Accepted Manuscript

Development of Novel Chitosan-Lignin Composites for Adsorption of Dyes and

Metal Ions from Wastewater

Vaishakh Nair, Ajitesh Panigrahy, R. Vinu

PII: S1385-8947(14)00620-2
DOI: http://dx.doi.org/10.1016/j.cej.2014.05.045
Reference: CEJ 12139

To appear in: Chemical Engineering Journal

Received Date: 30 March 2014

Revised Date: 10 May 2014
Accepted Date: 12 May 2014

Please cite this article as: V. Nair, A. Panigrahy, R. Vinu, Development of Novel Chitosan-Lignin Composites for
Adsorption of Dyes and Metal Ions from Wastewater, Chemical Engineering Journal (2014), doi: http://dx.doi.org/
10.1016/j.cej.2014.05.045

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Development of Novel Chitosan-Lignin Composites for Adsorption of Dyes
and Metal Ions from Wastewater

Vaishakh Nair,a Ajitesh Panigrahy,a R.Vinua,b,*

a
Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai –
600036, India
b
National Center for Combustion Research and Development, Indian Institute of Technology
Madras, Chennai – 600036, India

Abstract

It is important to devise new strategies to derive value from lignin, which is a

potential waste by-product from paper industries and present day biorefineries. In this
research, we report, for the first time, a facile preparation and characterization of a range of
chitosan-alkali lignin composites for the removal of harmful effluents present in wastewater.
The composites were characterized by the presence of weak bonding between β-1,4-
glycosidic linkage, amide and hydroxyl groups of chitosan, and ether and hydroxyl groups of
alkali lignin. Various reaction parameters like chitosan content in the composite, initial pH
and adsorbent dosage were optimized. Batch adsorption studies showed that chitosan-alkali
lignin(50:50) composite exhibited maximum percentage removal of anthraquinonic dye,
Remazol Brilliant Blue R (RBBR), and Cr(VI) compared to other composites, chitosan and
alkali lignin. Adsorption of RBBR on the composite followed Langmuir isotherm, and the
adsorption of both RBBR and Cr(VI) followed pseudo second order kinetics. A mechanism
of adsorption that involves (i) electrostatic interaction of protonated amino and hydroxyl
groups of the composite with anionic SO3- and HCrO4- groups of dye and Cr(VI),
respectively, and (ii) chemical interaction between amino and hydroxyl groups of the
composite, and carbonyl moiety of the dye, was proposed.

Keywords

Chitosan, alkali lignin, composite, adsorption, kinetics, chromium, dyes, mechanism

*
Corresponding Author. Phone: +91-44-2257 4187. E-mail: vinu@iitm.ac.in (R. Vinu)
1
1. Introduction

Lignin, an amorphous, crosslinked and aromatic polymer, is naturally found in

biomasses, and is also a major non-sugar component of wood [1]. Lignin is well known as a
waste by-product from pulp and paper industries. However, it is also a major reject from the
present day biorefineries that produce cellulosic ethanol after the separation of cellulose and
hemicellulose in the pretreatment step. Lignin is composed of propyl-phenolic subunits
containing phenolic, hydroxyl, carbonyl, methoxy and aldehyde groups that serve as potential
active sites for adsorption of dyes and metal ions [2-4]. The composition and structural units
of lignin differ depending on the source of biomass from which lignin is extracted. In paper
industries, depending upon the pulping process, different types of lignins are obtained as
waste by-products. The waste alkali lignin produced from kraft pulping process is inert and is
usually burnt for power [1,5], eventhough its rich chemical functionality can be utilized in a
better way to produce composites and value added chemicals. Reuse of lignin will not only
reduce the amount of the biowaste, but also provide additional revenue to the industries [1].
Recently, lignin has found applications in the form of adhesives, tanning agents and as a
precursor for producing activated carbon, which is a well known adsorbent [6]. This work
aims at modifying lignin for use as an adsorbent for waste water decontamination.

Wastewater discharge from dye, paint, paper, textile and electroplating industries
contain harmful chemicals like dyes and metal ions, which pollute the water bodies. The
presence of very low concentrations of even 10 ppm of dyes in water imparts a colour,
making it undesirable for use [7]. The reactive dyes that are discharged into the water bodies
are not biodegradable, and hence, are toxic to aquatic life. Remazol Brilliant Blue R (RBBR)
is an anthraquinonic dye used widely in paints, inks, chemical indicators, dyeing of cottons,
silk and as a starting material in the production of polymeric dyes [8]. Similarly, hexavalent
chromium, Cr(VI), is mostly generated by chemical processes like electroplating, leather
tanning, pigment manufacturing and mining [9]. Chromium metal ion exists in two valence
states, viz., Cr(III) and Cr(VI), of which the latter is highly toxic and carcinogenic [10] .

Adsorption is one of the superior physicochemical methods for wastewater

detoxification compared to other methods like coagulation, ion exchange, oxidation, chemical
precipitation, electrodeposition and membrane seperation, owing to high removal efficiency
for different types of effluents, ease of operation, availability of a variety of cheap
adsorbents, and the absence of sludge formation and harmful by-products [11]. Recent

2
investigations on the removal of effluents by adsorption are focused on utilizing readily
available and cheap bio-based materials like maize [12], agricultural waste [13], jute fiber
[14], rice husk [15] and mango seed [16]. Table 1 [4,13,15,17-22] presents a summary of
adsorption capacities of various bio-based materials for the removal of dyes and metal ions.
Researchers have utilized lignins extracted by organosolv and kraft pulping processes for
adsorption of dyes and metal ions [4,17,18,23]. Typically, non-sulphonated lignins like alkali
lignin can be used as adsorbents owing to their insolubility in water and high resistance to
chemical reactions. However, the structure of lignin varies based on the type of biomass (e.g.
softwood, hardwood, grassy), and hence, it is imperative that surface modified lignins and
lignin-based composites are developed as potential adsorbent materials.

Chitosan, a copolymer obtained by deacetylation of chitin [24], is a well known

biosorbent used for the removal of various types of pollutants like fluorides, dyes, heavy
metal ions and organic compounds found in waste water [19,25]. Chitosan is a copolymer of
2-glucosamine and N-acetyl-2-glucosamine units, wherein the former constitutes a major
fraction of the biopolymer chain. The adsorption characteristics of chitosan are due to the
large number of hydroxyl (-OH) and primary amine (-NH2) groups that act as highly active
adsorption sites [26]. In acidic condition, the amine groups are protonated and thereby aids in
the adsorption of dye/metal ion by electrostatic attraction. However, chitosan, as an
adsorbent, has some disadvantages such as dissolution in highly acidic solution, low surface
area, high cost, poor thermal and mechanical properties [27]. Physical or chemical
modification of chitosan using different materials has been studied to improve its properties
and adsorption capacity. Chitosan composites such as chitosan-cellulose [22], chitosan-
zeolite [28], chitosan-polyaniline [29], and graphite oxide-magnetic chitosan [30] have been
developed that exhibit better adsorption together with enhancement in other physical and
chemical properties. The development of chitosan-based biocomposites will bring down the
overall cost of the adsorbent owing to decrease in the use of expensive chitosan, and provide
an opportunity for utilizing the renewable by-products produced in industries.

Development of biodegradable chitosan-alkali lignin composites for dye and metal

ion adsorption is a new area of application of alkali lignin. To the best of our knowledge, this
is the first work to report the removal of effluents from wastewater using chitosan-alkali
lignin composites with enhanced physicochemical properties. In this work, novel chitosan-
alkali lignin composites were prepared and characterized using various techniques like
Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA),

3
scanning electron microscopy (SEM) and porosimetry to establish the molecular structure,
thermal stability, surface morphology and specific surface area of the composites,
respectively. The adsorption of RBBR and Cr(VI) ion on chitosan, alkali lignin and chitosan-
alkali lignin composites was evaluated. Adsorption conditions such as chitosan content in the
composite, solution pH and adsorbent concentration were optimized. Equilibrium adsorption
isotherms and adsorption kinetics were evaluated. The dye and metal ion adsorbed
composites were characterized and the mechanism of adsorption of RBBR and Cr(VI) on the
composite active sites was proposed.

2. Experimental Section

2.1. Materials

Chitosan (95% deacetylated) and Remazol Brilliant Blue R (C.I. 61200;

C22H16N2Na2O11S3; MW 626.54 g mol-1) were purchased from Sisco Research Laboratories,
India. Alkali lignin (CAS No. 8068051) was obtained from Sigma Aldrich. Orange G (C.I.
116230; C16H10N2Na2O7S2; MW 452.37 g mol-1) and Malachite Green (C.I. 42000;
C52H54N4O12; MW 927.02 g mol-1) were purchased from S.D. Fine Chem., and Thermo
Fisher Scientific, India, respectively. Rhodamine.B (C.I. 45170; C28H31CIN2O3; MW 479.02
g mol-1) and Alizarin Red S (C.I. 58005; C14H7NaO7S; MW 342.26 g mol-1) were obtained
from HiMedia Laboratories, India. Potassium dichromate (K2Cr2O7) was procured from
Ranbaxy Fine Chemicals, India. All the chemicals were used as received. All solutions were
prepared using double distilled water.

2.2. Preparation of Chitosan-Alkali Lignin Composites

A known concentration of alkali lignin was added to 100 mL of double distilled water
and stirred well. An aqueous solution of chitosan was prepared in 100 mL of aqueous acetic
acid (2% v/v) and stirred well to form a homogeneous solution. The alkali lignin solution was
then added to the dissolved chitosan solution, and stirred at 300 rpm for 3 hours. The
chitosan-alkali lignin mixture was then filtered and dried at room temperature for 48 hours.
The composite was powdered and then washed with double distilled water. The composite
was then vacuum filtered using 0.45µm nylon membrane and finally dried at 100 oC for 3
hours. Different concentrations of chitosan:alkali lignin composites, viz., 5:95 wt.%
(henceforth denoted as 5ChAL), 10:90 wt.% (10ChAL), 25:75 wt.% (25ChAL), 50:50 wt.%
(50ChAL) were prepared according to the above procedure. Preparation of the composite

4
using any further higher concentration of chitosan resulted in the formation of a jelly mass
owing to high crosslinking. Importantly, the main aim of the work is to utilize significant
amounts of alkali lignin in the composite to replace the costly chitosan, and hence,
composites upto 50ChAL were subjected to further investigation.

2.3. Characterization of ChAL Composites

The FT-IR spectra of the composites, chitosan and alkali lignin were recorded in
Agilent Cary 660 FT-IR spectrometer in the range of 4000 cm-1 - 400 cm-1 in transmittance
mode with 16 scans, and a resolution of 4 cm-1. The samples were analysed in the form of
KBr pellets. Thermogravimetric analyses (TGA) of the composites, chitosan, alkali lignin and
physical mixtures were performed in SDT Q 600 TGA (T.A. instruments) under nitrogen
atmosphere (100 mL min-1) from 25 oC to 900 oC at a heating rate of 20 oC min-1. In order to
evaluate the apparent activation energy of decomposition, 50ChAL, chitosan and alkali lignin
were subjected to TGA at multiple heating rates from 5 to 30 oC min-1. The surface
morphology of the composites was characterized using a Hitachi S-4800 High Resolution
SEM. The specific surface area and pore size of the materials were obtained by nitrogen
adsorption-desorption isotherm at 77 K using Micromeritics ASAP 2020 porosimeter.
Specific surface area and pore sizes were evaluated using Brunauer Emmett Teller (BET) and
Barrett Joyner Halenda (BJH) methods, respectively. Energy dispersive X-ray analyses
(EDS) of the composites and Cr(VI)-adsorbed composite were performed using JEOL JSM-
7610F Field Emission SEM.

2.4. Batch Experiments for Dye and Metal Ion Adsorption.

A stock solution of 500 mg L-1 of RBBR was prepared and was further diluted to
obtain different concentrations from 10 mg L-1 to 300 mg L-1. The adsorption experiments
were carried out at ambient temperature (27±2 oC) using 50 mL of the dye solution and 0.1g
of the adsorbent and continuously stirred at 250 rpm. The natural pH of the dye solution was
5.9±0.1. Aqueous solutions of Cr(VI) of different concentrations were prepared by diluting
500 mg L-1 of K2Cr2O7 stock solution. The volume of metal ion solution and the concentration
of the adsorbent used were similar to the experiments of dye adsorption. The adsorption
experiments of Cr(VI) were conducted at a pH of 2, as the percentage adsorption of Cr(VI)
for various chitosan composites was reported to be maximum at low acidic pH, while high
alkaline pH favors the adsorption of Cr(III) [31,32]. Solution pH was regulated using 0.1M
HCl and 0.1M NaOH. Samples were withdrawn at periodic time intervals from the reaction

5
mixture, centrifuged at 3500 rpm and analyzed to determine the concentration using
Shimadzu UV-1800 UV-Vis spectrophotometer. RBBR concentration was measured by
noting the decrease in absorbance of the peak at 595 nm, while the concentration of Cr(VI)
was measured similarly at 540 nm using 1,5-diphenyl carbazide as the complexing agent
[10]. The experiments were repeated thrice and the uncertainty in concentration at the end of
adsorption was less than 5%. The amount of dye or metal ion adsorbed, q t (mg g-1), was
calculated using the following equation:

qt = (C 0 − C t )V / W (1)

where Co and Ct (in mg L-1) denote initial concentration and concentration of the adsorbate
after time t, W is the weight of the adsorbent used (g), and V is the volume of the adsorbate
solution (L). The percentage removal of the adsorbate was calculated using the following
equation:

%Removal = (C0 − Ct ) × 100 / C0 (2)

3. Results and Discussion

3.1. Characterization of ChAL Composites

3.1.1. FT-IR Analysis

The FT-IR spectra of alkali lignin, chitosan and 50ChAL composite, as shown in
Fig.1, were analyzed to identify the key functional groups responsible for the binding of
alkali lignin and chitosan. A broad peak at 3453-3362 cm-1 corresponding to stretching of
phenolic and aliphatic -OH group is observed for alkali lignin. The peaks at 2939 and 2829
cm-1 are attributed to the stretching of C-H bond present in the aromatic, methoxy and alkyl
groups. The peaks at 1596 and 1515 cm-1 are typical of aromatic C=C stretching in the
phenolic group of lignin [33]. The peaks at 1461, 1423 and 1367 cm-1 correspond to O-H
bending of the phenolic group. The peaks at 1270 and 1213 cm-1 are due to C-O-C stretching
in α-O-4 and β-O-4 linkages of alkali lignin, respectively. The peaks at 1135 and 1085 cm-1
are due to C-O-C stretching in the alkyl substituted ether. The peak at 624 cm-1 is due to the
S-C stretching in thioether group.

For chitosan, the presence of a broad peak at 3463-3362 cm-1 corresponds to the
stretching of O-H and N-H bonds. The peaks at 2927 and 2857 cm-1 are attributed to C-H

6
stretching of the alkyl group. The peak at 1654 cm-1 represents bending of N-H in primary
amine group. Small peaks at 1560 and 1549 cm-1 are due to bending of N-H of secondary
amine. A peak at 1380 cm-1 corresponds to C-H bending of alkyl group. The peaks at 1157
and 1084 cm-1 are related to C-O stretching in the β-1,4-glycosidic linkage present in chitosan
[30]. The peak at 669 cm-1 is due to the out-of-plane bending of the O-H group. The FT-IR
spectrum of the 50ChAL composite had all the key features of alkali lignin and chitosan with
minor shifts and changes in peak intensities corresponding to the weak interaction between
the two components as shown in Table 2. The disappearance of peak at 1560-1549 cm-1
present in chitosan and the change in intensity of the peak of aromatic ring at 1596 cm-1 are
due to the interactions between aromatic ring of alkali lignin and the secondary amine group
of chitosan. There are shifts observed in the peaks corresponding to C-O stretching from
1157 cm-1 to 1145 cm-1 of β-1,4-glycosidic linkage in the chitosan, and 1085 cm-1 to 1074
cm-1 [29,34] of alkyl substituted ether of the alkali lignin. These signify the interactions due
to hydrogen bonding between the hydroxyl of alkali lignin with β-1,4-glycosidic linkage of
chitosan, and the interaction of the alkyl substituted ether of alkali lignin with hydroxyl group
of chitosan. There was no significant change in the peaks of primary amine, confirming no
interaction of primary amine groups of chitosan in the composite formation.

Scheme 1 depicts the interactions present in chitosan-alkali lignin composites as

ascertained from FT-IR characterization. All the interactions between chitosan and alkali
lignin are likely due to the formation of weak hydrogen bonds. The hydroxyl group present in
the phenolic ring of alkali lignin can interact with (a) β-1,4-glycosidic oxygen (shown as
dashed line 1 in scheme 1) and (b) hydroxyl group of chitosan (dashed line 3). A weak bond
is also formed between hydroxyl group of chitosan and methoxy group of alkali lignin
(dashed line 2). Finally, a weak interaction between aromatic ring of alkali lignin and
secondary amino group of chitosan is also depicted as dashed line 4.

3.1.2. Thermogravimetric Analysis

Thermogravimetric weight loss curves of chitosan, alkali lignin, composites and 50:50
physical mixture of chitosan and lignin (50:50 Ch:AL(phys)) are depicted in Fig.2(a). Initial
weight loss around 100 oC observed for chitosan, 50ChAL and the physical mixture can be
ascribed to the removal of physisorbed moisture from the samples. Final weight losses
observed for various samples at 900 oC follows the order: chitosan (78%) > 50:50
Ch:AL(phys) (67%) > 5ChAL (64%) > 50ChAL (63%) > 10ChAL (62%) ≈ 25ChAL (62%)

7
> alkali lignin (59%). It is clear that lower extent of decomposition occurs in the composites
owing to the presence of lignin that leads to the formation of a crosslinked and condensed
matrix of aromatic structures at high temperatures. In order to ascertain the temperature range
of decomposition of these materials, differential weight loss profiles were plotted as depicted
in Fig. SI 1 (in supplementary data). It is clear that chitosan exhibits a single-step, sharp
decomposition in the temperature range of 210 - 410 oC while alkali lignin and 50 ChAL
decomposes in a wide temperature range of 140 - 600 oC. The composite also exhibits a
higher percent degradation in the temperature range of 200 - 330 oC compared to alkali
lignin. Interestingly, the physical mixture decomposes in the range of 150 - 500 oC, with a
sharp peak at 305 oC. This temperature corresponds to the maximum weight loss rate, as
observed in the differential weight loss profile. A similar peak was also observed for chitosan
at 308 oC. However, there is no sharp transition for alkali lignin and 50ChAL composite. This
shows that in the physical mixture the decomposition of individual components shows an
additive effect owing to the physically separated phases of chitosan and alkali lignin.
Nevertheless, the composite is homogeneous in terms of binding of chitosan and lignin via
weak hydrogen bonds, and hence decomposes gradually without any signature peak of
chitosan. This also stands as evidence alongside FT-IR characterization to prove that the
synthesized composite contains chemically integrated domains of chitosan and lignin. The
differential weight loss profiles of chitosan and alkali lignin reported in this work are in line
with earlier reports [35,36].

In order to quantify the thermal stability of the composite with respect to its
constituents, chitosan and lignin, variation of apparent activation energy of decomposition
with conversion was evaluated using the integral isoconversional method of Kissinger-
Akahira-Sunose (KAS). The functional form of KAS method is given by [37]:

 β   Aα .R   Eα 
ln  2  = ln  −
−1    (3)
T   Eα .ln[(1 − α ) ]   R.Tα 
 α 

where β denotes sample heating rate, Tα, Eα and Aα denote temperature, apparent activation
energy and pre-exponential factor at a fixed value of conversion, α, respectively. This
equation corresponds to first order decomposition of the material in the conversion range of
20 – 50% [37]. This method involves determining the temperature at various chosen values of
conversion at different heating rates, and plotting ln(β/Tα2) versus 1/Tα. The slopes of the
curves at different conversion levels yield Eα. Fig. SI 2(a-c) (see supplementary data) depict
8
the KAS plots for alkali lignin, chitosan and 50ChAL composite. Fig. 2(b) depicts the
variation of Eα with conversion for the above three materials. It is clear that in the conversion
range of 30% to 45%, alkali lignin is thermally more stable than chitosan and 50ChAL owing
to higher Eα of 170 – 273 kJ mol-1. In the conversion range of 30% to 40%, Eα of 50ChAL
varies in the range of 140 – 165 kJ mol-1, while that of chitosan varies in the range of 152 –
169 kJ mol-1. Such low differences in apparent activation energy of c.a. 10 kJ mol-1 (i.e. c.a. 2
kcal mol-1) is within the experimental uncertainty involved in these calculations, and hence, it
can be concluded that 50ChAL composite and chitosan exhibit similar thermal stability,
while alkali lignin is more stable than the two. Interestingly, chitosan-lignin composites
reported by Chen et al. [34] with low lignin content (<30%) also exhibited a similar stability
to that of chitosan based on a qualitative analysis of differential weight loss profiles.

3.1.3. Surface Morphology and Specific Surface Area Analysis

The surface morphologies of chitosan, alkali lignin, 25ChAL and 50ChAL

composites, studied using SEM, are shown in Fig.3. It is observed that the surface of chitosan
is non-uniform and rough with short fibrous structures, while the alkali lignin particles are
larger in size with sharp edges and lesser surface roughness. From the SEM images of
25ChAL and 50 ChAL composites (Fig.3 (c) and (d)), the interfacial adhesion that binds the
chitosan flakes on lignin surface is very clear. The formation of chitosan agglomerates on
alkali lignin surface is clear at certain regions of the 50ChAL composite. EDS analysis of
50ChAL composite (Fig. SI 3 in supplementary data) clearly shows the presence of various
elements like Na, Mg, Al, Si, S, K and Ca in trace quantities that originate predominantly
from alkali lignin.

Porosimetry was done to determine the specific surface area and pore size distribution
of chitosan, alkali lignin and 50ChAL composite. Fig. SI 4 (in supplementary data) depicts
the adsorption-desorption isotherm of 50ChAL composite. From Table 3, it can be observed
that the surface area was 2.44 m2 g-1 for 50ChAL composite, which is higher than that of both
chitosan (2.1 m2 g-1) and alkali lignin (0.24 m2 g-1). The specific surface area of chitosan
evaluated in this work matches well with the literature [25]. This increase in surface area of
the composite is primarily due to the disintegration and transformation of the fibrous
structure of chitosan to a flaky structure during the preparation of the composite, as
confirmed by the SEM image of the 50ChAL composite. The average pore diameter of
50ChAL composite is significantly lesser than that of alkali lignin and comparable with that

9
of chitosan. However the average pore volume of 50ChAL composite is significantly higher
than that of alkali lignin and similar to chitosan. These changes in pore dimensions may be
attributed to the presence of crosslinks between chitosan and alkali lignin in the composite.
Importantly, large pore volume enhances the adsorption of organic compounds, as
interactions between the key functional groups that are responsible for adsorption will be
better if the active site inside the pore is well accessible to the organic compound.

3.2. Adsorption of Dyes

3.2.1. Effect of Chitosan Composition

Fig.4 depicts the percentage removal of 100 mg L-1 of RBBR using seven different
adsorbents namely chitosan, alkali lignin, 5ChAL, 10ChAL, 25ChAL, 50ChAL and 50:50
physical mixture of chitosan and alkali lignin. The adsorption experiments were carried out
for a period of 3 hours, corresponding to the attainment of equilibrium at the natural pH of
the solutions. It is clear that percentage removal of RBBR was more for 50ChAL composite
when compared to chitosan, alkali lignin and other ChAL composites. The equilibrium
adsorption capacity for chitosan, alkali lignin, 5ChAL, 10ChAL, 25ChAL and 50ChAL
composites were, 41.31 mg g-1, 16.23 mg g-1, 17.55 mg g-1, 20.9 mg g-1, 46.2 mg g-1 and
47.49 mg g-1, respectively. Adsorption of RBBR using the 50:50 physical mixture of
chitosan: alkali lignin was also studied. It is observed that only 71% of the dye was adsorbed
at the end of 3 hours, as against 95% of adsorption achieved in the case of 50ChAL
composite. This confirms that the high percentage removal of the dye in presence of 50ChAL
composite is due to the presence of weak hydrogen bonding interactions between chitosan
and alkali lignin, and it is not essentially an additive effect of the presence of chitosan and
alkali lignin. Additionally, it can be concluded from the specific surface area analysis that
high concentration of surface active centers in 50ChAL composite compared to chitosan and
alkali lignin is responsible for the observed effect. Further adsorption studies using all the
ChAL composites, chitosan and alkali lignin were performed for different dye concentrations
and it was observed that in all the experiments, 50ChAL composite exhibited superior percent
removal when compared to all other adsorbents (Fig. SI 5 in supplementary data). It is
observed that 25ChAL composite also exhibits good percentage removal of RBBR at
equilibrium. However, the percentage removal decreases for initial dye concentrations greater
than 100 mg L-1. Therefore, further experiments were conducted using 50ChAL composite to
evaluate the effect of solution pH, adsorbent dosage and kinetics of adsorption.

10
3.2.2. Effect of Initial Solution pH and Adsorbent Dosage

Solution pH is an important parameter that affects the adsorption of dyes. Solution pH

determines the level of electrostatic or molecular interaction between the adsorbent surface
and the adsorbate owing to charge distribution on the material. The surface charge of alkali
lignin, chitosan and 50ChAL composite was quantified by zero point charge or isoelectric
point (pHzpc) determined by pH drift method [38]. From Fig.5 (inset) it is clear that the pHzpc
of alkali lignin, chitosan and 50ChAL composite are 6.8±0.2, 8.4±0.2 and 2.4±0.2,
respectively. This shows that at pH lesser than 2.4, the surface of 50ChAL composite is
positively charged owing to protonation of amine and hydroxyl groups by the protons in
solution. Fig.5 depicts the adsorption profiles of RBBR on 50ChAL (2 g L-1) at various pH. It
is clear that under highly acidic regime (pH = 2), the percentage removal was 98% (q = 24.65
mg g-1), while in the alkaline regime (pH > 7) the percentage removal was only 87% (q =
21.9 mg g-1). This shows that under acidic conditions, the interaction between the protonated
amine and hydroxyl groups of the composite, and the anionic site of the dye eventually leads
to enhanced chemisorption of the dyes onto the composite. At a pH of 8, which is higher than
pHzpc, the net surface charge becomes negative, and this results in repulsive force between the
dye and the composite. As the amino groups of the composite are deprotonated, there is a net
reduction in the electrostatic interaction between the dye anion and the composite, which also
limits the chemical interaction between the composite surface and the anionic site of the dye.
At solution pH of 4 and 5.9, the percentage removal of RBBR was same as that under highly
acidic conditions, i.e. c.a. 96% (qt = 24.23 mg g-1). Therefore, the natural pH of the solution,
viz, 5.9, was chosen for further kinetic studies.

Different amounts of 50ChAL composite from 1 g L-1 to 4 g L-1 were used to study
the removal of 50 mg L-1 of RBBR. Fig. SI 6 (see supplementary data) shows that the
percentage removal of RBBR increased from 89% to 98% with an increase in adsorbent
dosage from 1 g L-1 to 4 g L-1. The adsorption capacities, qt, for 1 g L-1, 2 g L-1 and 4 g L-1
were evaluated to be 22.44 mg g-1, 24.23 mg g-1 and 24.5 mg g-1, respectively. It is well
known that an increase in adsorbent dosage increases the availability of adsorption sites for
the interaction of the dye with the composite surface. As adsorption capacities for 2 g L-1 and
4 g L-1 dosages of the composite were comparable, 2 g L-1 was chosen as the optimum
adsorbent dosage for further experiments.

11
3.2.3. Adsorption Kinetics

The kinetics of adsorption of RBBR on the composite was evaluated by utilizing

kinetic models that provide insights on the mechanism and the rate limiting steps involved,
i.e., whether the adsorption is mass transfer controlled or reaction controlled. The most
commonly used kinetic models for studying solid-liquid interaction are pseudo first order and
pseudo second order models which are based on adsorption capacity. In pseudo first order
kinetic model, adsorption is controlled by diffusion and mass transfer of the adsorbate to the
adsorption site, whereas in pseudo second order kinetic model, chemisorption is the rate
limiting step [24]. The adsorption kinetics of RBBR on chitosan and 50ChAL composite was
evaluated using pseudo first order and pseudo second order models. The rate equations are
given as follows [39]:

dqt
First order kinetic model: = k1 ( qe − qt ) (4)
dt

dqt
Second order kinetic model: = k2 ( qe − qt ) 2 (5)
dt

where qe (mg g-1) is the amount adsorbed corresponding to equilibrium, and k1 (h-1) and k2 (g
mg-1 h-1) are pseudo first order and pseudo second order rate constants of adsorption. The
linearized forms of the above rate equations are given by [40]:

First order kinetic model: log( qe − qt ) = log qe − k1t / 2.303 (6)

t 1 t
Second order kinetic model: = + (7)
qt k2 qe2 qe

The kinetic parameters in the above models were determined by plotting log (qe - qt) versus t
and t/qt versus t, respectively. The model values of qe were compared with the experimental
values to confirm the validity of the model. From Fig.6 it is observed that the kinetics of
RBBR adsorption for different initial concentrations is best described by the pseudo second
order kinetic model. The determination coefficients for pseudo first order model were as low
as 0.7 for various initial concentrations, while it was more than 0.99 for the pseudo second
order model for all the initial concentrations of RBBR. From Table 4 it is clear that the model
qe,cal matches well with the experimental q e,exp. This supports that RBBR adsorption on
50ChAL composite is due to chemisorption. Adsorption experiments were also performed at

12
different temperatures to verify if the mechanism is indeed chemisorption. Complete
adsorption of 50 mg L-1 of RBBR on 2 g L-1 of 50ChAL composite was achieved within 15, 5
and 2 minutes when the reaction temperatures were 25 oC, 40 oC and 60 oC, respectively. It is
also clear from Table 4 that the rate constant, k2, decreases with increase in dye
concentration, which indicates that the driving force for RBBR adsorption on 50ChAL
composite shifts from chemisorption to a mass transfer controlled regime at concentrations
greater than 300 mg L-1. Importantly, the rate constants for the adsorption of RBBR of
different initial concentrations on chitosan were significantly lesser than that on 50ChAL
composite. This quantifies the higher efficiency of 50ChAL composite for the adsorption of
RBBR than chitosan. Second order kinetics of adsorption of dyes was also evidenced earlier
for different biosorbents like green algae Scenedesmus quadricauda [20],
polyanaline/chitosan composite [29], and activated carbon from industrial fruit juice waste
[40].

3.2.4. Adsorption Isotherms

The equilibrium isotherm model is used to describe the interactions between the
adsorbate and adsorbent. The adsorption of RBBR on chitosan and 50ChAL composite was
studied using Langmuir and Freundlich isotherms. The Langmuir adsorption is based on a
monolayer surface coverage of the dye on the composite that contains a finite number of
adsorption sites of uniform adsorption energies, whereas the Freundlich isotherm is utilized
to understand adsorption on heterogeneous surfaces and multiple adsorption layers. Langmuir
and Freundlich isotherms are expressed by the following equations [41]:

K L qmax Ce
Langmuir isotherm: qe = (8)
1 + K L Ce

Freundlich isotherm: qe = K f Ce1/ n (9)

where Ce is the equilibrium concentration of adsorbate in the solution (mg L-1), KL (L mg-1) is
the Langmuir constant related to maximum adsorption capacity and energy of adsorption,
qmax (mg g-1) is the maximum adsorption capacity for monolayer formation, Kf ((mg g-1) (L
mg-1)1/n) is the Freundlich adsorption capacity and n-1 is the adsorption intensity. The
Langmuir and Freundlich parameters can be determined using the following linearized form
of equations [41].

13
 1 1 1
Langmuir isotherm: = + (10)
qe qmax K L qmax Ce

Freundlich isotherm: log qe = log K f + (1/ n) log Ce (11)

Kumar [41] evaluated various linear and non-linear forms of equilibrium models to
understand the adsorption of malachite green onto lemon peel and found that the model
parameters, KL and qmax, obtained by using the linear form of the Langmuir model as shown
in equation (10) matched well with the parameters obtained by non-linear fitting using
equation (8). The Langmuir adsorption parameters were evaluated by plotting 1/qe vs 1/Ce.
Fig.7 depicts the Langmuir plot of qe vs Ce for 50 ChAL composite and it is clear that the
model matches well with the experimental data with a determination coefficient greater than
0.99. Moreover, the fit of the Freundlich model with experimental data was poor with a low
determination coefficient (<0.8). This confirms that adsorption indeed follows monolayer
surface coverage model of Langmuir. The maximum adsorption capacity of RBBR on
50ChAL composite was 111.11 mg g-1 while it was 76.92 mg g-1 for chitosan, which shows
that the composite exhibits 33% enhancement in the maximum adsorption capacity for
monolayer formation. Moreover, the Langmuir constant, KL, that signifies that the energy of
adsorption is higher (0.169 L mg-1) for the adsorption of RBBR on 50ChAL than that on
chitosan (0.080 L mg-1). This signifies the existence of stronger bonds between RBBR and
50ChAL, and revalidates that one of the dominant modes of adsorption is chemisorption. The
above observations prove that the surface of the composite is more homogeneous than
chitosan for adsorption of RBBR. Table 1 provides a list of biosorbents used for adsorption of
different classes of dyes and metal ions. It can be observed that the adsorption capacity of
50ChAL composite for RBBR is superior to that of many biosorbents reported in the
literature.

Fig.8 shows the adsorption of different dyes like Rhodamine B (RB – xanthene
fluorescence dye), Malachite Green (MG – triphenylmethane dye), Orange G (OG – mono
azo dye), Alizarin Red (AZ.R – anthraquinonic dye) and RBBR on 50ChAL composite. It
can be observed that the percentage removal of anthraquinonic dyes on the composite was
more compared to other dyes. The percentage removal of RBBR and AZ.R was around 97%
and 88%, respectively, and this is mainly due to strong electrostatic and chemical interaction
of the anionic and ketonic groups present in the anthraquinonic dyes with the amine and
hydroxyl groups present in 50ChAL composite. Importantly, c.a. 78% of MG (cationic) and

14
OG (anionic) were also adsorbed onto the composite, which demonstrates that the composite
can be utilized for the adsorption of many other dyes. The adsorption of different class of
dyes on the composite is attributed mainly due to electrostatic interaction of the dye with the
different moieties present in the composite.

3.3 Adsorption of Chromium(VI)

The adsorption efficiency of the composite towards metal ion removal was evaluated
using Cr(VI) as the model metal ion. From literature, it is clear that the adsorption of Cr(VI)
is affected by the pH of the reaction medium. Cr(VI) exists in the form of HCrO4- ions in
aqueous solution below a pH of 4, while at a pH above 4, it exists as CrO42- and Cr2O72-
anions [26]. It has been observed that the adsorption of Cr(VI) is maximum at a pH less than
4. At a pH of 2, the composite is fully protonated, which results in a net positive charge on
the surface. This leads to electrostatic interaction between the composite and HCrO4- ions.
The percent removal of Cr(VI) in presence of chitosan, alkali lignin and various ChAL
composites are shown in Fig.9. The experiments were carried out with 20 mg L-1 of Cr(VI)
for 6 hours at a pH of 2. The percentage removal of Cr(VI) was 95% for 50ChAL composite,
while it was 73% for chitosan and nil for lignin. From Fig. SI 7 (see supplementary data), it is
clear that the percentage removal of 10 mg L-1 of Cr(VI) on 2 g L-1 of 50ChAL composite at
pH of 2, 3.3 and 5 were 100%, 96% and 14%, respectively. Interestingly, it is observed that
the composites with less than 50% chitosan, viz., 5ChAL, 10ChAL and 25ChAL do not
adsorb Cr(VI) even until 3 hours. The maximum removal of Cr(VI) at low pH was also
observed in the case of different adsorbents like polyaniline-chitosan [31] and Fe-crosslinked
chitosan complex [42]. Fig.10 depicts the EDS analysis of Cr(VI) adsorbed composite, which
confirms the presence of Cr(VI) that is partially localized on the surface of adsorbed chitosan.
This clearly shows the role of chitosan in the composite towards Cr(VI) adsorption.

The adsorption profile of Cr(VI) on chitosan was erratic without any trend, and this is
attributed to an observation that is reported to be unique for chitosan at highly acidic pH. It is
reported that chitosan dissolves in acidic medium, especially at a pH of 2 [26]. The
dissolution of chitosan was visually observed in our experiments, and after 6 hours, the
solution was homogeneous and chitosan was not recovered in the solid form. It is well known
that cellulose, a polysaccharide with repeating glucose units, solubilizes at high acid
concentrations (pH ~ 1-2) and results in the formation of glucose at ambient temperature
[43]. This is attributed to the hydrolytic cleavage of the glycosidic bonds present at the ends

15
of the chain under high H+ concentration. A similar reaction via unimolecular nucleophilic
substitution (SN1) also occurs in chitosan under acidic conditions, where the glucosamine and
acetyl glucosamine units are separated by the cleavage of the glycosidic bonds [44]. Owing to
depolymerization of chitosan, the low molecular weight oligomers easily dissolve in the
aqueous medium. Additionally, Cr(VI) ion present in aqueous solution complexes with the
monomers and oligomers of chitosan. It was earlier shown that chromium ions can complex
with glucose in presence of ionic liquids and catalyze glucose dehydration reactions [45]. It
can hence be discerned that the observed removal or reduction in concentration of Cr(VI) in
presence of chitosan at a pH of 2 in Fig. 9 is not because of adsorption of Cr(VI) onto the
solid matrix of chitosan, but complexation with monomers and oligomeric fragments of
chitosan in the aqueous phase. This validates the erratic variation of Cr(VI) concentration.

Nonetheless, in the presence of 50ChAL composite, complete recovery of the solid

composite was achieved at the end of 6 hour reaction period at a pH of 2. This elucidates the
chemical stability of the composite over chitosan under harsh, acidic conditions. Zhang et al
[46] also demonstrated a similar phenomenon, wherein zirconium cross-linked chitosan
composite was insoluble in acidic solution, while chitosan dissolved completely. Fig.10
depicts the EDS analysis of Cr(VI) adsorbed composite, which confirms the presence of
Cr(VI) that is partially localized on the surface of chitosan in the composite. This clearly
shows the role of chitosan in the composite towards Cr(VI) adsorption. Fig. SI 8 (in
supplementary data) depicts the FT-IR of Cr(VI)-adsorbed 50ChAL composite collected at
the end of 6 hour period. All the key peaks corresponding to lignin, chitosan and the
interactions are clearly observed. Hence, it can be concluded that the stability of chitosan in
the composite is improved owing to the weak bonding with lignin as depicted in Scheme 1.

3.3.1. Adsorption Kinetics

The kinetics of adsorption of Cr(VI) on 50ChAL composite was studied using pseudo
first order and pseudo second order kinetic models that were used for RBBR. As shown in
Fig.9 (inset), Cr(VI) adsorption on 50ChAL composite is best described by pseudo second
order kinetic model for different initial concentrations of 20, 40 and 50 mg L-1 with a
determination coefficient greater than 0.98. The determination coefficient was as low as 0.75
for the first order kinetic model. As shown in Table 4, model and experimental adsorption
capacities match well confirming that adsorption is indeed pseudo second order. Our
observations are in line with previous reports of Cr(VI) adsorption on chitosan [19] and

16
chitosan coated with poly(3-methyl thiophene) [11] that also showed a higher determination
coefficient for pseudo second order kinetic model.

3.4. Adsorption Mechanism

FT-IR spectra of RBBR-adsorbed and Cr(VI)-adsorbed composites were analyzed to

probe the mechanism of adsorption and possible active sites of the composite onto which dye
and Cr(VI) are adsorbed. It is evident from Fig. SI 8 (see supplementary data) and Table 5,
that RBBR and Cr(VI) adsorbed composites exhibit shifts in the peaks at 3453-3362, 1656,
and 669 cm-1, which correspond to primary amine and hydroxyl groups in the 50ChAL
composite. These changes are due to interaction of the above functional groups with the
anion and carbonyl groups of the dye. From the results of the equilibrium adsorption studies
and FT-IR spectra, the following specific reactions are proposed.

Electrostatic interaction of protonated amine and hydroxyl of the composite with anion (SO3-)
of the dye [29]

(50ChAL)-NH2 + H3O+ (50ChAL)-NH3+ + H2O (12)

(50ChAL)-NH3 + + Dye-SO3- (50ChAL)-NH3+……....O3- S-Dye (13)

(50ChAL)-OH + H3O+ (50ChAL)-OH2 + + H2O (14)

(50ChAL)-OH2 + + Dye-SO3- (50ChAL)-OH2+……… O3- S-Dye (15)

In the pH range of 6 and below, the following reaction between carbonyl group of the dye
with active amine of the 50ChAL composite is possible. Chemical interaction of amine and
carbonyl group in presence of H+ results in the formation of imine compounds [47]. This is
also supported by the absence of N-H bending vibration in the FT-IR spectra.

(50ChAL)-NH2 + O=C-(Dye) (50ChAL)-N=C-(Dye) (16)

Furthermore, under acidic conditions, the interaction of hydroxyl groups of the composite
with carbonyl groups of the dye can result in the formation of cyclic hemiketals according to
the following reaction [48].

(Dye)-C=O + HO-(50ChAL) (Dye)-CO(OH)-(50ChAL) (17)

Cr(VI) adsorption occurs primarily due to electrostatic interaction of the protonated amine
and hydroxyl groups present in the composite with the HCrO4- anion.

17
(50ChAL)-NH3 + + HCrO4- (50ChAL)-NH3 +……. O4-CrH (18)

(50ChAL)-OH2 + + HCrO4- (50ChAL)-OH2 +……..O4-CrH (19)

The mechanism of adsorption of RBBR and Cr(VI) on 50ChAL composite is depicted in

Scheme 2 wherein the active sites are shown by asterisk (*). Thus it is clear that protonated
amino and hydroxyl groups serve as electrostatic interaction sites for the dye and HCrO4-
anion, while chemical interactions between amino and hydroxyl groups of the composite with
carbonyl moieties of the dyes also play a significant role in dye adsorption. An ensemble of
the above investigations suggests that chitosan-alkali lignin composite is a promising material
for the adsorption of toxic organic compounds and metal ions. Further enhancement in the
rates of adsorption is certainly possible by utilizing lignin from different biomass sources and
extracted via different processes. It is also important to probe the mechanism and kinetics of
desorption of the chemisorbed dyes and metal ions from this composite, which will be
addressed in our future works.

4. Conclusions

The development of cheap, bio-based materials that exhibit superior adsorption of

toxic organic compounds and metal ions is necessary to alleviate the ever increasing pollution
of water bodies caused by the discharge of industrial effluents. In this work, novel chitosan-
alkali lignin composites were prepared with different compositions of chitosan and alkali
lignin. The weak interactions between β-1,4-glycosidic linkage, amide and hydroxyl groups
of chitosan, and ether, aromatic ring and hydroxyl groups of alkali lignin, impart enhanced
surface and chemical properties to the composite than chitosan and alkali lignin. The
composite with 50:50 chitosan:alkali lignin exhibited maximum adsorption of RBBR and
Cr(VI) compared to chitosan, alkali lignin and other composites. Adsorption of RBBR
followed Langmuir model, and pseudo second order kinetic model matched well with the
experimental data of both RBBR and Cr(VI) adsorption onto the composite. The adsorption
efficiency of 50ChAL composite was also demonstrated for a variety of dyes belonging to
anthraquinone, mono azoic, and triphenylmethane families. The mechanism of adsorption
was unravelled by carrying out a detailed surface characterization of the composite. The
active adsorption sites were found to be the amine and hydroxyl groups of the composite, and
the adsorption mechanism was due to electrostatic interaction of protonated amino and
hydroxyl groups with anion of the dye and Cr(VI). Chemical interactions were also observed
between amino and hydroxyl groups of the composite and carbonyl groups of the dye. This

18
work shows that by incorporating 50% by mass of lignin in the chitosan-lignin composite,
better adsorption efficiencies can be achieved for a range of dyes and Cr(VI). Owing to the
fact that lignin is a common waste by-product from paper and cellulosic bioethanol
industries, and the simple preparation method described in this work, the overall cost of the
composite adsorbent can be significantly reduced compared to that of chitosan.

Acknowledgements

R.V. thanks Department of Science and Technology (DST), India, for project funding
and Indian Institute of Technology Madras for new faculty seed grant. The National Center
for Combustion Research and Development is sponsored by DST, India. The authors thank
JEOL Asia Private Ltd. for EDS analysis.

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23
List of Tables

Table 1. List of different biosorbents and their sorption capacity for adsorption of dyes and
metal ions as reported in literature.

Table 2. Key changes in FT-IR peaks of 50ChAL composite and their significance.

Table 3. Specific surface area, average pore size, average pore volume and isoelectric pH of
the adsorbents.

Table 4. Pseudo second order kinetic parameters for the adsorption of RBBR on 50ChAL
composite and chitosan, and Cr(VI) on 50ChAL.

Table 5. Key changes in FT-IR peaks of RBBR-adsorbed and Cr(VI)-adsorbed 50ChAL.

List of Figures

Figure 1. FT-IR spectra of alkali lignin, chitosan and 50ChAL composite.

Figure 2. (a) Thermogravimetric curves of chitosan, lignin, ChAL composites and 50:50
physical mixture of chitosan and lignin (50:50 Ch:AL(phys)) at a heating rate of 20 oC min-1.
(b) Variation of apparent activation energy of decomposition of lignin, chitosan and 50ChAL
with conversion evaluated by isoconversional KAS method.

Figure 3. SEM images of (a) Chitosan (b) Alkali lignin (d) 25ChAL (d) 50ChAL composite.

Figure 4. Percentage removal of RBBR using different adsorbents (dye conc. = 100 mg L-1;
adsorbent dosage = 2 g L-1).

Figure 5. Effect of initial solution pH on RBBR removal (dye conc. = 50 mg L-1; adsorbent
dosage = 2 g L-1) (Inset: pH drift plots of (a) Chitosan (b) Alkali lignin (c) 50ChAL
Composite).

Figure 6. Pseudo second order adsorption kinetic model for 50ChAL composite (adsorbent
dosage = 2 g L-1).

Figure 7. Langmiur isotherm for adsorption of RBBR on chitosan and 50ChAL composite
(adsorbent dosage = 2 g L-1; t = 3 h) (Inset: Linear Langmiur plot of Chitosan and 50ChAL
composite).

Figure 8. Percentage removal of different dyes using 50ChAL composite (dye conc. = 50 mg
L-1; adsorbent dosage = 2g L-1).

24
Figure 9. Adsorption of Cr(VI) on different adsorbents (Cr(VI) conc. = 20 mg L-1; adsorbent
dosage = 2 g L-1; pH=2) (Inset: Pseudo second order kinetic model for adsorption of Cr(VI)
on 50ChAL composite).

Figure 10. EDS analysis of Cr(VI) adsorbed 50ChAL composite.(Inset: EDS Mapping of
Cr(VI) on 50ChAL composite)

List of Schemes

Scheme 1. Preparation of chitosan-alkali lignin composite. The dashed lines show the
possible weak bonding between chitosan and alkali lignin.

Scheme 2. Mechanism of RBBR and Cr(VI) adsorption on 50ChAL composite. Asterisks (*)
denote possible adsorption sites.

Supplementary Data

Figure SI 1. Thermogravimetric and differential weight loss curves of alkali lignin, chitosan,
50ChAL and 50:50 Ch:AL(phys).

Figure SI 2. Kissinger-Akahira-Sunose (KAS) plots depicting the variation of Ln(β/Tα2)

versus 1/Tα for different conversions, α, from 20 to 50 mass%, for (a) alkali lignin, (b)
chitosan and (c) 50ChAL composite.

Figure SI 3. EDS analysis of 50ChAL composite indicating the presence of Na, Mg, Al, Si, S,
K, Ca from lignin.

Figure SI 4. Adsorption-desorption isotherm plot of 50ChAL composite.

Figure SI 5. Percentage removal of RBBR of different initial concentrations at the end of 3

hours with chitosan, alkali lignin and ChAL composites.

Figure SI 6. Effect of dosage of 50ChAL composite on adsorption of RBBR (dye conc. = 50

mg L-1).

Figure SI 7. Effect of initial pH on adsorption of Cr(VI) on 50ChAL composite (Cr(VI) conc.

= 10 mg L-1; adsorbent dosage = 2 g L-1).

Figure SI 8. FT-IR spectra of as synthesized 50ChAL composite, RBBR-adsorbed 50ChAL

composite and Cr(VI)-adsorbed 50ChAL composite.

25
 Table 1. List of different biosorbents and their sorption capacity for adsorption of dyes and
metal ions as reported in literature.

Biosorption Capacity
Biosorbent Dye / Metal ion Reference
(mg g-1)
Lignin Cr(III) 17.97 [4]
Palm shell powder Reactive Blue 21 24.86 [13]
Peroxide treated rice husk Malachite Green 26.6 [15]
Tunisian activated lignin Methylene Blue 147 [17]
Lignin from sugarcane bagasse Methylene Blue 34.20 [18]
Chitosan Cr(VI) 7.94 [19]
Immobilized green algae
RBBR 68 [20]
Scenedesmus quadricauda
Garden Grass Cu(II) 58.34 [21]
Cellulose-chitosan composite Cu(II) 75.82 [22]
Chitosan-alkali lignin
RBBR 111.11 This work
composite

Table 2. Key changes in FT-IR peaks of 50ChAL composite and their significance.

Wavenumber, cm-1 Functional group Interaction in 50ChAL

Peaks corresponding to chitosan in the composite

1654 Bending of N-H of primary amine Presence of peak

1560-1549 bending of N-H of secondary Absence of peak

amine
1157 C-O stretching in the β-1,4- Decrease in wavenumber by
glycosidic linkage 12 cm-1

Peaks corresponding to alkali lignin in the composite

1596 aromatic C=C stretching in the Decrease in intensity of peak
phenolic group by 50%

1461, 1423, 1367 bending of O-H of the phenolic Decrease in wavenumber by

group 6,5,9 cm-1
1085 C-O-C stretching in the alkyl Decrease in wavenumber by
substituted ether 11 cm-1

26
Table 3. Specific surface area, average pore size, average pore volume and isoelectric pH of
the adsorbents.

Specific Average Pore Isoelectric

Average Pore
Adsorbent Surface Area Volume pH
Diameter (Å )
(m2 g-1) (cm3 g -1) (pHzpc)
Alkali Lignin 0.2430 809.835 0.00082 8.4±0.2
Chitosan 2.1039 415.854 0.01977 6.8±0.2
50ChAL 2.4403 303.975 0.01464 2.4±0.2

Table 4. Pseudo second order kinetic parameters for the adsorption of RBBR on 50ChAL
composite and chitosan, and Cr(VI) on 50ChAL.

Initial conc. qe,exp k2 qe,cal

(mg L-1) (mg g-1) (g mg-1 h-1) (mg g -1)
25 12.13 2.45 12.28
RBBR on
50 24.23 0.48 24.71
50ChAL
100 47.49 0.10 50.12
200 74.87 0.08 77.58
300 95.93 0.12 98.32
25 10.29 1.38 12.71
50 23.07 0.09 25.36
RBBR on
100 41.31 0.064 44.76
chitosan
200 67.83 0.066 69.93
300 85.74 0.115 88.73
20 9.430 0.105 10.80
Cr(VI) on
40 14.76 0.13 15.97
50ChAL
50 17.80 0.15 19.19

27
 Table 5. Key changes in FT-IR peaks of RBBR-adsorbed and Cr(VI)-adsorbed 50ChAL.

Wavenumber, Interacting RBBR-adsorbed Cr(VI)-adsorbed

cm-1 functional groups 50ChAL 50ChAL

Stretching of O-H, N-
Increase in wavenumber Increase in wavenumber
3453-3362 H group of phenolic
by 30 cm-1 by 20 cm-1
group, primary amine

Bending of N-H in Decrease in wavenumber

1654 Absence of peak
primary amine group by 8 cm-1

Out-of-plane bending
669 Absence of peak Absence of peak
of O-H

28
 Alkali lignin

-OH,-NH2 stretching

-C-H stretching
% Transmittance

Chitosan -OH bending

-NH
bending
50ChAL -C-Ostretching

-NH2 bending

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )

Fig. 1

29
 100 (a)

Sample mass (%)

50ChAL 50ChAL
80 25ChAL
o Alkali lignin
20 C/min 10ChAL
60
5ChAL

40 50:50 Ch:AL(phys)
Chitosan
20
100 200 300 400 500 600 700 800 900
o
Temperature ( C)
Apparent activation energy,

300
Alkali Lignin (b)
250
Ea (kJ mol-1)

Chitosan
50ChAL
200

150

100

50
20 25 30 35 40 45 50
Conversion (mass %)

Fig. 2

30
(a) Chitosan (b) Alkali lignin

(c) 25ChAL composite (d) 50ChAL composite

Alkali lignin
Alkali lignin
chitosan
chitosan

Fig. 3

31
 100

80

60
% Removal

40

Chitosan
20 Alkali Lignin
5ChAL
10ChAL
25ChAL
50ChAL
0 50:50 ChAL

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Time (h)

Fig. 4

32
 100

80

2 pH 12

60 4 pH Chitosan
% Removal

Alkali Lignin
5.9 pH 10
50 ChAL 8.4pHzpc

8 pH
8

40

Final pH
6

6.8pHzpc
4

20
2
2.4 pHzpc pH Drift Method

0
0 2 4 6 8 10 12
0 Initial pH

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Time (h)

Fig. 5

33
 2
0.25 50ChAL - RBBR R >0.99
-1
25 mg L
-1
50 mg L
0.20 -1
100 mg L
-1
200 mg L
t/qt ( h g mg )

-1
-1

300 mg L
0.15

0.10

0.05

0.00
0.5 1.0 1.5 2.0 2.5 3.0
Time (h)

Fig. 6

34
 100 Langmuir
Experimental

80

0.25

60
qe(mg g-1)

Chitosan
0.20 50ChAL
2
R >0.99

0.15
40

1/q e(g mg -1 )
0.10

0.05
20 -1 -1
Adsorbent q (mg g ) K (L mg )
max L
0.00
Chitosan 76.92 0.080
50ChAL 111.11 0.169 0.0 0.4 0.8 1.2 1.6
-1
0 1/Ce(Lmg )

0 20 40 60 80 100
-1
Ce (mg L )

Fig. 7

35
 100

80

60
% Removal

R.B (Xanthene fluorescence)

40
M.G (Triphenylmethane)
O.G (Mono azo)
AZ.R (Anthraquinone )
20 RBBR (Anthraquinone )

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Time (h)

Fig. 8

36
 100 -1
Cr(VI) conc. - 20 mg L

80

60
% Removal

0.7

0.6 50ChAL
-1
20mgL
Chitosan 0.5 40 mgL
-1

40 Alkali Lignin 50mgL

-1

t/q t(h g mg -1)

5ChAL 0.4

10ChAL 0.3
25ChAL
20 50ChAL 0.2

0.1

0.0
1 2 3 4 5 6
0
Time(h)

0 1 2 3 4 5 6
Time (h)

Fig.9

37
Fig.10

38
 HO OH
O CH 3 H 2N
H 2N
O
OH
OH O nO
HO O O
O O
H HO
HO SH + HO
NH
O CH3
HO H 3C
O Chitosan dissolved in 2% acetic acid solution
H 3C O
Stirred for 3 hours and dried at room temperature
O

O HO
H 3C HO O
H 3C O CH 3

Alkali lignin stirred in aqueous medium

HO
O
H
HO SH

HO H 3C
O
H 3C O
O

O 2
H 3C HO OH O CH 3
H 2N
H 2N 1
O
OH O
OH O O
O
O n
HO
NH HO
HO 3
O O CH 3
4
CH 3
HO
O
H
Hydrogen bonding HO SH

HO H 3C
O
H 3C O
Chitosan/Alkali Lignin Composite O

O
H 3C HO O
H 3C

Scheme 1

39
 ∗ + -
OH2 HCrO 4
Cr(VI) Anion
-
O3 S
O CH3
O Active sites
∗
OH
-
O H O3 S
O S O HS OH∗
O

RBBR ∗ +
OH2
O S O RBBR
H 3C O
- O
NH Cr(VI) Anion
O3 S
O -
H HCrO 4
H N H 3C O O C H3
∗O -
H O3 S NH
O O ∗ OH H
+
H N H H N
H N H ∗
∗ O H
OH O
OH O O O
O O
O n
NH ∗ HO
∗HO
O O H N H
∗ OH C H 3 ∗ -
O SO 3 -
O SO 3
∗ NH S O
OH O
O
O H
HS OH RBBR
Chemical interaction
OH∗ Electrostatic interaction
CH 3
O
O
O

O
CH 3

Scheme 2

40
 Supplementary Data

Development of Novel Chitosan-Lignin Composites for Adsorption of Dyes

and Metal Ions from Wastewater

Vaishakh Nair,a Ajitesh Panigrahy,a R.Vinua,b,*

a
Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai –
600036, India
b
National Center for Combustion Research and Development, Indian Institute of Technology
Madras, Chennai – 600036, India

Figure SI 1. Thermogravimetric and differential weight loss curves of alkali lignin, chitosan,
50ChAL and 50:50 Ch:AL(phys).

1.50
100
Alkali lignin
90 Chitosan 1.25

Derivative weight loss (%/ C)

80
50ChAL

o
50:50 Ch:AL(phys)
70 1.00
Sample mass (%)

60
0.75
50

40
0.50
30

20 0.25

10

0 0.00
0 100 200 300 400 500 600 700 800 900
o
Temperature ( C)

*
Corresponding Author. Phone: +91-44-2257 4187. E-mail: vinu@iitm.ac.in (R. Vinu)
41
Figure SI 2. Kissinger-Akahira-Sunose (KAS) plots depicting the variation of Ln(β/Tα2)
versus 1/Tα for different conversions, α, from 20 to 50 mass%, for (a) alkali lignin, (b)
chitosan and (c) 50ChAL

-9.2
(a) Alkali Lignin
2
-9.6 R > 0.99
20%
-10.0 25%
30%
35%
-10.4
Ln(β/T2α )

40%
45%
-10.8

-11.2

-11.6

1.30 1.35 1.40 1.45 1.50 1.55 1.60 1.65 1.70 1.75 1.80
-1
1000/Tα(K )

composite.

-8.8
(b) Chitosan
2
-9.2 R > 0.99

25%
-9.6 30%
35%
Ln(β/T2α )

40%
-10.0
45%
50%
-10.4

-10.8

-11.2

1.650 1.675 1.700 1.725 1.750 1.775 1.800 1.825 1.850

-1
1000/Tα(K )

42
 -9.2
(c) 50ChAL
2
-9.6 R > 0.98

-10.0 20%
Ln(β/T α ) 25%
30%
2

-10.4 35%
40%
45%
-10.8

-11.2

-11.6

1.45 1.50 1.55 1.60 1.65 1.70 1.75 1.80 1.85 1.90 1.95 2.00
-1
1000/Tα(K )

43
Figure SI 3. EDS analysis of 50ChAL composite indicating the presence of Na, Mg, Al, Si, S,
K, Ca from lignin.

44
Figure SI 4. Adsorption-desorption isotherm plot of 50ChAL composite.

45
Figure SI 5. Percentage removal of RBBR of different initial concentrations at the end of 3
hours with chitosan, alkali lignin and ChAL composites.

100 Chitosan
Alkali Lignin
5ChAL
10ChAL
25ChAL
80
50ChAL
% Removal

60

40

20

0
25 50 100 200
-1
Concentration (mg L )

46
Figure SI 6. Effect of dosage of 50ChAL composite on adsorption of RBBR (dye conc. = 50
mg L-1).

100

80

60
% Removal

-1 -1
40 1 g L , q = 22.44 mg g
-1 -1
2 g L , q = 24.23 mg g
-1 -1
4 g L , q = 24.50 mg g
20

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Time (h)

47
Figure SI 7. Effect of initial pH on adsorption of Cr(VI) on 50ChAL composite (Cr(VI) conc.
= 10 mg L-1; adsorbent dosage = 2 g L-1).

100

80

60 2 pH
% Removal

3.3 pH
5 pH
40

20

0 1 2 3 4 5
Time (h)

48
Figure SI 8. FT-IR spectra of as synthesized 50ChAL composite, RBBR-adsorbed 50ChAL
composite and Cr(VI)-adsorbed 50ChAL composite.

50ChAL

RBBR adsorbed 50ChAL

% Transmittance

(-NH2 bending)
(-OH
(-OH, -NH stretching)
2
bending)

Cr(VI) adsorbed 50ChAL

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )

49
Development of Novel Chitosan-Lignin Composites for Adsorption of Dyes
and Metal Ions from Wastewater

Vaishakh Nair,a Ajitesh Panigrahy,a R.Vinua,b,*

a
Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai –
600036, India
b
National Center for Combustion Research and Development, Indian Institute of Technology
Madras, Chennai – 600036, India

GRAPHICAL ABSTRACT

*
Corresponding Author. Phone: +91-44-2257 4187. E-mail: vinu@iitm.ac.in (R. Vinu)
50
Development of Novel Chitosan-Lignin Composites for Adsorption of Dyes
and Metal Ions from Wastewater

Vaishakh Nair,a Ajitesh Panigrahy,a R.Vinua,b,*

a
Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai –
600036, India
b
National Center for Combustion Research and Development, Indian Institute of Technology
Madras, Chennai – 600036, India

HIGHLIGHTS

• Chitosan-lignin composites with enhanced surface and chemical properties were developed

• Weak hydrogen bonding interactions between chitosan and lignin were established via FTIR

• Chitosan-lignin(50:50) composite exhibited high rates of removal of dyes and Cr(VI)

• Adsorption of Remazol Brilliant Blue R and Cr(VI) followed second order kinetics

• The active sites and the mechanism of adsorption on the composite are unravelled

*
Corresponding Author. Phone: +91-44-2257 4187. E-mail: vinu@iitm.ac.in (R. Vinu)
51