Cellulose
https://doi.org/10.1007/s10570-020-03011-1 (0123456789().,-volV)
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REVIEW PAPER
Applications and impact of nanocellulose based adsorbents
Kazım Köse . Miran Mavlan . Jeffrey P. Youngblood
Received: 7 October 2019 / Accepted: 20 January 2020
Ó Springer Nature B.V. 2020
Abstract Efficient separation and removal is neces-
sary in applications ranging from environmental
remediation to the food sector. A well-designed
adsorption system should meet the demands for high
efficiency in a cost and time effective manner. In
wastewater treatment, the ideal chemical feedstock
used to synthesize the adsorbents should themselves
been environmentally friendly (i.e. non-toxic) to avoid
subsequent environmental issues. Nanocellulose,
made of the most abundant organic biopolymer on
earth, fulfills many criteria to fit the profile of a highly
safe, but efficient adsorbent. A survey of the literature
reveals that nanocellulose materials have a proven
track record as viable alternatives as adsorbents. To
summarize these recent advances, this review
describes the methodologies under current use for
such designs and gives a systematic overview of these
technologies to promote a more focused research in
the future for nanocellulose based adsorbent materials.
K. Köse (&)
Department of Chemistry, Hitit University, 19040 Çorum,
Turkey
e-mail: kazimkose@hitit.edu.tr; kkose.ohp@gmail.com
K. Köse
J. P. Youngblood
Department of Materials Engineering, Purdue University,
West Lafayette, IN 47906, USA
M. Mavlan
Department of Chemistry, Purdue University,
West Lafayette, IN 47906, USA
Keywords Adsorption
Cellulose nanocrystal

Pollution
Wastewater treatment
Removal
Introduction
The high demand for excellent performance and low
cost permeates all disciplines such as health and
medicine, automation, environment and the biological
sciences (Ruiz-Palomero et al. 2017). Thus, the
respective industry sectors have worked intensely in
research and development to achieve these goals, but
an ever present concern is pollution from the very
processes themselves (Goh and Ismail 2018). Heavy
metals, organic dyes, drug residues, pesticides, pol-
yaromatics and biomolecules are just a few of the
possible contaminants which all can be carcinogenic
(Ye et al. 2018). The danger to drinking water is a
particularly serious threat which requires immediate
attention as societal impacts are great (Fuhrimann
et al. 2016; Salgot and Folch 2018). Various physical
and chemical methods exist that allow for removal of
contaminants from soil and water (Salgot and Folch
2018). Among the repertoire for treatment, adsorption
is a competitive method when compared to other
processes. The innate simplicity of its design, rela-
tively low cost, and industrial scalability makes
adsorption-based technologies alluring (Crini 2006;
Ho and McKay 2003; Jain et al. 2003; Li et al. 2019;
123

Mohammed et al. 2016; Wang et al. 2019). In
particular, metal ions and organic dyes have garnered
attention as targets (Karim et al. 2016) and numerous
studies have been conducted with adsorbents designed
for these types of sequestrations (Akveran et al. 2018;
Erol et al. 2016a; Köse 2016). The most popular
adsorbent to date has been activated carbon and its
dominance in the field has left little enthusiasm for
addressing alternative materials that could be
answered with newer and safer methods (Cazetta
et al. 2011; Hameed et al. 2007; Liu et al. 2013).
Activated carbon is frequently used as it has high
adsorption with low concentration of toxic byprod-
ucts, but it is plagued by a cumbersome production
process along with difficulty in regeneration on
industrial applicable scales (Bhatnagar et al. 2013;
Hokkanen et al. 2016; Keng et al. 2013; Marques et al.
2018). Traditionally, the fabrication of traditional
adsorbents has been high in energy requirements and
are prone to give off greenhouse gases (Peng et al.
2011). Moreover, macroporous adsorbents cause dif-
fusion limitations making nano-structured materials
are more suitable for this purpose (Mahfoudhi and
Boufi 2017). However, since nanomaterials can cross
many barriers in the body, they should be used with
caution (Mahfoudhi and Boufi 2017). Recently, new
polymeric materials that are simple in their synthesis
and can be diversified with a wide variety of grafted
molecules (Akveran et al. 2018; Andaç et al. 2016;
Köse 2016; Memmedova et al. 2015; Pospiskova and
Safarik 2013; Yilmaz et al. 2013). Microchannels and
micropores in these polymeric adsorbents serve as a
cohesive matrix that allow target molecules to extend
their residence times within the material (Çavuş et al.
2013; Çulha et al. 2015; Erol and Köse 2017; Erol
et al. 2016b; Saatçilar et al. 2002; Sarıca et al. 2018;
Uzun et al. 2008). However, the challenge of scala-
bility for these polymeric materials remains a major
roadblock and in many cases they are not useful for
removal of organic (or water-insoluble) molecules
without matrix deformation or deterioration (Akveran
et al. 2018). Additionally, the push for greener
technology for separation of pollutants from the
environment has recently garnered attention for the
development of new adsorbents (Gautam et al. 2018;
Khan et al. 2018; Thambiraj et al. 2018). Due to the
high surface area and porosity of nanomaterials in
general, but also specifically of cellulose
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Cellulose
nanomaterials here, utilization of CN as adsorbents
seems a logical extension.
While there have been a variety of other investi-
gated systems, cellulose nanomaterials (CN) serve as a
bio-renewable, environmentally friendly and inexpen-
sive solution to meet this demand with industrial
scalability and a low carbon footprint profile
(Chenampulli et al. 2013). In the present review, we
give a general overview of numerous studies that use
CN as adsorbents for removal of contaminants such as
heavy metals, dyes and other important target
molecules. Unfortunately, in surveying the literature,
current reviews covering nanocellulose and adsorption
are more diffuse and broader in terms of subject matter
or are focused on one application suite (Mahfoudhi
and Boufi 2017; Shak et al. 2018). Further, modifica-
tion methods and the wide scope of micropollutants
are mentioned in a limited manner, while nanocellu-
lose extraction and polymer nanohybrids with biomed-
ical applications at the fore are mentioned in great
detail. Therefore, we have written this review with a
focus on nanocellulose-based adsorbents across all
application-space and attempted to synthesize an
understanding of the role of surface modifica-
tion/chemistry, usefulness for application and advan-
tages/deficiencies, as well as simply creating an up-to-
date review. As part of this, our emphasis is on the
importance of between surface functionalization and
adsorption behavior as it becomes clear in reading that
the low selectivity and adsorption kinetics of conven-
tional cellulose-based materials can be improved by
modification (Mahfoudhi and Boufi 2017; Patel et al.
2019). Specifically excluded in this review are mem-
brane methods and utilization of CN to create foams,
aerogels, etc. for absorption, rather than adsorption.
While these methods are perfectly fine for removal of
contaminants, we consider them out of scope as they
rely on different mechanisms of action and so proper
cross-comparisons cannot be drawn.
Reasons to choose nanocellulose
The annual production of 1011–1012 tons of cellulose
biomass per year makes it the most abundantly
produced homopolysaccharide. The repeating beta
linked glucose units have a rigid hydrogen-bonded
framework (Clarkson and Youngblood 2018; Foster
et al. 2018; George and Sabapathi 2015; Grishkewich
Cellulose
et al. 2017; Jiang et al. 2016) with 3 available hydroxyl
groups per anhydroglucose unit that consist of a single
primary and 2 secondary OH moieties (Fig. 1) (Peng
et al. 2011). Cellulose can be extracted from various
raw materials such as ramie fibers, straw, wood,
cotton, bacterial organisms and also directly from
microcrystalline cellulose. The cellulose chains are
made up of aggregates of stable crystalline regions and
reactive amorphous domains (Fig. 2) (Moon et al.
2011; Yu et al. 2013). Selective dissolution of the
amorphous areas, such as with acid digestion, oxida-
tion or enzymatic treatment releases cellulose
nanocrystals (CNCs) with diameters that vary from 1
to 100 nm with tangent and length dimensions from 5
to 200 nm, respectively (Habibi et al. 2010; Matos
Ruiz et al. 2000; Peng et al. 2011; Yu et al. 2013).
However, mechanical or chemomechanical processes
such as high pressure homogenization or disk refining
produce a long entangled material replete with amor-
phous areas called cellulose nanofibrils (CNF) (Haya-
shi et al. 2005; Li et al. 2012a; Saito and Isogai 2004).
A third material can be derived from bacterial
bioproduction called bacterial cellulose (BC), which
is similar in crystallinity and form to CNCs, similar in
length to CNFs, yet has a different crystal structure
(Moon et al. 2011; Nechyporchuk et al. 2016; Tabar
et al. 2017).
Among the many distinguishing features that make
up the profile of cellulose nanomaterials are their large
and reactive surface areas (Ruiz-Palomero et al. 2017),
high aspect ratio (Jorfi and Foster 2015; Klemm et al.
2011; Lam et al. 2012; Olivera et al. 2016; Suman et al.
Fig. 1 Intra- and inter-molecular hydrogen bonds within the structure of crystalline cellulose
2015), high stiffness (Lam et al. 2012; Ruiz-Palomero
et al. 2017), high strength (Klemm et al. 2011; Lam
et al. 2012; Peng et al. 2011; Tang et al. 2013),
renewability (Hokkanen et al. 2013, 2014; Klemm
et al. 2011; Olivera et al. 2016; Peng et al. 2011; Tang
et al. 2013), and low toxicity (Jorfi and Foster 2015;
Lam et al. 2012; Olivera et al. 2016; Peng et al. 2011).
First and foremost, nanosized (cellulose) materials are
favored over microsized materials simply due to their
higher surface area, and thus, scavenging capacity
against contaminants (Grishkewich et al. 2017; Oliv-
era et al. 2016; Singh et al. 2014; Tingaut et al. 2012).
Importantly for adsorptive processes, the ease and
variety of functional groups that can be introduced
onto the CN scaffold allows manipulation of surface
chemistry to tune and optimize the cellulose backbone
for a particular application (Chauhan et al. 2000;
Chowdhury and Balasubramanian 2014; Gardner et al.
2008; Hasani et al. 2008; Kalia et al. 2011; Kamel et al.
2008; Kloser and Gray 2010). Modification to surface
hydroxyls to date include carboxyl, sulfonic and
amino group inclusions, and while these have mostly
been utilized for compatibilization of CN into polymer
matrices, the same methods can be used for adsorption
(da Silva Filho et al. 2009; Güçlü et al. 2003; Júnior
et al. 2010; Li et al. 2010; Shen et al. 2009; Zhao et al.
2011). Lastly, the advent of techniques that combine
fast and inexpensive processing (i.e. roll-to-roll man-
ufacturing) has lowered the potential cost of CN
products over other as processed nanomaterials such
as graphene due to the inexpensive raw material cost
(Fortunati et al. 2013; Jorfi and Foster 2015; Kumar
123

Fig. 2 Atomic force microscopy images of CNCs and CNFs (reprinted with a permission from Abushammala and Mao 2019)
et al. 2017; Ma et al. 2016; Ruiz-Palomero et al. 2017).
Owing to these factors, water treatment utilizing
adsorption, membrane filtration and disinfection have
all seen the use of CNCs as major contributors (Peng
et al. 2011). Many opportunities exist to develop
alternative low-cost adsorbents from agricultural and
industrial by-products with CNC showing excellent
adsorption capacities with the definite possibility of
replacing activated carbons (Ali and Gupta 2006;
Batmaz et al. 2014; Bhatnagar and Sillanpää 2010;
Crini 2006; Mohammed et al. 2015).
Cellulose nanomaterials as adsorbents
As an overall primer to adsorbents, non-specific
interactions such as hydrophobic, hydrogen bonding,
van der Waals, and polar molecular interactions are all
ways in which adsorption can operate (Hokkanen et al.
2016). The exact selection for fine tuning of an
adsorbent to a specific application depends on the
wastewater characteristic contaminants. Polar adsorp-
tion systems are typically strongly pH dependent and
are modified with the media in mind. For example, any
reliable interaction wanted from a negatively charged
surface will not operate well in a low pH wastewater as
complete protonation will eliminate the desired non-
covalent interactions (Erol and Köse 2017; Köse and
Denizli 2013; Köse et al. 2015). Additional factors,
such as the actual interaction time between the surface
and adsorbate, target molecule concentrations present,
temperature, ion exchange, and adsorbent dosage all
have influence on total performance of adsorbent
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Cellulose
(Belhalfaoui et al. 2009; Chen et al. 2003; Dwivedi
et al. 2014; Hokkanen et al. 2013, 2016; Zhang et al.
2003; Zhou et al. 2005).
For quantification of adsorption performance,
adsorption capacity can be calculated from the differ-
ence of analyte concentration before and after adsorp-
tion (Erol et al. 2018; Köse and Köse 2017) and
typically low cost easy methods such as UV–visible
Spectrophotometry, ion selective electrode or cyclic
voltammetry or higher cost but still widely available
techniques such as ICP-MS and LC–MS are used.
Labelling may be another option if the molecule
cannot be detected by typical instrumentation or has
too many interferences (Kozak et al. 2010; Winzen
et al. 2016). However, these methods are only
suitable if the analyte is in the proper concentration
range, which tends to be relatively high concentration
for pollutants. Still, these methods are perfect for
adsorbents intended for ‘‘rough’’ purification. If the
analyte starts at or is reduced to trace amounts,
enrichment is necessary, where methods such as
centrifugation (Erol and Köse 2017; Maftuleac 2013;
Margaretha et al. 2014; Wei et al. 2011) or evaporation
of the solvent are utilized. These methods are time
consuming and can introduce significant error as they
are ‘‘lossy and high cost processes’’. A key factor is to
optimize conditions to achieve the highest adsorption
performance regarding pH, interaction time, temper-
ature, and ionic conditions as allowed by actual or
proposed used conditions (Pourfadakari et al. 2017).
From this data, adsorption is typically fit to relevant
models such as the Langmuir or Freundlich adsorption
isotherms (Yue et al. 2019).
Cellulose
CN-based adsorbents are primarily synthesized in
three different ways. The first is the adaptation of a
functional structure to the CN (Dufresne 2013). These
functional groups can be sulfate-half ester groups,
cationic groups, aldehyde groups, carboxyl and car-
bonyl groups, etc. (Huang et al. 2018; Lin et al. 2016;
Sultan and Mathew 2018; Supramaniam et al. 2018).
The second method is incorporation of another
polymeric structure such as PEG, PLA, GMA, directly
onto the CN adsorbent. This is referred to as ‘‘graft-
ing’’, which can be performed in two ways as
‘‘grafting to’’ and ‘‘grafting from’’ (Habibi and
Dufresne 2008; Morandi et al. 2009). The last method
by which CN-adsorbent structures are obtained is by
polymerizing monomers in the presence of CN. Free
radical and emulsion polymerization are very common
methods in obtaining polymeric architecture in adsor-
bent production (Chen et al. 2015; Mauricio et al.
2015). Additionally, it is very common to increase
surface area by creating nano and micropolymeric
structures or, more commonly, porosity by creating
cryogels and aerogels (Du et al. 2019; Köse 2016;
Köse and Denizli 2013; Köse and Köse 2017).
Cryogels can be create by freezing the hydrogel,
disrupting the structure to allow ice crystallization to
create pores. Aerogels or foams can be then prepared
by freeze-drying these materials resulting in a light-
weight sponge like structure (De France et al. 2017;
Mondal 2017).
Unfortunately, only a limited amount of research
has been done on water treatment with use of CN-
based materials (Liu et al. 2014; Ma et al. 2011a, b;
Sehaqui et al. 2014). Cellulose nanocrystals-based
adsorbents have been proven to show significantly
higher adsorption capacity than non-traditional low-
cost adsorbent (Batmaz et al. 2014). Generally, in
contrast to micron-sized structures, the advantages of
CNs allows for increased contact due to greater
surface area, higher porosity, and better internal
diffusion (Chang et al. 2006; Lam et al. 2012; Li
et al. 2012b; Zhou et al. 2011). In addition, due to the
high aspect ratio and good mechanical properties, CN-
based porous materials can have lower density without
loss of mechanical strength, enabling higher pore
volumes and surface area (Brinkmann et al. 2016;
Frka-Petesic et al. 2015; Zhu et al. 2019). This
combined with the low toxicity and carbon footprint
along with biodegradability makes CNCs a viably
sustainable material to replace most adsorbent
materials for waster wastewater treatment (Jonoobi
et al. 2019; Li et al. 2013; Roman 2015; Walker 2012).
Commonly, binary systems of CN are investigated
to improve capacity or simply to bind the CN together
(Batmaz et al. 2014; Kurecic and Smole 2012). For
example, synergy between cellulose/silsesquioxane,
cellulose/clay and cellulose/polymer nanocomposites
have been investigated for water treatment (Olivera
et al. 2016). CNC-ALG hydrogels, for example, are
excellent candidates for removal of methylene blue (a
cationic dye), because of the overall negative charge
on the surface of the adsorbent (Mohammed et al.
2015). CN supported adsorbents can provide highly
polar negative charges (dependent on pH and zeta
potential) enabling the electrostatic interaction with
positively charged molecules through the polarity of
surface functional groups such as carboxylic acids and
sulfate ester (Bereli et al. 2012; Bilgin et al. 2018;
Köse and Uzun 2016). Voleksy showed that sulfate,
phosphate and carboxylic acid functionalized polysac-
charides were effective in metal cation bonding
(Volesky 2007) and thus it is no surprise that that
CNs showing similar functionality are applicable for
heavy metal removal due to the short intraparticle
diffusion distance and high surface area (Liu et al.
2015a; Qu et al. 2013). Sehauqi reported that the
specific surface area of CNF films was around 480 m2/
g (Sehaqui et al. 2011) which allows for removal of
contaminants even in very low concentrations
(Volesky 2007).
The greatest advantage of modification of adsor-
bents with nanocellulose or nanocellulose-based
adsorbents is the number of functional groups it
provides due to the high surface area and functional
group density. The numerous hydroxyl groups (or
other if chemically modified) on the nanocellulose
result in higher capacity of the target molecule to the
adsorbent (Anirudhan and Deepa 2015; Olivera et al.
2016; Putro et al. 2017; Shak et al. 2018; Taleb et al.
2016). Due to the small pores, open pore structures,
etc., the adsorption time can also be shortened. Unlike
other inorganic adsorbents, nanocellulose based mate-
rials are also totally biodegradable enabling both
sustainability and biological use without side effects
(Bhatnagar et al. 2015; Vartiainen et al. 2011). There
are also studies showing that percolated (CNCs) and
entangled (CNFs) networks held with strong hydrogen
bonding (Lin et al. 2012b) leads to improved mechan-
ical properties of the nanocomposite. (Rusli and
123

Eichhorn 2008). Lastly, due to the hydrophilic nature,
nanocellulose material favors the wetting of the
nanocellulose-based adsorbent by water which is very
important as most adsorbent applications are aqueous.
Modification of cellulose nanomaterials
for improved adsorption
It is widely accepted that the both the chemical and
physical composition’s synergy ultimately are respon-
sible for the adsorption performance of any material.
High specific area along with numerous pores enable
the sufficiently strong interaction between the absor-
bent and, for example, a target dye molecule. The
initial adsorption properties depend entirely on chem-
ical activation and modification of the host structure.
The target of adsorption often dictates the class of
surface modifications to be carried out, which can
either be target specific or those able to act on a wide
variety of substrates. The reverse process of desorp-
tion depends heavily on a flexible pore structure, but
regeneration cycles can increase both cost and
processed pollution. Once trapped, the adsorbed
molecule can transverse into the inner core of the
host structure due to a gradient in concentration. Thus,
proper tuning of the adsorbent is important for
efficiency.
Also, as discussed above, nanocellulose has plenty
of hydroxyl groups providing for high affinity to many
molecules that, coupled with its surface area, could for
good native capacity as well as sustainability. Unfor-
tunately, these same properties also lead to a tendency
for aggregation, thus limiting the available surface
area for adsorption and a major disadvantage. This can
be overcome somewhat by energy intensive processes
such as ultrasonication, although these are not perfect.
Hornification can be another issue where drying of the
CN leads to irreversible aggregation, so many of these
materials must stay wet at all times. Add to this the
need to tailor the material for a specific target,
chemical modification of the native surface is often-
times necessary for efficient utilization.
Physical structure is generally tuned via the method
utilized to fabricate the bulk adsorbent and is depen-
dent on the exact conditions of the method, be it
freeze-drying, hydrogel casting, etc. For example,
Peng et al. measured the effect of the drying method of
CNC to its surface activity and concluded that drying
123
Cellulose
technique indeed makes a significant difference (Peng
et al. 2013). However, due to the very bespoke nature
of each method, the results are generally not directly
comparable across the field and so will not be
reviewed here, other than to say that higher surface
areas will generally be preferable.
In regards to chemical modification, key interac-
tions can be tuned by simple modification of CNC
surfaces and the nature of the chemistry is directly
linked to overall adsorption performance towards a
given adsorbate (Hokkanen et al. 2016). Carboxyl,
hydroxyl, amino, and alkyl groups are excellent
candidates that show good adsorption performance
and access to these are achieved via esterification,
oxidation, etherification or polymer grafting (Qu et al.
2013) (Table 1; Fig. 3). The resulting new nanoma-
terial gains both new reactivity (for example nega-
tively or partial negative surface reactivity can
sequester heavy metal cations) and dispersion stability
that arises from electrostatic repulsion. The former
representing selective functionality and the latter
allows for increased surface area due to less aggrega-
tion of CN during fabrication (Volesky 2007; Zhao
et al. 2011). There have been three general methods
utilized to enhance adsorption of contaminants from
water: functionalization to make the CN more (1)
anionic, (2) cationic, and (3) hydrophobic.
Anionization of cellulose nanomaterials
Due to the need to remediate water from cationic
heavy metals, functionalization with anionic groups is
by far the most utilized functionalization of CN for
adsorption (Hokkanen et al. 2016). Mineral organic
acid and bases, oxidizing agents and other organic
compounds are all viable tools for induction of anionic
groups on the surface of nanocellulose. Regardless,
these anionic groups are typically pH-sensitive due to
the respective isoelectric point of the anionic center.
While many CN contain native negatively charged
groups such as sulfate ester (in the case of sulfuric acid
derived CNC) or carboxylic acid (in the case of
TEMPO-derived CNF), addition of further COO-
groups of CN allows for better targeting of positively
charged molecules (Olivera et al. 2016). In a study
conducted by Isogai et al., TEMPO oxidation afforded
carboxylates on C6 of the cellulose backbone
(TOCNF) (Isogai et al. 2011), which can then target
metals such as Pb(II), Ag(I), and La(II) ions for
Cellulose

Table 1 Preparation methods for CN-based adsorbents

Adsorbent Prep. method Advantages Disadvantages Application References

Amino-functionalized Sodium Higher amino group, Time consuming Dye adsorption Jin et al.
nanocrystalline cellulose peroxide providing process, expert- (2015)
oxidation and amphoteric needed reactions
grafting property, high
specific surface area
Silylated Nanocellulose Freeze-drying Water-based, easy to Toxic organic Oil removal Zhang
Sponges apply chemicals, energy et al.
consumption (2014)
Surface imprinted magnetic Molecular Regular shape, easy Toxic organic Adsorption of Hu et al.
carboxylated cellulose imprinting, control of size, no chemicals, fluoroquinolones (2018b)
nanocrystals radical additional solvent, polymerization yield
polymerization easy preparation
Amino-functionalized Grafting Easy chemical Time consuming, toxic Diclofenac Hu et al.
cellulose modification, chemical, expert adsorption (2019b)
nanocrystals/chitosan control by the needed, strict control
composite number of active of each step
sites
Peroxidase immobilized Cyanogen Easy process, cheap, Toxic chemicals, ligand Removal of Yang et al.
cellulose nanocrystals bromide strong binding leakage, limited Phenolic (2008)
activation, mobility, decrease Compounds
coupling, enzyme activity
covalent
binding
Cellulose nanocrystal- Chemical Easy to apply, strong Toxic chemicals, Dye removal Song et al.
reinforced keratin bio modification binding energy consumption, (2017)
adsorbent and freeze time consuming
drying
Partially hydrolyzed Heat treatment Easy to apply, fast, Energy consuming, Dye removal Zhou et al.
polyacrylamide/cellulose effective, no toxic time consuming, (2014)
nanocrystal residues careful handling,
nanocomposite hydrogels structural degradation
because of heat
Cellulose nanofibril (CNF) Michael- Easy to apply, cost Time consuming, toxic Heavy metal and Tang et al.
based aerogels addition or effective, covalent chemicals dye removal (2019)
Schiff-base bonding
reaction,
polymerization
TEMPO-oxidized cellulose Sulfuric acid Selectivity, easy Low reactivity in the Cu(II) adsorption Maaloul
nanofibers hydrolysis, storage, simple presence of air, light, et al.
TEMPO- humidity (Spier et al. (2017)
oxidation 2017)
Surface modified cellulose Surface Almost no restriction Careful handling, toxic DNA adsorption Demirci
acetate nanofibers initiated- of solvents, chemicals, limited et al.
RAFT polymerization at number of monomers, (2014)
polymerization nearly room end-purification,
temperature, high instability of
functional group chemicals for long
tolerance, time

removal from aquatic environment (Saito and Isogai carboxylate groups on the surface as the determining
2005). Sehaqui et al. also demonstrated the removal of factors. A linear relationship between the concentra-
Cu(II) using TOCNF with the pH and amount of tion of Cu(II) adsorbed was evident in the pH range

123

Fig. 3 a Some common classes of CNC surface modification, b Representative examples of polymer grafted CNCs
from 3 to 7 (Sehaqui et al. 2014). Sehaqui also showed
that following esterification with succinic anhydride to
provide carboxylic acid groups, lead was extracted out
from aqueous solutions further demonstrating this as a
promising technique. A variety of works are based on
the succinic anhydride method for introducing
123
Cellulose
carboxylic acid groups to improve adsorbency and
are reviewed (Olivera et al. 2016).
Cationization of cellulose nanomaterials
There are many fewer cases of creating cationic
groups on CN for adsorption of anionic molecules,
Cellulose
likely due to the lack of need for such materials.
However, amination of surface hydroxyls of nanocel-
lulose is the most common means of cationic
functionalization (Olivera et al. 2016). However as
with anionic surfaces, amines can be pH sensitive due
to the isoelectric point/pKa and thus are used at low
pH, although easy quaternization of amines to make
permanent cations can be done. Jin et al. grafted amino
groups on cellulose nanocrystals through sodium
periodate oxidation to afford the C-2 and C-3 dialde-
hyde and reaction with ethylenediamine (Jin et al.
2015). Hartmann et al. also aminated CNCs and
produced them by oxidation–reduction reaction with
quaternation with various alkyl chains (methylamine,
butylamine and hexylamine) by mechanical homog-
enization (Hartmann et al. 2016).
Hydrophobization of cellulose nanomaterials
Cellulose acetate is one of the most common synthetic
derivatives of cellulose and it is known that it can
coordinately bond with metal ions through the lone
pairs of the acetate groups. Regeneration is easy
enough to do as it only requires alkaline solution
(Sehaqui et al. 2016a). However, such modification
also provides a hydrophobic surface that can poten-
tially adsorb water-soluble organic molecules via
hydrophobic interactions. For example, a specific
affinity for target molecules such as mycotoxins
requires surface functionalization of CN with both
specific anions (such as sulfate groups) along with
fatty acids that introduce hydrophobicity to bind
hydrophobic zones on the mycotoxins (Zadeh and
Shahdadi 2015). Commonly, such hydrophobization is
introduced via esterification (Ruiz-Palomero et al.
2017).
Silylation is another process to make cellulose
nanomaterial hydrophobic (Thomas et al. 2018)
resulting in high flexibility (Gousse et al. 2004; Zhang
et al. 2014) and high porosity. The most common
chemical used for this process is
alkyldimethylchlorosilane (Moon et al. 2011). Iso-
propyl dimethylchlorosilane (Gousse et al. 2004),
chlorodimethyl isopropylsilane (Andresen et al. 2006)
and methyltrimethoxysilane (Zhang et al. 2014) were
also used to get highly selective and recyclable
nanomaterials. Zhang et al. have used
methyltrimethoxysilane for the modification of
nanocellulose sponges to prepare highly selective
nanomaterials for water treatment. Because of oleo-
philic character of the resultant nanomaterial, they
could remove dodecane spills on a water surface.
Urethanization is another modification method,
which is the urethane linkage formed by covalent
bonds between isocyanate and nanocellulose material
through hydroxyl groups, and is also known as
carbanylation and carbamation (Eyley and Thiele-
mans 2014; Thomas et al. 2018). For example, for both
CNC and CNF, Siqueira et al. have used n-octadecyl
isocyanate with 0.07 and 0.09 degree of substitution,
respectively, while Biyani et al. utilized 2-(6-iso-
cyanatohexylaminocarbonylamino)-6-methyl-4 [1H]-
pyrimidinone (in DMF) (Biyani et al. 2013).
Cellulose nanomaterials can also be modified using
carbodiimide chemistry such as N-ethyl-N-(3-
(dimethylamino)-propyl) (EDAC) to add amide func-
tional groups in pH range between 7 and 10. Ruiz
Palomero et al. have used amine-mediated cellulose
nanomaterial to add beta cyclodextrin for selective
detection of adanofloxacin in milk. They have
achieved 94% recoveries with very low detection
limit as 2.5 lg.
Applications areas of CN adsorbents
Water pollutants can be both anthropogenic or natural,
but domestic contaminants from society are the
dominating factor and result in heavy metal, pharma-
ceutical, polycyclic aromatic hydrocarbon, pesticide
and biomolecular contaminants. Although a variety of
treatment methods exist, adsorption is by far one of the
most attractive means for municipal waste water care
due to cost efficiency (Erol et al. 2016b; Fan et al.
2018; Freeman et al. 2018; Garg and Prasad 2017;
Jiang et al. 2018; Martı́nez-Huitle and Panizza 2018;
Orona-Návar et al. 2018; Reddy et al. 2016; Teng et al.
2018; Teodosiu et al. 2018; Zhang et al. 2016). A
major issue is that kinetics of competition between
pollutant targets can alter adsorption performance
(Hokkanen et al. 2016), and single analyte measure-
ment does not capture this. However, a well-designed
system can give excellent results (Peng et al. 2011;
Sharma et al. 2011; Unuabonah et al. 2008). CN have
only started to be explored for adsorbent uses and,
within this space, six main areas of application have
been explored with CN based adsorbents (Fig. 4).
Table 2 gives the summary of some research based on
123

CN and adsorption performance for reference through
the text.
Petroleum products
A minor area of interest is CN-based ultra-porous
aerogels to separate water/petroleum mixtures. These
are typically hydrophobized to take advantage of
differential surface energy-based wetting phenomena.
For example, a new sponge-like adsorbent was
obtained via vapor deposition of hydrophobic silanes
on CNF aerogels (Korhonen et al. 2011). The pore size
was less than 40 mm and it could sorb non-polar
liquids up to 45 times its own weight. The superhy-
drophobic light material both provided good perfor-
mance in the absorption of non-polar liquids and was
reusable (Cervin et al. 2012; Lee et al. 2014). In a
similar way, Wu et al. have used CNC nanopapers and
nanocoating with no water flux decline (after 12
cycles) and high-salt resistance to remediate crude oil
spills in seawater. Cellulose chains in CNC structure
Fig. 4 Some applications areas of CN adsorbents
123
Cellulose
limits the movement of hydrophilic groups resulting in
stable hydrophilicity which is necessary for the
application and superior to other known super-hy-
drophilic materials (Wu et al. 2019). In another study
Korhonen et al. have produced highly porous aerogels
with the titanium dioxide-functionalized CNFs result-
ing in an oleophilic coating. This modification
provides for the removal of organic pollutants and
oils from water. However, while selective with high
adsorption capacity, the use of freeze-drying may limit
economical large-scale (Korhonen et al. 2011). Oleic
acid modification was applied to increase the adsorp-
tion capacity of magnetic nanocellulose-magnetite
aerogels by exploiting hydrophobic property of oleic
acid in the study performed by Gu et al. (Gu et al.
2020). They have achieved the adsorption of ethyl
acetate, cyclohexane, and vacuum pump oil with the
rate of 56.32, 68.06, and 33.24 g g-1, respectively.
Moreover, oleic acid modification increased the
specific surface area almost fivefold.
 Table 2 Some cellulose nanomaterial based adsorbent and applications
Material Modification Adsorbent Adsorption Perf T. molecule References
Cellulose

(mg/g) (%)

Cellulose nanofibers (CNFs) Sulfur tethering S-Ligand tethered CNF 239.64 99 Pb(II) Abu-Danso et al. (2018)
Micro fibrillated cellulose Succinic anhydride treatment Succinic anhydride modified * 0.12 92.5 Cu(II) Hokkanen et al. (2013)
(MFC) mercerized nanocellulose
Cellulose Glycidylmethacrylate grafting GMA grafted magnetic 410.2 99.01 Ni(II) Donia et al. (2012)
(with ceric ammonium nitrate) nanocellulose
and tetraethylenepentamine
Cellulose nanocrystal Carboxylation, impregnation into Hydrogel beads 335.38 80 Pb(II) Hu et al. (2018a)
alginate hydrogel beads
Cellulose nanocrystal Carboxyl-functionalized Fe3O4 Magnetic beads 2.86 90 Pb(II) Luo et al. (2016)
nanoparticles, acid-activated
bentonite
Nanocellulose Acid hydrolysis, silver Pebbles bed column 9.42 99.48 Pb(II) Suman et al. (2015)
nanoparticle embedding
Cellulose nanocrystal Carboxylation, magnetic Composite magnetic 63.78 98.79 Pb(II) Lu et al. (2016)
composition nanoparticle
Cellulose Methylene bisacrylamide Hybrid cellulose aerogels 41.84 99.74 Cr(VI) Bo et al. (2018)
crosslinking and zeolitic
imidazolate framework (ZIF-8)
Cellulose nanocrystal Amination Biosorbent 2.45 98.33 Cr(VI) Singh et al. (2014)
Cellulose nanocrystal Carboxylation, polyethylene imine Nanocomposite 358.42 65 Cr(VI) Liu et al. (2017)
modification
Cellulose nanocrystal Incorporation of nanocellulose CNC reinforced keratin 1250 96 Reactive Black 5 Song et al. (2017)
Cellulose nanocrystal Oxidation, H2O2 treatment CNC extract 217.4 98.76 Methylene blue Yang et al. (2017)
Cellulose nanocrystal Partial hydrolysis, polyacrylamide Nanocomposite hydrogel 326 [ 90 Methylene Blue Zhou et al. (2014)
modification
Cellulose nanocrystal Crosslinking Hydrogel beads 255.5 7.61 Methylene Blue Mohammed et al.
(2016)
Cellulose nanocrystal Acid treatment Nanoparticle 87.77 88 Methylene Blue Shanmugarajah et al.
(2018)
Cellulose nanocrystal Carboxylation Nanoparticle 769 [ 92.3 Methylene Blue Batmaz et al. (2014)
Cellulose nanocrystal Interfacial polymerization using Nanoporous membrane – 99.9 Methyl Orange Bai et al. (2019)
polyethersulfone, piperazine,
1,3,5-benzene-tricarbonyl
trichloride

123
 Cellulose

Pharmaceutics

Suman et al. (2015)

Karim et al. (2014)

Yuan et al. (2017)

A significant contributor to evolved antibiotic resis-
Bai et al. (2019)

Jin et al. (2015)

tance is their low-level effluence in wastewater which
References

allows the sub-lethal concentrations for selective

resistance genes to accumulate. CNCs, extracted from
green seaweed and modified by acid hydrolysis, were
shown to successfully remove tetracycline hydrochlo-
ride from aqueous solutions (maximum adsorption
Reactive light yellow

occurring at pH 5.5) (Rathod et al. 2015). Any trapped

Victoria blue 2B

contamination
antibiotics were released in the presence of 5% HNO3
T. molecule

Congo Red

or NaOH to regenerate the CN binding sites proving

Microbial

Toluene
K-4G

ease of adsorbent recyclability. Hu et al. have

synthesized ofloxacin imprinted magnetic carboxy-
lated CNC for the removal of fluoroquinolones from
aqueous solution. This material had strong recognition
99.83
Perf
(%)

91

98

99

82

ability, a large surface area and ability to conduct easy

separation. They achieved a recovery ratio from 81.2
Adsorption

* 0.027

to 93.7% with an RSD of 0.6%–7.5%. According to

(mg/g)

the result they have achieved, the material obtained is

183
–

quite promising for the removal of antibiotics (Hu

et al. 2018b). They have desorbed ofloxacin from the
adsorbent using 30% acetic acid/methanol (v/v). This
nanocrystalline cellulose

method was applied for seven cycles and 70% of its

Nanoporous membrane

Composite membrane
Amino-functionalized

original value was achieved at the end of the seventh

Pebbles bed column

cycle. Phosphate ions were used to modify CN for the

Nanocomposite

removal of diclofenac from water (Abu-Danso et al.

Adsorbent

2019). In this study, Abu-Danso et al. obtained a

maximum diclofenac adsorption at pH 5.6 as 29.6 mg/
g as compared to maximum adsorption capacity
reached 107.9 mg/g in the experiment conducted with
Oxidation using sodium periodate,

increasing diclofenac concentration. Interestingly this

Interfacial polymerization using
polyethersulfone, piperazine,

study used cigarette filters as the CN source maxi-

c-Cyclodextrin modification
Ethylene diamine grafting
1,3,5-benzene-tricarbonyl

Chitosan modification via

nanoparticle embedding

mizing the sustainability aspect by using a waste

Acid hydrolysis, silver

material. Adsorbed diclofenac was eluted using 0.1 M

NaOH, 0.1 M HNO3 and H2O separately to reuse
adsorbent. Nitric acid was used for regeneration with
crosslinking
Modification

trichloride

80% removal efficiency at the end of the all cycles

contrary to other eluents which have removal capacity
less than 10%. Hu et al. have also studied the
adsorption of diclofenac by using a CN-chitosan
composite (Hu et al. 2019a). CNC-chitosan composite
was modified using ethylenediamine to exploit the
Cellulose nanocrystal

Cellulose nanocrystal

Cellulose nanocrystal

acid–base interaction between diclofenac sodium and

Cellulose nanofiber
Table 2 continued

the adsorbent. In acidic conditions (pH: 4.5 in that

Nanocellulose

study), amine functional groups were in the form of

NH3? which is electrostatically attractive towards
Material

negatively charged functional groups of diclofenac

sodium. The interaction time was found to be quite

123
Cellulose
short (50 min.) while adsorption capacity (444.44 mg/
g) was comparable to other studies in the literature.
NaOH (0.1 mol/L) was the regenerant during five
adsorption–desorption cycles with a subsequent
adsorption capacity decrease to 80.06%. In another
fluoroquinolone adsorption work, selective extraction
of the danofloxacin was achieved via CNC that was
TEMPO oxidized followed by addition of b-cyclodex-
trin via amidation (Ruiz-Palomero et al. 2015). A
recovery rate above 94% was achieved in the appli-
cation of the method in milk samples with regenera-
tion by washing with acetonitrile and phosphate
buffer. However, unlike the other non-specific inter-
actions described above, the use of cyclodextrin means
that the potential of the CN treated in this way depends
on the combination of complex with the molecule to
be separated. The governing interactions in this
process are a combination of van der Waals, hydrogen
bonds and hydrophobic interactions. Fan et al. used
polyethyleneimine to functionalize CN containing
sodium alginate microspheres for the efficient adsorp-
tion of diclofenac sodium (Fan et al. 2019). The reason
to use polyethyleneimine was to increase the number
of amino groups which is the key factor for the
diclofenac sodium adsorption through acid–base
interaction. Maximum adsorption was achieved at
pH:4.5 with an adsorbence of 43.9 mg/g. Regenera-
tion of the adsorbent using HCI (0.1 mol/L) for five
cycles was attempted although use of HCI caused
destruction of some binding zones so that the adsorp-
tion capacity decreased by 11.44%, although still
resulting in a performance above 80%. CuS hollow
nanospheres@N-doped cellulose nanocrystals hybrid
composites were used by Nekouei et al. for the
adsorption of ciprofloxacin from aqueous solution
exploiting the electrostatic attraction and p-p interac-
tions between CuS on the surface of microspheres and
the antibiotic (Nekouei et al. 2018). CNC provide
more –OH functional groups for the addition of more
N enabling the more sp2 hybridization through cova-
lent p electrons and more CuS addition responsible for
the main interaction with ciprofloxacin.
Biomolecules
While the adsorption of large biomolecules by cellu-
losics had previously been known from such avenues
as affinity membranes from electrospun cellulose
acetate nanofibers (Rojanarata et al. 2013). Large
biomolecules such as DNA have also successfully
been adsorbed onto surfaces of CNs, principally CNF
(Demirci et al. 2014). A buffer solution (potassium
hydrogen phthalate/hydrochloric acid, pH 3.0) was
used for regeneration. However, the strength of the
eluent was not enough to removal all DNA from the
matrix resulting in drastic performance decrease of
almost 11.5% for each cycle and performance loss of
approximately 54% was observed at the end of the fifth
cycle. Recovery of b-casein from an aqueous envi-
ronment was achieved with the use of a superab-
sorbent hydrogel based on CN containing amine
groups due to interactions between negatively charged
protein and positively charged sorbent (pH of 5.5),
with subsequent renewal with the use of HAc,
Mg(NO3)2, NH4OH and NaSCN treatment (Anirud-
han et al. 2015). The highest regeneration was
achieved with NaSCN resulting in decrease in the
adsorption capacity from 98.90 to 94.70% at the end of
the fourth cycle. CN and magnetic nanomaterials also
readily make hybrid nanocomposites with strong
adsorbent properties (Ruiz-Palomero et al. 2017).
For example, an adsorption study of immunoglobulin
was performed using poly(methacrylic-acid-co-vinyl
sulfonic acid) mixed with CN and magnetite compos-
ite (Anirudhan and Rejeena 2013). Magnetite allowed
for the CN matrix to obtain an ion-exchange sorbent
with magnetic properties (Bayramoğlu et al. 2008).
The maximum load capacity was increased at higher
ionic strength and near neutral pH (6.8) with subse-
quent release of the immunoglobulin base to regener-
ate the adsorbent. The potential obtained allows
selective separation of the immunoglobulin in a
mixture of proteins, which has resulted in great
interest in promising applications. Ishak et al. have
used TEMPO-modified magnetic CNC hybrid mate-
rial for protein adsorption in fish waste (Ishak et al.
2019). Protein recovery achieved was * 90% in an
aeration tank. Bovine Serum Albumin (BSA) adsorp-
tion onto pyridinium-grafted CNC in a study con-
ducted by Lombardo et al. (Lombardo et al. 2017). In
this study, both sulfated and carboxylated CNC were
used to understand the effects of surface chemistry. As
expected, because of negatively charged groups of
sulfate and carboxylate, no interaction was observed.
Investigation into whether single amino acids adsorbs
onto modified CN showed a remarkable adsorption
may occur at and above 2.7 M amino acid concentra-
tion (Zimnitsky et al. 2005). Anirudhan and Rejeena
123

grafted glycidyl methacrylate to the CN to promote the
polyacrylic acid modification through a crosslinker,
ethylene glycol dimethacrylate, providing an inter-
penetrating polymer network with free –COOH
groups (Anirudhan and Rejeena 2012). Adsorption
of lysozyme on the surface of adsorbent was achieved
through electrostatic interactions with the adsorbent at
pH:6. Kinetic calculation also shown the governing
force was chemical interaction during adsorption.
Industrial small organic molecules
Removal of industrial small organic molecules is a
major area for adsorption-based remediation. Here,
the focus will be on non-dye molecules as those are
listed separately. For example, the removal of chlo-
rinated phenolic compounds from wastewater was
achieved through the use of cyanogen bromide-
modified peroxidase conjugated CNC (Yang et al.
2008). CNF based porous organogels have also been
reported as promising adsorbents against molecules
soluble in organic solvents such as herbicides by
hydrocarbon-modification of CN to maximize the
hydrophobic interactions (Maatar et al. 2013). The
release of the adsorbed organic solute was carried out
using ethanol, where reversible capacity remained
almost unchanged over 10 adsorption/desorption
cycles. As with adsorption of biomolecules, cyclodex-
trin functionalized cellulose nanofiber composites was
used by Yuan et al. to remove toluene from aqueous
solutions (Yuan et al. 2017). Hybrid systems can show
synergistic effects here as well, as CNC and GO
composite adsorbents were used for the removal of
ionic 1-butyl-3-methylimidazolium chloride liquid
(Zhou et al. 2017). In this study, the CNC initially
showed lower performance, but upon GO addition
there was an increased performance with the optimum
level at GO content of 30%. While not a ‘‘small
industrial molecule’’ as described above, problematic
inorganic ions can also be removed. Sehaqui et al.
achieved the preparation of cationic CNF from waste
pulp residues with the etherification using gly-
cidyltrimethylammonium chloride for the adsorption
of the negatively charged ions: nitrate, fluoride,
phosphate and sulphate (Sehaqui et al. 2016b).
Depending on the different charge states of these
anions, multivalent ions (sulphate and phosphate)
adsorbed more selectively than the monovalent ones
(nitrate and fluoride).
123
Cellulose
Removal of textile dyes
Little industrial progress has been made in the removal
of dyes from wastewater by adsorption due to the
relative difficulty in regeneration and the low adsorp-
tion capacity of most systems (González et al. 2015;
Lin et al. 2012a; Liu et al. 2015b; Lu and Gibb 2008;
Nair and Vinu 2016; Renault et al. 2008; Yao et al.
2015; Zhang et al. 2017). Hence, coagulation, photo-
fouling, forward oxidation, membrane filtration and
electrochemical destruction are still the main methods
(Crini 2006; Gupta 2009; Yao et al. 2015). Song et al.
have described the benefits of CNC addition to
biosorbent in their work (Song et al. 2017). They
achieved considerably higher adsorption capacity for
CNC-modified keratin than that of the non-modified
for the removal of Reactive Black 5 and Direct Red 80,
with reported adsorption capacity of the biosorbent as
1201 and 1070 mg g-1, respectively. It was noted that
in this system pH is very important as it controls both
the surface properties of the adsorbent and the degree
of ionization of the dye molecules. Both of the dye
molecules were removed from the adsorbent using
NaOH and adsorption performance remained over
80% after five cycles. Amine-functionalized CNC are
promising materials for the removal of organic dyes
from water, because they are fully in the protonated
form at low pH, they can extract organic molecules in
an acidic environment (Jin et al. 2015). Zhou et al.
removed methylene blue (MB) from aqueous solution
using nanocomposite hydrogels (HPAM/CNC) syn-
thesized from partially hydrolyzed polyacrylamide
and increasing CNC content (Zhou et al. 2014). In a
similar vein, Mohammad et al. synthesized CNC-
alginate hydrogels and Yang et al. have used CNC
which is extracted from TEMPO-oxidized carex
meyeriana kunth (CMK) as adsorbents to remove
methylene blue from water (Mohammed et al. 2016;
Yang et al. 2017). Similarly, to the biomolecule case,
Benmassaoud et al. used hybrid CNC-magnetic
nanoparticles for extraction of Sudan dyes from food
samples using capillary liquid chromatography
(CLC). The CN hybrid material reduce Sudan levels
to 23.0, 15.0, 19.0 and 15.0 ng g-1 sudan I-IV,
respectively (Benmassaoud et al. 2017). Methanol
was the most suitable agent for the regeneration of the
matrix among ethanol and acetone. Polyethylenei-
mine-crosslinked CNF was coated with polydopamine
for removal of the textile dye methyl orange by Tang
Cellulose
et al. (Tang et al. 2019). Adsorption of 265.9 mg/g
methyl orange onto the adsorbent was controlled by a
second order chemical kinetic model indicating
chemical adsorption (Tang et al. 2019). Desorption
of methyl orange was achieved using 0.1 M NaOH
resulting in decrease in the adsorption capacity to 89%
after four cycles. Guan et al. have achieved superfast
dye-adsorption within 5 min using ZnO/CNC nanohy-
brids having dye-adsorption capacity of over 90%
(Guan et al. 2019). Moreover, this hybrid material
shows antibacterial activity against E. coli. arising
from ZnO. An interesting aspect in this study was the
change of shape of hybrid material depending on pH.
It takes spherical shape at around pH:8 and sheet-like
or flower-like around pH:10, which may be advanta-
geous depending on the matrix and target molecule.
These are by no means an exhaustive list, but represent
what can be done for dye removal cy CN addition.
Removal of heavy metals
A primary area of exploration for CN-based adsor-
bents is in heavy metal removal. Generally, heavy
metal adsorption takes place via interaction of the
metal center and the chosen anionic functional groups
on the adsorbent surface and can be monodentate or
bidentate (Hokkanen et al. 2016). The amount of
metals adsorbed at the respective rate is dependent on
a dissociation constant between the metal and specific
functional group, which have distinct pKa profiles,
however, functional group selection must adhere to a
pH target range appropriate for adsorption of the
pollutant (Suopajärvi et al. 2015). Luckily, color
change is a good indicator of successful metal
harvesting by the adsorbent (Liu et al. 2015a). In
some cases, noble metals such as Au(III), Pd(II) and
Pt(IV) were targets for ‘‘harvesting’’ while in other
cases environmental remediation of toxic materials
was desired (Hokkanen et al. 2016; Moon et al. 2016).
For example, Hu et al. prepared carboxylated
CNC/sodium alginate hydrogel beads for the removal
of Pb2? from aqueous solution, whereas sulfonated
CNC has also been reported for Pb2? removal,
indicating that many anionic functional groups may
be utilized (Hu et al. 2018a; Suopajärvi et al. 2015). As
is generally used for metal adsorption, 0.1 M HCI was
used as eluent between successive adsorption–desorp-
tion steps with a capacity decrease to 66%. In addition
to lead, Yu et al. used succinic anhydride-modified
CNC, which provides for a high density of carboxylate
groups, to remove both Pb2? and Cd2? from solution
(Liu et al. 2011; Yu et al. 2013). Furthermore, the
measured binding energies show that the interaction
takes place through C=O, C–O and COO- via
bidentate bridging or chelating with carboxyl groups,
instead of monodentate binding. Other metals have
been studied for removal (Ag?, Cu2? and Fe3?/Fe2?)
with the use of using CNCs derived from cellulose
sludge and bioethanol, and cellulose nanofibers
(CNF). Interestingly, a combination of metal ion
binding and growth of metal clusters in sizes ranging
from nanometer to micrometer occurred (Karim et al.
2016). Maaloul et al. screened four different cellulose
based adsorbents through 3 different methods for the
removal of cupper ions from aqueous media and
showed that a physisorption mechanism is dominant in
these cases (Johari et al. 2013; Maaloul et al. 2017).
For higher valent and more toxic metals, Liu et al.
synthesized CNC-PEI composite to remove Cr6?. The
highest adsorption capacity was reached at acidic pH
as 358.42 mg g-1 of composite material in this
interaction where Langmuir Adsorption Model param-
eters were obeyed showing that CNC-based materials
have promise for real-world problems (Liu et al.
2017). Regeneration studies performed using 0.1 M
HCI revealed no remarkable loss of adsorption
capacity after five cycles.
Regarding CNF-based adsorbents, CNFs have been
used for the removal of Hg2? ions. In an important
study, interfering ions such as Pb2?, Ni2? and Al3?
etc. which usually exist in wastewater were used to
determine the effect on adsorption (Bansal et al. 2018;
Wang et al. 2017). The effect of interfering ions was
almost negligible. Cu(II) was the most interfering
cation among eight different cations with the reduction
of 20% on the adsorption capacity. However, chloride
was the most interfering anion of five different anions
with the reduction capacity of 10% on the adsorption
capacity. This behavior can be attributed to –SH
groups of the ligand added to the CNF structure which
is L-cysteine. To increase adsorption capacity, Abou-
Zeid et al. have synthesized 2,3,6 tricarboxy cellulose
nanofiber (TPC-CNFs) for the removal of heavy
metals (Cu2?, Pb2? and Ca2?). However, the use of
crosslinking agents during the synthesis process had
adverse effects on the adsorption process (Abou-Zeid
et al. 2018; Yurkshtovich et al. 2004). Again, in an
effort to target more toxic materials, Abu-Danso et al.
123

removed Pb(II) and Cd(II) ions from aqueous simu-
lated and real media using S-ligand tethered SC(NH2)2
on cellulose nanofibers to better target metals (Abu-
Danso et al. 2018; Gregoret et al. 1991). The
advantage of the SC(NH2)2 group also explained the
ability to make multiple interactions with positively
charged species in the bonding region. Overall, CNF
also showed quite a bit of promise. In an elegant paper
really showing the effect of surface chemistry, Voisin
et al. also directly compared CNC, CNF, TEMPO-
oxidized CNF and Phosphorylated CNC (P-CNC) for
adsorption of Cu2?. Results showed that P-CNC was
about the same as TOCNF which was higher than CNF
which was also higher than plain CNC, with simple
cellulose being the lowest with little adsorption
(Voisin et al. 2017) (Fig. 5).
Summary and outlook
The plethora of techniques and factors that can be used
to modify nanocellulose based materials has been
reviewed to showcase that target specificity and
efficiency can be obtained in a time and cost-efficient
manner, while also allowing for sorbent sustainability
and bio-renewability. As can be seen from the studies,
CN has a higher affinity for positively charged
molecules or atoms. even when unmodified CN was
combined with polymeric structures. They exhibit
particularly high adsorption performance against
divalent metal cations such as Cu(II), Zn(II) or Pb(II).
Although they exhibit relatively good adsorption
Fig. 5 Adsorption capacities for Cu(II) of various forms of
cellulose: cellulose, cellulose nanofibrils, cellulose nanocrys-
tals, TEMPO-oxidized cellulose nanofibrils and phosphorylated
cellulose nanocrystals (reprinted with a permission from Voisin
et al. 2017)
123
Cellulose
performance against other, larger positively charged
molecules, such as biomolecules, the performance
may be reduced due to the steric hindrance of these
large molecules. Although less preferred in terms of
toxicity and safety, chemical modifications that
improve performance do not always show the adsorp-
tion efficiency desired due to increased non-specific
adsorption, among other reasons. This also affects the
desorption performance as well as the adsorption
capacity. In order to obtain high adsorption capacity,
ligands are selected as chemicals with the ability by
which strong interactions can be established. The
ligands from which target molecule can be easily
eluted also exhibit, unfortunately, low adsorption
performances. This can lead to performance loss such
as failure to remove the target molecule when weak
eluent agent is used in the regeneration processes,
deformation of the adsorbent when it is strong, and
disturbing the structure of the isolated target molecule.
Adsorption occurs usually through secondary interac-
tions such as electrostatic, hydrophobic and hydrogen
bonding. Therefore, the eluent to be selected must
have ionic strength able to break these interactions. Of
course, this should be at an optimum level for the
reasons mentioned above. Organic solvents such as
acetone, ethanol, methanol; strong acids such as
hydrochloric, sulfuric, nitric acid and strong bases
such as sodium hydroxide, potassium hydroxide are
regeneration chemicals commonly used with low
concentrations. Lastly, 4–10 adsorption–desorption
cycles were generally applied in the studies reviewed
and while some decrease in adsorption capacity was
observed using a well selected eluent, it was generally
within tolerated levels.
Generally speaking, nanostructures are more
advantageous than compact structures such as hydro-
gels. However, nanoparticles tend to agglomerate to
reduce surface energy. Therefore, nano-size structures
that provide high surface area can be a problem in
some cases in terms of internal diffusion and quantum
size. This is a greater problem for structures with
surface OH groups, such as nanocellulose, which
allow a lot of hydrogen bonding. Agglomeration
reduces the surface area, which in turn leads to a
reduced adsorption capacity. While this can be
overcome with hierarchical structures such as aero-
gels, cryogels, etc., collapse or contraction of the
network structure during solvent removal due to
capillary forces must be avoided. Although this is
Cellulose
solved by supercritical drying, this method is not cost
effective. The surface OH groups may be chemically
modified and the numbers reduced, but this also
requires further processing which is disadvantageous
in terms of time and cost.
Going forward, a more concentrated research effort
can further reduce cost of processing with increasing
performance parameters. The synthesis of effective
and selective adsorbents that are produced from
naturally produced nanomaterials can help play a role
in remediating the environment and in prevention of
its pollution in the first place. However, challenging
problems during the modification and implementation
stages are emerging. For example, while ideally
unmodified CN can be used effectively in adsorption,
surface modification will likely be necessary to allow
sorbent selectivity, resistance to interference, high
capacity, and high efficiency. Unfortunately, the yield
obtained in the modification step is still very low in
some modifications and most modification methods
are plagued by high cost, toxic by-products and/or
high energy consumption. Another barrier to com-
mercialization is the fact that CN production is still
low in capacity and relatively high cost preventing
wide-scale utilization in low end applications such as
sewage, industrial wastewater and environmental
remediation. However, this is not an issue for high
value applications such as treatment of pharmaceutical
wastewaters, where higher profit margins and lower
volumes may allow use. Considering this, besides the
general current research into surface modification and
lowering cost and more adsorbent specific directions
of improving selectivity, efficiency, etc., future
research in CN-based adsorbents may be served by
focusing on pharmaceutical and biomolecular appli-
cation-specific adsorbent targets due to increased
likelihood of cost-effectiveness. Regardless, CN-
based adsorbents overall are a promising sustainable
alternative to more traditional adsorbents.
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