Beruflich Dokumente
Kultur Dokumente
004
Synthesis and characterization of carboxymethyl cellulose/organic montmorillonite nanocomposites and its adsorption behavior for Congo Red dye
Min-min WANG, Li WANG*
College of Material Science and Art Design, Inner Mongolia Agricultural University, Huhhot 010018, P. R. China Abstract: A series of carboxymethyl cellulose/organic montmorillonite (CMC/OMMT) nanocomposites with different weight ratios of carboxymethyl cellulose (CMC) to organic montmorillonite (OMMT) were synthesized under different conditions. The nanocomposites were characterized by the Fourier transform infrared (FT-IR) spectrophotometer, X-ray diffraction (XRD) method, transmission electron microscope (TEM), scanning electron microscope (SEM), and thermal gravimetric (TG) analysis. The results showed that the introduction of CMC may have different influences on the physico-chemical properties of OMMT and intercalated-exfoliated nanostructures were formed in the nanocomposites. The effects of different reaction conditions on the adsorption capacity of samples for Congo Red (CR) dye were investigated by controlling the amount of hexadecyl trimethyl ammonium bromide (CTAB), the weight ratio of CMC to OMMT, the reaction time, and the reaction temperature. Results from the adsorption experiment showed that the adsorption capacity of the nanocomposites can reach 171.37 mg/g, with the amount of CTAB being 1.0 cation exchange capacity (CEC) of MMT, the weight ratio of CMC to OMMT being 11, the reaction time being 6 h, and the reaction temperature being 60. The CMC/OMMT nanocomposite can be used as a potential adsorbent to remove CR dye from an aqueous solution. Key words: carboxymethyl cellulose; organic montmorillonite; nanocomposite; adsorption; Congo Red dye
1 Introduction
Dyes are widely used in the textile, rubber, paper, and plastics industries. Over 7 105 tons of different commercial dyes and pigments are produced annually all over the world (Wang et al. 2011). Most dyes released during textile manufacturing, clothing, printing, and dyeing processes are considered hazardous and toxic to some organisms and may cause allergic dermatitis, skin irritation, and carcinogenic and mutagenic risks to humans and aquatic organisms (Zollinger 1987; Fungaro et al. 2009). Therefore, the demand for good-quality water
This work was supported by the Special Fund for National Forestry Industry Scientific Research in the Public Interest of China (Grant No. 201104004), the Natural Science Foundation of China (Grant No. 20867004), and the Program for Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region. *Corresponding author (e-mail: wl2083663@126.com) Received Apr. 13, 2012; accepted Aug. 23, 2012
is continuously rising owing to an increase in the population (Srinivas et al. 2009), and it is extremely important to remove dyes from industrial wastewater before it is discharged into the environment (Luo et al. 2011). A lot of methods, such as membrane (Xu and Lebrun 1999), oxidation (Lucas and Peres 2006), coagulation/flocculation (Papic et al. 2004), and biological treatment (Akhtar et al. 2004; Kahraman et al. 2005; Gonzalez-Gutierrez and Escamilla-Silva 2009), have been used to remove dyes from wastewater. However, these methods have considerable energy requirements and thus impose both economic and environmental costs (Kittinaovarat et al. 2010). Compared with other methods, adsorption is considered superior (El Mouzdahir et al. 2010). Adsorption using activated carbon is currently of great interest for the removal of dyes and pigments. In spite of its extensive use, activated carbon remains an expensive material since the higher the quality of the activated carbon is, the greater the cost. This has led to the search for cheaper substitutes (Ahmad et al. 2007). Today, attention has been focused on the low-cost alternative adsorbent materials such as clays and biopolymers. A lot of modifications have been made with montmorillonite (MMT) and cellulose. MMT, a very rich clay mineral, consists of layers of two tetrahedral silica sheets sandwiching one octahedral alumina sheet, and it has a high adsorption capacity due to its large specific surface area and high cation exchange capacity (Fu and Qutubuddin 2001). However, natural MMT adsorbs the anionic dyes only onto the external surface with broken bonds in very small amounts, and it is difficult to make it compatible with organic polymeric material. Therefore, the modification of MMT with surfactants is a method for hydrophobizing the mineral and increasing the adsorption capacity for organic pollutants. The surfactant-modified MMT can be extensively used for a wide variety of environmental applications (Churchman et al. 2006). Cellulose is the most abundant natural polymer in nature with excellent biodegradability and biocompatibility (De Melo et al. 2009). However, the strong intermolecular and intramolecular hydrogen bonds between the hydroxyl groups along the chain backbone not only limit the water solubility but also lead to the poor reactivity of cellulose (Bao et al. 2011). By contrast, the derivative modification of cellulose, carboxymethyl cellulose (CMC), can overcome these drawbacks (Wang and Wang 2010). It is an important artificial-natural polymer derived from cellulose (Zhao et al. 2009). Polymer-clay nanocomposites have recently attracted significant interest in scientific research and industrial applications (Liu 2007; Pavlidou and Papaspyrides 2008). In previous studies, there has been a lot of investigation of preparing natural polymer-clay nanocomposites and using them as adsorbents. For instance, Kittinaovarat et al. (2010) successfully prepared chitosan/modified MMT beads and evaluated their adsorption capacity for Reactive Red 120. Ngah et al. (2010) synthesized crosslinked chitosan-coated bentonite for tartrazine adsorption from aqueous solutions. The main objective of this study was to report a novel CMC/OMMT (organic MMT) nanocomposite with a high adsorption capacity, acceptable biodegradability, and non-toxicity. It is a potential candidate as an environmentally friendly adsorbent. A series
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of CMC/OMMT nanocomposites were synthesized and their structures were investigated. Furthermore, the effects of different preparation conditions on the adsorption capacity of CMC/OMMT nanocomposites were investigated.
2 Experimental setup
2.1 Materials
The cation exchange capacity (CEC) of calcium montmorillonite (Ca-MMT, produced by Chifeng Xinglonghuagong Co., Ltd. of Inner Mongolia, China) is 100 mmol/100 g. The molecular weight of hexadecyl trimethyl ammonium bromide (CTAB, produced by Tianjin Finite Chemical Research Institute) is 364.45 g/mol. Chloroacetic acid is produced by Tianjin Fuchen Chemical Reagent Factory. Lignocellulose (LNC) is produced by Beijing Qinlihengtong Technology Co., Ltd. The molecular weight of Congo Red (CR, produced by Beijing Dyestuffs Plant) is 696.66 g/mol. Other agents used were all of analytical grade and all solutions were prepared with distilled water.
composites were washed with distilled water until the pH value of the supernatant reached 7.0, and were then dried at 105 for 12 h. All samples as adsorbents were ground and sifted with a 200-mesh sieve.
2.6 Characterization
Fourier transform infrared (FT-IR) spectra of the samples were characterized using a FT-IR spectrophotometer (Bruker Tensor 27) in KBr pellets spectra in a range from 4 000 to 400 cm1. X-ray diffraction (XRD) analysis of the powdered samples were performed on an X-ray powder diffractometer with a Cu anode (Shimadzu XRD-6000), running at 40 kV and 30 mA and scanning from 3 to 18 at a rate of 3 per minute with a scanning electron microscope (SEM, JSM-5600LV). The morphology of the nanocomposite was characterized by transmission electron microscope (TEM, JSM-5600LV) at an acceleration voltage of 80 kV.
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vibrations of OH (3 425 cm1 and 2 924 cm1) of CMC disappeared. In addition, the characteristic absorption bands at 1 600 cm1 (asymmetric stretching of COO) and 1 446 cm1 (symmetric stretching of COO) of CMC were observed on the FT-IR spectrum of the nanocomposite. The information observed from the FT-IR spectra indicates that chemical reactions have occurred on both CMC and OMMT, which may have an influence on the absorption properties of the nanocomposite.
n = d sin
(2)
where d is the distance between two consecutive clay layers, is the wavelength of the intercept X-rays at the incident angle , and n is the diffraction order. According to Braggs law, it can be noted that OMMT shows a typical diffraction peak at 2 = 4.43, corresponding to a basal spacing of 19.92 nm (the interlayer distance of natural
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MMT is 1.49 nm). The presence of CMC chains destroyed the layer structure of OMMT. It can be seen from Fig. 2 that the diffraction peak of the nanocomposite nearly disappears. This result indicated that the CMC molecules were successfully intercalated into the spacing of layers of OMMT and destroyed the crystal structure of OMMT.
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Fig. 6 Effect of amount of CTAB on adsorption capacity Fig. 7 Effect of weight ratio of CMC to OMMT on of nanocomposite for CR adsorption capacity of nanocomposite for CR
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After 6 h, the molecular repulsion between CMC molecular chains weakened the dispersion of OMMT and affected the formation of nanocomposite. Under the experimental conditions, the optimal time for preparing CMC/OMMT nanocomposite is 6 h.
4 Conclusions
The novel CMC/OMMT nanocomposite was synthesized with the intercalation method. FT-IR, XRD, TEM, SEM, and TG analyses indicated that it was not physical but chemical reactions that had occurred on both CMC and OMMT, CMC molecules had intercalated into the interlayer of OMMT, and intercalated-exfoliated structures were formed in the CMC/OMMT nanocomposite. Furthermore, the nanocomposite exhibited an improved thermal performance. Experiments on the adsorption of CR dye with the CMC/OMMT nanocomposite were carried out and the results showed that when the amount of CTAB was 1.0 CEC of MMT, the weight ratio of CMC to OMMT was 11, the reaction time was 6 h, and the reaction temperature was 60, the nanocomposite showed a high adsorption capacity. The maximum adsorption capacity was 171.37 mg/g. As a novel nanocomposite material, the CMC/OMMT nanocomposite is a promising biosorbent for the removal of dyes from wastewater.
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