Accepted Manuscript

Adsorption removal of anionic dyes from aqueous solutions by chitosan nanoparticles

deposited on the fibrous carrier

Irina M. Lipatova, Larisa I. Makarova, Anna A. Yusova

PII: S0045-6535(18)31639-4
DOI: 10.1016/j.chemosphere.2018.08.158
Reference: CHEM 22076

To appear in: ECSN

Received Date: 28 June 2018

Revised Date: 28 August 2018
Accepted Date: 30 August 2018

Please cite this article as: Lipatova, I.M., Makarova, L.I., Yusova, A.A., Adsorption removal of anionic
dyes from aqueous solutions by chitosan nanoparticles deposited on the fibrous carrier, Chemosphere
(2018), doi: 10.1016/j.chemosphere.2018.08.158.

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 ACCEPTED MANUSCRIPT
Adsorption removal of anionic dyes from aqueous solutions
by chitosan nanoparticles deposited on the fibrous carrier

Irina M. Lipatova, Larisa I. Makarova, Anna A. Yusova

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PET fiber

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chitosan Adsorption of
anionic dyes
nanoparticles
CPF

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 ACCEPTED MANUSCRIPT
1 Adsorption removal of anionic dyes from aqueous solutions by chitosan nanoparticles

2 deposited on the fibrous carrier

4 Irina M. Lipatova*, Larisa I. Makarova, Anna A. Yusova

5 G.A. Krestov Institute of Solution Chemistry of Russian Academy of Sciences (ISC RAS),

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6 1, Akademicheskaya St., Ivanovo, 153045, Russia

7 *Corresponding author.

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8 E-mail address: i_lipatova@bk.ru

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9 Abstract

10 The synthesis, characterization and environmental application of chitosan based material

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11 stable in acidic media for adsorption of anionic dyes were investigated. The adsorption material
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12 is chitosan nanoparticles immobilized on a fibrous carrier (CPF). The choice of optimal

13 conditions for the preparation of chitosan particles and their immobilization on a chemically
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14 activated PET fiber is justified. Immobilized nanoparticles showed high adsorption rates and dye

binding capacity (300-1050 mg/g) depending on the dye type. As model adsorbates, anionic
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15

16 phthalocyanine dyes having different molecular sizes, different nature and number of anionic
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17 groups were used. The experimental isotherm data and a linear correlation coefficients (rL2 >
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18 0.99) showed that the adsorption of dyes on CPF was best predicted by the Langmuir isotherm.

19 The rate of adsorption was found to conform to pseudo-second-order kinetics with a good
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20 correlation (R2 > 0.99) with intra-particle diffusion as one of the rate determining steps. It is
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21 established that the sorption rate and the limiting sorption capacity decrease with increment of

22 size of the dye molecules. The process of adsorption of dyes on the CPF is pH-insensitive at pH

23 range of 2–8. The adsorption saturated CPF could be effectively regenerated by a simple alkaline

24 washing.

25

26 Keywords: adsorption, anionic dyes, chitosan nanoparticles, fibrous carrier.

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27 1. Introduction

28 The problem of industrial wastewater treatment, in particular in the textile and chemical

29 industries, has been receiving increasing attention in recent years. Wastewaters from dyeing

30 industries contain residual synthetic dyes that are resistant to aerobic digestion, and stable to

31 oxidizing agents (Hassan and Carr, 2018; Manu and Chaudhari, 2002; Mezohegyi et al, 2012).

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32 Moreover, many dyes and their degradation products have been associated with toxicity and/or

33 mutagenicity (Weisburger, 2002). The main methods of removing dyes from water are

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34 biodegradation (Manu and Chaudhari, 2002), chemical coagulation (Khouni et al, 2011),

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35 ozonolysis (Turhan and Turgut, 2009), photocatalytic oxidation (Shen et al, 2010), and sorption

36 (Annadurai et al, 2002; Hassan and Carr, 2018; Ho and McKay, 1998; ; Liu et al, 2017 Mall et

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37 al, 2005; Pant et al, 2014). The latter method, due to efficiency and cheapness, is considered as
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38 the most promising (Hassan and Carr, 2018). To remove dyes from water, both sorbents obtained

39 from natural raw materials (Annadurai et al, 2002; Güzel et al, 2014; Ho and McKay, 1998; Mall
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40 et al, 2005) and new synthetic composite sorbents (Liu et al, 2017; Pant et al, 2014) are used. It

41 is known that the activated carbon, traditionally used in sorption technologies, as well as most
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42 sorbents of natural origin, sorb more effectively cationic dyes (Annadurai et al, 2002; Hassan
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43 and Carr, 2018; Ho and McKay, 1998; Mall et al, 2005). However, an important place in
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44 coloring technologies is occupied by anionic dyes.

45 In recent years, a number of studies have demonstrated that a cationic biopolymer

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46 chitosan and composites based on it have a high ability to adsorb anionic dyes (Crini and Badot,
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47 2008; Vieira et al, 2018). Сhitosan is a low-cost and cost-effective material which could be

48 obtained from the wastes of the seafood processing industry (Crini and Badot, 2008). Various

49 chitosan-based composites have been designed to increase the efficiency of adsorption and

50 overcome of hydrodynamic limitations (Copello et al, 2011; Nesic et al, 2012). Chitosan, the

51 partial deacetylation product of chitin, is a polysaccharide composed by polymers of

52 glucosamine and N-acetyl glucosamine (Muzzarelli and Muzzarelli, 2005). The functional amino

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53 group provides chitosan an outstanding capacity and high rate of adsorption (Muzzarelli and

54 Muzzarelli, 2005; Rinaudo, 2006; Wong et al, 2008). The disadvantages of chitosan include the

55 lack of porosity and high sensitivity to changes in pH (Crini and Badot, 2008; Muzzarelli and

56 Muzzarelli, 2005). Chitosan begins to dissolve in water already at pH <5.5 (Muzzarelli and

57 Muzzarelli, 2005). The insolubility of chitosan in acidic media can be achieved through the use

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58 of polyanionic cross-linkers, such as alkali metal phosphates and sulfates. The introduction of

59 these salts into solutions with low polymer concentration leads to the formation of fine

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60 dispersions of submicron chitosan particles (Al-Remawi, 2012; Mezina and Lipatova, 2015;

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61 Tavares et al, 2012), which have a high ability to adsorb anionic organic compounds (da

62 Trindade et al, 2005; Fernandes et al, 2005). The results of preliminary studies (Lipatova and

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63 Moryganov, 2017; Mezina and Lipatova, 2015) allowed the authors of this work to assume that it
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64 is possible to obtain an environment-friendly sorbent with high sorption characteristics and

65 stability in acidic media by immobilization of chitosan particles on a fibrous carrier.

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66 The aim of this work was deposition of chitosan on the surface of fibrous carrier in the

67 form of a layer of nanoparticles and to study of the sorption ability of chitosan particles
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68 immobilized on a fiber (СPF) with respect to anionic dyes. As model adsorbates, anionic
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69 phthalocyanine dyes having different molecular sizes, different nature and number of anionic
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70 groups were used.

71
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72 2. Materials and methods

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73 2.1. Dyes and polymeric materials

74 As model of adsorbates anionic dyes, which are sulfo- and carboxy-substituted

75 phthalocyanines (Pc), were used. Samples of industrial dyes Direct blue-86 and С.I. Reactive
76 Blue 21 were purchased from “ARGO-C” (Ufa, Russia). Samples of sulfo-Al(OH)
77 phthalocyanine and octacarboxy-Co(II) phthalocyanine dyes were kindly supplied by the
78 Institute of organic Intermediates and Dyes (Moscow, Russia). Formulas and characteristics of
79 used dyes are given in Table 1. Тhe chemical structure of used dyes is given in supplementary
80 data (Fig.S1).
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81 Table 1.

82 Characteristics of used dyes.

abbreviation Formula commercial name λmax (nm) Purity (%) M.W. (g·mol-1)

DB CuPc(SO3Na)2 Direct blue-86 665 65 780

PS Al(OH)Рс(SO3Na)3 Photosens 679 98 863

TP СоPc(СООNa)8 675 97 1095

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Theraphthal

RB CuPc(SO3Na)2R1 *) С.I. Reactive Blue 21 664 55 1342

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*) R1=O2S NH SO2-CH2-CH2-O-SO3Na
83

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84 In the work was used chitosan (Sigma-Aldrich (USA)) with average-viscosity molecular

85 weight of 195 000 and a degree of deacetylation 85% according to the potentiometric titration

86
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Тhe carrier was industrial polyethylene terephthalate fiber (PET) (Serpukhov, Russia) in
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87 the form of a beam. The length of individual fibers was from 50 to 70 mm, and the diameter

88 values varied from 15 to 18 µm.

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89
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90 2.2. The preparation of dispersions of chitosan particles

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91 The initial chitosan solution was obtained by dissolving 0.4 g of chitosan in 100 mL of a

92 0.1M acetic acid solution. The dissolution was performed for 2 h with continuous stirring at
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93 room temperature, after which the solution was allowed to stand for 20 h. Chitosan nanoparticles

94 were formed using sulfate anions as crosslinking bridges. Chitosan sulfate aqueous dispersions
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95 were prepared by mixing a solution of chitosan with a solution of MgSO4·7H2O at a fixed

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96 concentration in a volume ratio of 1:1 with stirring. The concentration of chitosan in the mixtures

97 remained constant and was 2 g L-1. The parameter varied in this study was the ratio between the

98 sulfate anions from the MgSO4 solution to the amine groups from chitosan (rS/A), defined as

nSO 2− CMgSO4 ⋅ VMgSO4

99 rS / A = 4
= , (1)
nNH 2 M MgSO4 ⋅ nNH 2

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100 where nNH2 is the number of moles of amino groups in chitosan solution, and MMgSO4 is the molar

101 mass of magnesium sulfate. The parameter rS/A was controlled by varying the concentration of

102 magnesium sulfate, CMgSO4.

103

104 2.3. Сharacterization of chitosan sulfate dispersions

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105 The size of chitosan sulfate nanoparticles in aqueous dispersions was determined by the

106 method of dynamic light scattering and the ζ-potential by electrophoretic light scattering using

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107 Malvern ZetaSizer Nano (UK) equipment at 25°C with He–Ne 10 mW laser at the wavelength of

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108 633 nm. To prevent the aggregation of particles before the measurements, the dispersions were

109 diluted with distilled water in a ratio of 1:5.

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110
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111 2.4. Immobilization of chitosan-sulfate particles onto PET fiber

112 To increase the efficiency of particle immobilization, surface activation of the PET fiber
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113 by the method of weakly alkaline hydrolysis was used. The PET fiber was treated with aqueous

solutions of NaOH with concentration 0.125 mol·L-1 at the boiling point for 15 min. After
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114
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115 processing, the fiber was washed to neutral reaction of the wash water and then dried. Weighted

116 fiber sample was immersed in the chitosan-sulfate dispersion at the turbidity beginning point (5-
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117 7 minutes after mixing solutions of chitosan and salt) and aged for 5 min. The fiber was then

118 recovered from the dispersion, dried at T=50°C, and heat treated at T=130°C for 3 minutes. The
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119 resulting СPF was washed in distilled water to remove salts and poorly fixed particles, dried and
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120 weighed again to determine the weight of the deposited chitosan-sulfate particles. The weight of

121 the deposited particles was 10-12% by weight of the fiber weight.

122

123 2.5. AFM and SEM

124 The formation of a chitosan-sulfate particles layer from a mixed aqueous solution of

125 Сhitosan with MgSO4 was controlled by Atomic Force Microscopy (AFM). A thin layer of the

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126 precipitate was obtained by holding the PET substrate in a layer of a mixed solution of thickness

127 0.7 cm (concentration of chitosan was 2 g L-1; rS/A=0.85) for 30min. After this, the substrate was

128 carefully removed and dried in air at room temperature. The AFM-image of precipitation was

129 obtained by a semi-contact method using a Solver P47 PRO scanning probe microscope with a

130 resolution of the order of 1 nm.

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131 Scanning electron microscopy (SEM) was performed using a scanning electron

132 microscope Vega 3 SBH (Czech Republic) with a prefix for elemental analysis at a

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133 magnification of 852 times.

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134

135 2.6. Kinetics studies

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136 Batch sorption experiments were carried out in 250-mL conical flasks in the thermostatic
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137 shaker and maintained at temperature 25oC. The experiment was performed at pH range of 2.0–

138 11.0 which was adjusted using 0.1M HCl or 0.1M NaOH. Samples of CPF containing 0.006-
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139 0.007 g of immobilized chitosan particles were immersed in 90-100 ml of the dye solution. For

140 all dyes, the initial concentration was 50 mg·L-1. Samples of 1.0 mL were collected from the
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141 duplicate flasks at required time intervals and were analyzed for residual dye concentration in the
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142 solution using an UV–VIS spectrophotometer. The amount of dye adsorbed on the CPF, qe
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143 (mg·g-1), was calculated by a mass balance relationship:

144 qe =
(Co − Ce ) ⋅ V , (2)
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W
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145 where Co and Ce are the initial and equilibrium liquid-phase concentrations of dyes,

146 respectively (mg·L−1), V is the volume of the solution (L), and W is the weight of the dry

147 chitosan particles used (g).

148

149 2.7. Sorption isotherms

150 The isotherm studies were performed by varying the initial dye concentration from 10 to

151 130 mg L−1. Experiments were carried out in 100-mL conical flasks at temperature 25oC, at
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152 pH4.0 and pH6.0. Samples of CPF containing 0.002-0.003 g of immobilized chitosan particles

153 were immersed in 30-45 ml of the dye solution. The ratio of the volume of solution to the mass

154 of the particles in all cases was 15000. After reaching equilibrium, the residual concentration of

155 the dye in each flask was measured.

156

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157 3. Results and discussion

158 3.1. The sorbent obtaining

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159 3.1.1. Preparation of chitosan-sulfate nanoparticles

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160 At the first stage of the work, the task was to optimize the conditions for obtaining

161 dispersions of chitosan particles for application to a fibrous carrier. Chitosan nanoparticles were

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162 formed using sulfate anions as crosslinking bridges. At a given constant concentration of
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163 chitosan in mixtures (2 g·L-1), the molar ratio rS/A is the main factor determining the parameters

164 of the process and the characteristics of the particles. The crosslinking reaction between the
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165 protonated amino groups of chitosan and sulfate anions can be represented by the scheme:

166 [С6Н9О4-NH3+ ]n + n/2 SO42- → [С6Н9О4-NH3---SO4---NH3-С6Н9О4]n/2 ↓

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167 Fig. 1(а) shows optical microscopic image of the dispersion of chitosan-sulfate particles
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168 after 30 min from the moment of mixing of solutions of chitosan and salt at rS/A=0.85. The
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169 presented photograph shows the propensity of particles to form aggregates.

170
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(a) (b)
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(B)

2 µm

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(с) (d)

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171 Fig.1. Images of chitosan-sulfate particles (a) in an aqueous dispersion (optical microscopy), (b)

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172 on the surface of fibers (ECM), (c) on a PET substrate (AFM); (d) AFM image of a coating

173 obtained from a solution of non-crosslinked chitosan.

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174 To determine the yield of particles, mixtures of different compositions were left for 24

175 hours, then the dispersed solid phase was separated by centrifugation and dried to constant

176
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weight. The yield values of the particles were calculated as the ratio of the actual mass of the
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177 isolated particles to the maximum possible in accordance with the crosslinking reaction scheme
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178 set forth above. It was found that the yield of particles is significantly reduced with decreasing

179 rS/A (see Table 2). In addition, for mixtures with different ratios rS/A after reaching the
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180 equilibrium turbidity value, the values of zeta potential (ζ) and average particle size (dav) were
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181 determined.

182 Table 2.
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183 Influence of the rS/A in the initial mix on characteristics of chitosan-sulfate particles.
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№ r S/A Yield (%) dav (nm) (+) ξ (mV)(рН4)

1 1:0.6 42.8 240±6.5 38±0.4
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2 1:0.75 68.2 280±6.6 32±0.5

3 1:0.85 90.7 340±8.3 26±0.4
4 1:1 94.1 480±18 18±0.4
5 1:1.3 98.2 650±40 8±0.4
184

185 The results are shown in Table 2. It can be seen that the increase in salt concentration

186 (rS/A) resulted in a decrease in values for the zeta potential. Bearing in mind that chitosan is a

187 cationic polyelectrolyte, surface charge can be expected to be positive and, as a consequence,

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188 zeta potential values as well. The incorporation of SO42− as the ionic crosslinking agent into the

189 particles would decrease zeta potential. As the surface charge of particles decreases, their

190 resistance to aggregation decreases. Therefore, as rS/A increases, the average particle size

191 increases.

192 A higher positive charge of chitosan-sulphate particles should contribute to their more

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193 efficient deposition on the fiber surface and a higher ability to adsorb anionic dyes. Particles with

194 a relatively high zeta potential were obtained from mixtures with low rS/A. However, for these

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195 mixtures, a low yield of particles were found (see Table 2). In addition, as we showed earlier

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196 (Mezina and Lipatova, 2014), at small values of rS/A, the mixtures of solutions remain transparent

197 for a long time because of the low rate of formation of the dispersed phase (see Fig. S2).

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198 Therefore, the molar ratio between the sulfate anions to the amine groups rS/A=0.85 was chosen
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199 as optimal and most suitable for obtaining the sorbent.

200
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201 3.1.2. Immobilization of chitosan-sulfate particles on a fibrous carrier

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202 It was previously reported that chitosan-sulphate particles can be well fixed on various
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203 synthetic and natural fibers (Lipatova and Moryganov, 2017). In this paper, we used PET fiber as

204 the carrier, which has a negligible adsorption for the used dyes. This allowed us to evaluate the
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205 adsorption characteristics of only a layer of chitosan particles, without taking into account the

206 contribution of the carrier to this process. To increase the efficiency of particle immobilization,
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207 we used chemical activation of the fiber due to its weak alkaline hydrolysis. According to the
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208 literature data as a result of hydrolysis of the surface layer of fiber an additional amount of

209 carboxyl and hydroxyl groups is formed and initially smooth surface of PET becomes rough (at

210 nanoscale level) that promotes adhesion of the coating to the polyester substrate (Prorokova et al,

211 2014).

212 The problem of preventing aggregation of particles was solved by immersing the fiber in

213 a mixture of solutions of chitosan and salt immediately at the first signs of the appearance of

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214 turbidity. It is known that the surface of PET fiber in water acquires a negative charge

215 (Jacobasch et al, 1985). At the time of formation, chitosan-sulphate particles have a very small

216 size and, accordingly, a high surface energy. The process of settling positively charged particles

217 on a negatively charged fiber surface is more preferable than their aggregation. After removing

218 the fiber from the mixture and drying, a dense layer of particles is formed on its surface, which

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219 can be seen with the help of ECM microscopy (Fig. 1b).

220 The particle layer is not destroyed by washing and with prolonged exposure to the dye

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221 solution. This can be explained by the fact that the particles don’t settle on the fiber in the form

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222 of a discrete coating, but form sections of a continuous layer around the fiber in the form of a

223 sleeve.

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224 Nevertheless, the continuous layer of particles has a much more developed surface in
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225 comparison with the film from the solution of non-crosslinked chitosan. To illustrate this, we

226 obtained two coatings by drying on a PET plate using a solution of non-crosslinked chitosan and
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227 a dispersion of chitosan-sulfate particles. (see AFM image, Fig. 1c,d).

228
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229 3.2. Adsorption study

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230 3.2.1. Adsorption kinetics

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231 The results of the adsorption kinetics of dyes on the CPF at pH4 and pH6 are shown in

232 Fig 2(a) and (b), respectively. As can be seen, the character and ratio of the kinetic curves for
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233 both pH values are similar. As shown in Fig. 2 (a,b), at the first 10 min, the adsorption amounts
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234 increased dramatically; afterwards, the adsorption rates became lower, indicating that the

235 adsorption gradually reached the equilibrium. The initial rates (h) of adsorption of dyes on CPF

236 (for the first 10 minutes) are presented in Table 3. It was found that the adsorption of dyes with

237 relatively small molecular size (DB and PS) is higher than that of dyes with larger molecules (TP

238 and RB). In Fig. 2 (c), kinetic curves for the adsorption of the RB dye on different substrates are

239 presented for comparison. It was found that the initial adsorption rate of RB on the CPF is 10

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240 times greater than that on the powder chitosan, 14 times greater than that on the activated carbon,

241 and 160 times greater than that on the pure PET fiber without chitosan particles.

242 To obtain the insights of adsorption mechanism, three kinds of kinetic models were

243 applied to analyse the experimental data, which were the pseudo-first-order equation, the pseudo-

244 second-order equation and the intraparticle diffusion equation. The suitability of using kinetic

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245 models was determined by linearizing data in the coordinates of their integral equations.

246

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800 (a) 800
(b) 200
(с)
700 700 175
RB on:

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600 600 150 CPF
DB

q (mg/g)
PS DB powder chitosan
500 500 125
PS
q (mg/g)

activated carbon
q (mg/g)

TP
400
RB 400 TP 100 pure PET fiber

300 300
RB
75

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200 200 50

100 100 25

0 0
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0
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
Time (min) Time (min) Time (min)

1200 1200
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(d) (e)
1000 1000

800 DB 800
DB
qe (mg/g)

PS PS
qe (mg/g)

600 TP 600
TP
RB RB
400 400
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200 200

0
0
0 10 20 30 40 50
0 10 20 30 40 50
Ce (mg/l)
Ce (mg/l)
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247 Fig.2. Kinetic plots for adsorption of dyes (Co=50 mg·L-1): (а) pH4, (b) pH6, (c) of RB dye on
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248 different substrates at pH6; adsorption isotherms of dyes on the CPF (d) pH4 and (e) pH6.
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249

250 The pseudo-first-order Lagergren (Ho and Mckay, 1999) equation for the adsorption of liquid-

251 solid system can be represented in the following form:

252 ln( qe − qt ) = ln qe − k1t , (3)

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253 where k1 is the rate constant of pseudo-first-order adsorption; qt (mg·g-1) and qe (mg·g-1) are the

254 adsorption amount of dyes at time t (min) and at equilibrium, respectively. The plots of ln(qe-qt)

255 versus t gives straight lines with k1 as the slope and ln qe as the intercept.

256 To describe the kinetic regularities of the adsorption of organic compounds from aqueous

257 solutions, the pseudo-second-order equation of Ho and McKay is widely used (Douven et al

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258 2015). In a linear expression, this equation has the following form:

 t  1 1
259   = + (t ) , (4)

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2
 qt  k2 qe qe

260 where k2 is the rate constant of pseudo-second-order equation. qt (mg·g-1) and qe (mg·g-1) are the

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261 adsorption amount of dyes at time t (min) and at equilibrium, respectively. From plots of t/qt

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262 versus t, the k2 values and qe values can be obtained.
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263 For a primary assessment of the role of intra- and externally diffusion-limited adsorption,

264 a quantitative approach based on the Morris-Weber equation can be applied (Weber and Morris,
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265 1963). The intra-particle diffusion equation is described in the following form:

1
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266 qt = k p ⋅ t + C ,
2
(5)
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267 where kp is the rate constant of intra-particle diffusion model; qt (mg·g-1) is the adsorption

268 amount of dyes at time t (min); C is a constant for the experiment (mg·g-1).
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3,0 800
1,8

(a) (b) (с)

DB 1,6 700

PS
C

2,5
1,4 600
TP
1,2 DB
RB 500
log(Ap-At)

PS
qt, mg|g

2,0
1,0 DB
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TP
t/qt

400
PS
1,5
0,8
TP RB
300
0,6 RB
200
0,4
1,0
100
0,2

0,5 0,0 0
0 50 100 150 200 250 300 0 50 100 150 Timе,
200 min
250 300 350 400 0 2 4 6 8 10 12 14 16 18 20 22
Timе, min t1/2, min1/2

269 Fig.3. Application of the pseudo-first-order equation (а), the pseudo-second-order equation (b)

270 and the intra-particle diffusion model (c) for the analysis of the dyes adsorption at pH4.

271

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272 The graphical representations of the linear forms of the above equations (Fig. 3) allow us

273 to estimate the suitability of the known kinetic models for describing the adsorption process

274 without a detailed consideration of the mechanism. Similar results were obtained for adsorption

275 at pH6 (not shown). Fig. 3 (b) shows a good compliance with the pseudo-second-order equation

276 and the regression coefficients for the linear plots were higher than 0.995 for all the systems.

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277 Rate constants for pseudo-second order are presented in Table 3.

278 The dependencies of qt versus t1/2 are shown in Fig.3 (c). As can be seen, the plots for DB

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279 and PS consist of three linear sections with different slopes. A similar multilinearity has been

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280 observed in other systems for the dyes adsorption onto chitosan/montmorillonite membranes

281 (Nesic et al, 2012), cellulose-based wastes (Annadurai at al, 2002), chitosan (Uzun, 2006),

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282 Kevlar based nanofibrous particles (Nie et al, 2016). In the cited papers, three stages of the
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283 adsorption process are distinguished. The external surface adsorption (first step) is less apparent

284 and in Fig. 3 (c) is not shown. The second step, which was controlled by intra-particle diffusion,
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285 was the gradual adsorption step. The third stage refers to the final equilibrium stage. It is noticed

286 that third stage is absent for dyes RB and TP. The much longer period of intra-particle diffusion
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287 for these dyes is likely due to large size of their molecules.
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288 Table 3.
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289 Parameters of anionic dyes adsorption on the CPF: at pH4 and pH6.
pH=4 pH=6
h *) k2 qmax KL h k2 qmax KL (L·-1mg)
C
Dyes

(mg·g-1 (g·mg−1·min−1) (mg·g-1) (L·mg-1) (mg·g-1 (g·mg−1·min−1) (mg·g-1)

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·min-1) ·min-1)
DB 76.52 0.00021 1097±55 0.735 57.32 0.00023 1052±4 0.973
PS 47.85 0.00012 1049±43 0.267 39.64 0.00010 980±47 0.288
TP 4.69 0.00013 367±22 0.575 10.02 0.00017 339±23 0.712
RB 7.38 0.00019 296±18 0.475 8.76 0.00014 302±18 0.817
290 *) h - initial adsorption rates
291

292

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293 3.2.2. Adsorption isotherms

294 The adsorption isotherm curves for all dyes at pH4 and 6 showed a Langmurian shape,

295 i.e., initial slope at the beginning and a plateau covering most experimental points (Fig.2 d,e)

296 The Langmuir model is based on the assumption that adsorption exists up to the

297 formation of a homogeneous monolayer of the adsorbate interacting with the sorbent

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298 (Kinniburgh, 1986). Langmuir equation has the following form:

qmax ⋅ K L ⋅ Ce
299 qe = , (6)

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1 + K L ⋅ Ce

300 where KL is the Langmuir constant and qmax is the maximum amount of adsorption

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301 corresponding to complete coverage on the surface. The Langmuir isotherm Eq. (2) can be

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302 linearized into the following form (Kinniburgh, 1986):
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Ce 1 1
303 = + , (7)
qe K L ⋅ qmax qmax
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304 The results obtained from the Langmuir model for the removal of used dyes at pH4 and 6 are

305 shown in Table 3. Linearity of the dependence in the Сe/qe-Ce coordinates (with a high
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306 correlation coefficient, R = 0.994–0.998) showed strong positive evidence on the adsorption of
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307 dyes follows the Langmuir isotherm.

308 As it is shown in Table 3, the adsorption capacity decreases with increasing size of the
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309 dye molecules. It can be assumed that smaller dye molecules are able to penetrate deeper into the
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310 internal porous structure of chitosan particles. A similar effect was observed in other systems of
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311 adsorption of basic dyes on chitin (Maghami and Roberts, 1988) and of acid dyes on chitosan

312 (McKay et al, 1982). Immobilized nanoparticles showed a high binding capacity (average 300-

313 1050 mg/g by weight of particles), depending on the type of dye. The weight of the precipitated

314 particles was 10-12% by weight of the fiber weight. Consequently, the adsorption capacity for

315 the entire material will be on average 33-115 mg/g.

316

317
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318 3.2.3. Effect of pH

319 As seen from Table 3, the experimental data on the adsorption of dyes at pH4 and at pH6

320 are comparable. This result is interesting because сhitosan-containing sorbents are in most cases

321 pH-sensitive. The ability of such adsorbents to adsorb anionic dyes increases with decreasing pH

322 due to an increase in the degree of protonation of amino groups and, accordingly, of surface

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323 positive charge (Rinaudo and Pavlov, 1999). The chitosan particles were charged positively,

324 although sulfate ions were used as precipitant. This indicates that only a part of the amino groups

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325 is neutralized during particles formation. The residual amino groups would be responsible for the

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326 positive zeta potential. In chitosan sulfate particles, most of the amino groups of chitosan are

327 bound to sulfate ions, so they are less sensitive to changes in pH than non-crosslinked chitosan.

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328 It was experimentally found that the values of the zeta potential at pH 4 and 6 are 24 and 8 mV,
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329 respectively (see Table 2). However, it should be taken into account that the pH value also

330 affects the associative state of the dyes in the aqueous solution.
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331 Phthalocyanine dyes are typical amphiphilic macrocyclic compounds (see Fig.S1), which

332 are prone to self-association due to hydrophobic and π-π-electron intermolecular interactions
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333 (Snow, 2003). In an aqueous solution of such compounds, there is an equilibrium between the
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334 monomeric and the dimeric forms (2М↔D). It is known (Al-Degs et al, 2008) that when the pH
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335 of a medium is lowered, the equilibrium in solutions of acidic dyes shifts towards the dimeric

336 form because of the decrease in the degree of dissociation of ionogenic groups (see Fig.S3). The
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337 PS dye has an axial OH-ligand, which prevents dimerization, so it is monomeric at all pH values.
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338 At pH6, the surface of chitosan-sulphate particles is largely hydrophobic because of the low

339 degree of protonation of amino groups. In addition, during the transition from pH4 to pH6, the

340 dye-dye interactions are attenuated. All this creates conditions for the realization of hydrophobic

341 interactions between the surface of particles and the aromatic system of dyes. Among the dyes

342 used, the exception is PS. The hydrophilic OH ligand present in the PS molecule (see Fig.S3)

343 weakens the hydrophobic interaction with the particle surface, so its adsorption at pH 6 is lower

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344 than at pH 4, as shown in Table 3. PS dye is used as an example demonstrating the role of

345 hydrophobic interactions in the process under study. Conventional phthalicyanine dyes, as well

346 as dyes of other classes, behave like typical amphiphilic compounds. The data obtained in this

347 work allow us to state that when using chitosan-sulphate particles as a sorbent, a complex

348 sorption mechanism takes place that includes both ion exchange processes and hydrophobic

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349 binding. In acid media, the role of electrostatic interactions is great, and when the pH increases

350 and the free amino groups of chitosan are largely deprotonated, the role of hydrophobic bonds

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351 increases.

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900

800

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700
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600 DB
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qe, mg/g

500
RB
400
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300

200
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100

0
2 3 4 5 6 7 8
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рН
352

353 Fig. 4. Effect of solution pH on the adsorption performance. The initial concentration 60 g·L-1.
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354
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355 To investigate the applicability of the CPF, adsorption capacities at different pH values
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356 were measured. For the TP dye, the experiment was not performed at pH <4 because in an acidic

357 medium it loses its solubility and forms a precipitate. From Fig.4, no significant changes were

358 observed along with a change in the solution pH. CPF demonstrated effective removal towards to

359 used dyes at a pH in the range of 2-8. At pH> 8.5, a sharp decrease in adsorption was observed,

360 and at pH>10, a complete absence of adsorption was recorded. In addition, it was found that

361 when a CPF containing a previously adsorbed dye was immersed in an alkaline medium (pH>

362 10), the dye desorbed rapidly and completely. When the CPF was immersed again in the dye
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363 solution (pH = 2-8), it is again stained due to the adsorption of the dye. The results of this

364 experiment showed that CPF could be applied to remove оf anionic dyes from water in the pH

365 range 2-8. The results also indicated that the adsorption saturated CPF could be effectively

366 regenerated by a simple alkaline washing.

367

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368 4. Conclusions

369 A simple method for obtaining low-cost, highly effective adsorbtion material by

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370 immobilizing chitosan nanoparticles on a fibrous carrier (CPF) has been developed. Chitosan

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371 nanoparticles were formed using sulfate anions as crosslinking bridges. The carrier was a

372 chemically activated PET fiber. The resulting CPF showed high adsorption rates and capacities

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373 towards anionic dyes at pH range of 2–8. As model adsorbates, anionic phthalocyanine dyes
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374 having different molecular sizes, different nature and number of anionic groups were used. The

375 experimental isotherm data and a linear correlation coefficients (rL2 >0.99) showed that the
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376 adsorption of dyes on CPF was best predicted by the Langmuir isotherm. The adsorption rate

377 was found to conform to pseudo-second-order kinetics with a good correlation (R2 > 0.99) with
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378 intra-particle diffusion as one of the rate determining steps. It is established that the sorption rate
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379 and the limiting sorption capacity decrease with increment of size of the dye molecules.
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380 Compared with the original powder chitosan, CPF is stable in an acid medium and provides an

381 order of magnitude higher initial adsorption rate towards to anionic dyes. The process of
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382 adsorption of dyes on the CPF is pH-insensitive at pH range of 2–8. The adsorption saturated
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383 CPF could be effectively regenerated by a simple alkaline washing.

384 As our preliminary studies showed, any natural fibers can be successfully used as a

385 carrier, including wastes of textile production and agro-fibers. This makes it possible cheap

386 production of highly effective and eco-friendly adsorption material in large-scale.

387

388

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389 Acknowledgments

390 This work was performed within the framework of the state contract with the Federal

391 Agency of Scientific Organizations of Russia (contract № 01201260484).

392 The authors are grateful to Prof. E.A. Lukyanets (Institute of Organic Intermediates and

393 Dyes, Moscow, Russia) for providing Photosens and for his valuable help.

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394 This work was carried out with the help of the centre of the scientific equipment

395 collective use «The upper Volga region centre of physicochemical research».

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396

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397 Appendix A. Supplementary data

398 Supplementary data related to this article are attached.

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399
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400 References

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1 • A new well permeable sorbent based on chitosan was developed for water treatment.

2 • A new sorbent (CPF) was obtained by simple fixing of chitosan particles on the fiber.

3 • CPF shows high adsorption capacity towards anionic dyes.

4 • CPF shows an order of magnitude higher adsorption rate than the powdered chitosan.

5 • Dyes adsorption on СPF is pH-insensitive in the range of pH 2-8.

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