanoparticles. Ex situ method of synthesis can be obtained by first synthesizing the inorganic nanoparticles and then dispersing them in a polymer solution or a three-dimensional matrix. This method of synthesis is a popular one because it does not set limitation on the nature of nanoparticles and the host polymer which is used [16].
In this study, the γ-Fe2O3/polyrhodanine core–shell structure nanocomposite was fabricated by chemical oxidation polymerization [18]. At first, the synthesis of maghemite (γ-Fe2O3) nanoparticles was carried out in an ultrasonic bath in one step via chemical precipitation [29], then the polymer shell coated on the surface of maghemite nanoparticles was synthesized using FeCl3 as an oxidant. Eventually, the potential of the synthesized nanocomposite was studied in a fixed-bed column at different bed heights and influent Zn ion concentrations. There are few studies reporting on employing the maghemite/polyrhodanine nanocomposite as an adsorbent for removing metals and other pollutant from water in batch mode, this is one of the first studies on Zn ion separation from aqueous solution by maghemite/polyrhodanine nanocomposite in the fixed-bed column. Noticeably, to scale up a process, continuous flow fixed-bed column investigations are essential. Moreover, to analyze the breakthrough curves for Zn adsorption, Adams–Bohart, BDST, Thomas and Yoon–Nelson models were used.
Section snippets
Materials
The chemical materials used for fabrication of γ-Fe2O3 nanoparticles and γ-Fe2O3/polyrhodanine nanocomposite were Iron(II) Chloride Tetra hydrate (FeCl2.4H2O), Iron(III) Chloride FeCl3, Rhodanine (C3H3NOS2), ammonium hydroxide (NH4OH), Ethanol (C2H5OH) and Hydrochloric acid (HCl) from Merck Co. All these chemicals were used as received without any further Purification. Distilled water was used throughout the experiment.
Instrumentation
The morphology and nano-structure of the γ-Fe2O3 core–shell nanocomposite
Particle size and morphology of nanocomposite
TEM image of nanocomposite is shown in Fig. 2. From Fig. 2(a), it can be obviously seen that the synthesized nanocomposite had a core–shell structure which surface of γ-Fe2O3 coated with a thin layer of polyrhodanine. The dark color in the center is attributed to γ-Fe2O3 and the light colored around the center can be attributed to polyrhodanine. The average size of γ-Fe2O3/polyrhodanine core/shell nanoparticles is about 18 nm The maghemite core diameter is about 15 nm and thickness of the polymer
Conclusions
In summary, the maghemite nanoparticles were successfully synthesized by chemical precipitation method using ultrasonic radiation and γ-Fe2O3/polyrhodanine core–shell structure nanocomposite, via ex situ chemical oxidation polymerization. The characterization of the obtained products shows that nanoparticles are spherical, monodisperse and have an average core diameter of around 15 nm and shell thickness of 1.5 nm. The structural characterization of magnetic nanoparticles and nanocomposite was
References (53)
- et al.
Adsorption of zinc (Zn2+) from aqueous solution on natural bentonite
J. Desal.
(2011) - et al.
Kinetics and equilibrium studies for the removal of nickel and zinc from aqueous solutions by ion exchange resins
J. Hazard. Mater.
(2009) - et al.
Removal characteristics of Zn (II) from aqueous solution by alkaline Ca-bentonite
J. Desal.
(2011) - et al.
Removal of zinc ion from water by sorption onto iron-based nanoadsorbent
J. Hazard. Mater.
(2007) - et al.
Cation exchange removal of Zn from aqueous solution by NiO
J. Non-Crystal. Solids
(2011) - et al.
Determination of optimum conditions for removal of As(III) and As(V) by polyaniline/polystyrene nanocomposite
Synth. Met.
(2014) - et al.
Synthesis, characterization and Cr(VI) uptake studies of polypyrrole functionalized chitin,
Synth. Met.
(2014) - et al.
Removal of Pb(II) and Zn(II) from aqueous solution by ceramisite prepared by sintering bentonite, iron powder and activated carbon
Chem. Eng. J.
(2013) - et al.
Removal and recovery of Cr(VI) from wastewater by maghemite nanoparticles
J. Water Res.
(2005) - et al.
Chromium(VI) removal by maghemite nanoparticles
Chem. Eng. J.
(2013)
Facile synthesis, magnetic and microwave absorption properties of Fe3O4/polypyrrole core/shell nanocomposite
J. Alloys Compd.
Synthesis and characterization of novel conductive and magnetic nano-composites
J. Alloys Compd.
Synthesis and antifungal activity of (Z)-5-arylidenerhodanines
J. Bioorg. Med. Chem.
Polyrhodanine modified anodic aluminum oxide membrane for heavy metal ions removal
J. Hazard. Mater.
Facile fabrication of nanocomposite microspheres with polymer cores and magnetic shells by Pickering suspension polymerization
J. React. Funct. Polym.
Microemulsion synthesis and electromagnetic wave absorption properties of monodispersed Fe3O4/polyaniline core–shell nanocomposites
Synth. Met.
Polyaniline/CoFe2O4 nanocomposites: a novel synthesis, characterization and magnetic properties
Synth. Met.
Magnetic properties of hydrophilic iron oxide/polyaniline nanocomposites synthesized by in situ chemical oxidative polymerization
Synth. Met.
Synthesis of maghemite (γ-Fe2O3) nanoparticles by wet chemical method at room temperature
J. Mater. Lett.
Removal of Ni(II) ions from aqueous solutions using modified rice straw in a fixed bed column
J. Bioresour. Technol.
Fixed-bed column studies on the removal of copper using chitosan immobilized on bentonite
J. Carbohydr. Polym.
Guava (Psidium guajava) leaf powder: novel adsorbent for removal of methylene blue from aqueous solutions
J. Hazard. Mater.
Optical properties of γ-Fe2O3 nanoparticles dispersed on sol–gel silica spheres
J. Phys. E
Electrochemical synthesis and characterization of a new conducting polymer: polyrhodanine
Appl. Surf. Sci.
Synthesis, characterization, magnetic and electrical properties of the novel conductive and magnetic polyaniline/MgFe2O4 nanocomposite having the core–shell structure
J. Alloys Compd.
Cadmium(II) sorption and desorption in a fixed bed column using sunflower waste carbon calcium–alginate beads
J. Bioresour. Technol.
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