Application of a novel bi-functional nanoadsorbent for the simultaneous removal of inorganic and organic compounds: Equilibrium, kinetic and thermodynamic studies

doi:10.1016/j.molliq.2018.10.013

Journal of Molecular Liquids

Volume 273, January 2019, Pages 543-550

https://doi.org/10.1016/j.molliq.2018.10.013 Get rights and content

Highlights

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A novel bi-functional nanoadsorbent
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Removal of lead and cadmium ions
•
High adsorption capacity
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Equilibrium, kinetic and thermodynamic studies
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Simple and fast removal method

Abstract

The notion of hazardous pollutants removal in environmental water resources has gained widespread attention in the recent years. Generally, the pollutants have irreparable effects on aquatic ecosystems, organisms and human beings. Considering that, within 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. To evaluate the efficiency of the as-prepared adsorbent, influential parameters such as pH, adsorbate concentration, nanoadsorbent dosage and contact time were also investigated and optimized. Following on, the nanoadsorbent was then implemented for the simultaneous removal of Pb(II) and 2,4‑dichlorophenoxyacetic acid (2,4‑D) from the synthetic wastewater. The structural analysis revealed that Fe₃O₄@SiO₂@NH₂@SH nanoparticles have a core-shell spherical structure modified by both amine and thiol functional groups. The kinetic and isotherm studies underlined that the process of adsorption follows the second-order kinetic (R² > 0.99) and Langmuir isotherm (R² > 0.97) model. It was also found out that pH plays a key role in the adsorption system whose optimum value was determined to be 6. The thermodynamic studies showed that the adsorption process is of endothermic and spontaneous nature. Additionally, the results regarding the desorption process revealed that the nanoadsorbent could be used several times with almost no decline in the removal efficiency. Finally, it was concluded that bi-functional adsorbent could be potentially applied for the simultaneous removal of further inorganic and organic chemicals from various aqueous solutions.

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

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Application of a novel bi-functional nanoadsorbent for the simultaneous removal of inorganic and organic compounds: Equilibrium, kinetic and thermodynamic studies

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Choice of materials

Conclusions

Bull. Fac. Pharm. Cairo Univ.

Sci. Total Environ.

Water Res.

J. Colloid Interface Sci.

J. Environ. Chem. Eng.

Appl. Surf. Sci.

Coord. Chem. Rev.

J. Hazard. Mater.

J. Environ. Sci.

Nanomater. Nanotechnol.

Chem. Eng. J.

Anal. Chim. Acta

J. Hazard. Mater.

J. Hazard. Mater.

J. Colloid Interface Sci.

J. Hazard. Mater.

J. Colloid Interface Sci.

Appl. Surf. Sci.

Chem. Eng. J.

Bioresour. Technol.

J. Hazard. Mater.

J. Hazard. Mater.