Co-Fe-layered double hydroxide decorated amino-functionalized zirconium terephthalate metal-organic framework for removal of organic dyes from water samples

https://doi.org/10.1016/j.saa.2020.118270Get rights and content

Highlights

  • New adsorbent of Co-Fe-LDH@metal-organic framework was synthesized.

  • This adsorbent was used for removal of dyes from water samples.

  • The adsorbent has high maximum adsorption capacity.

  • The adsorbent was reused several times without any significant change in the efficiency.

Abstract

In this study, a new efficient adsorbent of Co-Fe-layered double hydroxides@metal-organic framework (Co-Fe-LDH@UiO-66-NH2) was synthesized and used for extraction of methylene blue (MB) and methylene red (MR) from water samples prior to their determination by UV–Vis spectrophotometer. The adsorbent was characterized by Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray (EDX), X-ray Diffraction (XRD), and Brunauer-Emmett-Teller (BET) analyses. The impact of various parameters such as pH of the aqueous phase, extraction time, amount of adsorbent, type and volume of eluent solvent, desorption time, and sample volume were studied. The maximum extraction recovery was obtained at an optimized pH 8.0 and extraction time 10.0 min. The adsorption process was fitted by the Langmuir model with a maximum adsorption capacity of 555.62 mg/g and 588.2 mg/g, respectively, for MB and MR. Under optimum conditions, the limit of detection (LOD) for MB was 0.7 μgL−1 and 0.9 μgL−1 for MR. Furthermore, the Co-Fe-LDH@UiO-66-NH2 composite showed high efficiency for the removal of the analytes from environmental water samples.

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.

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