Application of a novel bi-functional nanoadsorbent for the simultaneous removal of inorganic and organic compounds: Equilibrium, kinetic and thermodynamic studies
Graphical abstract
In the current study, a bi-functional nanoadsorbent Fe3O4@SiO2@NH2@SH was successfully synthesized for the simultaneous adsorption of two types of well-known contaminates namely heavy metals and pesticides. The physical and surface properties of the synthesized nanoparticles were characterized by XRD, FT-IR, SEM, TEM, BET and EDX analytical techniques.
Introduction
Owing to the irreversible effects on aquatic ecosystems, which have mainly originated from the activity of organisms and humans, the simultaneous removal of inorganic and organic chemical compounds from various water sources has been regarded as a great aquatic challenge. Amongst the chemicals, both heavy metal ions and pesticides constitute the most well-known hazardous environmental pollutants [1]. 2,4‑Dichlorophenoxyacetic acid (2,4‑D), categorized as a phenoxy herbicide, has been widely used to control broadleaf plants in wheat, rice and maize. It has also been used to prolong products durability and efficiency [2,3]. In 1987, the WHO confirmed 2,4‑D as a class of IIB carcinogen for the human beings. Additionally, it may induce adverse health effects including cytogenetic damage, hepatotoxicity, nephrotoxicity, liver and kidney toxicity, teratogenicity, endocrine disruption and apoptotic cell production [[2], [3], [4]]. On the other hand, Lead (Pb(II)) ions (known as heavy metals) cause serious health disorders such as anemia, cancer kidney, mental retardation, dermatitis, poisoning, liver, pulmonary hypertension, birth defects in human beings [1,5,6]. The above-mentioned compounds (2,4‑D and Pb(II)) can be entered together into both surface and groundwater resources by leaching from agricultural lands, chemical fertilizer plants and sewage of petrochemical companies [1,7,8]. In this regard, the WHO has also issued that the concentrations of 2,4‑D and Pb(II) should be lower than 70 and 10 μg/L in drinking water, respectively [1,8]. In order to manage this environmental concern, various techniques have been separately developed for the removal of heavy metal ions and pesticides from aquatic solutions such as advanced oxidation (Fenton, Photo-Fenton, UV/H2O2, UV/TiO2), ion exchange, ozonation, electrochemical, photochemical, photocatalytic, biological and adsorption methods [7,[9], [10], [11], [12], [13], [14], [15]]. Amongst them, adsorption has been the most frequently used technique for the removal of both organic and inorganic pollutants due to ease of operation, no residue or sludge formation, high recovery of adsorbent, low cost and an efficient removal of pollutants at trace levels. However, there is still an urgent need for the new technologies that can provide new treatments for the simultaneous removal of inorganic and organic chemical compounds [16]. Up to now, several research groups have studied on the separation of Pb(II) (inorganic) and 2,4‑D (organic) from wastewaters.
Fe3O4 nanoparticles have exhibited a great performance due to their large surface area, reasonable low reactivity, suitable magnetic properties and ease of separation [17]. However, pure magnetic nanoparticles are unstable and may be rapidly oxidized at low pHs. Therefore, a suitable coating is essential to prevent them from oxidation. For this reason, silica, gold and polymers have been reported to be applied as shell materials [18,19]. Amongst these, silica has gained lots of interest due to its ease of access, high adsorption capacity, high thermal resistance and high chemical reactivity via bond formation with organic ligands [20]. Recently, the use of bi-functional nanoadsorbents has been reported for the simultaneous removal of a certain number of chemicals. These adsorbents consist of several ligands which are chemically bonded to the surface of core-shell nanoparticles. The ligands are responsible for the simultaneous removal of several pollutants [21]. Modification of the surface of nanoparticles with proper ligands can lead to the following phenomena: a) the stability of nanoparticles in solution, b) increase in the nanoparticle solubility and c) the reduction of the particle accumulation and nonspecific bindings [21,22]. In a further related study, Singh et al., prepared the nanoparticles modified with amine, thiol and carboxyl groups followed by the evaluation of the removal efficiency for bacterial pathogens and toxic metal ions in water samples. Within the above-mentioned study, the surface of silica-coated magnetic nanoparticles was separately modified by thiol, amine, carboxyl and vinyl groups [23].
The goal of the present study was to evaluate the synthesis and application of a novel and highly efficient bi-functional nanoadsorbent for the simultaneous adsorption and removal of inorganic and organic compounds from aqueous solutions. Further on, equilibrium, kinetic and thermodynamic studies associated with the implication of the nanoadsorbent were all considered as well.
Section snippets
Materials
Ferric chloride (FeCl3·6H2O), ferrous chloride (FeCl2·4H2O), 3‑mercaptopropyl trimethoxysilane (MPTMS), 3‑aminopropyltrimethoxysilane (APTMS), Tetraethylorthosilicate (TEOS), ammonium hydroxide (NH4OH), lead nitrate (Pb(NO3)2), 2,4‑dichlorophenoxy acetic acid (2,4‑D), toluene, methanol and ethanol were purchased from Merck (Darmstadt, Germany). In all experiments, double distilled water (DI-water) was used and the initial pH of the solution was adjusted by the addition of 0.1 M NaOH and/or
Choice of materials
The magnetic nanoparticles compared with other sorbents such as mesoporous silica materials, polymers, graphenes and multiwall carbon nanotubes seem to be the best choice for the easy and fast extraction of targets owing to its magnetic characteristics. The magnetic nanoparticles can also be easily separated from the extraction media by using an external magnetic field. Therefore, the magnetic nanoparticles are more applicable for the removal of target molecules/ions from the contaminated media.
Conclusions
Within the current study, the application of Fe3O4@SiO2@NH2@SH nanomagnetic adsorbent for the simultaneous adsorption of inorganic and organic chemicals (Pb(II) and 2,4‑D) in aqueous solutions was investigated in detail. The bi-functional adsorbent was characterized by FT-IR, XRD, SEM, EDX and TEM analyses. The experimental parameters affecting the removal efficiency of the studied targets such as amount of adsorbent, contact time, pH and initial concentration of adsorbates were evaluated and
References (44)
- et al.
Enhanced photocatalytic–biological degradation of 2,4 dichlorophenoxyacetic acid
Bull. Fac. Pharm. Cairo Univ.
(2015) - et al.
Study on the degradation of 2,4‑dichlorophenoxyacetic acid (2,4‑D) and 2‑methyl‑4‑chloro‑phenoxyacetic sodium (MCPA sodium) in natural agriculture-soils of Fuzhou, China using capillary electrophoresis
Sci. Total Environ.
(2009) - et al.
Sargassum seaweed as biosorbent for heavy metals
Water Res.
(2000) - et al.
Effect of surface modification of an engineered activated carbon on the sorption of 2,4‑dichlorophenoxy acetic acid and benazolin from water
J. Colloid Interface Sci.
(2006) - et al.
2,4‑Dichlorophenoxyacetic acid removal from aqueous solutions via adsorption in the presence of biological contamination
J. Environ. Chem. Eng.
(2013) - et al.
Synthesis of surface molecular imprinted TiO2/graphene photocatalyst and its highly efficient photocatalytic degradation of target pollutant under visible light irradiation
Appl. Surf. Sci.
(2016) - et al.
“Gold rush” in modern science: fabrication strategies and typical advanced applications of gold nanoparticles in sensing
Coord. Chem. Rev.
(2018) - et al.
Preparation of water-compatible molecularly imprinted thiol-functionalized activated titanium dioxide: selective adsorption and efficient photodegradation of 2,4‑dinitrophenol in aqueous solution
J. Hazard. Mater.
(2018) - et al.
Selective removal of 2,4‑dichlorophenoxyacetic acid from water by molecularly-imprinted amino-functionalized silica gel sorbent
J. Environ. Sci.
(2010) - et al.
Functional oxide nanomaterials and nanocomposites for the removal of heavy metals and dyes
Nanomater. Nanotechnol.
(2013)
Thiol modified Fe3O4@ SiO2 as a robust, high effective, and recycling magnetic sorbent for mercury removal
Chem. Eng. J.
Multifunctional nanoparticles: analytical prospects
Anal. Chim. Acta
Efficient removal of pathogenic bacteria and viruses by multifunctional amine-modified magnetic nanoparticles
J. Hazard. Mater.
Effective heavy metal removal from aqueous systems by thiol functionalized magnetic mesoporous silica
J. Hazard. Mater.
Amino-functionalized Fe3O4@SiO2 core–shell magnetic nanomaterial as a novel adsorbent for aqueous heavy metals removal
J. Colloid Interface Sci.
Surface engineered magnetic nanoparticles for removal of toxic metal ions and bacterial pathogens
J. Hazard. Mater.
Kinetics and thermodynamic study of aniline adsorption by multi-walled carbon nanotubes from aqueous solution
J. Colloid Interface Sci.
Amino and thiol modified magnetic multi-walled carbon nanotubes for the simultaneous removal of lead, zinc, and phenol from aqueous solutions
Appl. Surf. Sci.
Highly efficient removal of heavy metal ions by amine-functionalized mesoporous Fe3O4 nanoparticles
Chem. Eng. J.
Study on the removal of pesticide in agricultural run off by granular activated carbon
Bioresour. Technol.
Effective removal of Cu(II) ions from aqueous solution by amino-functionalized magnetic nanoparticles
J. Hazard. Mater.
Equilibrium and thermodynamic parameters of single and binary mixture biosorption of lead (II) and copper (II) ions onto Pseudomonas putida: effect of temperature
J. Hazard. Mater.
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