Journal of Water Process Engineering 48 (2022) 102783

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Journal of Water Process Engineering

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

Superhydrophobic and super-oleophilic natural sponge sorbent for crude

oil/water separation
Maryam Kavousi Heidari a, 1, Mona Fouladi a, 1, Houman Asghari Sooreh b, Omid Tavakoli a, *
a
School of Chemical Engineering, College of Engineering, University of Tehran, Tehran 14176, Iran
b
School of Polymer Engineering, College of Engineering, University of Amirkabir, Tehran, Iran

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

Keywords: In this study, the separation of hydrocarbon derivatives from the water surface, one of the world's significant
Luffa sponge problems and challenges, was solved by synthesizing a superhydrophobic and super-oleophilic luffa sponge (LS)
Biodegradation in an easy, inexpensive, and environmentally friendly way. Using design expert 12 software, the values of
Superhydrophobic
graphene, wax, and time to absorb oil from the water surface were optimized. The optimal amounts of graphene,
Eco-friendly
Super-oleophilic
wax, and time were obtained at 0.108 g, 0.338 g, and 2.587 minutes, respectively. The TGA analysis showed that
the modified luffa sponge was temperature decomposed between 348.1 and 394.3 ◦ C and finally decomposed and
carbonized completely at 497.2 ◦ C. Also, the modified luffa sponge's hydrophobicity was investigated by contact
angle analysis. The results displayed that the modified sponge's contact angle with wax and graphene was 158◦ ,
which confirmed the modified luffa sponge's super-hydrophobicity. In addition, the sorption efficiency of the
modified Luffa sponge was higher than 91.32%, and oil/water sorption capacity was larger than 11.92 (g/g).
Also, the average oil of recovery after 10 cycles maintains separation sorption of around 91.32%. Finally, luffa
sponge/ graphene/ carnauba and beeswax can be used as biodegradable, super-hydrophobic, and super-
oleophilic sorbents in the industry.

1. Introduction In general, traditional procedures such as centrifugation, membrane,

One of the biggest problems in the world today is pollution caused by
oil spills in the seas and oceans, which has become a vital environmental
issue worldwide. These contaminants can enter seawater through
various methods, including direct or indirect discharges, including oil
extraction operations, tanker transportation, fuel oil, and many other
similar accidents [1,2]. In addition, because these hydrocarbons are
difficult to decompose biochemically and cause significant damage to
the environment and aquatic animals, they must be treated in the
environment before discharge. Therefore, treatment is highly regarded
for oil effluents; due to the harmful risks they pose to human health, the
environment, plants, and aquatic organisms. Finally, to prevent the
extensive human and financial damage that countries may suffer in this
event, oil water separation methods are essential for treating oily in­
dustrial wastewater. Also, various techniques have been developed to
eliminate and recover oil spills, each of which has advantages and dis­
advantages, such as mechanical, chemical, physical, and biological
techniques [3,4].
ultrasonic separation, gravity separation, photocatalysts, rotation,
coagulation, evaporation, and electrochemical and biological methods
are all extensively used for oil/water separation [5,6]. However, so­
phisticated separation tools, low separation sorption, and high cost
make these oil/water separation systems more challenging to use. For
example, in the method of removing oil stains by membranes, mem­
branes act selectively. In this way, larger particles do not pass through
the membrane cavities and are practically repelled, and in contrast,
smaller particles pass through the membrane cavities, and filtration is
performed. The most critical factor in the industry's non-commercial and
unusability of this method was the required facilities and the high cost of
membrane construction. In addition, manufactured membranes have a
long life and need to be replaced [7]. Also, the use of catalysts to
separate oil was first investigated in 1986, but the remarkable point was
the inability of catalysts to separate and remove oil stains on the water
surface. Based on the ability of the catalysts, oil stains would stick to
each other, clot, or settle simply by reducing the surface load of the
parts, which was helpful. However, it needed a membrane or mechanism

* Corresponding author.
E-mail address: otavakoli@ut.ac.ir (O. Tavakoli).
1
Maryam Kavousi Heidari and Mona Fouladi have contributed equally to this work.

https://doi.org/10.1016/j.jwpe.2022.102783
Received 28 January 2022; Received in revised form 4 March 2022; Accepted 7 April 2022
Available online 21 April 2022
2214-7144/© 2022 Published by Elsevier Ltd.
M.K. Heidari et al.
to remove the stains from the water again, which was why catalysts were
quickly removed from companies' options for removing oil stains [8]. So,
due to the drawbacks of separation methods like lesser recyclability,
poor selectivity, high operational cost, high toxicity, long time
requirement, the introduction of secondary pollutants, and inadequacy
use of different sorbent materials to be a common method for oil-water
treatment because of low cost, remediation process, availability, prac­
tical applications and eco-friendliness [9]. Specially modified of the
surface layers of sorbent materials, a superhydrophobic/ super-
oleophilic coating was obtained that can effectively remove oil and
water with the wide advantages like fast separation and high separation
sorption and sorption capacity [4].
In recent years, the use of materials with 3-dimensional (3D) porous
structures has always received much attention due to high promising
sorbent owing to its outstanding properties, such as metal foam and
meshes, fabrics and textiles, non-biodegradable sponges (PU, PV, PP,
and so on.), aerogel graphene, etc. These kinds of commercial sponges
have prominent features like the subsequent recovery of oils from their
pores and the ability to hold oil within their matrix [10]. Despite suc­
cessful reports of a high percentage of oil slicks absorbed by these porous
structures, but the disposal of these materials has always been an
environmental challenge. Because these materials do not decompose in
the environment and burning or spilling them causes environmental
pollution and wastes resources. [8,11,12].
One of the pioneers in removing oil stains from the water surface is
synthesizing oleophilic and hydrophobic sorbents based on poly­
urethane. This sorbent has a good performance in oil sorption. The us­
ability of the absorbed oil led to a change in the manufacture of
oleophilic sorbents. Because this sorbent has performed well, but two
factors led to the non-use of such sorbents in the industry. The first is the
high cost of producing these sorbents. The second is the environmental
damage that these polymer products show during prolonged exposure to
sunlight and at high temperatures due to the reaction of active mono­
mers that sometimes remain in the sorbents. In contrast, the use of
biodegradable sorbents has received much attention, as they are highly
sorption capacity, inexpensive, not toxic, provide oil reuse to industry,
and are safe for the environment, especially aquatic animals and birds.
Nevertheless, biomass-based materials with the ability to be renewable
and biodegradable due to their many advantages can be used as a suit­
able option to solve oil spills collection [13,14] among different types of
biodegradable sorbents [15]. Luffa cylindrica, a known sponge gourd or
vegetable sponge, belongs to the Cucurbitaceae family application for
oil-water purification [16]. Luffa sponge is a biological cell substance
mainly composed of lignin, hemicellulose, and cellulose [17]. Thus,
luffa cylindrical is a lignocellulosic material with a continuous 3D
macroporous surface with an inflexible structure resembling a polymer-
based sponge. Luffa sponge is very light and has a specific gravity of
0.92 g/cm3, permeability (79–93%), has a minimal bulk (30.02–0.04 g/
cm3), and surface space of 850 m2/m3 [18–21]. Luffa sponges are
accessible at a low cost and are commonly widespread in China, Japan,
Asia, and America. This sponge has various applications in daily life
because of its high water sorption capacity, exceptional mechanical
properties, degradability and renewable structure, and stable structure,
such as a filter for purification and filtration, decorative materials, and
kitchen cleaning and fuel for cooking [17,22]. Also, low surface energy
reagents have been used in all methods of modifying luffa sponges,
including polyurea glue, FAS-17, and polydimethylsiloxane stearic acid
(PDMS), alkyl ketone dimer (AKD), perfluorooctanoic acid. These low-
energy chemicals are neither renewable nor biodegradable. Also, sur­
face hydrophobicity mostly relates to the variance in surface energy
between the water droplet and the surface, which can be attained via
reducing the free surface energy or changing the surface roughness.
Thus, nanoparticles such as SiO2, ZnO, TiO2, Fe3O4 have been used to
improve the surface and increase the hydrophobicity of the sponge,
which are not only toxic but also pollute the environment. This method
has been followed to remove oil from seawater by sorption oil on the
2
Journal of Water Process Engineering 48 (2022) 102783
surface of the ultra-hydrophobic foam and thus greater sorption ca­
pacity. As a result, hydrophobic carbon compounds and wax can be used
to create hydrophobic and oil-friendly properties in the Luffa sponge
[23,24].
Bio-waxes with a hydrophobic nature, such as Carnauba wax (CW)
and beeswax produced by Apis melifera, a type of western bee, can be
converted to completely non-toxic substances immediately after disso­
lution in polar solvents. Coatings based on these bio-waxes have lower
energy levels and coarser textures [25–28]. These waxes can also be
used to produce super-hydrophobic surfaces because of their potential
applications in the wood, food packaging industries, and paper.
Carnauba wax includes hydrocarbons (1–3%), acids (3–6%), fatty al­
cohols (10–16%), and fatty acid esters (80–85%). It is around 20%
esterified fatty diols, 10% methoxylated or hydroxylated cinnamic acid,
and 6% hydroxylated fatty acids. Also, the beeswax composition is hy­
drocarbons (12%–16%) with a predominant chain length of C27–C33,
mainly heptacosane, nonacosane, hentriacontane, pentacosane, and
tricosane; free fatty acids (12%–14%), with a chain length of C24–C32. In
addition, carnauba wax and beeswax are composed of only one long-
chain fatty acid bonded to a long-chain alcohol group attached. Due to
their long, nonpolar carbon chains, waxes are extremely hydrophobic
(meaning they lack an affinity for water) [29,30]. These waxes are
among the natural resources with low energy levels. They have many
advantages such as easy manufacturing, abundance, commerciality, low
cost, renewable, eco-friendly, etc. Nevertheless, their most significant
advantage is the lack of organic solvents and chemicals, facilitating their
industrial use [31]. In a 2019 study, Wang et al. used rice bran wax and
carnauba wax as a covering and ethyl acetate as a solvent. The wax layer
formed the composite particle/film microstructures, making the super­
hydrophobic coating resistant to soaking in various oils and water and
highly corrosive. The ultra-hydrophobic and ultra-oleophilic luffa
sponge was able to selectively separate oil from the water surface with
necessary features, such as reusability (Period >10), separation sorption
(>91%), and high sorption capacity (9.5 g/g) [32]. In another study in
2018, Yu et al. proposed the manufacture of a modified luffa sponge.
After cleaning the surface of the luffa sponge with NaOH for 2 h to
remove impurities and prepare the luffa sponge to react with the
modified material. The SiO2 silica and water-based polyurea adhesive
were then combined in the organic ethanol solvent until a milky white
colloidal suspension was obtained, and then the luffa sponges were
immersed and dried in the obtaining solution. The results showed hy­
drophobicity, oleophilic, and high chemical and mechanical resistance
of the modified luffa sponge [33]. In another study in 2018, Yinlei Lin
et al. covered the surface of a hydrophilic luffa sponge using F-SiO2-NPs
(fluorine silica) nanoparticles prepared using the sol-gel method. The
results show high hydrophobicity and a contact angle of about 156◦ in
the modified luffa sponge, which can absorb oil stains [34].
Among different materials used for oil-water separation, graphene
nanosheet is emerging as a new research frontier for realizing waste­
water purification [35]. Graphene is a two-dimensional carbon material
that is made by bonding carbon atoms in a repetitive hexagonal struc­
ture. Graphene is one of the most robust carbon materials with high
conductivity and transparency due to its flat honeycomb pattern. Due to
the chemical resistance of graphene and its exceptional physical prop­
erties, it has been widely used in medicine, electronics, aviation, water
treatment, and catalysis [36]. Graphene nanosheets also have great
potential for removing oil contaminants from water due to their inherent
water repellency and high specific surface area. On the other hand, due
to the natural decomposition by microorganisms and enzymes and other
biological activities, a suitable option can be used to increase the hy­
drophobicity of the sponge surface. Graphene can also be used as a high-
porosity, three-dimensional hydrophobic-oil-friendly material, such as
graphene aerogels and graphene sponges, which have a sorption ca­
pacity of up to several times their mass. However, three-dimensional
graphene materials have insufficient compaction capacity, and thus
oils and organic solvents are not easily recoverable. Also, preparing
M.K. Heidari et al.
Fig. 1. Schematic of the process of synthesizing final modified luffa sponge with carnauba wax, beeswax, and graphene.
three-dimensional graphene is usually complex and expensive, leading
to limitations in its practical application in separating oil from water
[37–39]. In a study in 2018, Diwakar et al. Proposed making a modified
luffa sponge. They used alkaline to remove impurities from the luffa
sponge. The sponge's surface was then covered with modified graphene
by immersion and drying, and the hydrophilicity of the sponge was
changed to hydrophobicity. The results showed good stability of the
sponge in oil sorption [18].
In this study, we successfully obtained for the first time super­
hydrophobic and super-oleophilic properties of luffa sponges with gra­
phene nanosheet, natural waxes of carnauba, and beeswax on the luffa
surface using an immersed technique. The as-synthesized sorption is
reusable, highly efficient, eco-friendly, and cost-effective. Based on the
results, a mechanism is suggested to describe the observed characteris­
tics. Therefore, our goal is to use this large-scale sorbent to fabricate oil
separation from aquatic areas that are environmentally friendly and
cost-effective.
2. Materials and methods
2.1. Materials
Raw luffa fruit was obtained from farmers in Golestan province in
Iran (with the following characteristics: (dry fibers, light brown color,
with a length and diameter of 30 cm and 5 cm respectively) natural
beeswax and carnauba wax were obtained from local stores, (with the
following properties: beeswax yellow solid waxy; melting point around
64 ◦ C; specific gravity 0.952 g/cm3 at 25 ◦ C. Carnauba wax white solid
waxy; melting point around 80 ◦ C; specific gravity 0.994 g/cm3 at 25 ◦ C.
Sodium hydroxide (NaOH, 97%), ethanol (C2H5OH, 99%), graphene
nanosheet (thickness; 6–8 nm) were obtained from commercial sources
(Sigma Aldrich and Merck). Deionized water was prepared from a lab­
oratory. Also, crude oil with a density range of around 0.98 g/cm3 was
supplied by the Tehran refinery.
2.2. Preparation of sorbent
2.2.1. Preparation of luffa sponge
Briefly, first, the purchased raw luffa sponges were cut into pads with
dimensions of (2.5 cm × 3.5 cm) and thickness (3.8 cm). Then, the
alkalization process was performed to remove impurities, remove fine
and coarse particles, and increase the surface roughness and surface
preparation to increase the reaction with modifiers. Alkalization can
remove the gummy and fatty substances, hemicellulose and lignin, from
natural fiber. Hemicellulose, which includes more from hexosan, xylan,
3
Journal of Water Process Engineering 48 (2022) 102783
and polyuronide, has been shown to be very sensitive to Sodium Hy­
droxide. However, it has minimum effect on the lignin in the fibers.
Treatment with NaOH made the surface of the luffa rougher because
most of the impurities such as lignin and hemicellulose in the luffa
sponge were dissolved and removed [40]. In addition, these treatments
caused the flexibility and softening of the cell walls of the fibers and the
formation of nanopores between the well-arranged cellulose nanofibers,
so the surface of luffa is ready for modification [41].
First, the cut pads were washed with deionized water for 20 min, and
then the pads were immersed in NaOH solution (0.5 N) at room tem­
perature for one hour. The luffa sponges were then rinsed twice more
with deionized water for 10 min each, for a total of 20 min, and finally
left at room temperature for 24 h to dry completely. To ensure that the
sponges were dry, they were placed in an oven at 50 ◦ C for 1 h.
2.2.2. Preparation of oleophilic luffa sponge
Initially, 200 ml of ethyl acetate was heated to 70 ◦ C. Then different
amounts of total carnauba and beeswax (0.1 g, 0.3 g, and 0.5 g), which
were confirmed using design expert software, were the heated solution
of ethyl acetate on the stirrer was added and allowed to obtain a clear
and uniform solution. The solution was then moved to a water bath at a
temperature of about 50 ◦ C, and then the washed luffa pads were
immersed in the prepared solution for 5 s and then placed at room
temperature to dry. Immersion was repeated 3 times to ensure that the
waxes spread and settled on the surfaces of the luffa sponge [42].
2.2.3. Preparation of hydrophobic luffa sponge
Fig. 1 shows the schematic of synthesizing a modified luffa sponge
with carnauba wax, beeswax, and graphene. Finally, for the hydropho­
bicity of the luffa sponge obtained in the previous step, different
amounts of graphene nanosheets (0.15 g, 0.1 g, and 0.05 g) were
confirmed using design expert software. First, the graphene nanosheets
dispersed in the organic ethanol solvent were placed inside an ultrasonic
probe at 150 V for 30 min. The luffa sponges prepared in the previous
step were then immersed in graphene solutions at room temperature for
1 h, and finally, to dry, the luffa sponges were placed in an oven at 6 ◦ C
for 6 h. This was repeated 3 times to ensure that the nanosheets were
entirely on the surfaces of the luffa sponge [18]. In this step, the final
modified sponge (luffa/graphene/carnauba and beeswax) was ready.
2.3. Characterization of raw luffa and modified luffa sponges
The synthesized of the carnauba and beeswax/luffa sponge, gra­
phene/luffa sponge, and final modified sponge were performed using
Fourier transform infrared (FTIR, AVATAR, Thermo, USA) spectroscopy
M.K. Heidari et al. Journal of Water Process Engineering 48 (2022) 102783

Table 1 2.4. Sorption of oil stains using modified luffa sponge

Mass of Sponge before and after soaking.
Luffa Mass before Mass after Oil Sorption Raw luffa sponges modified with graphene nanosheet, carnauba, and
sponge soaking (g) soaking (g) sorption capacity (g/g) beeswax in a container of 500 cm3 (containing 3.5% by mass NaCl) and
(g) 10 g of crude oil with a density of 0.98 g/cm3 were immersed. Also, to
Uncoated 1.6 3.45 1.82 1.1 study and improve the effect of wax, graphene concentration, and
Coated 1.4 18.1 16.7 11.92 temperature on oil uptake from the water surface by the final modified
sponge, the response technique and central composite design (CCD)
were used. The nano-sponge pieces were placed in a container con­
Table 2 taining seawater and oil. After a specific time, they were taken out of the
A comparison of various foam sorbents materials. water, and their mass was measured. The following equation calculated
Foam sorbent Contact Sorption capacity Cycles References the oil/water sorption capacity (g/g) by luffa sponges:
angle or Separation
sorption
Kc = (Mb − Ma )/Ma (1)

Luffa/polyhedral 155◦ – 5 [49] In this equation, Ma is the mass of the primary luffa sponge, and Mb is
oligomeric the mass of the sponges after being saturated with oil stains.
silsesquioxane The following equation calculated the oil/water separation sorption
Luffa/carnauba and 151.7◦ 91% 10 [32]
(%) by luffa sponges:
rice bran wax
Polyurethane sponge/ 158◦ (80–160) g/g 15 [52] Ks (%) = 1 − (mb /ma ) × 100 (2)
GO/Fe3O4/oleic
acids In this equation, ma is the mass of the primary luffa sponge, and mb is
CNT sponge (20–40) g/g 10 [53]
–
the mass of the sponges saturated with oil stains.
Cellulose sponge 153◦ 92% 5 [54]
Melamine sponge/ 140◦ (60–109) g/g 12 [55] The following equation calculated the oil/water recyclability of the
SiO2 modified luffa sponge (%):
Polyurethane sponge/ 153◦ – 10 [56]
Fe3O4 Kr (%) = 1 − (mb /ma ) × 100 (3)
Polyurethane sponge/ 123◦ 95% 5 [57]
lignin where ma displays the mass of modified luffa after oil sorption and mb
Natural rubber (LNR) 150◦ 90% 20 [58] displays the mass of modified luffa after centrifugation.
Melamine sponge 153◦ 91.5% 35 [43]
All recycling experiments were done 3 times, and the average value
(MS)
was reported [43]. Moreover, for removing oil stains absorbed by luffa
sponges, recover the luffa sponge through a centrifuge at 3500 rpm for 5
min.
C-H2
(F)
2.5. Optimization of luffa sponge
(E)
According to study sources, time, wax, and graphene concentrations
Transmitance %

(D) are essential parameters in the rate of oil sorption by the luffa sponge, so
the experiments were designed based on these three variables. Tables 1
(C) O-H -CH3 and 2 show the levels of variables affecting oil sorption, respectively. To
-CH2- predict the desired conditions, the experimental values were investi­
(B) COO gated using Design-Expert 12 software and adapted based on the second-
C=O order polynomial regression model:
C-H3
C-H2 ∑ ∑ ∑
(A) O-H C-O Y = β0 + β i Xi + βij Xij + βii Xi2 (4)
C-H C=O C-C All tests were done in 3 replications. Analysis of variance (ANOVA)
4000 3500 3000 2500 2000 1500 1000 was done to assess the significance of each response in the model. To
confirm the suitability of the models, extra tests were performed ac­
Wavenumber (cm-1) cording to the optimal conditions predicted by Response Surface Method
(RSM), and the gained information was compared with the values pre­
Fig. 2. The FTIR spectra of (A) Raw luffa, (B) Wax, (C) Graphene, (D) Luffa/
dicted through the model.
wax, (E) Luffa/graphene, and (F) Luffa/wax/graphene.

3. Results and discussion

in the wavenumber range from 4000 cm− 1 to 400 cm− 1. The surface
morphology of the raw luffa sponge, carnauba and beeswax/luffa
3.1. Characterization of luffa and modified luffa sponges
sponge, graphene/luffa sponge, and the final modified sponge was
characterized via field emission-scanning electron microscopy (FE-SEM,
3.1.1. FTIR analysis
MIRA III, Czech Republic). Moreover, for identifying and confirming the
Fig. 2 demonstrates the FTIR spectra of raw luffa sponge, wax, gra­
composing elements and presence of different particles in the prepared
phene, and modified luffa sponge by wax and graphene. According to
nanofiber were used EDS and elemental mapping (FESEM, TESCAN,
the results, the bands in the raw luffa FTIR at 3285.04 cm− 1 and
Czech Republic), respectively. Also, a Contact-angle test was performed
2849.77 cm− 1 are related to the tensile vibration, the hydroxyl group
to measure changes in the hydrophobicity of the surface of sponges after
O–H and C–H in cellulose, respectively. The band of 1591.84 cm− 1
corrections were made on its surface. Thermal gravimetric analysis and
also indicates the tensile vibration of carbonyl C = O in the acetyl group
derivative thermal gravimetric were used to evaluate the temperature
related to hemicellulose and the aldehyde group in lignin. The band
resistance (TGA, Q600, USA) and the rate of material weight upon
1012.58 cm− 1 corresponds to the strong tensile vibration of C–O in
heating (DTG, Q600, USA), respectively.
cellulose, and the band 708.82 cm− 1 belongs to the C–C group. The

4
M.K. Heidari et al. Journal of Water Process Engineering 48 (2022) 102783

Fig. 3. SEM images of (A) Original Luffa sponge, (B) Alkannin luffa sponge, (C) luffa/wax sponge, (D) luffa/graphene sponge, and (E) Modified luffa sponge.

(A) (B)

30°
158° 158°

Fig. 4. (A) Water contact angle measurement for graphene/waxes luffa sponge and (B) Penetration of oil droplets into the graphene/waxes luffa sponge.

5
M.K. Heidari et al. Journal of Water Process Engineering 48 (2022) 102783

(A) (B)
120 TGA of raw luffa 120
TGA of modified luffa
DTG of raw luffa DTG of modified luffa
100 100

80 80

Weight (%)
Weight (%)

60 60

40 40

20 20

0 0

0 100 200 300 400 500 600 0 100 200 300 400 500 600 700

Temperature (°C) Temperature (°C)

Fig. 5. TGA & DTG analysis of (A) Raw luffa sponge and (B) Modified luffa sponge.

typical waxes. In addition, bands 1467, 1172, and 723 cm− 1 are asso­
21 ciated with the asymmetric tensile vibration of the C–H2 and C–H3
18
Before soaking (g) bonds, the symmetrical tensile vibration of the COO group, and the long
carbon chain, respectively [32,45,46]. In addition, the FTIR spectra of
After soaking (g)
Oil sorption (g)
15
Sorption capacity (g/g) graphene show the band at 1580 cm− 1 associated with the characteristic
band of the C6H6 bond. Also, the band at 1384 cm− 1 was attributed to
12
9 the − CH3 bending vibration. The band at 3438 cm− 1 was referred to as
6 the characteristic band of –OH [47]. Furthermore, the bands at 2922 and
Mass (g)

3 2853 cm− 1 were related to the stretching and vibrations of –CH3 and
1.1 –CH2–, respectively. Also, after modifications to the luffa sponge's sur­
face, including hydrophobic and oleophilic, the existing bands were not
much different from the raw sponge bands. Duo to the chemical reaction
between the surface of the sponge with the wax and graphene did not
occur, and only the intensity of the bands changed in some places. In
addition, the intensive bands of 2915.46 and 2847.27 cm− 1 are associ­
ated with the symmetrical tensile vibrations of the methylene (CH2)
group in natural wax [32].
0.0
Uncoated Coated 3.1.2. SEM analysis
Fig. 3 displays the SEM images of the luffa sponge before and after
Fig. 6. The final modified luffa sponge mass before and after soaking.
modification in different stages, which shows the successful changes in
each stage. According to Fig. 3A, before making any changes (alkalin­
100
ization, hydrophilicity, and hydrophobicity), the luffa skeleton has a
98 relatively irregular surface with shallow channels and relatively few
96 wrinkles. Also, the average diameter of raw luffa fibers determined by
94 Image J analysis was 1.45 ± 0.78 μm. According to Fig. 3B, after
92 washing and alkannin the surface of the luffa sponge using NaOH, the
Separation sorption (%)

90
changes are more palpable. Eventually, alkalinization causes dissolve or
88
remove low molecular mass impurities, reduce the microfibril angle of
86
83 rotation of the fiber material, making the surface rough and forming
many cavities, improving the ability of the fiber to react with modifi­
cation reagent. In addition, alkali modification caused fibrillation of the
fibers, which decreased the size of the fiber bundle, increased the length
to diameter ratio, and effectively enlarged the contact area with the
modifier. The alkali pretreatment dissolved some concomitant amor­
phous materials, such as lignin, hemicellulose, and pectin, which were
0 embedded in the crystalline region during the growth period imperfectly
1 2 3 4 5 6 7 8 9 10 11 12
crystallization of the fiber materials and changes in the characteristics of
Recycle numbers (n)
the surface topography. After pretreatment of the fiber, the fibers
Fig. 7. Separation sorption percentage of modified luffa. expanded in the alkali solution resulting in a weaker interfacial inter­
action between the fibrils and the intermediate cavity, and fiber wall
thickness increased. After alkali treatment, some channels appear, and
bands related to cellulose, lignin, and hemicellulose confirm the hy­
the luffa surface is more irregular because a large amount of the surface
drophilicity of the sponge surface [44]. Also, in the wax FTIR, the band
material was removed. Finally, the average diameter of alkanization
of 1736.93 cm− 1 shows the tensile vibration of the carbonyl group C = O
luffa fibers determined by Image J analysis was 1.49 ± 0.98 μm. Also,
bond, which is because of carboxylic acid, ester, and ketone groups in

6
M.K. Heidari et al.
Fig. 8. The stages of oil sorption by graphene/waxes/ luffa sponge.
according to Fig. 3C and D, by adding the optimum amount of carnauba
/beeswax and graphene nanosheets, respectively, many wrinkles are
covered, which is naturally more than the amount of coverage in the
final modified luffa sponge, Fig. 3F. In addition, the average diameter of
luffa/ carnauba and beeswax, luffa/ graphene, and modified luffa fibers
determined by Image J analysis were 1.54 ± 1.87 μm, 3.81 ± 1.84 μm,
and 3.22 ± 2.45 μm, respectively. Therefore, it can be concluded that
almost all cavities, holes, and wrinkles on the luffa surface are covered
with corrective materials, and the corrections have been done correctly.
Modified luffa sponge with graphene nanosheets created some impor­
tant changes in the morphology of luffa fibers. The results showed the
size distribution of nanofibers compared to raw luffa fibers broadened.
The result of this change because of low interaction between luffa fibers
and graphene nanosheet the majority of the graphene nanosheets
agglomerated on the fibers and formed some larger nanofibers; it could
be observed that the surface appearance of luffa sponge/ graphene/
carnauba and beeswax is non-uniform with large graphene nanosheets
agglomeration sites. It is noteworthy that the low tendency of graphene
nanosheets to luffa sponges barred their localization inside the nano­
fibers [48].
3.1.3. EDS analysis
Fig. 1S (A) shows the surface of the luffa sponge. According to the
figure, no sediment is found, and the luffa's smooth surface indicates the
absence of layers of any foreign matter on its surface. Also, Fig. 1S (B)
shows the EDS spectrum of raw luffa sponge. According to the results, a
strong carbon signal is confirmed in the structure of this plant material.
The structure of raw luffa sponge consists of carbon and weak signals of
O and N derived from surface-bound biological molecules. According to
the diagram, carbon peaks appear at approximately 0.5 keV, which is
surrounded in the luffa sponge structure by a thin layer of some organic
matter. Due to the vegetation of the luffa sponge and its cellulosic
structure, the presence of carbon and oxygen is expected; however, the
presence of N and its small peak relative to oxygen, speculation increases
that the structure of the luffa sponge is chitinous. The diagram also
shows that Al has a higher value than the other elements found. In
addition, the presence of calcium is due to the vegetation of the luffa
sponge because calcium is an essential component for strengthening
plants, which is found in abundance. Fig. 1S (J) shows the morpholog­
ical composition of the elements of the empty luffa sponge based on its
constituent elements. According to the results, this type of scattering
indicates the structure of a luffa sponge fabric in which all the elements
O, C, N, Na, Ca, Al, S are evenly distributed on its surface, and there is no
accumulation. This indicates the absence of external elements (other
than the elements that make up the raw luffa sponge). Fig. 1S (C-J) also
confirm the presence of elements O, C, N, Na, Ca, Al, S in the luffa
sponge.
According to Fig. 2S (A), sediments appeared on the luffa's surface,
and tubular structures and coarse and fine spherical particles appeared
on the surface of the luffa. Also, Fig. 2S (B) displays the constituent el­
ements of the modified luffa sponge are N, C, Ka, O, S, Na, and Al. Ac­
cording to the diagram, Si is also added to the Luffa sponge compounds.
7
Journal of Water Process Engineering 48 (2022) 102783
In addition, their concentration has increased due to the increase of
some element peaks. The increase in carbon level from 1120 to 3200
indicates that it has been added almost three times to its concentration
in a modified luffa sponge. Also, the chart shows that the final modified
luffa sponge has more calcium because calcium is of natural origin and is
found in abundance in natural materials (including those used to modify
the properties of luffa). Moreover, Fig. 2S (K) shows the elements pre­
sent on the surface of the modified luffa sponge. According to the im­
ages, the presence of elements O, Si, N, Na, Ca, Al, C, S on the modified
luffa sponge is confirmed.
3.2. Contact angle
Fig. 4A displays the water contact angle for the improved luffa
sponge. According to the results, it is about 158◦ , which indicates that
the changes have been applied correctly, and the modified luffa sponge
is entirely hydrophobic. In addition, when oil droplets settle on the
modified luffa sponge's surface, they are rapidly absorbed (contact
angle = 30◦ ), indicating an utterly oleophilic surface of the modified
luffa sponge (Fig. 4B). In a 2017 study, Zhe Wang et al. used polyhedral
oligomeric silsesquioxane (POSS) to modify the surface of a raw luffa
sponge to make it hydrophobic and oleophilic. The analysis results show
a contact angle of 155◦ with selective and high removal of oil stains
[49].
3.3. TGA & DTG analysis
TGA analysis is a way to study and discover how a substance behaves
in the face of heat. Fig. 5A and B show the Thermogravimetric analysis
(TGA) of raw luffa and modified luffa sponge, respectively. According to
the TGA analysis, raw luffa sponge lost some mass just before 100 ◦ C
because it contains moisture. Also, the results demonstrate that this
sponge was in a normal constant temperature phase from 100 to
278.1 ◦ C and underwent temperature decomposition between 278.1 and
339.1 ◦ C, then decomposed completely at 436.6 ◦ C. Eventually, the
mineral elements remained (in other words, they carbonized). However,
the TGA test of the modified luffa sponge, Fig. 5B, shows an increase in
the product's temperature resistance. According to the diagram, the
modified luffa sponge does not have moisture, so it does not have a mass
loss of empty luffa up to 100 ◦ C. Also, the modified luffa sponge has a
natural constant temperature phase from 0 to 348.1 ◦ C and is subjected
to temperature decomposition between 348.1 and 394.3 ◦ C and is fully
decomposed and carbonized at 497.2 ◦ C. Also, the DTG results showed
thermal decomposition of the modified luffa sponge slowed down at
high temperatures and prolonged the time of thermal decomposition.
In 2021, Yang et al. created a three-dimensional ultralight sponge
using electro-spun polyacrylonitrile (PAN) nanofibers and natural luffa
sponge. PAN nanofibers and luffa fibers were dispersed in an aqueous
solution using polyvinyl alcohol (PVA), and a three-dimensional ultra­
light sponge was formed using frees-drying technology. They also added
a spider web structure to the synthesized material to increase oil sorp­
tion. The results of TGA analysis clearly showed that two stages of mass
M.K. Heidari et al.
loss occurred in two different temperature zones. In the first stage, the
partial mass loss was about 100 ◦ C due to reducing the aqueous fraction.
Also, with increasing the amount of luffa sponge, the structure of the
sponge became more stable, and its decomposition became more com­
plex, which was due to the increase in the number of hydrogen bonds in
the sponge. In addition, as the hydrogen bonds decreased, the sponge
lost its stable structure and began to degrade rapidly [50].
In a report presented in 2019, Mingguang Yu et al. examined the
effect of Fe3O4-modified nanofibers on oil/water separation. The results
of TGA analysis showed that both fabrics of raw cotton and cotton
modified with Fe3O4 nanoparticles with diverse amounts of ferric
chloride and iron chloride started to decompose at temperatures up to
300 ◦ C. These observations displayed that the modification of the cotton
surface with Fe3O4 nanoparticles did not destroy the chemical structure
of raw cotton fabrics [51].
3.4. Optimization of sorption behavior of modified luffa sponge
The final modified sponge's oil/water separation sorption was stud­
ied using the response technique and central composite design (CCD).
Three parameters of graphene concentration (A), wax concentration (B),
and time (C) were measured to improve the percentage of removal (R)
(Table 1S). The important effect of each factor, curving, and contact
between them on response was considered by the software of Design
Experts. According to Table 2S, the values gained for the parameters of
p-value AB, AC, and BC are more than 0.05, and it appears that these
three factors don't have any important effect on the response and should
be removed (Table 4S). Also, the P-value of other parameters was fewer
than 0.05, and there is no need to eliminate them. Thus, the gained
equation for the response level R was calculated based on the Eq. (5).
R = 2.32614 + 868.353A + 201.634B + 6.693C − 4032.364A2 − 299.648B2
− 1.232C2
(5)
Fig. 3S (A) represents a contour plot and three-dimensional diagram
of the calculated response surface from the communication between
graphene and wax concentration while keeping time at zero levels.
According to the results, with rising graphene and wax concentration up
to 0.102 g and 0.31 g, respectively, the removal percentage has
increased up to 81%. Fig. 3S (B) displays the effect of graphene con­
centration and time on the removal percentage, keeping wax concen­
tration at zero levels. The graph demonstrates that the maximum
removal percentage (82%) happened at a graphene concentration of 0.1
g and a time of 3.12 min, which confirms the model. An interaction
between the remaining two parameters (wax concentration and time;
Fig. 3S (C)) differed slightly from the earlier responses. When a usual
possibility residuals' plot was created, a selection was made for the
regularity supposition, which was acceptable since closely all the re­
siduals fell almost along a straight line (Fig. 3S (D)). Since the nearer the
R2 value is to 1.0, the more reliable the model predicts the response, the
R2 gained here displays that the model has a good predictive ability.
Thus, from the Fig. 3S analysis and the responses attained in practice,
the optimum method conditions were graphene concentration 0.108 (g),
wax concentration 0.338 (g), and time 2.587 min. In addition, based on
the ANOVA results, the standard deviation was obtained 1.42.
3.5. Sorption of oil stains using final modified luffa sponge
First, the uncoated and final coated sponges were weighed before
immersion in water and oil solution, and after immersion, they were
removed for less than 5 min and then weighed again. Finally, Eq. (1)
calculated the amount of crude oil /water sorption capacity, Eq. (2)
calculated the amount of crude oil/water separation sorption and Eq. (3)
calculated the amount of recycle crude oil/water separation sorption.
Table 1 displays the sponge mass before and after soaking. Also,
8
Journal of Water Process Engineering 48 (2022) 102783
according to Fig. 6, the coated sponge's sorption capacity and separation
sorption are higher than the uncoated sponge, which confirms the
oleophilic and hydrophobicity of the modified luffa sponge. In addition,
according to Fig. 7, the percentage of separation sorption during 10
cycles almost has been the same but after the 11th cycle, the percentage
of separation sorption has decreased dramatically. It is due to the
reduction of oleophilic effects and properties of sorbent. Also, Fig. 8
shows the coated floating sponge on the water/ oil's surface because
graphene is hydrophobic and does not allow water to pass through it and
reach the fiber. In addition, it absorbs a large amount of oil on the
surface, so the modified luffa sponge's hydrophobicity and oleophilic
were proven.
In 2018, Diwakar et al. investigated the effect of a graphene-
modified luffa and raw luffa sponge on oil sorption rate from the
water surface. The results showed that the sorption rates of treated
sponges and raw sponges were 4.735 g and 2.533 g, respectively.
Doubling the oil uptake by graphene-modified luffa sponge is clear ev­
idence of increased oil uptake [18].
Finally, some foam sorbents' sorption capacity or separation sorption
has been reported in Table 2. The results for some sorbents like mel­
amine and polyurethane sponge were higher than the present work.
However, the luffa sponge was modified by graphene nanosheets and
natural waxes due to cost-effectiveness, ecofriendly, and accessibility.
Also, the most critical point is the biodegradability of this sorbent.
4. Conclusion
Recently, the use of biodegradable nano-sorbents to collect oil
pollution has received much attention. This study investigated the per­
formance of a biodegradable final modified sponge which was synthe­
sized by simple dip-coating technology for sorption of crude oil stains
from oil/water pollution. In this study, FTIR, SEM, and EDS analyzes
were used to investigate the morphological properties of the synthesized
nano-sorbents. Also, TGA analysis showed that the final modified luffa
sponge has a higher temperature resistance than the raw luffa sponge. In
addition, the contact angle for the modified sponge was 158◦ , which
confirmed that the final modified sponge was superhydrophobic. Ex­
amination of the sorption performance of the final modified sponge
showed oil/water separation sorption above 91.32% and sorption ca­
pacity above 11.92 g/g and can be reused for up to 10 cycles. The
synthesized nano-sorbent can be used in oil projects as a highly efficient
alternative method for separating crude oil /water separation on an
industrial scale.
CRediT authorship contribution statement
Maryam Kavousi Heidari: Substantial contribution to acquisition of
data, methodology and conceptualization, Data collection, Formal
analysis, Investigation, Writing – review & editing. Mona Fouladi:
Substantial contribution to acquisition of data, methodology and
conceptualization, Data collection, Formal analysis, Investigation,
Writing – review & editing. Houman Asghari Sooreh: Contribution to
acquisition of data, Data collection, Formal analysis, Writing the draft.
Omid Tavakoli: Validation, Visualization, Supervision.
Declaration of competing interest
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.
Acknowledgement
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
M.K. Heidari et al.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jwpe.2022.102783.
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