Cellulose (2021) 28:4865–4885

https://doi.org/10.1007/s10570-021-03828-4 (0123456789().,-volV)
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ORIGINAL RESEARCH

Cellulose reinforced electrospun chitosan nanofibers bio-

based composite sorbent for water treatment applications
Ilse Ileana Cárdenas Bates . Éric Loranger . Aji P. Mathew . Bruno Chabot

Received: 10 December 2020 / Accepted: 11 March 2021 / Published online: 23 March 2021
 The Author(s), under exclusive licence to Springer Nature B.V. 2021

Abstract Electrospun chitosan–polyethylene oxide/ effect of nanofiber’s coating weight on strength,

TEMPO-oxidized cellulose (CS–PEO/TOC) bio- permeability and adsorption capacity of the bio-based
based composite was fabricated for the first time for material. Mechanical properties of the composite were
water treatment applications. This new concept allows improved over the electrospun nanofiber mat. The CS–
cellulose and chitosan to be combined in a simpler and PEO provides greater elasticity (strain%) and the TOC
efficient way, avoiding the use of harmful solvents, provides a higher tensile strength to the material.
compared to previously published related work. The However, tensile index was reduced by 48% with
‘‘Sandwich-like’’ material is composed of a porous electrospinning time, while burst index was almost
oxidized cellulosic fibers central core (TOC hand- constant. The best conditions were achieved for 2 h
sheet) and a thin layer of electrospun CS–PEO electrospinning time. Under these conditions, a high
nanofibers on both sides of the core. Average diam- permeable material (290.13 L/m2 hbar) was devel-
eters for CS–PEO and TOC were 159.3 ± 33.7 nm oped. The adsorption capacity for Cu (II) ions reached
and 21.7 ± 5.1 lm, respectively. Fourier Transform up to 27% with only 12 mg of chitosan onto the CS–
Infrared Spectroscopy (FTIR) was carried out on the PEO/TOC (12.42 mg/g). The data fit better to the
bio-based composite. Results suggest that no covalent pseudo-second order model, suggesting chemisorption
bonds are involved but rather electrostatic interactions as the main mechanism involved for copper adsorp-
occur which allows bonding of the electrospun tion. This study opens-up potential opportunities for
nanofiber layers on TOC core and no delamination. the development of a robust material for wastewater
CS–PEO electrospinning time was varied to study the applications at an industrial scale.

I. I. Cárdenas Bates  É. Loranger 

A. P. Mathew  B. Chabot (&)
Institut d’Innovations en Écomatériaux, Écoproduits et
Écoénergies, Université du Québec à Trois-Rivières, 3351
boul. des Forges, C.P. 500, Trois-Rivières,
QC G9A-5H7, Canada
e-mail: [email protected]

I. I. Cárdenas Bates  É. Loranger 

A. P. Mathew  B. Chabot
Department of Materials and Environmental Chemistry,
Stockholm University, Frescativägen 8, 10691 Stockholm,
Sweden

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4866 Cellulose (2021) 28:4865–4885

Graphic abstract

Keywords Bio-based reinforced composite menstruation, osteoarthritis and lethargy, etc.… (Dra-
adsorbent  Electrospun chitosan nanofibers  TEMPO- gan et al. 2014; Amuda et al. 2016; Teow et al. 2018;
oxidized cellulose  Mechanical property  Water Vardhan et al. 2019). Besides, it is a common toxic
purification  Copper ions adsorption waste found in major manufacturing industries such as
petroleum, mining, pesticides, pulp and paper, fertil-
izers, dye/textiles, among others (Sehaqui et al. 2014;
Liu et al. 2016a; Ranade and Bhandari 2017; Vardhan
Introduction et al. 2019) and also a common reference materials
(Chen et al. 2017).
Rapid industrialization and urbanization growth has Various chemical and physical techniques such as
led to an alarming pollution problem in the aquatic ion-exchange, chemical precipitation, reverse osmo-
ecosystem, affecting the quality of life (Diagboya et al. sis, biological treatment, advanced oxidation and
2014; Ranade and Bhandari 2017). Among the most electrochemical methods have been applied to remove
dangerous pollutants, heavy metals are of great heavy metals from water (Tian et al. 2011; Abdullah
importance due to their high toxicity, non-biodegrad- et al. 2019; Vardhan et al. 2019). However, they are
ability and carcinogenic effect (Amuda et al. 2016; either costly or inefficient. Hence, other techniques
Anastopoulos and Kyzas 2016; Liu et al. 2016a). Their have been studied to improve efficiency and to reduce
accumulation in the environment is posing a serious costs. Nowadays, adsorption is generally considered
treat to living systems. Therefore, the removal of these as a promising technique due to its low cost, simplic-
metals is very important for human health and ity, possibility to reuse the adsorbent and high
environmental security. In this study, copper ions efficiency to remove heavy metals from aqueous
have been chosen as the target metal since their effluents (Anastopoulos and Kyzas 2016; Sarkar and
exposition to large doses produce weakness, insomnia, Adhikari 2018; Wang et al. 2018). In this technique,
gastrointestinal diseases, DNA damages, cessation of the choice of the most appropriate adsorbent is critical

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Cellulose (2021) 28:4865–4885 4867

from both techno-economic feasibility and environ- surface area per unit mass and small pores. The higher
mental points of view. In recent years, some efforts surface area of nanofiber web improve adsorption rate
have been made toward the study of new bio-based compared to other material shapes (Tian et al. 2011;
material adsorbents (biosorbents) as they are renew- Devarayan et al. 2013; Wang et al. 2018). Briefly,
able, unlimited and biodegradable (Paquin et al. 2013; during the electrospinning process, an electrically
Islam et al. 2014; Jiaping et al. 2016). Besides, these charged polymeric solution is ejected from a syringe
materials can be produced from industrial residues of tip as a continuous jet toward a collector. As the jet
biomass allowing them to be recycled. More recently, travels in air, the solvent evaporates allowing the
many publications have been reported on using formation of very thin fibers which are deposited on a
chitosan or cellulose as a biosorbent material for metallic collector (Muthu Kumar et al. 2019; Xue et al.
multiple heavy metals as they are the two most 2019). Polymers must previously be dissolved and
abundant natural polymers in the world, they involve properly mixed in order to get a homogeneous
economical chemical reagents and they show great solution. However, in the case of chitosan and
adsorption capacity towards heavy metals (Ahmad cellulose, these two biopolymers cannot be dissolved
et al. 2015; Zhang et al. 2016). During the last few in a common solvent due to the presence of strong
years, many researchers have demonstrated higher hydrogen bond in their molecular chains (Abdul
sorption capacities of chitosan/cellulose (CS/Ce) Khalil et al. 2016). To overcome this issue, several
blends compared to results obtained with chitosan or researchers (Du and Hsieh 2009; Salihu et al. 2012;
cellulose films/membranes taken individually (Du and Aquino et al. 2018; Li et al. 2018; Somsap et al. 2019)
Hsieh 2009; Morgado et al. 2011; Aquino et al. 2018; have used cellulose or chitosan derivatives such as
Somsap et al. 2019). This is because despite the great Dibutyryl chitin and cellulose acetate with co-solvents
adsorption capacity of chitosan, these media present systems such as Dichloromethane (DCM), Acetone,
low mechanical properties making them inadequate Acetic acid (AcOH) and Pyridine. Three other studies,
for industrial scale applications. Thus, addition of (Devarayan et al. 2013; Phan et al. 2018; Wang et al.
cellulose fibers as a reinforcing agent should improve 2018) on the contrary, succeeded by blending chitosan
the mechanical strength of the adsorbent material. with cellulose as such using a co-solvent system of
Besides, in addition to amine (NH2) and hydroxyl Trifluoroacetic acid (TFA)/AcOH or H2SO4/AcOH.
(-OH) groups in chitosan, cellulosic fibers also have Therefore, to date, there are very few reports on
hydroxyl groups which facilitates the chelation with electrospun Chitosan/Cellulose composites. A list of
metal ions (Salihu et al. 2012). Some studies on copper these related publications is provided in Table 1.
adsorption (Sehaqui et al. 2014; Liu et al. 2016b; Zhu Moreover, most of them use toxic solvents, such as
et al. 2017) using cellulosic fibers obtained through pyridine (carcinogenic), DCM (carcinogenic poten-
2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) medi- tial) and TFA that are also toxic. Also, as far as we
ated oxidation, have shown several advantages versus know, only Phan et al. (2018), Brandes et al. (2020)
other types of modified cellulose (Jradi et al. 2012; and Wang et al. (2018) have studied the potential of
Bideau et al. 2016). These advantages include the electrospun Chitosan/Cellulose bio-based materials as
presence of carboxylate (COO-) groups, which also an adsorbent for copper ions.
have a potential to retain metals ions or improve the Studies involving electrospun nanofiber mats are
crosslinking, giving greater potential physical resis- mostly carried out in the laboratory using batch-type
tance to the composite. set-up where the sorbent material is exposed to a fluid
Chitosan and cellulose polymers have been com- containing the contaminant for very long residence
bined into various shapes such as films, sponges, time to allow equilibrium to be achieved. In this
membranes, hydrogel beads, micro/nanospheres, process, the contaminant is mainly exposed to the
flakes, coated fibers, textile assemblies, hollow fibers active sites available on the outer surface of the
and electrospun webs (Salihu et al. 2012; Tetala and adsorbent, which limits its overall adsorption capacity
Stamatialis 2013). Among all of them, electrospun due to slow mass transfer through the mat (Li et al.
nonwoven webs have received great consideration, as 2016). To improve the adsorption capacity, continuous
electrospinning is a simple and unique technique to operation (dynamic adsorption system) is preferred. In
obtain long nano/microfibers that provides a large this process, the fluid containing the contaminant is

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4868 Cellulose (2021) 28:4865–4885

Table 1 Electrospun chitosan/cellulose composites and their applications

Matrix polymers Solvent system Mean fiber Application study References
diameters

Cellulose acetate/dibutyryl chitin Acetone/acetic acid 30–350 nm Unlisted Du and

Hsieh
(2009)
Cellulose/chitosan 1-Ethyl-3- * 200 nm Antistaphylococcal activity for Miao et al.
methylimidazolium wound healing (2011)
acetate/dimethyl
sulfoxide
Cellulose/chitosan 1-ethyl-3- N/A Antibacterial activity for wound Park et al.
methylimidazolium healing gauzes (2011)
acetate
Chitosan/cellulose acetate Trifluoroacetic acid/ 450–650 nm Unlisted Salihu et al.
dichloromethane (2012)
Cellulose/chitosan Trifluoroacetic acid/acetic 77 ± 33 nm (Ce Unlisted Devarayan
acid from bamboo) et al.
82 ± 44 nm (Ce (2013)
from cotton)
Cellulose monoacetate/chitosan Acetone/glutaraldehyde 1–2 lm Immobilization of proteases for Demirkan
detergent and textile et al.
industries (2018)
Poly (ethylene Acetic acid 88 ± 32 nm (5% Cell assay in cultures 3T3 Ridolfi et al.
oxide)/chitosan/cellulose CNCs) fibroplasts for applications in (2017)
nanocrystals 71 ± 32 nm tissue engineering
(10% CNCs)
*Chitosan/cellulose acetate Trifluoroacetic acid/acetic 122 ± 35 nm As (V), Pb (II) and Cu (II) Phan et al.
acid (4% CS) adsorption for wastewater (2018)
349 ± 96 nm purification
(6% CS)
*Cellulose Acid acetic/thioglycolic 30–350 nm Pb (II) and Cu (II) adsorption Wang et al.
nanocrystals/chitosan/ acid/ for wastewater purification (2018)
polyvinyl alcohol tetrahydrofuran/sulfuric
acid
Chitosan nanoparticles/ Ethanol/pyridine 150–1000 nm Platet adhesion and Li et al.
ethylcellulose/bacterial inflammatory response for (2018)
cellulose sulfate membrane blood compatibility
*Cellulose acetate/chitosan Trichloroacetic acid/ 368 ± 157 nm Cd (II) adsorption for Aquino
dichloromethane (15% CS) wastewater purification et al.
992 ± 343 nm (2018)
(5% CS)
Chitosan/cellulose acetate/ Acetic acid 156 ± 17 nm Antibacterial activity for food Somsap
gelatin/eugenol (0.1% eugenol) packaging et al.
288 ± 77 nm (2019)
(10% eugenol)
*Chitosan/polyethylene oxide/ Acetic acid 217 ± 52 nm Cd (II) adsorption for Brandes
phosphorylated nanocellulose wastewater purification et al.
(2019)
*Chitosan/phosphorylated Acetic Acid 372.3 ± 82.1 nm Cd (II), Cr (VI), Cu (II) and Pb Brandes
cellulose (CS–PEO) (II) adsorption for water et al.
21.5 ± 3.7 lm treatment (2020)
(PCF)

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Table 1 continued
Matrix polymers Solvent system Mean fiber Application study References
diameters

Chitosan/cellulose acetate Trifluoroacetic acid/ 88.14 ± 0.27 to Electrochemical enzymatic Yezer and
dichloromethane/formic 129.00 ± 0.18 biosensors Demirkol
acid (2020)
*Application studies in wastewater treatment

filtered through the porous sorbent where most of the strength and permeability. Finally, yet importantly,
adsorption sites can be accessed by the contaminant we also found a potential use in this material as an
(Zhang et al. 2019). Although nonwoven electrospun adsorbent for copper ions in aqueous solutions.
nanofiber mats can be tailor-made with high specific
surface area, high porosity and abundant binding sites,
they have low basis weight and exibit low mechanical Experimental
strength to withstand operating pressure applied
during filtration of liquid in dynamic adsorption Materials
system (Li et al. 2017b). To provide strength, electro-
spun nanofiber mats must be supported by a stronger Chitosan powder (CS, deacetylation of 75–85%, low
porous layer forming a bilayer composite sorbent. molecular weight), Polyethylene oxide used as a co-
Affinity membranes for pressure-driven filtration spinning agent (PEO, Mv * 900,000), Acetic acid
applications such as microfiltration (MF) and ultrafil- (AcOH, 99.7%), Murexide ACS reagent and Copper
tration (UF) were developed based on this concept (Vo (II) sulfate pentahydrate (CuSO45H2O) were pur-
et al. 2020). They are available on different geometries chased from Sigma-Aldrich Chemical Company USA.
including thin sheet, hollow fiber, spiral wound and TEMPO-oxidized cellulose fibers (TOC, 1700 mmol/
membrane stack. They are featuring physical adsorp- kg) were supplied by our laboratory. Sodium bicar-
tion as well as chemical adsorption where contami- bonate powder (NaHCO3, 99%) and Ethylenediamine
nants are bound to specific adsorption sites within the tetraacetic acid (EDTA, 99%) were purchased from
pore openings of the membrane. However, these Omega Chemical Company USA. All chemicals were
membranes are prone to fouling even at the relatively used without additional purification.
low pressure applied. Composite thin electrospun
nanofiber mats supported by a highly porous substrate Bio-based composite fabrication
layer is a potential way to provide a strong structural
material with high porosity and large surface area, and Standard handsheets at an oven dry (OD) weight of
with a lower fouling potential compared to affinity 60 g/m2 were made with TOC fibers according to
membranes. TAPPI Standard No. T 205 sp-02. Briefly, 8 L of a pulp
This study presents the development of a new fiber suspension at a consistency of 0.3% was prepared
original 3D structural assembly never reported in from an accurate weight of ovendried TOC fiber
previous publications combining both chitosan and sample. From this pulp suspension, the required
cellulose into a single adsorbent media. This assembly volume to make a 1.2 g (OD) handsheet was sampled
consist in fabricating an eco-responsible ‘‘Sandwich- and poured into a NORAM handsheet machine where
like’’ bio-based composite using a central core of the sheet is formed by filtration through a 150 mesh
TEMPO-Oxidized cellulose (TOC) fiber, coated on (approx. 100 lm opening size) wire screen (TAPPI
both sides by an ultrathin electrospun CS–PEO Standard No. T-205 sp-02. Seven handsheets were
nonwoven mat layer. Extensive characterization then made following the same process. Afterwards, the
revealed the unique surface properties of this bio- TOC handsheets were pressed as described in the
based composite, such as improved mechanical TAPPI standard method. Then, they were placed into

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special drying rings to prevent sheet shrinkage and Stabilization of CS–PEO/TOC nanofibrous mats
dried overnight in a conditioning room at 23 C and
50% of relative humidity (TAPPI Standard No. The CS–PEO/TOC bio-based composite should firstly
402-sp-03). Subsequently, a TOC handsheet was fixed be neutralized with an alkaline solution in order to
to the metal collector of the electrospinning unit. convert the protonated amino groups (NH3?) to
Then, a CS–PEO solution was electrospun on both primary amine groups (NH2). Otherwise, the CS–
sides of the TOC handsheet to form a ‘‘Sandwich- PEO nanofibers would not be stable in aqueous
like’’ composite where the oxidized cellulose fibers solutions due to the presence of high level of NH3?
are in the middle and the CS–PEO electrospun mats functional groups. However, cellulose naturally dis-
are on the outer surfaces (Fig. 1). perses in such an alkaline medium and this phe-
The electrospinning conditions to obtain the CS– nomenon is further increased for TOC due to the
PEO nanofibers were described in a previous work presence of the oxidized carboxyl groups (COO-). To
(Cardenas Bates et al. 2020). Briefly, the polymers solve this problem, several pH values were investi-
were firstly dissolved in their corresponding solvent; gated by adjustment of the concentration of a NaHCO3
CS in acetic acid 90% and PEO in water. Subse- solution in order to find the optimum one to maintain
quently, both solutions were mixed at a ratio of 4:3 by the aqueous stability of the material. Tests at pH B 6
weight of CS:PEO and stirred continuously for 2 h. were performed using only distilled water as its pH is
Finally, the blended solutions were kept at rest at room slightly acidic (* 5.8). After neutralization treatment,
temperature for 3 h before being electrospun over the the bio-based composite was rinsed several times with
TOC handsheet. distilled water. Then, it was dried in vacuum oven
Different CS–PEO electrospinning time were overnight to remove any residual solvent.
tested (2, 3 and 4 h) in order to study the effect of
the nanofiber coating weight on the physical and Characterization
chemical properties of the bio-based composite. The
samples are named as xCS–PEO/TOC, in which x All characterizations were made for CS–PEO, TOC
(h) is the CS–PEO electrospinning time. Thus, three and xCS–PEO/TOC biocomposites samples and all
different bio-based composites having different gram- measurements were repeated three times to guarantee
mages of CS–PEO layers were studied. A summary of good average results.
the samples is listed in Table 2. A nanofibrous mat of
single CS–PEO was also electrospun for 4 h and used
as the control sample.

Fig. 1 Experimental set-up of electrospinning for the preparation of the CS–PEO/TOC bio-based composite

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Table 2 CS–PEO/TOC mass ratio under different electrospinning time of CS–PEO

Sample CS–PEO electrospinning time CS–PEO: TOC mass Thickness Grammage (g/ Density (g/
(h) ratio (mm) m2) cm3)

CS–PEO 4 N/A 0.010 ± 0.003 3.27 ± 0.19 0.33 ± 0.02

TOC N/A N/A 0.075 ± 0.005 61.6 ± 0.9 0.82 ± 0.01
2CS–PEO/ 2 9:91 ± 0.037 0.088 ± 0.003 67.7 ± 0.9 0.77 ± 0.01
TOC
3CS–PEO/ 3 14:86 ± 0.005 0.091 ± 0.007 71.6 ± 0.9 0.79 ± 0.02
TOC
4CS–PEO/ 4 18:82 ± 0.005 0.102 ± 0.002 75.1 ± 0.9 0.74 ± 0.02
TOC

Microscopy and spectrometry used. The burst strength was also measured for each
sample according to TAPPI Standard No. T 403-om-
The morphology of the fibers was observed by 02. This test causes a specimen to deform into an
Scanning Electron Microscopy (SEM; SU1510 by approximately spherical shape until failure occurs by
HITACHI, Japan). The average fiber diameter was rupture. It was measured using a Mullen burst tester
calculated using a software from SEM images model C. In order to compare samples of sorbent
(Abràmoff et al. 2004) based on 50 fibers per sample. media, tensile index and burst index were calculated
The biocomposites were also analyzed by Fourier by dividing tensile stress and burst strength by the
Transform Infrared (FTIR-ATR; Nicolet iS10, handsheet grammage (g/m2). Both tests are thus
Thermo Scientific, USA) spectroscopy for the identi- related to the amount of material being loaded.
fication of functional groups and specific bonds
present in the material. The spectra were recorded Pore size and water flux
between 4000 and 500 cm-1 by the diamond crystal
method. Permeation tests were carried out using a dead-end
stainless-steel cell (HP4750 from Sterlitech, USA)
Mechanical properties with an active membrane area of 14.6 cm2. In order to
achieve steady water flux and ensure the pores are all
Mechanical properties of representative bio-based open, the CS–PEO/TOC bio-based composites were
composites samples were determined using standard precompacted with distilled water at 5 psi for 10 min
methods from the pulp and paper industry. Those before testing. Then, all experiments were carried out
methods were chosen because the main component of at 7 psi and room temperature, with 0.1 L of distilled
the bio-based composite material is a standard TOC water. The water flux was calculated using Eq. (1):
fiber handsheet as described previously. The samples V
were preconditioned for 24 h at 50% relative humidity J¼ ð1Þ
At
prior to measurements according to TAPPI Standard
No. T 402 sp-03. The tensile strength measures the where J is the water flux (L/m2 h), V is the filtrate
maximum tensile force developed in a test specimen volume (L), A is the area of the bio-based composite
before rupture. It was measured using a universal (m2), and t is the filtration time (h).
testing instrument; Instron 4201 with a 500 N load cell The permeability of the bio-based composites was
at a cross-head speed of 10 mm/min according to calculated from the water flux per unit membrane
TAPPI Standard No. T 494-om-01. However, due to pressure. The pore size distribution was measured by
the relatively small size of the electrospinning collec- the bubble point test defined by the American Society
tor used, it was not possible to prepare samples of for Testing and Materials Standard Organization
50 mm in length as described in the standard method. (ASTM F316-03 2019) also using the dead-end
Samples of 30 mm in length by 15 mm in width were stainless-steel cell. Bio-based composites were soaked

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in distilled water for 30 min prior experiments. The Results and discussion
gas pressure at the start of bubble forming was
reported as bubble point. The Young–Laplace equa- Morphology study of sorbent materials
tion as follows was used to determine the diameter of
the largest pores of the material: CS–PEO, TOC and CS–PEO/TOC bio-based com-
posites samples were carefully prepared under the
4c cos h
d¼ ð2Þ given conditions. They were examined by SEM to
P
study their structure and morphology. Figure 2a–c
where P is the bubble-point pressure (MPa), c the present the CS–PEO, TOC and 3CS–PEO/TOC sam-
surface tension of the air–liquid interface (N/m), h the ples, respectively. All materials exhibit a well-defined
liquid–solid contact angle when a gas bubble perme- network structure with uniform and continuous fibers.
ates a pore of the same radius, which means that the The CS–PEO nanofibrous mat shows bead-free
contact angle is 0, and d the larger pore average nanofibers with average diameters of
diameter (lm). 159.3 ± 33.7 nm. The TOC handsheet presents an
average diameter of 21.7 ± 5.1 lm.
Batch adsorption of copper ions In the case of the CS–PEO/TOC bio-based com-
posite, the SEM micrographs were taken from surface
Batch adsorption tests were made in order to deter- and cross-section (Figs. 2c and 3). As shown in Fig. 3,
mine the capacity of the material to capture copper the CS–PEO nanofibers coating on the TOC were
ions in solutions. For this, 100 mg of sorbent material highly homogeneous. Both CS–PEO and TOC mats
were soaked into 50 mL of CuSO45H2O aqueous kept their fiber structure when assembled with min-
solution at 100 ppm copper concentration. Each test imal morphological defects such as the presence of
was carried out at 200 rpm shaking speed, pH 6 and very few micro-beads. It can also be seen that a thin
room temperature. At every 30 min, the concentration CS–PEO electrospun nanofibers mat (Fig. 2c) is
of copper solution was determined by titration with entirely recovering the cellulose fibers (TOC pores),
EDTA until the copper concentration reached an which is believe to decrease the porosity of the CS–
equilibrium. The maximum adsorption capacity of the PEO/TOC bio-based composite when compared to
bio-based composite (qe) was calculated based on TOC mat alone. This will be confirmed later in the
Eq. (3): pore size and water flux section. A similar phe-
C0  Ce nomenon was observed by Goetz et al. (2016) who
qe ¼ V ð3Þ made electrospun cellulose acetate membranes coated
m
with chitin nanocrystals. Figure 3a shows the ‘‘sand-
where C0 and Ce are the initial and equilibrium copper wich-like’’ structure of the bio-based composite. In
concentration (ppm), respectively, V is the volume of Fig. 3b, the three layers (CS–PEO/TOC/CS–PEO in
copper solution (L), and m is the mass of the sorbent that order) can be easily seen, especially in Fig. 3c
material (mg). where the thin layer of CS–PEO electrospun nanofi-
For the kinetic studies, non-linear pseudo-first order bers is clearly visible on the surface of the TOC.
(4) and pseudo-second order models (5) were evalu-
ated to elucidate the adsorption mechanism involved Stabilisation of CS–PEO/TOC bio-based
in the adsorption process. composite in aqueous solutions


qt ¼ qe 1  expk1 t ð4Þ
A neutralization of the chitosan’s amino groups
k2 q2e t (NH3? to NH2) is needed for the CS–PEO layers in
qt ¼ ð5Þ order to prevent its dissolution in aqueous medium.
1 þ k 2 qe t
These NH2 groups are also required to attract copper
where k1 (min-1) and k2 (g/(g min)) are the pseudo ions by a chelation mechanism (Mekahlia and Bouzid
first order and pseudo second order adsorption rate 2009; Abdullah et al. 2019). Considering that the pKa
constants, respectively, and qt is the amount of copper of chitosan is * 6.5 (Phan et al. 2018; Zhang et al.
adsorbed (mg/g) at time t (min). 2018), a pH of around 8.5 is required to provide a

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Fig. 2 SEM micrographs showing morphology of the fibrous materials; a CS–PEO, b TOC, c 3CS–PEO/TOC bio-based composite
(surface)

Fig. 3 Morphology of the 3CS–PEO/TOC bio-based composite (cross section); a horizontal view, b vertical view of the three layers,
c vertical view with zoom on one side of the material

complete neutralization. However, at an alkaline pH, destruction of the fiber network of the TOC handsheet
the TEMPO cellulosic fibers (pKa * 4) (Spaic et al. and redispersion of the cellulose fibers in the aqueous
2014) is redispersed in water due to the repulsion solution. Therefore, only the CS–PEO layers are still
between the carboxylate (COO-) groups. Figure 4 unaffected and can be recovered. For pH lower than 8,
shows the behavior of the bio-based composite at the more acidic the solution was, the higher the loss of
different pH. The pH adjustment was done with a mass of the CS–PEO layers was observed because of
sodium bicarbonate solution. Results show that the the chitosan dissolution. Thus, only the TOC hand-
structure of the material is maintained at pH 8. This is sheet can be recovered. Therefore, pH 8 was selected
due to electrostatic interactions between polysaccha- as optimal, since it provides conditions to maintain the
rides (Soni et al. 2016; Mao et al. 2019). On the other structural integrity of the composite media as well as a
hand, at a pH higher than 8, repulsion between the high conversion of NH3? groups to NH2 in the
COO- groups of the TOC is important causing a chitosan.

Fig. 4 Photograph of the CS–PEO/TOC bio-based composite at different pH values

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4874 Cellulose (2021) 28:4865–4885

However, even if the visual structure of the material previous publication (Cardenas Bates et al. 2020)
after the stabilisation was maintained, SEM micro- where an homogeneous dispersion of all elements was
graphs in Fig. 5 demonstrate that its initial fibrous observed, confirming the homogeneity of the compo-
microstructure has changed. The morphology of the nents in the nanofibers.
CS–PEO nanofibers is different and is attributed to the
neutralization treatment. Figure 5b clearly shows that Molecular analysis by FTIR spectroscopy
the nanofibers were partly melted. This suggests that
welding of nanofibers at junction points between The spectra of CS–PEO nanofibrous mat, TOC
nanofibers as well as nanofibers and TOC fibers may handsheet and the CS–PEO/TOC bio-based composite
occurred. It is believed that this welding process may were assessed by FTIR-ATR spectroscopy (Fig. 6).
have reduced the available active sites of the The spectrum of CS–PEO displays characteristic
nanofibers but may have improve the bounding absorption bands at 1576 and 1654 cm-1. The first
strength (delamination force) between TOC and CS– band corresponds to the N–H bending vibrations
PEO layers. The mechanical enhancing effect due to (Aliabadi et al. 2013; Ridolfi et al. 2017) and the
the bonding points between the fibers has been second band corresponds to the C=O stretching of the
previously reported by Li et al. (2017a, b). This acetyl group from chitin, since, as we have previously
assumption will be further confirmed in the mechan- mentioned, chitosan is 75–85% deacetylated, so a few
ical properties section. This change in structure is acetyl groups are still present (Ridolfi et al. 2017; Phan
believed to be due to the dissolution of both PEO et al. 2018). The bands located at 1028 and 1075 cm-1
during rinsing with water after the neutralization correspond to the C–O–C stretching vibrations (Ali-
treatment and to the NH3?CH3COO- salt which is abadi et al. 2013; Ridolfi et al. 2017). The absorption
formed during the dissolution of chitosan in acetic band at 2880 cm-1 and the broad band between 3600
acid. This behavior has also been observed by other and 3100 cm-1 in all spectra, are attributed to the
authors (Salihu et al. 2012; Phan et al. 2018). The stretching vibration peak of alkane C–H and, to N–H
former explains that in an heterogeneous blend, one of present in chitosan and O–H stretching present in all
the components would dissolve on its own leaving the polymers, respectively. The spectrum of TOC hand-
other component in the form of porous or hollow sheet shows characteristic peaks of the TEMPO-
fibers. However, in a homogeneous blend, the attempt oxidized fibers corresponding to the carbonyl stretch-
to dissolve one of the components causes the break- ing vibration at 1597 cm-1 (vasCOO-) and
down of the overall structure. This is consistent with 1424 cm-1 (vsCOO-) (Jin et al. 2014; Sehaqui et al.
the EDX results of CS–PEO nanofibers reported in our 2014; Onyianta et al. 2017). Concerning the CS–PEO/

Fig. 5 Morphology of the 3CS–PEO/TOC bio-based composite after neutralization treatment with NaHCO3 at a 91500 and b 92500
magnifications

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Cellulose (2021) 28:4865–4885 4875

Fig. 6 FTIR Spectra of a CS–PEO, b TOC, c CS–PEO/TOC bio-based composite

TOC bio-based composite, the analysis of the FTIR provide specific adsorption sites for target contami-
spectrum confirms that the polymers are all present nants, but their mechanical strength are weak. In this
since their characteristic’s bands are detected. Also, no study, it is proposed to improve the mechanical
new peaks appeared, which means that there is no properties of CS–PEO electrospun nonwoven mats
formation of covalent bonds (e.g., amide bonds) but by addition of a cellulosic fiber (TOC) handsheet as a
rather electrostatic interactions. Likewise, there is no reinforcing structure porous core, on which thin
evidence of broadering or shifting in the peak position, chitosan nanofibers mat layers are electrospun on
indicating that no hydrogen bonds are present between both sides. Figure 7 shows representative stress–strain
CS–PEO and TOC. The values of the absorption bands curves of CS–PEO nanofiber mat, TOC, and bio-based
in all samples were taken from (Sigma Aldrich 2020). composite samples at various electrospinning time.
They are all in agreement with the literature data Table 3 also presents elongation at break (strain),
presented in similar works (Salihu et al. 2012; Young’s modulus, tensile strength and load at break
Aliabadi et al. 2013; Jin et al. 2014; Sehaqui et al. data from Fig. 7. Stress–strain curves show a typical
2014; Soni et al. 2016; Onyianta et al. 2017; Ridolfi elastic and plastic nature of the material. Each sample
et al. 2017; Phan et al. 2018; Wang et al. 2018; Mao presents an initial flat behavior before tensile stress
et al. 2019). start to be recorded. This could be attributed to several
phenomena including, a slight uncontrolled sample
Mechanical properties of sorbent materials slipping in the jaws at the start of stretch, but also
nanofiber straightening out or realignment under
To provide a suitable bio-based composite sorbent uniaxial stretching load application (Szczesny et al.
media for industrial wastewater treatment applica- 2017). The latter seems to be more important as the
tions, it is not only necessary to develop a material quantity of nanofibers increases with electrospinning
with specific adsorption capacities, but also to develop time. This behavior is consistent with other works (Li
a robust material capable of withstanding high-pres- et al. 2015, 2019; Phan et al. 2018; Szymańska-
sure drops during filtration of liquid. It is well known Chargot et al. 2019). Obviously, the CS–PEO elec-
that electrospun nonwoven mats can be tailor-made to trospun mat has low tensile strength properties

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4876 Cellulose (2021) 28:4865–4885

50
CS-PEO
TOC
2CS-PEO/TOC
40 3CS-PEO/TOC
Stress (MPa) 4CS-PEO/TOC

30

20

10

0
0 2 4 6 8 10

Strain (%)
Fig. 7 Stress–strain curves for CS–PEO, TOC and xCS–PEO/TOC

Table 3 Effect of TOC on mechanical properties of the biocomposites

Material Strain Young’s modulus Tensile strength Load at break Tensile index Burst index
(%) (MPa) (MPa) (N) (N m/g) (kPa m2/g)

CS–PEO 3.15 595.36 11.86 1.30 26.50 ± 2.60 \ 0.30

TOC 4.10 2370.09 46.69 56.03 60.60 ± 1.95 1.34 ± 0.18
2CS–PEO/ 7.94 841.54 34.42 52.40 51.58 ± 4.01 1.40 ± 0.23
TOC
3CS–PEO/ 6.41 534.75 17.65 34.42 32.01 ± 1.75 1.52 ± 0.01
TOC
4CS–PEO/ 6.24 377.33 14.38 30.19 26.78 ± 7.36 1.68 ± 0.02
TOC

compared to TOC (11.86 MPa vs. 46.69 MPa). The between TOC and CS–PEO materials. A synergetic
Young’s modulus is approximately 4 times higher for effect is clearly observed as both tensile strength and
TOC. CS–PEO mat is clearly a weaker material elongation at break are increased, when compared
compared to the TOC handsheet. This could be mostly with CS–PEO mat. However, the increase of CS–PEO
attributed to the lower amount of material (lower electrospinning time over the TOC has rather an
grammage), the porous structure of the non-woven adverse impact on the breaking tensile stress, Young’s
mat, and possibly poor nanofiber bonding especially at modulus, and elongation at break (see Table 3).
the joint (Zhou et al. 2011; Li et al. 2017a). On the Addition of electrospun nanofibers follows an inverse
contrary, TOC handsheet shows higher tensile relationship relative to electrospinning time. This
strength but lower potential for elastic deformation. tendency has also been reported in other publications
Biocomposite samples combining TOC and electro- (Liu and Bai 2005; Goetz et al. 2016; Weng et al.
spun nanofibers show intermediate patterns ranging 2017; Yang et al. 2018). This is likely because after

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Cellulose (2021) 28:4865–4885 4877

approximately 2 h of electrospinning, the electrospun cellulose and the interactions between CS–PEO and
chitosan nanofibers that continue to be deposited over TOC making polymer chains more stable and rigid
the TOC handsheet are no longer in contact with the than CS–PEO alone (Zhou et al. 2011; Phan et al.
cellulose fibers, but rather, are in contact with the 2018).
previously deposited chitosan nanofibers. Therefore, Based on the results presented, the 2CS–PEO/TOC
at this point, there are more chitosan intramolecular bio-based composite exhibited the best mechanical
interactions than intermolecular interactions with properties and therefore, the one to be optimized from
cellulose. According to (Yang et al. 2018), this leads now on. The tensile strength and strain values of this
to a non-homogeneous interaction in the bio-based bio-based composite were compared to previous
composite resulting with weaker interfacial and poorer related studies listed in Table 5. It can be observed
elastic strength properties. that the 2CS–PEO/TOC composite presents good
To study the effect of TOC handsheet reinforce- mechanical properties, both in ultimate elongation and
ment of the bio-based composite media, specific tensile strengths, when compared with the other
strength properties were analyzed. Table 3 also composites. Some authors obtained higher tensile
presents tensile and burst indexes to allow direct strength values. However, their ultimate elongation
comparison of samples irrespective of the amount of values were considerably lower (Karim et al. 2014;
material in the sample. The tensile strength is the Weng et al. 2017).
breaking force per cross-section area with units of Overall, the bio-based composite sorbent provides
MPa. In the paper industry, it is usually expressed as improved mechanical strength as shown by tensile
force per specimen width in kN/m. The tensile index in index and burst index. Although lower ultimate
N m/g is obtained by dividing the strength per width strength at break have been achieved, higher elonga-
by the grammage (g/m2). The burst index is the burst tion capability are developed especially for low
value in kPa measured with the instrument divided by electrospinning time. This is an indication that a softer
the grammage. Both values are thus normalized to the or more ductile material is developed. A compromise
grammage of the sample. The tensile index calculated between ultimate resistance and elongation should be
for each sample follows the trend presented previously find to make a robust adsorbent. However, this
and confirms that electrospinning of nanofibers on the material must also take into account other constraints
TOC handsheet improves the strength properties of a such as the permeability to liquid and the adsorption
nanofiber web and creates a bio-based composite capacity of the material.
structure for water treatment applications. However,
lower properties are developed with electrospinning Pore size and water flux
time. On the other hand, the tensile index seems to be
less sensitive especially at low electrospinning time Table 4 clearly shows that the water flux decreases
with values closed to those achieved for TOC sample when CS–PEO is electrospun on the bio-based com-
(51.58 vs. 60.60 N m/g). Analysis of burst index posite. This is attributed to two reasons: First, as
values are much more difficult to interpret. All values, mentioned previously, Fig. 3 displays that CS–PEO
except the one for the CS–PEO mat, are in the same nanofibers are deposited homogeneously over a TOC
range (see Table 3). It is thus difficult to draw handsheet, thus, partly plugging the pores of the
conclusions based only on burst index. However, it is cellulose fibers. Second, the pore size in CS–PEO
clear that electrospinning CS–PEO nanofibers on both nanofiber mats (3.22 lm) is smaller than the pore size
sides of a TOC handsheet improves significantly the in the TOC handsheets (6.59 lm). Those effects could
burst index relative to the nanofiber mat alone (see explain the reduction in water flux. A reduction in
Table 3). This behavior was already expected as some water flux is also observed when the CS–PEO
scientific papers have demonstrated that incorporation electrospinning time is increased from
of cellulose into a chitosan matrix improve the 140.02 Lm-2 h-1 for 2CS–PEO/TOC to 0.35
mechanical strength (Liu and Bai 2005; El Miri et al. Lm-2 h-1 for 4CS–PEO/TOC. This is because there
2015; Abdul Khalil et al. 2016; Soni et al. 2016; Jalvo are more nanofibers recovering the TOC handsheet
et al. 2017; Yadav et al. 2020). This enhancement is and thus higher opportunity for pore plugging. This
attributed to the excellent mechanical properties of means that the CS–PEO layers are the dominant factor

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4878 Cellulose (2021) 28:4865–4885

Table 4 Pore size and Material Pore size (lm) Water flux (Lm-2 h-1)
water permeability of all
biocomposites Largest pore Mean pore

CS–PEO 3.97 ± 0.54 3.22 ± 0.17 98.1 ± 9.3

TOC 8.75 ± 0.21 6.59 ± 0.10 1404 ± 426
2CS–PEO/TOC 3.96 ± 0.14 2.82 ± 0.34 140 ± 17
3CS–PEO/TOC 2.77 ± 0.28 1.64 ± 0.22 3.7 ± 0.4
4CS–PEO/TOC 1.85 ± 0.08 0.96 ± 0.03 0.35 ± 0.01

controlling the porosity of the material. In our case, the compared to previous related studies (Table 5). From
2CS–PEO/TOC material provided the most permeable the highlighted works in Table 1 (Electrospun cellu-
material and once again, the one to be optimized from lose/chitosan composites for wastewater treatment),
now on. As mentioned previously, a compromise only Brandes et al. (2020) evaluated the water flux of
regarding electrospinning time must be made to their composite materials. However, they did not
develop a suitable bio-based composite for this reported the average pore size. Therefore, in order to
particular application. compare our values with other similar works, chi-
Since the 2CS–PEO/TOC is the one presenting the tosan/cellulose based composites produced from other
best porosity and permeability characteristics, it’s techniques but also for water treatment applications
average pore size and water flux values have been have also been reported in Table 5. It can be seen that

Table 5 Permeability and mechanical properties of various cellulose/chitosan composites

Matrix polymers Water flux (L/m2 Average pore Strain (%) Tensile Reference
h MPa) size (nm) strength (MPa)

Cellulose acetate/chitosan 92.2 72 27.97 26.16 Liu and Bai

(2005)
Cellulose acetate/N,O-carboxymethyl 160 Unlisted 23.45 7.4 Boricha and
chitosan Murthy (2010)
Cellulose nanocrystals/entities 64 10–13 0.23 ± 0.5 318 ± 0.4 Karim et al.
chitosan (2014)
Cellulose acetate/poly (ethylene 0.77 Unlisted Unlisted Unlisted Waheed et al.
glycol)/chitosan (2014)
Cellulose/chitosan 8.63 0.78 Unlisted Unlisted Ghaee et al.
(2016)
Cellulose/chitosan 27.52 \ 1 nm Unlisted * 50 Weng et al. (2017)
Cellulose/chitosan 2 \ 200 Unlisted Unlisted Istirokhatun et al.
(2017)
Cellulose acetate/chitosan Unlisted Unlisted 5.5 17 Phan et al. (2018)
Cellulose nanocrystals/chitosan/ Unlisted Unlisted 25 Unlisted Wang et al. (2018)
polyvinyl alcohol
Cellulose acetate/chitosan Unlisted Unlisted 0.14167 mm/ 0.01515 Aquino et al.
mm (2018)
Phosphorylated cellulose/chitosan 109.6 Unlisted 4.54 21.49 Brandes et al.
(2020)
Bamboo cellulose/chitosan 31.2 0.7 nm Unlisted Unlisted Weng et al. (2020)
TEMPO-oxidized cellulose/ 2900.75 2.82 lm 7.94 34.42 Present study
poly(ethylene oxide)/chitosan

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Cellulose (2021) 28:4865–4885 4879

our 2CS–PEO/TOC sorbent has significantly higher properties, does not clearly stand out from the others
water flux compared to the previous reported cellu- CS–PEO/TOC composites copper adsorption. Still,
lose/chitosan composites. However, it is still less CS–PEO/TOC composites are better than TOC alone
permeable than composites made from other matrices but are way less effective than CS–PEO. The maxi-
(Ma et al. 2012; Goetz et al. 2016; Jabur et al. 2016; mum adsorption capacity of this composite was
Jalvo et al. 2017). Our bio-based composite also compared to data from the literature obtained with
features a macroporous structure (pore size[ 50 nm), different adsorbents (Table 8). Results show that the
which is very useful for water treatment sorbents, and 4CS–PEO/TOC bio-based composite has lower
rarely achieved by the electrospinning technique adsorption capacity towards copper ions than most
alone. of the compared adsorbents. Clearly, optimization of
the adsorption capacity is required. Therefore, further
Copper ions adsorption studies will be carried out on this issue.
In order to analyze the nature of the mechanism
The adsorption tests were studied using batch exper- involved during the adsorption process as well as the
iments at an initial copper ion concentration of role of the material’s surface, two adsorption kinetic
100 mg/L. The adsorption capacity of all biocompos- models were evaluated: Pseudo-first order (PFO) and
ites samples and the effect of contact time are Pseudo-second order (PSO). The parameters for both
illustrated in Table 6 and Fig. 8, respectively. Copper non-linear models were obtained using Matlab soft-
ions adsorption rose rapidly during the first 15 min, ware, and results are presented in Fig. 9 and Table 7.
and then slowly stabilized. This initial rise in copper Both models present high R2 values, showing that they
adsorption is attributed to the large presence of active are both involved in the rate of adsorption. This
sites that are available on the surface of the material. It indicates that a chemical and physical adsorption
is also shown that although oxidized cellulose fibers coexists during the interaction between the copper
are able of adsorbing copper ions (17.8%), CS–PEO ions and the xCS–PEO/TOC. However, Root mean
nanofibers have a much higher adsorption capacity square error (RMSE) values are smaller in the pseudo-
(91.5%). Therefore, it can be inferred that the higher second order model than in the pseudo-first order
the amount of CS–PEO, the higher the adsorption of model. This indicates that pseudo-second order model
copper ions. However, the xCS–PEO/TOC curves best fitted to the data. Besides, it is reported (Gerente
show that despite increasing the amount of chitosan, et al. 2007; Lakhdhar et al. 2016) that the plots of the
the adsorption capacity does not increase significantly. first-order equation are only applicable in the first
This behavior occurs because 3 and 4 h of electro- 30 min of interaction and not for the whole range of
spinning on each side of the TOC handsheet seals the contact time. Therefore, it is considered that the
core media resulting with a lower permeability to adsorption is mostly chemical. A similar behavior was
liquid. Therefore, the fast and easy accessibility of observed by Phan et al. (2018) and Wang et al. (2018)
copper ions to active sites are strongly reduced. who also obtained high R2 values for both models but
Composite 2CS–PEO/TOC, while being the best with a slightly better fit with the pseudo-second order
compromise for water permeability and mechanical model. Table 8 also compares the best kinetic fitting

Table 6 Comparison of copper adsorption capacity for all type of material

Material Copper adsorption capacity (%) Copper uptake per gram of total material (mg/g))

TOC 17.76 8.32

CS–PEO 91.45 36.76
2CS–PEO/TOC 23.53 11.36
3CS–PEO/TOC 27.12 12.42
4CS–PEO/TOC 29.24 14.76

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4880 Cellulose (2021) 28:4865–4885

Fig. 8 Effect of contact 40

time on the adsorption of
copper ions onto the five
different biocomposites 35

30

25

qe(mg/g) 20

15
TOC
10 CS-PEO
2CS-PEO/TOC
5 3CS-PEO/TOC
4CS-PEO/TOC

0
0 1 2 3 4 5 6 7 8
Time (h)

Fig. 9 Pseudo-first order

and Pseudo-second order 14
model of copper ions
adsorption onto the xCS–
PEO/TOC biocomposite 12

10
qe(mg/g)

8
2CS-PEO/TOC experimental data
3CS-PEO/TOC experimental data
6 4CS-PEO/TOC experimental data
2CS-PEO/TOC PFO
4 3CS-PEO/TOC PFO
4CS-PEO/TOC PFO
2CS-PEO/TOC PSO
2 3CS-PEO/TOC PSO
4CS-PEO/TOC PSO
0
0 50 100 150 200 250
Time (min)

model of our bio-based composite to data from models have been proposed: The bridge model and the
different adsorbents. Results show that the pseudo- pendant model. The first one presume that the metal
second order is generally the best fitting model for ion is bound to several nitrogen and oxygen atoms
Chitosan/Cellulose adsorbents. from the same molecular chain or from different
To date, the chemical interaction between copper chains (Yaku et al. 1977). On the contrary, the pendant
ions and chitosan is not know for sure. However, two

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Cellulose (2021) 28:4865–4885 4881

Table 7 Summary of kinetic models parameters for the adsorption of copper ions onto the xCS–PEO/TOC biocomposite
Pseudo first order model Pseudo second order model
-1 2
k1 (min ) qe (mg/g) R RMSE k2 (g/g min) qe (mg/g) R2 RMSE

2CS–PEO/TOC 0.046 10.93 0.976 0.607 0.005 12.21 0.996 0.249

3CS–PEO/TOC 0.074 12.07 0.994 0.321 0.010 12.88 0.998 0.177
4CS–PEO/TOC 0.059 14.48 0.992 0.454 0.006 15.72 0.999 0.109

Table 8 Maximum adsorption capacity of Cu2? of various chitosan/cellulose adsorbents

Adsorbent Best kinetic fitting Maximum adsorption Reference
model capacity

Chitosan/cellulose blend hollow fibers Unlisted 4.146 mg/g Liu and Bai (2005)
Chitosan/cellulose hydrogel beads Intraparticle 53.2 mg/g Li and Bai (2005)
diffusion
N,O-carboxymethyl chitosan/cellulose acetate uneven Unlisted 72.60% Boricha and Murthy
membrane (2010)
Chitosan/cellulose beads Pseudo-second 43.95 mg/g Thilagan et al.
order (2013)
Chitosan/cellulose acetate composite Unlisted 81.03% Ghaee et al. (2016)
Electrospun chitosan/cellulose nanofibers Pseudo-second 112.6 mg/g Phan et al. (2018)
order
Electrospun cellulose nanocrystals/chitosan/polyvinyl Pseudo-second 484.06 mg/g, 90.58% Wang et al. (2018)
alcohol nanofibrous films order
EDTA-modified chitosan/carboxymethyl cellulose non Pseudo-second 142.86 mg/g Manzoor et al.
porous mat order (2019)
Phosphorylated cellulose/electrospun chitosan nanofibers Unlisted 71.11% Brandes et al. (2020)
TEMPO-oxidized cellulose/electrospun chitosan– Pseudo-second 15.72 mg/g, 29.24% This study
polyethylene oxide nanofibers order

model consider that the metal ion is bound by only one that the TOC handsheet behaves as a reinforcing
nitrogen atom (Ogawa and Inukai 1987). structure to improve the mechanical strength of
electrospun nanofiber mats and provide good mechan-
ical properties for the bio-based composite material.
Conclusions The effect of CS–PEO electrospinning time on TOC
handsheet revealed that optimum strength and perme-
In this work, a xCS–PEO/TOC bio-based composite ability of the materials were achieved after 2 h of
sorbent media was fabricated for the first time with a electrospinning. Longer electrospinning time reduced
new environmentally friendly technique without the significantly both properties. However, while not
use of toxic solvents. The composite consists of an being at the same adsorption level of a CS–PEO
electrospun CS–PEO nonwoven layer deposited on nonwoven mat, the 2CS–PEO/TOC bio-based com-
both sides of an oxidized cellulose (TOC) handsheet as posite is the best compromise for optimization study.
a central core. The morphology studies showed that Further analysis will be conducted in order to inves-
the micro/nano fibers have very well-defined structure tigate the biofouling, recycling and regeneration
and a uniform diameter distribution. Results showed ability of this new sorbent composite media.

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4882 Cellulose (2021) 28:4865–4885

Optimization of the permeability and adsorption Brandes R, Brouillette F, Chabot B (2020) Phosphorylated
capacity in multi-contaminant environment will also cellulose/electrospun chitosan nanofibers media for
removal of heavy metals from aqueous solutions. J Appl
be carried out. Polym Sci 138:50021. https://doi.org/10.1002/app.50021
Cardenas Bates II, Loranger É, Chabot B (2020) Chitosan-PEO
nanofiber mats for copper removal in aqueous solution
using a new versatile electrospinning collector. SN Appl
Sci. https://doi.org/10.1007/s42452-020-03342-5
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regard to jurisdictional claims in published maps and
oxide/cellulose nanocrystal composite nanofibrous mats
institutional affiliations.
with homogeneous and heterogeneous microstructures.

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