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Preparation of Ag-containing ACF and its Application for Dye Removal

Lirong Yao PhD1,2, Xiaojuan Li2, Guangyu Zhang PhD2, Shanqing Xu2, Dehong Cheng PhD1, Yanhua Lu PhD1

1Eastern Liaoning University, Dandong, Liaoning CHINA

2School of Textile and Clothing, Nantong University, Nantong, Jiangsu CHINA

Correspondence to:

Yanhua Lu email: yanhualu@aliyun.com

ABSTRACT Silver containing activated carbon fiber (Ag/ACF) has excellent adsorption properties for removing dyes. Silver particles are loaded onto ACF after carbonization and activation at present, and the fibers have low washing resistance and impurities are introduced onto ACF. In this research, pre-treatment techniques were used. Nano-silver solution with a particle size about 10 nm was prepared by using β-cyclodextrin as a stabilizer and reducer, and then the nano-silver solution was used as pretreatment liquid for modifying viscose fiber. Nano-silver particles with functional groups have high activity and can be readily adsorbed on the surface of viscose fibers. Ag/ACF was successfully prepared by carbonizing and activating the Ag-containing viscose fiber. The number and content of nano-silver particles on the surface of ACF was controlled by changing the concentration of nano-silver solution. The results show that the Ag/ACF have a high washing resistance and more efficiently remove methyl orange (MO) and methylene blue (MB) than ACF. Keywords: β-cyclodextrin, Nano-silver, Viscose, Ag/ACF, adsorption property INTRODUCTION Activated carbon fibers (ACF) are widely used in separation, purification, and catalytic processes due to extended specific surface areas, high adsorption capacity, highly porous structure, and unique surfaces [1-2]. However, ACF is slow to remove dyes from aqueous solutions [3]. Therefore, many efforts have been made to prepare metal-containing ACF by various surface treatment methods [4, 5]. In practical applications [6-8], there are three key points in the preparation of the metal/ACF materials: (1) conserving the high specific surface area of the ACF after metal loading, (2) high antibacterial activity and (3) high washing resistance. As reported in the

literature [9-16], reprocessing is regularly used to load nano-silver particles onto the surface of ACF, that is, Ag-containing processing was carried out after preparation of ACF. The problems of reprocessing are: (1) the silver particles have low washing resistance because of the weak bonding between Ag particles and ACF, (2) the nano-silver particles have nonuniform distribution on the surface of ACF, (3) some impurities will be introduced into the ACF during reprocessing and they are difficult to remove. β-cyclodextrin, consisting of six glucose units having a toroid-shape molecular structure that can form non covalent host-gust complexes with various molecules, can be used as a stabilizer and reducer for preparation of silver nano particles, The functional hydroxyl groups introduced result in high reactivity [17, 18]. After preparing nano-silver particles with β-cyclodextrin, the functional particles are loaded onto the cellulose fiber [19, 20], and used for dye degradation [21]. In this paper, stable nano-silver with functional groups was prepared and used to prepare Ag-containing viscose fiber, resulting in good bonding between the metal ions and the ACF during carbonization and activation. The Zetasizer Nano ZS system, TEM, FTIR, XRD, SEM, XPS were used to characterize the silver nanoparticles and Ag/ACF. The effects of initial dye concentration, amount of adsorbent, contact time and pH on the ability of the ACF and Ag/ACF to remove MO and MB were investigated. EXPERIMENTAL Materials Analytical grade silver nitrate (AgNO3), hydrochloric acid (HCl), hydrochloric acid (NaOH) and

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β-cyclodextrin were purchased from Sinopharm Chemical Reagent Co. Ltd. (China). Viscose fiber was obtained from the Fulida Group (China). Nitric acid solution was purchased from Scas Ecoscience Technology Inc. (China). METHODS Preparation of Nano-silver Solution AgNO3 and β-cyclodextrin were separately dissolved in deionized water. Then AgNO3 aqueous solution was added dropwise into β-cyclodextrin aqueous solution under vigorous stirring to form a nano-silver solution [22]. The solution was diluted to 100 ppm, 500 ppm and 1000 ppm, respectively for subsequent use. Preparation of Ag-containing Viscose Fiber Viscose fiber was immersed in nano-silver solution with constant stirring for 80 min at 90℃, then washed with tap water several times to remove unstable silver. After dehydration, the prepared Ag-containing viscose fiber was oven-dried at 110℃ for 8h to remove as much water from the fiber as possible. Preparation of Ag/ACF Precursor fibers were impregnated with (NH4)2HPO4, and heated up 850℃ under nitrogen for carbonization. Steam was then introduced under constant temperature to activate them [23]. The Ag-containing ACF were designated ACF-100, ACF-500 and ACF-1000 after pretreatment with 100 ppm, 500 ppm and 1000 ppm nano-silver solution, respectively. Characterization of Silver Nanoparticles Samples were prepared by evaporating a nano-silver solution onto a 200 mesh copper grid coated with a carbon support film. A Tecnai G220 Transmission Electron Microscope (TEM, USA) operating at 300 kV accelerating voltage was used. The Zetasizer Nano ZS system (90Plus Zeta) from Brookhaven Company (USA) was used to test the size distribution of nano-silver solution and the Zeta potentials of MO or MB solution. UV-vis spectra from 200-900nm were obtained through UV/visible adsorption spectrophotometry.

Scanning Electron Microscopy (SEM) A Hitachi scanning electron microscope (model S-570, LaB6 gun, Kevex X-ray EDS) was used to characterize the morphology of nano-silver particles on the surface of samples.

X-ray Photoelectron Spectroscopy (XPS) The surface composition and chemical binding energies were evaluated using a XSAM 800 X-ray Photoelectron Spectroscope with VISION software for data acquisition and CASAXPS software for data analysis. The analysis was carried out with a monochromatic Mg Ka X-ray source (1253.6 eV), operating at 12 kV (15 mA), in FAT mode (Fixed Analyzer Transmission), with a pass energy of 100 eV, 100 mS per 0.1 eV, under vacuum of 2×10-7 Pa. Fourier Transform Infrared (FTIR) A Nicolet Nexus (Ramsey, MN) 470 Fourier transform infrared spectrophotometer with a resolution of 4 cm-1 was used to record the FTIR spectra. The samples were dried at 80℃ in vacuum for 2 h before testing. X-ray Diffraction (XRD) The samples are measured with D/MAX3C X-ray detector at voltage of 40 kV, current of 30 mA and scan rate of 2o/min. Bet Measurement The specific surface area and pore size of Ag/ACF were measured by Automatic Adsorption Apparatus (ASAP 2010, Micromeritics, USA). Samples were degassed at 300℃ for 12 h before the measurements. The BET and pore size were calculated according to N2 adsorption-desorption measurements at 77 K. Ultrasonic Washing Ag/ACF was washed under ultrasound 40 times (40 kHz and 5 min per cycle). Ag Content on ACF In accordance with EPA 3052-1996, the content of Ag on ACF was measured using an Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES, Varian Company, USA). Adsorption Properties of Ag/ACF The effect of variables such as initial dye concentration, amount of adsorbent, contact time and pH on the adsorptive removal of dye was investigated. The adsorption studies were carried out by shaking Ag/ACF and dye at pH = 7 solutions at 400 rpm for different times. The solution pH was adjusted with 0.1 M HCl or 0.1 M NaOH solution. The supernatant solution was isolated by centrifugation at 5000 rpm for 15 mins. The concentration of the residual dye was determined spectrophotometrically by monitoring the absorbance at 660 nm. Effect of pH

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on the adsorption of dye onto Ag/ACF was studied at 500 mg L-1 concentration. The effect of contact time was studied by withdrawing samples from the shaker at predetermined time intervals in the range of 0-190 min. The nonadsorbed dye concentration was then quantified. The effect of adsorbent mass was studied using different adsorbent doses (0.05-0.25 g/50 mL) of 100-600 mg·L-1 dye concentrate. The dye removal percentages were calculated using the following equation [24]:

Dye removal (%) = C

CC t−×100 (1)

Where C and tC are dye (MO or MB) initially and time t, dye concentration, respectively. RESULTS AND DISCUSSION Preparation and Characterization of Silver Nanoparticles Nano-silver solution was prepared by adding AgNO3 aqueous solution to β-cyclodextrin aqueous solution under vigorous stirring at 90°C. The Schematic diagram of the formation of Ag nanoparticles is shown in Figure 1. During the formation of silver nanoparticles, the electrostatic attractive force between Ag+ and β-cyclodextrin plays an important role [25], and the Ag+ ions are reduced to silver nanoparticles under stirring at high temperature. The silver nanoparticles have better dispersion and stability and higher reactivity as a result of the introduction of hydroxyl groups as shown in Figure 1.

FIGURE 1. Schematic diagram of formation of Ag nanoparticles.

Figure 2 presents TEM photographs of silver nanoparticles. The images in Figure 2 show that the diameter of silver nanoparticles are about 10nm in diameter, are uniform in shape and well dispersed. The data in Figure 3 further confirms that the Ag nanoparticles prepared have a narrow particle size distribution in the range of 7 µm ～ 12 µm.

The UV-vis adsorption spectra in Figure 4 exhibit the characteristic adsorption peak of nano-silver solution at 407.08 nm, confirming the nanocrystalline character of the Ag nanoparticles.

FIGURE 2. Morphology of Ag nano particles (TEM).

FIGURE 3. Size distribution of Ag nano particles.

FIGURE 4. UV-vis adsorption spectra of Ag/HBP aqueous.

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Morphology of Ag/ACF The schematic diagram of hydrogen bond formation between hydroxyl groups on the silver nanoparticle and viscose fiber is shown in Figure 5. The electrostatic force promotes attraction between the silver nanoparticles and viscose fiber because of the positive charge on the surface of the silver nanoparticles and negatively charged hydroxyl groups on the viscose fiber [25]. Such forces cause the particles to penetrate into the pores and grooves on the viscose fiber. Hydrogen bonds will form between the hydroxyl groups surrounding the particles, and the size of silver nanoparticles, accessibility to the viscose fiber and activity of the hydroxyl groups are the main factors influencing the combination and distribution of nanoparticles on the surface of the viscose fiber.

FIGURE 5. Scheme process of preparing Ag-containing viscose fiber.

SEM photographs of ACF before and after nano-silver solution treatment are showed in Figure 6. No silver particles are observed on the smooth surface of the untreated ACF, however, the number of Ag particles increases significantly after pretreatment as the concentration of the nano-silver in the solution increases. Two characteristics are notable in the photographs of Ag/ACF: (1) the Ag particles distribute along grooves in the surfaces of the viscose fibers. This may be due to the activity of the nano-silver particles and the capillary effects- the nano-silver particles will travel along grooves under capillarity action in aqueous solution. (2) The Ag particle size will increase with increasing concentration of the nano-silver solution- weight loss and shrinkage occur when the viscose fiber carbonized and the nano particles are activated and will be reunited during carbonization. Therefore, the carbonizing temperature and heating rate have an important effect on the particle size and distribution on the surface of ACF. (c)

FIGURE 6. Morphology of Ag/ACF. (a) untreated; (b) treated with nano-silver solution (100 ppm); (c) treated with nano-silver solution (500 ppm); (d) treated with nano-silver solution (1000 ppm).

Table I presents parameters used to prepare Ag/ACF. The data in Table I shows that the Ag content on ACF increases when the concentration of nano-silver solution increases and the ACF has a higher surface area than Ag/ACF. However, the surface area of Ag/ACF decreases and the mean pore size of Ag/ACF increases, which may contribute to the damage of pore structure during carbonization and activation and loading of Ag nanoparticles onto the surface of the viscose fiber.

TABLE I. Parameters of Ag/ACF.

Samples SBET (m2/g)

Mean pore size (nm)

Ag content (µg/g)

ACF 1279.24 2.0187 0 Ag/ACF-100 1235.41 2.2055 212 Ag/ACF-500 1154.53 2.4314 1835 Ag/ACF-1000 1072.16 2.5612 3520

In order to investigate the washing resistance of nano-silver particles on the ACF, ultrasonic washing was used. The results are shown in Figure 7. About 9.6 wt. % loss is found after washing 40 cycles at 40 kHz and 5 min per cycle. The results indicate that the nano silver particles on the surface of ACF have a high washing resistance.

(b)

(d)

(a)

(c) (d)

(a)

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FIGURE 7. Ag content of ACF under ultrasonic washing (Ag/ACF-1000).

XPS Analysis Figure 8 shows the XPS analysis of Ag/ACF before and after carbonization. Three Ag peaks are found in Ag/ACF. Ag is known to exhibit an Ag3d spectrum with Ag peak at 372.8 eV (Ag0

3/2), an Ag3p spectrum with Ag peak at 572.6 eV (Ag0

3/2) and an Ag4s spectrum with Ag peak at 1134.6 eV [12]. The results indicate that elemental Ag was introduced on the surface of Ag/ACF, the nano-silver particles on ACF were metallic silver and the valence of the silver is zero. Stronger Ag peaks are observed after carbonization, indicating that the relative content of elemental Ag increased. However, new N peak was observed in XPS photographs of Ag/ACF, which may be due to the nitrogen used during carbonization.

FIGURE 8. XPS analysis of Ag/ACF (viscose fiber treated with 1000 ppm nano-silver solution) (a) before carbonization; (b) after carbonization.

FTIR Analysis The FTIR spectra of viscose fiber loaded nano silver particles before and after carbonization are shown are Figure 9. A number of adsorption peaks around 3400 cm-1 in the spectrum of the viscose fiber indicate the existence of bonded hydroxyl groups. The peak observed at 2850 cm-1 can be assigned to C-H groups. The peak observed at 1742 cm-1 is due to C-O. The peak with an approximate maximum around 1424 cm-1 is due to the symmetric bending of CH3. After loading with nano-silver particles, the characteristic peaks of viscose fiber, such as the peak around 2950 cm-1 attributed to C-H stretching, peaks at 1060 cm-1 (O-H distortion vibration), 1235 cm-1 (O-H in-plane bending) and 1282 cm-1 (C-H deformation stretch vibration), 1164 cm-1 (asymmetry bridge bond C-O-C stretch vibration) decrease and the peak at 3400 cm-1 attributed to O-H stretching becomes more sharp.

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These changes are a result of the hydrogen bonds formed between the silver nanoparticles and viscose fiber (shown in Figure 5). After carbonization the characteristic peaks of viscose fiber all disappeared.

FIGURE 9. FTIR curve of Ag/ACF (viscose fiber treated with 1000 ppm nano-silver solution) (a) before carbonization; (b) after carbonization.

X-Ray Diffraction The X-ray diffraction (XRD) pattern of Ag/ACF is shown in Figure 10. No crystal peak was observed in the case of ACF; however, the pattern exhibits peaks at 2θ angles of 37.95, 44.18, 64.19, and 77.23 that correspond to the [111], [200], [220], and [311] crystal planes of a cubic lattice structure of silver nanoparticles, respectively. The results of the XRD analysis indicate that the pure silver particles are loaded on the ACF.

FIGURE 10. XRD curve of ACF and Ag/ACF (viscose fiber treated with 1000 ppm nano-silver solution). Adsorption Properties

The effect of initial dye concentration on removal of MO and MB by absorption is shown in Figure 11, with ACF as the control sample. As shown, the

removal MO and MB decreases with increasing initial concentration of dye and decreases sharply for ACF when the initial concentration of MO and MB reaches 500 mg/L. However, the adsorption capacity of Ag/ACF does not decrease at concentrations of MO and MB greater than 600 mg/L, indicating improved dye removal at similar conditions.

FIGURE 11. Effect of initial dye concentration on removal of MO and MB by Ag/ACF (0.1 g ACF and Ag/ACF-1000 in pH=7, 50 ml dye solution at 25℃ for 120 min).

Figure 12 shows the effect of adsorbent dose on removal of MO and MB. The levels of adsorbents used were 0.05 g, 0.1 g, 0.15 g, 0.2 g, 0.25 g, respectively. From Figure 12, it is notable that the removal of MO and MB increases with increasing adsorbent up to a level of 0.1 g adsorbent. Levels of 97.5 % MB and 85.4 MO can be removed by Ag/ACF when 0.05 g adsorbent is used; however, only 76.6 % MB and 72.8 MO are be removed by ACF at the same condition. This means that fewer Ag/ACF will be needed to remove equivalent amounts of dye as compared to ACF.

FIGURE 12.Effect of adsorbent dose on removal of MO and MB by Ag/ACF (ACF and Ag/ACF-1000 in pH=7, 50 ml 500 mg/L dye solution at 25℃ for 120 min).

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The effect of contact time on removal of MO and MB are shown in Figure 13. Contact time studies can provide higher understanding of the amount of dye adsorbed at various time intervals by a fixed amount of the adsorbent. First, it is notable that ACF shows a slow, gradual absorption over time, while Ag/ACF exhibits an initial rapid adsorption. The rapid adsorption at the initial contact time is due to the more active surface of the Ag/ACF, which leads to fast adsorption (30 min) of the dye from the solution at pH 7.0. The silver nanoparticles on the surface of ACF have a synergistic reaction with ACF [26, 27]. The later slow rate of dye adsorption probably occurred due to lower availability of active sites on the surface of adsorbent as well as slower pore diffusion of the solute into the adsorbent. The stepwise adsorption process consists of migration of the dye molecules that had diffused into the adsorbent surface to the boundary layer followed by movement into the porous structure of the adsorbent.

FIGURE 13. Effect of contact time on removal of MO and MB by Ag/ACF (0.1 g ACF and Ag/ACF-1000 in pH=7, 50 ml 500 mg/L dye solution at 25℃).

The zeta potentials of the samples at different pH values are shown in Figure 14. The surface of ACF is positively charged when solution pH＜6.5 and is negatively charged when solution pH＞6.5. The zeta potential of ACF increases after loading with nano-silver particles, resulting in improved electrostatic attraction between dyes. Figure 15 shows the effect of pH on adsorption properties. The adsorbents used show significantly different capabilities to remove MO and MB. The adsorption of MO decreases with increasing pH, however, the absorption of MB increases. This may be due the difference in charge between MO (acid dye) and MB (basic dye). The charge and subsequent adsorption of a given dye onto the ACF or Ag/ACF

surface can be accompanied by electrostatic interaction and/or chemical reaction. Therefore, the initial pH of the MO or MB solution controls the adsorption rate and capacity by changing the surface charge of the adsorbent.

FIGURE 14. Zeta potentials of samples under different pH (500 mg/L MO and MB solution at 25℃).

FIGURE 15. Effect of pH on removal of MO and MB by Ag/ACF (0.1 g ACF and Ag/ACF-1000 in 50 ml 500 mg/L dye solution at 25℃ for 120 min). CONCLUSION A nano-silver solution was successfully prepared by using β-cyclodextrin as a stabilizer and to reduce Ag+ to silver nanoparticles. The nano-silver solution was used to pretreat viscose fibers and Ag-containing activated carbon fibers (Ag/ACF) were produced by carbonization and activation. The results from TEM, UV-vis spectra and particle size analysis show that uniform spherical silver nanoparticles with a particle size about 10 nm and a narrow size distribution were prepared. SEM images show that the number of Ag nanoparticles increases significantly when the concentration of nano-silver solution increases. XPS data indicates that the Ag+ is reduced to Ag0. XRD

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results show that crystal planes of a cubic lattice structure of silver nanoparticles are formed on the ACF. The treated fibers show a high washing resistance under ultrasound application. Initial dye concentration, amount of adsorbent, contact time and pH are the main factors eaffecting the adsorption properties of ACF and Ag/ACF. The Ag/ACF has a stronger and more rapid adsorption of MO and MB over 30 min than ACF (no decrease even though the concentration of MO and MB is larger than 600 mg/L). Amounts of MO and MB removed differed as a function of the pH of the dye solution. ACKNOWLEDGMENT This work was supported by Liaoning Provincial Key Laboratory of Functional Textile Materials, National Natural Science Fund (51503105). REFERENCES [1] Liu, W.; Adanur, S.; Desulfurization Properties

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AUTHORS’ ADDRESSES Lirong Yao PhD Guangyu Zhang PhD Xiaojuan Li Shanqing Xu School of Textile and Clothing Nantong University Seyuan Road 9 Nantong, Jiangsu 226019 CHINA Yanhua Lu PhD Dehong Cheng PhD Liaoning Provincial Key Laboratory of Functional Textile Materials Eastern Liaoning University Wenhua Road 325 Dandong, Liaoning 118001 CHINA