Co-Fe-layered double hydroxide decorated amino-functionalized zirconium terephthalate metal-organic framework for removal of organic dyes from water samples
Graphical abstract
Introduction
Different types of dyes such as methylene blue, methyl red and etc. are found in various industrial effluents of plastic, leather, cosmetics, textile, paper, dyeing, food processing, and dye and printing manufacturing processes [1,2]. Synthetic azo dyes released into the water and environment can represent an important threat to health creatures and the environment due to the fact that they are carcinogenic or toxic in nature [1,3]. So, it is significant to remove organic dyes from wastewater effluents before discharging into the water and environment. Also, the organic commercial dyes are produced about >7× 105 t/year in the world. Ten percent loss of these organic compounds occurs through the textile coloration procedure and 2% of them are discharged during the manufacturing processes [4,5]. Therefore, due to environmental protection and human health, it is important to remove these pollutant dyes from wastewater samples from the environment. As a result, different materials such as wood, coal, fly ash, rice husk, clay, cotton waste, activated carbon, and other porous materials have been previously reported as a sorbent for the elimination of organic dyes from water samples [[6], [7], [8], [9], [10], [11], [12], [13]]. However, there is still very significant to find a suitable procedure for the rapid removal of these pollutant dyes from wastewater samples before their discharge into the environment.
Layer double hydroxides (LDHs) are a type of significant two-dimensional compounds containing of positively charged host layers and counter anions in the interlayers [14] with chemical formula of [M1-x2+Mxn+(OH)2](An−)x/n.mH2O that M3+ and M2+ are trivalent (such as Fe(III), Cr(III), etc.) and divalent metals (Co(II), Ni(II), etc.), and An− is an interlayer anion such as SO42−, NO3−, CO32−, and ClO4−] [15,16]. The high anion-exchange capacity, large surface area, structural memory effect, and good intercalation ability of LDHs make them versatile materials for applications such as adsorbent, catalyst, and scavenger [[14], [15], [16], [17]].
Metal-organic frameworks (MOFs) are an intriguing class of materials that are well-known as porous coordination polymers. These inorganic-organic hybrid structures are constructed from metal ions/clusters and organic ligands through moderate/strength coordination bonds. The high surface area, large porosity, tunable functionality, and properties, high mechanical and thermal stability, and the presence of open metal sites offer MOFs for various applications such as catalysis [[18], [19], [20], [21]], photocatalysis [22,23], adsorption [24], storage [25], drug deliver [26], removal of toxic compounds [27,28], and etc. [29,30]. However, most of MOF materials suffer from insufficient aqueous stability mainly over a broad range of pH. Research has shown that zirconium-based UiO-66 MOFs (University of Oslo 66) is one of the most stable MOFs, thus, they are good candidates for purification of water samples [31,32].
Hence, in this study, we synthesized a new porous hybrid adsorbent, namely Co-Fe-LDH@UiO-66-NH2 MOF, for separation and preconcentration of methyl red and methylene blue contaminants from wastewater samples. The 2D Co-Fe-LDH can enhance the accessibility of dyes to the active sites without any diffusion limitation and help prevent aggregation of the MOF particles. In addition, because of the magnetic properties of the LDH in the hybrid adsorbent, it can be easily separated from water samples by an external magnet. In the present study a robust MOF solid, UiO-66-NH2 is selected based on its amino-functionality, the structural stability, the large specific BET surface area, and the high porosity [32,33]. The porosity and large surface area of the 3D MOF permit easy diffusion of the substrates within the pores. In addition, the amino-functionality on the terephthalate ligand of the MOF can effectively enhance the adsorption efficiency of organic compounds via hydrogen-bonding formation [32]. The adsorbent has been characterized by scanning electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller surface area measurement, and Fourier-Transform-Infrared spectroscopy. Also, several parameters such as pH of the solution, amount of adsorbent, extraction and desorption time, sample volume and type and volume of eluent were investigated and optimized. The experiments showed that the hybrid sorbent was stable and reusable for dye adsorption from aqueous solutions. The data showed that the hybrid material, because of high surface area and adsorptive properties, has a high potential for adsorption of organic pollutants from industrial wastewater effluents.
Section snippets
Materials
The iron(III) nitrate nonahydrate (Fe (NO3)3·9H2O), cobalt(II) nitrate hexahydrate (Co(NO3)2·6H2O), 2-aminoterephthalic acid, sodium hydroxide (NaOH), N,N′-dimethylformamide (DMF), zirconium chloride (ZrCl4), methanol, acetonitrile and ethanol were used without purification and as purchased from Merck (Darmstadt, Germany).
Co-Fe-LDH
The cobalt-iron layer double hydroxide (Co-Fe-LDH) was prepared via co-precipitation methods as follow [34,35,37,and]: A 50 mL of homogeneous aqueous solution from 14.0 mmol
Characterization
UiO-66-NH2 is used in this work, because it is one of the most famous and stable MOFs with high stability, high surface area, amino-functionality, and ordered structure. The Co-Fe-LDH can minimize the substrate diffusion barrier because of properties of these 2D materials. Also, the layers can minimize the MOF particles aggregation and enhance their water stability, resulting in the adsorption efficiency of the composite. Scheme 1 indicates the synthetic steps of the composite.
Powder X-Ray
Conclusions
In this study, a porous Co-Fe-LDH@UiO-66-NH2 nanocomposite was synthesized by a simple procedure. The adsorbent was characterized via various techniques such as FT-IR, SEM, BET, and XRD. This hybrid adsorbent was used for fast and highly efficient extraction and determination of methylene blue and methyl red from environmental waters. The optimum conditions were: pH of the solution, 8.0; the amount of adsorbent, 5.0 mg; extraction time, 10.0 min. According to the Langmuir fit model, the maximum
CRediT authorship contribution statement
Mostafa Khajeh: Conceptualization, Data curation, Funding acquisition, Methodology, Project administration, Supervision, Validation, Visualization, Writing - original draft, Writing - review & editing. Ali Reza Oveisi: Investigation, Methodology, Resources, Writing - original draft, Writing - review & editing. Afsaneh Barkhordar: Formal analysis, Investigation, Software. Ziba Sorinezami: Formal analysis, Investigation, Software.
Acknowledgements
The University of Zabol is gratefully acknowledged for the financial support for this work (Grant number: UOZ-GR-9517-1).
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.
References (38)
- et al.
Adsorption behavior of metal–organic frameworks for methylene blue from aqueous solution
Microporous Mesoporous Mater.
(2014) - et al.
Equilibrium and kinetic studies of methyl orange and methyl violet adsorption on activated carbon derived from Phragmites australis
Desalination
(2010) - et al.
Removal of dyes from aqueous solution using fly ash and red mud
Water Res.
(2005) - et al.
Removal of methylene blue from aqueous solutions by an adsorbent based on metal-organic framework and polyoxometalate
J. Alloys Compd.
(2015) - et al.
Adsorptive removal of dyes from aqueous solution onto carbon nanotubes: a review
Adv. Colloid Interf. Sci.
(2013) - et al.
The utilization of leaf-based adsorbents for dyes removal: a review
J. Mol. Liq.
(2019) - et al.
Synthesis of zinc oxide nanoparticles–chitosan for extraction of methyl orange from water samples: cuckoo optimization algorithm–artificial neural network
Spectrochim. Acta A Mol. Biomol. Spectrosc.
(2014) - et al.
Simultaneous adsorption of methyl red and methylene blue onto biochar and an equilibrium modeling at high concentration
Chemosphere
(2016) - et al.
Facile synthesis of metal-organic framework UiO-66 for adsorptive removal of methylene blue from water
Chem. Phys.
(2020) - et al.
Brønsted-Lewis dual acid sites in a chromium-based metal-organic framework for cooperative catalysis: highly efficient synthesis of quinazolin-(4H)-1-one derivatives
J. Colloid Interface Sci.
(2020)
Nanoarchitecturing of open metal site Cr-MOFs for oxodiperoxo molybdenum complexes [MoO(O2)2@en/MIL-100(Cr)] as promising and bifunctional catalyst for selective thioether oxidation
Mol. Catal.
Functionalized metal-organic frameworks for photocatalytic degradation of organic pollutants in environment
Chemosphere
Bifunctional iridium-(2-aminoterephthalate)–Zr-MOF chemoselective catalyst for the synthesis of secondary amines by one-pot three-step cascade reaction
J. Catal.
Cobalt-aluminum mixed oxides prepared from layered double hydroxides for the total oxidation of benzene
Appl. Catal., A.
Activation of peroxymonosulfate by CoFe2O4 loaded on metal-organic framework for the degradation of organic dye
Chemosphere
Magnetic LDH-based CoO–NiFe2O4 catalyst with enhanced performance and recyclability for efficient decolorization of azo dye via Fenton-like reactions
Appl. Catal. B Environ.
Magnetic nanoparticle based dispersive micro-solid-phase extraction for the determination of malachite green in water samples: optimized experimental design
New J. Chem.
Spectrophotometric determination of Sudan blue ii in environmental samples after dispersive liquid-liquid microextraction
Quim Nova
Characterization of modified sawdust, kinetic and equilibrium study about methylene blue adsorption in batch mode
Korean J. Chem. Eng.
Cited by (31)
Review of MOFs and their applications in the preparation of loose nanofiltration membranes for dye and salt fractionation
2024, Desalination and Water TreatmentRecent progress in water decontamination from dyes, pharmaceuticals, and other miscellaneous nonmetallic pollutants by layered double hydroxide materials
2024, Journal of Water Process EngineeringRational synthesis of FeNiCo-LDH nanozyme for colorimetric detection of deferoxamine mesylate
2023, Spectrochimica Acta - Part A: Molecular and Biomolecular SpectroscopyRecent development in metal-organic framework-based hybrid nanocomposites for pollutants remediation from wastewater: Challenges and opportunities
2023, Environmental Technology and InnovationApplications of layered double hydroxides in sample preparation: A review
2023, Microchemical Journal