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Journal of the Taiwan Institute of Chemical Engineers

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Interfacial engineering of melamine sponges using hydrophobic TiO2

nanoparticles for effective oil/water separation
Er-Chieh Cho a, Cai-Wan Chang-Jian b, Yu-Sheng Hsiao c,∗, Kuen-Chan Lee d,∗,
Jen-Hsien Huang e,∗
a
Department of Clinical Pharmacy, School of Pharmacy, College of Pharmacy, Taipei Medical University, 250 Wuxing Street, Taipei City 110, Taiwan
b
Department of Mechanical and Automation Engineering, I-Shou University, No. 1, Sec. 1, Syuecheng Rd., Dashu District, Kaohsiung City 84001, Taiwan
c
Department of Materials Engineering, Ming Chi University of Technology, 84 Gungjuan Rd., Taishan District, New Taipei City 24301, Taiwan
d
Department of Science Education, National Taipei University of Education, No. 134, Sec. 2, Heping E. Rd., Da-an District, Taipei City 106, Taiwan
e
Department of Green Material Technology, Green Technology Research Institute, CPC Corporation, No. 2, Zuonan Rd., Nanzi District, Kaohsiung City 81126,
Taiwan

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

Article history: In this study, the surface modified TiO2 nanoparticles have been synthesized with oleic acid and trifluo-
Received 22 April 2016 roacetic acid (TFAA) as surfactants. The as-prepared TiO2 nanoparticles reveal small particle size with nar-
Revised 11 July 2016
row distribution, excellent dispersibility and high hydrophobicity. By interfacial modifying the melamine
Accepted 1 August 2016
sponge with the hydrophobic TiO2 nanoparticle, the wettability of the modified sponge can be tailored
Available online xxx
to be superhydrophobic to water while superoleophilic to oils. Combining with the porous structure of
Keywords: melamine sponge and the excellent hydrophobicity of the coated TiO2 , the modified sponge exhibits large
Oil absorbent absorption capacity (up to 88.1 g/g for chloroform), good selectivity and high recyclability for a wide range
Superhydrophobic of oils and organic solvents. The results indicate that the TiO2 modified sponges may potentially be useful
Superoleophilic as next-generation oil adsorbent materials.
Separation © 2016 Published by Elsevier B.V. on behalf of Taiwan Institute of Chemical Engineers.
Interfacial modification

1. Introduction
With industrial development, severe environmental and ecolog-
ical problems have been caused from the oil-spill, leakage of toxic
organic solvents and unexpected accidents. These environmental
issues lead to health problems for human beings, marine mam-
mals, aquatic ecosystems and plant. A number of methods have
been proposed to address the problems, such as oil booms [1],
burning [2], chemical dispersants [3–5] and bioremediation [6,7].
Unfortunately, these methods often cause secondary pollution dur-
ing the clean-up and cannot remove the contaminants effectively.
Therefore, development of novel materials for oil absorbent and
chemical recovery has attracted worldwide attention.
An ideal sorbent material requires low-cost, high adsorption ca-
pacity, selectivity and recyclability. Recently, carbon based sorbents
such as carbon nanotube (CNT) sponges [8–10], graphene aerogels
[11–14], and graphene sponges [15–18] have been extensively in-
vestigated due to their three-dimensional (3D) structure, low den-
sity, high surface area [19,20] and superhydrophobicity. The CNT
∗
Corresponding authors.
E-mail addresses: yshsiao@mail.mcut.edu.tw (Y.-S. Hsiao), kclee@tea.ntue.edu.tw
(K.-C. Lee), 295604@cpc.com.tw, r91524047@ntu.edu.tw (J.-H. Huang).
and graphene based sponges can take up 80–180 [11] and 60–
160 times [17] their own weight, respectively. Compared with the
traditional absorbent material such as active carbon, these porous
materials reveal much high sorption capacity. The 3D sponges
also can be regenerated simply by squeezing or directly burn-
ing. However, these materials require complex preparation process
such as freeze-drying [21,22], supercritical drying [23] or chemical
vapor deposition [24] which is unfavorable for mass production.
Melamine sponge is a kind of commercially available 3D porous
material. The melamine sponge can serve as a substrate for the
fabrication of oil absorbents due to its good absorption ability, low
density and excellent elasticity. Recently, much investigation has
been shown that the interfacial modification of melamine sponge
with CNT or graphene have turned the surface properties of the
sponges from hydrophilicity to hydrophobicity. The hydrophobic
melamine sponges absorbed a wide range of organic solvents and
oils with high absorption capacity and outstanding recyclability.
However, the CNT are expansive and the modified sponge shows a
poor surface coverage due to the high aspect ratio of CNT; and the
graphene modified sponge usually requires an additional reduction
process which involves toxic reducing agent.
To realize an ideal material used for modifying the melamine
sponges, in this study, we prepared alkyl-chain-capped TiO2
nanoparticle (OC-TiO2 ). With oleic acid as surfactant, the surface

http://dx.doi.org/10.1016/j.jtice.2016.08.002
1876-1070/© 2016 Published by Elsevier B.V. on behalf of Taiwan Institute of Chemical Engineers.

Please cite this article as: E.-C. Cho et al., Interfacial engineering of melamine sponges using hydrophobic TiO2 nanoparticles for effective
oil/water separation, Journal of the Taiwan Institute of Chemical Engineers (2016), http://dx.doi.org/10.1016/j.jtice.2016.08.002
JID: JTICE
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2 E.-C. Cho et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2016) 1–8
property of the TiO2 can be easily changed from hydrophilic to hy-
drophobic under the hydrothermal condition. The as-prepared TiO2
reveals excellent solubility and processability in common organic
solvents such as chloroform, toluene and 1,2-dichlorobenzene.
Moreover, the hydrophobicity of the OC-TiO2 can be further en-
hanced by treating with trifluoroacetic acid (TFAA). The average
particle size of as-prepared TiO2 is around 6 nm which is favor-
able to modify the melamine sponge with high surface coverage.
With dip-coating method, the hydrophobic TiO2 can be easily de-
posited on the surface of melamine sponge. The interfacially modi-
fied sponges reveal excellent superhydrophobic and superoleophilic
properties with high absorption capacity, selectivity and recyclabil-
ity for a wide range of organic compounds.
2. Experimental section
2.1. Preparation of modified TiO2
In a typical synthesis, 10 mmol of titanium tetraisopropoxide
was added to 35 g of degassed oleic acid and allowed to stir for
5 min. A 10 mmol of triethylamine in 6.4 g of ethyleneglycol was
subsequently added. Then, the solution was maintained in a close
system at 170 °C for 8 h through hydrothermal reaction. Subse-
quently, the OC-TiO2 was rapidly precipitated with addition of ex-
cess of ethanol. For the TFAA modified OC-TiO2 , 0.2 g OC-TiO2 , 5 ml
TFAA and 20 ml isopropanol was mixed through sonication. Subse-
quently, the mixture was fluxed at 80 °C for 2 h and then the pow-
der was collected by vacuum filtration. Finally, the treated powder
was washed (FOC-TiO2 ) with isopropanol to remove the residual
TFAA.
2.2. Preparation of TiO2 based absorbent
The commercial melamine sponge was cut into blocks (2 × 2
cm2 ) and ultrasonically cleaned in ethanol. Then, the blocks were
rinsed with distilled water and dried at 70 °C. After routine sol-
vent cleaning, the sponges were treated with UV ozone for 30 min.
The sponges were then dipped into the OC-TiO2 or FOC-TiO2 so-
lution, and finally dried in the vacuum oven at 100 °C. Finally, the
treated sponge was immersed into a dilute toluene solution which
contains PDMS (0.2 mg/ml) followed by drying at 120 °C overnight
to enhance the adhesion between the as-prepared TiO2 and the
sponge.
2.3. Characterization
X-ray diffraction (XRD) patterns of the samples were con-
ducted using a Philips X’Pert/MPD apparatus with Cu Kα radiation
(λ = 0.1542 nm). The thermal analysis was performed with MET-
TLER TOLEDO star system. The morphologies of the TiO2 nanopar-
ticles were investigated using transmission electron microscopy
(TEM) performed with a JEO 2100. The particle size distribu-
tion of the TiO2 was recorded with SYMPA TEC nanophox. Scan-
ning electron microscopy (SEM) images were acquired using a
Hitachi S-4700 coupled with an energy-dispersive spectrometer
(EDS). Fourier transform infrared (FTIR) spectra of the samples
were measured with a FTIR spectrometer (Thermo NICOLET is5). X-
ray photoelectron spectroscopy (XPS) spectra were recorded using
a PHI 50 0 0 VersaProbe (ULVAC-PHI, Chigasaki, Japan) system. The
absorption capacities (k) of modified sponges for various organic
solvents were measured. A weighed amount of modified sponge
was put into a flask containing of organic solvent and allows to
absorb for 5 min. Then k can be calculated through the defini-
tion, k = (Wsaturated absorption − Winitial )/Winitial . The water content of
the sample was measured with Mettler Toledo DL38 Karl-Fischer
titrator.
Please cite this article as: E.-C. Cho et al., Interfacial engineering of melamine sponges using hydrophobic TiO2 nanoparticles for effective
oil/water separation, Journal of the Taiwan Institute of Chemical Engineers (2016), http://dx.doi.org/10.1016/j.jtice.2016.08.002
[m5G;August 10, 2016;21:52]
3. Results and discussion
The phase composition and the crystalline structure of the pre-
pared OC-TiO2 are evaluated by XRD. Fig. 1a presents the XRD pat-
tern of the OC-TiO2 powder. Compared with JCPDS-84-1286 pat-
tern, all peaks can be assigned to the pure anatase structure. More-
over, the diffractogram of the OC-TiO2 do not present other impu-
rities. The as-prepared OC-TiO2 is highly soluble in common or-
ganic solvents such as toluene, hexane and THF due to the an-
chorage of alkyl chains on its surface. The TGA analysis was also
performed to measure the organic content of OC-TiO2 as shown in
Fig. 1b. The initial weight loss at temperature lower than 200 °C
corresponds to the evaporation of bound water. The second weight
loss starting at above 270 °C is contributed from the thermal de-
composition of the organic molecules modified onto the TiO2 sur-
face. The residue weight after heating at 900 °C is found to be 82.3
wt%, indicating that the organic content is around 20 wt%. Fig. 1c
and d shows the TEM images of OC-TiO2 with different magnifica-
tions. The TEM samples were prepared by pipetting OC-TiO2 solu-
tion (toluene, 0.1 wt%) onto the TEM grid. It can be seen that the
OC-TiO2 reveals a narrow size distribution and good dispersity. The
distribution of particle size is also shown in the inset of Fig. 1d.
The particle size ranges from 3.85 to 7.12 nm with an average parti-
cle size of 5.93 nm. It is believed that the as-prepared TiO2 powder
can be easily cast on various substrates (such as melamine sponge)
through solution process due to its small, uniform particle size and
excellent dispersability.
FTIR spectra of the prepared TiO2 powders were recorded to
verify whether oleic acid and TFAA molecules are indeed adsorbed
on the surface of the nanoparticles. As shown in Fig. 2b, it can be
seen that both OC-TiO2 and FOC-TiO2 show strong peaks located
at 2920, 2850, 1540, 1437 and 1090 cm−1 . The peaks at 2920 and
2850 cm−1 are known as the characteristic peaks of CH2 groups in
the hydrocarbon moiety [25]. Below 20 0 0 cm−1 , the characteris-
tic bands centered at 1540 and 1437 cm−1 are antisymmetric and
symmetric stretches of a COO− group on the TiO2 surface, respec-
tively [26]. Finally, the peak at 1090 cm−1 is contributed from the
absorption of C–O vibration [27]. Based on the frequency difference
between antisymmetric and symmetric stretches of COO− groups,
the mode of binding for carboxylate anchors onto the TiO2 sur-
face might be attributed to chelating bidentate [28,29]. The possi-
ble binding modes between TiO2 and carboxylate anchors are also
shown in Fig. 2c. Compared with OC-TiO2 powders, the FOC-TiO2
shows additional peaks at 1201 and 1140 cm−1 . The two peaks are
assigned to the C–F stretching vibration [30]. These results suggest
that the hydrophobic alkyl chains are indeed anchored on the TiO2
surface and the TFAA modification is also successfully achieved
during the post-treatment.
The surface chemical compositions of OC-TiO2 and FOC-TiO2 are
also analyzed by XPS. The XPS survey spectra of both the OC-TiO2
and FOC-TiO2 are shown in Fig. 3a. The OC-TiO2 contains only Ti, O,
and C, with sharp photoelectron peaks appearing at binding ener-
gies of 458 (Ti 2p), 531 (O 1s), and 285 eV (C 1s). Compared with
the spectrum of OC-TiO2 , an additional peak at 688 eV (F 1s) is
found in the spectrum of FOC-TiO2 . The high-resolution XPS spec-
tra and fitted curves of the F 1s and C 1s are also shown in Fig. 3.
It can be seen that the F 1s region consists of a single peak cor-
responding to the CF3 groups of the chemically adsorbed TFAA as
shown in Fig. 3b. Peak deconvolution of the C 1s XPS spectra of the
OC-TiO2 and FOC-TiO2 are presented in Fig. 3c and d, respectively.
In both cases C–C, C=C, C–H, C–OH and O–C=O convoluted compo-
nents can be observed (in OC-TiO2 these signals contributed from
the carboxylate adsorbates; in the FOC-TiO2 samples they come
from both the carboxylate adsorbates and the TFAA groups). How-
ever, a new peak show up in the FOC-TiO2 , a weak shoulder lo-
cated at a binding energy slightly below that of the C=O (arrow
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E.-C. Cho et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2016) 1–8 3

Fig. 1. The characterization of as-prepared OC-TiO2 nanoparticles. (a) XRD pattern; (b) TGA analysis of the as-prepared OC-TiO2 ; (c, d) the TEM image of the OC-TiO2 with
different magnifications. The inset: the particle size distribution of the OC-TiO2 . The OC-TiO2 reveals a uniform and small particle size which can form a stable colloidal
dispersion over 3 months without precipitation.

Table 1
Summary of the contact angle for water, ethylene glycol and diiodomethane
and their corresponding surface energy (γ ) of bare glass, OC-TiO2 and FOC-
TiO2 . The γ was calculated through the geometric mean approximation.

Contact angle (°)

Water Ethylene glycol Diiodomethane γ (mJ/m2 )

Bare glass 31.9 34.0 62.5 59.3

OC-TiO2 91.3 50.7 43.0 39.8
FOC-TiO2 97.7 64.4 55.1 30.6

Fig. 2. The further modification of OC-TiO2 with TFAA. (a) The comparison of FTIR
spectrum for OC-TiO2 and FOC-TiO2 and (b) the possible coordination modes of a
TFAA molecule.
marked in Fig. 3c). This signal might be arose from the existence
of C–Fx sites [31–34]. The XPS survey spectra further confirm that
the TFAA is chemisorbed on the TiO2 surface.
In order to study the effect of the interfacial modification on
the surface property of TiO2 , the contact angles of the OC-TiO2 and
FOC-TiO2 cast onto glass substrate were measured to calculate the
surface energy (γ ) as shown in Table 1. The contact angles were
measured with water, ethylene glycol, and diiodomethane. The
γ was calculated through the geometric mean approximation. The
contact angle measured from water for the bare glass is around
31.9°, indicating the surface can be wetted by the water. However
the contact angle of OC-TiO2 modified substrate is greater than
91.3°, suggesting that the hydrophobic surface of OC-TiO2 due to
the anchored alkyl chains. Based on the measured contact angles
of the modified TiO2 , the calculated γ of FOC-TiO2 (30.6 mJ/m2 )
is much smaller than that of OC-TiO2 (39.8 mJ/m2 ). This indicates
that the hydrophobicity of the OC-TiO2 can be further enhanced by

Please cite this article as: E.-C. Cho et al., Interfacial engineering of melamine sponges using hydrophobic TiO2 nanoparticles for effective
oil/water separation, Journal of the Taiwan Institute of Chemical Engineers (2016), http://dx.doi.org/10.1016/j.jtice.2016.08.002
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Fig. 3. Chemical composition analysis and peak deconvolution of OC-TiO2 and FOC-TiO2 . (a) XPS survey spectra for the OC-TiO2 and FOC-TiO2 ; (b) high-resolution XPS
spectrum of the F 1s peak of the FOC-TiO2 ; (c) high-resolution XPS spectra of the C 1s region of the OC-TiO2 and (d) FOC-TiO2 .

treating with TFAA due to the strong electron-withdrawing effect
of CF3 group [35,36].
The morphologies of the melamine sponges before and af-
ter coating with OC-TiO2 and FOC-TiO2 are examined by SEM as
shown in Fig. 4. The melamine sponge reveals a three-dimensional
structure with pore size in the range of 10 0–20 0 μm (Fig. 4a). The
surface of reticular skeleton is very smooth and the average diame-
ter is found to be ∼8 μm. After dip-coating with OC-TiO2 and FOC-
TiO2 , as expected, the modified sponges show the same porous
morphology and hierarchical structure. However the smooth retic-
ular skeletons become much rough with great surface coverage
after coating with OC-TiO2 (Fig. 4b) and FOC-TiO2 (Fig. 4c). The
uniform coating with high surface coverage is attributed from the
small particle size and good dispersability of the TiO2 powders.
The chemical composition of the raw, OC-TiO2 and FOC-TiO2 mod-
ified sponges were also analyzed by EDS which are also shown in
Fig. 4d, e and f, respectively. It can be clearly seen that the OC-
TiO2 modified sponge shows additional titanium peaks contributed
from the TiO2 compared with that of pristine sponge. Furthermore,
except for the titanium signal, the FOC-TiO2 sponge also reveals an-
other peak originated form fluorine, indicating the successful mod-
ification of the OC-TiO2 with TFAA.
The hydrophobicity of the modified sponges was characterized
by water contact angle measurement. As shown in Fig. 5a and b,
the OC-TiO2 and FOC-TiO2 modified sponge show great water re-
pellency with a water contact angle of 128.3° and 161.1°, respec-
tively. Compared with the contact angle measured from the mod-
ified glass substrates (see Table 1), both the OC-TiO2 and FOC-
TiO2 modified sponges deliver much larger contact angle (the wa-
ter contact angles of OC-TiO2 /glass and FOC-TiO2 /glass are 91.3 and
97.7°, respectively). The nanoscale protrusion of the hydrophobic
TiO2 in combination with microporous structure of the sponge cre-
ates a dually roughened surface, which is similar to that of lo-
tus leafs leading to an enhanced superhydrophobicity. There is no
apparent difference in the appearance between raw and modi-
fied sponges, except for their color. The color of the raw sponge
changed from white to pale yellow after coating with the TiO2 as
shown in Fig. 5c. Fig. 5d also depicts a photograph of the superhy-
drophobic FOC-TiO2 sponge can float on the water surface due to
its water repellency while the raw melamine sponge sinks to the
bottom. When immersing the modified sponge with an external
force, the mirror-like reflection can be found in the immersed part
of modified sponge as shown in Fig. 5e, due to the formation of an
entrapped air between the modified sponge and the surrounding
water; this phenomenon is due to the Cassie-Baxter nonwetting
behavior [37,38]. To demonstrate the separation performance, the
FOC-TiO2 modified sponge was put in a stable water/oil emulsions
as depicted in Fig. 5f. After shaking the vial containing sponge
and water/oil emulsions for 5 s, the emulsified oil/water mixtures
were well-separated and efficiently collected within the FOC-TiO2
sponge. The water/oil emulsion before and after separating with
FOC-TiO2 sponge was further monitored by an optical microscope
(Fig. 5g and h). It can be seen that all the oil microemulsions
are absorbed by the FOC-TiO2 sponge, indicating this technology
can be used to collect the expansive chemical from the emulsified
system.
The hierarchical macroporous FOC-TiO2 sponge with high
porosity and superhydrophobicity can be used as a sorbent for
the removal of organic solvents and oils from water. As exhib-
ited in Fig. 6a and b, the removal of toluene and chloroform (dyed
with [6,6]-phenyl-C61-butyric acid methyl ester) from surface and
bottom was also tested. Both the toluene and chloroform can be
rapidly removed within 5 s, while the modified sponge was in-
troduced to contact with the floated toluene and sank chloroform
(also see Movie S1 and Movie S2). In order to investigate the ab-
sorption capacity, the FOC-TiO2 sponge was used to absorb various
kinds of organic liquids and oils. As shown in Fig. 6c, it reveals
that the FOC-TiO2 sponge exhibits excellent absorption capacity in
the range 37.2–88.1 times its own weight depending on the den-
sity, viscosity, and surface tension of the absorbed solvents. The

Please cite this article as: E.-C. Cho et al., Interfacial engineering of melamine sponges using hydrophobic TiO2 nanoparticles for effective
oil/water separation, Journal of the Taiwan Institute of Chemical Engineers (2016), http://dx.doi.org/10.1016/j.jtice.2016.08.002
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Fig. 4. The typical SEM images of the raw and modified sponges with different magnification. (a) Raw melamine sponge; (b) OC-TiO2 modified sponge and (c) FOC-TiO2
modified sponge; the EDS analysis of (d) raw melamine sponge; (e) OC-TiO2 modified sponge and (f) FOC-TiO2 modified sponge. The addition peak assigned for fluorine
suggests the successful modification of the OC-TiO2 with TFAA.

Fig. 5. Superhydrophobic property of FOC-TiO2 modified sponge. (a) The water contact angle of OC-TiO2 modified sponge and (b) FOC-TiO2 modified sponge; (c) photograph
of a water droplet on the surface of raw melamine sponge and FOC-TiO2 sponge (the water has been dyed with methylene blue); (d) photograph of bare sponge and FOC-TiO2
sponge after being placed on water; (e) mirror-reflection can be observed when the FOC-TiO2 sponge was immersed into water, which is a convictive and direct evidence
for proving the hydrophobicity of FOC-TiO2 sponge; (f) photographs of the oil/water emulsion before and after separation; (g) the optical microscope images of the oil/water
emulsion before and (h) after separation.

Please cite this article as: E.-C. Cho et al., Interfacial engineering of melamine sponges using hydrophobic TiO2 nanoparticles for effective
oil/water separation, Journal of the Taiwan Institute of Chemical Engineers (2016), http://dx.doi.org/10.1016/j.jtice.2016.08.002
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Fig. 6. The oil absorption performance of FOC-TiO2 modified sponge. (a) The snapshots of the removal process of organic solvent (toluene) floated on the water surface by
using FOC-TiO2 sponge; (b) and the organic solvent (chloroform) sank in the bottom; (c) absorption capacity of the FOC-TiO2 modified sponge on various organic liquids and
oils. k here is defined as k = (Wsaturated absorption − Winitial )/Winitial .

Fig. 7. The selectivity of FOC-TiO2 modified sponge for water/oil separation. The water content of (a) the flesh organic liquids and (b) the recovered organic liquids. The
results indicate that the increase in water content for the six liquids is ranged between 16 and 210 μg/g.

removal process of toluene on the water surface using modified
sponge with large scale is also shown in Movie S3.
Except for the large absorption capacity, a high-quality oil/water
separation material should be able to separate oil/water mixtures
with high selectivity. To further study the selectivity of the modi-
fied sponge on the oil/water separation, we also analyze the water
content of the organic solvents and oils collected by the FOC-TiO2
sponge. The organic liquids were collected by the FOC-TiO2 sponge
on the water surface or in the bottom of water (depends on the
density of organic solvent) and then squeezed out for the mea-
surement of water content. Fig. 7 shows the water content of the
original and recovered organic liquids. All the fresh organic sol-
vents contain water contents ranged between 126 and 355 μg/g.
Remarkably, the all recovered solvents reveal a slight increase in
the water content (Fig. 7b). The increases in water content for the
six organic liquid including diesel, ether, hexane, toluene, ether ac-
etate and motor oil are 16, 55, 19, 210, 48 and 43 μg/g, respectively.
These results suggest that the FOC-TiO2 sponge not only show a
large absorbance capacity but also high selectivity for the oil/water
separation.
For the practical application, the mechanical property of the
sponge can directly reflect its recyclability. Fig. 8a and b shows
the stress–strain curves of the raw sponge and FOC-TiO2 sponge
at maximum strain of 50 %, respectively. As shown in Fig. 8a, the
raw sponge can be compressed to large strain (50%) at relatively
low stress (16.4 kPa), suggesting its nature of elasticity. After 500
cycles, the raw sponge just show a slight decrease in compress
stress (14.6 kPa) at the strain of 50%, indicating its great compres-
sive durability. For the FOC-TiO2 sponge, it delivers a comparable
stress (15.5 kPa) compared with that of raw sponge under a strain
of 50%. This suggests that the coating of FOC-TiO2 would not alter
the sponge’s flexibility and mechanical strength. Moreover, after
500 loading/unloading cycles, the compress stress of FOC-TiO2
sponge did not experience a violent change and maintain its 88%
of its initial strength value as shown in Fig. 8c. These features
are favorable for the application of the modified sponge for high

Please cite this article as: E.-C. Cho et al., Interfacial engineering of melamine sponges using hydrophobic TiO2 nanoparticles for effective
oil/water separation, Journal of the Taiwan Institute of Chemical Engineers (2016), http://dx.doi.org/10.1016/j.jtice.2016.08.002
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Fig. 8. The mechanical property of modified sponge as function of cycling and its recyclability. Compressive stress–strain curves of (a) raw sponge; (b) FOC-TiO2 modified
sponge at a strain value of 50% for 500 cycles; (c) the variation of stress for raw and FOC-TiO2 modified sponges during 500 cycles at strain value of 50% and (d) absorption
recyclability of the FOC-TiO2 modified sponge for chloroform, pump oil and hexane.
recyclability. Finally, the recyclability of the FOC-TiO2 sponge was
also tested to evaluate its oil/chemical cleanup application. Fig. 8d
shows the recyclable use of the FOC-TiO2 sponge for removal of
chloroform, pump oil and hexane. It can be seen that no obvious
change was found after 20 cycles, indicating the excellent recycling
performance.
4. Conclusion
Well-dispersed TiO2 nanoparticles with hydrophobic coating
have been obtained through a facile hydrothermal reaction, in
which oleic acid and TFAA are used as interfacially modified
agent. By dip coating, the well-dispersed and hydrophobic TiO2
nanoparticles can be successfully introduced into the macroporous
system of the melamine sponges. Combining the hydrophobic
characteristic of the chemisorbed groups on TiO2 and the sur-
face roughness caused by the dual effect of modified TiO2 and
hierarchical structure of the sponge, the modified sponges reveal
a superhydrophobic and superoleophilic property. The modified
sponges are ready to use for oil adsorption with high capacity,
selectivity and recyclability. It is believe that the modified-sponge
is a promising candidate for large-scale removal of oil or organic
solvent spills, recovery of chemicals and barrier separation.
Acknowledgments
We are grateful to the Ministry of Science and Technology
(MOST 104-2113-M-152-001-MY2, MOST 105-2320-B-038-014) and
CPC Corporation (105-3011) for financial support. We would also
like to thank the research fundings from Taipei Medical Univer-
sity (TMU102-AE1-B02, TMUTOP103004-2). The research endeav-
ors at Ming Chi University of Technology were supported in part
by the Ministry of Science and Technology (MOST 103-2221-E-131-
002-MY2), by the Chang Gung Memorial Hospital, Linkou, Taiwan
Please cite this article as: E.-C. Cho et al., Interfacial engineering of melamine sponges using hydrophobic TiO2 nanoparticles for effective
oil/water separation, Journal of the Taiwan Institute of Chemical Engineers (2016), http://dx.doi.org/10.1016/j.jtice.2016.08.002
[m5G;August 10, 2016;21:52]
7
(CMRPG3E2091), and by the Academia Sinica Research Project on
Thematic Project (AS-104-TP-A11).
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.jtice.2016.08.002.
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