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  • For Review Only Modified montmorillonite with alkylamine

    chloroanthraquinone as a colorimetric sensor for detection and separation of Cu2+ from an aqueous solution

    Journal: Songklanakarin Journal of Science and Technology

    Manuscript ID SJST-2019-0273.R2

    Manuscript Type: Original Article

    Date Submitted by the Author: 13-Nov-2019

    Complete List of Authors: Thongkum, Duangrat; Naresuan University, Chemistry Nomnuch, Thitiporn; Naresuan University, Chemistry Chuenchomnakjad, Saksit; Rajamangala University of Technology Lanna, Program of Industrial Engineering

    Keyword: adsorption, chloroanthraquinone, colorimetric sensor, copper ion, montmorillonite

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    Songklanakarin Journal of Science and Technology SJST-2019-0273.R2 Thongkum

  • For Review Only

    Original Article

    Modified montmorillonite with alkylamine chloroanthraquinone as a colorimetric

    sensor for detection and separation of Cu2+ from an aqueous solution

    Duangrat Thongkum1*, Thitiporn Nomnuch1, and Saksit Chuenchomnakjad2

    1Department of Chemistry, Faculty of Science, Naresuan University,

    Mueang, Phitsanulok, 65000 Thailand

    2 Program of Industrial Engineering, Rajamangala University of Technology Lanna

    Phitsanulok, Mueang, Phitsanulok, 65000 Thailand

    * Corresponding author, Email address: [email protected]

    Abstract

    To compare the adsorption capacity of Cu2+ between Mt and Mt modified with

    alkylamine chloroanthraquinone colorimetric sensor (Mt-L), the adsorption properties of

    Mt and Mt-L with Cu2+ were studied by using UV-vis spectroscopy. Their structures were

    characterized by FTIR spectroscopy and XRD techniques. The adsorbent quantity on the

    removal efficiency of Cu2+, effect of pH, effect of initial Cu2+ concentration, equilibrium

    adsorption time, adsorption kinetic and adsorption isotherm were determined. The results

    revealed that the maximum adsorption efficiency was 54% with an initial Cu2+

    concentration of 3.5010-3 M, 40.0 g/L of Mt-L and an initial pH of 5.0. The adsorption

    kinetic displayed the pseudo-second order model and the adsorption isotherm

    corresponded to the Langmuir isotherm. The qm of Mt-L was calculated to be 9.5511 mg/g

    which was higher than the adsorption of Cu2+ on Mt (2.6260 mg/g). Therefore, Mt-L was

    a great potential adsorbent for Cu2+ ion adsorption in aqueous solution.

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    Keywords: adsorption, chloroanthraquinone, colorimetric sensor, copper ion,

    montmorillonite

    1. Introduction

    Copper is a heavy metal which is considered as one of the most toxic mineral

    contaminant in soil and water resources. The effects on human health caused by copper

    are liver damage, Wilson disease, Alzheimer’s disease, etc (Borchard et al., 2018;

    Roberts, 2011; Squitti et al., 2018). The maximum permissible limit for copper in drinking

    water by the World Health Organization (WHO) is 2 mg/L (Datta, Uslu, & Kumar, 2015;

    Uddin, 2017). Therefore, it is necessary to cleanup water and metal-contaminated waste

    water before its discharge to environment.

    There are many techniques for the treatment of water and waste water

    contaminating heavy metals, such as, chemical precipitation, solvent extraction,

    membrane filtration, ion exchange, electrochemical removal and coagulation (Fan, Zhou,

    Jiang, Huang, & Lang, 2014; Rasouli, Aber, Salari, & Khataee, 2014). However,

    adsorption is considered as an efficient, simple and low-cost technique (Shirzad-Siboni,

    Khataee, Hassani, & Karaca, 2015; Wu et al., 2011). Many studies have reported the

    adsorption of metallic ions from water by various adsorbents such as activated carbon,

    zeolite and clay mineral (Burakov et al., 2018; Uddin, 2017).

    Clay minerals are hydrous aluminosilicates, sometimes with variable amounts of

    alkali metals, alkaline earth metals and other cations (Bhattacharyya & Gupta, 2008;

    Uddin, 2017). The characteristics of clay minerals are high specific surface area, high

    cation exchange capacity (CEC), chemical and mechanical stability, as well as low-cost

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    (Gonçalves dos Santos, Grassi, & Abate, 2015). During the past decades, the metal ion

    adsorption studies by clay minerals were mainly focused on montmorillonite (Mt).

    Abdellaoui et al. (2019) studied the divalent heavy metals adsorption behavior by

    commercial montmorillonite and reported the Cu2+ adsorption capacity increases with an

    increase in pH of the solution. This behavior can be attributed to the surface charge of the

    clays and the competence between the H+ and the divalent ions by the adsorption sites at

    lower pH. However, when the pH increases, the clays become negatively charged surface,

    and the repulsive force decreases. Therefore the removal of Cu2+ begins to increase. The

    adsorption and separation of Cu2+ from an aqueous solution using montmorillonite had

    been investigated by Datta et al. (2015). In the kinetic experiments, the maximum

    adsorption capacity for the separation of Cu2+ ion from aqueous solution was found

    (predicted by the Langmuir model) to be 2.6260 mg/g. However, little has been reported

    that investigate modified-Mt with colorimetric sensor to detect Cu2+ in aqueous solution

    and also to optimize the adsorption capacity of Cu2+ as well.

    The purposes of this present study are to compare the adsorption capacity of Cu2+

    ion in aqueous solution between Mt and Mt modified with alkylamine

    chloroanthraquinone colorimetric sensor or Mt-L and to evaluate the adsorption

    parameters such as adsorbent dosage, pH and Cu2+ ion concentration. In addition, the

    color, the adsorption kinetic and the adsorption isotherm studies were determined to

    understand the adsorption mechanism of Cu2+ ion on modified-Mt surfaces.

    2. Materials and Methods

    2.1 Materials

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    Montmorillonite-K10 (CEC 120 cmol/kg) and Cu(NO3)2·3H2O were purchased

    from Sigma Aldrich. All of the solvents used were of analytical grade and they were

    purified by distillation under nitrogen gas before using. The colorimetric sensor L was

    synthesized according to the literature (Kaur & Kumar, 2008; Ranyuk et al., 2011) by

    using the substitution reaction between 1,8-dichloroanthraquinone (0.40 g, 1.5 mmol) and

    2-picolylamine (0.22 mL, 2 mmol) with K2CO3 (0.30 g, 2 mmol) in toluene (40 mL). The

    mixture solution was refluxed for 2-3 days under nitrogen atmosphere. Initially the

    solution was yellow and upon heating turned to red. Then, the solvent was removed under

    reduced pressure. The residue was dissolved in CH2Cl2, and 3M HCl was added to adjust

    pH 1. The resulting residue was extracted with CH2Cl2 and water. The organic phase was

    dried over anhydrous Na2SO4, filtered and evaporated. The crude residue was purified by

    column chromatography (SiO2, CH2Cl2) to yield red solid (45%). The final product was

    characterized by FTIR, 1H-NMR and 13C-NMR spectroscopic techniques.

    2.2 Characterization techniques

    The functional groups of Mt and Mt-L were recorded by attenuated total

    reflectance Fourier transform infrared spectroscopy (ATR-FTIR) on a PerkinElmer in the

    spectral range 4000-400 cm-1. The X-ray diffraction patterns were performed with a

    Panalytical XRD instrument at 2 value range 5-80 degree using Cu K  = 0.154 nm.

    The absorbance of Cu2+ was measured with a SPECORD 200 PLUS UV-Vis

    spectrophotometer over the wavelength range 200-1000 nm.

    2.3 Modification of Mt

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    The synthesis of L modified Mt (Mt-L) was prepared in 250 mL of volumetric

    flask by dispersion 6 g of Mt in 1.5:1 ratio of CH3CN:H2O for 2 h at room temperature

    using a magnetic stirrer. Then, the 6.0010-5 M of L in the same ratio of solvent was

    added to Mt dispersive solution. The mixture was then adjusted to the pH with 0.1 M

    NaOH and 0.1 M HCl while stirring for 2 h. After that, th