Carbohydrate Polymers 153 (2016) 600–618

Contents lists available at ScienceDirect

Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Review

Potential applications of cellulose and chitosan

nanoparticles/composites in wastewater treatment: A review
Sharon Olivera a , Handanahally Basavarajaiah Muralidhara b,∗ , Krishna Venkatesh b ,
Vijay Kumar Guna b , Keshavanarayana Gopalakrishna b , Yogesh Kumar K. c
a
Research Scholar, CET, Jain University, Jakkasandra Post, Kanakapura Taluk, Ramanagara District, Bangalore 562 112, Karnataka, India
b
Centre for Incubation, Innovation, Research and Consultancy (CIIRC), Jyothy Institute of Technology, Thataguni, off Kanakapura Road, Bangalore 560 082,
Karnataka, India
c
School of Engineering and Technology, Jain University, Jakkasandra Post, Kanakapura Taluk, Ramanagara District, Bangalore 562 112, Karnataka, India

a r t i c l e i n f o a b s t r a c t

Article history: This work concerns the investigation of potential candidature of cellulose and chitosan–based nano–sized
Received 21 March 2016 materials for heavy metals and dyes removal. Cellulose and chitosan being the first two abundant
Received in revised form 14 July 2016 biopolymers in nature offer wide opportunities to be utilized for high–end applications such as water
Accepted 5 August 2016
purification. The nano–sized cellulose and nano–sized chitosan present superior adsorption behavior
Available online 8 August 2016
compared to their micro–sized counterparts. This area of research which explores the possible usage
of nano–biopolymers is relatively new. The present review article outlines the development history of
Keywords:
research in the field of cellulose and chitosan, various methods employed for the functionalization of the
Nanocellulose
Nanochitosan biopolymers, current stage of research, and mechanisms involved in adsorption of heavy metals and dyes
Nanocomposite using nanocellulose and nanochitosan. The significance of research using nano–biopolymers and future
Adsorption prospects are also identified.
Wastewater treatment © 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
2. History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
2.1. History of cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
2.2. History of chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
3. Fabrication of nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
3.1. Fabrication of nanocelluloses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
3.2. Fabrication of chitosan nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
4. Recent developments in wastewater purification using cellulose nanoparticles/composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
4.1. Nanocellulose–based adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
4.1.1. Carboxylated cellulose nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
4.1.2. Succinylated nanocelluloses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
4.1.3. Amino–modified nanocelluloses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
4.2. Nanocellulose–based composites as adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
4.2.1. Magnetic cellulose nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
4.2.2. Cellulose/Silsesquioxane nanocomposite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .604
4.2.3. Cellulose/Clay nanocomposite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
4.2.4. Cellulose/Polymer nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
4.2.5. Miscellaneous–nanocellulose based adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
5. Recent developments in wastewater purification using chitosan nanoparticles/composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607

∗ Corresponding author.
E-mail addresses: hb.murali@gmail.com, hbmuralidhara@yahoo.co.in (H.B. Muralidhara).

http://dx.doi.org/10.1016/j.carbpol.2016.08.017
0144-8617/© 2016 Elsevier Ltd. All rights reserved.
 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618 601

5.1. Nanohitosan–based adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607

5.1.1. Aminated chitosan nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
5.2. Chitosan nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
5.2.1. Chitosan magnetite composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
5.2.2. Chitosan–hydroxyapatite nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
5.2.3. Chitosan–montmorillonite nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
5.2.4. Cellulose–carbon nanotube composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
5.2.5. Miscellaneous chitosan nano–composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
6. Mechanisms of adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
6.1. Nanocellulose with heavy metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .612
6.2. Nanocellulose with dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613
6.3. Nanochitosan with heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613
6.3. Nanochitosan with dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613
7. Relevance of nanocellulose and nanochitosan adsorbents in current scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
8. Conclusions and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615

1. Introduction good amount of literature is available for the adsorption of heavy

metals and dyes by employing these potential adsorbents.
Today’s world is faced with serious dangers of air, land and The present review work highlights the application of nanopar-
water pollutions. Water pollution in particular, has raised seri- ticles/nanocomposites of cellulose and chitosan for adsorption of
ous concerns. In addition to the shortage of resources of water, heavy metals and dyes from aqueous solutions. There is some com-
production of large volumes of wastewater has put a lot of peting literature available that includes the usage of nanomaterials
pressure on the humankind. The conventional technologies like for the stated purpose (Ahmad et al., 2015; Carpenter, de Lannoy, &
coagulation–flocculation, oxidation, membrane separation, ion Wiesner, 2015; Vakili et al., 2014). However, those studies are not
exchange, electro–precipitation, evaporation and floatation are exhaustive in the sense that they either take into account the appli-
inadequate to deal with the wastewater treatment problem. cations of nanocellulose and nanochitosan individually for water
Adsorption is known to be one of the best of the technologies for purification or, the studies are solely confined to heavy metal ions
the decontamination of water. Even though activated carbon based or dyes removal. The aim of the present article is to present an
technology is still used for treating wastewater, it is not cost– and authoritative explanation for the potential candidature of these
energy–efficient. Hence adsorption using low–cost adsorbents has nano–sized adsorbents for wastewater purification and to close the
become an attractive choice. Biopolymers such as chitosan and missing gap in literature in this area of research.
cellulose present an interesting option (Kalia & Avérous, 2011).
A number of studies have been made for the adsorptive removal 2. History
of heavy metals and dyes utilizing cellulose– and chitosan–based
materials (Ahmad, Ahmed, Swami, & Ikram, 2015; Güçlü, Gürdağ, 2.1. History of cellulose
& Özgümüş, 2003; No & Meyers, 2000; O’Connell, Birkinshaw, &
O’Dwyer, 2008; Zhou, Zhang, Zhou, & Guo, 2004). The word cellulose originates from cellule, a French word which
Cellulose and chitosan constitute the first and second most means a living cell, and glucose. This word was coined by Anselme
abundant biopolymers on earth. They are natural, renewable, envi- Payen, a French chemist in 1838 after he unraveled the presence
ronmentally benign, cost–efficient, non–toxic, bio–degradable and of cellulose in plant tissues (Crawford, 1981; Payen, 1838; Young
bio–compatible (Crini & Badot, 2008; Muzzarelli, 2012; Rajawat, & Rowell, 1986). Payen found the chemical formula of cellulose to
Kardam, Srivastava, & Satsangee, 2013; Roy, Semsarilar, Guthrie, be C6 H10 O5 through elemental analysis (Harris, 2011). Cellulose
& Perrier, 2009). Cellulose is majorly derived from plant sources was used as a precursor material for the synthesis of celluloid, the
such as grasses, reeds, stalks and woody parts of the vegetation. first man–made thermoplastic. It was used to be called as ‘Parke-
Animals, algae, fungi, amoebae, cellular slime molds, green algae sine’ after Alexander Parkes, who patented it in 1862, before being
and bacteria also contribute in the production of celluloses (Azizi acquired by Hyatt manufacturing company in 1870 (Fenichell,
Samir, Alloin, & Dufresne, 2005; Brown, 2004; Zogaj, Nimtz, Rohde, 1996). Cellulose was used for the fabrication of rayon (artificial
Bokranz, & Römling, 2001). Cellulose consists of over ten thou- silk) in 1890s as “Chardonnet silk” (Kauffman, 1993). In 1912, Swiss
sand repeating units of ␤–(l → 4)–d–glucose linkages and has the chemist Jacques E. Brandenberge perfected cellophane, a trans-
formula (C6 H10 O5 )n (Liu, 2014) while chitosan which is normally parent, water repellant film produced using regenerated cellulose
derived from de–acetylation of chitin is made up of ␤–(l → 4) link- (Rodney, 2004). A German chemist Hermann Staudinger elucidated
ages of N–acetyl–d–glucosamine and d–glucosamine. Chitosan is the polymer structure of cellulose in 1920 (Staudinger, 1920). Sig-
found mainly in crustacean shells such as shrimp, crab, lobster, nificant work related to the building of cellulose structural model
crawfish, and cell walls of fungi as well as cuticles of insects based on glucopyranose was done through the interpretation of
(Jayakumar, Tamura, Prabaharan, Kumar, Nair, & Furuike, 2011). XRD data by Sponsler and Dore (1926). This model was accepted
With the advancement in nanosciences, development of cellu- in 1939 (Kiessig, 1939). The chemical as well as physical charac-
lose and chitosan based materials having nano–sizes has become teristics of cellulose were thoroughly investigated in subsequent
possible. Cellulose and chitosan nanoparticles/nanocomposites years. Jones of England tried to elucidate the structure of cellu-
become materials of choice because of attractive surface area, lose with the available X–ray data using computer model in 1960.
chemical accessibility, ease of functionalization and absence of X–ray studies on cellulose were further facilitated by development
internal diffusion (Chang, Chang, & Chen, 2006; Hokkanen, Repo, of sophisticated computer models that were used for the structural
Suopajärvi et al., 2014; Suman Kardam, Gera, & Jain, 2015). A fairly investigations of small carbohydrate molecules. Sarko and Muggli,
and Gardner and Blackwell in 1974 reported X–ray and modeling
602 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618

studies on cellulose obtained from the alga Valonia ventricosa. They unique properties of nano–adsorbents for water purification pur-
proposed a parallel chain model which stated that cellulose crys- pose (Kalia & Avérous, 2011; Kana, Radi, & Elsabee, 2013; Li et al.,
tallites were made up of parallel chains, even though the chain 2008; Liu, Wang, Yu, & Meng, 2013; Mahgoub & Samaras, 2014;
packing differed, being down in one model and up in the other. Perera & Rajapakse, 2014; Sharma, Srivastava, Singh, Kaul, & Weng,
This was a controversial model which saw heated discussions over 2009; Vakili et al., 2014).
its validation because of the hypothesis that predicted the probable
mechanism for the solid state transformation from a parallel–chain
3. Fabrication of nanoparticles
form to an antiparallel chain form. In 1978, French used the same
data as Jones did for cellulose obtained from ramie and found
3.1. Fabrication of nanocelluloses
resemblance with the observed and calculated diffraction inten-
sities that were in accordance with that of Sarko–Muggli and
The wood pulp fibers are the most common raw materials used
Gardner–Blackwell, but for an antiparallel model. Successive stud-
for the production of cellulose nanofibers (CNF) also referred to
ies by Hieta, Kuga and Usuda in Japan using electron microscopy
as microfibrillated cellulose (MFC) and nanocrystalline cellulose
of stained microfibrils substantiated the parallel model (Cellulose,
(NCC). The pioneering works in the synthesis of cellulose nanofibers
2012). Marchessault and Sarko (1967) explained the polymorphism
were carried out by Herrick, Casebier, Hamilton, and Sandberg
of cellulose. The hypothesis that it can exist in 6 different forms
(1983) and Turbak et al. (1983). They successfully produced CNFs
namely cellulose (I, II, IIII , IIIII , IVI and IVII ) was confirmed with the
by repeated treatments of cellulose wood pulp/water suspensions
help of nuclear magnetic resonance (NMR), infrared and diffrac-
using a mechanical homogenizer.
tion studies (Blackwell, 1982; Gautam, Bundela, Pandey, Awasthi,
The CNFs may be fabricated by a number of approaches
& Sarsaiya, 2010). The native cellulose was shown to exhibit two
such as mechanical treatment which makes use of cryogenic
allomorphs, cellulose I␣ and cellulose I␤ with the help of high res-
grinders or microfluidizers, high–pressure homogenizers and
olution, solid state 13 C NMR spectroscopy (Atalla & Vanderhart,
ultrasonic homogenizers (Yano, Seki, & Ishida, 2008), steam explo-
1989). The literature on microfibrillated cellulose or nanocellulose
sion (Cherian et al., 2011) and electrospinning (Fung, Yuen,
was first published in 1980. Turbak et al. separated this mate-
& Liong, 2011). Mechanical treatments are usually preceded
rial from wood pulp by using high pressure and high temperature
by pre–treatments such as enzymatic/mechanical pre–treatment
homogenizers (Turbak, Snyder, & Sandberg, 1983).
(Pääkkö et al., 2007) and carboxymethylation (Wågberg et al., 2008)
Cellulose was chemically synthesized for the first time in 1992
or oxidation (Saito, Kimura, Nishiyama, & Isogai, 2007) in order
(Kobayashi, Kashiwa, Shimada, Kawasaki, & Shoda, 1992). Studies
to overcome the problems of high energy consumption that is
on cellulose “whiskers” as materials or as material reinforcements
attributed to fiber delamination during nanofibrillation process.
were first reported in the late ‘90 s by the French scientists Dufrense,
The diameters of the CNFs thus formed may be in a range of
Cavaille and others (Dufresne, 2000; Dufresne, Cavaillé, & Helbert,
5–60 nm.
1997; Favier et al., 1995; Helbert, Cavaille, & Dufresne, 1996; Matos
Cellulose nanocrystals/nanowhiskers can be manufactured
Ruiz, Cavaille, Dufresne, Gerard, & Graillat, 2000). A number of cel-
mainly by strong acid hydrolysis of native cellulosic fibers by using
luloses with nano–sizes were synthesized and tested for a range
hydrochloric or sulfuric acid. Their dimensions will be dependent
of applications including food and emulsion/dispersion, medical,
on the properties of cellulose source, hydrolysis time, agitation and
cosmetic, pharmaceutical, and hygiene/absorbent products and
temperature (Habibi, Lucia, & Rojas, 2010). Their diameters may
energy devices etc. (Habibi and Lucia, 2012; Klemm et al., 2011;
vary from 5 to 70 nm and the typical lengths are between 100 and
Lucia & Rojas, 2009; Mikkonen et al., 2010; Moon, Martini, Nairn,
250 nm. Alternate method of preparation of cellulose nanocrystals
Simonsen, & Youngblood, 2011; Oksman, Mathew, Bondeson, &
uses an ionic liquid such as 1–butyl–3–methylimdazolium hydro-
Kvien, 2006; Pääkkö et al., 2007; Siró & Plackett, 2010; Šturcová,
gen sulfate (bmimHSO4 ) as a catalyst during ionic hydrolysis (Man
Davies, & Eichhorn, 2005).
et al., 2011).
Another class of nanocelluloses known as bacterial nanocel-
2.2. History of chitosan
luloses (BNCs) is formed typically from low–molecular–weight
sugars and alcohols as the source materials. BNCs are mainly pro-
The discovery of chitin bio–polymer was made from mushrooms
duced using the Acetobacter xylinum or Gluconacetobacter xylinus
in 1811 by Henri Braconnot, a French professor of natural history
that are grouped under gram–negative acetic acid bacteria. They
(Bhatnagar & Sillanpää, 2009). Chitin was also observed in insects in
usually have diameters of 20–100 nm. Even though BNCs have their
1823 by Odier (Muzzarelli, Muzzarelli, Phillips, & Williams, 2009).
molecular formulae similar to that of plant–based nanocelluloses,
The existence of nitrogen in chitin was established by Lassaigne
they differ greatly in their nanofiber structure (Hokkanen, 2014).
in 1843 (Jeuniaux, 1996). Chitosan, the de–acetylated product of
chitin was synthesized in 1859 by Professor C. Rouget (Bhatnagar
& Sillanpää, 2009; Ghosh, 2014). Ledderhose in 1878 hypothe- 3.2. Fabrication of chitosan nanoparticles
sized that chitin was comprised of glucosamine and acetic acid
(Koide, 1998). Research on chitosan was intensified in the early One of the well–known processes for the synthesis of chitosan
20th century. The rich sources of chitin such as crab and shrimp nanoparticles is the ionic gelation of chitosan and tripolyphosphate.
shells were utilized (Kavitha, Keerthi, & Mani, 2011). Rammel- Chitosan particles of mean sizes between 40 and 100 nm have been
berg in 1930s confirmed the existence of chitosan in these sources prepared by this method (Du, Xu, Han, Xu, & Miao, 2008; Qi & Xu,
(Illani & Nawi, 2010). In 1950, the use of X–ray analysis technique 2004). Ionic gelation is most popular among researchers because of
was found to be highly useful in identifying the availability of its simplicity and ease of preparation of nanoparticles. The forma-
chitosan in natural resources (Sandeep, Sangameshwar, Mukesh, tion of nanoparticles of chitosan is attributed to the electrostatic
Chandrakant, & Avinash, 2013). It was only after the ‘80s that chi- interactions between positively charged amino group of chitosan
tosan found increased importance in water treatment applications and anionic cross–linking agent like TPP. The synthesis is generally
(Badawy & Rabea, 2011; Kumar, 2000; Mckay, Blair, & Gardner, accomplished by adding polyethelene glycol crosslinking agent to
1984; Onsosyen & Skaugrud, 1990; Selmer-Olsen, Ratnaweera, & a solution of chitosan polymer in acetic acid containing a stabilizer
Pehrson, 1996). Today the development of chitosan–based nano- such as Tween 80. The size and surface charge of the nanoparticles
materials and nanocomposites is of a great scope to exploit the will be dependent on the ratio of chitosan to the stabilizing agent.
 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618
Fig. 1. Ionic gelation technique.
Reproduced with permission from (Rajalakshmi et al., 2014).
Fig. 1 represents the ionic gelation technique (Rajalakshmi, Aruna,
Vinesha, & Rupangada, 2014).
Other methods of manufacturing nanoparticles of chitosan
include reverse micellar method (Chen, Lee, & Park, 2003),
self–assembling method (Liu, Chen, & Park, 2005), micro–emulsion
method, emulsification solvent diffusion method, premix mem-
brane emulsification method, emulsion–droplet coalescence tech-
nique, spray–drying and desolvation method (Rajalakshmi et al.,
2014).
Chitosan nanofibers can be produced by methods like sol–gel
method, chemical vapor deposition method, electrospinning
method, thermal oxidation method etc. Among these, electro-
spinning is an attractive choice and highly adopted method of
preparation of chitosan nanofibers today (Zhao et al., 2011).
4. Recent developments in wastewater purification using
cellulose nanoparticles/composites
4.1. Nanocellulose–based adsorbents
The ever increasing global demand to prepare sustainable and
eco–friendly products by using natural resources has paved the way
to intensive research on biomaterials such as celluloses and thus the
potential of micro– and nano–sized celluloses for high–end appli-
cations has been explored rigorously. Nanocelluloses are highly
prospective candidates for water treatment. They integrate the
fundamental cellulose characteristics such as hydrophilicity, wide
functionalization ability, and the ease of fabrication of variable
semi–crystalline fiber textures with the nanoscale properties like
large surface area, high aspect ratio, quantum size effects as well as
chemical accessibility (Hokkanen, Repo, & Sillanpää, 2013; Kardam,
Rohit, & Srivastava, 2012). Although there are a number of studies
available on micro–sized celluloses, nanocelluloses are mostly pre-
ferred as they exhibit higher scavenging capacity towards water
pollutants. It was found from one of the studies that compared the
effectiveness of micro– and nano–sized celluloses for water treat-
ment that the nanocellulose efficiently adsorbed 62.40% of Cr3+ and
5.98% of Cr6+ which was higher compared to the micro–cellulose
which could only remove 42.02% and 5.79% of Cr3+ and Cr6+
ions respectively from aqueous solution (Singh, Arora, Sinha, &
Srivastava, 2014).
Nanocelluloses comprise of large number of hydroxyl groups by
virtue of their chemical structure. Excessive number of hydroxyl
functionalities can exert adverse effects and curtail their appli-
603
cations (Hasani, Cranston, Westman, & Gray, 2008; Kamel, Ali,
Jahangir, Shah, & El-Gendy, 2008; Kloser & Gray, 2010). However,
these reactive OH groups will impart functional flexibility to the
host and hence facilitate the modification of nanocelluloses so as
to improve their adsorption behavior in wastewater treatment.
Functionalized nanocelluloses have shown outstanding adsorp-
tion performance towards water contaminants. Few of the recent
studies on functionalized nanocellulose–based materials from the
literature are summarized in the following subsections.
4.1.1. Carboxylated cellulose nanomaterials
Carboxylation modification of nanocelluloses has been exten-
sively studied for the sorption of hazardous contaminants
especially heavy metal ions. Carboxylation serves to strengthen the
COO− groups and renders the adsorbent effective for picking up the
toxic metal ions from water. The presence of carboxylate groups
was found to be beneficial in the case of CNFs utilized for the scav-
enging of uranyl (UO22+ ) ions. The strong negative charges that were
attributed to carboxylate groups on the surface of CNFs helped in
the adsorption of about 167 mg g−1 of uranyl ions. This reported
capacity is at least 2 times greater than the conventional adsor-
bents such as montmorillonite, polymer particles etc. (Ma, Hsiao, &
Chu, 2011). Chemical modification of cellulosic nanofibers (NCFs)
obtained from rice straw through graft co–polymerization using
acrylic or maleic or itaconic acid was conducted in order to tailor the
nanofibers for the sorption of heavy metal impurities like Cr3+ , Ni2+ ,
Pb2+ and Cd2+ . The length of NCFs was in micrometer scale while
diameter was in the range of 40–80 nm. Graft co–polymerization
was seen to increase the concentration of COO groups which
resulted in enhanced adsorption of heavy metals because of ion
exchange process between COO− groups and metal ions. The heavy
metal removal efficiency of NCFs was above 90% in both single and
multi–metal solution systems (Srivastava, Kardam, & Raj, 2012).
4.1.2. Succinylated nanocelluloses
Succinic anhydride–based functionalization has been pursued
as another alternate to cellulose modification. Efficient, stable and
recyclable modified sorbents are formed when this type of modi-
fication is done on nanocelluloses. Yu et al. (2013) carried out the
functionalization of cellulose nanocrystals with succinic acid and
employed for the removal of Pb2+ and Cd2+ from aqueous solution.
They reported that the succinylated CNCs adsorbed 366 mg g−1 of
Pb2+ and 256 mg g−1 of Cd2+ . These values are way higher than that
exhibited by un–modified CNCs which showed adsorption capaci-
ties of only 25 and 2 mg g−1 of Pb2+ and Cd2+ respectively (Yu, Tong,
Ge, Wu et al., 2013). Another succinic anhydride–modified CNC
adsorbent was utilized for the remediation of Cr3+ ions. This mate-
rial showed the removal ability of 94.84% for Cr3+ . This scavenging
activity was found to be greater than the un–modified counterpart
which showed the removal efficiency of 62.4% (Singh et al., 2014).
Mercerization treatment prior to succinic anhydride functionaliza-
tion of nanocelluloses resulted in the improvement of the surface
area and availability of higher number of OH groups for succiny-
lation. The modified adsorbent was used for the removal of Zn2+ ,
Ni2+ , Cu2+ , Co2+ and Cd2+ in batch experiments. Adsorption capaci-
ties of 1.338, 0.744, 1.900, 1.610 and 2.062 mmol g−1 were observed
for Co2+ , Ni2+ , Cu2+ , Zn2+ , and Cd2+ respectively (Hokkanen et al.,
2013).
4.1.3. Amino–modified nanocelluloses
Amination is a modification method used to strengthen the
bio–active functional groups (NH+ 3
). Amine modification uses the
amine functionalities for the chelating action on heavy metals
and dyes. Studies have indicated that amine functionalization
effectively increases the adsorption capacity of the nanocellulose
sorbent materials. The most recently published works have concen-
604 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618
Fig. 2. Sodium periodate oxidation and amination reaction of cellulose
nanowhiskers.
Reproduced with permission from (Jin, Li et al., 2015).
trated on amine–modified celluloses as adsorbents for anionic dyes.
Functionalization of cellulose nanowhiskers with ethylenediamine
increased the primary amine groups. This increase of amino groups
enhanced the uptake of dye acid red GR when acidic conditions
were maintained. This behavior of amino–modified nanocrys-
talline cellulose (ANCC) was explained taking into consideration the
chemical reaction between increased number of protonated amine
sites and anionic dye sites. ANCC adsorbed 555.6 mg g−1 of acid red
GR which was more than that of reactive light yellow K–4G and
congo red 4BS. Chemisorption type of adsorption was identified
from pseudo second order kinetics data followed by ANCC. The dye
adsorption decreased under alkaline conditions as surface of ANCC
was negatively charged which resulted in reduced interaction of
dye and adsorbent (Jin, Li, Xu, & Sun, 2015). Fig. 2 shows the ami-
nation modification of cellulose nanowhiskers for subsequent use
in dye removal.
Polyvinylamine–modified cellulose nanocomposite was
explored for removal of anionic dyes, namely, reactive light yellow
K–4G, congo red 4BS and acid red GR and it adsorbed 1250.9,
869.1 and 1469.7 mg g−1 of the dyes respectively as estimated
from Sips model. The type of adsorption was chemisorption as
identified from pseudo second order kinetics data (Jin, Sun, Xu, &
Xu, 2015). Aminopropyltriethoxysilane (APS)–treated CNFs were
investigated for the uptake of Cd2+ , Cu2+ and Ni2+ . The amino
group on APS and hydroxyl group on the cellulose matrix exerted
synergistic effects while removing heavy metals from water.
However, contribution of amino groups was greater towards the
decontamination of heavy metals. APS/MFC was able to capture
2.734, 3.150, 4.195 mmol g−1 of Ni2+ , Cu2+ and Cd2+ respectively
(Hokkanen, Repo, Suopajärvi et al., 2014). In another study, ami-
nated CNCs were tested for the adsorption of Cr6+ and the removal
efficiencies were compared with that of bare CNCs. The aminated
CNCs showed 98.33% removal whereas the sorption ability of the
CNCs was only 5.98% (Singh et al., 2014).
4.2. Nanocellulose–based composites as adsorbents
Novel functional materials based on biopolymers are of great
interest for water purification as the hybrid materials offer
attractive properties such as flexibility, low density, tough-
ness and high adsorption capacity. They are also biocompatible,
biodegradable and environmental–friendly. The development of
nanocomposite/polymer adsorbent systems is highly encouraged
today because of their large removal efficiency and the spon-
taneous decontamination of water pollutants (Omer, Elbadawi,
& Yassin, 2013; Sharma et al., 2009). Various types of cellulose
based nanocomposites such as magnetic cellulose nanocom-
posites, cellulose/silsesquioxane nanocomposites, cellulose/clay
nanocomposites and cellulose/polymer nanocomposites have been
investigated for wastewater treatment.
4.2.1. Magnetic cellulose nanocomposites
Incorporation of magnetic particles in the polymer matrix is
being explored as a promising modification method in recent inves-
tigations (Donia, Atia, & Abouzayed, 2012; Luo & Zhang, 2009; Nata,
Sureshkumar, & Lee, 2011; Yu, Tong, Ge, Zuo et al., 2013; Zhu et al.,
2011). Owing to their abundance in nature, cellulose materials are
thought of ideal materials for the dispersion of magnetite (Fe3 O4 )
and (Fe2 O3 ). The magnetic cellulose nanocomposites can be easily
generated by the application of external magnetic field. Hence they
have drawn increased attention.
In a novel approach, a bacterial cellulose–based magnetite
nanocomposite was subjected to amine modification using
1,6–hexanediamine and investigated for the adsorption of arsenate
ions. The amine functional groups and the incorporated magnetite
materials acted synergistically for the removal of As5+ ions. This
material adsorbed 90 mg g−1 of As5+ which was about 15 times
more than aminated magnetite adsorbent (Nata et al., 2011). This
result is 3 times better than that obtained for the cellulose@Fe2 O3
nanocomposite synthesized by using one–pot co–precipitation of
medical cotton and Fe2 O3 precursors (Yu, Tong, Ge, Zuo et al.,
2013). A tetraethylenepentamine–functionalized magnetic cellu-
lose composite was used for the decontamination of metal ions
such as Hg2+ , Cu2+ and Ag+ . This adsorbent could remove 2, 1.5
and 1.2 mmol g−1 of Hg2+ , Cu2+ and Ag+ respectively. When tested
on battery waste–contaminated sample containing Al3+ , Cu2+ , Ni2+ ,
Zn2+ and Cr3+ , the composite exhibited sorption efficiency of
65–100% (Donia et al., 2012).
Activated carbon (AC) impregnated magnetic cellulose beads
were utilized for the elimination of organic dyes from wastew-
ater. Fe2 O3 nanoparticles and AC particles occupied as fillers in
cellulose matrix and imparted spherical structure. The adsorbent
achieved 6.5 × 10−3 and 4.4 × 10−3 mmol g−1 of methyl orange and
methylene blue respectively. Adsorption equilibrium was reached
in 180 min and kinetics obeyed pseudo second order model. This
dye removal process was proposed as a clean and safe alternate for
wastewater remediation (Luo & Zhang, 2009).
In a study of heavy metal removal by magnetic nanocel-
lulose composites, mercury (II) ions were adsorbed onto
2–mercaptobenzamide modified itaconic acid–grafted–magnetite
nanocellulose composite from synthetic chlor–alkali contaminated
water. This novel composite adsorbed Hg2+ through multilayer
sorption process as indicated by its concordance with Freundlich
model and the adsorption capacity was 240 mg g−1 . The kinetic
data revealed that the adsorption process involved ion exchange
followed by complexation mechanism (Anirudhan & Shainy, 2015).
4.2.2. Cellulose/Silsesquioxane nanocomposite
Nanocellulose hybrid materials containing high–reactive poly-
hedral oligomeric silsesquioxane having multi–N–methylol groups
(R–POSS) were prepared by crosslinking graft reaction. POSS per-
form the role of model nanofillers. The hybrids were used for the
elimination of reactive dyes, namely, reactive blue B–RN and reac-
tive yellow B–4RFN. Equilibrium removal capacities of 22.3 and
17.4 mg g−1 were achieved for B–4RFN and B–RN respectively. The
adsorption removal ratio from aqueous solutions was 89.1 and
83.6% respectively for B–4RFN and B–RN while the control cellulose
showed removal percentages of only 4.12 and 2.90 for B–4RFN and
 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618 605

B–RN respectively. Langmuir model described adsorption equilib-

rium better than Freundlich model (Xie, Gao, & Gao, 2010). Studies
of impact of temperature upon adsorption capacities of nanocellu-
lose hybrid containing polyhedral oligomeric silsesquioxane with
R–POSS for B–4RFN and B–RN showed reduction of capacity with
the increase of temperature (Xie, Zhao, & He, 2011).

4.2.3. Cellulose/Clay nanocomposite

Clays are of particular research interest as adsorbents for dyes
currently. Clays like montmorillonite (MMT) have been employed
for the removal of dyes because of their impressive surface area
and cation exchange capacity. However they are proved ineffective
while treating anionic dyes such as congo red. Hence modifica-
tion of MMT with carboxymethyl cellulose (CMC) is proposed as
a feasible alternate. This also helps improve the inherent limita-
tions of CMC caused due to excess negative surface charge leading
to poor sorption ability and lower water solubility. Congo red dye
removal was evaluated on CMC/MMT nanocomposite in a study.
The nanocomposite exhibited adsorption capacity of 161.1 mg g−1
which was higher than plain carboxymethylcellulose (CMC) which
showed a capacity of 62.4 mg g−1 . Raise of adsorption temperature
from 30 to 50 ◦ C resulted in the increase of adsorption ability of
CMC/MMT from 161.1 to 298.3 mg g−1 . This was described on the
basis of rise in mobility of dye ions and possible swelling effect in
Fig. 3. Synthesis of the adsorbent [P(IA/MAA)-g-NC/NB] and removal process of
the internal structure of the nanocomposite. Increase of pH from Co(II) ions.
4 to 12 resulted in drop of sorption capacity down to 32.5 mg g−1 . Reproduced with permission from (Anirudhan et al., 2016).
The fall of congo red removal capability with the rise in pH was
explained to be the result of electrostatic repulsion between anionic
4.2.5. Miscellaneous–nanocellulose based adsorbents
dye ions and increased negatively charged sites in solution (Zhao &
Graft co–polymerization of NCFs using vinyl sulphonic acid
Wang, 2012).
treatment improved the sorption capacity for Cr3+ , Ni2+ , Cd2+ and
The grafting of nanobentonite onto nanocellulose matrix was
Pb2+ ions more than 90%. The enrichment of sulphonic group of
found useful for the treatment of heavy metals. A poly(itaconic
NCFs due to polymerization was proposed to be responsible for
acid/methacrylic acid)–grafted–nanocellulose/nanobentonite
such a good adsorption behavior (Kardam, Rohit et al., 2012). Phos-
composite containing multi–carboxyl groups was used to
phorylation of nanoscaled cellulose sludge introduced functional
determine the efficacy of a simulated nuclear industrial water
groups that improved the loading capacity of Fe3+ and Cu2+ . The
contaminated with Co2+ ions. The synthesis procedure of the
adsorbent adsorbed 115 and 117 mg g−1 of Fe3+ and Cu2+ , respec-
adsorbent and its heavy metal disinfection action are represented
tively (Liu et al., 2015). NCFs having average grain size of 6 nm
in Fig. 3. In this adsorption study, the removal of cobalt from
were able to remove 8.55 mg g−1 of Ni2+ , 9.42 mg g−1 of Pb2+ ,
nuclear water that was concordant with batch removal process
and 9.7 mg g−1 of Cd2+ in a biosorption experiment (Kardam, Raj,
was practically demonstrated. It was proposed that the adsorbent
Srivastava, & Srivastava, 2014).
could be readily employed in the real process for treating the
A study of Pb2+ biosorption by employing cellulosic nanofibers
effluent of nuclear industrial water. The carboxyl groups were
yielded adsorption of about 94.2% of Pb2+ . Adsorption reached equi-
found to be responsible for the uptake of Co2+ from the polluted
librium in 40 min in this case (Kardam, Raj, Arora, & Srivastava,
water (Anirudhan, Deepa, & Christa, 2016).
2012). Another study involved electrochemical analysis was
employed for the determination of Pb2+ and Cd2+ using a nanocel-
lolosic fiber–modified carbon paste electrode. The proposed
4.2.4. Cellulose/Polymer nanocomposites mechanism indicated the ionized ionic aldehyde, carboxylate, and
Partially hydrolyzed polyacrylamide/cellulose nanocrystal hydroxyl groups of nanocellulosic fibers took part in adsorption
(HPAM/CNC) nanocomposite hydrogels were studied for methy- mechanism (Rajawat et al., 2013).
lene blue dye removal. Adsorption capacity of the nanocomposite Adsorption of vanadium (V) from aqueous solutions was investi-
was seen to enhance upon improving the HPAM anionic nature, gated using biophosphonated nanocellulose. Vanadium ions were
raising CNC content up to 20% and reducing the value of pH. A effectively taken up by the adsorbent and the complexing ability
Langmuir equilibrium uptake of 224.8 mg g−1 was observed for of biophosphonate groups with vanadium ions was attributed to
HPAM/CNC nanocomposite containing 20% CNC at a pH of 6.5. be the reason for adsorption. An adsorption capacity of as high as
Kinetics of adsorption was corroborated with second order model 1.98 mmol g−1 was reported for biophosphonated nanocelluloses
(Zhou, Wu, Lei, & Negulescu, 2014). (Sirviö, Hasa, Leiviskä, Liimatainen, & Hormi, 2016).
Anti–microbial properties of silver nanoparticles (AgNPs) Quaternized cellulose nanofibrils (Q–NFC) were investigated for
loaded cellulose nanofibers and cellulose–graft–polyacrylonitrile removal of acid green 25 and congo red removal. Nanofibrils con-
(Cell–g–PAN) copolymer nanofibers towards Escherichia coli, taining a trimethylammonium chloride content of 1.32 mmol g−1
Salmonella typhi, and Staphylococcus aureus were evaluated. While could adsorb 0.683 and 0.664 g g−1 of acid green 25 and congo
cellulose nanofibers with AgNPs exhibited a disinfection that red, respectively. Uniform nanoscale character and high surface
was between 91 and 99%, Cell–g–PAN copolymers comprising area of Q–NFC was thought to be responsible for quick equilibrium
AgNPs achieved 100% disinfection of bacteria–contaminated water kinetics which caused the dyes to be picked up in tens of seconds.
(Gouda, Hebeish, & Al-Omair, 2014). However, the it took about 72 h to desorb 92% of congo red from
606 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618

Fig. 4. Schematic illustration of the preparation of surface quaternized cellulose nanofibrils from pulp fibers.
Reproduced with permission from (Pei et al., 2013).

Table 1
Adsorption capacities of nanocelluloses and cellulose nanocomposites for various heavy metals and dyes.

Cellulose nanoparticles/composites Heavy metal ion Adsorption Capacity References

Fe3 O4 /bacterial cellulose nanocomposite Pb(II) 65.0 mg g−1 Zhu et al. (2011)
Fe3 O4 /bacterial cellulose nanocomposite Mn(II) 33.0 mg g−1 Zhu et al. (2011)
Mechanochemical maghemite As(V) 15.0 mg g−1 Giménez, Martínez, de Pablo, Rovira, and Duro (2007)
Hexanediamine–modified Fe3 O4 /bacterial cellulose As(V) 36.5 mg g−1 Nata et al. (2011)
nanocomposite
Cellulose nanocrystals Pb(II) 367.6 mg g−1 Yu, Tong, Ge, Wu et al. (2013)
Sodic cellulose nanocrystals Pb(II) 465.1 mg g−1 Yu, Tong, Ge, Wu et al. (2013)
Cellulose nanocrystals Cd(II) 259.7 mg g−1 Yu, Tong, Ge, Wu et al. (2013)
Sodic cellulose nanocrystals Cd(II) 344.8 mg g−1 Yu, Tong, Ge, Wu et al. (2013)
Fe2 O3 nanomaterial As(III) 1.3 mg g−1 Luther, Borgfeld, Kim, and Parsons (2012)
Fe2 O3 nanomaterial As(V) 4.6 mg g−1 Luther et al. (2012)
Cellulose@Fe2 O3 nanoparticles As(III) 23.2 mg g−1 Yu, Tong, Ge, Zuo et al. (2013)
Cellulose@ Fe2 O3 nanoparticles As(V) 32.1 mg g−1 Yu, Tong, Ge, Zuo et al. (2013)
Nano–magnetic cellulose Hg(II) 2 mmol g−1 Donia et al. (2012)
Nano–magnetic cellulose Cu(II) 1.5 mmol g−1 Donia et al. (2012)
Carbonated hydroxyapatite modified nanocellulose Ni(II) 2.021 mmol g−1 Hokkanen, Repo, Westholm et al. (2014)
Carbonated hydroxyapatite modified nanocellulose Cd(II) 1.224 mmol g−1 Hokkanen, Repo, Westholm et al. (2014)
Carbonated hydroxyapatite modified nanocellulose PO3−
4
0.843 mmol g−1 Hokkanen, Repo, Westholm et al. (2014)
Carbonated hydroxyapatite modified nanocellulose NO−3
0.209 mmol g−1 Hokkanen, Repo, Westholm et al. (2014)
Aminopropyltriethoxysilane (APS) Ni(II) 2.734 mmol g−1 Hokkanen, Repo, Suopajärvi et al. (2014)
modified–nanocellulose
Aminopropyltriethoxysilane modified–nanocellulose Cu(II) 3.150 mmol g−1 Hokkanen, Repo, Suopajärvi et al. (2014)
Aminopropyltriethoxysilane modified–nanocellulose Cd(II) 4.195 mmol g−1 Hokkanen, Repo, Suopajärvi et al. (2014)
Ethylenediamine–modified cellulose Zn(II) 1.059 mmol g−1 Zhao et al. (2007)
Succinic anhydride–modified mercerized Zn(II) 1.610 mmol g−1 Hokkanen et al. (2013)
nanocellulose

Cellulose nanoparticles/composites Dye Adsorption Capacity References

−1
Nano–cellulose hybrid containing reactive polyhedral oligomeric Reactive Yellow B–4RFN 22.3 mg g Xie et al. (2010)
silsesquioxanes with multi–N–methylol
−1
Nano–cellulose hybrid containing reactive polyhedral oligomeric Reactive Blue B–RN 17.4 mg g Xie et al. (2010)
silsesquioxanes with multi–N–methylol
Ethylenediamine–modified nanocrystalline cellulose Acid Red GR 555.6 mg g−1 Jin, Li et al. (2015)
Carboxymethylcellulose/montmorillonite nanocomposite Congo Red 161.1 mg g−1 Zhao and Wang (2012)
Partially hydrolyzed polyacrylamide/cellulose nanocrystal nanocomposite Methylene Blue 224.8 mg g−1 Zhou et al. (2014)
Surface quaternized cellulose nanofibrils Congo Red 664.0 mg g−1 Pei et al. (2013)
Surface quaternized cellulose nanofibrils Acid Green 25 683.0 mg g−1 Pei et al. (2013)
 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618
the dye–saturated adsorbent. Fig. 4 shows the isolation of Q–NFC
from pulp fibers to be employed for dye removal (Pei, Butchosa,
Berglund, & Zhou, 2013). Adsorption capacities of nanocelluloses
and cellulose nanocomposites for various heavy metals and dyes
are shown in Table 1.
5. Recent developments in wastewater purification using
chitosan nanoparticles/composites
5.1. Nanohitosan–based adsorbents
Chitosan nanoparticles have become potential materials of
choice for water treatment because of their small size, large sur-
face area, quantum size effects, and absence of diffusion limitations.
They exhibit superiority compared to the micro–sized chitosan
materials in terms of faster adsorption rates and adsorption capac-
ities (Dyal et al., 2003).
Nanochitosan particles prepared by ionotropic gelation of chi-
tosan and tripolyphosphate cross–linking agent were tested for
Pb(II) adsorption. Maximum adsorption capacity of 398.0 mg g−1
was reported from Langmuir isotherm (Qi & Xu, 2004). Sivakami
et al. (2013) explored chitosan nanorods for the adsorption of
Cr(VI) and observed an uptake of 323.6 mg g−1 by the adsor-
bent. Kinetics study suggested that adsorption process was
pseudo–second–order in nature (Sivakami et al., 2013). Another
recent work employed nanochitosan for Cd(II) removal and found
an adsorption capacity of 358 mg g−1 . Pseudo–second–order kinet-
ics was involved in adsorption (Seyedi, Anvaripour, Motavassel, &
Jadidi, 2013).
Chitosan nanofibers prepared by electrospinning, owing to
their higher surface area per unit mass, huge porosity with
finer pores and easy exposure of functional groups to metal
ions, become potential candidates for the adsorption of Pb2+
and Cu2+ . The recorded adsorption capacities were 263.2 and
485.4 mg g−1 for Pb2+ and Cu2+ respectively. It was reported that the
nanofibers retained their inherent characters like biocompatibil-
ity, hydrophilicity, bioactivity, non–antigenicity, and non–toxicity
(Haider & Park, 2009).
The removal of arsenate in the presence of competing anions
such as sulfate, chloride and nitrate ions was studied using chi-
tosan and nanochitosan as the adsorbents. It was found that
sulfate ions (initial concentration = 1240 ␮g g−1 ) impacted the
adsorption capacity of nanochitosan towards arsenate ions (ini-
tial concentration = 3000 ␮g l−1 ) negatively while chloride (initial
concentration = 4610 ␮g g−1 ) and nitrate ions (initial concentra-
tion = 4050 ␮g g−1 ) had negligible effect (Kwok, Koong, Chen, &
McKay, 2014).
Chitosan nanoparticles are expected to favor greater adsorption
of toxic dyes because of their higher surface area. Hu, Zhang, Chan,
and Szeto (2006) synthesized nanochitosan of particle size 180 nm
by using the usual gelation reaction between amino functionali-
ties of chitosan and negatively charged sodium tripolyphosphate
(TPP). Adsorption behavior of nanochitosan was investigated for
Acid Green 27 (AG27) dye of anthraquinone type. Experiments con-
ducted for the determination of equilibrium adsorption of dye (Qe )
based on the amount of the nanoparticles in the mixed solution
(Qes ) of AG27 and nanochitosan, and the weight of chitosan in
the nanoparticles (Qep ) gave the Langmuir monolayer adsorption
capacity (Q0 ) of 2103.6 mg g−1 and 1051.8 mg g−1 , respectively for
Qep and Qes (Hu et al., 2006). This result turned out to be greater
than that observed for micro–sized chitosan which showed a Q0
value of 645.1 mg g−1 (Wong, Szeto, Cheung, & McKay, 2003). The
adsorption mechanism proposed stated that adsorption was due to
electrostatic interactions between the positive amino group on the
chitosan and the anionic dye (Hu et al., 2006). Chitosan nanopar-
607
ticles were also studied for the adsorption of Acid Red 73 (AR73),
Acid Orange 10 (AO10), Acid Orange 12 (AO12) and Acid Red 18
(AR18) dyes. In a synthesis method similar to the work of Hu
et al. (2006), chitosan nanoparticles of particle size in the range
0.0663–1.763 ␮m were obtained. They could adsorb 2.13, 1.77, 4.33
and 1.37 mmol l−1 of AR73, AO10, AO12 and AR18 respectively at
an optimal pH of 4. It is noteworthy that these adsorption capacities
are higher than that observed for normal chitosan which exhibited
1.54, 2.66, 1.11 and 1.25 mmol l−1 for AO10, AO12, AR18 and AR73,
respectively (Wong et al., 2003). The reason for lower removal
capacities observed at a pH of 6 was attributed to the reduced
availability of protons which resulted in diminished ionic inter-
action between dye and amino groups of chitosan. It was found
that adsorption isotherms best fitted Langmuir model with corre-
lation factor above 0.99 for all the acid dyes than Freundlich or
Redlich–Peterson model with lower correlation values (Cheung,
Szeto, & McKay, 2009). Chitosan nanoparticles synthesized by ionic
gelation between chitosan and tripolyphosphate were employed
for the removal of eosin Y dye. The particles were of spherical
shape with mean diameter of 69.33 nm. Nanochitosan adsorbed
3.333 g g−1 of eosin Y. They could be desorbed by increasing the pH.
Hence nanochitosan was recyclable. Adsorption isotherms were
well fitted with Langmuir model (Du et al., 2008).
Zinc oxide nanoparticles were immobilized onto chitosan and
used for the sorption of acid black 26 (AB26) and direct blue
78 (DB78). Adsorption capacities of nanoparticles were 34.5 and
52.6 mg g−1 respectively for DB78 and AB26. Adsorption was
assumed to take place because of electrostatic interaction between
positively charged adsorption sites and dye anions. Equilibrium
adsorption data fitted excellently with Langmuir and Temkin for
AB26 and DB78, respectively (Salehi, Arami, Mahmoodi, Bahrami,
& Khorramfar, 2010).
Chitosan nanodispersion was assessed for adsorption of C.I.
Reactive Red 120 (RR120) dye. Its adsorption property was
compared with dissolved chitosan. The nanodispersion adsorbed
910.0 mg g−1 of the dye while the dissolved chitosan absorbed
51.0 mg g−1 of dye. It was also seen that the rate of adsorption of chi-
tosan nanodispersion was greater than that of dissolved chitosan
(Momenzadeh, Tehrani-Bagha, Khosravi, Gharanjig, & Holmberg,
2011).
5.1.1. Aminated chitosan nanomaterials
The amination of nano–sized chitosan materials is often carried
out in order to improve the adsorption performance and selectivity
of adsorption. As NH2 groups present in chitosan are known to be
responsible for the electrostatic interaction with the contaminant
species, attempts have been made to increase the NH2 groups
by using modification agents such as ethylenediamine, hexanedi-
amine, diethylenetriamine etc. (Crini & Badot, 2008; Kamari, Ngah,
Chong, & Cheah, 2009; Kyzas & Lazaridis, 2009).
Ethylenediamine–functionalized magnetic chitosan nanopar-
ticles (EMCN) were prepared and examined for the adsorptive
removal of Acid Orange 10 and Acid Orange 7 dyes. It was observed
from TEM that the nanoparticles were monodispersed and had a
similar mean diameter of 13.5 nm. EMCN showed adsorption of
2.25 mmol g−1 for and 3.47 mmol g−1 for AO10 and AO7 respec-
tively. Adsorption results were correlated well with Langmuir
model than Dubinin–Radushkevich and Freundlich models (Zhou,
Jin, Liu, Liang, & Shang, 2011).
Magnetic chitosan nanocomposites based on
hexanediamine–functionalized magnetite nanoparticles were
subjected for the adsorption of Cd2+ , Cu2+ and Pb2+ . The nanocom-
posites were first mixed with the contaminant solutions using
sonication method so as to allow sufficient interaction and
subsequently checked for heavy metals removal efficiency.
Nanocomposite displayed a Pb(II) removal efficiency of about 95%
608 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618
in as early as 10 min after subjecting it for ultrasound radiation in
weak de–ionized water and retained this efficiency until 40 min.
Copper and cadmium percentage removal capacities were 89% and
92% respectively (Liu, Hu, Fang, Zhang, & Zhang, 2008). Similarly,
ethylenediamine–functionalized magnetic chitosan nanoparticles
(EMCN) were evaluated for adsorption of Pd(II) and Pt(IV) metal
ions. EMCN was proved to be a good sorbent by exhibiting maxi-
mum loading capacities of 171 and 138 mg g−1 for Pb2+ and Pt4+
respectively. A mixture of 0.4 M HNO3 –1.0 M thiourea was utilized
as the effective desorbing agent and regeneration in the range of
86.6–97.3% could be successfully attained (Zhou, Xu, Liang, & Liu,
2010). Magnetic chitosan modified using diethylenetriamine was
used for adsorption of Cr6+ , Cu2+ , and Zn2+ from aqueous solution.
It was proposed that adsorption of metal ion on the heterogeneous
surface of aminated sorbent consisted both multilayer chemical
and physical adsorptions. FTIR spectrum revealed the role of NH2
and OH during chemisorption. Upon saturating the sorbent
with metal ions, reusability testing showed that the losses of
efficiency of Cr(VI), Cu(II) and Zn(II) were about 11.4, 11.3, and
14.7% respectively (Li, Bi, Liu, Dong, & Wang, 2011).
5.2. Chitosan nanocomposites
Chitosan nanomaterials have been subjected to modification
by using carboxylation, amination, incorporation of magnetic
particles, hydroxyapatites, multi–walled carbon nanotubes, mont-
morillonite etc. They find applications in the removal of Cr6+ ,
Fe3+ , Zn2+ , Cu2+ , congo red, methyl orange, methyl blue and so on
(Aliabadi, Irani, Ismaeili, & Najafzadeh, 2014; Chang et al., 2006;
Chang and Chen, 2005; Chen et al., 2012; Fan, Zhang, Luo, Lu, Qiu, &
Sun, 2012; Liu et al., 2008; Namdeo & Bajpai, 2008; Peng et al., 2010;
Salam, Makki, & Abdelaal, 2011; Wang & Wang, 2007a; Zhou et al.,
2010; Zhou, Nie, Branford-White, He, & Zhu, 2009; Zhua, Jianga,
Xiaob, & Lib, 2010).
5.2.1. Chitosan magnetite composites
Magnetic chitosan nanoparticles or nanocomposites have been
researched on for wastewater treatment with greater passion in the
recent years because of their high surface reactivity, efficient sor-
bent regeneration by mere application of external magnetic field,
huge selectivity and large metal chelating capacity owing to the
occurrence of the hydroxyl and amine groups in the chitosan link-
age (Elwakeel, 2010; Elwakeel, Atia, & Donia, 2009; Hritcu, Dodi,
& Popa, 2012; Liu et al., 2008; Ren, Zhang, & Zhao, 2008; Yuwei &
Jianlong, 2011).
It is known that the incorporation of magnetic nanoparticles into
the porous polymer matrix can improve the adsorption capacity by
means of ionic interactions (Luo & Zhang, 2009). The use of exter-
nal magnetic field helps in easy recovery and reuse of the target
contaminants from the solution. Chang and Chen (2005) studied
carboxymethylated chitosan–conjugated Fe3 O4 nanoparticles for
the capture of Cu(II) ions. This nano–adsorbent comprised Fe3 O4
as cores and chitosan as ion exchange groups. The formation of
magnetic chitosan nanocomposite is represented in Fig. 5. Char-
acterization using TEM and XRD revealed that the nanocomposite
contained monodisperse particles and possessed high specific area
as a result of uniform spreading of bound chitosan over the Fe3 O4
nanoparticles’ surface, making almost all chelation sites available.
The adsorption data correlated best with Langmuir model and
exhibited highest adsorption capacity of 21.5 mg g−1 of Cu2+ (Chang
& Chen, 2005). The same researchers carried out adsorption stud-
ies of Co(II) ions and achieved a Langmuir adsorption capacity of
27.5 mg g−1 (Chang et al., 2006). In both cases, the fast adsorp-
tion of Co2+ and Cu2+ was attributed to larger surface area of the
nano–adsorbent and the absence of internal diffusion resistance.
Magnetic composite microspheres (MCM), containing Fe3 O4
nanoparticles and poly (acrylic acid) (PAA) grafted chitosan (CS)
synthesized by simple chemical co–precipitation method were
analyzed for Cu(II) sorption. This novel adsorbent resulted in
the loading capacity of 178.0 mg g−1 Cu(II). Adsorption data fol-
lowed Langmuir model. The un–grafted magnetic composite
microspheres (CS–MCM) exhibited adsorption capacity of only
108.0 mg g−1 of Cu(II). Desorption studies were undertaken with
0.1 mol dm−3 of EDTA solution. CS–MCM and CS/PAA–MCM could
be regenerated completely even after 6 cycles and hence could be
considered for practical application (Yan et al., 2012).
The nanocomposites chitosan–magnetite (CMNs), synthesized
by chemical co–precipitation of Fe(II) and Fe(III) ions by NaOH
in the presence of chitosan, preceding the hydrothermal reaction
were evaluated for the adsorption of Fe(III) ions. The novel CMN
material combines the supreme metal binding potential of chi-
tosan and enormous surface area, dispersed character, relaxation
from convectional columns consisting of fixed packed particles and
rigid membranes, and easy regeneration when magnetic field of
suitable strength is applied. It was found that nano–sized mag-
netic particles were incorporated well inside the nanocomposites
and, formed particles of diameters of 508 and 84 ␮m obeyed Fre-
undlich isotherm and showed the maximum loading capacities
of 5.97 and 35.98 mg g−1 , respectively (Namdeo & Bajpai, 2008).
Yuwei and Jianlong (2011) prepared a similar sorbent having size in
the range of 8–40 nm with slight modification in the synthesis pro-
cedure and utilized in the adsorption of Cu2+ ions. The maximum
Langmuir capacity determined was 35.5 mg g−1 . A tentative mech-
anism proposed implied NH2 and OH groups were involved in
the uptake of Cu2+ ions by magnetic chitosan particles. Reusability
studies on the copper saturated adsorbent indicated that desorp-
tion with ethylendiamine tetraacetic acid (EDTA) could result in
efficient removal of about 90% even after 4 cycles (Yuwei & Jianlong,
2011).
␣–ketoglutaric acid modified chitosan–coated magnetic
nanoparticles (␣–KA–CCMNPs) were evaluated for the adsorp-
tion of Cu2+ ions from aqueous solution. This sorbent exhibited
96.15 mg g−1 of maximum adsorption capacity following Langmuir
equation whereas plain CCMP could take up only 60.61 mg g−1
Cu(II). The adsorbent maintained the regeneration ability of over
91% even after 7 consecutive cycles of adsorption and desorption
using 100 mmol l−1 of Na2 EDTA as eluent (Zhou et al., 2009).
A thiourea–modified Fe3 O4 –imprinted chitosan/TiO2 composite
was studied for Cd(II) adsorption. Adsorption followed Langmuir
equation and maximum adsorption capacity of 256.4 mg g−1 of
Cd(II) was reported for a pH of 7.0 (Chen et al., 2012).
A graphene oxide modified magnetic cyclodextrin–chitosan
adsorbent (CCGO) was examined for Cr(VI) removal. The maximum
adsorption capacity of 67.7 mg g−1 was reported according to Lang-
muir model. Regeneration studies revealed that only 5% of capacity
loss was observed after 5 cycles (Li et al., 2013). The synthesis pro-
cedure for CCGO is illustrated in Fig. 6.
The highest ever reported adsoption capacity values of Ni2+
and Co2+ were reported by Hritcu et al. (2012) for composite
chitosan–magnetite microparticles. Langmuir model fitted the best
for adsorption data and maximum adsorption capacities were
833.34 and 588.24 mg g−1 for Ni2+ and Co2+ respectively. The sor-
bent was proven to be reusable up to 3 consecutive cycles of
adsorption–desorption (Hritcu et al., 2012).
In an attempt to facilitate the separation of metal–saturated
adsorbent from aqueous solutions upon adsorption, magnetic
␥–Fe2 O3 /crosslinked chitosan composite (M␥–Fe2 O3 /CSCs) was
developed using micro–emulsion method and utilized for the
adsorption of toxic methyl orange (MO) dye. Characterizations
confirmed that interaction between ␥–Fe2 O3 and crosslinked chi-
tosan had taken place and surface morphology of chitosan changed
 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618 609

Fig. 5. An illustration for the carboxymethylation and binding onto Fe3 O4 nanoparticles of chitosan.
Reproduced with permission from (Chang et al., 2006).

Fig. 6. Synthesis of CCGO and their application for removal of Cr(VI) with the help of an external magnetic field.
Reproduced with permission from (Li et al., 2013).

on incorporation of ␥–Fe2 O3 . Particle size of M␥–Fe2 O3 /CSCs was
found to be greater than that of magnetic ␥–Fe2 O3 nanopar-
ticles. It also possessed smaller particle diameter and larger
surface area compared to crosslinked chitosan that proved ben-
eficial in the sorption of MO dye. The saturated magnetization
(␴s) of the nanocomposite presented a favorable value which
helped in the separation of metal saturated adsorbent from solu-
tion in 10 s. The tested adsorbents such as magnetic ␥–Fe2 O3
nanoparticles, crosslinked chitosan, 2:5 M␥–Fe2 O3 /CSCs and 1:10
␥–Fe2 O3 /CSCs displayed adsorption capacities of 0.10 mg g−1 ,
20.10 mg g−1 , 29.37 mg g−1 and 29.50 mg g−1 respectively. Adsorp-
tion kinetics 1:10 ␥–Fe2 O3 /CSCs obeyed pseudo–second–order
kinetics (Zhua et al., 2010). Micro–emulsion process was utilized for
the synthesis of chitosan/kaolin/␥–Fe2 O3 nanocomposite as well.
Kaolin and ␥–Fe2 O3 were encapsulated in chitosan beads and the
embedding of magnetic ␥–Fe2 O3 served to enhance the adsorp-
tion capacity of MO dye due to increased ionic interaction. It was
possible to remove 71.0% of MO in 180 min of adsorption from a
20 ppm MO solution at pH = 6.0 by 1.0 g l−1 composites. Pores and
pleats observed from SEM images were attributed for such adsorp-
tion behavior of the nanocomposite. The presence of competitive
ions was found to decrease the dye uptake in the order: no addi-
tion  Cl− > NO3− > SO2− 2− 3−
4 » CO3 > POPO4 (Zhu, Jiang, & Xiao, 2010).
Magnetic chitosan–Fe(III) hydrogel synthesized by chelation pro-
cess was applied for the adsorption of C. I. Acid Red 73. The dye
uptake by this adsorbent was 294.5 mg g−1 . The kinetics of adsorp-
tion revealed the adsorption to be a fast process achieving a dye
uptake of 90% in just 5 min and reaching equilibrium in 10 min.
The higher rate of adsorption in first 5 min is attributed to higher
initial concentration. Second order rate constant reduced with the
610 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618
reduction in initial concentration and sorption system followed
second–order–rate model. Adsorbent maintained 90% of adsorp-
tion ability after 5 regeneration cycles (Shen, Shen, Wen, Wang, &
Liu, 2011).
␤–Cyclodextrin–chitosan (CDC) modified Fe3 O4 nanoparticles
(CDCM) have been explored as attractive option for dyes adsorp-
tion by taking advantage of physical properties, chemical stability,
inclusion and adsorption behavior of the immobilized cyclodex-
trins on chitosan. The incorporation of magnetic particles makes
separation process simple and fast with the aid of magnetic
field. Overall, the high surface area and absence of internal diffu-
sion resistance make the nanocomposite better sorbent than the
micon–sized counterparts. The synthesis and application of CDCM
for dye removal is represented in Fig. 7. SEM images of synthesized
CDCM showed a number of spherical particles with diameters of
100 nm and they were assumed to play a major role in adsorption.
CDCM effectively adsorbed 2.78 g g−1 of methyl blue. Kinetic model
was well fitted with pseudo–second–order and rate limiting step
was owed to chemisorption, high specific surface area as well as
absence of internal diffusion resistance. Desorption using NaOH in
ethanol was carried out. Adsorption was 90% when repeated the
fourth time. This shows that the sorbent is recyclable (Fan et al.,
2012).
Continuation of this work included the evaluation of the load-
ing of methyl blue dye over magnetic ␤–cyclodextrin–chitosan
supported on graphene oxide (MCCG) and comparison with that
of bare ␤–cyclodextrin–chitosan. Owing to the huge surface
area of GO, hydrophobicity of ␤–cyclodextrin, and the plentiful
hydroxyl and amino functional groups of chitosan, MCCG exhib-
ited better dye uptake than ␤–Cyclodextrin–chitosan. Adsorption
capacity of MCCG was 84.3 mg g−1 while ␤–Cyclodextrin–chitosan
removed 50.1 mg g−1 of methylene blue. Kinetics of adsorption
was best correlated to pseudo–second–order kinetics model. The
recorded saturation magnetization of the MCCG composite was
55.13 emu g−1 which meant that MCCG composite possessed a
large magnetism. Composite also demonstrated good cyclic stabil-
ity up to 5 cycles (Fan, Luo, Sun, Qiu, & Li, 2013).
5.2.2. Chitosan–hydroxyapatite nanocomposites
Hydroxyapatite materials are reported to be prospective
materials for defluoridation application. However, they can-
not be used in powdered form on fixed bed columns or
any other flow–through systems as this can result in exces-
sive pressure drops. Bio–inorganic composites composed of
nano–hydroxyapatite (n–HAp) with chitin and chitosan are
of interest in heavy metals adsorption. The introduction of
n–HAp into the biopolymeric matrix renders mechanical strength
improvement and provides stability to the polymer. The chitin–
and chitosan–based nHAp–modified nanocomposites were tested
for Cr(VI) adsorption in one of the studies. Equilibrium adsorption
experiments showed that n–HAp/chitin and n–HAp/chitosan
composites took up 284.5 and 345.0 mg g−1 of Cr(VI) ions, respec-
tively. Sorption process agreed both Freundlich and Langmuir
models (Kousalya, Rajiv Gandhi, & Meenakshi, 2010). The same
composite materials were utilized for removal of Cu(II) in another
study. About 26.1 and 21.5 mg g−1 of Cu2+ ions were captured
by n–HAp/chitosan and n–HAp/chitin respectively with a min-
imum contact time of 30 min at pH 6 (Gandhi, Kousalya, &
Meenakshi, 2011). These sorbents were also found effective in the
removal of Cd(II) ions. n–HAp/chitin could remove 92.6 mg g−1
while n–HAp/chitosan could sorb 123.5 mg g−1 Cd(II) (Salah,
Mohammad, Hassan, & El-Anadouli, 2014). Aliabadi et al. (2013)
used electrospun n–Hap/chitosan membrane for the removal
of Ni2+ , Pb2+ and Co2+ . The composite membrane accomplished
the removal of Ni2+ , Pb2+ and Co2+ by adsorbing 56.1, 71.8 and
66.2 mg g−1 respectively (Aliabadi et al., 2014).
The potential of nanohydroxyapatite/chitosan composite was
investigated for adsorptive uptake of congo red (CR) dye. The
composite was noted to have uniform dispersion of nanohydrox-
yapatite in the composite matrix. Electrostatic interaction between
chitosan and CR is only the major pathway of adsorption. The
nanocomposite adsorbed 769.0 mg g−1 of CR dye which is higher
than that observed for commercial activated carbon (Hou, Zhou,
Wu, & Wu, 2012).
5.2.3. Chitosan–montmorillonite nanocomposites
Chitosan nanocomposites based on montmorillonite
(CTS/MMT) have been investigated for the removal of congo red
(CR) dye in a series of studies. In the first of the studies, sorption
behavior of CTS/MMT was compared with that of plain chitosan
(CTS) or montmorillonite (MMT). Results showed that CTS/MMT
nanocomposite exhibited better adsorption capacity than the aver-
age values of that of CTS and MMT at any pH. The two plausible
pathways of CR removal are: (a) Ionic attraction between proto-
nated amino groups of chitosan and anionic dye, (b) chemisorption
of CR by CTS/MMT composite. Kinetic study described the depen-
dence of rate of adsorption of CR dye upon the concentration of dye
at the surface of the absorbent and the absorbance of CR adsorbed
at equilibrium. Thus, adsorption was a pseudo–second–order
reaction. Langmuir model was the best fit (Wang & Wang, 2007a).
Improvement to this study was made in an investigation of
chitosan/organo–montmorillonite nanocomposites (CTS/OMMT)
for adsorption of congo red. The nanostructured exfoliated
nanocomposite was able to achieve an uptake of 290.8 mg g−1
which was greater than that of organo–montmorillonite
(CTS/OMMT) which was equal to 192.4 mg g−1 . Mechanism
was found to be due to chemisorption (Wang & Wang, 2007b).
Another approach combined N,O–carboxymethyl–chitosan (CMC)
with montmorillonite for adsorption of congo red. The avail-
ability of amine (–NH2 ) groups, hydroxyl (–OH) and carboxyl
(–COOH) in CMC favor higher adsorption and flocculation of
dye molecules. Montmorillonite shows large surface area and
superior cation exchange capacity. Thus the composite formed
was effective in adsorbing 74.2 mg g−1 of CR (Wang & Wang,
2008). Kinetic and isotherm studies made on all of these chi-
tosan/montmorillonite nanocomposites were concluded to follow
pseudo–second–order model and the Langmuir model as they
stated adsorption equilibrium of CR on nanocomposites efficiently.
5.2.4. Cellulose–carbon nanotube composites
Cellulose–CNT composites produced by covalently grafting
CNTs onto the cellulose are considered for water treatment because
of the potential intrinsic characteristics of the individual moieties
as well as the formed composite. In a novel approach, multiwalled
carbon nanotubes were combined with chitosan and used for heavy
metals sorption. The metal ions studied were Cd2+ , Cu2+ , Zn2+ ,
and Ni2+ . The sorbent removed the metals efficiently (Salam et al.,
2011).
Multiwalled carbon nanotubes immobilized chitosan hydrogen
beads were subjected to congo red (CR) dye removal. Only 0.01 wt.%
CNT impregnation on chitosan could bring about removal capacity
of 450.4 mg g−1 for CR. Equilibrium isotherm data obeyed Langmuir
model better than Freundlich or Sips model (Chatterjee, Lee, & Woo,
2010).
A nanocomposite based on multi–walled carbon nanotube
(MWCNT) modified with chitosan (CS) and poly–2–hydroxyethyl
methacrylate (pHEMA) was tested for methyl orange adsorp-
tion. The grafting of MWCNT in chitosan helped improve
adsorption capacity and mechanical strength of the compos-
ite formed. The nanocomposite had 35–40 nm of thickness. It
adsorbed 416.7 mg g−1 (Langmuir adsorption) of methyl orange
 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618 611

Fig. 7. Synthesis route of CDCM and their application for removal of MB with the help of an external magnetic field.
Reproduced with permission from (Fan et al., 2012).

Fig. 8. Adsorption schematic diagram of MO on pHEMA–CS-f-MWCNTs.

Reproduced with permission from (Mahmoodian et al., 2015).

(Mahmoodian et al., 2015). The schematic of dye removal by the hydroxyl groups) (3) high chemical reactivity of these groups and
CS–pHEMA–MWCNT composite is depicted in Fig. 8. (4) flexible structure of the polymer linkage (Peng et al., 2010).
Ionic gelation of high–molecular chitosan and poly(acrylic acid)
was employed to obtain chitosan nanoparticles with sizes rang-
ing from 100 to 195 nm and product nanoparticles were tested for
5.2.5. Miscellaneous chitosan nano–composites
adsorption of Ni(II). The adsorbent removed 435 mg g−1 of Ni(II)
Peng et al. (2010) described the biosorption of Cu2+ by grafting
(Wang & Kuo, 2008).
Saccharomyces cerevisiae biomass on chitosan–coated magnetic
Another study used poly ethylene oxide (PEO)/Chitosan
nanoparticles surface (SICCM). Equilibrium adsorption studies indi-
nanofiber membrane for the sorption of Cu2+ , Ni2+ , Cd2+ , and
cated that Cu(II) adsorption data complied with Langmuir equation
Pb2+ . Selectivity of adsorption was seen to follow the order:
and measured maximum adsorption capacity was 144.9 mg g−1 .
Pb2+ < Cd2+ < Cu2+ < Ni2+ . The kinetic studies showed that adsorp-
Sorbent showed removal efficacy of 96.8% for initial metal concen-
tion was corroborated with both the pseudo–first–order and
tration of 60 ppm at a pH of 4.5. The reasons for such a superior
pseudo–second–order kinetic models (Aliabadi, Irani, Ismaeili, Piri,
adsorption behavior were attributed to (1) large hydrophilicity as a
& Parnian, 2013). The adsorption capacities of various chitosan
result of high number of hydroxyl groups of glucose units, (2) Avail-
nanoparticles/composites for heavy metal ions and dyes are pro-
ability of a number of functional groups (acetamido, primary amino
vided in Table 2.
which help adsorb heavy metals in wastewater treatment and/or
612 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618

Table 2
Adsorption capacities of various chitosan nanoparticles/composites for heavy metal ions and dyes.

Chitosan nanoparticles/composites Metal ion Adsorption Capacity References

Mono–disperse chitosan–bound Fe3 O4 magnetic nanoparticles Cu(II) 21.5 mg g−1 Chang and Chen (2005)
Mono–disperse chitosan–bound Fe3 O4 magnetic nanoparticles Co(II) 27.5 mg g−1 Chang et al. (2006)
Chitosan–magnetite nanocomposites Fe(III) 36.0 mg g−1 Namdeo and Bajpai (2008)
Chitosan–magnetite nanocomposites Cu(II) 35.5 mg g−1 Yuwei and Jianlong (2011)
␣–ketoglutaric acid modified chitosan–coated magnetic nanoparticles Cu(II) 96.2 mg g−1 Zhou et al. (2009)
Saccharomyces cerevisiae immobilized chitosan–coated magnetic nanoparticles Cu(II) 144.9 mg g−1 Peng et al. (2010)
Ethylenediamine–modified magnetic chitosan nanoparticles Pt(IV) 171.0 mg g−1 Zhou, Xu, Liang and Liu (2010)
Ethylenediamine–modified magnetic chitosan nanoparticles Pb(II) 138.0 mg g−1 Zhou et al. (2010)
Thiourea–modified magnetic ion–imprinted chitosan/TiO2 composite Cd(II) 256.4 mg g−1 Chen et al. (2012)
Chitosan/poly(acrylic acid) magnetic composite microspheres Cu(II) 174.0 mg g−1 Yan et al. (2012)
Composite chitosan–magnetite microparticles Co(II) 588.2 mg g−1 Hritcu, Dodi and Popa (2012)
Composite chitosan–magnetite microparticles Ni(II) 833.3 mg g−1 Hritcu et al. (2012)
Graphene oxide functionalized magnetic cyclodextrin–chitosan Cr(VI) 67.7 mg g−1 Li et al. (2013)
Nano–hydroxyapatite modified chitin Cr(VI) 284.5 mg g−1 Kousalya et al. (2010)
Nano–hydroxyapatite modified chitosan Cr(VI) 345.0 mg g−1 Kousalya et al. (2010)
Electrospun n–HAp/chitosan membrane Pb(II) 71.8 mg g−1 Aliabadi et al. (2014)
Electrospun n–HAp/chitosan membrane Co(II) 66.2 mg g−1 Aliabadi et al. (2014)
Electrospun n–HAp/chitosan membrane Ni(II) 65.7 mg g−1 Aliabadi et al. (2014)
Nano–hydroxyapatite modified chitin Cd(II) 92.6 mg g−1 Salah et al. (2014)
Nano–hydroxyapatite modified chitosan Cd(II) 123.5 mg g−1 Salah et al. (2014)
Chitosan nanoparticles Pb(II) 398.0 mg g−1 Qi and Xu (2004)
Chitosan nanorods Cr(VI) 323.6 mg g−1 Sivakami et al. (2013)
Nanochitosan Cd(II) 358.0 mg g−1 Seyedi et al. (2013)
Electrospun chitosan nanofibers Cu(II) 485.4 mg g−1 Haider and Park (2009)
Electrospun chitosan nanofibers Pb(II) 263.2 mg g−1 Haider and Park (2009)
Poly ethylene oxide (PEO)/Chitosan nanofiber membrane Ni(II) 175.1 mg g−1 Aliabadi et al. (2013)
Poly ethylene oxide (PEO)/Chitosan nanofiber membrane Cu(II) 163.7 mg g−1 Aliabadi et al. (2013)
Poly ethylene oxide (PEO)/Chitosan nanofiber membrane Cd(II) 143.8 mg g−1 Aliabadi et al. (2013)
Poly ethylene oxide (PEO)/Chitosan nanofiber membrane Pb(II) 135.4 mg g−1 Aliabadi et al. (2013)
Chitosan–poly(acrylic acid) nanopartices Ni(II) 435 mg g−1 Wang and Kuo (2008)
Chitosan/organoclay bionanocomposites Cr(VI) 357.14 mg g−1 Pandey and Mishra (2011)

Chitosan nanoparticles/composites Dye Adsorption Capacity References

Chitosan nanoparticles Acid Orange 10 1.77 mmol l−1 Cheung et al. (2009)
Chitosan nanoparticles Acid Orange 12 4.33 mmol l−1 Cheung et al. (2009)
Chitosan nanoparticles Acid Red 18 1.37 mmol l−1 Cheung et al. (2009)
Chitosan nanoparticles Acid Red 73 2.13 mmol l−1 Cheung et al. (2009)
1:10 magnetic ␥–Fe2 O3 /crosslinked chitosan composite Methyl Orange 29.50 mg g−1 Zhua et al. (2010)
Ethylenediamine–modified magnetic chitosan nanoparticles Acid Orange 7 1215.0 mg g−1 Zhou et al. (2011)
Ethylenediamine–modified magnetic chitosan nanoparticles Acid Orange 10 1017.0 mg g−1 Zhou et al. (2011)
Magnetic chitosan–Fe(III) hydrogel C. I. Acid Red 73 294.5 mg g−1 Shen et al. (2011)
␤–cyclodextrin–chitosan modified Fe3 O4 nanoparticles Methyl Blue 2780.0 mg g−11 Fan et al., (2012)
Chitosan/organo-montmorillonite nanocomposites Congo Red 290.8 mg g−1 Wang and Wang (2007b)
N,O–carboxymethyl–chitosan/montmorillonite nanocomposite Congo Red 74.2 mg g−1 Wang and Wang (2008)
Chitosan nanoparticles Eosin Y 3333.0 mg g−1 Du et al. (2008)
Chitosan hydrogel beads/multiwalled carbon nanotubes Congo Red 450.4 mg g−1 Chatterjee et al. (2010)
Chitosan nanodispersion C. I. Reactive Red 910.0 mg g−1 Momenzadeh et al. (2011)
120 (RR120)
Hydroxyapatite/chitosan nanocomposite Congo Red 769.0 mg g−1 Hou et al. (2012)
Poly HEMA–chitosan–MWCNT nanocomposite Methyl Orange 416.7 mg g−1 Mahmoodian et al. (2015)
Zinc oxide nanoparticles/chitosan Direct Blue 78 34.5 mg g−1 Salehi et al. (2010)
Zinc oxide nanoparticles/chitosan Acid Black 26 52.6 mg g−1 Salehi et al. (2010)

6. Mechanisms of adsorption Mechanistic investigations of heavy metals sorption on suc-

6.1. Nanocellulose with heavy metals
The possible mechanism of removal of heavy metals from
aqueous solutions by nanocelluloses can occur through a process
involving a solid phase (nanocellulose) and a liquid phase (sol-
vent) consisting of dissolved heavy metal species to be sorbed.
Nanocellulose can take up the metal ions by pathways involving
chemical adsorption, complexation reaction, adsorption on surface
and pores, ion exchange, chelation, adsorption by physical forces,
entrapment in inter and intrafibrillar capillaries and spaces of the
structural nanocellulose framework due to concentration gradi-
ent and diffusion through cell wall and membrane (Basso, Cerrella,
& Cukierman, 2002; Qaiser, Saleemi, & Mahmood Ahmad, 2007;
Sarkanen & Ludwig, 1971; Sud, Mahajan, & Kaur, 2008). Fig. 9 pro-
vides a representation of possible adsorption mechanisms.
cinic acid modified cellulose nanocrystals (SCNCs) show that
adsorption mechanism takes place by complexation whereas their
sodic counterparts (NaSCNCs) follow ion–exchange mechanism
(Yu, Tong, Ge, Wu et al., 2013). Sulfonated wheat pulp nanocel-
luloses have been confirmed to exhibit either of complexation or
ion–exchange mechanism for the removal lead ions (Suopajärvi,
Liimatainen, Karjalainen, Upola, & Niinimäki, 2015). The predom-
inating adsorption mechanism in succinic anhydride modified
mercerized nanocellulose happens through chemisorption of the
adsorbent with ester functions including hydroxyl ions or sodium
ions as functional groups (Hokkanen et al., 2013). A mixed mech-
anism of complex formation/anion is observed for the uptake
of Hg(II) by magnetic nanocellulose hybrid (Donia et al., 2012).
Nanocelluloses modified with carbonated hydroxyapatite exhibit
ion exchange involving exchange of OH− ions as the best fea-
sible pathway of sorption (Hokkanen, Repo, Westholm et al.,
 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618
Fig. 9. Plausible mechanism of biosorption.
Reproduced with permission (Sud et al., 2008).
2014). Nanocellulosic fibers exhibit a mechanism which includes
the interaction of their COO− functional groups with metal ions
(Kardam, Rohit et al., 2012). Aminopropyltriethoxysilane–modified
cellulose nanoparticles show a mechanism dependent on interac-
tion between amino and/or hydroxyl groups with heavy metals
(Hokkanen, 2014).
6.2. Nanocellulose with dyes
Karim et al. (2014) explained the binding of Rhodamine dyes
with nanocellulose crystals on the basis of hydrogen bonding and
electrostatic attraction. They proposed that nanocelluloses with
high negative charges formed a stable bond with dyes with positive
charges. Fig. 10 represents the mechanism of electrostatic inter-
action between dyes and cellulose–O− on the membrane surface
(Karim, Mathew, Grahn, Mouzon, & Oksman, 2014).
6.3. Nanochitosan with heavy metals
Mechanism of removal of heavy metal ions by nanochitosan
usually happens by electrostatic interaction, ion–exchange, metal
chelation and formation of ion–pairs (Bhatnagar & Sillanpää, 2009).
Graphene oxide–based magnetic cyclodextrin–chitosan nanocom-
posite showed adsorption mechanism based on either electrostatic
interaction between negatively charged HCrO− 4 with protonated
ammonium (R − NH+ 3
) ion or CCGO OH+ 2 , or redox reaction which
includes the reduction of Cr6+ to Cr3+ ions (Li et al., 2013). The
mechanism of adsorption is represented in Fig. 11.
Pb(II) uptake mechanism by magnetic chitosan nanocompos-
ites showed that NH2 and OH groups played prominent role
(Liu et al., 2008). Studies of Cu(II) removal employing the magnetic
nanoparticles of chitosan indicated that NH2 and OH functional
613
groups of chitosan played important role in adsorbing Cu(II) (Yuwei
& Jianlong, 2011). Another study on nanochitosan–chromium(VI)
interactions pointed out to electrostatic attraction between oppo-
sitely charged ions as the responsible mechanism (Sivakami
et al., 2013). Chitin/chitosan nano–hydroxyapatite composite could
remove Cu(II) by ion–exchange mechanism (Gandhi et al., 2011).
6.3. Nanochitosan with dyes
Dye removal mechanism of nanochitosan can occur due to
a variety of processes such as chemical bonding, ion–exchange,
hydrogen bonds, hydrophobic attractions, van der Waals force,
physical adsorption, aggregation mechanisms, dye interactions
etc., which can take place simultaneously (Crini & Badot, 2008).
Adsorption mechanism of acid dyes with nano–sized chitosan as
well as modified nanochiosan materials was found to be because of
the electrostatic interaction between negatively charged dye ions
and protonated amino groups of chitosan (Cheung et al., 2009; Zhou
et al., 2011). The proposed mechanism of adsorption follows the
following steps:
The first step involves the dissolution of acid dye in aqueous
solution and dissociation of its sulfonate groups (D–SO3 Na) and
the conversion to anionic dye ions as shown:
D − SO3 Na → D − SO3− + Na+
Simultaneously, protonation of amino groups of chitosan takes
place as represented by the equation:
R − NH2 + H+ ↔ R − NH+
3
614 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618

CH3
H3C CH3
O +Cl -
H3C
N NH2
N O NH2+Cl-

Electrostatic
attraction

hydrogen bonding

OH HO
OH HO OH
OH
O
O O
O O O
O SO3-
O OH
OH
OH OH
OH OH

Surface of hybrid membrane Surface of hybrid membrane

a) b)
Fig. 10. A schematic representaion of the mechanisms of binding of the dyes with CNCs via (a) hydrogen bond formation and (b) electrostatic attraction.
Reproduced with permission from (Karim et al., 2014).

Fig. 11. Proposed mechanism of Cr(VI) removal by CCGO.

Reproduced with permission from (Li et al., 2013).

Finally what follows is the ionic interaction between the oppo- hydrogel by the sulphonate groups of the dye resulting in chelat-
sitely charged moieties in solution ing action of between the dye and Fe(III) center. The mechanism of
uptake of C. I. Acid Red 73 by magnetic chitosan nanocomposite is
R − NH+
3
+ D − SO3− ↔ R − NH3 . . .O3 S − D shown in Fig. 12.
Surface complexation, ion exchange and hydrogen bonding
When dyes are to be adsorbed from alkaline effluent, the
mechanisms were assumed to contribute in the case of hydrox-
adsorption mechanism involves chelating interactions rather than
yapatite/chitosan nanocomposite employed for congo red dye
electrostatic interactions as demonstrated by Shen et al. (2011) in
adsorption (Hou et al., 2012). Chitosan/montmorillonite nanocom-
the study of removal of C.I. Acid Red 73 by magnetic chitosan–Fe(III)
posite was thought to interact with congo red dye either through
hydrogel. As protonation of amino groups is suppressed at alkaline
ionic interaction between positive groups of nanocomposite and
pH, the dominating pathway includes the replacement of water
anionic dye, or through chemisorption between nanocomposite
molecules co–ordinated to Fe(III) center in the chitosan–Fe(III)
 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618
Fig. 12. Proposed interactions mode between dyes and chitosan–Fe(III) hydrogel.
Reproduced with permission from (Shen et al., 2011).
and dye. Pathway for adsorption behavior of nanochitosan on
acid green 27 was a similar one (Hu et al., 2006; Wang & Wang,
2007a).
7. Relevance of nanocellulose and nanochitosan
adsorbents in current scenario
Wastewater purification using cellulose– and chitosan–based
nano–sized adsorbents is thought of as an alternate technology
for the energy–intensive and expensive activated carbon–based
adsorption. As chitosan and cellulose as such do not exhibit
fair adsorption performance (Abdelmouleh et al., 2004; Vismara,
Melone, Gastaldi, Cosentino, & Torri, 2009), they need to be tai-
lored suitably to obtain a positive outcome. Synthesizing them
in nano–size and modifying with physical or chemical means
will serve to enhance the adsorption capacities to great extent.
Nano–sized cellulose– and chitosan–based materials are viewed as
a potential solution to the wastewater treatment problem. In con-
trast to the traditional submicron and micron–sized cellulose and
chitosan materials having severe limitations with regard to adsorp-
tion behavior, nano–sized counterparts are able to offer attractive
properties such as smaller size, higher porosities leading to larger
surface area and lack of internal diffusion and quantum size effects
(Chang et al., 2006; Lam, Male, Chong, Leung, & Luong, 2012; Li et al.,
2012; Zhou et al., 2010). Formation of hybrids or nanocomposites
is useful to increase the cyclic stability of sorbent (Klemm, Philipp,
Heinze, Heinze, & Wagenknecht, 2004; Wang & Wang, 2007a).
Insertion of magnetic nanoparticles helps in easy separation of
nano–sized cellulose and chitosan sorbents (Li et al., 2011; Yang
et al., 2014; Yu, Tong, Ge, Zuo et al., 2013; Zhou et al., 2011). Heavy
metals as well as dyes adsorption by cellulose– and chitosan–based
nanoparticles/composites have been found to be remarkably higher
compared to the micron sized celluloses and chitosans respectively
(Fan et al., 2013; Hu et al., 2006; Jin, Li et al., 2015; Kardam et al.,
2014; Liu et al., 2013; Momenzadeh et al., 2011; Pei et al., 2013; Sun
et al., 2014). Overall, nano–sized cellulose and chitosan are highly
relevant for their usage in wastewater purification.
615
8. Conclusions and future perspectives
Cellulose and chitosan are known for their abundance, renew-
able nature, bio–degradability, versatility and ease of structural
modification. They are used as adsorbents for the removal of
dyes and heavy metals. However, their applications are limited
due to larger size, smaller internal porosities, lower surface area
and presence of internal diffusion. Thus, nano–sized cellulose and
chitosan become the materials of choice for wastewater treat-
ment as they present superior properties for adsorption. Novel
methods of syntheses combined with efficient functionalization
yield nano–adsorbents which are able to effectively take up con-
taminants from wastewater. At present, there is large scope
for evaluating the removal ability of nano–sorbents for a num-
ber of contaminants including specially dyes and heavy metal
ions. Cellulose– and chitosan–based nano–sorbents can be used
as replacement for conventional expensive active carbon–based
adsorption technology as well as toxic magnetic material–based
process. Commercialization of the nano–biopolymers is seen as the
next big step forward.
Conflict of interest
All the authors declare that there is no conflict of interest.
References
Abdelmouleh, M., Boufi, S., Belgacem, M., Duarte, A., Salah, A. B., & Gandini, A.
(2004). Modification of cellulosic fibres with functionalised silanes:
Development of surface properties. International Journal of Adhesion and
Adhesives, 24(1), 43–54.
Ahmad, M., Ahmed, S., Swami, B. L., & Ikram, S. (2015). Adsorption of heavy metal
ions: Role of chitosan and cellulose for water treatment. Langmuir, 79, 109–155.
Aliabadi, M., Irani, M., Ismaeili, J., Piri, H., & Parnian, M. J. (2013). Electrospun
nanofiber membrane of PEO/chitosan for the adsorption of nickel, cadmium:
Lead and copper ions from aqueous solution. Chemical Engineering Journal, 220,
237–243.
Aliabadi, M., Irani, M., Ismaeili, J., & Najafzadeh, S. (2014). Design and evaluation of
chitosan/hydroxyapatite composite nanofiber membrane for the removal of
heavy metal ions from aqueous solution. Journal of the Taiwan Institute of
Chemical Engineers, 45(2), 518–526.
616 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618
Anirudhan, T., & Shainy, F. (2015). Effective removal of mercury(II) ions from
chlor-alkali industrial wastewater using 2-mercaptobenzamide modified
itaconic acid-grafted-magnetite nanocellulose composite. Journal of Colloid and
Interface Science, 456, 22–31.
Anirudhan, T., Deepa, J., & Christa, J. (2016). Nanocellulose/nanobentonite
composite anchored with multi-carboxyl functional groups as an adsorbent for
the effective removal of Cobalt(II) from nuclear industry wastewater samples.
Journal of Colloid and Interface Science, 467, 307–320.
Atalla, R. H., & Vanderhart, D. L. (1989). Studies on the structure of cellulose using
Raman spectroscopy and solid state 13 C NMR. In C. Schuerch (Ed.), Cellulose and
wood: chemistry and technology proceedings of the tenth cellulose conference (pp.
169–187). New York: John Wiley and Sons.
Azizi Samir, M. A. S., Alloin, F., & Dufresne, A. (2005). Review of recent research into
cellulosic whiskers, their properties and their application in nanocomposite
field. Biomacromolecules, 6(2), 612–626.
Badawy, M. E., & Rabea, E. I. (2011). A biopolymer chitosan and its derivatives as
promising antimicrobial agents against plant pathogens and their applications
in crop protection. International Journal of Carbohydrate Chemistry, 2011.
Basso, M., Cerrella, E., & Cukierman, A. (2002). Lignocellulosic materials as
potential biosorbents of trace toxic metals from wastewater. Industrial &
Engineering Chemistry Research, 41(15), 3580–3585.
Bhatnagar, A., & Sillanpää, M. (2009). Applications of chitin-and
chitosan-derivatives for the detoxification of water and wastewater—a short
review. Advances in Colloid and Interface Science, 152(1), 26–38.
Blackwell, J. (1982). The macromolecular organization of cellulose and chitin. In
Cellulose and other natural polymer systems. pp. 403–428. Springer.
Brown, R. M. (2004). Cellulose structure and biosynthesis: What is in store for the
21 st century? Journal of Polymer Science Part A: Polymer Chemistry, 42(3),
487–495.
Carpenter, A. W., de Lannoy, C.-F., & Wiesner, M. R. (2015). Cellulose nanomaterials
in water treatment technologies. Environmental Science & Technology, 49(9),
5277–5287.
Cellulose. (2012). Cellulose and renewable materials division. A division of American
Chemical Society. http://cell.sites.acs.org/history.htm#cellulose (accessed
13.07.16)
Chang, Y.-C., & Chen, D.-H. (2005). Preparation and adsorption properties of
monodisperse chitosan-bound Fe3 O4 magnetic nanoparticles for removal of
Cu(II) ions. Journal of Colloid and Interface Science, 283(2), 446–451.
Chang, Y.-C., Chang, S.-W., & Chen, D.-H. (2006). Magnetic chitosan nanoparticles:
Studies on chitosan binding and adsorption of Co(II) ions. Reactive and
Functional Polymers, 66(3), 335–341.
Chatterjee, S., Lee, M. W., & Woo, S. H. (2010). Adsorption of congo red by chitosan
hydrogel beads impregnated with carbon nanotubes. Bioresource Technology,
101(6), 1800–1806.
Chen, X.-G., Lee, C. M., & Park, H.-J. (2003). O/W emulsification for the
self-aggregation and nanoparticle formation of linoleic acid modified chitosan
in the aqueous system. Journal of Agricultural and Food Chemistry, 51(10),
3135–3139.
Chen, A., Zeng, G., Chen, G., Hu, X., Yan, M., Guan, S., et al. (2012). Novel
thiourea-modified magnetic ion-imprinted chitosan/TiO2 composite for
simultaneous removal of cadmium and 2,4-dichlorophenol. Chemical
Engineering Journal, 191, 85–94.
Cherian, B. M., Leão, A. L., de Souza, S. F., Costa, L. M. M., de Olyveira, G. M.,
Kottaisamy, M., et al. (2011). Cellulose nanocomposites with nanofibres
isolated from pineapple leaf fibers for medical applications. Carbohydrate
Polymers, 86(4), 1790–1798.
Cheung, W., Szeto, Y., & McKay, G. (2009). Enhancing the adsorption capacities of
acid dyes by chitosan nano particles. Bioresource Technology, 100(3),
1143–1148.
Crawford, R. L. (1981). Lignin biodegradation and transformation. New York: Wiley.
Crini, G., & Badot, P.-M. (2008). Application of chitosan, a natural
aminopolysaccharide, for dye removal from aqueous solutions by adsorption
processes using batch studies: A review of recent literature. Progress in Polymer
Science, 33(4), 399–447.
Donia, A., Atia, A., & Abouzayed, F. (2012). Preparation and characterization of
nano-magnetic cellulose with fast kinetic properties towards the adsorption of
some metal ions. Chemical Engineering Journal, 191, 22–30.
Du, W. L., Xu, Z. R., Han, X. Y., Xu, Y. L., & Miao, Z. G. (2008). Preparation,
characterization and adsorption properties of chitosan nanoparticles for eosin
Y as a model anionic dye. Journal of Hazardous Materials, 153(1), 152–156.
Dufresne, A., Cavaillé, J. Y., & Helbert, W. (1997). Thermoplastic nanocomposites
filled with wheat straw cellulose whiskers. Part II: Effect of processing and
modeling. Polymer Composites, 18(2), 198–210.
Dufresne, A. (2000). Dynamic mechanical analysis of the interphase in bacterial
polyester/cellulose whiskers natural composites. Composite Interfaces, 7(1),
53–67.
Dyal, A., Loos, K., Noto, M., Chang, S. W., Spagnoli, C., Shafi, K. V., et al. (2003).
Activity of Candida rugosa lipase immobilized on ␥-Fe2 O3 magnetic
nanoparticles. Journal of the American Chemical Society, 125(7), 1684–1685.
Elwakeel, K. Z., Atia, A. A., & Donia, A. M. (2009). Removal of Mo(VI) as oxoanions
from aqueous solutions using chemically modified magnetic chitosan resins.
Hydrometallurgy, 97(1), 21–28.
Elwakeel, K. Z. (2010). Removal of Cr(VI) from alkaline aqueous solutions using
chemically modified magnetic chitosan resins. Desalination, 250(1), 105–112.
Fan, L., Zhang, Y., Luo, C., Lu, F., Qiu, H., & Sun, M. (2012). Synthesis and
characterization of magnetic ␤-cyclodextrin–chitosan nanoparticles as
nano-adsorbents for removal of methyl blue. International Journal of Biological
Macromolecules, 50(2), 444–450.
Fan, L., Luo, C., Sun, M., Qiu, H., & Li, X. (2013). Synthesis of magnetic
␤-cyclodextrin–chitosan/graphene oxide as nanoadsorbent and its application
in dye adsorption and removal. Colloids and Surfaces B: Biointerfaces, 103,
601–607.
Favier, V., Canova, G., Cavaillé, J., Chanzy, H., Dufresne, A., & Gauthier, C. (1995).
Nanocomposite materials from latex and cellulose whiskers. Polymers for
Advanced Technologies, 6(5), 351–355.
Fenichell, S. (1996). Plastic: the making of a synthetic century. Harper Business.
Fung, W.-Y., Yuen, K.-H., & Liong, M.-T. (2011). Agrowaste-based nanofibers as a
probiotic encapsulant: Fabrication and characterization. Journal of Agricultural
and Food Chemistry, 59(15), 8140–8147.
Güçlü, G., Gürdağ, G., & Özgümüş, S. (2003). Competitive removal of heavy metal
ions by cellulose graft copolymers. Journal of Applied Polymer Science, 90(8),
2034–2039.
Gandhi, M. R., Kousalya, G., & Meenakshi, S. (2011). Removal of copper(II) using
chitin/chitosan nano-hydroxyapatite composite. International Journal of
Biological Macromolecules, 48(1), 119–124.
Gautam, S., Bundela, P., Pandey, A., Awasthi, M., & Sarsaiya, S. (2010). A review on
systematic study of cellulose.
Ghosh, U., Heavy metal removal through (chitosan-ZnO) composite membrane
from waste water, Doctoral Dissertation 2014.
Giménez, J., Martínez, M., de Pablo, J., Rovira, M., & Duro, L. (2007). Arsenic
sorption onto natural hematite, magnetite, and goethite. Journal of Hazardous
Materials, 141(3), 575–580.
Gouda, M., Hebeish, A., & Al-Omair, M. (2014). Development of silver-containing
nanocellulosics for effective water disinfection. Cellulose, 21(3), 1965–1974.
Habibi, Y., & Lucia, L. A. (2012). Nanocelluloses: Emerging building blocks for
renewable materials. Polysaccharide building blocks: A sustainable approach to
the development of renewable biomaterials (105).
Habibi, Y., Lucia, L. A., & Rojas, O. J. (2010). Cellulose nanocrystals: Chemistry,
self-assembly, and applications. Chemical Reviews, 110(6), 3479–3500.
Haider, S., & Park, S.-Y. (2009). Preparation of the electrospun chitosan nanofibers
and their applications to the adsorption of Cu(II) and Pb(II) ions from an
aqueous solution. Journal of Membrane Science, 328(1), 90–96.
Harris, D.M., Molecular and chemical dissection of cellulose biosynthesis in plants,
Doctoral Dissertation 2011.
Hasani, M., Cranston, E. D., Westman, G., & Gray, D. G. (2008). Cationic surface
functionalization of cellulose nanocrystals. Soft Matter, 4(11), 2238–2244.
Helbert, W., Cavaille, J., & Dufresne, A. (1996). Thermoplastic nanocomposites filled
with wheat straw cellulose whiskers. Part I: Processing and mechanical
behavior. Polymer Composites, 17(4), 604–611.
Herrick, F. W., Casebier, R. L., Hamilton, J. K., & Sandberg, K. R. (1983).
Microfibrillated cellulose: Morphology and accessibility. Journal of Applied
Polymer Science. Applied Polymer Symposium (United States), 37. ITT Rayonier
Inc., Shelton, WA.
Hokkanen, S., Repo, E., & Sillanpää, M. (2013). Removal of heavy metals from
aqueous solutions by succinic anhydride modified mercerized nanocellulose.
Chemical Engineering Journal, 223, 40–47.
Hokkanen, S. (2014). Modified nano-and microcellulose based adsorption
materials in water treatment. Acta Universitatis Lappeenrantaensis.
Hokkanen, S., Repo, E., Suopajärvi, T., Liimatainen, H., Niinimaa, J., & Sillanpää, M.
(2014). Adsorption of Ni(II), Cu(II) and Cd(II) from aqueous solutions by amino
modified nanostructured microfibrillated cellulose. Cellulose, 21(3),
1471–1487.
Hokkanen, S., Repo, E., Westholm, L. J., Lou, S., Saino, T., & Sillanpää, M. (2014).
Adsorption of Ni2+ , Cd2+ , PO4 3− / and NO3 −/from aqueous solutions by
nanostructured microfibrillated cellulose modified with carbonated
hydroxyapatite. Chemical Engineering Journal, 252(September (15)), 64–74.
Hou, H., Zhou, R., Wu, P., & Wu, L. (2012). Removal of Congo red dye from aqueous
solution with hydroxyapatite/chitosan composite. Chemical Engineering
Journal, 211, 336–342.
Hritcu, D., Dodi, G., & Popa, M. I. (2012). Heavy metal ions adsorption on
chitosan-magnetite microspheres. International Review of Chemical Engineering,
4(3), 364–368.
Hu, Z., Zhang, J., Chan, W., & Szeto, Y. (2006). The sorption of acid dye onto chitosan
nanoparticles. Polymer, 47(16), 5838–5842.
Illani, M. A., & Nawi, M. (2010). Characterization and antimicrobial analysis of
chitosan composite biodegradable films with addition of lemon grass essential oil.
Pahang: Universiti Malaysia.
Jayakumar, R., Tamura, H., Prabaharan, M., Kumar, P. S., Nair, S., & Furuike, T.
(2011). Novel chitin and chitosan materials in wound dressing. INTECH Open
Access Publisher.
Jeuniaux, C. (1996). A brief survey of the early contribution of European scientists
to chitin knowledge. Advances in Chitin Sciences, 1–9.
Jin, L., Li, W., Xu, Q., & Sun, Q. (2015). Amino-functionalized nanocrystalline
cellulose as an adsorbent for anionic dyes. Cellulose, 1–14.
Jin, L., Sun, Q., Xu, Q., & Xu, Y. (2015). Adsorptive removal of anionic dyes from
aqueous solutions using microgel based on nanocellulose and polyvinylamine.
Bioresource Technology, 197, 348–355.
Kalia, S., & Avérous, L. (2011). Biopolymers: biomedical and environmental
applications. John Wiley & Sons.
Kamari, A., Ngah, W. W., Chong, M., & Cheah, M. (2009). Sorption of acid dyes onto
GLA and H2 SO4 cross-linked chitosan beads. Desalination, 249(3), 1180–1189.
 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618
Kamel, S., Ali, N., Jahangir, K., Shah, S., & El-Gendy, A. (2008). Pharmaceutical
significance of cellulose: A review. Express Polymer Letters, 2(11), 758–778.
Kana, M. T. A., Radi, M., & Elsabee, M. Z. (2013). Wastewater treatment with
chitosan nano-particles. International Journal of Nanotechnology and
Application, 3(2), 39–50.
Kardam, A., Raj, K. R., Srivastava, S., & Srivastava, M. (2014). Nanocellulose fibers
for biosorption of cadmium, nickel, and lead ions from aqueous solution. Clean
Technologies and Environmental Policy, 16(2), 385–393.
Kardam, A., Raj, K. R., Arora, J. K., & Srivastava, S. (2012). Artificial neural network
modeling for biosorption of Pb(II) ions on nanocellulose fibers. Bionanoscience,
2(3), 153–160.
Kardam, A., Rohit, R. K., & Srivastava, S. (2012). Novel nano cellulosic fibers for
remediation of heavy metals from synthetic water. International Journal of
Nano Dimension, 3(2), 155–162.
Karim, Z., Mathew, A. P., Grahn, M., Mouzon, J., & Oksman, K. (2014). Nanoporous
membranes with cellulose nanocrystals as functional entity in chitosan:
Removal of dyes from water. Carbohydrate Polymers, 112, 668–676.
Kauffman, G. B. (1993). Rayon: The first semi-synthetic fiber product. Journal of
Chemical Education, 70(11), 887.
Kavitha, K., Keerthi, T., & Mani, T. T. (2011). Chitosan polymer used as carrier in
various pharmaceutical formulations: Brief review. International Journal of
Applied Biology and Pharmaceutical Technology, 2, 249–258.
Kiessig, H. (1939). Untersuchungen über die Gitterstruktur der natürlichen
Cellulose. Zeitschrift für Physikalische Chemie B, 43, 79–102.
Klemm, D., Philipp, B., Heinze, T., Heinze, U., & Wagenknecht, W. (2004). General
considerations on structure and reactivity of cellulose: section 2. 1-2.1.4. Wiley
Online Library.
Klemm, D., Kramer, F., Moritz, S., Lindström, T., Ankerfors, M., Gray, D., et al. (2011).
Nanocelluloses: A new family of nature-based materials. Angewandte Chemie
International Edition, 50(24), 5438–5466.
Kloser, E., & Gray, D. G. (2010). Surface grafting of cellulose nanocrystals with
poly(ethylene oxide) in aqueous media. Langmuir, 26(16), 13450–13456.
Kobayashi, S., Kashiwa, K., Shimada, J., Kawasaki, T., & Shoda, S. i. (1992).
Enzymatic polymerization: The first in vitro synthesis of cellulose via
nonbiosynthetic path catalyzed by cellulase. In Makromolekulare chemie.
Macromolecular symposia. pp. 509–518. Wiley Online Library.
Koide, S. (1998). Chitin-chitosan: Properties, benefits and risks. Nutrition Research,
18(6), 1091–1101.
Kousalya, G., Rajiv Gandhi, M., & Meenakshi, S. (2010). Removal of toxic Cr(VI) ions
from aqueous solution using nano-hydroxyapatite-based chitin and chitosan
hybrid composites. Adsorption Science & Technology, 28(1), 49–64.
Kumar, M. N. R. (2000). A review of chitin and chitosan applications. Reactive and
Functional Polymers, 46(1), 1–27.
Kwok, K. C., Koong, L. F., Chen, G., & McKay, G. (2014). Mechanism of arsenic
removal using chitosan and nanochitosan. Journal of Colloid and Interface
Science, 416, 1–10.
Kyzas, G. Z., & Lazaridis, N. K. (2009). Reactive and basic dyes removal by sorption
onto chitosan derivatives. Journal of Colloid and Interface Science, 331(1), 32–39.
Lam, E., Male, K. B., Chong, J. H., Leung, A. C., & Luong, J. H. (2012). Applications of
functionalized and nanoparticle-modified nanocrystalline cellulose. Trends in
Biotechnology, 30(5), 283–290.
Li, Q., Mahendra, S., Lyon, D. Y., Brunet, L., Liga, M. V., Li, D., et al. (2008).
Antimicrobial nanomaterials for water disinfection and microbial control:
Potential applications and implications. Water Research, 42(18), 4591–4602.
Li, H., Bi, S., Liu, L., Dong, W., & Wang, X. (2011). Separation and accumulation of
Cu(II), Zn(II) and Cr(VI) from aqueous solution by magnetic chitosan modified
with diethylenetriamine. Desalination, 278(1), 397–404.
Li, X., Wang, Y., Yang, X., Chen, J., Fu, H., & Cheng, T. (2012). Conducting polymers in
environmental analysis. TrAC Trends in Analytical Chemistry, 39, 163–179.
Li, L., Fan, L., Sun, M., Qiu, H., Li, X., Duan, H., et al. (2013). Adsorbent for chromium
removal based on graphene oxide functionalized with magnetic
cyclodextrin–chitosan. Colloids and Surfaces B: Biointerfaces, 107, 76–83.
Liu, C.-G., Chen, X.-G., & Park, H.-J. (2005). Self-assembled nanoparticles based on
linoleic-acid modified chitosan: Stability and adsorption of trypsin.
Carbohydrate Polymers, 62(3), 293–298.
Liu, X., Hu, Q., Fang, Z., Zhang, X., & Zhang, B. (2008). Magnetic chitosan
nanocomposites: A useful recyclable tool for heavy metal ion removal.
Langmuir, 25(1), 3–8.
Liu, B., Wang, D., Yu, G., & Meng, X. (2013). Adsorption of heavy metal ions, dyes
and proteins by chitosan composites and derivatives—A review. Journal of
Ocean University of China, 12(3), 500–508.
Liu, P., Borrell, P. F., Božič, M., Kokol, V., Oksman, K., & Mathew, A. P. (2015).
Nanocelluloses and their phosphorylated derivatives for selective adsorption
of Ag+ , Cu2+ and Fe3+ from industrial effluents. Journal of Hazardous Materials,
294, 177–185.
Liu, P., Nanopolysaccharides for adsorption of heavy metal ions from water,
Licentiate Thesis 2014.
Lucia, L. A., & Rojas, O. (2009). The nanoscience and technology of renewable
biomaterials. John Wiley & Sons.
Luo, X., & Zhang, L. (2009). High effective adsorption of organic dyes on magnetic
cellulose beads entrapping activated carbon. Journal of Hazardous Materials,
171(1), 340–347.
Luther, S., Borgfeld, N., Kim, J., & Parsons, J. (2012). Removal of arsenic from
aqueous solution: A study of the effects of pH and interfering ions using iron
oxide nanomaterials. Microchemical Journal, 101, 30–36.
617
Ma, H., Hsiao, B. S., & Chu, B. (2011). Ultrafine cellulose nanofibers as efficient
adsorbents for removal of UO/in water. ACS Macro Letters, 1(1), 213–216.
Mahgoub, S., & Samaras, P. (2014). Nanoparticles from biowastes and microbes:
focus on role in water purification and food preservation. 2nd International
Conference on Sustainable Solid Waste Management.
Mahmoodian, H., Moradi, O., Shariatzadeha, B., Salehf, T. A., Tyagi, I., Maity, A., et al.
(2015). Enhanced removal of methyl orange from aqueous solutions by poly
HEMA–chitosan-MWCNT nano-composite. Journal of Molecular Liquids, 202,
189–198.
Man, Z., Muhammad, N., Sarwono, A., Bustam, M. A., Kumar, M. V., & Rafiq, S.
(2011). Preparation of cellulose nanocrystals using an ionic liquid. Journal of
Polymers and the Environment, 19(3), 726–731.
Marchessault, R., & Sarko, A. (1967). X-ray structure of polysaccharides. Advances
in Carbohydrate Chemistry, 22, 421–482.
Matos Ruiz, M., Cavaille, J., Dufresne, A., Gerard, J., & Graillat, C. (2000). Processing
and characterization of new thermoset nanocomposites based on cellulose
whiskers. Composite Interfaces, 7(2), 117–131.
Mckay, G., Blair, H., & Gardner, J. (1984). The adsorption of dyes onto chitin in fixed
bed columns and batch adsorbers. Journal of Applied Polymer Science, 29(5),
1499–1514.
Mikkonen, K. S., Mathew, A. P., Pirkkalainen, K., Serimaa, R., Xu, C., Willför, S., et al.
(2010). Glucomannan composite films with cellulose nanowhiskers. Cellulose,
17(1), 69–81.
Momenzadeh, H., Tehrani-Bagha, A. R., Khosravi, A., Gharanjig, K., & Holmberg, K.
(2011). Reactive dye removal from wastewater using a chitosan
nanodispersion. Desalination, 271(1), 225–230.
Moon, R. J., Martini, A., Nairn, J., Simonsen, J., & Youngblood, J. (2011). Cellulose
nanomaterials review: Structure, properties and nanocomposites. Chemical
Society Reviews, 40(7), 3941–3994.
Muzzarelli, R., Muzzarelli, C., Phillips, G., & Williams, P. (2009). Chitin and chitosan
hydrogels. Handbook of Hydrocolloids, 849–888.
Muzzarelli, R. (2012). Nanochitins and nanochitosans: Paving the way to
eco-friendly and energy-saving exploitation of marine resources. Polymer
Science: A Comprehensive Reference, 10, 153–164.
Namdeo, M., & Bajpai, S. (2008). Chitosan–magnetite nanocomposites (CMNs) as
magnetic carrier particles for removal of Fe(III) from aqueous solutions. Colloids
and Surfaces A: Physicochemical and Engineering Aspects, 320(1), 161–168.
Nata, I. F., Sureshkumar, M., & Lee, C.-K. (2011). One-pot preparation of amine-rich
magnetite/bacterial cellulose nanocomposite and its application for arsenate
removal. RSC Advances, 1(4), 625–631.
No, H. K., & Meyers, S. P. (2000). Application of chitosan for treatment of
wastewaters. In Reviews of environmental contamination and toxicology. pp.
1–27. Springer.
O’Connell, D. W., Birkinshaw, C., & O’Dwyer, T. F. (2008). Heavy metal adsorbents
prepared from the modification of cellulose: A review. Bioresource Technology,
99(15), 6709–6724.
Oksman, K., Mathew, A., Bondeson, D., & Kvien, I. (2006). Manufacturing process of
cellulose whiskers/polylactic acid nanocomposites. Composites Science and
Technology, 66(15), 2776–2784.
Omer, M. I., Elbadawi, A., & Yassin, O. (2013). Synthesis and structural properties of
MgFe2 O4 ferrite nano-particles. Journal of Applied and Industrial Sciences, 1,
20–23.
Onsosyen, E., & Skaugrud, O. (1990). Metal recovery using chitosan. Journal of
Chemical Technology and Biotechnology, 49(4), 395–404.
Pääkkö, M., Ankerfors, M., Kosonen, H., Nykänen, A., Ahola, S., Österberg, M., et al.
(2007). Enzymatic hydrolysis combined with mechanical shearing and
high-pressure homogenization for nanoscale cellulose fibrils and strong gels.
Biomacromolecules, 8(6), 1934–1941.
Pandey, S., & Mishra, S. B. (2011). Organic–inorganic hybrid of chitosan/organoclay
bionanocomposites for hexavalent chromium uptake. Journal of Colloid and
Interface Science, 361(2), 509–520.
Payen, A. (1838). Memoir on the composition of the tissue of plants and of woody
material. Comptes Rendus Biologies, 7, 1052–1056.
Pei, A., Butchosa, N., Berglund, L. A., & Zhou, Q. (2013). Surface quaternized
cellulose nanofibrils with high water absorbency and adsorption capacity for
anionic dyes. Soft Matter, 9(6), 2047–2055.
Peng, Q., Liu, Y., Zeng, G., Xu, W., Yang, C., & Zhang, J. (2010). Biosorption of
copper(II) by immobilizing Saccharomyces cerevisiae on the surface of
chitosan-coated magnetic nanoparticles from aqueous solution. Journal of
Hazardous Materials, 177(1), 676–682.
Perera, U., & Rajapakse, N. (2014). Chitosan nanoparticles: Preparation,
characterization, and applications. In Seafood processing by-products. pp.
371–387. Springer.
Qaiser, S., Saleemi, A. R., & Mahmood Ahmad, M. (2007). Heavy metal uptake by
agro based waste materials. Electronic Journal of Biotechnology, 10(3), 409–416.
Qi, L., & Xu, Z. (2004). Lead sorption from aqueous solutions on chitosan
nanoparticles. Colloids and Surfaces A: Physicochemical and Engineering Aspects,
251(1), 183–190.
Rajalakshmi, R., Aruna, U., Vinesha, V., & Rupangada, V. (2014). Chitosan
nanoparticles—An emerging trend in nanotechnology. International Journal of
Drug Delivery, 6(3), 204–229.
Rajawat, D. S., Kardam, A., Srivastava, S., & Satsangee, S. P. (2013). Nanocellulosic
fiber-modified carbon paste electrode for ultra trace determination of Cd(II)
and Pb(II) in aqueous solution. Environmental Science and Pollution Research,
20(5), 3068–3076.
618 S. Olivera et al. / Carbohydrate Polymers 153 (2016) 600–618
Ren, Y., Zhang, M., & Zhao, D. (2008). Synthesis and properties of magnetic Cu(II)
ion imprinted composite adsorbent for selective removal of copper.
Desalination, 228(1), 135–149.
Rodney, C. (2004). Scientific American inventions and discoveries. New Jersey: John
Wiley & Sons Inc.
Roy, D., Semsarilar, M., Guthrie, J. T., & Perrier, S. (2009). Cellulose modification by
polymer grafting: A review. Chemical Society Reviews, 38(7), 2046–2064.
Saito, T., Kimura, S., Nishiyama, Y., & Isogai, A. (2007). Cellulose nanofibers
prepared by TEMPO-mediated oxidation of native cellulose.
Biomacromolecules, 8(8), 2485–2491.
Salah, T. A., Mohammad, A. M., Hassan, M. A., & El-Anadouli, B. E. (2014).
Development of nano-hydroxyapatite/chitosan composite for cadmium ions
removal in wastewater treatment. Journal of the Taiwan Institute of Chemical
Engineers, 45(4), 1571–1577.
Salam, M. A., Makki, M. S., & Abdelaal, M. Y. (2011). Preparation and
characterization of multi-walled carbon nanotubes/chitosan nanocomposite
and its application for the removal of heavy metals from aqueous solution.
Journal of Alloys and Compounds, 509(5), 2582–2587.
Salehi, R., Arami, M., Mahmoodi, N. M., Bahrami, H., & Khorramfar, S. (2010). Novel
biocompatible composite (chitosan-zinc oxide nanoparticle): Preparation,
characterization and dye adsorption properties. Colloids and Surfaces B:
Biointerfaces, 80(1), 86–93.
Sandeep, A., Sangameshwar, K., Mukesh, G., Chandrakant, R., & Avinash, D. (2013).
A brief overview on chitosan applications. Indo American Journal of
Pharmaceutical Research, 3(12), 1564–4574.
Sarkanen, K. V., & Ludwig, C. H. (Eds.). (1971). Lignins: Occurence, Formation,
Structure and Reactions. New York: Wiley-Interscience.
Selmer-Olsen, E., Ratnaweera, H., & Pehrson, R. (1996). A novel treatment process
for dairy wastewater with chitosan produced from shrimp-shell waste. Water
Science and Technology, 34(11), 33–40.
Seyedi, S. M., Anvaripour, B., Motavassel, M., & Jadidi, N. (2013). Comparative
cadmium adsorption from water by nanochitosan and chitosan. International
Journal of Engineering and Innovative Technology, 2(9), 145–148.
Sharma, Y., Srivastava, V., Singh, V., Kaul, S., & Weng, C. (2009). Nano-adsorbents
for the removal of metallic pollutants from water and wastewater.
Environmental Technology, 30(6), 583–609.
Shen, C., Shen, Y., Wen, Y., Wang, H., & Liu, W. (2011). Fast and highly efficient
removal of dyes under alkaline conditions using magnetic chitosan-Fe(III)
hydrogel. Water Research, 45(16), 5200–5210.
Singh, K., Arora, J. K., Sinha, T. J. M., & Srivastava, S. (2014). Functionalization of
nanocrystalline cellulose for decontamination of Cr(III) and Cr(VI) from
aqueous system: Computational modeling approach. Clean Technologies and
Environmental Policy, 16(6), 1179–1191.
Siró, I., & Plackett, D. (2010). Microfibrillated cellulose and new nanocomposite
materials: A review. Cellulose, 17(3), 459–494.
Sirviö, J. A., Hasa, T., Leiviskä, T., Liimatainen, H., & Hormi, O. (2016).
Bisphosphonate nanocellulose in the removal of vanadium(V) from water.
Cellulose, 23(1), 689–697.
Sivakami, M., Gomathi, T., Venkatesan, J., Jeong, H.-S., Kim, S.-K., & Sudha, P. (2013).
Preparation and characterization of nano chitosan for treatment wastewaters.
International Journal of Biological Macromolecules, 57, 204–212.
Sponsler, O., & Dore, W. (1926). The structure of ramie cellulose as derived from
X-ray data. Fourth Colloid Symposium Monograph, 41, 174–202.
Srivastava, S., Kardam, A., & Raj, K. R. (2012). Nanotech reinforcement onto
cellulosic fibers: Green remediation of toxic metals. International Journal of
Green Nanotechnology, 4(1), 46–53.
Staudinger, H. (1920). Über polymerisation. Berichte der deutschen chemischen
Gesellschaft (A and B Series), 53(6), 1073–1085.
Šturcová, A., Davies, G. R., & Eichhorn, S. J. (2005). Elastic modulus and
stress-transfer properties of tunicate cellulose whiskers. Biomacromolecules,
6(2), 1055–1061.
Sud, D., Mahajan, G., & Kaur, M. (2008). Agricultural waste material as potential
adsorbent for sequestering heavy metal ions from aqueous solutions—A
review. Bioresource Technology, 99(14), 6017–6027.
Suman Kardam, A., Gera, M., & Jain, V. (2015). A novel reusable nanocomposite for
complete removal of dyes, heavy metals and microbial load from water based
on nanocellulose and silver nano-embedded pebbles. Environmental
Technology, 36(6), 706–714.
Sun, X., Yang, L., Li, Q., Zhao, J., Li, X., Wang, X., et al. (2014). Amino-functionalized
magnetic cellulose nanocomposite as adsorbent for removal of Cr(VI):
Synthesis and adsorption studies. Chemical Engineering Journal, 241, 175–183.
Suopajärvi, T., Liimatainen, H., Karjalainen, M., Upola, H., & Niinimäki, J. (2015).
Lead adsorption with sulfonated wheat pulp nanocelluloses. Journal of Water
Process Engineering, 5, 136–142.
Turbak, A. F., Snyder, F. W., & Sandberg, K. R. (1983). Microfibrillated cellulose, a
new cellulose product: Properties, uses, and commercial potential. Journal of
Applied Polymer Science. Applied Polymer Symposium (United States), 37. ITT
Rayonier Inc., Shelton, WA.
Vakili, M., Rafatullah, M., Salamatinia, B., Abdullah, A. Z., Ibrahim, M. H., Tan, K. B.,
et al. (2014). Application of chitosan and its derivatives as adsorbents for dye
removal from water and wastewater: A review. Carbohydrate Polymers, 113,
115–130.
Vismara, E., Melone, L., Gastaldi, G., Cosentino, C., & Torri, G. (2009). Surface
functionalization of cotton cellulose with glycidyl methacrylate and its
application for the adsorption of aromatic pollutants from wastewaters.
Journal of Hazardous Materials, 170(2), 798–808.
Wågberg, L., Decher, G., Norgren, M., Lindström, T., Ankerfors, M., & Axnäs, K.
(2008). The build-up of polyelectrolyte multilayers of microfibrillated cellulose
and cationic polyelectrolytes. Langmuir, 24(3), 784–795.
Wang, J. W., & Kuo, Y. M. (2008). Preparation and adsorption properties of
chitosan–poly (acrylic acid) nanoparticles for the removal of nickel ions.
Journal of Applied Polymer Science, 107(4), 2333–2342.
Wang, L., & Wang, A. (2007). Adsorption characteristics of Congo Red onto the
chitosan/montmorillonite nanocomposite. Journal of Hazardous Materials,
147(3), 979–985.
Wang, L., & Wang, A. q. (2007). Removal of Congo red from aqueous solution using
a chitosan/organo-montmorillonite nanocomposite. Journal of Chemical
Technology and Biotechnology, 82(8), 711–720.
Wang, L., & Wang, A. (2008). Adsorption behaviors of Congo red on the
N,O-carboxymethyl-chitosan/montmorillonite nanocomposite. Chemical
Engineering Journal, 143(1), 43–50.
Wong, Y., Szeto, Y., Cheung, W., & McKay, G. (2003). Equilibrium studies for acid
dye adsorption onto chitosan. Langmuir, 19(19), 7888–7894.
Xie, K.-L., Gao, Y., & Gao, X.-R. (2010). Mathematical analysis of equilibrium
isotherm for reactive dyes using nano-cellulose containing polyhedral
oligomeric silsesquioxanes. International Journal of Nonlinear Sciences and
Numerical Simulation, 11(6), 429–434.
Xie, K., Zhao, W., & He, X. (2011). Adsorption properties of nano-cellulose hybrid
containing polyhedral oligomeric silsesquioxane and removal of reactive dyes
from aqueous solution. Carbohydrate Polymers, 83(4), 1516–1520.
Yan, H., Yang, L., Yang, Z., Yang, H., Li, A., & Cheng, R. (2012). Preparation of
chitosan/poly (acrylic acid) magnetic composite microspheres and
applications in the removal of copper(II) ions from aqueous solutions. Journal
of Hazardous Materials, 229, 371–380.
Yang, R., Aubrecht, K. B., Ma, H., Wang, R., Grubbs, R. B., Hsiao, B. S., et al. (2014).
Thiol-modified cellulose nanofibrous composite membranes for chromium(VI)
and lead(II) adsorption. Polymer, 55(5), 1167–1176.
Yano, H., Seki, N., & Ishida, T. (2008). Manufacture of nanofibers and nanofibers
manufactured thereby. JP 2007–2229, 17.
Young, R. A., & Rowell, R. M. (Eds.). (1986). Cellulose: Structure, Modification and
Hydrolysis. New York: Wiley-Interscience.
Yu, X., Tong, S., Ge, M., Wu, L., Zuo, J., Cao, C., et al. (2013). Adsorption of heavy
metal ions from aqueous solution by carboxylated cellulose nanocrystals.
Journal of Environmental Sciences, 25(5), 933–943.
Yu, X., Tong, S., Ge, M., Zuo, J., Cao, C., & Song, W. (2013). One-step synthesis of
magnetic composites of cellulose@ iron oxide nanoparticles for arsenic
removal. Journal of Materials Chemistry A, 1(3), 959–965.
Yuwei, C., & Jianlong, W. (2011). Preparation and characterization of magnetic
chitosan nanoparticles and its application for Cu(II) removal. Chemical
Engineering Journal, 168(1), 286–292.
Zhao, Y. H., & Wang, L. (2012). Adsorption characteristics of Congo red from
aqueous solution on the carboxymethylcellulose/montmorillonite
nanocomposite. Advanced Materials Research, 450, 769–772. Trans Tech Publ.
Zhao, H., Kwak, J. H., Zhang, Z. C., Brown, H. M., Arey, B. W., & Holladay, J. E. (2007).
Studying cellulose fiber structure by SEM, XRD, NMR and acid hydrolysis.
Carbohydrate Polymers, 68(2), 235–241.
Zhao, L.-M., Shi, L.-E., Zhang, Z.-L., Chen, J.-M., Shi, D.-D., Yang, J., et al. (2011).
Preparation and application of chitosan nanoparticles and nanofibers. Brazilian
Journal of Chemical Engineering, 28(3), 353–362.
Zhou, D., Zhang, L., Zhou, J., & Guo, S. (2004). Cellulose/chitin beads for adsorption
of heavy metals in aqueous solution. Water Research, 38(11), 2643–2650.
Zhou, Y.-T., Nie, H.-L., Branford-White, C., He, Z.-Y., & Zhu, L.-M. (2009). Removal of
Cu2+ from aqueous solution by chitosan-coated magnetic nanoparticles
modified with ␣-ketoglutaric acid. Journal of Colloid and Interface Science,
330(1), 29–37.
Zhou, L., Xu, J., Liang, X., & Liu, Z. (2010). Adsorption of platinum(IV) and
palladium(II) from aqueous solution by magnetic cross-linking chitosan
nanoparticles modified with ethylenediamine. Journal of Hazardous Materials,
182(1), 518–524.
Zhou, L., Jin, J., Liu, Z., Liang, X., & Shang, C. (2011). Adsorption of acid dyes from
aqueous solutions by the ethylenediamine-modified magnetic chitosan
nanoparticles. Journal of Hazardous Materials, 185(2), 1045–1052.
Zhou, C., Wu, Q., Lei, T., & Negulescu, I. I. (2014). Adsorption kinetic and
equilibrium studies for methylene blue dye by partially hydrolyzed
polyacrylamide/cellulose nanocrystal nanocomposite hydrogels. Chemical
Engineering Journal, 251, 17–24.
Zhu, H.-Y., Jiang, R., & Xiao, L. (2010). Adsorption of an anionic azo dye by
chitosan/kaolin/␥-Fe2 O3 composites. Applied Clay Science, 48(3), 522–526.
Zhu, H., Jia, S., Wan, T., Jia, Y., Yang, H., Li, J., et al. (2011). Biosynthesis of spherical
Fe3 O4 /bacterial cellulose nanocomposites as adsorbents for heavy metal ions.
Carbohydrate Polymers, 86(4), 1558–1564.
Zhua, H.-Y., Jianga, R., Xiaob, L., & Lib, W. (2010). A novel magnetically
separable-Fe2 O3 /crosslinked chitosan adsorbent: Preparation, characterization
and adsorption application for removal of hazardous azo dye. Journal of
Hazardous Materials, 179, 251–257.
Zogaj, X., Nimtz, M., Rohde, M., Bokranz, W., & Römling, U. (2001). The
multicellular morphotypes of Salmonella typhimurium and Escherichia coli
produce cellulose as the second component of the extracellular matrix.
Molecular Microbiology, 39(6), 1452–1463.