Accepted Manuscript

Title: Nanocellulose based biosorbents for wastewater

treatment: Study of isotherm, kinetic, thermodynamic and
reusability

Authors: Jindrayani Nyoo Putro, Alfin Kurniawan, Suryadi

Ismadji, Yi-Hsu Ju

PII: S2215-1532(17)30093-4
DOI: http://dx.doi.org/doi:10.1016/j.enmm.2017.07.002
Reference: ENMM 99

To appear in:

Received date: 18-4-2017

Revised date: 12-6-2017
Accepted date: 11-7-2017

Please cite this article as: Jindrayani Nyoo Putro, Alfin Kurniawan, Suryadi Ismadji, Yi-
Hsu Ju, Nanocellulose based biosorbents for wastewater treatment: Study of isotherm,
kinetic, thermodynamic and reusability, Environmental Nanotechnology, Monitoring
and Managementhttp://dx.doi.org/10.1016/j.enmm.2017.07.002

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 Nanocellulose based biosorbents for wastewater treatment: Study of isotherm,
kinetic, thermodynamic and reusability

Jindrayani Nyoo Putro1, Alfin Kurniawan1, Suryadi Ismadji1,2*, Yi-Hsu Ju1*

1
Department of Chemical Engineering, National Taiwan University of Science and
Technology, No. 43, Sec 4, Keelung Rd,. Da’an District, Taipei City 106, Taiwan.
2
Department of Chemical Engineering, Widya Mandala Surabaya Catholic University,
Kalijudan 37, Surabaya 60114, Indonesia.

*Corresponding authors: yhju@mail.ntust.edu.tw; suryadiismadji@yahoo.com

Highlights
 The application of nanocellulose as adsorbents are reviewed.
 Isotherm, kinetic and thermodynamic of adsorption are studied.
 Regenerative is investigated for possible upscale implementation.

ABSTRACT

The advance technology in 21st century has given human ease of life and huge problem in

environmental sector. Recently, the improvement on nanomaterial has attracted

researchers in the preparation of nanocellulose adsorbents. The stability of nanocellulose

as adsorbent also shows good prospects in upgrading scale as regenerative aspects

indicates good performance after several adsorption-desorption cycle. This review paper

provides a comprehensive review on the use of nanocellulose and its modified forms for

the wastewater treatment. Various aspects on the validity of adsorption isotherms and

kinetic models as well as theoretical aspects of the thermodynamic of adsorption are also
1
given in this paper. Future perspective on the use of NCC and its modified forms for

industrial application is also discussed.

Keywords: nanocellulose; isotherms; kinetics; adsorption

1. Introduction

Water as source of life, is essential to every aspect in human’s life. However, at

present our world faces water scarcity due to rapid growth of population, development of

industry, climate change, mismanagement of water use, etc. Currently, around 700

million peoples suffer from water scarcity in 43 countries and more than two million

children under the age of five died every year by water-related disease (UN-Water, 2007,

2014). The contamination of water and water pollution are big problems for more than

60% of the world human population. Industrial and urban activities are likely to give

major contribution to water pollution. Since water scarcity and water pollution are major

global problems, therefore, a strict water usage policy and water management is urgently

required.

Hazardous contaminants enter water mostly through the direct discharge of industrial

effluents and urban activities. The presence of hazardous contaminants in water

environment creates severe problems for human and water ecosystem. Currently, a

number of technologies are available for the removal of hazardous substances from

industrial effluents such as biological treatments using aerobic and anaerobic

microorganisms, advanced chemical oxidation, membrane separation, photo catalysis

2
oxidation and adsorption. Among all available methods for the treatment of industrial

effluents, adsorption is still the most widely used method in wastewater treatment due to

low capital cost, can remove most of all kinds of pollutants, and easy regeneration (Crini,

2005). Several types of adsorbents have been used for the removal of various kinds of

pollutants such as are activated carbon, montmorillonite, zeolites, kaolin, microorganism,

and agricultural wastes (Veglio and Beolchini, 1997; Yin et al., 2007; Demirbas, 2008;

Bhattacharyya and Gupta, 2008; Malamis and Katsou, 2013). Due to its abundant

availability and broad range of applicability, lignocellulosic materials have attracted the

attention of various researchers to utilize it for environmental application. One of the

promising applications of lignocellulosic material is as the adsorbent for water

purification or wastewater treatment. Cellulose is one of the major components in

lignocellulosic material. This natural polymer has been investigated as bio-sorbent in its

natural or chemically modified form. In natural form, it exists in agricultural wastes such

as banana peel, saw dust, corncob, and bagasse (Annadurai et al., 2002; Ngah and

Hanafiah, 2008). Modified cellulose can be divided into two groups, which are direct

modification and monomer grafting. The main routes of direct cellulose modification in

the preparation of adsorbent materials are esterification, etherification, halogenation,

oxidation, alkaline treatment, and silynation (O’Connel et al., 2008; Hokkanen et al.,

2016). Monomer grafting or graft copolymerization is a process where side chain grafts

are covalently attached to the main chain of a polymer backbone to form a branched

copolymer. Well known techniques that commonly used in graft copolymerization are

photografting, high energy radiation grafting, and chemical initiation grafting (O’Connel

et al., 2008; Hokkanen et al., 2016).

3
 Currently, isolation of cellulose in the form of nanocrystal and nanofibers has been

extensively studied due to its wide application in industry such as enzyme immobilization,

adsorption, catalysis, drug delivery, biosensors and bio-imaging (Lam et al., 2012). The

separation of nanocrystalline cellulose (NCC) can be conducted by acid hydrolysis,

esterification, oxidation, silylation, cationization, acetylation, and polymer grafting (Peng

et al., 2011). Whilst the extraction of nanofibrils cellulose (NFC) must be carried out by

mechanical treatment such as homogenization, cryo-crushing, microfluidization, grinding

and sonication (Zhao et al., 2007; Siro and Plackett 2010; Spence et al., 2011) or via

fermentation by bacteria (Klemm et al., 2009). Both NCC and NFC have nanometer scale

in diameter, but the length of NFC is in micrometer while NCC has nanometer length

(Brinchi et al., 2013). This nanomaterial has already been studied as adsorbent for

removal of various kinds of hazardous pollutants, and the results of the studies indicate

that these materials possess high adsorption capacity, are environmental friendly and low

cost adsorbent (Lam et al., 2012). Despite that many review articles have been published

dealing with the use of lignocellulosic materials as the adsorbent in water and wastewater

treatment (most of them mention in specific type of adsorbate such as heavy metals and

organic compounds), however, there is no review discuss about the use of nanocellulose

for environment remediation especially as adsorbent. In this review, we discuss recent

studies on the use of nanocellulose adsorbents for adsorption of heavy metals, dyes, and

organic compounds. The emphasis of this review paper is to provide a comprehensive

discussion on the adsorption mechanisms of hazardous pollutants onto nanocellulose and

its modified forms through equilibrium and kinetic studies. Future perspective on the use

of nanocellulose adsorbents for water remediation is also given in this review.

4
2. Preparation of various nanocellulose adsorbents

Cellulose is a linear polysaccharides consisted of two anhydroglucose rings linked

by β-1,4 glycoside bonds in a repeated manner (Eichhorn et al., 2010). It can be found

within the fiber walls of plants, the lateral size of cellulose chains is around 0.3 nm

(Ioelovich, 2008). Cellulose fibrils are arranged in crystalline and amorphous region,

where the length of crystalline is 50-150 nm and the amorphous length is 25-50 nm

(Figure 1) (Ioelovich, 2008; Moon et al., 2011). To produce NCC, the removal of

amorphous region is needed. The most common procedure to eliminate this amorphous

part is through acid hydrolysis using sulfuric acid; this method is first published by

Ranby and Ribi (1950). Apart from acid hydrolysis, there are other procedures like

oxidation, enzymatic hydrolysis, ionic liquid (IL), carbamation, amidation, esterification,

silylation, and cationization. For oxidation, there are two well-known commonly used

chemicals: 2,2,6,6-tetramethylpiperidinyl-1-oxyradical (TEMPO) and ammonium

persulfate (APS). TEMPO oxidation is always combined with NaBr and NaOCl as the

co-oxidizing agent (Montanari et al., 2005; Saito et al., 2007; Lin et al., 2012). Unlike

TEMPO, APS does not require any chemical addition (Zhang et al., 2016). This oxidation

is exceptionally different from any other procedures that transform the hydroxyl groups

in cellulose fiber; it converts the hydroxymethyl groups of cellulose fibers (Habibi et al.,

2010). The oxidated NCC by TEMPO can be further modified by amidation by using

carbodiimides derivatives as the amidation agent, and N-Hydroxysuccinimide (NHS) is

added as the amine source to allow the migration ON of O-acylisourea (Bulpitt and

Aeslichmann, 1999; Habii, 2014). Another method called carbamation can also be used

5
to modify hydroxyl groups of NCC by reacting it with an isocyanate (Eyley and

Thielemans, 2014).

For the IL pretreatment, it is definitely affected by the anion side than cation. The

reaction occurred in the NCC preparation is also completely depends on the anion type in

the IL. Han reported the use of [BMIM]+[Cl]- to produce NCC, the free [Cl]- associates

with the hydroxyl group of cellulose, while [BMIM]+ attacks the oxygen atom in the

hydroxyl group (Han et al., 2013). On the other hand, Man used [BMIM]+[HSO4]- which

resulted in sulfate-NCC (Man et al., 2011). From the works of Han (2013) and Man

(2011), it can be concluded that the anion completely control the formation of NCC.

Esterification is the reaction that usually occurs when acid is used as the reactant to

produce NCC. The most common reactant used is sulfuric acid, which results in NCC–

OSO3H due to the grafting of anionic sulfate ester groups (Dufresne, 2013). Other

reactants that have been investigated to produce NCC by Fischer esterification is the

combination of HCl and organic acid like acetic, citric, malonic, and malic acid (Braun

and Dorgan, 2009; Spinella et al., 2016). Using phosphoric acid also can form NCC with

better thermal stability than sulfonated NCC; Espinosa et al. (2013) assumed the

formation of NCC by one ester bond. Kokol et al. (2015) reported that there is tautomeric

equilibrium occurred in the process, where two possible products can be formed: a) P-

NCC that behaves as monobasic acid and b) P-NCC that exhibits two acid groups.

Enzymatic hydrolysis has been favorably considered to produce NCC because it

does not use harsh chemicals, has lower energy requirement and is environmental

friendly (Anderson et al., 2014). Filson et al. (2009) studied the effect of heating method

(conventional and microwave) on endoglucanase hydrolysis and reported that at 50 °C for

6
45 min, the highest NCC yield for both conventional heating (29%) and microwave

heating (38.2%) can be obtained; the average zeta potential for NCC is -31.37 mV, which

indicates considerably stable NCC suspension for an extended time.

For cationization, the cellulose is already in the form of nanocrystalline after acid

hydrolysis (Hasani et al., 2008; Odabas et al., 2016). In acid hydrolysis, the surface of

NCC will be modified by commonly used reactants which are 2,3-

epoxypropyltrimethylammonium chloride (EPTMAC), water, and NaOH. EPTMAC will

react with the hydroxyl groups of NCC; the reaction is etherification that leads to the

cationization of NCC. Besides etherification, another reaction occurs between EPTMAC

and water to form diol (Odabas et al., 2016). Silylation is another type of reaction usually

used to modify the NCC surface in order to break the limitation of flocculated dispersion

of NCC in non-polar medium. Chlorosilane is used as the silylating agent due to its long

alkyl moieties which can lead to stable silylated NCC (Gousse et al., 2002). Polymer

grafting is also one of the famous NCC modification methods. There are two grafting

methods, “grafting to” and “grafting from”. “Grafting to” technique is direct attachment

of polymer chains to NCC surface. Differ from “grafting to” technique, “grafting from” is

in situ growth of polymer chains on NCC surface by an initiator addition. The “grafting

from” occurs through ring opening polymerization (ROP) with the addition of stannous

octoate (Sn(Oct)2) as the polymerization agent and the other way is via atom transfer

radical polymerization (ATRP) by the addition of 2-bromoisobutyrylbromide (BIBB) as

the initiator agent (Morandi et al., 2009; Habibi et al., 2010). A summary of chemical

modification of NCC is given in Table 1.

7
 Prior to NCC formation, NFC should be obtained first. There two procedures to

obtain this NFC. The first procedure is via mechanical treatment with the sole purpose of

defibrillating the cellulose fibers, and the second procedure is fermentation to produce

bacteria cellulose (BC). BC can be produced by many kinds of bacteria, and the most

studied is the genera Acetobacter (Klemm et al., 2009). This BC has high purity and high

crystallinity cellulose nanofibers, unlike NFC from lignocellulose biomass, but the

process is time consuming and low in yield. The production of NFC by mechanical

treatment produce high NFC yield in short time, however the energy consumption to

extract NFC is high. For example extraction using homogenizer requires energy around

70,000 kWh/t (Lavoine et al., 2012). Thus, chemical or enzymatic pretreatment is usually

used combined with mechanical treatment to suppress the high energy consumption.

Ultrasonication is another method that can be used to extract nanofiber from natural

materials, which can be a convenient and environmental friendly technique. The concept

of this method is to harness the acoustic cavitation which leads to the formation of

microjets and shock waves, this microjets and shock waves later can disrupt the relatively

weak van der Waals forces among fibers (Zhao et al., 2007).

Preparation of composites from nanocellulose has also been conducted to enhance

adsorption capacity. Materials that were used to combine with nonocellulose to produce

composite include bentonite, hydroxyapatite, polyacrylamide, metal, chitosan, and

polyvinylamine (Zhou et al., 2014; Anirudhan et al., 2015; Jin et al., 2015; Hokkanen et

al, 2015, 2016; Liu et al., 2016). Synthesize of these composites can be carried out

through crosslinking using some chemical agents.

3. Adsorption process

8
 Adsorption is a spontaneous process where forces of attraction exist between

adsorbent and adsorbate. Based on surface interaction, adsorption is divided in four types:

ion exchange, physisorption, chemisorption, and specific adsorption. Ion exchange

adsorption involves an attachment of ionic species to the opposite charge at the surface of

an adsorbent (Weber Jr., 1985). Physisorption occurs when van der Waals forces are

involved, this type of adsorption has the characteristics of low enthalpy (less than 80

kJ/mol), can be monolayer or multilayer adsorption, no dissociation of adsorbed species,

and decreasing adsorption capacity with increasing temperature (Ruthven, 1984). On the

contrary, chemisorption involves chemical forces or bonding between adsorbent and

adsorbate that resulting in a change in the chemical form of adsorbate. Due to its strong

interaction, chemisorption has high enthalpy (80 to 800 kJ/mol), adsorption occurs at

monolayer only, and involves dissociation of adsorbed species (Ruthven et al., 1984).

Specific adsorption is resulted from specific interaction between adsorbate molecules and

adsorbent which do not result in chemical change of adsorbate. This type of adsorption

has binding energy value in between those of physisorption and chemisorption (Weber Jr.,

1985).

To understand the mechanism of an adsorption process, usually it can be conducted

with either isotherm or kinetic point of view. There are three types of adsorption

isotherms for a solid-liquid system, as shown in Figure 2: type I (favorable), type II

(linear), and type III (unfavorable). For favorable adsorption isotherm, adsorption

normally occurs on microporous adsorbents where pore size is not greater than the

molecular diameter of the adsorbate (Ruthven, 1984). Type II shows linear isotherm at

low concentration, this type is well known as the classical Langmuir form (Basmadjian,

9
1997), and type III is commonly observed for a wide range of adsorbents pore size

(Ruthven, 1984).

Adsorption is influenced by adsorbate-solvent properties, system properties, and

adsorbent properties. For adsorbate-solvent properties, it can be shown in the form of

solubility. If the adsorbate molecule has high solubility in water, then adsorption removal

will decrease. System properties such as pH can give major influences on adsorption

mechanism. In many published works, the authors always studied the effect of pH since

in some pH the adsorbent can either be protonated or deprotonated. Adsorbent properties

are usually referred to surface area and the distribution of area with respect to pore size as

a primary determinant in adsorption capacity (Weber Jr., 1985). Adsorption occurs in

three consecutives step as shown in Figure 3: bulk diffusion, external diffusion, and

intraparticle diffusion. Bulk diffusion is usually rapid due to the effect of mixing.

External diffusion concerns about the diffusion of adsorbate molecule through a

hydrodynamic boundary layer. Then adsorbate molecules diffuse to the active sites of

adsorbent, where this step is called intraparticle diffusion. Usually, the rate limiting step

lays on the second step where it controls the diffusion of solute through boundary layer to

the external surface of adsorbent (Weber Jr., 1985).

3.1. Adsorption isotherm

In order to obtain proper design of an adsorption process, reliable adsorption

equilibria data are required. Adsorption equilibria can be represented in mathematical

form called adsorption isotherm. Various adsorption models are available to represent the

10
liquid phase adsorption equilibria, and the most widely used models are Langmuir and

Freundlich.

Langmuir model was originally developed to describe monolayer surface adsorption

on flat surface based on a kinetic viewpoint. The model assumes that the rate of

adsorption equals to the rate of desorption from flat surface. Langmuir is the simplest

theoretical adsorption model. Three assumptions were used to develop this model:

 Energy of adsorption is constant over all adsorption sites due to surface homogeneity.

 Adsorption occurs on definite sites on adsorbent surface (adsorption on

homogeneous surface is localized).

 Adsorption energy is the same at all sites, and each active adsorption site only

accommodates one molecule of adsorbate.

By applying these assumptions and kinetic principle, the Langmuir equation is expressed

as

K LCe
qe  qmax (1)
1  K LCe

Equation (1) can also be written in linearized form as

Ce 1 1
 Ce  (2)
qe qmax K L qmax

where KL is the affinity constant which is related to the heat of adsorption according to

the following equation

-H
K L  Ko exp (3)
RT

The affinity constant is temperature dependent. For physical adsorption, adsorption

affinity decreases with increasing temperature. Since this parameter measures how strong

11
an adsorbate molecule is attracted onto a surface, a decrease of this parameter indicates

that uptake of the adsorbate decreases with increasing temperature. While chemisorption

is endothermic, with increasing temperature, affinity constant also increases leading to

the increase of the uptake of adsorbate. Monolayer adsorption capacity is expressed as

qmax. This parameter is also temperature dependent

qmax  qmax
o
exp  T  To  (4)

Here qomax is the adsorption capacity of the adsorbent at reference temperature To, while δ

is coefficient expansion of the adsorbate. Parameter δ is independent on the type of

adsorbents. The values of qmax obtained from the fitting of adsorption experimental data

show that temperature plays important role on the uptake of solute (see Table 2). If

physical adsorption controls the process, the increase of temperature gives negative effect

on the amount adsorbed. In case chemisorption controls the adsorption process, the

uptake of solute increases with increasing temperature.

Another approach to study the adsorption isotherm was proposed by Samiey and

Tehrani (2016). They proposed an adsorption isotherm regional analysis model

(abbreviated as ARIAN). In this model, the adsorption isotherm was divided into several

regions. Region 1 obeys the Henry’s law which is valid at low concentrations; region 2

comprises monolayer surface aggregate formation and can be represented by the classical

isotherm models such as Langmuir, Freundlich, Temkin, and Dubinin-Raduskevich. The

third region represents bilayer isotherm, in this region the adsorption occurs mostly in the

first and second layer.

Langmuir model could represent the adsorption experimental data of organic and

inorganic compounds on nanocellulose adsorbents better than the other adsorption

12
models (Zhen et al., 2009; Xie et al., 2011; Yu et al., 2013; He et al., 2013; Pillai et al.,

2013; Kardam et al., 2014; Zhou et al., 2014; Singh et al., 2014; Zhou et al., 2014;

Batmaz et al., 2014; He et al., 2014; Hokkanen et al., 2014, 2015, 2016; Rathod et al.,

2015; Samiey and Tehrani, 2015; Qiao et al., 2015; Mohammed et al., 2015; Chan et al.,

2015; Anirudhan et al., 2015; Zhang et al., 2016; Sirvio et al., 2016; Ruan et al., 2016;

Hu et al., 2016; Kumari et al., 2016). These evidences indicate that adsorptions of

hazardous pollutants onto nanocellulose adsorbents are monolayer adsorption.

Modification of nanocellulose gave significant effects on the adsorption performance of

the materials. In most cases, it can increase the adsorption capacity of the adsorbents,

since more functional groups from modifying agents were attached on the surface of

nanocellulose, and the surface become more heterogeneous. An increase of surface

heterogeneity of nanocellulose adsorbent also increases the adsorption affinity between

adsorbent and adsorbate molecules; the surface of nanocellulose is covered with more

adsorbate molecules. However, in a few cases, adsorption affinity can also decrease due

to morphological change of adsorbent such as widened porous structure or loosened

network inside the adsorbent. The decrease of adsorption affinity also depends on the

solute in the system (Chen et al., 2009; Yu et al., 2013; Zhou et al., 2014; Batmaz et al.,

2014; Qiao et al., 2015; Sirvio et al., 2016; Zhang et al., 2016). Hokkanen et al. (2013)

studied the effect of moisture content in the adsorbent; they found that high water content

in the nanocellulose (81%) has little impact on heavy metal removal.

Another model widely used to correlate adsorption experimental data is Freundlich

isotherm. Freundlich model is an empirical equation that is most widely used to represent

13
experimental adsorption data in aqueous system. The Freundlich equation has the

following form

qe  K F Ce1/ n (5)

Here n represents the heterogeneity of adsorbent, while KF indicates the adsorption

capacity of the adsorbent. Equation (5) can be expressed as

1
log qe  log K F  log Ce
n (6)

Plotting log qe versus log Ce, a straight line is obtained with a slope of 1/n and intercept

of log KF. Favorable adsorption is achieved when the value of n is between 1 and 10. 1/n

< 1 indicates strong interaction between adsorbate molecule and adsorbent, while 1/n

close to 1 implies equal adsorption energies on all sites.

The values of n in all systems studied show favorable adsorption toward the

nanocellulose adsorbents (Table 3). However in the adsorption of Cu(II) on NFC-

Polyethyleneimine and Pd(II) on cysteine functionalized 2,3-dialdehyde cellulose, the

heterogeneity constant was slightly higher than the criterion of favorable adsorption (n >

10), this was attributed to the modification of nanocellulose adsorbent that greatly

increase the surface area and indicated that adsorption process was irreversible (Zhang et

al., 2016; Ruan et al., 2016). For the adsorption of U(VI) by cellulose camphor soot

nanofibers, Singh and Balasubramanian (2014) stated that Freundlich isotherm model

gave the best fit compared to Langmuir, Temkin, and Dubinin-Raduskevich equations,

indicating that the adsorption of U(VI) onto heterogeneous cellulose camphor soot

nanofibers was a chemisorption process involving oxides and acetate groups of the fibers.

Unusual result was observed in the adsorption experimental data of Sirvio et al. (2016).

14
In their study, they used four different procedures to create bisphosphonate nanocellulose

as the adsorbent for vanadium (V). Out of the four adsorbents, bisphosphonate

nanocellulose 3 gave better fitting with Freundlich isotherm model while other

adsorbents fit better using Langmuir isotherm model. This phenomenon possibly was due

to the heterogeneous surface of bisphosphonate nanocellulose 3. Ruan et al. (2016)

conducted palladium adsorption using cysteine functionalized 2,3-dialdehyde cellulose.

They used two different stirring times (2 days and 13 days) to produce the adsorbents.

Their results showed that better adsorption capacity was obtained by using shorter stirring

period (2 days). Longer stirring made the surface area of the adsorbent became less

accessible to adsorbate molecules. Adsorption data of mercury (II) on 2-

mercaptobenzamide modified itaconic acid-grafted-magnetite nanocellulose composite

showed good fitting using Freundlich isotherm model. Adsorption capacity decreased

with increasing temperature, confirming that heterogeneity of the surface of adsorbent

decreased with increasing temperature (Anirudhan et al., 2015).

Another frequently used isotherm model is Sips which is an empirical adsorption

isotherm with 3 parameters. Sips is a combination of Langmuir and Freundlich isotherm

model, therefore this model is often called as Langmuir-Freundlich isotherm.

( K s Ce )ns
qe  qmax
1  ( K s Ce )ns (7)

Ks is related to adsorption affinity, n is the heterogeneity coefficient, when n = 1, eq. (7)

becomes the Langmuir isotherm. Sips isotherm was proposed in order to obtain better fit

when the adsorbed amount keeps increasing at high concentration.

15
 Sips model has been used to represent the adsorption equilibrium data of hazardous

pollutants over a wide variety of adsorbents. From Table 4, it can be seen that Sips model

could represent the adsorption experimental data of several systems (Hokkanen et al.,

2013; Anirudhan et al., 2015; Jin et al., 2015; Hokkanen et al., 2014, 2014; Anirudhan

and Shainy, 2015; Anirudhan et al., 2016). In low adsorbate concentration, the Sips

model reduces to Freundlich isotherm, while at higher concentration it follows the

Langmuir model in terms of saturation capacity (Anirudhan et al., 2015; Hokkanen et al.,

2015), which gives the idea of multilayer adsorption at low concentration and monolayer

adsorption at high concentration (Anirudhan and Shainy et al., 2015). For the adsorption

of inorganic in wastewater, Hokkanen et al. (2014) observed that the adsorption of anion

PO43- and NO3- followed the Sips model, while the adsorption of Ni2+ and Cd2+ followed

the Langmuir isotherm. In another study, the data of adsorption of phosphate anion using

ferric hydroxide-coated CNF hybrid was fitted better using Langmuir isotherm than Sips

isotherm. The ability of the adsorption equations to represent the adsorption experimental

data depends on the adsorption systems, different systems have different adsorption

mechanism (Cui et al., 2016). For the removal of anionic dyes using microgel based on

nanocellulose and polyvinylamine, the equilibrium experimental data of acid red, congo

red, and reactive light yellow can be well represented by Sips isotherm model. Small

values of Ks for the adsorption of acid red and reactive light yellow indicate that

interaction between adsorbent and dyes molecules is smaller than the attraction force

between adsorbate molecules; multilayer adsorption is more likely to occur. In the case of

the adsorption of congo red, the affinity constant Ks is larger, the surface was covered

more with adsorbate molecule as a result of the stronger affinity of adsorbate molecule

16
towards the surface and the possible occurrence of homogeneous monolayer adsorption

(Jin et al., 2015).

Other isotherm equations usually used to represent the adsorption of hazardous

substances onto nanocellulose adsorbents are Temkin, Redlich-Peterson, Polanyi-Manes,

and Dubinin-Radushkevich. Temkin isotherm was developed to describe the adsorption

of hydrogen gas on platinum electrodes in acidic solutions, in other words this model was

developed for a chemisorption system. Temkin equation has the mathematical form as

follows

RT
qe  ln(bCe )
a (8)

Where a and b are characteristic constants of Temkin equation. Kumari et al. (2016)

investigated the adsorption of methylene blue on cellulose nanowhiskers-based

polyurethane foam. The adsorption experimental data were represented by Temkin

isotherm model, however, it is obvious that Temkin cannot describe the adsorption data

well. As mentioned before, Temkin model was developed for chemisorption, while the

adsorption of methylene blue onto cellulose nanowhiskers-based polyurethane foam was

mainly controlled by physical adsorption. These different adsorption mechanisms is the

main reason of the failure of Temkin model to represent their adsorption experimental

data.

Dubinin-Radushkevich (D-R) equation originally was developed to describe

adsorption isotherm of sub-critical vapors in microporous solids. This adsorption

isotherm and Polanyi-Manes model are best to describe experimental data in which the

sorption is caused by van der Waals forces. The D-R equation has the form as follows

17
  1  Ce  
2

qe  qmax exp   RT ln  
2 
 Eo   Cs  
 (9)

Here β represents the affinity coefficient of adsorbate and is proportional to liquid molar

volume, Eo represents the characteristic energy towards a reference adsorbate. Polanyi-

Manes model has the following form:

  RT C b pm 
qe  qmax exp a pm   ln e  
  Vs Cs  
 (10)

Where apm and bpm are the fitting parameters of Polanyi-Manes model, Vs is the molar

volume of solute.

Similar to Sips model, Redlich-Peterson is another three parameters empirical

adsorption isotherm. This equation is capable to represent experimental adsorption

equilibria over a wide concentration range. The mathematical form of Redlich-Peterson

can be written as

K RP Ce
qe  
1  aRP Ce (11)

Where KRP, aRP, and  are fitting parameters of Redlich-Paterson equation. The Dubinin-

Radushkevich, Polanyi-Manes, and Redlich-Peterson equations were employed to

correlate the adsorption data of tetracycline onto NCC. It was found that Redlich-

Peterson and Polanyi-Manes isotherm models could represent the adsorption equilibria

better than D-R equation (Rathod et al., 2015).

3.2. Kinetic of adsorption

The ability to predict sorption kinetics for the adsorption of certain compound is

very important for the proper design of an adsorption system. For this reason, many

18
sorption kinetic models have been developed and tested for various adsorption kinetic

systems. The available adsorption kinetic models were developed according to certain

fundamental approaches such as interfacial kinetics, shrinking core concept and intra-

particle surface diffusion theory.

Among the available kinetic models, pseudo first order and pseudo second order

are most widely used to correlate the kinetic sorption data of hazardous substances on

nanocellulose and its modified forms. In kinetic adsorption studies, the amount of solute

adsorbed by adsorbent is recorded as a function of time. Through the kinetic profile of

adsorption, the type of adsorption mechanism that controls the adsorption process can be

obtained.

Pseudo-first order kinetic was first proposed by Lagergren (1898). This model was

developed according to fundamental approach of interfacial kinetics. The differential

form of this equation can be expressed as follows

dq
=k1 (qe  q) (12)
dt

With boundary conditions: t = 0, q = 0 and t = t, q = q. The integration of Eq. (12) gives

the following result

ln(qe  q)  ln qe - k1t
(13)

The linear form of eq. (13) is

k1t
log(qe  q)  log qe  (14)
2.303

The pseudo-second order kinetic model was proposed by Blanchard et al. (1984),

expressed as

19
dq
=k 2 (qe  q)2 (15)
dt

Integrating Eq. (9) with the boundary conditions t = 0, q = 0 and t = t, q = q, gives

1 1
  k2t (16)
qe  q qe

Eq. (16) can be rearranged into linear form, which was introduced by Ho (1995)

t t 1
  (17)
q qe k2 qe2

Pseudo-first and pseudo-second order models use the adsorption capacity of solid

phase to describe adsorption rate (Febrianto et al., 2009; Ho, 2006). The distinct

difference between pseudo-first and pseudo-second order kinetic models is in the

mechanisms of adsorption. Pseudo-first was created with the same assumption used in

Langmuir model, which is “one-site-occupancy” adsorption, where the adsorbate

molecule can only “react” with one site of adsorbent (Rudzinski and Plazinski, 2006). As

previously described in the mechanism of an adsorption process, there are three

consecutive mass transfer steps in pseudo-first order kinetic model, and external diffusion

is the rate limiting step; the adsorption is usually physisorption (Ho and McKay, 1999).

Pseudo-second order kinetic model deals with two sites occupancy adsorption, where one

molecule of adsorbate can “react” with more than one adsorbent site, this model is

identified as chemisorption, which involves covalent bonding and ion exchange (Ho,

2006; Rudzinski and Plazinski, 2006). This model has the fundamental trait of surface

reactions where intra-particle diffusion plays the role of rate limiting step. In the case of

heterogeneous adsorbent, it also fits the adsorption data better than pseudo-first (Plazinski

20
et al., 2013). The derivation of pseudo-second order model was inspired by the Langmuir

kinetic model in which adsorption energy is uniform at all sites (Plazinski et al., 2013).

Most of the kinetic adsorption data in Table 5 can be represented by the pseudo-

second-order (Chen et al., 2009; Xie et al., 2011; Yu et al., 2013; He et al., 2013; Pillai et

al., 2013; Zhou et al., 2014; Zhou et al., 2014; Anirudhan et al., 2015; Anirudhan and

Shainy, 2015, 2015; Samiey and Tehrani, 2015; Qiao et al., 2015; et al., 2015; Hokkanen

et al., 2014, 2015, 2016; Zhang et al., 2016; Sirvio et al., 2016; Anirudhan et al., 2016;

Cui et al., 2016; Hu et al., 2016; Kumari et al., 2016), only a few adsorption kinetic

systems follow the pseudo-first-order (Hokkanen et al., 2014; Singh et al., 2014; Singh et

al., 2014). Therefore, the main control mechanism in the adsorption using nanocellulose

as the adsorbent is chemisorption, the bonding between adsorbate molecules and the

surface functional groups in nanocellulose plays important role during the process.

However, some contradictories between the control mechanisms determined by the

interpretation of equilibria data and kinetic data are found in several studies. Through

kinetic data interpretation using pseudo-first and pseudo second order models, it was

found the adsorption was controlled by chemisorption mechanism. However, visual

representation of the adsorption equilibria data exhibits mechanism opposite to

chemisorption; adsorption capacity of adsorbent decreased with increasing temperature

(Mohammed et al., 2015; Anirudhan and Shainy et al., 2015; Anirudhan et al., 2016).

Plazinski et al. (2009) gave extensive review on sorption kinetic models, especially on

pseudo-second-order and pseudo-first-order. It was found that pseudo-second-order is

able to represent kinetic data in which intraparticle diffusion plays the limiting rate step;

pseudo-first-order sorption model actually assumes that surface reaction is the rate

21
limiting step in the sense that chemical reaction occurs in the adsorbent phase [94]. In

most cases, the pseudo-first-order is rarely found to describe the kinetic data well,

compared to the pseudo-second-order equation. The only explanation to this problem is

that equation (12) physically can only describe sorption kinetic data that are not far from

equilibrium (Palzinski et al., 2009). To solve this problem, three possible solutions were

proposed by Plazinski et al. (2009): (1) receiving possible lowest qe value which does not

generate errors, (2) eliminating data points in which q is higher than qe, or (3) applying

the linear form of pseudo-first-order Eq. (14) since it is less sensitive to experimental

error than Eq. (12). However these solutions are limited only when the adsorption system

is close to equilibrium (q ≈ qe). In the case of opposite mechanisms obtained from the

interpretation of both adsorption equilibria and kinetic, these two kinetic models cannot

be used to identify the mechanism of adsorption process, since they plot kinetic data

independently despite of the physisorption or chemisorption mechanism in the adsorption

process.

For the representation of the adsorption kinetic data of vanadium ion onto

bisphosphonate nanocellulose 4 and 3, Sirvio et al. (2016) obtained negative values of

rate constants (time constants) for pseudo-second-order and pseudo-first-order models.

The negative values of time constant k1 and k2 are strong indication that both kinetic

models fail to represent the adsorption kinetic data.

4. Adsorption thermodynamic

The thermodynamic point of view of a system sometimes can be used to define the

nature of the adsorption process. Several thermodynamic parameters commonly used in

the adsorption process are Gibb’s free energy change (ΔG°), standard enthalpy change

22
(ΔH°), and standard entropy change (ΔS°). These parameters can be obtained from the

adsorption equilibria data by using the following equations:

G   RT ln K D (18)

S   H   1
ln K D    (19)
R  R T

Where R is the gas constant, T is the temperature of the adsorption system, and KD is the

linear sorption distribution coefficient. KD is obtained through the plot of ln(qe/Ce) vs Ce

and then extrapolating to Ce equal to zero. Using linear regression of equation (19), the

values of ΔH° and ΔS° can be obtained.

Interpretation of the adsorption experimental data on modified nanocellulose

adsorbent using Eqs. (18) and (19) give positive ΔS° (see Table 6) which suggests

increasing randomness at the solid-solution interfaces during adsorption of hazardous

pollutants. For adsorption using NCC alginate hydrogel beads, negative ΔS° was obtained

indicating there is no noticeable change in the adsorbent structure or decreasing

randomness during adsorption (Mohammed et al., 2015; Anirudhan and Shainy et al.,

2015). Negative ΔG° represents spontaneity of adsorption and is thermodynamically

feasible. Most thermodynamic data exhibit decreased value of ΔG° with increasing

temperature (Mohammed et al., 2015; Anirudhan and Shainy et al., 2015, 2015), a strong

indication that the adsorption process is more spontaneous and thermodynamically

feasible at higher temperature. However a few studies obtained the opposite trend

indicating decrease in the uptake amount at increasing temperature. For the criteria of

physisorption and chemisorption, it can be seen from the absolute magnitude of the

change in ΔG°. For physisorption, ΔG° ranges from -20 to 0 kJ/mol and for

chemisorption between -400 and -80 kJ/mol (Yu et al., 2001). From that criteria, it can be

23
concluded that most of the adsorption systems possess physisorption characteristics

(Pillai et al., 2013; Singh et al., 2014; Rathod et al., 2015; Mohammed et al., 2015; Hu et

al., 2016; Kumari et al., 2016; Anirudhan and Shainy, 2015, 2015; Cui et al., 2016;

Hokkanen et al., 2016), a few system with chemisorption mechanism (Anirudhan et al.,

2016). If the value of ΔG° is between physisorption and chemisorption, it can be

considered as physisorption enhanced by chemisorption (Batmaz et al., 2014).

Interestingly the adsorption of crystal violet by NCC showed the combination of

physisorption and chemisorption at 10-30°C while at 40 and 50°C, the adsorption by

modified NCC exhibited chemisorption mechanism (Qiao et al., 2015). In most

adsorption studies, the standard enthalpy change showed endothermic nature (Pillai et al.,

2013; Batmaz et al., 2014; Singh et al., 2014; Rathod et al., 2015; Anirudhan and Shainy

et al., 2015, 2015; Mohammed et al., 2015; Qiao et al., 2015; Anirudhan et al., 2016; Cui

et al., 2016; Hu et al., 2016; Hokkanen et al., 2016), while some exhibited exothermic

nature (Batmaz et al., 2014; Anirudhan and Shainy, 2015; Mohammed et al., 2015).

5. Reuse of adsorbent

The reusability of adsorbent is a crucial factor for the application in industrial

wastewater treatment since it significantly affects the operational cost. Due to economic

consideration, regeneration of adsorbent is necessary especially for expensive adsorbents.

Two regeneration techniques are available: physical and chemical regeneration. Physical

regeneration is associated with the use of temperature, while chemical regeneration uses

chemical solvent to desorp adsorbate from solid adsorbent. To the best of our knowledge,

no physical regeneration has been conducted to recover modified nanocellulose

adsorbents since it uses high temperature that can degrade nanocellulose structure.

24
Therefore, regeneration of modified nanocellulose adsorbent all used chemical reagents

such as acid and alkaline solution (Table 7).

Regeneration using strong acid or base gave high regeneration efficiency (> 50%)

for 2 to 6 adsorption-desorption cycles (Pillai et al., 2013; Kardam et al., 2014; He et al.,

2014; Hokkanen et al., 2014, 2015; Zhou et al., 2014; Anirudhan and Shainy, 2015;

Mohammed et al., 2015; Rathod et al., 2015; Qiao et al., 2015; Anirudhan et al., 2015,

2016; Kumari et al., 2016; Liu et al., 2016; Zhang et al., 2016). However, in some cases,

like in the adsorption of lead and nickel by succinic anhydride modified NCC, the

adsorbent regeneration using hydrochloric acid destroyed the active sites resulting in low

regeneration efficiency. The regeneration of sodium bicarbonate and succinic modified

NCC using saturated NaCl solution gave high regeneration efficiency due to continuous

ion exchange between numerous sodium ion and metal adsorbed (Yu et al., 2013). The

recovery of succinic anhydride modified nanocellulose by nitric acid did not give

satisfactory result. However, after 15 s additional ultrasonic treatment, the regeneration

efficiency increases up to 96% - 100%. It was reported that ultrasonic treatment could

dissociate the intertwined fibers, which caused the decreasing adsorption performance.

The performance of weak acids like acetic, formic and ascorbic acids on recovering

nanofibers was also investigated, and the results indicated that weak acids were not

suitable for regeneration purpose (Hokkanen et al., 2013). The regeneration of carbonated

hydroxyapatite modified nanocellulose after adsorption of Cd2+ using nitric acid showed

high regeneration efficiency even after 4 cycles. However, in the adsorption of Ni2+,

adsorption capacity decrease with increasing number of cycle. Similar phenomenon was

obtained for the adsorption of PO43- and NO3-, using sodium hydroxide as the

25
regenerating agent (Hokkanen et al., 2014). For the adsorption of methylene blue, it

seems that the recovery of adsorbent using NH4OH/NH4Cl and HCl did not give good

result, while regeneration using NaOH and the combination of HCl/C2H6O gave high

efficiency, around 97% and 80%, respectively (Mohammed et al., 2015; Chan et al., 2015;

Kumari et al., 2016; Liu et al., 2016).

6. Future Perspective

Thousands of adsorption studies have been conducted in order to search alternative

adsorbents for water purification and wastewater treatment process. Thousands of

adsorbent candidates are already available, ranging from low cost adsorbents such as

agricultural waste to advanced materials such as carbon nanotubes. However, none of

those materials is currently used industrially and still need further studies to bring these

kinds of materials as industrial adsorbents.

Numerous factors need to be considered before these alternative adsorbents can be

materialized as commercial adsorbents for water purification or wastewater treatment

process. These factors are:

 Have higher or at least comparable adsorption capacity with currently available

commercial adsorbents (activated carbons and zeolites).

 Since the main purpose of the adsorbent is for wastewater treatment, therefore, the

production cost or the raw material cost should be cheaper than activated carbons.

 The alternative adsorbents can be regenerated easily without losing its adsorption

performance.

 Available in large quantities with uniform adsorption capacity.

26
  The production of alternative adsorbents should be environmental friendly.

Based on the above criteria we will discuss the possibility of using nanocellulose and its

modified forms as alternative adsorbents for the removal of hazardous pollutants from

wastewater.

In terms of adsorption capacity, original nanocellulose or NCC possesses low

adsorption capacity (Table 3). After modification with some chemical agents its

adsorption capacity increased up to several hundred percent. This indicates that the

original nanocellulose or NCC is not a suitable adsorbent for industrial application.

Modification using succinic anhydrate and sodium bicarbonate can increase the

adsorption capacity of NCC more the ten times (Hokkanen et al., 2013; Yu et al., 2013).

Currently, NCC is produced through hydrolysis using concentrated inorganic acids

at temperature above 40oC. After hydrolysis the remaining inorganic acid must be

removed. In laboratory, this can be accomplished by dialysis for 3 days, and the separated

inorganic acid must be neutralized before discharged as wastewater. As mentioned in

previously, the original NCC has low adsorption capacity (mostly below 30 mg/g), in

order to enhance its adsorption capacity, modification using certain chemicals is required,

and separation and treatment of unused modifying chemicals is needed. With this

complex procedure, the production cost of these alternative adsorbents will be higher

than activated carbon.

Regeneration or recovery of NCC and its modified forms is mostly conducted using

chemicals and in after regeneration, excess regenerating chemicals should be treated

properly otherwise it will create another environmental problem. Correct concentration of

acid/base is required in order to maintain structure as well as surface chemistry of the

27
adsorbent. From results of studies on the reuse of NCC adsorbents, up to 97% of the

adsorption capacity can be retained after several runs. This indicates that NCC adsorbents

are reusable.

Since raw material for producing NCC are available in huge amount, and any kinds

of lignocellulosic materials can be used as the precursors for NCC preparation, therefore,

theoretically the availability of NCC and its modified forms in large quantities is not a

big problem. Currently, there are several companies worldwide that produce NCC in

industrial scale with main application mostly for composites, paints, coating, adhesives,

etc.

Based on the above discussion, modified forms of NCC have potential application

as the alternative adsorbents for the removal of hazardous pollutants. However, for

industrial scale application, more efforts should be dedicated in order to develop greener

process without using hazardous modifying chemical agents (as example using clay

materials to make clay-NCC composites), to develop more efficient process for the

production of NCC, etc. Furthermore, for in the near future, adsorption studies using

NCC should be focused on multicomponent system and using real wastewater as solution

model. If successful in laboratory scale, adsorption experiments should be conducted in

pilot plant scale.

7. Conclusion

Many researchers have conducted studies on the adsorption of hazardous pollutants using

NCC and its modified forms as adsorbents. The adsorption equilibria data were correlated

using isotherms such as Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Redlich

28
and Peterson. Langmuir isotherm could represent the adsorption equilibria data well for

most of the adsorption systems. Pseudo-first and pseudo-second orders are the most

widely used kinetic models to describe kinetic data. From experimental results of the

reuse of NCC adsorbents, up to 97% of the adsorption capacity can be retained after

several run cycles.

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43
Nomenclature

TC: Tetracycline hydrochloride CR: Congo Red 4BS

JG: Janus Green RY: Reactive Light Yellow K-4G

MB: Methylene Blue RB: Reactive Blue 21

CV: Crystal Violet NC: New Coccine

AR: Acid Red GR U: Ultrasonication

Superscripted letters

a: consisted of carboxylated NCF, amine functionalized magnetite nanoparticles and

poly(vinyl alcohol) (PVA) blended chitosan
b: T=55°C

c: T=65°C

d: T=75°C

e: T=75°C+LiCl

f: stirred for 2 days

g: stirred for 13 days

h: P=%Polyacrylamide, C=%NCC, number=pH (example: P30C20-6.5 means that the

material consisted of 30% polyacrylamide, 20% NCC, pH 6.5)

i: second region

j: third region

k: after 2 cycles, 15 seconds of ultrasonication was done.

44
 Table 1. Chemical modification of NCC
Chemical Reaction Type of NCC Ref.
Sulfonated NCC
Lin et al.,
H2SO4 Esterification
2014

Carboxylated NCC
Zhang et
APS, TEMPO Oxidation
al., 2016

Phosphorylated NCC
Suflet et
H3PO4 Esterification
al., 2006

Cationized NCC

Hasani et
EPTMAC Etherification
al., 2008

Silylated NCC

Gousse
Chlorosilanes Silylation et al.,
2002

PCL Grafting from NCC

Poly(ε-
caprolactone)/PCL Habibi et
ROP
and al., 2010
Sn(Oct)2

Polystyrene Grafting from NCC

Morandi
Polystyrene and
ATRP et al.,
BIBB
2009

PCL Grafting onto NCC

Habibi et
PCL Grafting
al., 2008

45
 Table 2. Langmuir parameters conditions for adsorption of organic and inorganic wastewater

Adsorbent Solute Operational condition Langmuir parameters Ref.

pH T (°C) KL (L/mg) qmax (mg/g) R2

Inorganic wastewater

BC Cu(II) 4.5 25 0.0106 11.17 0.962 Chen et al.,

2009
Carboxymethylated-BC 0.0336 20.35 0.965

BC Pb(II) 0.0842 24.59 0.976

Carboxymethylated-BC 0.0582 65.53 0.961

Nanocellulose hybrids Cu(II) 6.0 30 0.0437 24.51 0.991 Xie et al.,

2011
Ni(II) 0.0872 8.18 0.989

NCC Pb(II) 5.5 252 0.0400 27.90 0.972 Yu et al.,

46
 2013
Succinic anhydride modified NCC 1.8100 367.60 0.998

Sodium bicarbonate and succinic modified 4.1300 465.10 0.999

NCC

NCC Cd(II) 6.0 252 0.0900 1.90 0.995

Succinic anhydride modified NCC 2.2900 259.70 0.998

Sodium bicarbonate and succinic modified 41.8800 344.80 0.999

NCC

Xanthated nano banana cellulose Cd(II) 6.0 25 0.1100 154.26 0.990 Pillai et al.,

2013

NFC Cd(II) 6.0 0.6300 11.23 0.950 Kardam et

al., 2014
Pb(II) 1.8100 10.20 0.970

47
 Ni(II) 0.3300 11.23 0.980

Succinic anhydride modified nanocellulose Zn(II) 5.0 25 0.9056 20.01 0.902 Hokkanen et

(wet) al., 2013

Ni(II) 0.2098 8.28 0.964

Cu(II) 0.9267 22.94 0.849

Co(II) 0.0602 14.96 0.984

Cd(II) 6.1836 44.06 0.923

Succinic anhydride modified nanocellulose Zn(II) 5.0 25 0.9056 105.26 0.902

(dry)
Ni(II) 0.2098 43.67 0.964

Cu(II) 0.9267 120.73 0.849

Co(II) 0.0602 78.85 0.984

48
 Cd(II) 6.1836 231.79 0.923

Novel magnetic hydrogel beads (m- Pb(II) 4.5 25 84.42x10-6 175.40 0.997 Zhou et al.,

CS/PVA/CNFC)a 2014

Succinated NCC Cr(III) 6.5 1.4900 2.88 0.987 Singh et al.,

2014
Cr(IV) 2.5 0.4800 2.77 0.968

Cellulose camphor soot nanofibers U(VI) 6.0 30 0.0616 5.16 0.995 Singh et al.,

2014

Amino modified microfibrillated cellulose Cd(II) 5.0 25 0.5453 405.91 0.892 Hokkanen et

al., 2014
Cu(II) 0.0641 195.59 0.770

Ni(II) 0.8892 156.30 0.969

Carbonated hydroxyapatite modified Ni(II) 5.0 25 4.9927 133.64 0.931 Hokkanen et

49
nanocellulose al., 2014
Cd(II) 6.0161 115.56 0.878

PO43- 6.0 0.0736 86.52 0.977

NO3- 0.0591 11.16 0.561

Quarternary ammonium-functionalized NCF Cr(VI) 3.0 25 2.2400 17.66 0.990 He et al.,

2014

Poly(itaconic acid)-poly(methacrylicacid)- U(VI) 5.5 30 0.8510 119.63 0.857 Anirudhan et

grafted-nanocellulose/nanobentonite al., 2015

40 0.6610 131.68 0.921

50 0.5510 146.55 0.842

Magnetic iron nanoparticles modified As(V) 2.0 25 0.0022 184.30 0.990 Hokkanen et

microfibrillated cellulose al., 2015

2-mercaptobenzamide modified itaconic Cd(II) 6.0 20 0.0170 224.49 0.935 Anirudhan

50
acid-grafted-magnetite nanocellulose and Shainy.
30 0.0190 244.85 0.960
composite 2015

40 0.0260 247.85 0.972

50 0.0810 257.20 0.848

NFC Cu(II) 5.0 30 0.1700 18.90 0.975 Zhang et al.,

2016
NFC-Polyethyleneimine 0.1700 52.32 0.985

Biphosphonate nanocellulose 1b V(V) 3.0 25 0.0332 57.56 0.991 Sirvio et al.,

2016
Biphosphonate nanocellulose 2c 0.0504 68.26 0.993

Biphosphonate nanocellulose 3d 0.0414 80.50 0.978

Biphosphonate nanocellulose 4e 0.0573 100.86 0.996

Cysteine functionalized 2,3-dialdehyde Pd(II) 22.5 0.03x10-4 130.40 0.998 Ruan et al.,

cellulose 2Df 2016

51
Cysteine functionalized 2,3-dialdehyde 0.02 x10-4 60.70 0.998

cellulose 13Dg

Calcium hydroxyapatite/microfibrillated Cr(VI) 5.0 25 0.3117 115.58 0.831 Hokkanen et

cellulose al., 2016

Poly(itaconic acid)-poly(methacrylicacid)- Co(II) 6.0 20 0.0250 241.80 0.990 Anirudhan et

grafted-nanocellulose/nanobentonite al., 2016

30 0.0570 205.70 0.970

40 0.0740 262.80 0.940

50 0.0960 266.40 0.950

Ferric hydroxide-coated CNF hybrid PO43- 4.5 15 0.9667 28.82 0.993 Cui et al.,

2016
25 0.8911 32.05 0.996

35 1.1473 35.21 0.985

52
 45 1.1613 46.73 0.981

Organic wastewater

NCC TC 5.0 15 0.6030 9.168 0.978 Rathod et al.,

2015
30 1.2870 11.348 0.962

45 2.0450 13.253 0.984

NCC MB 7.0 221 0.0193 101.16 0.974 He et al.,

2013

Partially hydrolyzed polyacrylamide/NCC MB - 25 0.461x10-3 172.41 0.998 Zhou et al.,

(P30C10-6.5)h 2014

Partially hydrolyzed polyacrylamide/NCC 0.196x10-3 255.75 0.997

(P30C20-6.5)h

53
Partially hydrolyzed polyacrylamide/NCC 0.089x10-3 358.42 0.997

(P30C20-5.0)h

NCC JGi - 35 1.2406 20.0 0.993 Samiey and

Tehrani,
45 1.0054 21.6 0.991
2015

55 0.9659 21.5 0.997

MB - 35 0.1203 13.1 0.994

45 0.0881 16.7 0.983

55 0.1059 14.7 0.990

JGj 35 0.7916 22.7 0.935

45 0.7989 22.7 0.953

55 0.8288 22.3 0.938

54
NCC MB 9.0 25 0.0137 118.0 0.990 Batmaz et

al., 2014
50 0.0123 115.0 0.990

Carboxylated NCC MB 9.0 25 0.0091 769.0 0.990

NCC CV 6.0 30 1.0230 185.20 0.997 Qiao et al.,

2015
NCC grafted maleic anhydride 1.1290 243.90 0.986

NCC Alginate hydrogel beads MB 7.0 25 0.0020 256.41 0.998 Mohammed

et al., 2015

NCC-Polyvinylamine microgel AR 3.5 0.03x10-3 873.80 0.920 Jin et al.,

2015
CR 0.21x10-3 1619.90 0.960

RY 0.04x10-3 1210.60 0.800

Modified microcrystalline cellulose RB 2.0 30 0.5800 191.95 0.996 Hu et al.,

55
 2016
40 0.7500 273.50 0.990

50 0.8400 408.90 0.991

NFC MB 9.0 20 0.1780 122.2 0.996 Chan et al.,

2015
40 0.2610 114.6 0.998

60 0.2530 110.6 0.995

Cellulose nanowhiskers-based polyurethane MB 6.0 55 0.7800 110.50 0.999 Kumara et

foam al., 2016

56
 Table 3. Freundlich parameters conditions for adsorption of organic and inorganic wastewater

Adsorbent Solute Operational condition Freundlich parameters Ref.

pH T (°C) n KF (mg1-1/nL1-1/n/g) R2

Inorganic wastewater

BC Cu(II) 4.5 25 7.8321 5.389 0.838 Chen et al.,

2009
Carboxymethylated-BC 3.8860 4.189 0.950

BC Pb(II) 3.3472 3.347 0.959

Carboxymethylated-BC 2.0143 2.014 0.898

Nanocellulose hybrids Cu(II) 6 30 1.0765 0.906 0.970 Xie et al.,

2011
Ni(II) 1.3273 0.682 0.977

Xanthated nano banana cellulose Cd(II) 6.0 25 0.4200 26.940 0.980 Pillai et al.,

57
 2013

NFC Cd(II) 6.0 0.2123 5.750 0.920 Kardam et

al., 2014
Pb(II) 0.1451 7.060 0.940

Ni(II) 0.3448 3.910 0.970

Novel magnetic hydrogel beads (m- Pb(II) 4.5 25 2.2360 9.265 0.966 Zhou et al.,

CS/PVA/CNFC)a 2014

Aminated NCC Cr(III) 6.5 5.882 0.830 0.968 Singh et al.,

2014
Cr(IV) 2.5 12.500 0.580 0.967

Cellulose camphor soot nanofibers U(VI) 6.0 30 2.020 0.860 0.998 Singh et al.,

2014

Poly(itaconic acid)- U(VI) 5.5 30 3.278 48.740 0.990 Anirudhan et

58
poly(methacrylicacid)-grafted- al., 2015
40 3.344 52.470 0.980
nanocellulose/nanobentonite

50 3.194 55.960 0.840

Magnetic iron nanoparticles modified As(V) 2.0 25 1.167 0.296 0.968 Hokkanen et

microfibrillated cellulose al., 2015

2-mercaptobenzamide modified Cd(II) 6.0 20 1.905 13.58 0.998 Anirudhan

itaconic acid-grafted-magnetite and Shainy,

30 1.938 15.95 0.997
nanocellulose composite 2015

40 2.207 22.16 0.992

50 2.660 41.47 0.978

NFC Cu(II) 5.0 30 4.190 6.71 0.903 Zhang et al.,

2016
NFC-Polyethyleneimine 10.410 31.05 0.919

Biphosphonate nanocellulose 1b V(V) 3.0 25 2.16 0.65 0.912 Sirvio et al.,

59
 2016]
Biphosphonate nanocellulose 2c 2.20 0.91 0.878

Biphosphonate nanocellulose 3d 2.46 0.98 0.993

Biphosphonate nanocellulose 4e 2.08 1.44 0.890

Cysteine functionalized 2,3- Pd(II) 22.5 12.17 82.63 0.964 Ruan et al.,

dialdehyde cellulose 2Df 2016

Cysteine functionalized 2,3- 9.34 33.20 0.972

dialdehyde cellulose 13Dg

Calcium Cr(VI) 5.0 25 3.76 109.48 0.959 Hokkanen et

hydroxyapatite/microfibrillated al., 2016

cellulose

Poly(itaconic acid)- Co(II) 6.0 20 1.98 16.31 0.980 Anirudhan et

poly(methacrylicacid)-grafted- al., 2016

30 2.45 27.97 0.990

60
nanocellulose/nanobentonite
40 2.33 29.70 0.980

50 2.38 32.33 0.970

Ferric hydroxide-coated CNF hybrid PO43- 4.5 15 2.860 3.77 0.945 Cui et al.,

2016
25 2.840 4.13 0.975

35 2.940 4.43 0.962

45 2.750 4.76 0.955

2-mercaptobenzamide modified Hg(II) 8.0 20 2.740 44.05 0.991 Anirudhan

itaconic acid-grafted-magnetite and Shainy,

30 2.207 22.16 0.992
nanocellulose composite 2015

40 1.938 15.95 0.995

50 1.904 13.58 0.994

61
Organic wastewater

NCC TC 5.0 15 1.517 1.729 0.914 Rathod et al.,

2015
30 1.692 3.05 0.904

45 1.748 4.67 0.911

Partially hydrolyzed MB 25 2.625 44.49 0.825 Zhou et al.,

polyacrylamide/NCC (P30C10-6.5)h 2014

Partially hydrolyzed 2.062 37.74 0.894

polyacrylamide/NCC (P30C20-6.5)h

Partially hydrolyzed 1.653 29.06 0.938

polyacrylamide/NCC (P30C20-5.0)h

NCC MB 9.0 25 3.638 18.56 0.970 Batmaz et

62
 al., 2014
50 3.597 17.27 0.970

NCC CV 6.0 30 3.78 44.70 0.683 Qiao et al.,

2015
NCC grafted maleic anhydride 4.66 76.50 0.803

NCC Alginate hydrogel beads MB 7.0 25 1.540 1.931 0.988 Mohammed

et al., 2015

NCC-Polyvinylamine microgel AR 3.5 2.910 120.3 0.985 Jin et al.,

2015
CR 1.780 267.30 0.770

RY 3.820 237.10 0.974

Modified microcrystalline cellulose RB 2.0 30 5.263 111.70 0.856 Hu et al.,

2016
40 6.667 175.95 0.878

50 7.692 208.04 0.863

63
NFC MB 9.0 20 4.46 12.8 0.859 Chan et al.,

2015
40 4.52 13.7 0.806

60 4.24 37.5 0.745

Cellulose nanowhiskers-based MB 6.0 55 10.0 70.20 0.977 Kumari et

polyurethane foam al., 2016

64
 Table 4. Sips parameters conditions for adsorption of organic and inorganic wastewater

Adsorbent Solute Operational condition Sips parameters Ref.

pH T (°C) ns Ks (L/mg) qmax (mg/g) R2

Inorganic wastewater

Succinic anhydride modified Zn(II) 5.0 25 0.426 0.8210 20.01 0.993 Hokkanen

nanocellulose (wet) et al.,

Ni(II) 0.540 0.0799 8.28 0.949
2013

Cu(II) 0.808 0.8842 22.94 0.857

Co(II) 0.606 0.0422 14.96 0.989

Cd(II) 0.579 4.9388 44.06 0.962

Succinic anhydride modified Zn(II) 5.0 25 0.426 0.8210 105.26 0.864

nanocellulose (dry)
Ni(II) 0.737 0.1760 43.67 0.977

65
 Cu(II) 0.808 0.8842 120.73 0.857

Co(II) 0.737 0.0552 78.85 0.991

Cd(II) 0.579 4.9388 231.79 0.962

Amino modified microfibrillated Cd(II) 5.0 25 1.100 0.4774 390.29 0.894 Hokkanen

cellulose et al.,
Cu(II) 2.387 0.0907 164.77 0.965
2014

Ni(II) 1.038 1.0729 181.48 0.970

Carbonated hydroxyapatite modified Ni(II) 5.0 25 0.735 0.1019 36.16 0.965 Hokkanen

nanocellulose et al.,
Cd(II) 0.293 0.0173 189.75 0.917
2014

PO43- 6.0 0.673 0.0480 92.50 0.979

NO3- 4.538 0.0475 470.68 1.000

66
Poly(itaconic acid)- U(VI) 5.5 30 3.267 0.960 121.57 0.990 Anirudhan

poly(methacrylicacid)-grafted- et al.,
40 2.347 0.230 138.72 0.990
nanocellulose/nanobentonite 2015

50 2.057 0.280 155.06 0.970

Magnetic iron nanoparticles modified As(V) 2.0 25 0.866 2.54x10-4 470.65 0.919 Hokkanen

microfibrillated cellulose et al.,

2015

2-mercaptobenzamide modified Cd(II) 6.0 20 1.887 0.051 227.49 0.990 Anirudhan

itaconic acid-grafted-magnetite and

30 1.930 0.034 242.32 0.997
nanocellulose composite Shainy,

40 2.202 0.023 249.09 0.997 2015

50 2.865 0.016 262.27 0.996

Calcium Cr(VI) 5.0 25 0.355 0.0057 610.43 0.923 Hokkanen

67
hydroxyapatite/microfibrillated et al.,

cellulose 2016

Poly(itaconic acid)- Co(II) 6.0 20 1.312 0.029 333.20 0.990 Anirudhan

poly(methacrylicacid)-grafted- et al.,
30 1.724 0.046 350.80 0.990
nanocellulose/nanobentonite 2016

40 2.272 0.077 370.10 0.990

50 3.067 0.125 396.10 0.990

Organic wastewater

Modified microcrystalline cellulose RB 2.0 30 1.136 0.360 256.41 0.972 Hu et al.,

2016
40 1.316 0.430 337.57 0.967

50 2.500 0.670 547.29 0.976

NCC-Polyvinylamine microgel AR 3.5 0.426 3.9x10-5 877.3 0.984 Jin et al.,

68
 2015
CR 1.520 1.3x10-4 1491.6 0.995

RY 0.310 5.3x10-5 1152.6 0.978

69
 Table 5. Kinetic studies on inorganic and organic wastewater

Pseudo-first order Pseudo-second order

Adsorbent Solute C0 qe,exp Ref.
(mg/L) (mg/g)
qe,cal (mg/g) k1 (min-1) R2 qe,cal (mg/g) k2 (g/mg min) R2

Inorganic wastewater

BC Cu(II) 100 9.67 7.42 0.0776 0.922 10.50 0.0221 0.999 Chen et al., 2009

CM-BC 12.63 10.56 0.0542 0.967 13.12 0.0185 0.995

BC 22.56 20.38 0.0510 0.988 25.06 0.0044 0.995

CM-BC 60.42 49.76 0.0538 0.961 63.90 0.0027 0.997

Nanocellulose hybrids Cu(II) 25.4 - - - - - 503.50 1.000 Xie et al., 2011

Ni(II) 22.3 - - - - - 32.99 0.999

NCC Pb(II) 300 50.20 - - - 43.10 0.0162 0.994 Yu et al., 2013

70
Succinic anhydride modified NCC 299.70 - - - 303.00 0.001 0.999

Sodium bicarbonate and succinic

299.90 - - - 300.30 0.5200 1.000
modified NCC

NCC Cd(II) 200 7.40 - - - 7.10 0.1864 0.990

Succinic anhydride modified NCC 150.22 - - - 154.32 0.0111 0.996

Sodium bicarbonate and succinic

166.50 - - - 166.66 0.0417 0.999
modified NCC

Xanthated nano banana cellulose Cd(II) 50 24.40 15.90 0.13 0.960 25.70 0.0100 0.990 Pillai et al., 2013

100 47.90 32.30 0.12 0.940 50.50 0.0070 0.990

200 92.60 58.70 0.11 0.970 95.20 0.0070 0.990

300 128.70 88.10 0.14 0.970 131.50 0.0060 0.990

71
Novel magnetic hydrogel beads (m-
Pb(II) 100 131.90 90.87 0.0120 0.970 139.90 3.03x10-4 0.999 Zhou et al., 2014
a
CS/PVA/CNFC)

Succinated NCC Cr(III) 10 0.47 0.987 Singh et al., 2014

Aminated NCC Cr(IV) 10 0.52 0.987

U(VI) 50 - 343.60 0.069 0.996 288.60 0.021 0.886 Singh et al., 2014

100 - 342.60 0.021 0.998 678.90 0.011 0.843

Cellulose camphor soot nanofibers 150 - 409.80 0.045 0.996 692.20 0.023 0.892

200 - 456.90 0.036 0.998 594.98 0.0381 0.876

250 - 482.20 0.048 0.962 893.0 0.038 0.890

Cd(II) 38.22 327.11 318.12 0.5038 0.642 328.24 0.3380 0.927 Hokkanen et al.,
Amino modified microfibrillated
2014
cellulose Cu(II) 21.61 186.19 147.43 0.0235 0.798 162.68 0.0123 0.895

72
 Ni(II) 19.96 173.73 174.91 0.1190 0.970 184.79 0.0566 0.942

Carbonated hydroxyapatite modified Ni(II) 191.10 55.64 55.53 4.58 1.000 55.64 158.7 1.000 Hokkanen et al.,

nanocellulose 2014
Cd(II) 99.78 29.17 28.70 4.25 1.000 28.76 93.4 0.998

PO43- 161.45 19.66 19.37 3.02 1.000 19.37 71.8 0.993

NO3- 105.41 25.73 25.73 1.00 1.000 27.96 1.56 0.998

Poly(itaconic acid)- U(VI) 100 49.74 57.02 0.21x10-2 0.950 49.98 0.74x10-3 0.990 Anirudhan et al.,

poly(methacrylicacid)-grafted- 2015
150 74.32 82.32 0.10x10-2 0.940 74.97 0.82x10-3 0.990
nanocellulose/nanobentonite

200 99.87 107.87 0.09x10-2 0.930 98.07 0.94x10-3 0.980

250 121.02 127.30 0.08x10-2 0.950 115.65 1.26x10-3 0.980

Magnetic iron nanoparticles modified Hokkanen et al.,

-4
As(V) 50.95 300.89 0.099 0.854 319.92 5.01x10 0.957
microfibrillated cellulose 2015

73
2-mercaptobenzamide modified itaconic Cd(II) 50 24.83 23.29 1.23x10-2 0.960 24.62 8.02 0.998 Anirudhan and

acid-grafted-magnetite nanocellulose Shainy, 2015

100 49.60 46.85 1.29 0.963 49.42 4.04 0.997
composite

150 73.73 70.84 1.37 0.967 74.51 3.11 0.998

200 99.71 94.36 1.49 0.963 99.15 2.06 0.998

NFC Cu(II) 100 20.16 19.61 1.04 0.991 20.42 0.15 0.999 Zhang et al., 2016

NFC-Polyethyleneimine 20 14.24 13.83 0.51 0.989 15.04 0.053 0.999

50 34.27 33.22 0.77 0.991 35.09 0.056 0.999

100 45.66 44.43 0.81 0.986 46.73 0.045 0.999

Biphosphonate nanocellulose 1b V(V) 11.20 9.16 2.80 0.00046 0.987 9.16 0.0128 0.999 Sirvio et al., 2016

Biphosphonate nanocellulose 2c 9.68 1.63 0.00046 0.730 9.68 0.0206 0.999

74
Biphosphonate nanocellulose 3d 10.70 1.22 -0.0025 0.866 10.70 0.0149 0.999

Biphosphonate nanocellulose 4e 10.19 0.45 0.030 0.867 10.19 -0.3435 1.000

Calcium hydroxyapatite/microfibrillated Hokkanen et al.,

Cr(VI) 10399 46.83 49.60 1.075 0.887 46.84 1.365 1.000
cellulose 2016

Poly(itaconic acid)- Co(II) 50 25.39 24.21 0.118 0.950 25.69 0.006 0.990 Anirudhan et al.,

poly(methacrylicacid)-grafted- 2016
100 50.34 47.29 0.153 0.900 50.25 0.004 0.970
nanocellulose/nanobentonite

150 73.09 68.24 0.177 0.920 733.38 0.004 0.980

200 104.45 98.46 0.234 0.880 106.20 0.003 0.970

Ferric hydroxide-coated CNF hybrid PO43- 19.79 0.0012 0.665 34.72 0.0004 0.974 Cui et al., 2016

2-mercaptobenzamide modified itaconic Hg(II) 50 24.78 25.54 0.005 0.990 Anirudhan and

acid-grafted-magnetite nanocellulose Shainy, 2015

100 47.77 51.07 0.003 0.992

75
composite
150 68.12 54.76 0.002 0.994

200 88.70 98.27 0.001 0.991

Organic wastewater

NCC TC 5 3.19 1.32 0.014 0.804 3.28 0.571 0.989 Rathod et al.,

2015
10 4.84 1.95 0.009 0.818 4.97 0.415 0.991

20 5.66 2.16 0.007 0.837 5.87 0.352 0.994

NCC MB 32.6 - 17.70 2.18 0.904 19.10 0.2084 0.998 He et al., 2013

54.3 - 25.90 1.66 0.953 28.40 0.0934 0.998

64.3 - 31.50 1.36 0.917 35.00 0.0584 0.999

131.5 - 50.20 1.30 0.948 55.60 0.0360 0.994

76
 188.7 - 56.70 1.34 0.894 63.10 0.0317 0.997

320.8 - 68.40 1.04 0.664 75.70 0.0211 0.965

465.1 - 78.40 0.68 0.969 88.20 0.0103 0.967

Partially hydrolyzed MB 5 Zhou et al., 2014

- 16.28 0.019 0.970 45.41 0.0033 0.999
polyacrylamide/NCC (P30C10-6.5)h

Partially hydrolyzed
- 11.77 0.011 0.871 43.42 0.0044 0.999
polyacrylamide/NCC (P30C20-6.5)h

Partially hydrolyzed
- 21.60 0.014 0.982 40.87 0.0017 0.997
polyacrylamide/NCC (P30C20-5.0)h

NCC (T=35°C) JG 6.13 7.6 7.1 7.7x10-3 0.986 9.0 9.0x10-4 0.983 Samiey and

Tehrani, 2015
12.26 13.7 13.1 7.2x10-3 0.975 16.3 4.8x10-4 0.989

77
 20.44 17.7 22.0 3.8x10-3 0.996 33.4 0.8x10-4 0.885

NCC (T=45°C) 6.13 7.4 7.8 5.4x10-3 0.991 8.9 9.0x10-4 0.979

12.26 13.2 13.3 5.4x10-3 0.982 16.1 4.1x10-4 0.973

20.44 18.0 20.9 4.2x10-3 0.992 25.5 1.8x10-4 0.911

NCC (T=55°C) 6.13 7.4 6.8 14.0x10-3 0.962 8.2 18.9x10-4 0.993

12.26 13.7 13.8 6.6x10-3 0.934 16.4 5.2x10-4 0.979

20.44 17.2 19.7 6.0x10-3 0.995 26.3 2.0x10-4 0.946

NCC (T=35°C) MB 4.80 2.9 2.9 18.3x10-3 0.995 3.6 55.3x10-4 0.994

9.60 4.9 4.6 29.2x10-3 0.997 5.6 58.9x10-4 0.997

14.39 6.6 6.4 35.0x10-3 0.994 7.9 40.2x10-4 0.985

78
NCC (T=45°C) 4.80 2.9 3.1 18.3x10-3 0.994 3.7 63.3x10-4 0.942

9.60 5.4 5.3 30.6x10-3 0.939 6.4 56.9x10-4 0.987

14.39 6.9 6.6 50.1x10-3 0.986 7.8 78.5x10-4 0.996

NCC (T=55°C) 4.80 2.9 3.1 18.9x10-3 0.993 3.5 79.0x10-4 0.922

9.60 5.4 5.3 31.1x10-3 0.931 6.6 50.8x10-4 0.979

14.39 6.7 6.6 45.4x10-3 0.958 7.7 85.3x10-4 0.984

NCC CV 400 90.8 75.2 0.005 0.947 96.3 7.4x10-4 0.999 Qiao et al., 2015

NCC grafted maleic anhydride 98.7 87.9 0.013 0.982 102.6 9.4x10-4 0.999

NCC Alginate hydrogel beads MB 100 10.41 3.03 0.025 0.839 10.48 0.0337 0.999 Mohammed et al.,

2015
200 17.24 5.43 0.031 0.955 17.51 0.0183 1.000

79
 400 35.28 14.58 0.030 0.936 35.97 0.0066 0.999

600 50.29 24.75 0.034 0.932 51.81 0.0035 0.999

800 72.84 35.77 0.032 0.945 74.63 0.0026 0.999

NCC-Polyvinylamine microgel AR 199.9 96.10 0.0063 0.935 202.80 2.28x10-5 0.995 Jin et al., 2015

CR 199.8 5.40 0.0110 0.808 200.00 0.0086 1.000

RY 196.9 126.40 0.0146 0.882 201.20 3.48x10-4 0.998

Modified microcrystalline cellulose RB 140.98 70.57 0.013 0.975 134.77 6.4x10-4 0.997 Hu et al., 2016

183.53 102.17 0.012 0.939 172.71 4.0x10-4 0.998

200.00 116.25 0.026 0.995 213.22 3.9x10-4 0.999

Cellulose nanowhiskers-based Kumari et al.,

MB 50 43.50 45.93 0.2110 0.982 46.87 0.0056 0.992
polyurethane foam 2016

80
 Table 6. Thermodynamic studies on the adsorption of heavy metals and dyes

T ΔG° ΔS° ΔH°

Sorbent Solute Ref.
(°C) (kJ/mol) (kJ/mol K) (kJ/mol)

Calcium hydroxyapatite/microfibrillated Cr(VI) 5 -9.94 0.05 4.02 Hokkanen

cellulose et al., 2016

23 -10.81

45 -11.95

Xanthated nano banana cellulose Cd(II) 25 - 1.00x10-5 1.76x10-5 0.002 Pillai et al.,

2013
-5
30 -1.01x10

35 -1.02x10-5

Cellulose camphor soot nanofibers U(VI) 30 -2.18x10-5 0.097 22.43 Singh et al.,

2014

2-mercaptobenzamide modified itaconic Cd(II) 20 -4.25 0.089 30.44 Anirudhan

acid-grafted-magnetite nanocellulose and Shainy,

30 -3.04
composite 2015

40 -2.47

50 -1.57

Poly(itaconic acid)- Co(II) 20 -149.57 0.52 4.36 Anirudhan

poly(methacrylicacid)-grafted- et al., 2016

30 -154.82

81
nanocellulose/nanobentonite
40 -160.08

50 -165.33

Ferric hydroxide-coated CNF hybrid PO43- 15 -9.81 0.12 23.83 Cui et al.,

2016
25 -10.41

35 -11.49

45 -13.37

NCC TC 15 -1.63 9.845 22.64 Rathod et

al., 2015
35 -4.13

45 -7.05

NCC MB 25 -20.8 0.58 -3.45 Samiey and

Tehrani,
50 -22.2
2015

NCC CV 10 -53.70 1.10 257.60 Qiao et al.,

2015
20 -64.70

30 -75.70

40 -86.70

82
 50 -97.70

NCC grafted maleic anhydride 10 -122.52 1.43 282.17

20 -136.82

30 -151.12

40 -165.42

50 -179.72

NCC Alginate hydrogel beads MB 25 -14.66 -12.50 -18.39 Mohammed

et al., 2015
35 -14.54

45 -14.41

55 -14.29

Modified microcrystalline cellulose RB 30 -4.11 0.24 69 Hu et al.,

2016
40 -6.33

50 -8.84

Cellulose nanowhiskers-based MB 25 -4.70 0.41 120.8 Kumara et

polyurethane foam al., 2016

35 -5.62

45 -7.46

83
 55 -18.33

65 -19.40

2-mercaptobenzamide modified itaconic Hg(II) 20 -11.93 0.18 -67.23 Anrudhan

acid-grafted-magnetite nanocellulose and Shainy,

30 -10.04
composite 2015

40 -8.15

50 -6.27

84
 Table 7. Regeneration performances of modified nanocellulose adsorbent

Adsorbent Sorbate Regenerant Concentration Cycle Efficiency Ref.

Poly(itaconic acid)- U(VI) HCl 0.1 M 6 89.60% Anirudhan et al., 2015

poly(methacrylicacid)-grafted-

nanocellulose/nanobentonite

Magnetic iron nanoparticles modified As(V) NaOH 1.0 M 4 69.16% Hokkanen et al., 2015

microfibrillated cellulose

Succinic anhydride modified NCC Pb(II) HCl 3 48% Yu et al., 2013

Cd(II) 3 30%

Sodium bicarbonate and succinic Pb(II) NaCl 3 88%

modified NCC
Cd(II) 3 100%

Xanthated nano banana cellulose Cd(II) HCl 0.1 M 4 87.5% Pillai et al., 2013

85
NFC Cd(II) HCl 0.5 M 4 74.38% Kardam et al., 2014

Pb((II) 4 72.25%

Ni(II) 4 63.35%

Cd(II) HNO3 0.5 M 4 80.43%

Pb((II) 4 83.19%

Ni(II) 4 76.84%

Succinic anhydride modified Zn(II) HNO3 1M 2 14.15% Hokkanen et al., 2013

nanocellulose
Ni(II) 2 18.64%

Co(II) 2 25.41%

Cd(II) 2 28.36%

86
 Zn(II) HNO3 + U 1M 2k 95.28%

Ni(II) 2k 95.76%

Co(II) 2k 97.54%

Cd(II) 2k 95.52%

Zn(II) CH2O2 0.1 M 2 39.39%

C6H8O6 2 25.49%

CH3COOH 2 22.00%

Novel magnetic hydrogel beads (m- Pb(II) HNO3 0.01 M 4 90.1% Zhou et al., 2014

CS/PVA/CNFC)a

Amino modified microfibrillated cellulose Ni(II) HNO3 0. 1 M 2 20.49% Hokkanen et al., 2014

NaOH 2 155.34%

87
 EDTA 2 25.81%

Cu(II) HNO3 2 0.09%

NaOH 2 110.82%

EDTA 2 27.43%

Cd(II) HNO3 2 25.65%

NaOH 2 101.12%

EDTA 2 24.53%

Carbonated hydroxyapatite modified Ni(II) HNO3 1.0 M 4 6.16% Hokkanen et al., 2014

nanocellulose
0.1 M 4 9.83%

0.01 M 4 24.48%

88
 Cd(II) HNO3 1.0 M 4 0

0.1 M 4 5.51%

0.01 M 4 99.98%

PO43- NaOH 1.0 M 4 8.26%

0.1 M 4 11.82%

0.01 M 4 12.52%

NO3- NaOH 1.0 M 4 0

0.1 M 4 0

0.01 M 4 0

Quarternary ammonium-functionalized Cr(VI) NaOH 0.1 M 4 84.9% He et al., 2014

NCF

89
2-mercaptobenzamide modified itaconic Cd(II) HCl 0.1 M 5 86.3% Anirudhan and Shainy,

acid-grafted-magnetite nanocellulose 2015

composite

NFC-Polyethyleneimine Cu(II) HCl 1M 4 70.21% Zhang et al., 2016

Poly(itaconic acid)- Co(II) HCl 0.1 M 6 88.9% Anirudhan et al., 2016

poly(methacrylicacid)-grafted-

nanocellulose/nanobentonite

2-mercaptobenzamide modified itaconic Hg(II) HCl 0.1 M 5 86.0% Kumara et al., 2016

acid-grafted-magnetite nanocellulose

composite

Ethylenediamine NFC/Chitosan MB NH4OH/NH4Cl 3 10% Liu et al., 2016

NC 3 98%

90
NCC TC HNO3 5% 3 79.3% Rathod et al., 2015

NaOH 3 74.4%

NCC grafted maleic anhydride CV C2H6O 50% 4 80% Qiao et al., 2015

NCC Alginate hydrogel beads MB HCl/ C2H6O 5 ~97% Mohammed et al.,

2015

NFC MB HCl 0.1 M 6 34% Chan et al., 2015

Cellulose nanowhiskers-based MB NaOH 0.1 M 20 80% Kumara et al., 2016

polyurethane foam

91
 Amorphous region Crystalline region
25-50 nm 50-150 nm

Figure 1. Cellulose fiber

Amount adsorbed

Fluid Concentration

Figure 2. Three types of adsorption isotherms

Bulk diffusion External diffusion Intraparticle diffusion

Bulk solution Boundary layer Adsorbent

Figure 3. Three consecutive mass transfer in adsorption

92