Cellulose (2015) 22:24432456

DOI 10.1007/s10570-015-0649-4

ORIGINAL PAPER

Amino-functionalized nanocrystalline cellulose

as an adsorbent for anionic dyes
Liqiang Jin . Weigong Li . Qinghua Xu .
Qiucun Sun

Received: 7 January 2015 / Accepted: 3 May 2015 / Published online: 10 May 2015
Springer Science+Business Media Dordrecht 2015

Abstract In this present work, amino-functionalized

nanocrystalline cellulose (ANCC) was prepared by a
process involving, (1) extraction of nanocrystalline
cellulose (NCC) from fully bleached hardwood kraft
pulp by sulfuric acid hydrolysis, (2) sodium periodate
oxidation of NCC to yield the corresponding C-2/C-3
dialdehyde nanocellulose (DANC) and (3) grafting
with ethylenediamine to obtain ANCC through a
reductive amination treatment. Properties of DANC
and ANCC were characterized by conductometric
titration, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction and atomic force microscopy. It
was found that the primary amine groups of ANCC
(0.771.28 mmol g-1) increased with the increase of
ethylenediamine dosage. The successful grafting was
further evidenced by Kaiser test and FT-IR analysis.
Zeta potential measurements showed that ANCCs
were amphoteric, and their isoelectric points were
between pH of 78. Chemical modifications of the
cellulose nanowhiskers reduced the crystallinity but
the initial cellulose I polymorph was retained. The
cross-sectional dimension of nanowhiskers was

L. Jin (&)
School of Chemistry and Pharmaceutical Engineering,
Qilu University of Technology, Jinan 250353, China
e-mail: jlq@qlu.edu.cn
W. Li  Q. Xu  Q. Sun
Key Laboratory of Paper Science and Technology of
Ministry of Education, Qilu University of Technology,
Jinan 250353, China

slightly decreased from about 510 to 38 nm after

the oxidation, and a better dispersibility was observed.
ANCC sample was then applied as an adsorbent to
remove anionic dyes in aqueous solutions. It demonstrated the maximum removal efficiency at acidic
conditions. The acid red GR adsorption on ANCC
fitted well with the Langmuir model, with a maximum
theoretical adsorption capacity of 555.6 mg g-1. The
adsorption of congo red 4BS, acid red GR and reactive
light yellow K-4G followed pseudo second order
kinetics, indicating a chemisorption nature.
Keywords Nanocellulose  Periodate oxidation 
Amino-functionalization  Adsorption  Anionic dyes

Introduction
More than 10,000 different dyes and pigments are used
in chemical industries, such as textile, plastic, paper,
printing, carpet, cosmetic and food industries to
provide color to their products (Bhattacharyya and
Ray 2015; Yagub et al. 2014). However, around
15 wt% of dyes remains in industrial wastes and are
discharged to water body (Kayranli 2011). The
presence of dyes, not only imparts waste water
undesirable visual pollution, but also reduces water
reoxygenation capacity, resulting in acute and chronic
toxicities and difficulties in water treatment by
conventional methods (Piccin et al. 2012). Due to

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2444

the increasing use of dyes, the dye wastewater is

becoming an environmental threat, and the removal of
these pollutants from wastewater has been a challenge
(El-Zahhar et al. 2014).
Various processes such as coagulation/flocculation,
membrane treatment, ion exchange, electrodialysis,
electrolysis, and adsorption (Pearce et al. 2003) are
used for removal of these non-biodegradable dyes
from water. Adsorption has been found to be superior
to other techniques in terms of flexibility and
simplicity of design, initial cost, insensitivity to toxic
pollutants and ease of operation and is considered an
ideal method for removing dyes or other pollutants
(Crini 2006; Deng et al. 2012; Unuabonah and Taubert
2014). The adsorbents used in water treatment may be
mineral, organic or biological in origin, including
activated carbons, zeolites, clays, silica beads, biomass and polymeric resins (Murphy et al. 2008;
Unuabonah et al. 2012). In order to provide costeffective, greener and more sustainable solutions for
dye removal, there has been a strong desire to develop
adsorbents from low cost agriculture, wood and
shellfish byproducts or wastes (Pei et al. 2013). Most
adsorptions of contaminants rely on the surface
interactions between adsorbents and adsorbates, therefore, the functional groups on the adsorbents surface
play an important role in determining the effectiveness, capacity, selectivity and reusability of the
adsorbent material (Dural et al. 2011; Karim et al.
2014). Furthermore large surface area and abundance
of adsorption sites are essential for adsorption and
removal of contaminants from wastewater (Liu et al.
2014). Nanomaterials, due to their good adsorption
efficiency, higher surface area and greater active sites
for interaction with pollutants, are increasingly used in
dye removal (Savage and Diallo 2005). It is desirable
to develop nanomaterial adsorbents to enhance the
adsorption capacity, adsorption rate and shorten the
reaction time (Yagub et al. 2014).
Cellulose has been considered to be an ideal
candidate for the removal of dyes owing to the facts
that cellulose is the most abundant organic raw
materials on the earth, and it is inexpensive, renewable, biodegradable and biocompatible (Roy et al.
2009). Nanocellulose, extracted from cellulosic fibers
by applying mechanical, chemical, physical or biological methods, demonstrates excellent properties,
including high aspect ratio, large specific surface area,
reactive surface of -OH groups, and high Youngs

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Cellulose (2015) 22:24432456

modulus. The unique properties may impart nanocellulose high adsorbability for dyes. By enzymatic or
chemical pretreatments of wood pulp fiber, the energy
consumption of the subsequent mechanical treatment
could be lowered for producing cellulose nanofibers
(Fujisawa et al. 2011; Isogai et al. 2011), thus facilitate
the production at a larger scale, which encouraged us
to develop nanocellulose based dye adsorbents with
high adsorption capacity (Pei et al. 2013). Ma et al.
(2012) developed a multilayered nanofibrous microfiltration (MF) membrane, by impregnating ultrafine
cellulose nanowhiskers into an electrospun polyacrylonitrile (PAN) nanofibrous scaffold supported by a
poly(ethyleneterephthalate) (PET) nonwoven substrate. The impregnated CNCs possessed very high
negative surface charge density and thus provided
high adsorption capacity to remove positively charged
dyes, i.e. crystal violet dye. Karim et al. (2014)
reported a fully biobased composite membrane for
water purification fabricated with cellulose nanocrystals (CNCs) as functional entities in chitosan matrix
via freeze-drying process followed by compacting.
The membranes removed 98, 84 and 70 % of
positively charged dyes like Victoria Blue 2B, Methyl
Violet 2B and Rhodamine 6G, respectively. The
removal of dyes was expected to be driven by the
electrostatic attraction between the negatively charged
CNCs and the positively charged dyes.
Cellulose tends to exhibit a high adsorption
capacity for pollutant after suitable chemical modification on its surface with the aim of incorporating
molecules that contain basic groups, particularly those
that are rich in nitrogen, sulfur and oxygen (Musyoka
et al. 2011). Pei et al. (2013) prepared quatinized
cellulose nanofibrils (Q-NFC) by mechanical disintegration of wood pulp fibers which were pretreated
through a reaction with glycidyltrimethylammonium
chloride. The Q-NFC nanofibrils possessed high
anionic dye adsorption capability. Silva et al. (2013)
reported the surface modification of cellulose with
aminoethanethiol in the absence of solvent to improve
its adsorbability. The modified cellulose showed
superior performance in the adsorption of a reactive
red dye.
Different approaches have been explored to
chemically modify the nanocellulose, such as esterification, oxidation, silylation and polymer grafting
(Habibi et al. 2010; Ifuku et al. 2007; Missoum et al.
2013; Pahimanolis et al. 2011; Zaman et al. 2012).

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Cellulose (2015) 22:24432456

Most of covalent modifications predominantly occurred on the primary hydroxyl groups at the C-6
position of the cellulose backbone. Periodate oxidation offers a facile method for functionalization of
hydroxyl groups in cellulose nanowhiskers (Li et al.
2009; Lu et al. 2014; Pan and Ragauskas 2014). The
resulted dialdehyde nanocellulose can act as a reactive
intermediate for further derivatization and opens
possibilities for many other chemical reactions (Cheng
et al. 2014; Dash et al. 2012; Sirvio et al. 2014), thus
widening the potential application of nanocellulose
(Kalaskar et al. 2010). A chemical pretreatment for
producing CNCs with periodate oxidation and reductive amination was reported by Visanko et al. (2014).
The butylamino-functionalized CNCs were obtained
after the pretreatment and the subsequent mechanical
homogenization, which could be utilized in stabilizing
the o/w emulsions due to its amphiphilic nature. Dash
and Ragauskas (2012) prepared a novel nanometric
carrier molecule by grafting for amine-containing
biologically active molecules and drugs employing
functionalized cellulose nanowhiskers. The nanowhiskers were grafted with a spacer molecule, gamma
aminobutyric acid, using a periodate oxidation and
Schiffs base condensation reaction sequence.
The aim of the present study is to incorporate
primary amine groups onto the surface of cellulose
nanowhiskers, and then evaluate its dye removal
efficiency. Nanocrystalline cellulose was firstly oxidized by sodium periodate to yield the corresponding
C-2/C-3 dialdehyde nanocellulose (DANC), and then
grafted with ethylenediamine to obtain amino-functionalized NCC (ANCC) with free primary amino
groups through a reductive-amination treatment.
Properties of DANC and ANCC were characterized
by FT-IR, XRD and AFM. Furthermore, adsorption
capacity and kinetics of ANCC for anionic dyes were
investigated.

Experimental
Materials
Fully bleached aspen kraft pulp with a cellulose
content of 84.3 %, a hemicelluloses content of
10.9 %, and a weight average fiber length of
0.755 mm, as an original material used for preparation
of the nanocrystalline cellulose, was provided by the

Silver Star Paper Co. Ltd, Jinan, China. Ethylenediamine and sodium periodate were purchased from
Sigma-Aldrich Co. Ltd. The following commercial
anionic dyes, acid red GR (acid dye), congo red 4BS
(direct dye), and reactive light yellow K-4G (reactive
dye) were supplied by Tianjin Ruiji Chemical Co. Ltd
and their chemical structures are shown in Fig. 1.
Preparation of NCC
Nanocrystalline cellulose (NCC) were prepared by
sulfuric acid hydrolysis of fully bleached kraft pulp
according to the method by Lu and Hsieh (2012)
Aspen kraft pulp was firstly ground using a Wiley mill
(mini mill, Thomas Scientific, USA) at a speed of
approximately 1700 rpm to pass through a 20-mesh
screen, and the fraction passing through was collected
for the hydrolysis step. 10 g (o.d.) of the milled pulp
was hydrolyzed by using 85 ml of 64 wt% sulfuric
acid for 30 min at 45 C. At the end of the reaction, the
suspensions were then centrifuged to remove the acid,
and then diluted with deionized water and washed via
centrifugation. The acquired precipitate was transferred onto a cellulose dialysis membrane with a
molecular weight cut-off of 12,00014,000 and
dialyzed against deionized water for 4 days until the
suspension became homogeneous and the pH value
became constant. NCC with a yield of about 30 % was
acquired, and stored at a temperature of 5 C as its
original wet state.
Sodium periodate oxidation of cellulose
nanowhiskers
250 ml of cellulose nanowhiskers (0.4 wt%) and
various amounts of sodium periodate, corresponding
to 1.5, 3, 6 and 9 mmol g-1 NCC, were mixed and
stirred for 48 h in the absence of light at 40 C. The
residual sodium periodate was then removed by
adding 10 ml of ethylene glycol. The product was
dialyzed against deionized water for 3 days using a
dialysis membrane with a molecular weight cut-off of
12,00014,000. The acquired dialdehyde nanocrystalline cellulose (DANC) was stored at temperature of
5 C as its original wet state. The dialdehyde content
of DANC was determined by the Schiff base reaction
between aldehyde groups and hydroxylamine hydrochloride (Kim et al. 2004). The dialdehyde content
(DC) of each sample was calculated through Eq. (1),

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Cellulose (2015) 22:24432456

2446

Fig. 1 Chemical structures of dyes a acid red GR; b congo red 4BS and reactive light yellow K-4G

DCmmol g1

CV2  V1
m

where, V1 is the amount of sodium hydroxide for

DANC titration, ml; V2 is the amount of hydrochloric
acid for control titration in ml; C is the concentration
of sodium hydroxide, mol l-1 and m is the weight of
each sample, g.
Preparation of amino-functionalized
nanocrystalline cellulose (ANCC)
200 ml of DANC suspension (0.5 wt%) was ultrasonicated for 5 min, and then various amounts of
ethylenediamine were added. The mixture was continuously stirred for 6 h at 30 C, followed by the
in situ reduction of the resulting imine intermediate at
room temperature employing 0.58 g of NaBH4. After
stirring for 3 h, the product was dialyzed (MWCO:
12,00014,000) against deionized water until it
reached a neutral pH to obtain ANCC. The content
of amine groups was determined by conductometric
titration according to the literature (Filpponen and
Argyropoulos 2010). The pH of ANCC suspension
was adjusted to 3 by HCl at room temperature and
stirred for 15 min. The suspension was subsequently
titrated with NaOH (0.01 mol l-1) solution until the
pH was 12. The conductivity of the suspension was
recorded. The amine group content was calculated
based on the following Eq. (2),
C  V2  V1
AGC
m

Kaiser test
Kaiser test was performed according to the literature
(Hemraz et al. 2013). A few drops of phenol (about
80 % in ethanol), KCN in water/pyridine, and ninhydrin (6 % in ethanol) solutions were added to a few
milligrams of NCC, DANC and ANCC samples in test
tubes. The mixture was then heated at 120 C for
5 min, and any change in color was noted.
FT-IR
FT-IR spectra of cellulose nanowhiskers were conducted on an IRPrestige-21 Fourier transform infrared
spectrometer (Shimadzu Company, Japan). The samples were freeze-dried before preparing the KBr
tablets. The spectra were recorded with width ranging
from 400 to 4000 cm-1, and resolution of 2 cm-1.
X-ray diffraction analysis
X-ray diffraction (XRD) analyses were performed
with a D8 Powder X-ray Diffractometer (Bruker AXS,
Germany), which was equipped with a CuXa X-ray
tube. The crystallinity index (CrI) was calculated
based on the Eq. (3) below (Segal et al. 1959),
CrI

where, AGC is the amino group content, mmol g-1;

C is the concentration of NaOH solution; V1 and V2 are
the minimum and maximum consumptions of NaOH
in the lowest conductivity (ml), respectively and m is
the freeze dried content of ANCC.

123

Characterization

I002  Iam
I002

where, CrI is the crystallinity index; I002 is the intensity

of the crystalline peak at the maximum at 2h between
22 and 23 for cellulose I, and Iam is the intensity at
minimum at 2h between 18 and 19 for cellulose I.
The crystal size was calculated according to the
Scherrer formula as below,

Cellulose (2015) 22:24432456

D 0:89

k
b1=2 cos h

2447

Characterization of ANCC

where, k is the radiation wavelength of X ray,

0.154056 nm; h is the Bragg diffraction angle, corresponding to the (002) plane in this case, and b1/2 is the
full width of the diffraction peak measured at half
maximum height (FWHM) of the instrument corrected
line profile.
AFM
A Mutimode 8 Nanoscope V System AFM (Bruker
Corporation, Germany) was used to characterize the
surface morphology of NCC, DANC and ANCC
samples. A drop of dilute nanocellulose suspension
was deposited onto a clean mica surface and air dried
overnight at ambient conditions. Images from several
different places on the samples were scanned.
Adsorption of anionic dyes
The freeze dried ANCC were mixed with 100 mg l-1
dye solution and continuously stirred at 180 rpm.
Samples were withdrawn at periodic time intervals
from the reaction mixture. The nanocellulose adsorbed
with dyes was then removed by centrifugation at
4000 rpm for 5 min. The adsorption of the supernatant
was measured using a UVvisible spectrometer (8453,
Angilent). The residual dye concentration could be
obtained using a standard curve derived from a series
of dye solutions with known dye content. The
adsorbed amount of dyes was calculated according
to the following Eq. (5),
qt

C0  Ct V
m

Results and discussions

Nanocrystalline cellulose was extracted from fully

bleached hardwood kraft pulp by sulfuric acid hydrolysis and then oxidized by sodium periodate to
yield the corresponding C-2/C-3 dialdehyde nanocellulose (DANC). The effect of sodium periodate
amount on the aldehyde group content of DANC is
shown in Fig. 2. It was shown that the aldehyde
content was increased with the increased dosage of
NaIO4, and reached the maximum (8.81 mmol g-1)
when NaIO4 addition was 9 mmol/g. This is in
consistent with the results of Cheng et al. (2014),
who prepared 2,3-dialdehyde cellulose films using
regenerated cellulose films by periodate oxidation. It
was reported by Sirvio et al. (2011) that periodate
oxidation can be improved by using elevated temperature and metal salts as oxidation activators.
The oxidized nanowhiskers with aldehyde group
content of 8.81 mmol g-1 were then grafted with
ethylenediamine to obtain ANCC employing a reductive amination treatment. The schematic pathway for
sodium periodate oxidation and reductive amination
of nanocellulose is shown in Scheme 1. During the
reaction, one of the amine groups reacts with the
aldehyde group of DANC to generate an imine bond
and then reduced to CN bond by NaBH4, while the
other one remains as a free primary amine.
The relationship between ethylenediamine addition
and amino group amount is shown in Fig. 3. It was
demonstrated that the primary amine groups were

where, qt is the adsorbed amount after time t, C0 and Ct

are initial concentration and concentration of the
adsorbate after time t, respectively, mg l-1; V is the
volume of the solution, l, and m is the weight of the
ANCC used, g.
The percentage removal of the dye was calculated
using the following Eq. (6),
%removal

C0  Ct
 100
C0

The study of pH influence was performed by

varying the pH between 4 and 9.

Fig. 2 The relationship between the amount of sodium

periodate and aldehyde group content

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Cellulose (2015) 22:24432456

2448
OX
O

OX
O

NaIO4

NaIO3+H2O+

HO

OH

2H2NCH2CH2NH2

OX
O
H2NH2CH2CHN

OX
O

NaBH 4

O
H2NH2CH2CN

NHCH2CH2NH2

O
NCH2CH2NH2

X = H, SO3H

Scheme 1 Sodium periodate oxidation and amination reaction of cellulose nanowhiskers

Fig. 3 Effect of ethylenediamine addition on amino group

content

successfully grafted onto the surface of nanowhiskers,

and the amino group content increased with the
increase of ethylenediamine addition. The amino
group content was higher than that reported by Way
et al. (2012), who prepared NCC-NH2 through a threestep procedure. NCC obtained via HCl hydrolysis of
tunicate was firstly oxidized by TEMPO/NaClO/
NaBr, then the resulted NCC-COOH reacted with an
excess (25 equiv) of mono Boc-protected ethylene
diamine using standard peptide coupling techniques.
The higher amino group content may probably
because more aldehyde groups formed during the
periodate oxidation than the carboxylic moieties

123

(310 mmol/kg) by TEMPO/NaBr/NaClO oxidation.

The presence of the free primary amine group on the
nanowhiskers surface was also confirmed by the
Kaiser test, which is shown in Fig. 4. The appearance
of a dark blue color was a strong indication for the free
amines.
The zeta potential of ANCCs versus pH values is
shown in Fig. 5. Obviously, the zeta potential of
ANCCs was significantly affected by the pH value of
the solution. It was positive at low pH due to the
protonation of amines (NCC-NH3?). With the increase of the pH value, the zeta potential decreased
and became negative in the alkaline region, resulting
from the deprotonation of amine groups (NCC-NH2)
and dissociation of sulfate groups on the surface. The
results indicated an amphoteric property of ANCC and
rendered it pH responsive, which can widen its
potential industrial application. The zeta potential
reached zero at pH of about 78, that is to say, the
isoelectric points of the ANCC samples are between
pH of 78. It was noted that with the increase of
ethylenediamine addition, the isoelectric point increased. It may probably because more amine groups
were introduced onto the nanowhiskers surface.
The FT-IR spectra of NCC, DANC and ANCC
samples are presented in Fig. 6. Compared with the
spectrum of unmodified NCC (Fig. 6a), two new
absorption bands at around 1731 and 885 cm-1
appeared in the spectrum of DANC (Fig. 6b),

Cellulose (2015) 22:24432456

Fig. 4 Kaiser test of NCC, DANC and ANCC samples

Fig. 5 Zeta potential of ANCC samples at varied pH

Fig. 6 FT-IR spectra of a NCC; b DANC and c ANCC (with 20

equiv of ethylenediamine)

corresponding to the characteristic absorption peaks of

the aldehyde group (C=O) and hemiacetal bonds
between newly achieved aldehyde groups and their

2449

Fig. 7 X-ray diffraction patterns of a NCC; b DANC and

c ANCC (with 20 equiv of ethylenediamine)

neighboring hydroxyl groups, respectively. This result

indicated that the hydroxyl groups on the molecular
chain of NCC were partially oxidized to aldehyde
groups, resulting in the dialdehyde NCC. The band at
1731 cm-1 was absent in the spectrum of ANCC
(Fig. 6c), which supported the successful reaction of
DANC with ethylenediamine. FT-IR spectra of ANCC
gave a new adsorption band at 1583 cm-1, which was
corresponded to NH bending vibration (Barazzouk
and Daneault 2012; Oh et al. 2005). The two bands in
the region of 3300 cm-1 typical for NH of primary
amines were not observed, they may probably overlap
with the strong broad OH stretching band, as
previously reported by Hemraz et al. (2013).
The wide angle X-ray diffraction patterns of freezedried NCC, DANC and ANCC are demonstrated in
Fig. 7. The peaks at 2h = 1418, 22.5 and 34.5
were characteristic of the structure of cellulose I
(Klemm et al. 2005). The CrI and crystallite size of
NCC, DANC and ANCC are calculated and shown in
Table 1. Compared with that of NCC (63.0 %), the
crystallinity index of DANC was reduced to 56.3 %. It
was found that the cellulose I polymorphic form was
retained after the oxidation, although the initial
crystallinity was reduced. The results were consistent
with those of Lindh et al. (2014) and Lu et al. (2014),
who also found the crystallinity decrease during the
nanocellulose periodate oxidation. The loss of crystallinity is considered to result from the opening of
glucopyranose rings and destruction of their ordered
packing (Kim et al. 2000; Varma and Chavan 1995).
The crystallite size of nanowhiskers before and after
chemical modification decreased insignificantly.

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2450

Table 1 Crystallinity index and crystallite size of cellulose

nanowhishkers
Samples

Crystallinity
index (%)

Crystallite
size (nm)

NCC

63.0

3.68

DANC

56.3

3.35

ANCC

59.8

3.26

Surface morphology and size distribution of the

cellulose nanowhiskers were characterized by AFM.
The AFM height images for the NCC, DANC and
ANCC are shown in Fig. 8 (upper part). It was
observed that the functionalization did not significantly affect the surface morphology characteristic of
nanowhiskers. The dispersibility of nanowhiskers
after chemical modification (Fig. 8b, c) were improved compared to that of the NCC (Fig. 8a), maybe
due to the incorporation of relatively hydrophilic
groups on the surface (Dash et al.2012; Sabzalian et al.
2014).
The height profile of the line along the length of the
cellulose whiskers was plotted, as shown in Fig. 8
(lower part), which revealed that the width of
nanowhiskers was slightly decreased from about
510 to 38 nm after the oxidation. The results agree

well with that of Sabzalian et al. (2014), who showed

that the diameter of periodate oxidized fibers became
smaller than that of the original fibers.
Adsorption of dyes
Effect of solution pH
ANCC sample prepared with 20 equiv of ethylenediamine per glucose unit was used as an adsorbent to
remove the acid red GR in the aqueous solution.
pH is one of the most important process variables
when considering dye adsorption. The solution pH
determines the level of electrostatic or molecular
interaction between the adsorbent and the adsorbate
owing to the charge distribution on the material (Nair
et al. 2014). In the present study, the effect of pH on
the dye removal percentage was evaluated at a pH
range of 4.09.0, as shown in Fig. 9. From Fig. 9
(inset), it is clear that the isoelectric point (pHpzc)of
ANCC is about 8.0, which means that at pH\8.0, the
surface of ANCC is positively charged, while
negatively charged at pH more than 8.0. It is obvious
that under acidic region (pH 4.7), the percentage
removal of dye was 67.3 % (qt = 134.7 mg g-1),
higher than the percentage removal of 52.2 %

Fig. 8 Dimensional dynamic AFM images for of a NCC; b DANC and c ANCC (with 20 equiv of ethylenediamine). Z-profile graph
was taken across the image from an arbitrary horizontal line

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2451

(with a BET surface area of 12.5 m2 g-1) and is more

stable in acidic solutions.
Adsorption isotherm

Fig. 9 Effect of initial solution pH on acid red GR removal

(dye conc. = 100 mg l-1; adsorbent dosage = 0.5 g l-1) (inset
the zeta potential of different pH for ANCC with 20 equiv of
ethylenediamine)

(qt = 104.5 mg g-1) in the neutral region (pH 6.7).

This demonstrates that at acidic conditions, the
interaction between the protonated amine and the
anionic site of the dye enhanced the adsorption of dyes
onto the ANCC. At a pH of 9, the dye percentage
removal was only 31.3 % (qt = 62.6 mg g-1). In the
alkaline region, the ANCC surface charge became
negative, consequently limiting the chemical interaction between ANCC surface and the anionic site of the
dye due to electrostatic repulsion. The results demonstrated that surface characteristics of ANCC, which
showed a direct dependence on the zeta-potential,
affected the adsorption efficiency greatly. The results
were consistent with literatures reported before
(Ibrahim et al. 2010; Liu et al. 2012), which found
that due to the presence of functional groups, anionic
dye adsorption was favored at pH \ pHpzc where the
surface became positively charged, whereas cationic
dye adsorption was favored at pH [ pHpzc.
The adsorption characteristics of ANCC are due to
the hydroxyl (-OH) and primary amine (-NH2)
groups that act as highly active adsorption sites. These
are similar with chitosan, a well known natural
biopolymer with high adsorption capacity and low
cost for the removal of dyes (Vakili et al. 2014). For
acidic dyes, both ANCC and chitosan show better
adsorption in the acidic conditions due to protonation
of amino groups. However, chitosan is apt to dissolute
in acidic solution, which will limit its adsorption
performance (Nair et al. 2014). Compared to chitosan,
ANCC in this study has high specific surface area

Adsorption isotherm models is used to described the

interaction between the adsorbate and adsorbent. The
adsorption of acid red GR onto the ANCC was
evaluated using classic isotherm models, Langmuir
and Freundlich models. The Langmuir isotherm model
is based on a monolayer adsorption onto a surface with
a finite number of adsorption sites of uniform adsorption energies (Nair et al. 2014). It can be expressed in
the following linear form,
1
1
1

qe qmax KL qmax Ce
where, Ce is the equilibrium concentration of adsorbate in the solution, mg l-1; qe is the amount of solute
adsorbed per mass of adsorbent, mg g-1; KL is the
Langmuir adsorption equilibrium constant, l g-1 and
qmax is the maximum adsorption capacity for monolayer formation.
The Freundlich isotherm model is an empirical
equation, which is utilized to understand adsorption on
heterogeneous surfaces adsorption capacity and multiple adsorption layers (Silva et al. 2013). It can be
expressed by the following equation,
ln qe ln Kf 1=n ln Ce
where, qe and Ce have the same meaning as in the
Langmuir equation; Kf and 1/n are the two Freundlich
constants.
Figure 10 shows the Langmuir isotherm for adsorption of acid red GR on ANCC. The high correlation
coefficient (R2 = 0.992) demonstrated that the model
provided a good theoretical correlation to the adsorption equilibrium. However, the fit of Freundlich model
with experimental data was poor with an R2 of 0.882,
indicating that the adsorption followed the monolayer
surface coverage model of Langmuir under the dye
concentration range studied. The theoretical maximum
adsorption capacity (555.6 mg g-1) matched well with
the experimental values (516.1 mg g-1).
Adsorption kinetics
The adsorption of different anionic dyes, congo red
4BS (direct dye), acid red GR (acid dye) and reactive

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2452

Fig. 10 Langmuir isotherm for adsorption of acid red GR on

ANCC (adsorbent dosage = 0.5 g l-1; t = 7 h) (inset linear
Langmuir plot of adsorption)

light yellow K-4G (reactive dye) on ANCC were

evaluated and shown in Fig. 11. It was noted that the
percentage removal of Congo red 4BS (about 100 %,
qt = 199.5 mg g-1) was more compared to other
dyes. This was mainly due to strong electrostatic and
chemical interaction of the anionic and amine groups
present on congo red 4BS with the amine and hydroxyl
groups on ANCC. The removal efficiency of acid red
GR and reactive light yellow K-4G were 68
(qt = 134.7 mg g-1) and 91 % (qt = 183.0 mg g-1),
respectively, which demonstrated that ANCC can be
utilized for the adsorption of different anionic dyes at a
low dosage.
The adsorption kinetics of congo red 4BS, acid red
GR and reactive light yellow K-4G by ANCC were
investigated to describe the dye adsorption rate and
eventually explore the mechanism of adsorption and
the rate limiting steps involved. The most commonly
used kinetic models for investigating solidliquid
interactions are pseudo first order and pseudo second
order models, which are based on adsorption capacity
(Zhou et al. 2014). In first order model, adsorption is
controlled by diffusion and mass transfer of the
adsorbate to the adsorption site, whereas in a second
order model, chmisorption is the rate limiting step (ElZahhar et al. 2014). The pseudo second order model
considers that the limiting stage of the adsorption
process involves valence forces through the sharing or
exchange of electrons between the adsorbent and the
adsorbate (Vargas et al. 2012).
The first and second order rate equations are
expressed as follows,

123

Cellulose (2015) 22:24432456

Fig. 11 Percentage removal of different anionic dyes using

ANCC (dye conc. = 100 mg l-1; adsorbent dosage = 0.5 g l-1)

First order kinetic model: logqe  qt

log qe  k1 t=2:303
Second order kinetic model:

t
1
1

t
2
qt k 2 qe qe

where, qe and qt are the amount of adsorbed dye per

unit mass of adsorbent (mg g-1) at equilibrium and at
time t, respectively; k1 is the pseudo first order sorption
rate constant (h-1), and k2 is the rate constant of
pseudo second order adsorption (g mg-1 h-1).
The linear plot of log (qe - qt) versus t and t/qt
versus t were plotted and shown in Fig. 12 and 13,
respectively. The kinetic parameters were calculated
by the intercepts and slopes of the lines, which were
listed in Table 2. R2 for the second order model were
greater than 0.99 for all the three dyes, while R2 for the
first order model were between 0.872 and 0.968.
Moreover, the calculated equilibrium adsorption values from pseudo first order model were much lower
than the experimental values. The values of qe cal by
the second order model and qe exp matched well, which
confirmed that the kinetics of adsorption by ANCC for
the three anionic dyes was best described by the
pseudo second order model. This indicated that
adsorption of anionic dyes onto ANCC was mainly
controlled by chemisorption behavior. Second order
kinetics of dye adsorption was also observed for
biosorbents such as modified cellulose (Wang and Li
2013), chitosan/lignin composite (Nair et al. 2014),
tannery solid waste (Piccin et al. 2012), and lignocellulose originating from biodiesel production (Magriotis et al. 2014). It was also clear from Table 2 that

Cellulose (2015) 22:24432456

2453

efficiency of ANCC for the adsorption of congo red

4BS.

Conclusions

Fig. 12 Pseudo first order sorption rate plot for sorption of dyes by
ANCC (dye conc. = 100 mg l-1; adsorbent dosage = 0.5 g l-1)

Fig. 13 Pseudo second order sorption rate plot for sorption of

dyes by ANCC (dye conc. = 100 mg l-1; adsorbent
dosage = 0.5 g l-1)

the rate constant, k2, for the adsorption of acid red GR

and reactive light yellow K-4G, was much lower than
that for congo red 4BS, which qualifies the higher
Table 2 Pseudo first and
second order parameters for
the adsorption of dyes on
ANCC

Dyes

In this study, nanocrystalline cellulose, extracted from

fully bleached hardwood kraft pulp by sulfuric acid
hydrolysis, was firstly oxidized by sodium periodate to
yield the corresponding C-2/C-3 DANC. The oxidized
nanowhiskers were then grafted with ethylenediamine
to obtain amino-functionalized NCC (ANCC) through
reductive amination reaction. The free primary amine
groups of ANCCs increased with the increase of
ethylenediamine addition. The presence of the free
amine group on the nanowhiskers surface was also
confirmed by the Kaiser test and FT-IR analysis. Zeta
potential of ANCCs was significantly affected by the
pH value. It was positive at low pH and became
negative in the alkaline region, indicating an amphoteric property of ANCC and rendered it pH responsive,
which can widen its potential industrial application.
The isoelectric points of the ANCC samples are
between 7 and 8. The crystallinity indices were
reduced after periodate oxidation and amino-functionalization, while the structure of cellulose I was
maintained. AFM analysis revealed that the functionalization did not significantly affect the surface
morphology characteristic of nanowhiskers. The
width of nanowhiskers was slightly decreased from
about 510 to 38 nm after the oxidation. ANCC was
applied as an adsorbent to remove the anionic dyes in
the solution, and showed high adsorption capability. It
demonstrated the maximum removal efficiency at
acidic conditions. The adsorption isotherms of ANCC
could be well described by Langmuir model. ANCC

Acid red GR

Congo red 4BS

Reactive light yellow K-4G

1.1345

1.1784

0.8735

38.74

0.83

71.48

0.944

0.872

0.968

First order
K1 (h-1)
qe

cal

(mg g-1)

R2
Second order
K2 (g mg-1h-1)
qe

cal

0.065

3.575

0.030

(mg g-1)

138.9

200

188.7

0.999

1.000

0.999

(mg g-1)

137.1

199.5

183.0

R2
qe

exp

123

2454

can be utilized for the adsorption of different anionic

dyes. The removal percentage of direct dye was more
than those of acid and reactive dyes. The adsorption of
the anionic dyes onto ANCC followed pseudo second
order kinetics, indicating that dye adsorption on
ANCC was mainly controlled by chemisorption
behavior.
Acknowledgments The authors would like to thank the
National Natural Science Foundation of China (Grant No.
31370581), Shandong Provincial Outstanding Youth Scholar
Foundation for Scientific Research (Grant Nos. 2009BSB01053
and BS2010CL041), and the funding of Shandong provincial
Science and Technology Development Project (Grant No. 13fz02).

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