Amino-functionalized Nanocrystalline Cellulose

8/18/2019 Amino-functionalized Nanocrystalline Cellulose

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O R I G I N A L P A P E R

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

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 (FT-IR), X-ray diffraction and atomic force microscopy. It

was found that the primary amine groups of ANCC

(0.77–1.28 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 7–8. Chemical modifications of the

cellulose nanowhiskers reduced the crystallinity but

the initial cellulose I polymorph was retained. The

cross-sectional dimension of nanowhiskers was

slightly decreased from about 5–10 to 3–8 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 demon-

strated 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 toprovide 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

L. Jin (&)

School of Chemistry and Pharmaceutical Engineering,

Qilu University of Technology, Jinan 250353, China

e-mail: [email protected]

W. Li Q. Xu Q. SunKey Laboratory of Paper Science and Technology of

Ministry of Education, Qilu University of Technology,

Jinan 250353, China

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DOI 10.1007/s10570-015-0649-4

Cellulose (2015) 22:2443–2456

/ Published online: 1 ay 20150 M

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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) areused 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, bio-

mass and polymeric resins (Murphy et al. 2008;Unuabonah et al. 2012). In order to provide cost-

effective, 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, there-

fore, the functional groups on the adsorbents surface

play an important role in determining the effective-

ness, 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 idealcandidate 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, renew-

able, biodegradable and biocompatible (Roy et al.

2009). Nanocellulose, extracted from cellulosic fibers

by applying mechanical, chemical, physical or biolo-

gical methods, demonstrates excellent properties,

including high aspect ratio, large specific surface area,

reactive surface of -OH groups, and high Young’s

modulus. The unique properties may impart nanocel-

lulose 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 usto develop nanocellulose based dye adsorbents with

high adsorption capacity (Pei et al. 2013). Ma et al.

(2012) developed a multilayered nanofibrous micro-

filtration (MF) membrane, by impregnating ultrafine

cellulose nanowhiskers into an electrospun polyacry-

lonitrile (PAN) nanofibrous scaffold supported by a

poly(ethyleneterephthalate) (PET) nonwoven sub-

strate. 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 nanocrys-

tals (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 adsorptioncapacity for pollutant after suitable chemical modifi-

cation 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 disinte-

gration 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 withaminoethanethiol 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 esterifi-

cation, 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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Most of covalent modifications predominantly oc-

curred on the primary hydroxyl groups at the C-6

position of the cellulose backbone. Periodate oxida-

tion 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 reactiveintermediate for further derivatization and opens

possibilities for many other chemical reactions (Cheng

et al. 2014; Dash et al. 2012; Sirviö et al. 2014), thus

widening the potential application of nanocellulose

(Kalaskar et al. 2010). A chemical pretreatment for

producing CNCs with periodate oxidation and reduc-

tive 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. Dashand Ragauskas (2012) prepared a novel nanometric

carrier molecule by grafting for amine-containing

biologically active molecules and drugs employing

functionalized cellulose nanowhiskers. The nanowhis-

kers were grafted with a spacer molecule, gamma

aminobutyric acid, using a periodate oxidation and

Schiff’s 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 oxi-dized by sodium periodate to yield the corresponding

C-2/C-3 dialdehyde nanocellulose (DANC), and then

grafted with ethylenediamine to obtain amino-func-

tionalized 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. Ethylenedi-

amine 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 pulpwas 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 trans-

ferred onto a cellulose dialysis membrane with a

molecular weight cut-off of 12,000–14,000 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 itsoriginal 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 wasdialyzed against deionized water for 3 days using a

dialysis membrane with a molecular weight cut-off of

12,000–14,000. The acquired dialdehyde nanocrys-

talline 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 hy-

drochloride (Kim et al. 2004). The dialdehyde content

(DC) of each sample was calculated through Eq. (1),

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DC ðmmol g1Þ ¼C ðV 2 V 1Þ

mð1Þ

where, V 1 is the amount of sodium hydroxide for

DANC titration, ml; V 2 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 ultra-

sonicated for 5 min, and then various amounts of

ethylenediamine were added. The mixture was con-

tinuously 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:

12,000–14,000) 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),

AGC ¼C ðV 2 V 1Þ

mð2Þ

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

C is the concentration of NaOH solution; V 1 and V 2 are

the minimum and maximum consumptions of NaOH

in the lowest conductivity (ml), respectively and m is

the freeze dried content of ANCC.

Characterization

Kaiser test

Kaiser test was performed according to the literature

(Hemraz et al. 2013). A few drops of phenol (about80 % in ethanol), KCN in water/pyridine, and ninhy-

drin (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 con-

ducted on an IRPrestige-21 Fourier transform infrared

spectrometer (Shimadzu Company, Japan). The sam-ples 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 ¼ I 002 I am

I 002ð3Þ

where, CrI is the crystallinity index; I 002 is the intensity

of the crystalline peak at the maximum at 2h between

22 and 23 for cellulose I, and I am 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,

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

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D ¼ 0:89 k

b1=2 cos h ð4Þ

where, k is the radiation wavelength of X ray,

0.154056 nm; h is the Bragg diffraction angle, corre-

sponding 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 severaldifferent 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 UV–visible 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 ¼ðC 0 C tÞV

m ð5Þ

where, qt is the adsorbed amount after time t, C 0 and C tare 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 ¼C 0 C t

C 0 100 ð6Þ

The study of pH influence was performed by

varying the pH between 4 and 9.

Results and discussions

Characterization of ANCC

Nanocrystalline cellulose was extracted from fully

bleached hardwood kraft pulp by sulfuric acid hy-

drolysis and then oxidized by sodium periodate toyield the corresponding C-2/C-3 dialdehyde nanocel-

lulose (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 Sirviö et al. (2011) that periodateoxidation can be improved by using elevated tem-

perature 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 reduc-

tive 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 C–N bond by NaBH 4, while theother 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

Fig. 2 The relationship between the amount of sodium

periodate and aldehyde group content

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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 three-

step 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

(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 in-

crease 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 7–8, that is to say, the

isoelectric points of the ANCC samples are between

pH of 7–8. It was noted that with the increase of

ethylenediamine addition, the isoelectric point in-

creased. 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),

NaIO4 NaIO3+H2O+

O

O

OX

OH

HO

OO

OX

OO

X = H, SO3H

O

O

OX

NCH2CH2 NH2H2 NH2CH2CN

2 H2 N

C H2 C H2 NH2

NaBH4

O

O

OX

NHCH2CH2 NH2H2 NH2CH2CHN

Scheme 1 Sodium periodate oxidation and amination reaction of cellulose nanowhiskers

Fig. 3 Effect of ethylenediamine addition on amino group

content

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corresponding to the characteristic absorption peaks of

the aldehyde group (C=O) and hemiacetal bonds

between newly achieved aldehyde groups and their

neighboring hydroxyl groups, respectively. This result

indicated that the hydroxyl groups on the molecularchain 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 N–H bending vibration (Barazzouk

and Daneault 2012; Oh et al. 2005). The two bands in

the region of 3300 cm-1 typical for N–H of primary

amines were not observed, they may probably overlap

with the strong broad O–H stretching band, aspreviously reported by Hemraz et al. (2013).

The wide angle X-ray diffraction patterns of freeze-

dried NCC, DANC and ANCC are demonstrated in

Fig. 7. The peaks at 2h = 14–18, 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 initialcrystallinity 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 crys-

tallinity 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.

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)

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

c ANCC (with 20 equiv of ethylenediamine)

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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 significant-

ly affect the surface morphology characteristic of

nanowhiskers. The dispersibility of nanowhiskers

after chemical modification (Fig. 8b, c) were im-

proved compared to that of the NCC (Fig. 8a), maybedue 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

5–10 to 3–8 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 ethylenedi-

amine 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 pHrange of 4.0–9.0, 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 %

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

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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(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 interac-

tion between ANCC surface and the anionic site of the

dye due to electrostatic repulsion. The results demon-

strated that surface characteristics of ANCC, whichshowed 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. Theseare 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

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

stable in acidic solutions.

Adsorption isotherm

Adsorption isotherm models is used to described the

interaction between the adsorbate and adsorbent. Theadsorption 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 adsorp-

tion energies (Nair et al. 2014). It can be expressed in

the following linear form,

1

qe¼

1

qmaxþ

1

K L qmaxC e

where, C e is the equilibrium concentration of adsor-bate in the solution, mg l-1; qe is the amount of solute

adsorbed per mass of adsorbent, mg g-1; K L is the

Langmuir adsorption equilibrium constant, l g-1 and

qmax is the maximum adsorption capacity for mono-

layer formation.

The Freundlich isotherm model is an empirical

equation, which is utilized to understand adsorption on

heterogeneous surfaces adsorption capacity and mul-

tiple adsorption layers (Silva et al. 2013). It can be

expressed by the following equation,

ln qe ¼ ln K f þ ð1=nÞ ln C e

where, qe and Ce have the same meaning as in the

Langmuir equation; K f and 1/n are the two Freundlich

constants.

Figure 10 shows the Langmuir isotherm for adsorp-

tion of acid red GR on ANCC. The high correlation

coefficient (R2 = 0.992) demonstrated that the model

provided a good theoretical correlation to the adsorp-

tion equilibrium. However, the fit of Freundlich model

with experimental data was poor with an R2 of 0.882,

indicating that the adsorption followed the monolayersurface 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

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)

1 3

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light yellow K-4G (reactive dye) on ANCC wereevaluated 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 alow 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 solid–liquid

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 theadsorbate to the adsorption site, whereas in a second

order model, chmisorption is the rate limiting step (El-

Zahhar 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,

First order kinetic model: log qe qt ð Þ¼ log qe k 1t =2:303

Second order kinetic model: t

qt ¼

1

k 2q2eþ

1

qet

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; k 1 is the pseudo first order sorption

rate constant (h-1), and k 2 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 val-

ues 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 thepseudo 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 lignocel-

lulose originating from biodiesel production (Ma-

griotis et al. 2014). It was also clear from Table 2 that

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)

Fig. 11 Percentage removal of different anionic dyes using

ANCC (dye conc. = 100 mg l-1

; adsorbent dosage = 0.5 g l-1

)

1 3

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the rate constant, k 2, 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

efficiency of ANCC for the adsorption of congo red

4BS.

Conclusions

In this study, nanocrystalline cellulose, extracted fromfully 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 thepH value. It was positive at low pH and became

negative in the alkaline region, indicating an ampho-

teric 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-function-

alization, while the structure of cellulose I was

maintained. AFM analysis revealed that the function-

alization did not significantly affect the surface

morphology characteristic of nanowhiskers. Thewidth of nanowhiskers was slightly decreased from

about 5–10 to 3–8 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

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

)

Table 2 Pseudo first and

second order parameters for

the adsorption of dyes onANCC

Dyes Acid red GR Congo red 4BS Reactive light yellow K-4G

First order

K 1 (h-1

) 1.1345 1.1784 0.8735

qe cal (mg g-1) 38.74 0.83 71.48

R2 0.944 0.872 0.968

Second order

K 2 (g mg-1

h-1

) 0.065 3.575 0.030

qe cal (mg g-1

) 138.9 200 188.7

R2

0.999 1.000 0.999

qe exp (mg g-1

) 137.1 199.5 183.0

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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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Amino-functionalized Nanocrystalline Cellulose

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