Accepted Manuscript

Title: A review on chitosan-based adsorptive membranes

Author: Ehsan Salehi Parisa Daraei Ahmad Arabi Shamsabadi

PII: S0144-8617(16)30822-0
DOI: http://dx.doi.org/doi:10.1016/j.carbpol.2016.07.033
Reference: CARP 11332

To appear in:

Received date: 25-4-2016

Revised date: 3-7-2016
Accepted date: 8-7-2016

Please cite this article as: Salehi, Ehsan., Daraei, Parisa., & Shamsabadi, Ahmad
Arabi., A review on chitosan-based adsorptive membranes.Carbohydrate Polymers
http://dx.doi.org/10.1016/j.carbpol.2016.07.033

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 1

A review on chitosan-based adsorptive membranes 2

Ehsan Salehi a, Parisa Daraei b,*, Ahmad Arabi Shamsabadi c 3

a
Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak 38156, 5

Iran. 6

b
Department of Chemical Engineering, Kermanshah University of Technology, 7

Kermanshah 67178, Iran 8

c
Department of Chemical and Biological Engineering, Drexel University, Philadelphia, PA 9

19104, USA 10

11

* Corresponding author 12

Parisa Daraei 13

Ph: +98 83 37267530 14

Fax: +98 83 37267540 15

email: parisa_daraey@yahoo.com, p.daraei@kut.ac.ir 16

First author (Ehsan Salehi) email: ehsan1salehi@gmail.com 17

18

1
 19

Highlights 20

 Chitosan-based adsorptive membranes were reviewed. 21

 Chitosan adsorbents in the form of membrane are preferred for separation. 22

 Chitosan might be a free-standing membrane sheet or be used in composite membranes. 23

 Chitosan membranes are used for removing dyes and metal ions form aqueous media. 24

 Chitosan-based membranes can be regenerated using simple eluting solutions. 25

26

27

2
 28

Abstract 29

Membrane adsorbents have emerged as powerful and attractive tools for the removal of 30

hazardous materials such as dyes and heavy metal ions, mainly in trace amounts, from water 31

resources. Among membrane adsorbents, those prepared from or modified with chitosan 32

biopolymer and its derivatives are cases of interest because of chitosan advantages including 33

biocompatibility, biodegradability, nontoxicity, reactivity, film and fiber forming capacity 34

and favorable hydrophilicity. This review is oriented to provide a framework for better insight 35

into fabrication methods and applications of chitosan-based adsorptive membranes. Critical 36

aspects including thermokinetic analyses of adsorption and regeneration capacity of the 37

membrane adsorbents have been also overviewed. Future of chitosan-based adsorptive 38

membranes might include efforts for the improvement of mechanical stability and reusability 39

and also most targeted application of appropriate copolymers as well as nanostructures in 40

preparing high performance adsorptive membranes. 41

42

Keywords: Adsorptive membrane; Chitosan; Heavy Metals; Adsorption; Dye removal. 43

44

3
 45

1. Introduction 46

Increasing industrialization and urbanization worldwide has resulted in serious pollution and 47

loss of safe water resources. Traditional processes are not often sufficiently effective in 48

purification of pollutants from dilute solutions, mainly those that should meet rigorous 49

standards before disposal. In addition to these shortcomings, high cost of conventional 50

processes have resulted in investigation of more effective operations or even integrate two or 51

more alternatives to overcome the separation problems (Cestari, Vieira & Mattos, 2006; 52

Elliott & Huang, 1981; Guibal, 2004; Nasef & Yahaya, 2009). 53

Adsorption is considered as a well-established operation for water and wastewater treatment, 54

especially for the removal of dyes and heavy metal contaminants. The effectiveness of 55

adsorbents used in adsorption processes mainly depends on their morphology and chemistry 56

(Bleiman & Mishael, 2010; Celis, Adelino, Hermosin & Cornejo, 2012; Irani, Amjadi & 57

Mousavian, 2011; Keshtkar, Irani & Moosavian, 2013). Activated carbons are the most 58

common adsorbents due to their effectiveness, versatility, and good capacity for adsorption of 59

heavy metals, dyes and other toxic compounds. However, high cost for full-scale applications 60

convinced researchers to find cheaper alternatives (Crini & Badot, 2008; Karnib, Kabbani, 61

Holail & Olama, 2014; O’Connell, Birkinshaw & O’Dwyer, 2008). 62

Application of biopolymers is one of the prominent achievements in adsorption of dyes, 63

heavy metal ions and other contaminants, even at low concentrations (Crini, 2006; Ngah, 64

Teong & Hanafiah, 2011; Song et al., 2016). Chitin, extracted from crustaceans shell, is the 65

second most abundant biopolymer in nature after cellulose. Also, chitosan, the most important 66

and practical derivative of chitin, is a polysaccharide biopolymer with a high content of amine 67

and hydroxyl functionalities which has attracted a progressive attention in treatment and 68

purification fields (Guibal, 2004). This polymer is a natural amino-polysaccharide with high 69

4
binding capacity, wide availability, and unique functionalities (Boddu, Abburi, Talbott, Smith 70

& Haasch, 2008; Dalida, Mariano, Futalan, Kan, Tsai & Wan, 2011; Ngah & Fatinathan, 71

2008; Pillai, Paul & Sharma, 2009; Rinaudo, 2006; Vijaya, Popuri, Boddu & Krishnaiah, 72

2008; Wan, Kan, Rogel & Dalida, 2010). Amino and hydroxyl groups of chitosan make it a 73

potential adsorbent for dyes, macromolecules and heavy metals (Kumar, 2000; Serizawa, 74

Kamimura, Kawanishi & Akashi, 2002). Amino groups of chitosan can adsorb anionic dyes 75

strongly through electrostatic attraction in acidic media; however, sensitivity of chitosan to 76

pH should be considered in practice (Chiou, Ho & Li, 2004). Totally, the lone pair electrons 77

of O and N atoms are responsible for adsorptive role of chitosan where may be positively 78

charged if enough protons are in the vicinity of chitosan chains or negatively charged in high 79

concentration of basic media. This derives both physical and/or chemical adsorption onto 80

chitosan (Sakkayawong, Thiravetyan & Nakbanpote, 2005). 81

Chitosan is soluble in weak acidic solutions and this weakens the chitosan films stability in 82

acidic media. Therefore, solubility of chitosan is a serious concern in using this biopolymer 83

for aquatic environment applications below pH 6.5 (Tonglairoum, Sutananta, Rojanarata, 84

Ngawhirunpat & Opanasopit, 2014). Some reagents such as glutaraldehyde, glyoxal, 85

formaldehyde, epichlorohydrin, and isocyanates have been used as cross-linkers to eliminate 86

solubility concerns and improve mechanical properties of chitosan containing sorbents 87

(Chiou, Ho & Li, 2004; Crini & Badot, 2008). Despite promising adsorptive properties, 88

numerous techniques are still being introduced to enhance the adsorption capacity as well as 89

to develop the variety of species to be adsorbed by chitosan. Enhancement in adsorption 90

capacity and resistance to acidic environments are attained by preparation of chitosan 91

composites using montmorillonite, polyurethane, activated clays, bentonite, PVA, PVC, 92

kaolinite and perlite (Lee, Jeong, Min, Lyoo & Lee, 2009; Ngah, Teong & Hanafiah, 2011; 93

Swayampakula, Boddu, Nadavala & Abburi, 2009; Wang & Wang, 2007; Zhu, Jiang & Xiao, 94

5
2010). Chitosan and its derivatives have been used to prepare composite adsorbents in 95

different forms such as beads, flakes, powders, sheets and membranes (Rinaudo, 2006; 96

Zhang, Zeng & Cheng, 2016). Dispersed adsorbents such as beads, flakes and powders 97

although providing for high active surface area and treatment performance are problematic 98

since they must be separated from the final product after process treatment. Chitosan-based 99

membranes are preferred to other forms of chitosan adsorbents due to ease of separation after 100

process and requirement of no post-treatment filtration. Other advantages of membrane type 101

adsorbents are higher capacity for adsorption, faster kinetics, better reusability, ease of 102

stacking and scale-up and also probability of non-adsorptive separation mechanism enhancing 103

the filtration performance. 104

Lack of sufficient mechanical resistance is the most important concern for application of the 105

chitosan-based membranes as adsorbents. Some attempts have been conducted to overcome 106

this shortcoming (Premakshi, Ramesh & Kariduraganavar, 2015; Seo et al., 2014). Applying 107

chitosan as thin film composites i.e. utilizing a proper support, is a straightforward way to 108

enhance the mechanical resistance of chitosan flat sheet membrane (Daraei et al., 2013). Also, 109

embedding compatible nanobiomaterials has been reported to achieve better physical strength 110

for chitosan membrane (Karim, Mathew, Grahn, Mouzon & Oksman, 2014). 111

The chitosan-containing membrane adsorbents might be investigated from thermodynamics 112

and kinetics outlooks. Thermokinetic analyses results can help us to obtain deeper 113

understanding about the effectiveness of the modification methods applied for the chitosan- 114

based membranes. 115

In this review, preparation of various types of chitosan-based and chitosan-containing 116

membranes has been overviewed. In addition, advanced modification methods, 117

characterization tests, separation mechanisms and analyses of performance regarding chitosan 118

membranes have been reviewed. 119

6
 120

2. Fabrication of chitosan membrane adsorbents 121

Apart from being adsorptive, some other characteristics of chitosan biopolymer such as 122

solubility in water, high degree of shrinkage after drying, biodegradability, diversity of 123

derivatives and high polarity are very important and affective factors in resultant membrane 124

properties. These characteristics make chitosan incompatible with a wide variety of synthetic 125

polymers prevalently used in membrane world. This fact can greatly affect the preparation 126

procedure of chitosan membrane either as free standing sheets or supported ones. These 127

characteristics make chitosan incompatible with wide variety of synthetic polymers 128

prevalently used in membrane world. Being soluble in weak acidic media restricts fabrication 129

methods of chitosan-based membranes rather than other polymeric membranes. The 130

fabrication methods include several creative procedures to achieve sometimes porous and 131

sometimes dense, either composite or supported films. Almost all the studies are aimed at 132

enhancing the adsorptive property as well as permeability and physicochemical stability of 133

the membrane. The following sections summarize procedures for preparation of chitosan- 134

based membranes. 135

136

2.1. Blended and supported chitosan membranes 137

In the membrane fabrication, polymer blending and coating are promising strategies that may 138

be employed to improve the performance of polymeric membranes and to simultaneously 139

apply whole or some parts of the properties of both polymers. Blending or coating of 140

compatible or even incompatible polymers may combine their respective advantages and 141

generate new prospects for polymer-based membranes. To prepare a blended membrane, the 142

miscibility of polymers is the main issue. Miscible polymers show acceptable interactions 143

with the constituent polymer, and ensure homogeneity and reinforcement of the resultant 144

7
membranes (Shao, Low, Chung & Greenberg, 2009). 145

Polymer blending is a highly preferred technique to fabricate chitosan membranes mainly due 146

to its simplicity (Bowen, Doneva & Yin, 2002). Additionally, coating chitosan on another 147

polymeric support through various procedures has been proposed by many researchers to use 148

simultaneous capabilities of both support material and separating chitosan top layer. Chitosan 149

and its derivatives are potential polymer alternatives for introducing hydroxyl and amine 150

groups onto the most considered polymers applied in membrane preparation like PES, PS, 151

and PVDF. Chitosan can also affect the membrane surface charge (Ji, An, Zhao & Gao, 152

2015), which implies susceptibility of this biopolymer in inducing positive charge onto the 153

other polymeric membranes. Introducing hydrophilic groups to hydrophobic polymers (e.g., 154

PES) can increase the water permeability of the resultant membrane. For instance, chitosan 155

was coated on PES substrate to increase the separation efficiency of heavy metal ions 156

(Boricha & Murthy, 2009). To obtain better mechanical properties (strength, rigidity and 157

toughness) for the coated membrane, acrylonitrile butadiene styrene (ABS) was used as a 158

modifier in chitosan. Homogenous mixture of chitosan (in acidic water) and ABS (in THF 159

solvent) were prepared and coated on PES UF membranes. After solvent evaporation, the 160

fabricated membranes were dried in a vacuum oven and used for adsorptive removal of 161

mercury and sodium ions (Boricha & Murthy, 2009). In another investigation, 162

N,Ocarboxymethyl chitosan (NOCC) was blended with cellulose acetate (CA) to fabricate 163

nanofiltration (NF) membranes in acetone solvent (Boricha & Murthy, 2010; Boricha & 164

Murthy, 2011). After solvent evaporation, film-cast NOCC and CA membranes were cross- 165

linked with glutaraldehyde (GA). In the blended membrane, NOCC contributed to enhance 166

separation performance for metal ions and CA acts as a polymer matrix providing mechanical 167

strength for the membranes. The maximum rejection for chromium and copper ions were 168

found to be 83.40% and 72.60% at 1 MPa applied pressure and 16 LPM feed flow rate, 169

8
respectively (Boricha & Murthy, 2010). The later study well showed that chitosan/CA blend 170

would result in a NF membrane working at low trans-membrane pressure with an almost high 171

water flux. This is a valuable outcome in nanofilter design and originated from adsorptivity 172

and hydrophilicity of chitosan biopolymer. 173

Liu and Bai (Liu & Bai, 2006) prepared highly porous adsorptive hollow fiber membranes by 174

blending chitosan (CS) and cellulose acetate (CA) and used them for copper ion removal 175

from aqueous solutions in batch adsorption mode. These membranes were prepared via wet- 176

spinning of CS and CA blend into NaOH solution as non-solvent. CA in the blend hollow 177

fiber membranes acts as a matrix support and CS provides the functional sites for the metal 178

ion adsorption. All the CS/CA hollow fibers displayed sponge-like and macrovoid-free 179

structures. According to their results, other properties such as porosity, surfaces area and pore 180

size distribution depended on the CS to CA proportion ratios and also type of coagulants. 181

Adsorption experiments showed that the CS/CA blend hollow fiber membranes offer good 182

adsorption capacity (between 35.3–48.2 mg/g), fast adsorption rate and short equilibrium 183

times (less than 70 min) for adsorption of copper ion. 184

Adsorptive membranes containing chitosan and its derivatives blended with polysulfone (PS) 185

were successfully prepared and characterized by Kumar et al. (Kumar, Isloor & Ismail, 2014). 186

Phase inversion method was employed to obtain ultrafiltration (UF) adsorptive membranes 187

for Cu(II), Ni(II) and Cd(II) removal. Increase of chitosan content in PS/CS blend resulted in 188

increased metal ion rejection. Another approach in application of blended UF membranes for 189

the separation of heavy metals and biomolecules was proposed by Kanagaraj et al. (Kanagaraj 190

et al., 2015). The blend solutions based on poly(ether imide) (PEI) and N-phthaloyl chitosan 191

(NPHCs) were prepared and after casting was dried followed by immersing in water 192

coagulation bath. The results showed that the enhanced hydrophilicity and pore size reduced 193

the protein rejection and increased the permeate flux by increasing the NPHCs content. On 194

9
the other hand, the blended membranes showed enhanced metal ion removal for trivalent 195

ions. These outcomes were resulted from the increased charge density of the ions and 196

enhanced formation constant of ion–polymer compelex. Also, the increased hydrophilicity 197

resulted in an optimum flux recovery ratio of 88.6% for the PEI/NPHCs blend membrane 198

with a 2 wt% NPHCs. 199

Chitosan was blended with polymeric membrane matrix via preparation of chitosan 200

nanoparticles followed by mixing them into the polymer matrix (Han, Liu & Bai, 2007). With 201

the use of a surfactant (SDS) in chitosan aqueous solution, chitosan/SDS nanoparticles 202

formed and were dispersed in organic non-acidic solvent (NMP). Dissolving CA polymer in 203

aforementioned suspension prepared a dope solution to be coagulated in water during phase 204

inversion. High chitosan content hollow fiber membranes with great copper ion adsorption 205

efficiency were obtained (Han, Liu & Bai, 2007). 206

Coating chitosan is not limited to the polymeric supports. There are different examples for 207

application of chitosan as modifying layer for inorganic supports. For instance, chitosan 208

porous film was coated on inner surface of tubular ceramic membrane to improve the 209

adsorptive removal of copper ion from water (Steenkamp, Neomagus, Krieg & Keizer, 2001). 210

Almost complete removal of copper using chitosan coated ceramic membrane was achieved 211

in the later study. In another report, chitosan impregnated ceramic membrane made of local 212

clay and kaolin support followed by dipping in chitosan solution was prepared for polymer- 213

enhanced ultrafiltration of mercury and arsenic ions from water (Jana, Saikia, Purkait & 214

Mohanty, 2011). In the case of ceramic support, the polarity of ceramic material and chitosan 215

is an advantage to produce stable and uniform coating on such supports without the use of 216

cross-linking agent to connect chitosan onto the support surface. 217

218

2.2. Composite membranes 219

10
A mixture of immiscible additives with polymeric components results in composite formation 220

with some new characteristics and applications (Hussain, Hojjati, Okamoto & Gorga, 2006; 221

Mallakpour & Khadem, 2015; Paul & Robeson, 2008; Thakur & Kessler, 2015). Fabrication 222

of composite membranes (and especially nano composite ones) is an interesting and 223

progressive field of study due to improved and even new properties of polymeric composites 224

(Bet-moushoul, Mansourpanah, Farhadi & Tabatabaei, 2016; Jhaveri & Murthy, 2016; Ng, 225

Mohammad, Leo & Hilal, 2013). Mostly, a kind of micro or nanomaterial is added into 226

membrane structure, loaded on the surface or dispersed inside the matrix, to achieve 227

additional beneficial performance from a common or pre-known membrane (Yin & Deng, 228

2015). Of course, chitosan has great potential to be employed in composite membrane 229

preparation. 230

Chitosan-based nanocomposites are fabricated via different procedures and studied for 231

several aims. Addition of nanoparticles such as ZnO (Malini, Thirumavalavan, Yang, Lee & 232

Annadurai, 2015), carbon (Ding, Liang, Sun, He & Gao, 2015), rod-like chitin whisker (Ma, 233

Qin, Li, Zhao & He, 2014), carbon nanotubes (CNTs) (Bibi, Yasin, Hassan, Riaz & Nawaz, 234

2015; Ong, Ahmad, Zein, Sudesh & Tan, 2011), TiO2 (Yang, Li, Jiang, Lu & Chen, 2009), 235

graphene oxide (Shao, Chang, Zhang, Huang, Yao & Guo, 2013), etc. into the chitosan matrix 236

has been addressed in literature. An improved mechanical and tensile strength (Ma, Qin, Li, 237

Zhao & He, 2014; Shao, Chang, Zhang, Huang, Yao & Guo, 2013), high permeability and 238

selectivity (Ong, Ahmad, Zein, Sudesh & Tan, 2011; Yang, Li, Jiang, Lu & Chen, 2009) and 239

great adsorption capability (Ding, Liang, Sun, He & Gao, 2015) were offered by chitosan 240

nanocomposite membranes. Chitosan and its derivatives have been extensively used to 241

prepare composite adsorbents in different categories such as beads, flakes, powders, sheets, 242

hydrogels and membranes (Haldorai & Shim, 2014; Li, Deng, Deng, Liu & Li, 2010). Among 243

them, chitosan composite membrane adsorbents are of growing interest due to high 244

11
adsorption capacity, fast kinetics, favorable reusability, abundant hydrophilicity, good 245

film/fiber forming capability, reduced fouling, promising reactivity, flexibility to be applied 246

in both batch and flow modes, ease of stack-assembling and scale up (Haldorai & Shim, 247

2014; Li, Deng, Deng, Liu & Li, 2010; Liu, Zhang & Yang, 2010; Zha, Li, Chang & Yan, 248

2008). 249

Liu et al. (Liu, Zhang & Yang, 2010) used chitosan/activated carbon fiber (ACF) and TiO2 250

nano-particles to prepare cross-linked composite membranes (UF/MF) for removing low 251

concentrations (1-50 ppm) of dichlorophenol from water in low operating pressures. TiO2, a 252

stable and high photo-reactive nanoparticle, was used to improve membrane flux and also its 253

stability. Composite membranes were synthesized by coating ACF/chitosan/TiO2 solution on 254

a terylene fiber according to a multi-step chemical grafting technique. Circular pieces of 255

terylene fiber was immersed in chitosan solution containing PEG (as pore-former) and ACF, 256

and then washed with NaOH solution to remove the residual acid. Finally, CS/ACF 257

composite membrane was dipped in TiO2 solution, air-dried and cross-linked in 258

glutaraldehyde solution. They observed synergetic effects of TiO2 incorporation in 259

ACF/chitosan layer i.e., faster separation kinetics, higher flux and photocatalytic oxidation of 260

dichlorophenol in addition to adsorptive removal increment. 261

Karim et al. (Karim, Mathew, Grahn, Mouzon & Oksman, 2014) synthesized a bio-composite 262

membrane adsorbent by using cellulose nanocrystals (CNCs) as functional entities in chitosan 263

matrix via freeze-drying procedure followed by physical compaction. After synthesizing the 264

CNCs (Bondeson, Mathew & Oksman, 2006), CNTs-embedded chitosan/CNCs solution was 265

casted and freeze-dried at -75 ᵒC for 24 h to be solidified. The prepared porous composite 266

membranes were then pressed between aluminum plates in a compression molding machine 267

without heating to obtain compacted membranes. Cross-linking was performed by using 268

gluteraldehyde vapors at room temperature. These membranes were applied for dye removal. 269

12
A three layer nano-composite membrane was synthesized using Kevlar fabric support and 270

applied in adsorptive filtration of n-hexane/water mixture by Karimnejad et al. (Karimnezhad, 271

Salehi, Rajabi, Azimi, Derakhshan & Ansari, 2014). Para-aminobenzoate alumoxane (PAB- 272

A) and boehmite-epoxide were used as the first and second layer of the coating and provided 273

the Kevlar surface for the stabile attachment of chitosan as the active skin layer. These 274

nanocomposite membranes were prepared through a three-step dip-coating procedure. Kevlar 275

fabrics were immersed in PAB-A solution, immediately oven-dried then soaked in boehmite– 276

epoxide solution and oven-dried again. Finally, the membranes were immersed in chitosan 277

solution and then soaked in NaOH solution followed by washing with water and drying in 278

ambient temperature. The dense structure of pure chitosan flat sheet membrane led to low 279

water permeability and derived more attempts to introduce nanofillers to increase the 280

permeation flux without noticeable selectivity lost. In a MWCNT blended chitosan 281

membrane, the scientific justification of permeability enhancement was offered based on 282

nanometric cracks called nanochannels between MWCNT additive and chitosan polymeric 283

background (Salehi et al., 2012). In fact, a polar-nonpolar interaction between hydrophilic 284

chitosan and hydrophobic aromatic rings of carbon nanotubes caused formation of channel- 285

like wrinkles in the chitosan polymer background. Also, a magnetic anisotropy of benzene 286

ring in MWCNT might be considered for increased diffusion of positive ionic species as 287

addressed in Fig. 1. 288

The minerals have been also suggested as appropriate nanofillers for chitosan membranes. 289

Low-cost clay nanoparticles including organically modified montmorillonite (cloisite A and 290

B) were embedded in chitosan matrix to prepare chitosan thin film nanocomposite on a 291

commercial PVDF microfiltration membrane (Daraei et al., 2013). Highly water permeable 292

and pH sensitive nanofiltration membrane with increased dye removal efficiency was 293

obtained using nanoclay additives in chitosan structure. Moreover, adding clay nanoparticles 294

13
resulted in stable chitosan film on PVDF support without utilizing any cross-linking agent as 295

well as any post-preparation treatment (Daraei et al., 2013). 296

The use of nanofillers is an innovative, effective and interesting approach in tailoring 297

desirable characteristics to the nanocomposites. Application of nanostructures in polymeric 298

matrix of chitosan can result in modified nanocomposite chitosan membrane adsorbents (Liu, 299

Chen & Chang, 2009; Salehi, Madaeni, Rajabi, Derakhshan, Daraei & Vatanpour, 2013; 300

Salehi et al., 2012). The homogeneity of CNTs/chitosan composite structure and nanofiller 301

dispersion success was improved by Liu et al (Liu, Chen & Chang, 2009) using poly(styrene 302

sulfonic acid)-functionalized carbon nanotubes. They explained a chemical reaction between 303

sulfone groups of modifying polymer and amino groups of chitosan for uniform dispersion 304

and resulting high mechanical resistance of CNTs/chitosan nanocomposite. 305

Except for addition of nanofillers into the chitosan matrix, there were other ways to apply 306

chitosan in composite membranes. For instance, coating organic and inorganic nanoparticles 307

with chitosan and its derivatives has been also suggested as a versatile method to fabricate 308

chitosan containing nanocomposite membrane. In the study investigating dye removal 309

capability of nanocomposite nanofiltration membrane, carboxymethyl chitosan was coated on 310

Fe3O4 and mixed with PVA to prepare the membrane (Zinadini, Zinatizadeh, Rahimi, 311

Vatanpour, Zangeneh & Beygzadeh, 2014). In another report, chitosan wrapped CNTs was 312

used as nanofillers in PVA membrane to achieve higher permselectivity (Peng, Pan, Sun, Lu 313

& Jiang, 2007). 314

315

2.3. Porous chitosan membranes 316

Porosity is one of the most important characteristics of polymeric membranes which can 317

greatly affect the separation performance. Many studies tried to control the porosity of 318

membranes to obtain a break-even threshold between permeability and selectivity according 319

14
to the involved separation mechanisms (Bessbousse, Verchère & Lebrun, 2010; Dai et al., 320

2015). In the case of chitosan membranes, a well-defined porous structure can provide better 321

conditions for enhanced permeability and adsorption of contaminants. This fact is due to 322

reduction of mass transfer resistances in the porous structures, enhancement of void 323

adsorption capacity and an increase in the water absorption property (Zeng & Fang, 2004; 324

Zeng & Ruckenstein, 1996). Pore generators (porogens) are additives used to prepare porous 325

matrices principally according to selective dissolution mechanism. Poly (ethylene glycol), 326

poly (vinyl pyrrolidone), poly (ethylene oxide), silica, alumina, zirconia and inorganic salts 327

(e.g., NaCl and CaCO3) are examples of organic and inorganic porogens used in chitosan- 328

based membrane preparation (Amiji, 1995; Santos, Neto, Fonseca & Pereira, 2008; Zeng, 329

Fang & Xu, 2004). 330

Adsorptive removal of iron and manganese ions from aqueous solutions with microporous 331

chitosan/polyethylene glycol (CS/PEG) blend membranes was studied by Reiad et al. (Reiad, 332

Salam, Abadir & Harraz, 2012). To prepare blend membranes, chitosan dissolved in dilute 333

acetic acid solution was mixed by PEG dissolved in water and 2% glutaraldehyde solution as 334

cross-liker. After drying, the casted film was neutralized with 2% aqueous NaOH solution 335

followed by washing with DI water and keeping in water bath (80–90°C) to dissolve PEG and 336

generate porous structure. By increasing CS to PEG ratio in the blend, an enhancement in 337

adsorption capacity of metal ions was observed but the stability of membranes decreased. 338

Furthermore, adsorption capacity of CS/PEG membrane increased for iron ions. Also, Li et al. 339

(Li, Nan, Chen & Xu, 2011) employed high amount of PEG (more than 50%) in chitosan 340

dope and observed nanoporous morphology for the membranes developed for controlled drug 341

release. They explained that it was hydrogen-bonding between PEG and the chitosan 342

molecules making some PEG insoluble and left them in the membrane structure. 343

Chao et al. (Chao, Yu & Chuang, 2006) employed NaCl and silica gel as porogens and 344

15
genipin as cross-linking agent to prepare highly adsorptive chitosan membranes. NaCl 345

reduced the crystallinity index of chitosan membranes and showed better sorption 346

performance for RR 189 (a commercial dye) and Cu2+ rather than other membranes. The 347

macroporous chitosan membranes with high porosity were fabricated with 4wt% CS in acetic 348

acid followed by adding NaCl powder and genipin aqueous solutions. After homogenizing, 349

the casted solution was left to be dried at 50C. The dried membrane was immersed in NaOH 350

solution to neutralize the residual acid. Finally, the membrane was immersed in deionized 351

water to dissolve the NaCl particles and to remove the remaining NaOH. 352

Ghaee et al. (Ghaee, Shariaty-Niassar, Barzin & Zarghan, 2012) investigated competitive 353

adsorption of copper and nickel ions on the macroporous chitosan membranes. Particulate 354

leaching method was used to synthesize macroporous chitosan membrane. In this method, 355

different porogens (NaCl and silica gel) were employed in the casting solution to generate 356

membrane pores. After membrane preparation, porogens were dissolved in water and/or 357

NaOH solution (Santos, Neto, Fonseca & Pereira, 2008) and left pores in membrane matrix. 358

In the practical procedure, the solution obtained by dissolving chitosan with concentration of 359

6 wt.% in 10 wt.% aqueous acetic acid solution was mixed with silica gel as the porogen 360

at silica/chitosan ratio of 3/1. The membrane was dried at room temperature then immersed 361

in an aqueous solution of sodium hydroxide and washed with distilled water. 362

Another suggested inorganic porogen for chitosan porous membranes is silica (SiO2) particles 363

(Alias, Ariff & Mohamad, 2015; Gümüşderelioğlu & Agi, 2004). Removing silica particles to 364

form the pores would be possible using NaOH solution (as eluent) after casting and drying the 365

membrane films (Alias, Ariff & Mohamad, 2015). 366

Macroporous chitosan/polyvinyl alcohol (CS/PVA) membrane adsorbents were synthesized 367

by solvent evaporation an polyethylene glycol as porogen by Salehi et al. (Salehi & Madaeni, 368

2014). Employment of PEG generated the macrovoids in the dense structure of CS/PVA 369

16
membranes through particulate leaching mechanism. The adsorption capacity of the porous 370

membranes was almost 2.6 folds greater than those of the dense membranes. Size and density 371

of the macrovoids increased with high PEG content up to 5 wt%. Low mechanical stability of 372

the resultant porous structures prohibited synthesizing CS/PVA membranes with higher 373

porogen contents. Porous membranes were synthesized by introducing exact amounts of PEG 374

to the CS solution before blending with PVA. It was observed that there was a limitation for 375

using porogens in chitosan dope solution due to reduction of mechanical strength. However, 376

the presence of other additives might affect the porogen influences. Tang et al. (Tang, Zhang, 377

Wang, Fu & Zhang, 2009) proved that inserting MWCNTs into the chitosan membrane 378

matrix had a positive effect on mechanical resistance. 379

380

2.4. Imprinted membranes 381

Selectivity is the outstanding advantage of a membrane which should be carefully targeted 382

during preparation and modification procedures. One of the interesting methods to obtain 383

selective membrane adsorbents is imprinting technique which overcomes the lack of 384

selectivity caused by limited specific binding capacity. An ion/molecular-imprinted 385

membrane contains artificial receptor sites, introduced in the membrane matrix during 386

preparation. These recognition sites can memorize and identify the target species among other 387

available species in the solution. Actually, imprinting is referred to the process in which 388

specialized configured voids are included in background polymer by adding the target during 389

membrane preparation steps and then immediately leaching the target to evacuate the active 390

sites (Trotta, Biasizzo & Caldera, 2012) (see the scheme in Fig. 2). Because of being 391

specialized, the imprinting method increases selective adsorption of the ions or molecules by 392

the membranes as schematically indicated in Fig. 3 (Salehi, Madaeni & Vatanpour, 2012; 393

Vatanpour, Madaeni, Zinadini & Rajabi, 2011; Wang, Zhang, Ma, Song, Hou & Li, 2009). 394

17
Chitosan has also demonstrated an excellent potential for being imprinted for selective 395

adsorption of ions (Xu, Huang, Zhu & Ye, 2015). However, there are limited reports on 396

imprinted chitosan membranes which suggest the possibility of developing new ideas for 397

examination of new imprinted chitosan-based membranes. A study was conducted by 398

Shawky (Shawky, 2009) in which they prepared ion-imprinted membranes from Ag-CS and 399

Ag-CS/PVA cross-linked with GA. A casting solution was prepared using AgNO3, CS and 400

PVA which individually dissolved in dilute acetic acid solution. After film casting, the water 401

was allowed to be evaporated in room temperature and the dried sheet was immersed in 402

NaOH solution. Leaching removal of the Ag ions was conducted via washing membranes 403

with EDTA and HNO3 to complete the imprinting procedure. This study introduced EDTA as 404

preferred eluting solution to regenerate the active sites. The imprinted membranes were tested 405

for selective removal of silver ions from aqueous solutions. Ag(I)-imprinted CS and Ag- 406

CS/PVA had superior removal capacity and selectivity for Ag(I) ions compared to non- 407

imprinted one. 408

A similar procedure was proposed by Zarghami et al. (Zarghami, Kazemimoghadam & 409

Mohammadi, 2014) to fabricate copper-selective imprinted chitosan membrane via cross- 410

linking the blended CS/PVA using GA and impregnating copper ions as template. Again, 411

homogenous solutions of chitosan and PVA in acetic acid solution were prepared and mixed 412

with GA solution and different amounts of CuSO4.5H2O under continuous stirring. After film 413

formation, the film was washed with NaOH solution (to neutralize the excess acid), deionized 414

(DI) water (to remove the unreacted GA), HCl (to remove the copper ions) and 0.05 M NaOH 415

(to regenerate the binding sites), respectively. The washing procedure was finalized by further 416

rinsing with DI water. The enhanced removal of copper ions was successfully obtained using 417

Cu(II)-imprinted membrane. 418

Wang et al. (Wang, Zhang, Ma, Song, Hou & Li, 2009) dissolved CS and PVA in acetic acid 419

18
and mixed AgNO3(0.01M) and GA as imprinting and cross-linking agents, respectively. They 420

employed Na2S2O3 solution for extracting Ag ions. Their results showed that Ag(I)-imprinted 421

membrane presented large adsorption capacity to Ag(I) ion. During the imprinting process, 422

metal ion might be coordinated to the N atoms from –NH2 in CS and O atoms from –OH in 423

PVA. The imprinted membrane with specific recognition for Ag(I) was appropriate for being 424

used in the field of selective enrichment of low concentrations of Ag(I) in the waste solutions. 425

The interesting point of imprinting technique for chitosan biopolymer is the variety of species 426

which can be imprinted i.e. the diversity of materials with possibility of being selectively 427

adsorbed. For instance, Jiang et al. (Jiang, Yu & Wu, 2006) modified the chitosan membrane 428

through imprinting technique for investigation of stereochemical-based separation for an 429

organic material from aqueous solution. (CS)/glycidoxypropyltrimethoxysilane (GPTMS) 430

hybrid membrane was prepared in aqueous phase by a modified sol–gel process using L- 431

phenylalanine as imprinting molecule and GPTMS as crosslinking agent. It was observed that 432

the other isomers had facilitated passage through the membrane and an improved chiral 433

resolution was offered by imprinting method. Another study developed a similar investigation 434

for extraction of L-tyrosine using chitosan-gelatin imprinted membrane (Zheng, Lian & 435

Yang, 2014). 436

The number of studies on imprinting technique might be few but they all monitor a very 437

attractive field of research on chitosan-based imprinted membranes to develop the technique 438

for separation and enrichment of a wide range of materials including drugs, precious metals, 439

organic pesticides and etc. with this nontoxic polymer. 440

441

3. Applications of chitosan membrane adsorbents 442

The chitosan-based membranes have been widely applied to remove various contaminants 443

mostly from water and aqueous resources. A large number of experiments have been 444

19
conducted to show the adsorptive ability of chitosan-based membranes for removing dyes and 445

metal ions from aqueous media. 446

Dyes are mostly used in textile industry, raised from discharging the dye-polluted wastes 447

without efficient treatment, and regarded as serious menace to human health and environment 448

(Ali, Hameed & Ahmed, 2009; Buthelezi, Olaniran & Pillay, 2012; Kant, 2012; Padhi, 2012). 449

Heavy metal ions are also very toxic and perilous and should be eliminated from wastewater 450

and drinking water (Duruibe, Ogwuegbu & Egwurugwu, 2007). Generally, dyes are classified 451

according to their chemical structure, method and domain of usage and their chromogen 452

(Crini & Badot, 2008). Anionic (directly, acid and reactive dyes), cationic (basic) dyes and 453

non-ionic (disperse) dyes are a classification proposed by Mishra and Tripathy (Mishra & 454

Tripathy, 1993). Azo and anthraquinone colorants are the main classes of synthetic dyes and 455

pigments which represent about 90% of all organic colorants. Degradation, adsorption and 456

filtration processes have been widely used for decolorization of water (Gupta, Khamparia, 457

Tyagi, Jaspal & Malviya, 2015; Ong, Keng, Lee, Ha & Hung, 2011; Sivamani & Leena, 458

2009). However, there are a large number of studies on dye adsorption using chitosan-based 459

sorbents (Ngah, Teong & Hanafiah, 2011; Vakili et al., 2014). Heavy metal ions are the other 460

contaminants which might be removed by chitosan and its derivatives during adsorption 461

process (Ngah, Teong & Hanafiah, 2011). 462

The capability of lab-made chitosan-based membranes for dye and metal ion removal is 463

pointed out through the following sections. 464

465

3.1. Dye removal 466

As previously mentioned, chitosan is a high molecular weight biopolymer that is considered 467

as nontoxic, heterogeneous, linear, cationic and biodegradable polysaccharide produced from 468

the alkaline de-acetylation of chitin (Rinaudo, 2006; Riva, Ragelle, des Rieux, Duhem, 469

20
Jérôme & Préat, 2011). Some intrinsic advantages of chitosan-based membranes such as low 470

cost, high adsorption capability, selectivity, versatility and biodegradability have made them 471

the best candidates for dye removal (Gupta, 2009; Haldorai & Shim, 2014; Li, Deng, Deng, 472

Liu & Xin, 2010; Vakili et al., 2014). Based on literatures, some types of chitosan sorbent 473

(e.g., beads, gels, granules, flakes) are more attended for dye removal applications compared 474

with membranes; however, there are some studies which have been prepared and/or modified 475

chitosan membranes for dye removal purposes. Daraei et al. (Daraei et al., 2013) fabricated 476

thin film composite (TFC) membrane by nano-clay (Cloisite 15A and 30B)/chitosan nano- 477

composite coated on the commercial polyvinylidene fluoride (PVDF) microfiltration 478

membrane. A film casting method was used for coating of chitosan solution (2wt %) mixed 479

with nanoclay(0.5-2%) on the PVDF support, moistened with distillated water followed by 480

washing with NaOH and water. In this procedure, PVDF/chitosan TFC membrane was 481

fabricated without applying a cross-linker agent. The coating layer containing Cloisite 30B 482

was denser rather than that of Cloisite 15A. Considering the permeate flux, the Cloisite 15A 483

mixed TFC membranes seemed to be more efficient for methylene blue removal from water. 484

In fact, methylene blue removal increased with applying organoclay particles in chitosan 485

matrix. Acidic dye (acid orange7) was well removed by Cloisite 30B/chitosan coated 486

membrane at acidic pHs due to electrostatic interactions of clay and chitosan in the presence 487

of high concentration of proton. 488

Karim et al. (Karim, Mathew, Grahn, Mouzon & Oksman, 2014) synthesized biocomposite 489

membranes using cellulose nanocrystals (CNCs) as functional filler in chitosan matrix via 490

freeze-drying process followed by compacting. Cross-linking was done by putting the 491

compacted membranes in a desiccator with gluteraldehyde vapors (25%) at room temperature 492

for 48 h. These membranes were used for dye removal. 493

The other research article reported applying natural filler to increase filtration ability of 494

21
chitosan membrane by montmorillonite (MMT) (Nesic, Velickovic & Antonovic, 2012). In 495

this study, different ratios of montmorillonite (10–50%) were embedded in the membranes. 496

Solvent evaporation was used after casting the solution on a petri dish. Enhancement of 497

adsorption capacity was observed with increasing the amount of MMT in membranes. pH and 498

temperature sensitivity was examined for the composite membrane in removing dye from 499

water. 500

Zinadini et al. (Zinadini, Zinatizadeh, Rahimi, Vatanpour, Zangeneh & Beygzadeh, 2014) 501

applied chitosan as modifier for magnetite nanoparticles to induce the new O-carboxymethyl 502

chitosan (CC)–coated Fe3O4 into PES nanofiltration (NF) membranes. They dispersed Fe3O4 503

powder into CC solution at pH 7 with continues stirring. Then, CC– Fe3O4 nanocomposite 504

was separated from the reaction mixture by magnetic bar to be washed and dried. The 505

modified nanoparticles were dispersed in N, N-dimethylacetamide (DMAc) and sonicated to 506

be used as solvent for PES. The PES solution was casted and immersed in water to form flat 507

sheet membrane. The mixed matrix membranes had higher water flux compared to the 508

unfilled PES membrane. Direct Red 16 dye was efficiently removed using the nanocomposite 509

membrane. This case study offered an adsorptive-assisted mechanism of filtration for a 510

chitosan-involved membrane. Actually, the increment of dye removal was driven by negative 511

charge of membrane surface originated from addition of O-carboxymethyl chitosan coated 512

Fe3O4 nanoparticles into the membrane matrix. 513

In another study, similar nanocomposite membrane was fabricated by means of chitosan 514

modified montmorillonite. The chitosan–montmorillonite (CS–MMT) nanosheets were added 515

into the PES membrane matrix via mixing with dope solution (Zhu, Tian, Zhang, Zhang & 516

Liu, 2015). Higher hydrophobicity and water flux, favorable antifouling and mechanical 517

property as well as efficient rejection of Reactive Black 5 and Reactive Red 49 dyes were 518

observed. Another pH/temperature-sensitive membrane was prepared by He et al. (He, Du, Li 519

22
& Zhou, 2016) to remove direct dyes (Blue 71 and Red 31) using a hybrid chitosan 520

membrane consist of oxidized starch and silica. An optimum dye removal condition was 521

obtained at pH= 9.82 and 60 C. 522

A combined method of electrospinning and spraying was applied for fabrication of 523

nanofibrous chitosan membrane modified by carboxylated MWCNTs to eliminate methylene 524

blue and methyl orange (Shi et al., 2016). 525

Altogether, the chitosan was considered as an appropriate background or modifier biopolymer 526

for membranes because of its adsorptive property. For improved dye removal, additives were 527

added into chitosan mostly with the aim of changing membrane surface charge (Bai, Zhang, 528

Wang, Zhang & Liu, 2013) to provide enhanced electrostatic and/or chemical bonding 529

adsorption of dyes. An example of probable electrostatic interactions and hydrogen-bonding 530

for adsorption of direct Blue 71 is proposed in Fig. 4 according to the similar scheme 531

represented by Pirillo et al. (Pirillo, Pedroni, Rueda & Luján Ferreira, 2009) for Alizarin and 532

Eriochrome Blue Balck R dyes adsorbed on chitosan. In the same manner, the pH-sensitivity 533

of chitosan membrane would be reasonable according to changes in chitosan membrane 534

surface charge when being exposed to various concentrations of proton or hydroxide ions in 535

the feed solution. 536

537

3.2. Heavy metal adsorption 538

Many processes are conventionally used for the removal of heavy metals form water and 539

wastewater; however, trace concentrations of heavy metals in effluents remains as a great 540

concern where restrict standards should be passed before discharge (Bailey, Olin, Bricka & 541

Adrian, 1999; Ngah & Hanafiah, 2008). Various operations including ion exchange, flotation, 542

electro-coagulation, solvent extraction, membrane filtration, and adsorption have been used 543

for the elimination of metals from aqueous environments (Akhtar, Akhtar & Khalid, 2007; 544

23
Devi & Mishra, 2010; Wang, Xia, Ling, Zhao, Chovelon & NICOLE, 2006). Rather most of 545

these processes are not appropriate alternatives for elimination of trace amounts of metal ions 546

because of slight driving force, inadequate reactivity and large amounts of required materials, 547

energy consumption and high cost. The membrane adsorption is a potential alternative over 548

conventional processes for the removal of heavy metal ions from dilute aqueous solutions 549

(He, Nie, Branford-White, Zhu, Zhou & Zheng, 2008; Madaeni, Zinadini & Vatanpour, 2011; 550

Vatanpour, Madaeni, Zinadini & Rajabi, 2011). The membrane adsorption proposes several 551

advantages such as excellent removal efficiency, favorable hydrodynamic, high flow rate, low 552

pressure drop, fast kinetic, reusability, small footprint, no requirement of post-treatment and 553

ease of scale up (Ghaee, Shariaty-Niassar, Barzin & Matsuura, 2010; Vieira, Guibal, Silva & 554

Beppu, 2007). Despite having crucial advantages, a membrane would be a superior choice 555

especially where selectivity is desired. Hence, studies have been oriented to obtain higher 556

selectivity, nontoxicity, great permeability with available low-cost materials for membrane 557

fabrication. On account of intrinsic affinity of chitosan and its derivatives, many studies have 558

been conducted for fabrication of chitosan based sorbents for heavy metal elimination 559

(Franco, Maia, Porto, Messias, Fukushima & Campos-Takaki, 2004; G., 2013; Li & Bai, 560

2006; Mohanasrinivasan et al., 2014; Ngah & Hanafiah, 2008). The chitosan-based 561

membranes were introduced as powerful tools for heavy metal removal, as well (Kamiński & 562

Modrzejewska, 1997). 563

Liu and Bai (Liu & Bai, 2006) fabricated porous adsorptive hollow fiber membranes from 564

chitosan (CS) and cellulose acetate (CA) and used the membranes for copper ion removal 565

from water. They found that higher CS content in the blend resulted in membranes with more 566

affinity towards copper ions. They explained the possibility of adsorption to adsorption- 567

assisted filtration mechanism for CA/CS membranes in water or wastewater treatment. 568

Salehi et al. (Salehi et al., 2012) prepared chitosan/PVA thin adsorptive membranes 569

24
embedded with amino functionalized multi-walled carbon nanotubes for copper ion 570

adsorption. The copper ion adsorption on the membranes was more favorable at higher CNTs 571

contents as well as increased temperatures. 572

They also incorporated poly(ethylene) glycol (PEG) into the membranes to achieve 573

macroporous membrane adsorbents for enhanced ions removal. The maximum possible PEG 574

loading which preserved mechanical stability as well as adsorption capacity of the 575

membranes was reported 5 wt.% (Salehi, Abdi & Aliei, 2014; Salehi & Madaeni, 2014; 576

Salehi, Madaeni, Rajabi, Derakhshan, Daraei & Vatanpour, 2013). They found that adsorptive 577

membrane containing combined MWCNT-NH2 and PEG additives demonstrated superior 578

sorption capacity (35 mg/g) and favorable stability when applied in both static and flow 579

processes. This study reported elevated adsorption efficiency for a chitosan membrane as a 580

result of generation of interconnected porous network by PEG and nanochannels. Besides, the 581

amine groups on MWCNTs can introduce additional adsorption sites for metal chelation. Fig. 582

5 depicts the scheme of coordination bond which can be formed by functional groups of 583

chitosan and the additive. 584

Of course, a metal ion can produce various complexes with different numbers of coordination 585

bonds. This can result in various coordination bonds based on spatial arrangement of the 586

chitosan chains and the functional groups of the additive. 587

Application of micro-porous PEG/chitosan membranes for iron and manganese ions removal 588

from aqueous solutions was probed by Reiad et al. (Reiad, Salam, Abadir & Harraz, 2012). 589

They showed that after 60 min equilibrium adsorption time, the membranes adsorbed Fe(II) 590

ions higher than Mn(II). Adsorption capacity of the membrane adsorbents enhanced with 591

increasing CS to PEG ratio especially in acidic pHs. Maximum adsorption capacities of 80 592

mg/g (for iron ions) and 35 mg/g (for manganese ions) were achieved for CS/PEG (2:1) 593

membranes. 594

25
Separation of Cd (II), Pb(II) and Hg(II) from aqueous solutions was proposed by Procion 595

Brown MX 5BR immobilized poly (hydroxyethylmethacrylate/chitosan) composite 596

membranes (Genç, Arpa, Bayramoğlu, Arıca & Bektaş, 2002). The equilibrium time of 597

adsorption was around 45 min with maximum amounts of adsorbed heavy metal of 18.5, 22.7 598

and 68.8 mg/g for Cd(II), Pb(II) and Hg(II), respectively. In another work, they fabricated 599

similar membranes with Procion Green H-4G for these heavy metals with the same 600

equilibrium time of adsorption (Genç, Soysal, Bayramoğlu, Arıca & Bektaş, 2003). The 601

maximum amounts of adsorption capacity increased for Cd(II) to 43.6mg/g and for Pb(II) to 602

68.81 mg/g and decreased for Hg(II) to 48.22 mg/g by using the recent dye-reactive ligand. 603

This means that it would be possible to specify the performance of membrane for adsorption 604

of a distinct metal ion by immobilizing specified ligands in chitosan membrane. 605

Aliabadi et al. (Aliabadi, Irani, Ismaeili & Najafzadeh, 2014) tested performance of 606

chitosan/hydroxyapatite (CS/HAp) composite nano-fiber membranes for the removal of lead, 607

cobalt and nickel ions from aqueous solution. Their results showed that the maximum 608

adsorption capacity of synthesized composite membranes was 296.7 mg/g for lead, 213.8 609

mg/g for cobalt and 180.2 mg/g for nickel within the equilibrium time near 30 min at 45 ᵒC. 610

Copper and mercury ion adsorption on chitosan membranes was investigated in batch mode 611

by Vieira et al. (Vieira, Guibal, Silva & Beppu, 2007). Cross- linked chitosan was 612

synthesized by immersion of chitosan in the epichlorohydrin solution or contacting with 613

glutaraldehyde solution followed by immersing in water. In their experiments, chitosan 614

membranes presented more affinity for mercury ions than that for copper ions. As in the 615

previous work (Salehi et al., 2012), the crosslinking reaction increased the adsorption 616

capacity for both metals. The presence of copper ions in the mixture exhibited more 617

significant interference on mercury adsorption. The impact of cross-linking in chitosan 618

membranes was also investigated for chromium ions removal from aqueous solutions. The 619

26
maximum adsorption capacity (1400 mg/g) was obtained by using epichlorohydrin- 620

crosslinked chitosan membranes at pH 6.0 (Baroni, Vieira, Meneghetti, Da Silva & Beppu, 621

2008). Vieira et al. (Vieira & Beppu, 2006b) confirmed an improved metal ion adsorption for 622

a cross-linked chitosan membrane and explained the eclipsing effect of cross-linking in 623

decrement of available amino groups of chitosan. The eclipsing increases the impacts of other 624

complexation points such as unreacted aldehyde ends and hydroxyl groups of chitosan in 625

metal ion uptake. Additionally, they concluded that the type of cross-linking agents affects 626

the amount of heavy metal removal. 627

Whereas the adsorption process is critically affected by the surface area of adsorbent, the 628

morphology of chitosan adsorptive membranes can be another effective parameter in removal 629

efficiency. For instance, the effect of dense and macro-porous chitosan membrane 630

morphology on copper ion adsorption was addressed by Ghaee et al. (Ghaee, Shariaty- 631

Niassar, Barzin & Zarghan, 2012). They fabricated the dense membrane by spreading the 632

chitosan pure solution onto a flat polycarbonate films and the porous membrane by 633

embedding silica particles in the casting solution. Increasing the silica content resulted in 634

more porous membrane and rougher surface. Higher porosity suggested more available amino 635

groups as reactive adsorption sites which led to increased copper adsorption. In another 636

research (Ghaee, Shariaty-Niassar, Barzin & Matsuura, 2010), the competitive adsorption of 637

copper and nickel ions on macro-porous chitosan membrane was investigated. The leaching 638

method was used for preparation of porous chitosan membrane by silica gel and NaCl as 639

porogens. The method resulted in higher copper adsorption rather than nickel ion. An 640

elevated adsorption of heavy metals by impregnating ferromagnetic NiFe2O4 into chitosan 641

was also obtained (Li & Bai, 2006). 642

Through the above reports, chitosan played the main role in preparing an adsorptive 643

membrane for chelation of heavy metals; however, adsorption capacity can be further 644

27
elevated by using some modifying material and/or methods. 645

646

4. Further remarks 647

4.1. Adsorption thermokinetics 648

Thermodynamic and kinetic aspects of adsorption in chitosan-based adsorptive membranes 649

are important considerations from practical viewpoint. Kinetics and thermodynamics reveal 650

valuable information about rate-controlling mechanism(s) involved in adsorption, thermal 651

sensitivity and favorability extent, solute-surface and solute-solute interactions, required time 652

for the equilibrium, and also process optimization and scale up. Mechanisms like external 653

mass transfer, reaction on the external surface of adsorbent, intra particle diffusion and 654

chemical reaction on the internal active sites may be better understood in the light of the 655

kinetic modeling. Kinetics of adsorption on chitosan and chitosan based materials have 656

attracted a great attention in several research articles (Aliabadi, Irani, Ismaeili & Najafzadeh, 657

2014; Bayramoğlu, Yılmaz & Arıca, 2003; Cestari, Vieira, Matos & dos Anjos, 2005; Cheng, 658

Liu, Han & Ma, 2010; Esmaeili & Beni, 2014; Ghaee, Shariaty-Niassar, Barzin & Zarghan, 659

2012; Lopes, dos Anjos, Vieira & Cestari, 2003; Nesic, Velickovic & Antonovic, 2012; Nie, 660

Chen & Zhu, 2007). The adsorption kinetics is generally controlled by the rate of uptake onto 661

the adsorbent surface as well as diffusion toward the active sites. Various modification 662

methods either induced to chitosan or conducted on blended nanofillers could affect the 663

adsorption thermokinetics. 664

Many studies on kinetics of adsorption on the chitosan-based membranes have been 665

conducted. For instance, electrospun PVA/chitosan nanofiber membrane was investigated for 666

its adsorption kinetics using Ni and Co ions as adsorbates (Esmaeili & Beni, 2014). The study 667

fitted the adsorption data to the pseudo first-order, pseudo second-order, and intraparticle 668

diffusion models. The best fitted model was reported to be the pseudo first-order. Moreover, 669

28
adsorption was addressed as endothermic and well described by the Dubinin–Radushkevich 670

isotherm equation. In contrary with the latter study, Cheng et al. (Cheng, Liu, Han & Ma, 671

2010) introduced the pseudo second-order kinetic model for adsorption of copper ions onto a 672

modified chitosan transparent thin membrane confirming a chemical-controlling adsorption 673

mechanism. Non-linear fitting method was applied in this study and revealed ―external mass 674

transfer‖ as the rate-controlling step for entire range of copper concentrations in the solution. 675

A coordination bonding of copper and nickel ions on macroporous chitosan membrane was 676

also addressed by Ghaee et al. (Ghaee, Shariaty-Niassar, Barzin & Zarghan, 2012) through 677

the pseudo second-order kinetic model. They also studied competitive adsorption beside 678

mono-component one. For mono-component adsorption, Redlich–Peterson and Langmuir- 679

Freundlich models were better fitted to the equilibrium data for copper and nickel ions, 680

respectively. Besides, Jain–Snoeyink and extended Langmuir and Freundlich models were in 681

better agreement for copper and nickel ions adsorbed from bi-component solutions, 682

respectively. 683

Incorporating a ligand with chitosan-based membrane presented the same chemical 684

adsorption mechanism (pseudo second-order model) for non-metallic specie i.e. enzyme 685

(papain) (Bayramoğlu, Yılmaz & Arıca, 2003; Nie, Chen & Zhu, 2007). The pseudo second- 686

order model for heavy metal adsorption on chitosan/hydroxyapatite composite nanofiber 687

membrane was also suggested by Aliabadi et al. (Aliabadi, Irani, Ismaeili & Najafzadeh, 688

2014). They found that adsorption was exothermic with mono-layer coverage on the 689

membrane surface based on the Langmuir-type trend of the equilibrium data. 690

In another work, a rather complicated kinetic mechanism including pseudo second-order 691

model followed by intra-particle diffusion was introduced for dye adsorption on 692

chitosan/montmorillonite composite membrane by Nesic et al. (Nesic, Velickovic & 693

Antonovic, 2012). They confirmed that the intra-particle diffusion during adsorption process 694

29
was not the only rate-controlling step for adsorption of dye on the membrane. Freundlich 695

isotherm was in better accordance with the equilibrium data in this case. 696

The traditional Lagergren adsorption kinetic equations and Avrami kinetic equation were both 697

investigated for vanillin-modified chitosan membrane (Cestari, Vieira, Matos & dos Anjos, 698

2005). The later study discussed about the relationship between the contact time and possible 699

adsorption mechanism. According to this report, despite good fitness of pseudo second-order 700

model the alternative Avrami kinetic equations could better disclose the complex mechanisms 701

involved in adsorption of copper ions on chemically modified chitosan membrane. Avrami 702

model was also applied by Lopes et al. to study the adsorption kinetic of Hg(II) on thin 703

chitosan membrane adsorbents (Lopes, dos Anjos, Vieira & Cestari, 2003). With the aid of the 704

model parameters, two distinct (time interval) regions could be recognized with clearly 705

different adsorption mechanisms on account of the kinetic order parameter. 706

Similarly, the adsorption of organic substances like dimethylformamide (DMF) on porous 707

chitosan membranes followed chemical interaction-based adsorption according to pseudo 708

second-order kinetic model (Li, Chen & Liu, 2011). 709

Salehi et al. (Salehi et al., 2012) developed a mathematical model for copper adsorption 710

behavior of chitosan/PVA thin adsorptive membranes modified with amino functionalized 711

MWCNTs including investigation of kinetics and thermodynamics. They verified a good 712

agreement between experimental data and the predicted ones to decide the pseudo second- 713

order kinetic model for the modified chitosan membrane used in removal of Cu(II) ions. 714

Moreover, adsorption was found spontaneous, endothermic and entropy-driven according to 715

the thermodynamic criterions. In another study, modifying chitosan membrane with 716

zirconium (IV) resulted in faster kinetics of phosphate ions adsorption qua the equilibrium 717

was occurred within 20 min (Liu, Hu, Wang, Zhang & Huang, 2015). In this work, a 718

chemical adsorption including electrostatic interaction and ion exchange reaction was 719

30
confirmed based on pseudo second-order kinetic model fitted to the experimental data. The 720

physicochemical nature of interactions between adsorbate and chitosan–-cyclodextrin was 721

validated by Zha et al. (Zha, Li, Chang & Yan, 2008). They detected a chemical adsorption 722

mechanism based on the amount of the activation energy obtained. Again, the same kinetic 723

model was obtained for chitosan modified nylon membrane (He, Nie, Branford-White, Zhu, 724

Zhou & Zheng, 2008) which confirms the same functionality of chitosan in both forms of 725

being membrane bulk material or used as modifier for another polymer in background. 726

The pseudo-second order kinetic model was also confirmed for direct dye adsorption (He, Du, 727

Li & Zhou, 2016) and glyphosate herbicide removal (Carneiro et al., 2015) using chitosan- 728

based membranes. In both of the last works, adsorption equilibrium was well described by the 729

Freundlich model indicating multi-layer adsorption and heterogeneous nature of active sites. 730

Altogether, the chemical structure of chitosan makes it appropriate for coordination bond 731

between amine group of chitosan and any adsorbate having an atom with vacant orbital in 732

valence shell and/or electrostatic interaction for electrically charged spices. This leads to 733

almost always a pseudo-second order kinetic model, introducing more favorable uptake rate 734

than pseudo-first order, for adsorption mechanism in the case of chitosan-based membranes. 735

736

4.2. Regeneration and reuse 737

Generally, a membrane separation process with any dominating separation mechanism is 738

always influenced by depreciation during its lifetime. Therefore, studies not only investigated 739

the membrane performances but also greatly paid attention to the enhancement of membrane 740

durability as well as regeneration of an inefficient membrane amortized during operation. The 741

strategies employed to achieve a desirable performance recovery is mainly depended on the 742

adsorption mechanisms i.e., physical or chemical attachment of adsorbates onto the active 743

sites. Hence, reusability is one of the most important characteristics of any kind of 744

31
adsorbents. Reusability has critical effect on the process economy and working capital can be 745

decreased by applying reusable adsorbents. This factor also reflects durability of adsorbent 746

which means the resistance of adsorbent against chemical, thermal and mechanical 747

decomposition during long-time processes. Membrane adsorbents should be tested with 748

successive adsorption/regeneration cycles to verify their capacity for reuse (Ghaee, Shariaty- 749

Niassar, Barzin & Zarghan, 2012; Wan, Kan, Rogel & Dalida, 2010). In each cycle, the 750

membrane is firstly immersed in a solution with a determined initial concentration of solute 751

or is used for filtration of contaminant solution for a certain time and then the membrane is 752

kept in exposure to the eluting solution. 753

The use of chitosan for fabrication of adsorptive membranes is restricted by cost of the 754

biopolymer. Therefore, recycling of these types of membranes is inevitable for the process 755

design. Aliabadi et al. (Aliabadi, Irani, Ismaeili & Najafzadeh, 2014) applied five 756

adsorption/desorption cycles for lead, cobalt and nickel with HNO3 as eluting agent using 757

chitosan/hydroxyapatite (CS/HAp) composite nano-fiber membranes. Their results revealed 758

that the composite nano-fiber membrane can be reused frequently without significant 759

adsorption capacity loss. Actually, metal ions have great tendency to form coordination 760

complex with NH2 and OH groups of chitosan (Wang, Du, Fan, Liu & Hu, 2005). An acidic 761

regenerator can replace protons with metal ions in an occupied adsorption site and release the 762

metal ion if there are enough H+ ions available. Then, regeneration of active sites on chitosan 763

would be accessible with strong acid (like HNO3 and HCl) solutions. Genc et al. (Genç, Arpa, 764

Bayramoğlu, Arıca & Bektaş, 2002) performed desorption experiments on Procion Brown 765

MX 5BR immobilized poly(hydroxyethylmethacrylate/chitosan) for the removal of Cd(II), 766

Pb(II) and Hg(II) with the HNO3. Higher than 95% desorption ratios were obtained after five 767

adsorption/desorption cycles. Regeneration of Chitosan/PEG membranes used for Fe(II) and 768

Mn(II) removal was performed by Reiad et al. (Reiad, Salam, Abadir & Harraz, 2012), using 769

32
HCl. The regenerated membranes were able to adsorb almost the same amount of metal ions 770

even after four cycles i. e. a perfect regeneration was obtained. 771

Some studies introduced a chelating agent for regeneration of saturated chitosan adsorptive 772

membrane. EDTA is well-known as the hexadentate ligand that can easily and strongly 773

surround the metal ions especially in basic media. A schematic of the chelation of 774

metal/EDTA is indicated in Fig. 6. The stable complexation of metal ions by EDTA makes it 775

a favorable choice for being employed as regenerator. The stability of metal/EDTA chelate is 776

related to the great formation constant of complexes (ranged around 107 to 1036 for various 777

mono, bi and trivalent metal ions). A practical effort was reported by Ghaee et al. (Ghaee, 778

Shariaty-Niassar, Barzin & Zarghan, 2012) that washed the macroporous chitosan membranes 779

used for the separation of nickel and copper ions with distillated water followed by stirring in 780

EDTA solution for three successive cycles. The desorption ratios of copper and nickel ions 781

after the first cycle were 68.74 and 45.97%, respectively. For the subsequent cycles, these 782

values decreased due to reduction of driving force and occurrence of irreversible adsorption. 783

They followed the same procedure to reuse membranes applied for the adsorption of copper 784

ions (Ghaee, Shariaty-Niassar, Barzin & Matsuura, 2010). Again, Salehi et al. (Salehi, 785

Madaeni, Rajabi, Derakhshan, Daraei & Vatanpour, 2013; Salehi et al., 2012) repeated the 786

adsorption–desorption experiments four times for Chitosan/PVA/MWCNT (2%) and three 787

times for other modified membranes which all were used for copper adsorption. At first, the 788

membranes were washed with distilled water to remove loosely attached copper ions. This 789

was followed by immersing the membranes in dilute Na2EDTA eluting solution for 6 h. 790

Adsorption capacity loss was about 11% for plain membranes; however, this value was less 791

than 4% for the MWCNTs embedded membranes (Salehi et al., 2012). Desorption percentage 792

values of functionalized membranes were between 70% to 80% (Salehi, Madaeni, Rajabi, 793

Derakhshan, Daraei & Vatanpour, 2013). Their results emphasized the important role of 794

33
nanoparticles in reusability of the membrane adsorbent. Deactivation of a part of reactive 795

sites after each desorption step and adsorbent degradation were found as two main factors for 796

observed decline in adsorption capacity. Also, the simple available NaCl solution was 797

suggested for reusing chitosan membranes. Vieira and Beppu (Vieira & Beppu, 2005, 2006b) 798

applied EDTA and NaCl solutions to study desorption behavior of natural and crosslinked 799

chitosan membranes for Hg(II) ions removal. Results showed that EDTA was not an 800

appropriate reagent for desorption of mercury ions on crosslinked-chitosan. Low percentage 801

of Hg(II) desorption on crosslinked-chitosan for both reagents was due to decrease in the 802

quantity of amino groups of chitosan, hydrophobicity enhancement and reduction in the 803

crystalinity of the polymer structure (Vieira & Beppu, 2006a). For all the membranes, higher 804

values of desorption was achieved using NaCl solution compared with EDTA. This may be 805

connected to two factors. Firstly, stable complexes such as (HgCl2) and complexes with 806

negative charge (HgCl3- and HgCl42-) can be formed. Secondly, the electrostatic interactions 807

of chitosan with sodium ions, decreases the interaction between chitosan and mercury and so 808

promote desorption. In another attempt, they investigated adsorption/desorption cycles for 809

natural and GA-cross-linked chitosan membranes using NaCl solution as eluent (Vieira & 810

Beppu, 2006a). The cross-linked chitosan membranes presented higher adsorption/desorption 811

capacity than the pristine chitosan which showed a slight dissolution in the second cycle. 812

Therefore, for long term use the cross-linked adsorbent was probably a better choice and its 813

low desorption rates might be compensated with its high adsorption capacity. Another 814

investigation was performed using NaCl solution on neat and cross-linked chitosan membrane 815

in challenge with chromium ions (Baroni, Vieira, Meneghetti, Da Silva & Beppu, 2008). 816

Cross-linked chitosan membranes showed the best chromium ion desorption compared to neat 817

chitosan, although the latter membrane showed lower adsorption capacity. 818

Regeneration of chitosan/ACF/TiO2 membrane used to remove dichlorophenol from aqueous 819

34
 solutions was obtained by oxidizing adsorbed 2,4-dichlorophenol (2,4-DCP) via in situ 820

(during adsorption) or ex situ (after completion of adsorption) photocatalytic and/or chemical 821

oxidation using Fenton reagents (Fe2+ and H2O2) (Liu, Zhang & Yang, 2010). After each 822

adsorption test, each piece of composite membrane was dipped in distilled water under UV- 823

irradiation. The ex situ regeneration technique showed better performance; however, the 824

efficiency of 2,4-DCP oxidation had higher in situ adsorption and photocatalytic oxidation. In 825

Fenton regeneration, reagents are very violent oxidants that may affect the structure of the 826

composite membranes. Thus, the UV photocatalytic degradation would be better to regenerate 827

the composite membrane. Fenton oxidation treatment may also increase membrane 828

hydrophilicity because of formation of O-containing groups in the polymeric structure. 829

Altogether, efficient and not complicated methods can be proposed for regeneration of 830

chitosan based membranes to ensure the reusability and durability of them. 831

832

5. Further perspectives 833

On the basis of the aspects considered in this review, the potential studies on chitosan 834

membranes might be summarized as below: 835

 Chitosan-based membranes often suffer from lack of sufficient stability, especially when 836

applied in flow (dynamic) adsorption mode. More studies on the reinforcement methods of 837

chitosan membrane adsorbents are necessary. As a key point, these methods should preserve 838

adsorptive functional groups of chitosan polymer along with providing reinforcement. 839

 The limited number of studies on molecular-imprinted chitosan membranes encourages more 840

attention to this kind of chitosan membrane to achieve specialized separation aims with a 841

biocompatible nontoxic membrane. 842

 The novel and more facile methods of regenerating chitosan-based membranes might be 843

considered by applying self-regenerative functions in membrane matrix or surface as it has 844

35
 done for chitosan adsorbent (not in the form of membrane). The idea of adding TiO2 845

(photocatalyst) and cross-linking chitosan for obtaining self-regenerative adsorbent of azo 846

dye (as contaminant) was developed by Yu F. et al (Yu et al., 2014). 847

 Incorporation of various metal oxide nanostructures can be tested as additives/fillers for the 848

modification of chitosan-based membrane adsorbents (Salehi, Hosseini, Ansari & Hamidi, 849

2016). The similar studies might be developed for other kind of nanomaterials having 850

additional properties like magnetism or chemical reactivity for more special separation 851

purposes. 852

 Modeling and simulation of transport phenomena in chitosan membrane adsorbents have 853

rarely been addressed in literature (Salehi, Davarnejad & Madaeni, 2015). Such studies would 854

be conductive and beneficial and can improve our understanding on mechanisms involved in 855

adsorptive membrane transport. 856

857

36
 858

References 859

Akhtar, K., Akhtar, M. W., & Khalid, A. M. (2007). Removal and recovery of uranium from 860

aqueous solutions by Trichoderma harzianum. Water Research, 41(6), 1366-1378. 861

Ali, N., Hameed, A., & Ahmed, S. (2009). Physicochemical characterization and 862

Bioremediation perspective of textile effluent, dyes and metals by indigenous Bacteria. 863

Journal of hazardous materials, 164(1), 322-328. 864

Aliabadi, M., Irani, M., Ismaeili, J., & Najafzadeh, S. (2014). Design and evaluation of 865

chitosan/hydroxyapatite composite nanofiber membrane for the removal of heavy metal ions 866

from aqueous solution. Journal of the Taiwan Institute of Chemical Engineers, 45(2), 518- 867

526. 868

Alias, S. S., Ariff, Z. M., & Mohamad, A. A. (2015). Porous membrane based on chitosan– 869

SiO 2 for coin cell proton battery. Ceramics International, 41(4), 5484-5491. 870

Amiji, M. M. (1995). Permeability and blood compatibility properties of chitosan-poly 871

(ethylene oxide) blend membranes for haemodialysis. Biomaterials, 16(8), 593-599. 872

Bai, X., Zhang, Y., Wang, H., Zhang, H., & Liu, J. (2013). Study on the modification of 873

positively charged composite nanofiltration membrane by TiO 2 nanoparticles. Desalination, 874

313, 57-65. 875

Bailey, S. E., Olin, T. J., Bricka, R. M., & Adrian, D. D. (1999). A review of potentially low- 876

cost sorbents for heavy metals. Water Research, 33(11), 2469-2479. 877

Baroni, P., Vieira, R., Meneghetti, E., Da Silva, M., & Beppu, M. (2008). Evaluation of batch 878

adsorption of chromium ions on natural and crosslinked chitosan membranes. Journal of 879

hazardous materials, 152(3), 1155-1163. 880

Bayramoğlu, G., Yılmaz, M., & Arıca, M. Y. (2003). Affinity dye–ligand poly (hydroxyethyl 881

methacrylate)/chitosan composite membrane for adsorption lysozyme and kinetic properties. 882

37
Biochemical engineering journal, 13(1), 35-42. 883

Bessbousse, H., Verchère, J.-F., & Lebrun, L. (2010). Increase in permeate flux by porosity 884

enhancement of a sorptive UF membrane designed for the removal of mercury (II). Journal of 885

Membrane Science, 364(1), 167-176. 886

Bet-moushoul, E., Mansourpanah, Y., Farhadi, K., & Tabatabaei, M. (2016). TiO 2 887

nanocomposite based polymeric membranes: a review on performance improvement for 888

various applications in chemical engineering processes. Chemical Engineering Journal, 283, 889

29-46. 890

Bibi, S., Yasin, T., Hassan, S., Riaz, M., & Nawaz, M. (2015). Chitosan/CNTs green 891

nanocomposite membrane: Synthesis, swelling and polyaromatic hydrocarbons removal. 892

Materials Science and Engineering: C, 46, 359-365. 893

Bleiman, N., & Mishael, Y. G. (2010). Selenium removal from drinking water by adsorption 894

to chitosan–clay composites and oxides: batch and columns tests. Journal of hazardous 895

materials, 183(1), 590-595. 896

Boddu, V. M., Abburi, K., Talbott, J. L., Smith, E. D., & Haasch, R. (2008). Removal of 897

arsenic (III) and arsenic (V) from aqueous medium using chitosan-coated biosorbent. Water 898

Research, 42(3), 633-642. 899

Bondeson, D., Mathew, A., & Oksman, K. (2006). Optimization of the isolation of 900

nanocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose, 13(2), 171-180. 901

Boricha, A. G., & Murthy, Z. (2009). Acrylonitrile butadiene styrene/chitosan blend 902

membranes: preparation, characterization and performance for the separation of heavy metals. 903

Journal of Membrane Science, 339(1), 239-249. 904

Boricha, A. G., & Murthy, Z. (2010). Preparation of N, O-carboxymethyl chitosan/cellulose 905

acetate blend nanofiltration membrane and testing its performance in treating industrial 906

wastewater. Chemical Engineering Journal, 157(2), 393-400. 907

38
Boricha, A. G., & Murthy, Z. V. P. (2011). Dilute solution viscometry study on the 908

miscibility of N, O-carboxymethyl chitosan-cellulose acetate blends. Journal of Polymer 909

Engineering, 31(4), 333-340. 910

Bowen, W. R., Doneva, T. A., & Yin, H.-B. (2002). Separation of humic acid from a model 911

surface water with PSU/SPEEK blend UF/NF membranes. Journal of Membrane Science, 912

206(1), 417-429. 913

Buthelezi, S. P., Olaniran, A. O., & Pillay, B. (2012). Textile dye removal from wastewater 914

effluents using bioflocculants produced by indigenous bacterial isolates. Molecules, 17(12), 915

14260-14274. 916

Carneiro, R. T., Taketa, T. B., Neto, R. J. G., Oliveira, J. L., Campos, E. V., de Moraes, M. 917

A., da Silva, C. M., Beppu, M. M., & Fraceto, L. F. (2015). Removal of glyphosate herbicide 918

from water using biopolymer membranes. Journal of environmental management, 151, 353- 919

360. 920

Celis, R., Adelino, M., Hermosin, M., & Cornejo, J. (2012). Montmorillonite–chitosan 921

bionanocomposites as adsorbents of the herbicide clopyralid in aqueous solution and 922

soil/water suspensions. Journal of hazardous materials, 209, 67-76. 923

Cestari, A. R., Vieira, E. F., Matos, J. D., & dos Anjos, D. S. (2005). Determination of kinetic 924

parameters of Cu (II) interaction with chemically modified thin chitosan membranes. Journal 925

of Colloid and Interface Science, 285(1), 288-295. 926

Cestari, A. R., Vieira, E. F., & Mattos, C. R. (2006). Thermodynamics of the Cu (II) 927

adsorption on thin vanillin-modified chitosan membranes. The Journal of Chemical 928

Thermodynamics, 38(9), 1092-1099. 929

Chao, A.-C., Yu, S.-H., & Chuang, G.-S. (2006). Using NaCl particles as porogen to prepare 930

a highly adsorbent chitosan membranes. Journal of Membrane Science, 280(1), 163-174. 931

Cheng, Z., Liu, X., Han, M., & Ma, W. (2010). Adsorption kinetic character of copper ions 932

39
onto a modified chitosan transparent thin membrane from aqueous solution. Journal of 933

hazardous materials, 182(1), 408-415. 934

Chiou, M.-S., Ho, P.-Y., & Li, H.-Y. (2004). Adsorption of anionic dyes in acid solutions 935

using chemically cross-linked chitosan beads. Dyes and Pigments, 60(1), 69-84. 936

Crini, G. (2006). Non-conventional low-cost adsorbents for dye removal: a review. 937

Bioresource Technology, 97(9), 1061-1085. 938

Crini, G., & Badot, P.-M. (2008). Application of chitosan, a natural aminopolysaccharide, for 939

dye removal from aqueous solutions by adsorption processes using batch studies: A review of 940

recent literature. Progress in polymer science, 33(4), 399-447. 941

Dai, J., Xu, X.-l., Yang, J.-h., Zhang, N., Huang, T., Wang, Y., Zhou, Z.-w., & Zhang, C.-l. 942

(2015). Greatly enhanced porosity of stretched polypropylene/graphene oxide composite 943

membrane achieved by adding pore-forming agent. RSC Advances, 5(27), 20663-20673. 944

Dalida, M. L. P., Mariano, A. F. V., Futalan, C. M., Kan, C.-C., Tsai, W.-C., & Wan, M.-W. 945

(2011). Adsorptive removal of Cu (II) from aqueous solutions using non-crosslinked and 946

crosslinked chitosan-coated bentonite beads. Desalination, 275(1), 154-159. 947

Daraei, P., Madaeni, S. S., Salehi, E., Ghaemi, N., Ghari, H. S., Khadivi, M. A., & Rostami, 948

E. (2013). Novel thin film composite membrane fabricated by mixed matrix 949

nanoclay/chitosan on PVDF microfiltration support: Preparation, characterization and 950

performance in dye removal. Journal of Membrane Science, 436, 97-108. 951

Devi, N. B., & Mishra, S. (2010). Solvent extraction equilibrium study of manganese (II) with 952

Cyanex 302 in kerosene. Hydrometallurgy, 103(1), 118-123. 953

Ding, W., Liang, C., Sun, S., He, L., & Gao, D. (2015). On-Chip Fabrication of Carbon 954

Nanoparticle–Chitosan Composite Membrane. Journal of Materials Science & Technology, 955

31(11), 1087-1093. 956

Duruibe, J., Ogwuegbu, M., & Egwurugwu, J. (2007). Heavy metal pollution and human 957

40
biotoxic effects. International Journal of Physical Sciences, 2(5), 112-118. 958

Elliott, H., & Huang, C. (1981). Adsorption characteristics of some Cu (II) complexes on 959

aluminosilicates. Water Research, 15(7), 849-855. 960

Esmaeili, A., & Beni, A. A. (2014). A novel fixed-bed reactor design incorporating an 961

electrospun PVA/chitosan nanofiber membrane. Journal of hazardous materials, 280, 788- 962

796. 963

Franco, L. d. O., Maia, R. d. C. C., Porto, A. L. F., Messias, A. S., Fukushima, K., & 964

Campos-Takaki, G. M. d. (2004). Heavy metal biosorption by chitin and chitosan isolated 965

from Cunninghamella elegans (IFM 46109). Brazilian Journal of Microbiology, 35(3), 243- 966

247. 967

G., H. A. (2013). Synthesis of Chitosan and Its Use in Metal Removal. 968

Genç, Ö., Arpa, C., Bayramoğlu, G., Arıca, M., & Bektaş, S. (2002). Selective recovery of 969

mercury by Procion Brown MX 5BR immobilized poly (hydroxyethylmethacrylate/chitosan) 970

composite membranes. Hydrometallurgy, 67(1), 53-62. 971

Genç, Ö., Soysal, L., Bayramoğlu, G., Arıca, M., & Bektaş, S. (2003). Procion Green H-4G 972

immobilized poly (hydroxyethylmethacrylate/chitosan) composite membranes for heavy 973

metal removal. Journal of hazardous materials, 97(1), 111-125. 974

Ghaee, A., Shariaty-Niassar, M., Barzin, J., & Matsuura, T. (2010). Effects of chitosan 975

membrane morphology on copper ion adsorption. Chemical Engineering Journal, 165(1), 46- 976

55. 977

Ghaee, A., Shariaty-Niassar, M., Barzin, J., & Zarghan, A. (2012). Adsorption of copper and 978

nickel ions on macroporous chitosan membrane: equilibrium study. Applied Surface Science, 979

258(19), 7732-7743. 980

Guibal, E. (2004). Interactions of metal ions with chitosan-based sorbents: a review. 981

Separation and Purification Technology, 38(1), 43-74. 982

41
Gümüşderelioğlu, M., & Agi, P. (2004). Adsorption of concanavalin A on the well- 983

characterized macroporous chitosan and chitin membranes. Reactive and functional polymers, 984

61(2), 211-220. 985

Gupta, V. (2009). Application of low-cost adsorbents for dye removal–A review. Journal of 986

environmental management, 90(8), 2313-2342. 987

Gupta, V., Khamparia, S., Tyagi, I., Jaspal, D., & Malviya, A. (2015). Decolorization of 988

mixture of dyes: A critical review. Global Journal of Environmental Science and 989

Management, 1(1), 71-94. 990

Haldorai, Y., & Shim, J.-J. (2014). An efficient removal of methyl orange dye from aqueous 991

solution by adsorption onto chitosan/MgO composite: A novel reusable adsorbent. Applied 992

Surface Science, 292, 447-453. 993

Han, W., Liu, C., & Bai, R. (2007). A novel method to prepare high chitosan content blend 994

hollow fiber membranes using a non-acidic dope solvent for highly enhanced adsorptive 995

performance. Journal of Membrane Science, 302(1), 150-159. 996

He, X., Du, M., Li, H., & Zhou, T. (2016). Removal of direct dyes from aqueous solution by 997

oxidized starch cross-linked chitosan/silica hybrid membrane. International journal of 998

biological macromolecules, 82, 174-181. 999

He, Z.-Y., Nie, H.-L., Branford-White, C., Zhu, L.-M., Zhou, Y.-T., & Zheng, Y. (2008). 1000

Removal of Cu 2+ from aqueous solution by adsorption onto a novel activated nylon-based 1001

membrane. Bioresource Technology, 99(17), 7954-7958. 1002

Hussain, F., Hojjati, M., Okamoto, M., & Gorga, R. E. (2006). Review article: polymer- 1003

matrix nanocomposites, processing, manufacturing, and application: an overview. Journal of 1004

composite materials, 40(17), 1511-1575. 1005

Irani, M., Amjadi, M., & Mousavian, M. A. (2011). Comparative study of lead sorption onto 1006

natural perlite, dolomite and diatomite. Chemical Engineering Journal, 178, 317-323. 1007

42
Jana, S., Saikia, A., Purkait, M., & Mohanty, K. (2011). Chitosan based ceramic ultrafiltration 1008

membrane: preparation, characterization and application to remove Hg (II) and As (III) using 1009

polymer enhanced ultrafiltration. Chemical Engineering Journal, 170(1), 209-219. 1010

Jhaveri, J. H., & Murthy, Z. (2016). A comprehensive review on anti-fouling nanocomposite 1011

membranes for pressure driven membrane separation processes. Desalination, 379, 137-154. 1012

Ji, Y.-L., An, Q.-F., Zhao, F.-Y., & Gao, C.-J. (2015). Fabrication of chitosan/PDMCHEA 1013

blend positively charged membranes with improved mechanical properties and high 1014

nanofiltration performances. Desalination, 357, 8-15. 1015

Jiang, Z., Yu, Y., & Wu, H. (2006). Preparation of CS/GPTMS hybrid molecularly imprinted 1016

membrane for efficient chiral resolution of phenylalanine isomers. Journal of Membrane 1017

Science, 280(1), 876-882. 1018

Kamiński, W., & Modrzejewska, Z. (1997). Application of chitosan membranes in separation 1019

of heavy metal ions. Separation science and technology, 32(16), 2659-2668. 1020

Kanagaraj, P., Nagendran, A., Rana, D., Matsuura, T., Neelakandan, S., Karthikkumar, T., & 1021

Muthumeenal, A. (2015). Influence of N-phthaloyl chitosan on poly (ether imide) 1022

ultrafiltration membranes and its application in biomolecules and toxic heavy metal ion 1023

separation and their antifouling properties. Applied Surface Science, 329, 165-173. 1024

Kant, R. (2012). Textile dyeing industry an environmental hazard. Natural science, 4(1), 22. 1025

Karim, Z., Mathew, A. P., Grahn, M., Mouzon, J., & Oksman, K. (2014). Nanoporous 1026

membranes with cellulose nanocrystals as functional entity in chitosan: removal of dyes from 1027

water. Carbohydrate Polymers, 112, 668-676. 1028

Karimnezhad, H., Salehi, E., Rajabi, L., Azimi, S., Derakhshan, A. A., & Ansari, M. (2014). 1029

Dynamic removal of n-hexane from water using nanocomposite membranes: Serial coating of 1030

para-aminobenzoate alumoxane, boehmite-epoxide and chitosan on Kevlar fabrics. Journal of 1031

Industrial and Engineering Chemistry, 20(6), 4491-4498. 1032

43
Karnib, M., Kabbani, A., Holail, H., & Olama, Z. (2014). Heavy metals removal using 1033

activated carbon, silica and silica activated carbon composite. Energy Procedia, 50, 113-120. 1034

Keshtkar, A. R., Irani, M., & Moosavian, M. A. (2013). Comparative study on PVA/silica 1035

membrane functionalized with mercapto and amine groups for adsorption of Cu (II) from 1036

aqueous solutions. Journal of the Taiwan Institute of Chemical Engineers, 44(2), 279-286. 1037

Kumar, M. N. R. (2000). A review of chitin and chitosan applications. Reactive and 1038

functional polymers, 46(1), 1-27. 1039

Kumar, R., Isloor, A. M., & Ismail, A. (2014). Preparation and evaluation of heavy metal 1040

rejection properties of polysulfone/chitosan, polysulfone/N-succinyl chitosan and 1041

polysulfone/N-propylphosphonyl chitosan blend ultrafiltration membranes. Desalination, 1042

350, 102-108. 1043

Lee, H. C., Jeong, Y. G., Min, B. G., Lyoo, W. S., & Lee, S. C. (2009). Preparation and acid 1044

dye adsorption behavior of polyurethane/chitosan composite foams. Fibers and Polymers, 1045

10(5), 636-642. 1046

Li, L.-H., Deng, J.-C., Deng, H.-R., Liu, Z.-L., & Li, X.-L. (2010). Preparation, 1047

characterization and antimicrobial activities of chitosan/Ag/ZnO blend films. Chemical 1048

Engineering Journal, 160(1), 378-382. 1049

Li, L.-H., Deng, J.-C., Deng, H.-R., Liu, Z.-L., & Xin, L. (2010). Synthesis and 1050

characterization of chitosan/ZnO nanoparticle composite membranes. Carbohydrate research, 1051

345(8), 994-998. 1052

Li, N., & Bai, R. (2006). Development of chitosan-based granular adsorbents for enhanced 1053

and selective adsorption performance in heavy metal removal. Water science and technology, 1054

54(10), 103-113. 1055

Li, S. F., Chen, Q., & Liu, M. (2011). Kinetics and Equilibrium Studies on Adsorption of 1056

Dimethylformamide by Macroporous Chitosan Membranes. Advanced Materials Research 1057

44
(Vol. 233, pp. 1141-1145): Trans Tech Publ. 1058

Li, X., Nan, K., Chen, H., & Xu, Y. (2011). Preparation and characterization of chitosan 1059

nanopores membranes for the transport of drugs. International journal of pharmaceutics, 1060

420(2), 371-377. 1061

Liu, C., & Bai, R. (2006). Adsorptive removal of copper ions with highly porous 1062

chitosan/cellulose acetate blend hollow fiber membranes. Journal of Membrane Science, 1063

284(1), 313-322. 1064

Liu, L. F., Zhang, P. H., & Yang, F. L. (2010). Adsorptive removal of 2, 4-DCP from water 1065

by fresh or regenerated chitosan/ACF/TiO 2 membrane. Separation and Purification 1066

Technology, 70(3), 354-361. 1067

Liu, Q., Hu, P., Wang, J., Zhang, L., & Huang, R. (2015). Phosphate adsorption from aqueous 1068

solutions by Zirconium (IV) loaded cross-linked chitosan particles. Journal of the Taiwan 1069

Institute of Chemical Engineers. 1070

Liu, Y.-L., Chen, W.-H., & Chang, Y.-H. (2009). Preparation and properties of 1071

chitosan/carbon nanotube nanocomposites using poly (styrene sulfonic acid)-modified CNTs. 1072

Carbohydrate Polymers, 76(2), 232-238. 1073

Lopes, E. C., dos Anjos, F. S., Vieira, E. F., & Cestari, A. R. (2003). An alternative Avrami 1074

equation to evaluate kinetic parameters of the interaction of Hg (II) with thin chitosan 1075

membranes. Journal of Colloid and Interface Science, 263(2), 542-547. 1076

Ma, B., Qin, A., Li, X., Zhao, X., & He, C. (2014). Structure and properties of chitin whisker 1077

reinforced chitosan membranes. International journal of biological macromolecules, 64, 341- 1078

346. 1079

Madaeni, S., Zinadini, S., & Vatanpour, V. (2011). Convective flow adsorption of nickel ions 1080

in PVDF membrane embedded with multi-walled carbon nanotubes and PAA coating. 1081

Separation and Purification Technology, 80(1), 155-162. 1082

45
Malini, M., Thirumavalavan, M., Yang, W.-Y., Lee, J.-F., & Annadurai, G. (2015). A 1083

versatile chitosan/ZnO nanocomposite with enhanced antimicrobial properties. International 1084

journal of biological macromolecules, 80, 121-129. 1085

Mallakpour, S., & Khadem, E. (2015). Recent development in the synthesis of polymer 1086

nanocomposites based on nano-alumina. Progress in polymer science, 51, 74-93. 1087

Mishra, G., & Tripathy, M. (1993). A critical review of the treatments for decolourization of 1088

textile effluent. Colourage, 40, 35-35. 1089

Mohanasrinivasan, V., Mishra, M., Paliwal, J. S., Singh, S. K., Selvarajan, E., Suganthi, V., 1090

& Devi, C. S. (2014). Studies on heavy metal removal efficiency and antibacterial activity of 1091

chitosan prepared from shrimp shell waste. 3 Biotech, 4(2), 167-175. 1092

Nasef, M. M., & Yahaya, A. H. (2009). Adsorption of some heavy metal ions from aqueous 1093

solutions on Nafion 117 membrane. Desalination, 249(2), 677-681. 1094

Nesic, A. R., Velickovic, S. J., & Antonovic, D. G. (2012). Characterization of 1095

chitosan/montmorillonite membranes as adsorbents for Bezactiv Orange V-3R dye. Journal 1096

of hazardous materials, 209, 256-263. 1097

Ng, L. Y., Mohammad, A. W., Leo, C. P., & Hilal, N. (2013). Polymeric membranes 1098

incorporated with metal/metal oxide nanoparticles: a comprehensive review. Desalination, 1099

308, 15-33. 1100

Ngah, W. W., & Fatinathan, S. (2008). Adsorption of Cu (II) ions in aqueous solution using 1101

chitosan beads, chitosan–GLA beads and chitosan–alginate beads. Chemical Engineering 1102

Journal, 143(1), 62-72. 1103

Ngah, W. W., & Hanafiah, M. (2008). Removal of heavy metal ions from wastewater by 1104

chemically modified plant wastes as adsorbents: a review. Bioresource Technology, 99(10), 1105

3935-3948. 1106

Ngah, W. W., Teong, L., & Hanafiah, M. (2011). Adsorption of dyes and heavy metal ions by 1107

46
chitosan composites: A review. Carbohydrate Polymers, 83(4), 1446-1456. 1108

Nie, H.-L., Chen, T.-X., & Zhu, L.-M. (2007). Adsorption of papain on dye affinity 1109

membranes: Isotherm, kinetic, and thermodynamic analysis. Separation and Purification 1110

Technology, 57(1), 121-125. 1111

O’Connell, D. W., Birkinshaw, C., & O’Dwyer, T. F. (2008). Heavy metal adsorbents 1112

prepared from the modification of cellulose: A review. Bioresource Technology, 99(15), 1113

6709-6724. 1114

Ong, S.-T., Keng, P.-S., Lee, W.-N., Ha, S.-T., & Hung, Y.-T. (2011). Dye waste treatment. 1115

Water, 3(1), 157-176. 1116

Ong, Y. T., Ahmad, A. L., Zein, S. H. S., Sudesh, K., & Tan, S. H. (2011). Poly (3- 1117

hydroxybutyrate)-functionalised multi-walled carbon nanotubes/chitosan green 1118

nanocomposite membranes and their application in pervaporation. Separation and 1119

Purification Technology, 76(3), 419-427. 1120

Padhi, B. (2012). Pollution due to synthetic dyes toxicity & carcinogenicity studies and 1121

remediation. International Journal of Environmental Sciences, 3(3), 940. 1122

Paul, D., & Robeson, L. (2008). Polymer nanotechnology: nanocomposites. Polymer, 49(15), 1123

3187-3204. 1124

Peng, F., Pan, F., Sun, H., Lu, L., & Jiang, Z. (2007). Novel nanocomposite pervaporation 1125

membranes composed of poly (vinyl alcohol) and chitosan-wrapped carbon nanotube. 1126

Journal of Membrane Science, 300(1), 13-19. 1127

Pillai, C., Paul, W., & Sharma, C. P. (2009). Chitin and chitosan polymers: Chemistry, 1128

solubility and fiber formation. Progress in polymer science, 34(7), 641-678. 1129

Pirillo, S., Pedroni, V., Rueda, E., & Luján Ferreira, M. (2009). Elimination of dyes from 1130

aqueous solutions using iron oxides and chitosan as adsorbents: a comparative study. Química 1131

Nova, 32(5), 1239-1244. 1132

47
Premakshi, H., Ramesh, K., & Kariduraganavar, M. (2015). Modification of crosslinked 1133

chitosan membrane using NaY zeolite for pervaporation separation of water–isopropanol 1134

mixtures. Chemical Engineering Research and Design, 94, 32-43. 1135

Reiad, N. A., Salam, O. E. A., Abadir, E. F., & Harraz, F. A. (2012). Adsorptive removal of 1136

iron and manganese ions from aqueous solutions with microporous chitosan/polyethylene 1137

glycol blend membrane. Journal of Environmental Sciences, 24(8), 1425-1432. 1138

Rinaudo, M. (2006). Chitin and chitosan: properties and applications. Progress in polymer 1139

science, 31(7), 603-632. 1140

Riva, R., Ragelle, H., des Rieux, A., Duhem, N., Jérôme, C., & Préat, V. (2011). Chitosan 1141

and chitosan derivatives in drug delivery and tissue engineering. Chitosan for biomaterials II 1142

(pp. 19-44): Springer. 1143

Sakkayawong, N., Thiravetyan, P., & Nakbanpote, W. (2005). Adsorption mechanism of 1144

synthetic reactive dye wastewater by chitosan. Journal of Colloid and Interface Science, 1145

286(1), 36-42. 1146

Salehi, E., Abdi, J., & Aliei, M. H. (2014). Assessment of Cu (II) adsorption from water on 1147

modified membrane adsorbents using LS-SVM intelligent approach. Journal of Saudi 1148

Chemical Society. 1149

Salehi, E., Davarnejad, R., & Madaeni, S. (2015). Kinetic-based long-time correlations for 1150

dialysis permeation through thin nanocomposite membrane adsorbents. Journal of the Iranian 1151

Chemical Society, 12(12), 2125-2132. 1152

Salehi, E., Hosseini, S. M., Ansari, S., & Hamidi, A. (2016). Surface modification of 1153

sulfonated polyvinylchloride cation-exchange membranes by using chitosan polymer 1154

containing Fe3O4 nanoparticles. Journal of Solid State Electrochemistry, 20(2), 371-377. 1155

Salehi, E., & Madaeni, S. (2014). Influence of poly (ethylene glycol) as pore-generator on 1156

morphology and performance of chitosan/poly (vinyl alcohol) membrane adsorbents. Applied 1157

48
Surface Science, 288, 537-541. 1158

Salehi, E., Madaeni, S., Rajabi, L., Derakhshan, A., Daraei, S., & Vatanpour, V. (2013). 1159

Static and dynamic adsorption of copper ions on chitosan/polyvinyl alcohol thin adsorptive 1160

membranes: Combined effect of polyethylene glycol and aminated multi-walled carbon 1161

nanotubes. Chemical Engineering Journal, 215, 791-801. 1162

Salehi, E., Madaeni, S., Rajabi, L., Vatanpour, V., Derakhshan, A., Zinadini, S., Ghorabi, S., 1163

& Monfared, H. A. (2012). Novel chitosan/poly (vinyl) alcohol thin adsorptive membranes 1164

modified with amino functionalized multi-walled carbon nanotubes for Cu (II) removal from 1165

water: preparation, characterization, adsorption kinetics and thermodynamics. Separation and 1166

Purification Technology, 89, 309-319. 1167

Salehi, E., Madaeni, S., & Vatanpour, V. (2012). Thermodynamic investigation and 1168

mathematical modeling of ion-imprinted membrane adsorption. Journal of Membrane 1169

Science, 389, 334-342. 1170

Santos, D., Neto, C., Fonseca, J., & Pereira, M. (2008). Chitosan macroporous asymmetric 1171

membranes—Preparation, characterization and transport of drugs. Journal of Membrane 1172

Science, 325(1), 362-370. 1173

Seo, S.-J., Kim, J.-J., Kim, J.-H., Lee, J.-Y., Shin, U. S., Lee, E.-J., & Kim, H.-W. (2014). 1174

Enhanced mechanical properties and bone bioactivity of chitosan/silica membrane by 1175

functionalized-carbon nanotube incorporation. Composites Science and Technology, 96, 31- 1176

37. 1177

Serizawa, T., Kamimura, S., Kawanishi, N., & Akashi, M. (2002). Layer-by-layer assembly 1178

of poly (vinyl alcohol) and hydrophobic polymers based on their physical adsorption on 1179

surfaces. Langmuir, 18(22), 8381-8385. 1180

Shao, L., Chang, X., Zhang, Y., Huang, Y., Yao, Y., & Guo, Z. (2013). Graphene oxide 1181

cross-linked chitosan nanocomposite membrane. Applied Surface Science, 280, 989-992. 1182

49
Shao, L., Low, B. T., Chung, T.-S., & Greenberg, A. R. (2009). Polymeric membranes for the 1183

hydrogen economy: contemporary approaches and prospects for the future. Journal of 1184

Membrane Science, 327(1), 18-31. 1185

Shawky, H. A. (2009). Synthesis of ion‐imprinting chitosan/PVA crosslinked membrane for 1186

selective removal of Ag (I). Journal of Applied Polymer Science, 114(5), 2608-2615. 1187

Shi, J., Wu, T., Teng, K., Wang, W., Shan, M., Xu, Z., Lv, H., & Deng, H. (2016). 1188

Simultaneous electrospinning and spraying toward branch-like nanofibrous membranes 1189

functionalised with carboxylated MWCNTs for dye removal. Materials Letters, 166, 26-29. 1190

Sivamani, S., & Leena, G. (2009). Removal of Dyes from Wastewater using Adsorption-A 1191

Review. IJBST, 2(4), 47-51. 1192

Song, W., Gao, B., Xu, X., Wang, F., Xue, N., Sun, S., Song, W., & Jia, R. (2016). 1193

Adsorption of nitrate from aqueous solution by magnetic amine-crosslinked biopolymer 1194

based corn stalk and its chemical regeneration property. Journal of hazardous materials, 304, 1195

280-290. 1196

Steenkamp, G., Neomagus, H., Krieg, H., & Keizer, K. (2001). Centrifugal casting of ceramic 1197

membrane tubes and the coating with chitosan. Separation and Purification Technology, 1198

25(1), 407-413. 1199

Swayampakula, K., Boddu, V. M., Nadavala, S. K., & Abburi, K. (2009). Competitive 1200

adsorption of Cu (II), Co (II) and Ni (II) from their binary and tertiary aqueous solutions 1201

using chitosan-coated perlite beads as biosorbent. Journal of hazardous materials, 170(2), 1202

680-689. 1203

Tang, C., Zhang, Q., Wang, K., Fu, Q., & Zhang, C. (2009). Water transport behavior of 1204

chitosan porous membranes containing multi-walled carbon nanotubes (MWNTs). Journal of 1205

Membrane Science, 337(1), 240-247. 1206

Thakur, V. K., & Kessler, M. R. (2015). Self-healing polymer nanocomposite materials: A 1207

50
review. Polymer, 69, 369-383. 1208

Tonglairoum, P., Sutananta, W., Rojanarata, T., Ngawhirunpat, T., & Opanasopit, P. (2014). 1209

Thermally crosslinked Chitosan-EDTA/PVA Electrospun Nanofiber Mats: Crosslinking 1210

Conditions. Advanced Materials Research (Vol. 1060, pp. 192-195): Trans Tech Publ. 1211

Trotta, F., Biasizzo, M., & Caldera, F. (2012). Molecularly imprinted membranes. 1212

Membranes, 2(3), 440-477. 1213

Vakili, M., Rafatullah, M., Salamatinia, B., Abdullah, A. Z., Ibrahim, M. H., Tan, K. B., 1214

Gholami, Z., & Amouzgar, P. (2014). Application of chitosan and its derivatives as 1215

adsorbents for dye removal from water and wastewater: A review. Carbohydrate Polymers, 1216

113, 115-130. 1217

Vatanpour, V., Madaeni, S. S., Zinadini, S., & Rajabi, H. R. (2011). Development of ion 1218

imprinted technique for designing nickel ion selective membrane. Journal of Membrane 1219

Science, 373(1), 36-42. 1220

Vieira, R., Guibal, E., Silva, E., & Beppu, M. (2007). Adsorption and desorption of binary 1221

mixtures of copper and mercury ions on natural and crosslinked chitosan membranes. 1222

Adsorption, 13(5-6), 603-611. 1223

Vieira, R. S., & Beppu, M. M. (2005). Mercury ion recovery using natural and crosslinked 1224

chitosan membranes. Adsorption, 11(1), 731-736. 1225

Vieira, R. S., & Beppu, M. M. (2006a). Dynamic and static adsorption and desorption of Hg 1226

(II) ions on chitosan membranes and spheres. Water Research, 40(8), 1726-1734. 1227

Vieira, R. S., & Beppu, M. M. (2006b). Interaction of natural and crosslinked chitosan 1228

membranes with Hg (II) ions. Colloids and Surfaces A: Physicochemical and Engineering 1229

Aspects, 279(1), 196-207. 1230

Vijaya, Y., Popuri, S. R., Boddu, V. M., & Krishnaiah, A. (2008). Modified chitosan and 1231

calcium alginate biopolymer sorbents for removal of nickel (II) through adsorption. 1232

51
Carbohydrate Polymers, 72(2), 261-271. 1233

Wan, M.-W., Kan, C.-C., Rogel, B. D., & Dalida, M. L. P. (2010). Adsorption of copper (II) 1234

and lead (II) ions from aqueous solution on chitosan-coated sand. Carbohydrate Polymers, 1235

80(3), 891-899. 1236

Wang, L., & Wang, A. (2007). Adsorption characteristics of Congo Red onto the 1237

chitosan/montmorillonite nanocomposite. Journal of hazardous materials, 147(3), 979-985. 1238

Wang, X.-j., Xia, S.-q., Ling, C., Zhao, J.-F., Chovelon, J.-m., & NICOLE, J.-r. (2006). 1239

Biosorption of cadmium (II) and lead (II) ions from aqueous solutions onto dried activated 1240

sludge. Journal of Environmental Sciences, 18(5), 840-844. 1241

Wang, X., Du, Y., Fan, L., Liu, H., & Hu, Y. (2005). Chitosan-metal complexes as 1242

antimicrobial agent: synthesis, characterization and structure-activity study. Polymer Bulletin, 1243

55(1-2), 105-113. 1244

Wang, X., Zhang, L., Ma, C., Song, R., Hou, H., & Li, D. (2009). Enrichment and separation 1245

of silver from waste solutions by metal ion imprinted membrane. Hydrometallurgy, 100(1), 1246

82-86. 1247

Xu, L., Huang, Y.-A., Zhu, Q.-J., & Ye, C. (2015). Chitosan in Molecularly-Imprinted 1248

Polymers: Current and Future Prospects. International journal of molecular sciences, 16(8), 1249

18328-18347. 1250

Yang, D., Li, J., Jiang, Z., Lu, L., & Chen, X. (2009). Chitosan/TiO 2 nanocomposite 1251

pervaporation membranes for ethanol dehydration. Chemical Engineering Science, 64(13), 1252

3130-3137. 1253

Yin, J., & Deng, B. (2015). Polymer-matrix nanocomposite membranes for water treatment. 1254

Journal of Membrane Science, 479, 256-275. 1255

Yu, F., Chen, L., Ma, J., Sun, Y., Li, Q., Li, C., Yang, M., & Chen, J. (2014). Self- 1256

regenerative adsorbent based on the cross-linking chitosan for adsorbing and mineralizing azo 1257

52
dye. RSC Advances, 4(11), 5518-5523. 1258

Zarghami, S., Kazemimoghadam, M., & Mohammadi, T. (2014). Cu (II) removal 1259

enhancement from aqueous solutions using ion-imprinted membrane technique. Chemical 1260

Papers, 68(6), 809-815. 1261

Zeng, M., & Fang, Z. (2004). Preparation of sub-micrometer porous membrane from 1262

chitosan/polyethylene glycol semi-IPN. Journal of Membrane Science, 245(1), 95-102. 1263

Zeng, M., Fang, Z., & Xu, C. (2004). Novel method of preparing microporous membrane by 1264

selective dissolution of chitosan/polyethylene glycol blend membrane. Journal of Applied 1265

Polymer Science, 91(5), 2840-2847. 1266

Zeng, X., & Ruckenstein, E. (1996). Control of pore sizes in macroporous chitosan and chitin 1267

membranes. Industrial & engineering chemistry research, 35(11), 4169-4175. 1268

Zha, F., Li, S., Chang, Y., & Yan, J. (2008). Preparation and adsorption kinetics of porous γ- 1269

glycidoxypropyltrimethoxysilane crosslinked chitosan–β-cyclodextrin membranes. Journal of 1270

Membrane Science, 321(2), 316-323. 1271

Zhang, L., Zeng, Y., & Cheng, Z. (2016). Removal of heavy metal ions using chitosan and 1272

modified chitosan: A review. Journal of Molecular Liquids, 214, 175-191. 1273

Zheng, X.-F., Lian, Q., & Yang, H. (2014). Synthesis of chitosan–gelatin molecularly 1274

imprinted membranes for extraction of L-tyrosine. RSC Adv., 4(80), 42478-42485. 1275

Zhu, H.-Y., Jiang, R., & Xiao, L. (2010). Adsorption of an anionic azo dye by 1276

chitosan/kaolin/γ-Fe 2 O 3 composites. Applied Clay Science, 48(3), 522-526. 1277

Zhu, J., Tian, M., Zhang, Y., Zhang, H., & Liu, J. (2015). Fabrication of a novel ―loose‖ 1278

nanofiltration membrane by facile blending with Chitosan–Montmorillonite nanosheets for 1279

dyes purification. Chemical Engineering Journal, 265, 184-193. 1280

Zinadini, S., Zinatizadeh, A., Rahimi, M., Vatanpour, V., Zangeneh, H., & Beygzadeh, M. 1281

(2014). Novel high flux antifouling nanofiltration membranes for dye removal containing 1282

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carboxymethyl chitosan coated Fe3O4 nanoparticles. Desalination, 349, 145-154. 1283

1284

1285

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List of abbreviations 1286

(2,4-DCP) 2,4-dichlorophenol
ABS Acrylonitrile butadiene
styrene
ACF Activated carbon fiber
CNTs Carbon nanotubes
CA Cellulose acetate
CNCs Cellulose nanocrystals
CS Chitosan
CS/HAp Chitosan/hydroxyapatite
CS/PEG Chitosan/polyethylene
glycol
CS/PVA Chitosan/polyvinyl alcohol
CS–MMT Chitosan–montmorillonite
DI Deionized
DMF Dimethylformamide
EDTA Ethylenediaminetetraacetic
acid
GA Glutaraldehyde
MMT Montmorillonite
MWCNTs Multiwalled carbon
nanotubes
DMAc N, N-dimethylacetamide
NOCC N,Ocarboxymethyl
chitosan
NF Nanofiltration
NMP N-methylpyrrolidone
NPHCs N-phthaloyl chitosan
CC O-carboxymethyl chitosan
PAB-A Para-aminobenzoate
alumoxane
PEI Poly(ether imide)
PES Polyethrsulfone
PEG Polyethyleneglycol
PS Polysulfone
PVDF Polyvinylidene fluoride
SDS Sodium dodecyl sulfate
THF Tetrahydrofuran
TFC Thin film composite
UF Ultrafiltration
1287

1288

55
List of Figures 1289

1290

Fig. 1. Ring current caused by free electron displacement in benzene ring as a responsible for 1291

the magnetic anisotropy and subsequent magnetic potential field around the CNTs resulting in 1292

cation diffusion 1293

Fig. 2. Scheme of imprinting process basis including casting the film involving the template 1294

species and leaching the template out of casted film 1295

Fig. 3. Scheme of selective adsorption of target by imprinted membrane and removal of target 1296

from feed flow (note the decreased number of target in permeate side) 1297

Fig. 4. Probable electrostatic interaction and H-bonding of a direct dye with chitosan chains 1298

Fig. 5. Coordination of metal ion (Mn+) by amine groups of chitosan and additive based on 1299

chemical theory 1300

Fig. 6. Schematic model of metal ion (Mn+)/EDTA chelate structure 1301

1302

56
 1303

1304

1305

Fig. 1. Ring current caused by free electron displacement in benzene ring as a responsible for the 1306

magnetic anisotropy and subsequent magnetic potential field around the CNTs resulting in cation 1307

diffusion 1308

1309

1310

1311

1312

57
 1313

Fig. 2. Scheme of imprinting process basis including casting the film involving the template species 1314

and leaching the template out of casted film 1315

1316

1317

1318

Fig. 3. Scheme of selective adsorption of target by imprinted membrane and removal of target from 1319

feed flow (note the decreased number of target in permeate side) 1320

1321

58
 1322

1323

Fig. 4. Probable electrostatic interaction and H-bonding of a direct dye with chitosan chains 1324

1325

1326

Fig. 5. Coordination of metal ion (Mn+) by amine groups of chitosan and additive based on chemical 1327

theory 1328

1329

1330

1331

59
 1332

1333

1334

Fig. 6. Schematic model of metal ion (Mn+)/EDTA chelate structure 1335

1336

1337

1338

1339

1340

1341

60