Fe3O4@SiO2 nanoparticles-supported Cu(II) complex: An efficient and reusable nanocatalyst for treating environmental pollutants in aqueous medium
Graphical abstract
Introduction
Environmental pollution affects the quality and the natural life cycle and has detrimental consequences for human, animal, and plant life [1]. In recent years, effluents have been the focus of attention due to their toxic and perilous substances, such as organic nitroarene dyes, that cause environmental damage [2]. Therefore, several protocols like chemical degradation, photoreduction, reverse osmosis, and coagulation were utilized in the destruction of nitro compounds and organic dyes [[3], [4], [5]]. Despite these efforts, due to the elevated costs and the formation of hazardous by-products, these procedures are not effective and sufficient in the decomposition of dyes and nitrogen compounds. Therefore, it is essential to establish highly effective and eco-friendly manners for the destruction of these compounds [[6], [7], [8]].
Heterogeneous catalysts are mainly used in the form of NPs regarding their larger available catalytic surface [9,10]. Recently, metal complexes have been the subject of intense interest in different fields, e.g., materials science, biotechnology, and modern chemistry [11]. Generally, the metal nano complex possesses a central metal ion or atom and one or more ligands. Catalysts have two kinds of homogeneous and heterogeneous. Homogeneous catalysts are utilized as the reactants in a similar phase, while the heterogeneous catalysts are used as the solid phase reactions occurring at the surface. Separating catalysis from the reaction mix is one of the most significant problems in homogeneous catalysis, and the other is their reuse. One of the best solutions to this problem is to provide heterogeneous catalysts with appropriate supports such as chitosan [12,13], graphene oxide [14], TiO2 [15], and perlite [16]. Therefore, the industry supports the use of heterogeneous catalysts due to their ease of operation, easy operation, and separation. Recently, metal and metal oxides NPs have been considered because of their use in wastewater treatment [17,18]. One of the methods of synthesizing heterogeneous catalysts, which is probably the best method, is to immobilize of complexes on solid bases like metal and metal oxides. Magnetic iron oxide NPs (Fe3O4 MNPs) have received a huge deal of interest within metal oxide NPs, probably because of their special applications, including small size, high magnetic permeability, good stability, easy recovery, low cost, and separation of metal NPs, large specific surfaces, and the possibility of preventing the accumulation of metal NPs [[19], [20], [21], [22], [23], [24], [25], [26], [27], [28]]. Nevertheless, Fe3O4 NPs easily aggregate and are not stable owing to their high free surface energy and anisotropic dipolar attraction, thereby decreasing/reducing the surface area, the reactivity, and catalytic activity. Thus, suitable protection coatings and Fe3O4 modifications with diverse compounds (e.g., silica) are imperative to avoid such limitations [29].
One of the most prevalent contaminants in hazardous waste sites is hexagonal chromium, which is a highly toxic compound as well [30]. Thus, removing Cr(VI) from the effluent system is of great importance. The easiest way to get rid of Cr(VI) is by degrading it to Cr(III). Cr(III) is highly insoluble in water, and it is easily eliminated because of the creation of insoluble hydroxides with regulating the pH in aqueous media, unlike Cr(VI), which is very soluble in water. Formic acid (HCO2H) is utilized for reducing chromium(VI) to chromium(III) [31,32]. Recently, it has been considered an eco-friendly and low-cost reducing factor. Different from other monocarboxylic acids, HCOOH possesses strongly reducing features and passes through direct mineralization to H2 and CO2 while discharging the metal catalysts with no intermediates [[33], [34], [35]]. Zhang et al. [36] studied and discussed the oxidation of penicillin and persulfate activation by using a core-shell structured catalyst (Fe3O4@C/CDs-Ag). Further, they argued their catalyst exhibited excellent repetitive capacity. Niu et al. [37] prepared a magnetic γ-Fe2O3/CeO2 catalyst using the oxidation precipitation method for tetracycline degradation. Their result showed that the catalyst was efficient, stable, and easily recyclable. Eshaq et al. [38] synthesized a core/shell structured FeVO4@BiOCl as an enduring heterogeneous catalyst for the photocatalytic degradation of p-NP. Moreover, they believe that their catalysts possess higher degradation reusability and performance in sonophotocatalytic degradation.
According to the literature, the successful synthesis of a copper(II) complex through immobilizing the metformin ligand on the magnetite NPs coated with silica (Fe3O4@SiO2) surface and its use as a magnetically reusable catalyst for reduction of Cr(VI), MB, CR, and 4-NP have not been reported. In this paper, the copper(II) complex was processed by immobilizing the metformin on the magnetite NPs coated with silica (Fe3O4@SiO2) surface as a novel, profitable, and magnetically recoverable nanocatalyst. Moreover, the catalytic performance of [Fe3O4@SiO2-Met-Cu(II)] was assessed for reducing Cr(VI), 4-NP, CR, and MB within aqueous media. Also, compared to related research, this catalyst showed less reaction time.
Section snippets
Materials and instruments
All high-purity chemical materials were bought from the Merck and Aldrich chemical companies. The Shimadzu 800IR 100FT-IR spectrometer was used to record the FT-IR spectra. To obtain UV–Visible spectra, a Hitachi, U-2900 double-beam spectrophotometer was used with the wavelengths within the range of 200–800 nm. The TESCAN4992 device was used to perform an energy-dispersive X-ray (EDS) analysis. An accurate magnetometer of Iran Kavir VSM was used to perform vibrating sample magnetometer
Characterizing the catalyst
The steps of the synthesis of [Fe3O4@SiO2-Met-Cu(II)] are presented in Scheme 1. EDS, FT-IR, VSM, TG-DTG, XRD, FESEM, and TEM analyses were used to characterize the prepared catalyst.
The FT-IR analysis was performed to approve the coordination of the Cu atom by the metformin ligand and immobilizing the complex over the surface of Fe3O4@SiO2 (Fig. 1). The FeO band's absorption peaks in the Fe3O4 MNPs appeared at around 628 cm−1. The absorption peak at 462 cm−1, 802 cm−1, 1083 cm−1 are attributed
Catalyst reusability
Synthesizing recyclable nanocatalysts with high catalytic performance is an important issue from green and environmental viewpoints. The reusability of the magnetic nano complex [Fe3O4@SiO2-Met-Cu(II)] in the reduction reaction of 4-Nitrophenol was evaluated in this study. The [Fe3O4@SiO2-Met-Cu(II)] nano complex catalyzed the 4-NP reduction several times. By ending the reduction reaction, an external magnetic field was considered for isolating the catalyst and reused in the successive run
Conclusions
This research provides a facile and convenient manner for immobilizing the organic copper complex on the surface of Fe3O4@SiO2 as a magnetic heterogeneous and reusable catalyst for the reduction/degradation of 4-NP, Cr(VI), CR, and MB in the medium conditions. FESEM, VSM, FT-IR, XRD, TG-DTG, and EDS methods were utilized to characterize [Fe3O4@SiO2-Met-Cu(II)]. This protocol has advantages such as higher yield, reduced environmental hazards, and the procedure is very comfortable. Also, compared
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
Here, the Research Council of the Iran University of Science and Technology is thanked for the partial supports.
References (38)
- et al.
In-situ synthesis of magnetic nanoparticle immobilized heterogeneous catalyst through mussel mimetic approach for the efficient removal of water pollutants
Coll. Interf. Sci. Commun.
(2019) - et al.
Recent advancements in silica nanoparticles based technologies for removal of dyes from water
Coll. Interf. Sci. Commun.
(2019) - et al.
Biosynthesis of au nanoparticles by Gymnocladus assamicus and its catalytic activity
Mater. Lett.
(2013) - et al.
Copper mesoporous materials as highly efficient recyclable catalysts for the reduction of 4-nitrophenol in aqueous media
Polyhedron.
(2018) - et al.
Pd-based nanoparticles: plant-assisted biosynthesis, characterization, mechanism, stability, catalytic and antimicrobial activities
Adv. Colloid Interf. Sci.
(2020) Synthesis and catalytic properties of metal nanoparticles: size, shape, support, composition, and oxidation state effects
Thin Solid Films
(2010)- et al.
Chitosan-coated magnetic nanoparticles used as substrate immobilization carrier for α-arbutin biosynthesis process
Coll. Interf. Sci. Commun.
(2021) - et al.
Functionalized graphene oxide anchored to Ni complex as an effective recyclable heterogeneous catalyst for Sonogashira coupling reactions
J. Organomet. Chem.
(2019) - et al.
Synthesis and characterization of titanium dioxide nanoparticles using Euphorbia heteradena Jaub root extract and evaluation of their stability
Ceram. Int.
(2015) - et al.
Green synthesis of perlite supported silver nanoparticles using Hamamelis virginiana leaf extract and investigation of its catalytic activity for the reduction of 4-nitrophenol and Congo red
J. Alloys Compd.
(2016)
Heavy metal removal from water/wastewater by nanosized metal oxides: a review
J. Hazard. Mater.
Metallic Ni nanoparticles embedded in hierarchical mesoporous Ni(OH)2: a robust and magnetic recyclable catalyst for hydrogenation of 4-nitrophenol under mild conditions
Polyhedron.
Synthesis, characterization and catalytic activity of Fe3O4@SiO2 nanoparticles supported copper(II) complex as a magnetically recoverable catalyst for the reduction of nitro compounds, Nigrosin and methylene blue
Sep. Purif. Technol.
Synthesis of Fe3O4@SiO2-Au/Cu magnetic nanoparticles and its efficient catalytic performance for the Ullmann coupling reaction of bromamine acid
Chin. Chem. Lett.
Catalytic and antimicrobial activities of magnetic nanoparticles supported N-heterocyclic palladium(II) complex: a magnetically recyclable catalyst for the treatment of environmental contaminants in aqueous media
Sep. Purif. Technol.
Facile deposition of gold nanoparticles on core-shell Fe3O4@polydopamine as recyclable nanocatalyst
Solid State Sci.
Palladium(II) anchored on polydopamine coated-magnetic nanoparticles (Fe3O4@PDA@Pd(II)): a heterogeneous and core–shell nanocatalyst in Buchwald–Hartwig C–N cross coupling reactions
Polyhedron.
SO3H-dendrimer functionalized magnetic nanoparticles (Fe3O4@D–NH–(CH2)4–SO3H): synthesis, characterization and its application as a novel and heterogeneous catalyst for the one-pot synthesis of polyfunctionalized pyrans and polyhydroquinolines
Polyhedron.
Synthesis and assembly of gold and Iron oxide particles within an emulsion droplet; facile production of Core@Shell particles
Coll. Interf. Sci. Commun.
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