Journal of Environmental Chemical Engineering 9 (2021) 105063

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Superhydrophobic modification of cellulose sponge fabricated from

discarded jute bags for oil water separation
Dheeraj Ahuja a, Shiva Dhiman b, Gaurav Rattan b, Sheetal Monga b, Sonal Singhal c,
Anupama Kaushik b, *
a
Department of Chemical Engineering, Deenbandhu Chhotu Ram University of Science & Technology, Murthal, Sonipat, Haryana, India
b
Dr. S.S. Bhatnagar University Institute of Chemical Engineering & Technology, Panjab University, Chandigarh 160014, India
c
Department of Chemistry, Panjab University, Chandigarh 160014, India

A R T I C L E I N F O A B S T R A C T

Editor: Dr. G.L. Dotto Recent oil spills endanger the aquatic ecosystem besides huge loss of natural resources, hence require immediate
attention. To develop economical solution for combating oil spills, discarded jute bags, with 60–65% cellulose
Keywords: were used to fabricate cellulose sponge using sol-gel method followed by freeze drying. The sponge surface was
Dip coating rendered superhydrophobic by dip coating with Tetraethyl-orthosilicate/Hexadecyltrimethoxy Silane (TEOS/
FE-SEM
HDTMS). The pristine and dip coated hydrophobic cellulose sponge (DHCS) were characterized for structure,
Cellulose sponge
morphology and hydrophobicity. FE-SEM confirmed the hydrophobic coating of TEOS/HDTMS on sponge sur­
Oil sorption
Contact angle face, while superhydrophobicity was established with static contact angle of 151◦ . DHCS exhibited oil water
Superhydrophobic separation efficiency of 98.5% and 97.2% and equilibrium adsorption efficiency of 35.55 g/g and 31.37 g/g for
diesel oil and motor oil, respectively. The adsorption follow pseudo-second order kinetics with regression co­
efficients, R2 > 0.99. Equilibrium studies indicated that the Freundlich isotherm was best fit isotherm for oil
water removal by DHCS. DHCS displayed significant recyclability with slight reduction of adsorption capacity to
85.2% for diesel oil and 82.5% for motor oil of its initial value after 10 cycles.

1. Introduction organic compounds, poly-aromatic hydrocarbons in leaked fuel oil cause

In day to day life, petroleum is an important energy source used in
automobiles, airplanes and ships. However, unscrupulous use of oil
leads to environmental problems due to lack of supervision and wastage
of oil. Apart from this, oil spills during oil exploration, transportation
and storage into the water bodies have caused grave environmental
concerns worldwide and are dangerous for marine ecosystem [1]. Most
recent oil spills including leakage of Japanese owned vehicle containing
diesel and fuel oil in biodiversity hotspot of Mauritius, leakage of fuel
storage tank in Norilsk, Russia and Trans Mountain, Canada have made
to imperative to develop effective, though simple techniques for removal
of oil from spill sites. These oils pills have caused adverse impacts to
economy, ecology and environment besides impairing public health and
society [2,3]. The formation of a dense oil slick over the oceanic surface
has been confirmed to be life threatening to marine biodiversity. It not
only endangers the growth of native species in the water body but also
imperils offshore and onshore ecosystem [4]. The hydrocarbons, volatile
severe physical and health impacts such as asthma, inflammation,
headache, cardiovascular disorders, reproductive deformities, respira­
tory irritation, liver and kidney tumors and increased risk of cancer in
humans [5]. Hence it is essential to develop novel methods to mitigate
the dangerous impacts of oil spills.
There are many techniques which have been used to spruce up these
oil spills. These can be classified into three types, including chemical
methods which include use of solidifiers dispersants, biological methods
and mechanical methods booms, skimming agents and adsorbents
[6–8]. Skimming, although is a frequently used method but is time
consuming, expensive and less efficient. Chemical dispersants are being
used to sever oil slicks into droplets, which diffuse in different directions
due to actions of waves getting easily scattered in water [6]. Dispersants
also augment biodegradation of crude oil as they aid oil degrading
bacteria to attach to oil droplets with large surface area. However, this
technique has limitations including toxicity and volatility of chemical
dispersants making them hazardous for marine ecosystem. One recent

* Corresponding author.
E-mail addresses: dheerajahuja84@gmail.com (D. Ahuja), anupamasharma@pu.ac.in (A. Kaushik).

https://doi.org/10.1016/j.jece.2021.105063
Received 13 September 2020; Received in revised form 2 January 2021; Accepted 8 January 2021
Available online 13 January 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
D. Ahuja et al.
approach targets symbiotic algae-bacteria for removal contaminants in
water containing oil in presence of nutrients, including wastewaters
from oil mill effluents, as they are capable of oxidizing aromatic and
aliphatic oil constituents. These microorganisms are not only capable of
degrading petrochemicals but also eliminate pathogens, enhance dis­
solved oxygen concentration and present a unique strategy for nutrient
recycling [9]. However, the technique is in its nascent stage and requires
in-depth knowledge for specific identification and cultivation of these
micro-organisms for further commercialization. Other methods include
gravity separation, air flotation, centrifuging, electrochemical treat­
ment, ultrasonic wave and biochemical methods [10]. These traditional
approaches can effectively separate the oil/water mixtures, however,
they cannot be utilized for emulsified oil/water mixtures or removing oil
droplets in microscopic scale [11]. Recently, ultrafiltration membrane
based on pore structure size are being utilized for the separation of
specific size materials and can also separate various industrial emulsions
with efficacy. However, these membranes have low porosity leading to
fouling and degradation. Surfactant adsorption and pore plugging may
also take place in membrane separation process resulting in decrease in
sorption capacity [12]. The other major drawback is that membrane
synthesis process is complex and expensive. Use of physical adsorbents
thus is the most effective method owing to it being economical, facile
implementation, environmentally friendly, complete removal and
absence of secondary pollution [7,13,14].
Lignocellulosic biomass, which constitutes 30–60% cellulose, is
believed to be the only carbon-neutral renewable source, which is
abundant in nature and can decrease CO2 emission [15,16]. In India,
jute also known as golden fiber, is one of the most important natural
fiber after cotton due to its production, which is highest in the world,
and its versatility in usage. It is the cheapest and strongest natural fiber
with advantages like low density,less abrasive behavior to processing
equipment, good dimensional stability and high specific strength in
addition to lower water resistance as compared to other granular ad­
sorbents [17,18]. They are mainly used for making sacks for packing
grains, mats, carpets and low end products, where there is not much
value addition. Once used, the sacks/ gunny bags or mats are discarded
causing waste accumulation. Moreover, the major limitation is that its
strength decreases on treating with water for longer duration and de­
grades through microorganism attack leading to yellow color. This
limitation can be overcome by modification of jute fibers [19]. As the
jute fibers contain high amount of cellulose i.e. 60–65% along with
higher crystallinity (73.4%) of jute fibers [20], they offer a tremendous
source of cellulose.
CNFs are excellent nanomaterials with spectacular mechanical,
chemical and barrier properties. Presence of strong hydrogen bonds in
its non-branched chains makes them insoluble in common solvents and
water. The presence of hydroxyl groups makes cellulose an economical
adsorbent. However, the utilization of cellulose as an adsorbent requires
chemical modification requiring many organic solvents making it cost­
lier in addition to post processing difficulties and environmental con­
cerns. Hence, jute cellulose has become a focus of intense interest as it
can be easily modified using cost effective chemical methods for its
application to various waste water remediation [19,21]. Further, the
adsorbent prepared can be easily exhausted by burning producing no
toxic gases and very less toxic ash [17]. All these make the jute cellulose
as a potential adsorbent.
Quintessential properties of an adsorbent for oil-water separation is
that it should be hydrophobic and should have good affinity towards oil,
zero water adsorption, high surface area, recyclability, fast kinetics,
economical and easy and expansive availability [7,22]. Polymer sponges
because of their low density, good elasticity, three dimensional skeleton
and porous structure show exemplary adsorption of oil and water,
making them ideal substrate for oil-water separation. Porous cellulosic
sponges due to their highly cellular nature, low density, large surface
roughness and area have proved to be interesting material for oil water
separation [23]. These porous sponges allow effective long-lasting
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Journal of Environmental Chemical Engineering 9 (2021) 105063
adsorption without leaching and can convert pollutant into stable
solid waste. Besides, the open-cell structures of these sponges provide
competent routes and sites for organic liquid dispersion [22,24]. Hy­
drophobic sponges are porous bulk materials that have potential to
separate oil from water however repel water from mix of oil water and in
the downstream can be reinvigorated through pressing, washing,
distillation or scorching. However, owing to hydrophilic nature of cel­
lulose, it is difficult to separate oil and organic solvents from water.
Hence, the surface needs to be modified through a coating of hydro­
phobic materials increasing their selectivity towards oil [25–27].
Organosilicons are preferred source of modification because of their
hydrophobic nature. The various organosilicons reported include
vinyltrimethoxy silane [28], octadecyltrichloro silane, methyltrichloro
silane [10], heptadecafluoro-1,1,2,2-tetrahydrodecyl trimethoxysilane
[29], fluoroalkyl silane, and dodecafluoro heptylpropyl trimethoxyl
silane [30]. They result in the decrease in the surface energy of the
sponge thereby making it superhydrophobic. Hexadecyltrimethox­
ysilane, is a non-fluoro compound an excellent material for modification
of sponge surface due to its low surface energy and presence of hydro­
phobic functional groups [31]. Till date, a variety of processes inclusive
of chemical vapor deposition [32], electrodepositing [33], dip coating
[34], sol gel [35] etc. have been utilized for the development of super­
hydrophobic and superoleophilic sponges. In the recent past, a super­
hydrophobic silica film with excellent roughness was synthesized by
Crick and coworkers [32] using hybrid chemical vapor deposition
technique. But. It cannot be utilized for commercial application due to
high cost of raw materials, complex process, scale up probability and
unconfirmed recyclability [36,37].
The sol gel pathways are facile routes towards the development of
sponges and aerogels with hydrophobic characteristics because of their
low processing temperature, control over composition and structure of
the product, easy scale up [38–40]. This process has widely been focused
to synthesize superhydrophobic surfaces through construction of nano­
structures silica and followed modification with low surface energy
chemicals [41,42]. Dip coating with oleophilic nanomaterials and pig­
ments is a simple and inexpensive method to attain hydrophobicity.
Many researchers have done work in this regard. In the recent study,
spray coating of octadecyltrichlorosilane (OTS)-modified SiO2 nano­
particles of 50 nm were used by Li et al. to impart hydrophobicity to
paper [34]. While, higher size nanoparticles of OTS-modified silica in
the size range of 240–245 were coated on filter paper to synthesize a
super hydrophobic coating [43]. Till now, finite research has been re­
ported on cellulose sponges from biomass [44,45] but to our knowledge
no work is published on jute fiber or crop residue based super­
hydrophobic cellulose sponge. Researchers have used cellulose acetate,
cellulose diacetate, cellulose triacetate [46], cellulose carbamate, alpha
cellulose and cotton pulp [47,48] etc.
This study involves extraction of pure crystalline CNFs from dis­
carded jute bags using alkaline delignification pretreatment. The process
leads to physical deterioration of biomass cell wall i.e. hemolytic
degradation and glycoside bonds hydrolysis resulting in enhanced sol­
ubility of lignin and hemicellulose in soda solution, leaving the cellulose
as the solid residue [49]. The CNFs were dissolved in NaOH/urea green
solution to yield porous cellulose sponge using sol-gel technique fol­
lowed by freeze drying. Cellulose sponge (CS) was then made super­
hydrophobic by salinization with TEOS/HDTMS ethanol solution. They
were further characterized using FTIR, X-ray diffraction (XRD), Field
Emission Scanning Electron Microscope (FESEM) and Water Contact
angle. Oil sorption test was conducted on hydrophobic sponge to explore
its efficacy towards oil water separation applications.
2. Experimental
2.1. Chemicals and raw material
Discarded jute bags i.e. pristine jute fibers (PJFs) were collected from
D. Ahuja et al.
local grain market. Sodium hydroxide (NaOH), hydrogen peroxide
(H2O2) and hydrochloric acid (HCl) were purchased from SRL chemicals
India. Epichlorohydrin, ammonia solution (NH3⋅H2O, 25%), calcium
carbonate (CaCO3), and tetra ethyl ortho silicate (TEOS), ethanol and
urea were bought from Fischer Scientific and hexadecyltrimethoxysilane
(HDTMS) from Sigma Aldrich. All chemicals were of analytical grade.
The overall scheme for the fabrication of superhydrophobic sponges is
shown in Fig. 1.
2.2. Cellulose extraction from discarded jute bags
CNFs were extracted from PJF using alkali delignification, a well-
established protocol in our lab [50]. In brief, discarded bags were
washed with tap water to remove extraneous impurities and dried in sun
in open before use. Dried PJFs were cut into pieces and dewaxed. The
dewaxed fibers were then subjected to alkali delignification followed by
bleaching. The series of steps completely remove hemicellulose and
lignin. Thereafter, the bleached fibers were hydrolyzed with 0.1 N HCl
for the isolation of cellulose microfibril bundles, which were defibril­
lated to CNFs by using high shear mechanical homogenization.
2.3. Fabrication of cellulose sponge (CS)
CNFs in known quantity (2 g) were dissolved in green solvent con­
taining 7 wt% NaOH, 12 wt% urea and 81 wt% distilled water at
≈ − 20 ◦ C in deep freezer [51]. The cellulose suspension was then
ultracentrifuged at 5 ◦ C and 3000 RCF (Relative Centrifugal Force) for
twenty minutes to remove undissolved cellulose and impurities [25].
Thereafter, required amount of cross linker, Epichlorohydrin was added
with subsequent addition of foaming agent, CaCO3. Obtained solution
was magnetically stirred at ambient temperature for 30 min and then
heated at 60 ◦ C for 20 h in a beaker to get the gel with controlled
specimen shape. The gel was then immersed in 0.01 N HCl for coagu­
lation and removal of CaCO3. Thereafter, NaOH and urea were recov­
ered by washing with double distilled water. Finally, gel was freeze
dried overnight at − 50 ◦ C to obtain highly porous Cellulose Sponge (CS)
[25]. The overall methodology for developing superhydrophobic sponge
from discarded gunny bags of jute is shown in Scheme 1.
2.4. Fabrication of dip coated hydrophobic cellulose sponge
For the fabrication of dip coated hydrophobic cellulose sponge
(DHCS), 5 ml of TEOS together with 3 ml of HDTMS were dissolved in
25 ml of ethanol. The mixture solution was mixed with NH3.H2O
Fig. 1. (a) FTIR spectra of PJF, MFCs & NFCs (b) XRD diffractographs of PJF, MFCs and NFCs.
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Journal of Environmental Chemical Engineering 9 (2021) 105063
(25COC%) in 25 ml ethanol with vigorous mixing for 12 h at ambient
temperature [52]. The mixture solution was then ultrasonicated for
30 min to get a homogeneous suspension. The above prepared solutions
were then directly padded on to the dried CS, prepared earlier, using dip
coating and the extra coating liquid was removed utilizing squeeze
rollers. The coated sample was then cured at 110◦ C for 1 h [52]. The
above procedure was repeated thrice for multiple coating and after each
coating the contact angles were measured. The overall scheme of DHCS
fabrication is given in Scheme 2.
2.5. Characterization of cellulose nanofibers, cellulose sponge and dip-
coated hydrophobic cellulose sponge
FTIR spectrophotometer of Perkin Elmer RZX was used to determine
the chemical structure of raw, chemically and mechanical treated jute
fibers and CS and DHCS. The spectral range varied from 4000 to
450 cm− 1 and resolution was 2 cm− 1. Each sample was scanned twice.
Crystallinity of CNFs, CS and DHCS was studied using of Philips. For
this radiations were CuKα (λ = 1.54 A◦ ) with voltage and intensity of
40 kV and 40 mA, respectively. Crystallinity was calculated using Eq. 1
[53,54]:
ITotal − IAm
Crystallinity = 100 × (1)
ITotal
Where, ITotal is the maximum intensity of the (002) lattice diffraction and
IAm is the intensity diffraction at 18◦ 2θ diffraction angle.
Hitachi 2100 Transmission Electron Microscope (TEM) was used to
determine the size of CNFs. For this, dilute suspension of CNFs was
dropped on carbon coated grids and dried at ambient temperature. In­
strument was accelerated at a voltage of 80 kV for capturing the images.
Morphology of cellulose microfibrils, CS and DCHS was studies using
Scanning Electron Microscope (SEM), JSM JEOL-6490. The samples
were made conducting by platinum sputter coating. Morphology of
DHCS was also studied using FESEM model HITACHI SU8000. Micro­
graphs were captured at different magnifications using 20 kV acceler­
ating voltage.
The OCA contact angle system coupled using high resolution camera
was used to examine coating effect on hydrophobicity of CS and DHCS.
For this, water droplets were released on the top or bottom surface of CS
and DHCS and angle was recorded. Each sample angle was measured
thrice and their mean value was taken as the final value.
D. Ahuja et al.
Scheme 1. Overall methodology for developing 3-D Superhydrophobic sponge from discarded gunny bags of jute.
2.6. Oil sorption capacity of super hydrophobic sponge
Oil sorption capacity of the DHCS was studied by employing two
different kinds of oil i.e. diesel and motor oil. The studies were carried
out both in static and dynamic state at 20 ◦ C and neutral pH. For dy­
namic state, varying quantity of oil was splashed into 4 beakers con­
taining 160 ml of supply water, to obtain 1–4 mm thick oil film on the
surface of water. This emulsion was stirred steadily at 550 rpm. A square
piece of DHCS was weighed and kept in each of the beaker for half an
hour. Thereafter, it was removed and allowed to drain for 2 min. The
soaked sponge specimens were pressed and retrieved mixture was
ultracentrifuged for the separation of water from oil following
D4007–81 (ASTM-1998a) standards. The sorption capacity of sponge
was calculated from Eq. (2) after estimating the quantity of water and oil
absorbed.
mo mw
CS,O = or CS,w = (2)
mi mi
Where, Cso is oil sorption capacity (g/g) of sponge, Csw is water sorption
4
Journal of Environmental Chemical Engineering 9 (2021) 105063
capacity (g/g) of sponge, mo is the amount of oil absorbed (g), mi is
initial weight of sponge (g) and mw is the amount of water absorbed (g)
by sponge. Each test was repeated four times and their mean was taken
as the final value. Similar procedure was followed for static phase; the
major difference was that the magnetic stirrer was switched off. The
separation efficiency of DHCS was measured by using it to separate oil/
water mixture with certain oil water ratio. Typically, a known volume of
oil was added to 100 ml of water. A weighed amount of sponge was
dipped in it. When the equilibrium was achieved, oil-absorbed sponge
was removed and the oil concentration of mixture was measured using
gravimetric method. Separation efficiency is given by Eq. (3).
W1 − W
ηeff = × 100 (3)
W2
Where, W1 is the sum weight of separated oil, sponge and beaker, W2 is
the weight of the oil before separation and W is the sum weight of
sponge and beaker. The soaked DHCS were pressed and were again used
as adsorbents. The absorption-pressing method was reciprocated several
times to check its reusability [55]. 10 cycles were performed for each
D. Ahuja et al. Journal of Environmental Chemical Engineering 9 (2021) 105063

Scheme 2. Coating of Cellulose sponge with TEOS/ HDTMS to make it superhydrophobic.

sample. i) Pseudo First-Order-Kinetic Model

Generally, non-linearized form of pseudo first-order-kinetic
2.7. Adsorption kinetic studies for oil/water mixture on DHCS model is represented by the following Eq. (4a) [56]
qt = qe [1 − exp(k1 t)] (4a)
The most vital consideration while designing an adsorption system
for oil water separation is its adsorption kinetics i.e. rate at which
adsorption occurs or the rate of adsorbate update. This aids in opti­ It can also be expressed by the following Eq. (4b) [50]:
mizing the contact time between the two, adsorbate and adsorbent.
dqt
Since the adsorption is a mass transfer phenomenon and occurs gradu­ = k1 (qe − qt ) (4b)
dt
ally not instantaneously, it’s important to realize the mass transfer re­
sistances, which in turn influence the attainment of equilibrium. Pseudo- Where, qe and qt are the amounts of solute adsorbed per mass of the
first-order, Pseudo-Second-Order and Weber and Morris Intra-Particle adsorbent (g/g) at equilibrium and at any time t, respectively, and k1
diffusion models are some frequently used models for kinetic estima­ is the rate constant of first-order adsorption (min− 1). When boundary
tion of an adsorbent-adsorbate system. conditions are reached, t = 0, q = 0 and t = t, q = qt, the Eq. (4)
reduces to Eq. (5):

5
D. Ahuja et al.
ln(qe − qt ) = lnqe − k1 t (5)
The constant, k1 were calculated from the slope of the plot of ln
(qe-qt) vs t. Eq. (5) can be further written as Eq. (6)
log(qe − qt ) = log⁡(qe ) −
k1
t (6)
2.303
ii) Pseudo Second-Order-Kinetic Model
The pseudo-second order kinetic model in non-linearized form
can be expressed as [57]:
q2e k2 t
qt = (7a)
1 + k2 qe t
It can also be represented by the following Eq. (7b) [51]:
dqt
= k2 (qe − qt )2 (7b)
dt
When boundary conditions are applied, t = 0, q = 0 and t = t, q = qt
the integration yield Eq. (8):
1 1 1 1
= × + (8)
qt (k2 × q2e ) t qe
Where, k2 is the rate constant of pseudo second-order adsorption.
The value of qe and k2 were calculated from slope and intercept of
graph between 1/qt and 1/t, respectively. Amount of solute adsorbed
at equilibrium, qe is inverse of intercept, while the rate constant k2
= (intercept)2/slope.
iii) Weber and Morris Intra-Particle Diffusion Model
This model is used to locate the migration of adsorbate parti­
cles from the surface of adsorbent into its internal pores during
the diffusion process. This is represented by Eq. (9) [52]:
qt = kp × t 0.5
+C (9)
Where, kp is the intra-particle diffusion rate constant; and C (g/g) is a
constant, which describes the boundary layer thickness. The value of
kp is obtained from the slope of plot, qt versus t0.5. If the linear line
crosses the origin, it means that the intra-particle diffusion is the rate
controlling step. On the other hand, if it does pass through the origin,
other possible factors including mass transfer rate and surface
adsorption rate also contribute to overall adsorption.
2.8. Isotherm adsorption modeling for oil/water mixture on DHCS
The adsorption isotherm relates the amount of adsorbate adsorbed
onto a solid adsorbent and the equilibrium concentration of the adsor­
bate in the solution at a given temperature. The experimental equilib­
rium values, qe and Ce are fitted to isotherm models to establish the
appositeness of the model. To appropriateness of any model is contin­
gent on the error level i.e. correlation coefficient (R2) or Average Rela­
tive Error (ARE) [58].
In this study, three most frequently used isotherm models were
employed with varying initial concentrations of diesel and motor oil in
water (i.e. 5, 10, 15, 20 and 25 g/L) to fit the equilibrium adsorption
data, including: Langmuir, Freundlich and Dubinin-Radushkevich
isotherm at absolute temperature (298 K) and constant pH.
Langmuir parameters are determined by non-linear form and linear
form of isotherm model. Non-linear and linear expressions of Langmuir
isotherm model can be illustrated as Eq. (10) [59] and (11) [53],
respectively:
Ce
q e = q m Kl (10)
1 + Kl Ce
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Journal of Environmental Chemical Engineering 9 (2021) 105063
1 1 1
= + (11)
qe qm Kl Ce qm
Where, qm (g/g) and Kl (L/g) are the monolayer capacity at high con­
centration and equilibrium constant, respectively. Ce is the concentra­
tion of solution at equilibrium (g/L) and qe represents the amount of
adsorbate adsorbed at equilibrium (g/g). The constant, Kl is calculated
from the slope of 1/qe vs 1/Ce.
The Freundlich isotherm assumes a non-homogenous surface of
adsorbent and describes multilayer adsorption of oil on adsorbent sur­
face. Eq. (12) was used to express the non-linear expression of Freund­
lich isotherm model [59]:
qe = KF C1/n
e (12)
Whereas, the linear form of Freundlich isotherm model can be written as
Eq. (13) [53]:
1
logqe = logKF + logCe (13)
n
Parameters, KF and 1/n are Freundlich capacity factor and Freund­
lich intensity, respectively. Ce is the concentration of solution at equi­
librium (g/L) and qe represents the amount of adsorbate adsorbed at
equilibrium (g/g).
Dubinin-Radushkevich (D-R) Isotherm is used to determine the
pseudo-energy of adsorbed adsorbate on the surface of the adsorbent.
The non-linear and linear equations of this isotherm are expressed as
follows [59]:
Non − linear expression:qe = qD exp⁡( − βε2 ) (14)
Linear expression:lnqe = lnqD − β.ε2 (15)
Where, ε is given by the expression ε = RT.ln⁡(1 + C1e ).
The other coefficients, qD is the theoretical maximum capacity (g/g),
Ce is the concentration of solution at equilibrium (g/L), qe represents the
amount of adsorbate adsorbed at equilibrium (g/g), T is the absolute
temperature (K), R is the gas constant (J/mol. K), β is the activity co­
efficient constant at specific energy absorbance and ε is Polanyi’s po­
tential. The constant, β is proportional to mean free energy per molecule
of the adsorbate, E (kJ/mol) in solution onto the surface of adsorbent,
which can be expressed as Eq. (16):
E=
− 1
(16)
1
(− 2.β)2
2.9. Error functions
In this work, the Coefficient of determination (R2), Adjusted Coeffi­
cient of determination (R2adj) and the average relative error (ARE) three
different error functions were examined. Coefficient of determination
(R2) is used to evaluate the comparison of kinetic and isotherm models
with experimental data. It is given as Eq. (17) [56]:
∑n ( )2
i=1 qe,cal − qe,exp i
R2 = 1 − ∑ [ ( ) ]2 (17)
n
i− 1 qe,cal − qe,exp
i
Where, qe, cal represents the theoretical amount of adsorbate adsorbed at
equilibrium (g/g), qe, exp represents the experimental value of amount of
adsorbate adsorbed at equilibrium on adsorbent (g/g) and n is the
number of experimental points.
The adjusted Coefficient of Determination (R2adj) is defined in terms
of R2 as follows, where n is the number of observations in the data set,
while k is number of independent variables. The adjusted R2 is a sta­
tistical measure that shows the proportion of variation elucidated by
estimated regression.
D. Ahuja et al.
[( ) ]
2
1 − R (n − 1)
R2adj = 1 −
n− k− 1
While R2 increases with the increase in independent variables, R2adj
increases with only those independent variables that increase the
explanatory power of regression equation, making it much more
meaningful.
The average relative error is defined as the ratio of the absolute error
(i.e. difference of theoretical and experimental value) to the actual
experimental measurement: It can be expressed as Eq. (18) [56]:
⃒ ⃒
100∑n ⃒qe,cal − qe,exp ⃒
ARE = [ ⃒ ⃒
⃒qe,exp ⃒ ]i (18)
n hydrogen bonding. The peak intensity has extremely reduced in case of
i=1
3. Result and discussion
3.1. Characterizations of CNFs
FTIR spectra were recorded for pristine jute fibers, cellulose micro­
fibrils and CNFs to ensure removal of lignin and hemicellulose at
different stages of pretreatment and CNF isolation. FTIR spectra of PJFs,
cellulose micro fibrils and CNFs are depicted in Fig. 1(a). The various
peaks along with associated bonds are tabulated in Table 1. From Fig. 1,
bands at 1510 and 1426 cm− 1 corresponding to aromatic skeletal ring
vibration of lignin were seen in case of PJF, however for MFCs and CNFs
band at 1510 cm− 1disappeared while the peak at 1426 cm− 1showed a
significant decrease in intensity owing to partial removal of the lignin
[60].
The peak at 1258 cm− 1 corresponds to hemicelluloses, which got
vanished completely in case of cellulose micro fibrils and CNFs indi­
cating complete removal of hemicellulose [64]. Crystalline regions
associated with cellulose glucose units was also revealed in CNFs via
peak at 897 cm− 1 [63].
XRD profiles of the PJFs, MFCs and CNFs are shown in Fig. 1(b). The
crystallinity was calculated using Eq. (1) and was found to be 44.85,
84.23 & 97.82% for PJFs, MFCs and CNFs, respectively. From the re­
sults, it can be observed that the CNFs exhibit a higher crystallinity, as
depicted from enhanced peak intensity at 2θ = 22.6◦ , this may be
because of efficacious replacement of nano-cellulosic polysaccharides
and disintegration of non-crystalline phases [23,66]. Further, from the
results it was also confirmed that hydrolysis ensues preferentially in the
amorphous region due to acidic dissolution, while crystalline regions are
more stable towards chemical attack. The crystallinity enhanced to
84.20% and 94.54% for MFCs and NFCs, respectively from 44.98% for
PJF. The improvement in crystallinity for MFCs and NFCs has been
broadly explained [67].
TEM pictures of CNFs finally obtained after ultrasonication with high
shear homogenization are shown in Fig. 2(a and b). From the figure, it
can be observed that ultrasonication and homogenization results in
disintegration of CNFs from cell bundle. The obtained nanofibrils
diameter was between 5 and 60 nanometers. Structure of cellulose mi­
crofibrils was investigated using SEM and are shown in Fig. 2(c and d).
The figures revealed discrete fiber bundles with mean width around
10–15 micrometer, lesser than the mean size of PJF. This reduction in
Table 1
FTIR peaks and their depictions for PJFs, MFCs and NFCs.
Bands/Peaks Depictions
3200–3500 ‒OH stretching vibration [61].
2850–2920 Symmetric stretching vibrations of ‒CH3 & ‒CH2 [62]
1635 Adsorbed water or moisture [63]
1510 Aromatic Skeletal vibrations (lignin) [60].
1425 Aromatic Skeletal vibrations (lignin) [60].
1258 Hemicellulose [64]
897 C‒H deformation/ Cellulosic glucose unit [64]
655 C‒OH out of plane bending [65].
Journal of Environmental Chemical Engineering 9 (2021) 105063
size may be because of separation of lignin, hemicellulose and pectin
(17a) from PJFs at the time of chemical treatment. Further, it was also
observed that obtained cellulose microfibrils were cylindrical in shape
with smooth surface.
3.2. Characterizations of cellulose sponge (CS) and dip coated
hydrophobic cellulose sponge (DHCS)
FTIR spectra of CNFs, CS and DHCS are depicted in Fig. 3(a). The
peaks around 3350–3400 cm− 1 correspond to the ‒OH stretching vi­
brations, observed only in the case of CNFs and CS, while in case of
DHCS, no peak was observed indicating the complete absence of
CS, which is due to destruction of ordered crystalline structure of cel­
lulose during its dissolution in NaOH/Urea and regeneration and
crosslinking. The absence of the peak in DHCS is a clear indication of
hindered interactions with water molecules, which is characteristic of
hydrophobicity. Also, the ‒OH stretching vibrations observed a shift for
DHCS, indicating the strong interactions between the hydroxyl groups of
cellulose and HDTMS. The peak at 2820–2850 cm− 1 and
1008–1100 cm− 1 corresponds to the asymmetric C‒H stretching vibra­
tions and C‒C stretching vibrations, respectively.
The increase in hydrophobicity was also confirmed by decrease in
the intensity of C˭O and C‒O stretching vibrations of DHCS. Peak around
800 cm− 1 seen in case of CS and DHCS is due to bending of Si‒O‒Si,
which is a hydrolysis product of HDTMS [68,69], which enhances the
hydrophobicity of CS.
XRD spectra were recorded to confirm the presence of TEOS/HDTMS
coating on DHCS. Fig. 3(b) shows the XRD patterns of CS, and DHCS,
whereas the inset shows the XRD profiles of CNFs. The broad peak at
2Ө = 22.5◦ seen in both CS and DHCS is due to the highly crystalline
nature of cellulose [44,70]. From the figure, it can be observed that CNFs
shows diffraction peaks at 2Ө = 16.8◦ , 22.4◦ and 26.5◦ while the cel­
lulose sponge regenerated from NaOH/urea solution shows the diffrac­
tion peaks at 2Ө = 15.9◦ , 22.4◦ , 26.5◦ and 33.9◦ indicating that
regeneration resulted in the transformation of native cellulose I to cel­
lulose II [71,72]. The peak intensities of XRD peaks of CS became much
weaker as compared to CNFs as a result of reduced crystallinity of cel­
lulose. This reduction in crystallinity is attributed to the regeneration
process during which inter and intra-molecular hydrogen bonds of CNFs
were broken when CNFs are dissolved in NaOH/urea solution. A rear­
rangement of hydrogen bonds occurs during the regeneration process,
where crosslinking takes place in presence of cross linker, epichloro­
hydrin leading to a disordered crystalline structure giving way to more
amorphous regions. These amorphous regions are advantageous when
cellulose is coated with TEOS/ HDTMS as they provide more specific
surface area, facilitating improvement in adsorption capacity [73].
The XRD patterns of DHCS shows the diffraction peaks at
2Ө = 32.4◦ , 34.9◦ , 40◦ , 45.3◦ and 57.5◦ correspond to the diffraction
from the (220), (311), (111), (400) and (511) lattice planes of face
centered cubic Si, indicating that the coating has been successful on the
sponge surface [74–76]. The typical diffraction peaks of CS were also
seen in case of DHCS however, with weak intensity. It can be due to
strong interactions of cellulose hydroxyl groups with HDTMS.
SEM images of CS at surface, cross-section of CS and DHCS at
different magnifications are depicted in Fig. 4(a–f). From Fig. 4(a and
b)), it is revealed that the surface of CS is smooth and almost non-porous
indicating removal of compact surface layer that results in increase
absorbency, while the cross-section of CS (Fig. 4(c and d)) shows 3-D
highly porous structure with randomly distributed pores of different
sizes. This porous structure implies good absorbency of the sponge due
to increased surface area. SEM images (Fig. 4(f)) of DHCS at higher
magnification show that the silica particles form layers of small spher­
ical particles on the porous surface, thereby reducing the surface energy
and improving surface roughness of the sponge, which is necessary for
the superhydrophobicity of the resultant material. The formation of
7
D. Ahuja et al. Journal of Environmental Chemical Engineering 9 (2021) 105063

Fig. 2. (a and b) TEM images CNFs (c and d) SEM micrographs of MFCs.

Fig. 3. (a) FTIR spectra (b) XRD patterns of cellulose nanofibers, Cellulose Sponge and Coated Cellulose sponge.

layer on the cellulose sponge may be attributed either to the strong
chemical bonding of cellulose hydroxyl groups with HDTMS or to the
strong hydrogen bonding between cellulose and SiO2 [25]. Fig. 4(e, f
and h) clearly exhibits that the micro/nano rough surface microstruc­
ture of cellulose foam coated with silica nanoparticles.
This multi-layer deposition of nanoparticles on the surface of sponge
produces super-hydrophobic sponge that was also demonstrated by FTIR
results and water contact angle measurements. SEM images of DHCS at
low magnification (Fig. 4(e)) shows that the nanoparticles of silica are
uniformly distributed and packed closely and aggregated over the in­
teriors of the sponge surface. This aggregation may be attributed to the
long chain alkyl group grafting on the surface of silica nanoparticles.
Morphology of the dip coated cellulose sponge with multiple coat­
ings was also studied using FE-SEM and are shown in Fig. 4(g and h).
Fig. 4(g) shows appearance of spherical coatings on cellulose sponge
shown with a black circle that leads to the roughening of sponge surface
thereby covering the pores and hence leads transformation from hy­
drophilic to superhydrophobic. The images also show the accumulation

8
D. Ahuja et al.
Fig. 4. (a and b) SEM images of Sponge Surface, (c and d) SEM images of sponge cross section, (e and f) SEM images of TEOS/HDTMS coated cellulose sponge (g and
h) FE-SEM images of coated superhydrophobic sponge.
of nanoparticles in the coatings that was done layer by layer to make the
superhydrophobic sponge and is highlighted in Fig. 4(g and h).
The phenomenon of superhydrophobicity is well explained by two
approaches, depending upon the liquid-solid interfacial area: Wenzel
model and Cassie-Baxter model. Wenzel model describes the homoge­
neous wetting regimes wherein the water droplet strongly adheres to the
9
Journal of Environmental Chemical Engineering 9 (2021) 105063
rough surface due to robust solid-liquid contact. Thus, the movement of
the drop requires large external force, which is not preferred. The
superhydrophobicity of intricate hierarchical structures is comprehen­
sively described by Cassie-Baxter model. The model assumes that a large
amount of air remains entrapped beneath the drop, forming air/ vapor
pockets, which lowers the adhesion between the two surfaces due to
D. Ahuja et al.
incomplete contact. When the roughness level is adequate, with a proper
intrinsic contact angle, level of superhydrophobicity, wherein the liquid
drops are movable can be accomplished.
Static water contact angle measurements (WCA) were used to
explore the wettability of CS and DHCS. For WCA measurements, water
droplet was poured on CS and DHCS sample. The contact angle images of
cellulose sponge without coating along with different levels of coating
are depicted in Fig. 5(a–e). From Fig. 5(a), it is apparent that WCA for
cellulose sponge without coating is less than 5◦ indicating that the water
droplet poured on the surface of cellulose sponge is completely absor­
bed. This is attributed to the hydrophilic characteristics of cellulose
sponge. On the other hand, CS with first coating shows a water contact
angle of 98.78◦ revealing that water retains on outer region without
entering deep inside, when poured on top of DHCS. Further, with second
and third successive coatings, the water contact angle increased to
105.54◦ and 131.98◦ ,respectively implying that the DHCS follows
Fig. 5. Contact angle images of the cellulose sponge with number of HDTMS/TEOS coating (a) Pristine CS (b) after first coating (c) after second coating (d) after third
coating (e) after fourth coating.
10
Journal of Environmental Chemical Engineering 9 (2021) 105063
Cassie-Baxter model [77,78]. The DHCS with four coating exhibits a
water contact angle of 151.71◦ making it super-hydrophobic.
From the wettability experiments, it can be illustrated that the cel­
lulose sponge coated with HDTMS/TEOS are best suited for the oil water
separation and oil water adsorption because of superhydrophobic nature
implication.
3.3. Oil sorption analysis of DHCS
With outstanding properties like highly porous structure, good
flexibility and superhydrophobicity, DHCS exhibits great potential for
oil water separation, hence may be useful in handling of oil spills. DHCS
has abundant micropores on the surface (can be seen in TEM images),
which is occupied by air. When brought in contact with oil, air is
replaced by oil due to capillary effect, Vander Waals forces and hydro­
phobic interactions [79], resulting in higher adsorption capacity. Oil
D. Ahuja et al.
sorption characteristics of super hydrophobic cellulose sponge at
different contact times with diesel and motor oil both in static and dy­
namic media is depicted in Fig. 6(a) and (b), respectively. From the
figures, it is evident that for both motor oil and diesel, DHCS exhibited
good adsorption capacity. It was 35.55 times for the diesel oil while for
motor oil, it was 31.37 times of its own weight for dynamic system. For
static system, it was slightly lower i.e. 28.94 and 27.41 times for diesel
oil and motor oil, respectively. The sorption was found to be higher for
diesel oil as compared to the motor oil. This may be due to much lower
viscosity of diesel oil i.e. 1.6 mPa.s as compared to motor oil with a
viscosity of 61.76 mPa.s. The molecules of low viscosity oil move faster
in the pore channels to causing faster swelling as compared to high
viscosity oil. Moreover, and viscosities of oil are lower the in dynamic
state as compared to the static state. For oil removal by the sponge in
oil-water mixture by the sponge, mainly physio sorption plays a critical
role. When the sponge is kept in contact with the oil or organic solvents,
they get absorbed into the inner part of sponge due to driving force. This
driving force mainly is due to hydrophobic interactions between the
sponge surface and the oil as well as the capillary effect of three
dimensional network of interconnected pores [80]. The adsorption ca­
pacity of developed superhydrophobic sponge as compared to other
commercially available sponges like polydimethylsiloxane functional­
ized melamine sponge (45.4–71.5 g/g) [81], cellulose aerogel sponge
(24.4 g/g) [82], polybenzoxazine/ reduced graphene wrapped cellulose
sponge (61.1 g/g) [83] was reasonably good and studies are encour­
aging. More importantly, superhydrophobic sponge developed in this
study is derived from waste biomass and it is much easier to realize its
Fig. 6. (a) Oil sorption characteristics at different contact times for a dynamic system (b) Oil sorption characteristics at different contact times for a static system.
11
Journal of Environmental Chemical Engineering 9 (2021) 105063
large scale production.
The separation efficiency of the sponge diesel oil and motor oil was
98.5% and 97.2%, respectively. To verify the reusability, 10 cycles were
performed. After each cycle, the absorbed oil was separated by manual
squeezing. The adsorption capacity of the sponge reduced slightly to
85.2% for diesel oil and 82.5% for motor oil of its initial value after 10
cycles, indicating stable adsorption and good recyclability. Further, it
was also observed that the sorption of water was negligible as compared
to oil i.e. 0.35–0.50% of its own weight. This implies that synthesized
super hydrophobic sponge have significant applications as these results
suggest that the sorbent pickup extensive quantity of oil without any
external stimuli for oil water separation.
The adsorption of diesel and motor oil with different initial con­
centration (5, 10, 15, 20 and 25 g/L) in dynamic and static system is
shown in Fig. 7(b) and (c), respectively. It is evident that with increase in
initial concentration of oil, the equilibrium adsorption capacity (qe) for
diesel/water mixture increased to 23.4 and 23.7 g/g for dynamic and
static system, respectively. Also, an increment of 23.9 and 22.8 g/g in qe
value for motor oil/water mixture was observed in dynamic and static
system, respectively. The value of qe was more for diesel/water mixture
than motor oil/water mixture in static as well as dynamic system
because of higher separation efficiency of diesel which is 98.5% while it
was 97.2% for motor oil. The large adsorption capacity was mainly
attributed to the hydrophobicity of the DCHS, which has been corrob­
orated by contact angle studies. Also, oil adsorption by the sponge is
very quick and the adsorption process reached an equilibrium in the first
15 min, suggesting that the adsorption depended on the rapid transfer of
D. Ahuja et al.
Fig. 7. (a) Intra particle diffusion model (b) Performance of dip-coated hydrophobic cellulose sponge under different initial concentration of diesel and motor oil in
dynamic system at adsorption time = 15 min and temperature = 25 ◦ C (c) Performance of dip-coated hydrophobic cellulose sponge under different initial con­
centration of diesel and motor oil in static system at adsorption time = 15 min and temperature = 25 ◦ C.
oil to the surface of sponge in the beginning. Greater specific surface
area along with hydrophobicity contributed to the large adsorption ca­
pacity of the oil.
3.4. Adsorption kinetic studies for oil/water mixture on DHCS
Adsorption kinetics modeling is very important to check whether the
adsorption process follows physical or chemical adsorption mechanism.
Three adsorption kinetics models i.e. Pseudo First-Order-Kinetic Model,
Pseudo Second-Order-Kinetic Model and Intra-particle diffusion Model
were employed to investigate the sorption of oil by DHCS. Weber and
Morris Intra-particle diffusion model was used to observe whether the
adsorption system is controlled by diffusion. The parameters for all the
three kinetics models has been represented in Table 2. The regression
coefficients (R2) indicated that the pseudo-second order kinetics model
fitted best with the experimental data, and the intra-particle diffusion
kinetics model also showed similar values as that of experimental values.
The calculated value of qe from linear pseudo second-order-kinetic
model for diesel and motor oil (dynamic system) is 35.6 and 31.0 g/g,
respectively, and from non-linear pseudo second-order-kinetic model is
34.8 and 30.65 g/g, respectively, which are in good agreement with the
experimental data (35.6 and 31.3 g/g for diesel and motor oil, respec­
tively) than the pseudo first-order-kinetic model. Similarly, calculated
values of qe from linear pseudo second-order-kinetic models for diesel
and motor oil (static system) are 30.3 and 29.4 g/g, respectively, while
qe values obtained from non-linear pseudo second-order-kinetic model
are 28.58 and 26.86 g/g, respectively, which are in good agreement
with the experimental data (29.1 and 27.3 g/g for diesel and motor oil,
respectively). However, in both the cases, the values of the linear fit
12
Journal of Environmental Chemical Engineering 9 (2021) 105063
were closer to the experimental data (Tables 2a and 2b).
Intra-particle diffusion model evaluates the rate controlling steps
during adsorption process. The plot in Fig. 7(a), did not pass the origin,
indicating that the internal diffusion is not the only rate-limiting step in
the adsorption process. Moreover, there are two distinct linear segments
in the plot i.e. a biphasic behavior, as shown in Fig. 7(a), signifying that
it is a multi-step adsorption process. The constants, kp1 and kp2 represent
the slope of two segments. The intra-particle diffusion rate constant kp1
has higher value than kp2, which means that the external surface
adsorption was a rapid step and the diffusion of diesel within the ad­
sorbents was a relatively slower step [77]. It can be concluded from the
intra-particle diffusion model that external and internal diffusion
happened simultaneously during the overall adsorption process.
3.5. Isotherm adsorption modeling for oil/water mixture on DHCS
The results of various parameters evaluated by linear and non-linear
adsorption isotherm modeling for oil/water mixture by DHCS are
tabulated in Tables 3a and 3b. Non-linear fitting plots of Langmuir,
Freundlich, and Dubinin-Radushkevich isotherm models for adsorption
of diesel and motor oil on the adsorbent in dynamic and static systems
have been shown in Fig. 8(a) and (b). It could be seen that the experi­
mental data fitted best in Freundlich isotherm with coefficient of
determination (R2) > 0.98, rather than Langmuir isotherm and D-R
isotherm which showed R2 of 0.963 and 0.958, respectively. This makes
it apparent that the adsorption of oil onto DHCS is asymmetric or
multilayered and Freundlich index, 1/n lies between 0.1 and 0.5, sug­
gesting that the material is a favorable adsorbent. Heterogeneity in
Freundlich isotherm is expressed by the value of n. If n ≥ 1, the
D. Ahuja et al. Journal of Environmental Chemical Engineering 9 (2021) 105063

Table 2a
Parameters for three linearized forms of kinetic models of oil adsorption onto DHCS.
Model Parameters Diesel (Dynamic) Diesel (Static) Motor oil (Dynamic) Motor oil (Static)

Pseudo First-Order Kinetic qe 7.49 10.18

22.3 19.9
K1 0.164 0.193
0.191 0.216
R2 0.990 0.974
0.872 0.880
R2 (adj) 0.986 0.964
0.821 0.832
ARE 5.87 10.25
8.85 15.25
Pseudo Second-Order Kinetic qe 30.3 29.4
35.6 31.0
K2 0.042 0.033
3.15 3.58
R2 0.999 0.999
0.996 0.997
2
R (adj) 0.999 0.999
0.994 0.996
ARE 0.071 0.067
0.34 0.27
Intra-particle Diffusion C1 21.2 17.37
16.04 15.45
Kp1 2.08 2.63
4.97 4.10
2
R 0.984 0.968
0.968 0.984
R2 (adj) 0.968 0.936
0.936 0.968
ARE 1.09 2.84
2.98 1.29
C2 28.46 26.66
34.96 30.66
Kp2 0.154 0.154
0.154 0.154
R2(*) 0.767 0.767
0.767 0.767
ARE 0.076 0.069
0.042 0.081

R2adj could not be calculated as the numerator is zero (N = 3, parameter = 2).

Table 2b
Parameters for non-linearized form of kinetic models of oil adsorption onto DHCS.
Model Parameters Diesel (Dynamic) Diesel (Static) Motor oil (Dynamic) Motor oil (Static)

Pseudo First-Order Kinetic qe 37.66 30.10 33.75 28.75

K1 0.340 0.607 0.375 0.495
R2 0.751 0.770 0.774 0.852
R2 (adj) 0.651 0.678 0.684 0.793
ARE 5.50 2.51 4.63 2.68
Pseudo Second-Order Kinetic qe 34.80 28.58 30.65 26.86
K2 0.017 0.045 0.018 0.033
R2 0.970 0.969 0.971 0.982
R2 (adj) 0.958 0.957 0.959 0.975
ARE 0.84 0.67 0.87 0.63
Intra-particle Diffusion C1 16.92 21.18 15.39 16.92
Kp1 4.778 2.12 4.13 2.83
R2 0.947 0.975 0.973 0.965
R2 (adj) 0.894 0.950 0.946 0.930
ARE 2.480 0.800 1.650 1.285
C2 35.14 28.54 30.64 26.83
Kp2 0.117 0.137 0.161 0.117
R2 0.798 0.772 0.682 0.748
ARE 0.054 0.080 0.088 0.073

adsorption mechanism is homogeneous and it’s a physical process and if
n ≤ 1, then it is heterogeneous [53]. As the calculated values of n for
diesel and motor oil for both dynamic and static systems vary from 2.63
to 3.26, the adsorption is assumed to be homogeneous. Since the sponge
is highly hydrophobic, more quantity of oil could be trapped in the pores
besides direct adsorption onto the surface of the sponge.
For D-R isotherm calculations, E is a parameter used in predicting the
type of adsorption. The results show that the values of E for both oils in
dynamic as well as static systems are lower than 8 kJ/mol. It can be
concluded that the adsorption is mainly controlled by physical adsorp­
tion (physisorption) [78] i.e. the forces of attraction between sponge and
oil are Vander Waal interactions. As qm of Langmuir isotherm and qD of
D-R isotherm represent the calculated maximum adsorption capacity of
oil onto DHCS adsorbent, it was observed that qD values for both diesel

13
D. Ahuja et al. Journal of Environmental Chemical Engineering 9 (2021) 105063

Table 3a
Values of the parameters of different linearized form of adsorption isotherms.
Isotherm Parameters Diesel (Dynamic) Diesel (Static) Motor oil (Dynamic) Motor oil (Static)

Langmuir qm 58.8 58.8

66.6 62.5
KL 17.0 8.5
15.01 8.0
R2 0.957 0.963
0.958 0.961
R2 (adj) 0.914 0.926
0.916 0.922
ARE 3.21 2.92
3.15 2.99
Freundlich n 2.8 2.71
3.26 2.9
KF 72.4 55.71
77.80 60.81
R2 0.990 0.993
0.993 0.993
2
R (adj) 0.980 0.986
0.986 0.986
ARE 2.10 1.42
1.40 1.45
Dubinin-Radushkevic qD 58.4 52.6
64.8 57.7
E 7.07 4.08
7.07 7.07
2
R 0.952 0.943
0.958 0.943
R2 (adj) 0.904 0.886
0.916 0.886
ARE 3.95 4.62
3.90 4.21

Table 3b
Values of the parameters of different non-linearized form of adsorption isotherms.
Isotherm Parameters Diesel (Dynamic) Diesel (Static) Motor oil (Dynamic) Motor oil (Static)

Langmuir qm 63.52 61.54

67.81 65.82
KL 9.84 4.99
13.13 5.72
R2 0.939 0.951
0.945 0.947
2
R (adj) 0.878 0.902
0.890 0.894
ARE 4.76 4.36
3.82 4.18
Freundlich n 2.71 2.63
3.19 2.83
KF 73.87 56.34
78.80 61.43
2
R 0.987 0.992
0.992 0.992
R2 (adj) 0.974 0.984
0.984 0.984
ARE 1.90 1.50
1.30 1.44
Dubinin-Radushkevic qD 60.17 54.08
66.12 59.05
E 2.11 1.71
2.31 1.77
R2 0.943 0.934
0.952 0.930
2
R (adj) 0.886 0.868
0.904 0.860
ARE 4.52 4.86
3.44 4.52

and motor oil (in dynamic and static systems) are closer to the experi­
mental values than qm values.
A comparison of the different adsorbents used for oil water separa­
tion on the basis of their cost and adsorption capacity is tabulated in
Table 4.
3.6. Techno economics and reusability of DHCS
The cost estimation for dip coated cellulose sponge prepared from
waste jute bags has been tabulated in Table S1 in supplementary data.
From the table it can be seen that cost for 100 g of DHCS for oil water

14
D. Ahuja et al. Journal of Environmental Chemical Engineering 9 (2021) 105063

Fig. 8. (a) Non-linear fitting plots of (i) Langmuir, (ii) Freundlich, and (iii) Dubinin-Radushkevich isotherm models for adsorption of diesel on the adsorbent (b) Non-
linear fitting plots of (i) Langmuir, (ii) Freundlich, and (iii) Dubinin-Radushkevich isotherm models for adsorption of motor oil on the adsorbent.

porous three dimensional structure sponges. WCA results confirmed that

Table 4
superhydrophobicity was attained after multiple coatings of TEQS/
Comparison of diesel adsorption capacity and economic of various adsorbents.
HDTMS yielding a static contact angle of 151.71◦ . The oil-water sepa­
Adsorbents Economics Adsorption References ration experiments showed an increase in oil sorption with respect to
capacity (diesel)
contact time from 45.7% to 97.2% and 46–98.5%, for motor oil and
(g/g)
diesel oil, respectively. Repeated oil-water separation experiments
Raw Cotton fiber Economical 15 [84] established that the developed sponges maintained their structural sta­
Cotton modified using P-SiO2 Costly 20 [85]
nanoparticles
bility even after 10 cycles and depicted only a marginal drop i.e.12–15%
Kapook modified using P-SiO2 Costly 23 [85] of adsorption capacity. The adsorption capacity was comparable to
nanoparticles commercially available sponges. Overall, it was concluded that the
Aerogels prepared from Moderate 24.4 [82] cellulose isolated from waste jute bags shows excellent potential for
cellulose
developing low cost superhydrophobic materials for cleaning up crude
Mesoporous Silica Aerogels Costly 13.6 [86]
Treated bark Moderate 2 [87] oil spills and the strategy can be extended to other waste biomass/ crop
Modified jute fibers Moderate 8.48 [88] residues.
Sponge modified by Costly 8.9 [89]
trisilanophenyl POSS
CRediT authorship contribution statement
Surfactant grafted PDA-PAN Costly 62.53 [90]
nanofibers
Polydimethylsiloxane Costly 45.4–71.5 [81] D.A., S.D. and A.K. conceptualized the problem. S.D. and D.A. per­
functionalized melamine formed the experiments. D.A., S.D., G.R. and S.S. organized the char­
sponge (g/g) acterization and their analyses. D.A. and A.K. contributed to drafting,
Polybenzoxazine/ reduced Costly 61.1 [83]
writing, and editing of the manuscript. S.M., D.A. and A.K. contributed
graphene wrapped cellulose
sponge in the revision of the manuscript.
Dip Coated Cellulose nanofibers Moderate 35.55 This study
sponges
Declaration of Competing Interest

separation is $ 22.71, which is relatively high. But the high cost is
associated with advantage that its separation efficiency is reasonably
good with very small amount of sponge. Further, adsorption capacity of
the sponge reduced slightly to 85.2% for diesel oil and 82.5% for motor
oil of its initial value after 10 cycles (Fig. S1), indicating stable
adsorption and good recyclability. Moreover, the sorption of water was
negligible as compared to oil i.e. 0.35–0.50% of its own weight. This
implies that synthesized super hydrophobic sponge can be utilized
commercially for oil water separation as the DHCS pickup extensive
quantity of oil without any external stimuli for oil water separation.
4. Conclusion
To summarize, facile method of dip coating with TEOS/HDTMS has
been demonstrated, to produce excellent super-hydrophobic, mechani­
cal robust and recyclable cellulose sponge from discarded jute bags. SEM
images of the cellulose sponge confirmed the cross linked and highly
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
Authors are highly thankful to University Grants Commision, India,
Council for Scientific Instrumentaion & Research, New Delhi, India for
Project Sanction no. 22(0798)/19/ EMR-II dated 24.7.2019, Depart­
ment of Science and Technology for providing grant vide SEED/TIASN/
008/2018 dated: 06/06/2018 to one of the authors and TEQIP-III grant
to Dr. S.S. Bhatnagar University Institute of Chemical Engineering &
Technology, Panjab University, Chandigarh for procurement of chemi­
cal and instruments.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the

15
D. Ahuja et al.
online version at doi:10.1016/j.jece.2021.105063.
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