Article

Cite This: Ind. Eng. Chem. Res. 2018, 57, 4955−4966 pubs.acs.org/IECR

Novel Fabrication of Solar Light-Heated Sponge through Polypyrrole

Modification Method and Their Applications for Fast Cleanup of
Viscous Oil Spills
Chenxi Yang,†,‡ Bo Bai,*,§,∥ Yunhua He,†,‡ Na Hu,§,∥ Honglun Wang,§,∥ and Yourui Suo§,∥
†
Key Laboratory of Subsurface Hydrology and Ecological Effects in Arid Region of the Ministry of Education, Chang’an University,
No. 126 Yanta Road, Xi’an 710054, Shaanxi, China
‡
College of Environmental Science and Engineering, Chang’an University, Xi’an 710054, P. R. China
§
Key Laboratory of Tibetan Medicine Research, Northwest Institute of Plateau Biology, Chinese Academy of Sciences, Xining
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810008, China
∥
Qinghai Provincial Key Laboratory of Tibetan Medicine Research, Xining 810001, P. R. China

ABSTRACT: Oil spills are becoming a global challenge since the

viscous oil is difficult to clean up by the conventional absorbents
because of their high viscosity. To overcome this dilemma, we
report the novel fabrication of a polypyrrole (PPy)-polyethylene
glycol (PEG)-polymerized octadecylsiloxane (PODS) coated
sponge using versatile chemical polymerization and dip-coating
methods, employing the photothermal property of PPy to heat the
viscous oil. The benefits from photothermal composite lie in that
they can reduce the viscosity of oil, increase the oil-diffusion
coefficient, and speed up the oil-absorption rate. The formation of
obtained products was confirmed by Fourier transform infrared
(FTIR) spectroscopy, scanning electron microscopy (SEM), and
the wettability. The experiments indicate that the oil-absorption
capacity was increased by 32.6%, and the time was reduced by 40.0% compared with that nonheated PPy−PEG-PODS-MS.
More importantly, we presented a method of in situ pumping for oil recovery. The amount of oil recovery was increased 47.0%,
and the oil recovery time was reduced by 70.0% compared with the method of squeezing.

1. INTRODUCTION
In recent years, water pollution caused by the oil spillage and oil
contamination from industries has become increasingly serious
with the acceleration of urbanization and industrialization
process.1,2 For solving these oil-leakage problems, various
methods including combustion,3 chemical degradation,4 and
absorbent materials have been attempted.5,6 In contrast, the
absorption is one of the most promising measures for the
removal of oil contaminations due to the possibility of
transforming oil pollutant into a solid or semisolid phase for
further removal.7 Owing to the economic and high-efficiency
merits for the removal and collection of oil contaminations,
some classical absorbent materials including inorganic mineral
materials8 and natural materials9 have been widely utilized for
the oil spill cleanup. The good oil-absorption ability of these
absorbents was assigned to the merits of high porosity and
surface hydrophobic and oleophilic properties.10 However, it
has been verified that these materials still have limitationa for
viscous oil. For instance, the reported absorption quantity of
the hydrophobic modification of kapok fiber for diesel, soybean
oil, and crude oil is only 71.7, 89.3, and 66.4 g/g, respectively.11
The reason for the lower absorption capacity of crude oil may
be attributed to the high viscosity of crude oil. More
specifically, the viscosity of crude oil ranges from 103 to 105
mPa·s at room temperature, which is much higher than the
model oils (below 500 mPa·s).12,13 Hereby, the diffusion of
such viscous oils into the absorbents matrix is very slow, which
results in low oil-absorption speed and inefficient usage of the
above-mentioned materials.14 Therefore, the new oil absorption
materials with adequate buoyancy, high absorption capacity,
good reusability, and high ability to decrease the viscosity of oil
are significant for the development of the advanced absorbents.
Recently, polypyrrole (PPy) nanoparticles have received
great attention on biomedical application due to their
outstanding stability, controllable size, and good photothermal
properties.15,16 Typically, PPy nanoparticles have been reported
to have a good adhesion to a variety of materials, such as
hydrophilic glass17 and various curvatures.18,19 Moreover, PPy
is robust under mild stirring in water and seawater (35 000 ppm
of NaCl solution).17 What’s more, the excellent photothermal
properties of PPy were assigned to the broad spectrum
Received: January 12, 2018
Revised: March 22, 2018
Accepted: March 26, 2018
Published: March 26, 2018

© 2018 American Chemical Society 4955 DOI: 10.1021/acs.iecr.8b00166

Ind. Eng. Chem. Res. 2018, 57, 4955−4966
Industrial & Engineering Chemistry Research
Scheme 1. Proposed Formation Mechanisms of PPy-PEG-MS and PPy-PEG-PODS-MSa
a
Dynamic network structure formed between melamine, PEG, PODS, and PPy through electrostatic interactions and hydrogen bonding.
absorption (from visible to near-infrared) and holds high
photothermal conversion efficiency. For example, the viscosity
of crude oil decreased by 41.3% and the oil-absorption time was
reduced by 94.6% when the oil temperature only increased
from 26.1 to 34 °C according to the research of Ge and co-
workers.14 As a consequence, the research has provided a
feasibility for the use of the photothermal properties of PPy to
heat the oil and hereby reduce the viscosity of the oil, enhance
the oil absorption capacity, and decrease the time of absorption.
The extended applications of sponge-substrates for oil-
absorption were ascribed to their oleophilicity, low density,
high porosity, and good elasticity of sponge substance. Based
on the above considerations, herein the melamine sponge
(MS),20−22 an inexpensive commercial sponge, was elaborately
selected as a substrate to develop a new solar thermal sponge
through attaching the PPy nanoparticles onto the MS surface.
The core of such innovation lies in that the high-efficiency
photothermal PPy nanoparticle were uniformly surrounded
onto the surface of MS for the first time. The remarkable
benefits from this photothermal composite material lies in that
they can reduce the viscosity of oil using photothermal PPy
agents, increase the oil-diffusion coefficient, and speed up the
oil-absorption rate during the potential applications as oil
absorbent. The formation of PODS and PPy nanoparticles23
was confirmed by FTIR, SEM, EDS, and the wetting behavior
of water and oil. The experiments of oil-absorbance perform-
ance demonstrate that the oil absorption capacity was increased
and the time was reduced compared with that of nonheated
PPy-PEG-PODS-MS due to the reducing viscosity of oil.
Overall, the experimental work has provided a promising
approach to ameliorate the traditional absorbents that cannot
fast cleanup the viscous oil and could apply it to deal with oil
spills at sea in the future. Based on excellent properties of PPy,
we can further design other advanced material through a PPy
modification route, which has great photothermal properties.
2. EXPERIMENTAL SECTION
2.1. Material. Melamine sponge (MS) was obtained from
the local supermarket (Shaanxi, China). Iron(III) chloride
hexahydrate (FeCl3·6H2O), ethanol, methylbenzene, castor oil,
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and polyethylene glycol 600 (PEG 600) were supplied by
Tianjin Chemical Reagent Factory (Tianjin, China). Pyrrole
(Py) was purchased from Macklin. Octadecyltrichlorosilane
(OTS) was furnished by Sinopharm Chemical Regent
(Shanghai, China). A self-priming pump was obtained from
Taobao.
2.2. Preparation of PPy-PEG-PODS-MS. The raw
melamine sponge was cleaned ultrasonically in ethanol and
distilled water. Then, 0.01 mol of Py and PEG 600 were
dispersed in 100 mL of deionized water and stirred for 30 min.
The 2 × 2 × 3 cm3 melamine sponge was added to the solution.
Subsequently, FeCl3 solution (1.6875 g in 20 mL of deionized
water) was added slowly to the suspension and the polymer-
ization temperature was controlled at 5 °C in an ice bath. After
reaction for 0.5, 1, 2, and 3 h, the products were collected by
filtering and then washed thoroughly with deionized water.
The modification of PODS coating on the PPy-PEG-MS was
performed by a self-assembly of OTS. First, the OTS-toluene
solution was prepared by magnetic stirring the mixture of the
50 mL of toluene and 1 mL of OTS at 15 °C. Then, the PPy-
PEG-MS was immersed into the OTS-toluene solution. The
modification was maintained at 15 °C for 10 min. The resulting
material was washed several times with deionized water and
dried in a drying oven at 60 °C.
2.3. Characterization. The functional groups, EDS photo-
electron spectroscopy, and the morphology of the products
were confirmed using a PerkinElmer FTIR System 2000 in the
600−4000 cm−1 range via KBr pellet and Hitachi S-4800
scanning electron microscope. Contact angles were obtained by
a Krüss CCA200 contact angle analyzer at different oil
temperature and the values were averages from measurements
on at least three different positions for each sample. UV−vis-
NIR spectra were obtained using a Tianjin WFZ-26A UV−vis
spectrophotometer.
2.4. Measurements of Oil Absorption Capacity. For
purpose of investigating the maximal oil absorption capacity of
the hydrophobic/oleophilic PPy-PEG-PODS-MS for viscous
oil, the experiments of oil absorption were carried out in the
pure oils, and the final maximal oil absorption capacity was
determined by an average value of 3 times experiments with
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xenon lamp and without xenon lamp. We used the castor oil
instead of high viscous crude oil. The oil absorbency of the
sample was determined by weighing the samples before and
after the absorption, and calculated by the following formula:
Q = (M t − M i)/M i (1)
Where Q is the oil absorption capacity of the absorbents
calculated as grams of oil per gram of sample, Mt is the weight
of the wet absorbents after draining (g), and Mi is the initial
weight of absorbents (g). Besides, we also used the in situ
pumping to measure the oil absorption capacity.
3. RESULTS AND DISCUSSION
3.1. Formation and Characterization of PPy-PEG-
PODS-MS. The PPy-PEG-PODS-MS absorbent was prepared
Figure 1. FT-IR spectrometry analysis of MS (a), PODS-MS (b), PPy-
PEG-PODS-MS (c), and PPy-PEG- MS (d).
through the following two steps: chemical oxidation polymer-
ization of Py and self-assemble of PODS onto the sponge
skeleton. The proposed mechanism for the reactions is
schematically represented in Scheme 1.
In step 1, PPy was polymerized from Py monomer through
the chemical oxidation polymerization reaction within the
aqueous phase following a protocol described in the literature,
using Fe3+ as the oxidant and PEG 600 as the stabilizer.24−26
Specifically, Py was oxidized by the Fe3+ with the loss of π
electron, giving rise to a Py radical cation, which is the key
intermediate deciding the subsequent polymerization. After-
ward, two such radical cations can dimerize to form a bond
linking the two Py ring with the expulsion of H+. Also, the two
Py ring can be oxidized again, subsequently combining with the
intermediate of the Py radical cation to form a tripolymer. In
such a similar way, the longer chain PPy molecules were able to
be generated through the continual polymerization proce-
dure.27−29 Meanwhile, the Fe3+ ions within the suspension were
simultaneous reduced to the Fe2+ ions. Such formation
procedure of PPy can be visually confirmed by a visible
alteration of the color of the suspensions from limpidity to
dark. Whereafter, the obtained PPy and PEG were further
cross-linked by hydrogen bonding, and thus the PPy-PEG
clusters with the complicated cross-linking network structure
were formed on account of electrostatic interactions between
PPy and PEG molecular. Afterward, the cross-linking PPy-PEG
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Figure 2. SEM micrographs of MS (a), PODS-MS (b), PPy-PEG- MS
(c), and PPy-PEG-PODS-MS (d).
could be captured on the surface of MS through hydrogen
bond interaction or electrostatic interaction. Relying on these
effects, a large number of PPy nanoparticles were firmly
attached onto the surface of the MS substrate. Such a procedure
was also coupled with a color change of MS from white to dark.
Step 2 is the process of hydrophobic modification. During this
process of hydrophobic modification by OTS treatment,30,31
the formation of hydrophobic coating have two steps,
consisting of hydrolysis and condensation. First, the hydroxyl
groups of OTS were generated in situ by precursor hydrolysis.
Subsequently, the hydroxyl groups produced from OTS
hydrolysis can react with the hydroxyl groups of PEG on MS.
At the same time, the hydrolysis OTS molecules self-assembled
and cross-linked by Si−O−Si condensation with each other
would take place synchronously. Ultimately, the longer-chain
hydrophobic coating of PODS was fixed on the melamine fiber
surface.
Predicting from their structure and composition, the as-
prepared PPy-PEG-PODS-MS should be very valuable and
notable for the development of advanced absorbent for oil
spillage. First, the MS substrate has outstanding absorption
ability for liquids due to the high porosity and three-
dimensional skeleton. What’s more, the pore walls of MS
substrates possess natural tensile strength, which endows the
products with n ample hollow shape. Such unique properties
inevitably provide the excellent advantages for the oil
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Figure 3. EDS Analysis of MS and PODS-MS (a) and PPy-PEG-MS
and PPy−PEG-PODS-MS (b).
absorption. Second, by chemical oxidation polymerization, the
obtained PPy was firmly adhered to the surface of MS through
the cross-link of PEG. Whereby, the remarkable photothermal
property from the PPy substance were decorated on the surface
of the as-prepared sponge. The as-prepared photothermal
sponge has the ability to harvest solar energy. For instance,
prominently decreased the viscosity of the oil, increased the oil-
diffusion coefficient in the pores of the as-prepared sponge, and
consequently speeded up the oil-absorption rate can be
achieved by heating the viscous oil through utilization of the
photothermal property. Third, according to the theory of
Nakajima,32 depending solely on the lowest surface energy
surface, the largest water contact angle that can be obtain is
only 115.2°. In order to improve the hydrophobicity, he
provided a new theory that is the hydrophobicity of a smooth
solid surface can be enhanced by roughening the surface.
Therefore, with the combination of the roughness structure of
the coating and the layer of low surface energy long-chain alkyls
of PODS, the sponge could not be wetted by water droplets
and exhibited the outstanding hydrophobicity. Moreover, the
low surface energy of PODS increased the affinity of the oil
with sponge and increased the lipophilicity of the composite
materials. From these points of view, the formed PPy-PEG-
PODS-MS composite materials, combined the synergistically
photothermal property of PPy and hydrophobicity of PODS in
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Figure 4. (a) Photograph of the original MS, PODS-MS, and PPy-
PEG-PODS-MS placed on the water. (b) The different contact angle
of oil and water on different materials.
MS, have opened a suitable route for fast cleanup of viscous oil
spill.
To validate the successful synthesis of the PPy-PEG-PODS-
MS, the FTIR spectra of the MS, PODS-MS, PPy-PEG-MS,
and PPy-PEG-PODS-MS were recorded, respectively. The
results are exhibited in Figure 1. In Figure 1a, The spectrum of
the MS displayed prominent peaks at 837, 1078, 1549, and
3425 cm−1, which were assigned to the triazine ring bending,
C−O stretching, CN stretching, and N−H (of the secondary
amine) stretching, respectively.33 Peaks at 1307 cm−1 were
indicative of C−H bending. Moreover, two small peaks at 2862
and 2895 cm−1 were attributed to C−H stretching. The above
peaks were characteristic absorption bands in MS. Furthermore,
compared with the FTIR spectrum of MS (Figure 1a), PPy-
PEG-MS (Figure 1d) and PPy-PEG-PODS-MS (Figure 1c) had
new absorption peaks after chemical polymerization.34,25 The
bands at approximately 1358, 1620, and 1449 cm−1 may be
attributed to the typical skeletal vibration and in-plane
deformation vibration of the Py rings, which indicates the
ring structure was not affected by polymerization. The band
observed at around 1037 cm−1 was assigned to CH in
plane vibration. The peak at 942 cm−1 corresponded to the 
CH out of plane vibration indicating the presence of PPy.
The presence of these peaks was characteristic for absorption
peaks in PPy. The peaks at 1256 and 879 cm−1 were
characteristic for PEG peaks, indicating the existence of PPy
and PEG in PPy-PEG-MS (Figure 1d) and PPy-PEG-PODS-
MS (Figure 1c). By dip-coating with OTS treatment for MS
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Figure 5. (a) UV−vis-NIR spectra of PPy nanoparticles synthesized at different time intervals. (b) The temperatures of MS, PODS-MS, PPy-PEG-
MS, and PPy-PEG-PODS-MS at different irradiation duration and absorption capacity of oil at different times.

Table 1. Photothermal Efficiency Data of PPy-PEG-PODS-MS at Different Time Periods

1 2 3 4 5 6 7 8 9 10
Qe (J) 18 47 61 79 95 108 120 123 132 144
Qs (J) 36 72 108 144 180 216 252 288 324 360
η (%) 50.0 65.3 56.5 54.9 52.8 50.0 47.6 42.7 40.7 40.0

and PPy-PEG-MS,35,36 PODS-MS (Figure 1b) and PPy-PEG-
PODS-MS (Figure 1c) had new absorption peaks. The as-
prepared sponge showed sharp adsorption of CH2 stretching
mode at 2977 and 2880 cm−1. For FTIR details between 900
and 1600 cm−1, new absorption bands appearing at 1108 cm−1
from the coating layer are assigned to Si−O−Si bond
asymmetric stretching mode confirming the formation of long
chain linear polysiloxane,37,38 implying the existence of PODS
within the structure of PODS-MS (Figure 1b) and PPy-PEG-
PODS-MS (Figure 1c). On the whole, it can be conclude that
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thin coating on the MS skeleton was composed of PPy and
PODS.
The surface characteristics of samples were further registered
in SEM images. Figure 2 displays the surface morphology of the
MS (a), PODS-MS (b), PPy-PEG-MS (c), and PPy-PEG-
PODS-MS (d), respectively.
Figure 2a showed an intrinsic three-dimensional intercon-
nected network and a smooth surface, which offered highly
accessible open pores. These plentiful native pores in MS could
provide a more active site for absorption of target oil.39 Figure
2b is the SEM image of intermediate PODS-MS samples. It is
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Figure 6. Effect of photothermal heating on the oil-absorption kinetics. (a) Plots of oil density (d1) and θ versus oil temperature. (b) d1 cos θ /2
calculated according to the values in panel a. (c) The change of oil viscosity and surface tension as a function of oil temperature. (d) Liquid
absorption coefficient (Ks) derived from versus oil temperature and the square root of the ratio of the oil surface tension to the oil viscosity ( γ /μ ).

Table 2. Kinetic Absorption Parameters of the Different Materials for Oil

pseudo-first-order pseudo-second-order
materials Qexp/(g/g) K1/(g/g·min) Qcal R2 K2/(g/g·min) Qcal R2
MS 22.00 0.5241 49.47 0.8657 0.003900 38.04 0.9846
PODS-MS 23.90 0.5954 60.83 0.8594 0.005074 37.65 0.9874
PPy−PEG-PODS-MS 29.15 0.5940 90.62 0.6930 0.0020962 55.87 0.9853

clearly observed that the surface of MS was covered by a PODS
membrane. Unlike the smooth surface of MS, PODS-MS
exhibited a rough surface in the image. Such morphology
change provides assertive evidence that the PODS were
successfully fixed onto the MS surface. The surface profiles of
the PPy-PEG-MS are demonstrated in Figure 2c, and obviously,
the loading of lots of PPy nanoparticles resulted in a rough
surface topographic features of PPy-PEG-MS. The sizes of PPy
nanoparticles were 1−2 μm. In Figure 2d, it was visible that
there were lots of wrinkles and nanoparticles on the surface of
the MS skeleton. Such a unique hybrid structure of the final
products have combined the advantages of both PPy nano-
particles and PODS membrane, which are beneficial to increase
the hydrophobicity and lipophilicity. Moreover, the porous
structure, inheriting from their parent MS, maintained high
absorbability features after modification process due to the fact
that all of them revealed the same highly porous three-
dimensional intercrossed network structure.
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The elemental composition of the sponge at each step of
modification was examined by EDS photoelectron spectrosco-
py, and the results are shown in Figure 3. In Figure 3a, MS has
four peaks and PODS-MS has six peaks. The six peaks of
PODS-MS were C, N, O, Pt, Cl, and Si elements. The peaks of
Cl and Si were due to the layer of coating that was generated by
the hydrolysis of chlorine groups of OTS to hydroxyl groups
and subsequent assembly on the surface of the melamine
sponge.7 Moreover, Pt was due to the introduction by spraying
method before analyzing the elements. In Figure 3b, the Cl of
PPy-PEG-MS and PPy-PEG-PODS-MS was the residue of
FeCl2 in the sponge after the chemical oxidation polymer-
ization. The increased of N was attribute to the reason that we
presented the PPy to the sponge.40 Elemental analysis proved
that we successfully synthesized the PPy-PEG-PODS-MS by
methods of modification.
3.2. Wettability of Materials. As is generally known,
surface wettability is significant to solve the oil spill at sea.41,42
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Figure 7. Absorption kinetics of MS, PODS-MS, and PPy-PEG-
PODS-MS in castor oil.
In consideration of practical application, the sponge floats on
the oil surface at the initial stage because of its lightweight and
the high viscosity of some sticky oils. Later, as the oil was
absorbed by the sponge, the weight of sponge increased and
gradually sank in the oil until it reached the oil−water interface.
Finally, the sponge began to sink into the sea inevitably, causing
secondary pollution. Hereby, studying the wettability of the
sponge is very valuable for the oil spill problem. In the present
study, the wettability of as-prepared materials was studied by
measuring the contact angle on the sample surface, and the
results are represented in Figure 4b. Meanwhile, in order to
study the effect of photothermal properties on the wettability,
the MS, PODS-MS, PPy-PEG-MS, and PPy-PEG-PODS-MS
were irradiated under a xenon lamp, and the results of
wettability were also shown in Figure 4b. As depicted in Figure
4b, water contact angles (WCAs) of MS, PPy-PEG-MS, PODS-
MS, and PPy-PEG-PODS-MS were 20°, 32°, 138°, and 123°,
respectively. Similarly, WCAs of MS, PPy-PEG-MS, PODS-MS,
and PPy-PEG-PODS-MS under the irradiation were 19°, 32°,
139°, and 120°, respectively. It is obvious that the WCAs of MS
and PPy-PEG-MS were lower than that of PODS-MS and PPy-
PEG-PODS-MS. Such phenomenon could be explained by the
hydrophilic groups of imine groups and hydroxyl groups of the
materials.43 That is, the higher WCAs of PODS-MS and PPy-
PEG-PODS-MS were tentatively assigned to the result of
modification by OTS.31 In contrast, the WCAs with xenon
lamp irradiation were almost unchanged because of the fact that
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the temperature hardly changes the surface tension and
viscosity of water. In order to further compare wettability of
samples, the high viscous castor oil was used to measure their
own oil contact angles (OCAs). The OCAs of MS, PPy-PEG-
MS, PODS-MS, and PPy-PEG-PODS-MS were 20°, 23°, 19°,
and 18°, respectively. When the MS, PPy-PEG-MS, PODS-MS,
and PPy-PEG-PODS-MS species were irradiated with the
xenon lamp, the OCAs were 19°, 14°, 20°, and 15°,
respectively. It is obvious that the OCAs of PPy-PEG-MS
and PPy-PEG-PODS-MS with xenon lamp irradiation were
lower than MS and PODS-MS. This trend indicate the change
of OCAs was attributed to the higher temperature of oil with
xenon lamp irradiation, resulting in the decrease of oil viscosity
and surface tension.
In order to visualize the wettability of the material, the
samples were put into water and the results were recorded in
Figure 4a. In Figure 4a, the MS sank in water quickly whereas
the PPy-PEG-PODS-MS and PODS-MS floated on the water
surface. If the PODS modified sponge is immersed into the
water on purpose by a compulsive force, it can be observed that
PPy-PEG-PODS-MS and PODS-MS floated on the top of the
water immediately after the mandatory force was released, and
hereafter no water has been squeezed out from the sample.
Such phenomenon indicated that PODS successfully deposited
on the surface of the sponge and the as-prepared sponge had
very good buoyancy and was water repellent. Based on the
hydrophobic and buoyancy properties of PPy-PEG-PODS-MS,
we can use them to deal with an oil spill at sea or organic
solvent contamination in sewage.
3.3. Oil Absorption through Photothermal Induction.
Prior to utilizing the as-prepared sponge, the photo harvest and
photothermal conversion capability should be evaluated. In the
course of our research, the UV−vis-NIR spectrum showed that
the PPy had pronounced absorption of NIR,44 and the results
were exhibited in Figure 5a. In Figure 5a, the UV−vis-NIR
absorbance increase with the increase of reaction time. Such
augments of UV−vis-NIR absorbance can be attributed to the
attachments of PPy nanoparticles, which lead to the rise of the
absorbance for NIR and visible light. More significantly, the
wide range of light from UV to visible light and near-infrared
have well matched the spectrum of sunlight,17 indicating hereby
that the attachments of PPy nanoparticles onto the sponge
substrate is beneficial to solar light harvesting.
To further evaluate the photothermal conversion perform-
ance of PPy-PEG-PODS-MS, the temperatures responses of
MS, PODS-MS, PPy-PEG-MS, and PPy-PEG-PODS-MS to
different irradiations duration through simulating sunlight were
recorded.17,44 The results are shown in Figure 5b.
In Figure 5b, the temperature of PPy-PEG-PODS-MS
gradually increased and reached an equilibrium temperature
at 45 °C after 20 min with the xenon lamp irradiation. In
contrast, the temperature of MS and PODS-MS slightly
increased and achieved an equilibrium temperature at 27 and
28 °C without PPy coating, respectively. Such alternation was
assigned to poor light harvesting efficiency. What’s more, the
maximum temperature of PPy-PEG-PODS-MS below PPy-
PEG-MS was due to the fact that the PODS coating partially
wraps up the PPy nanoparticles, reducing the PPy nanoparticles
that can harvest the sunlight. Base on the above phenomenon,
we can draw the conclusion that the increase in temperature
clearly demonstrated the efficient photothermal conversion
capability of the sponge due to the contribution of the PPy
nanoparticles on the surface of MS.
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Figure 8. (a) Oil absorption capacity and desorption capacity by squeezing. (b) The oil absorption and desorption of MS, PODS-MS, PPy-PEG-MS,
and PPy-PEG-PODS-MS with xenon irradiation. (c) The oil recovery by in situ pumping.
In a real scenario of cleanup of oil by photothermal property
of PPy-PEG-PODS-MS, the light energy coefficient of
utilization has significant value in practical application.
Accordingly, to gain more insight into the heat transmission
and energy utilization of cleanup viscous oil in experiments, the
light energy to heat the oil efficiency (η)14,45 of the
photothermal material can be estimated by eq 2:
η = Q e/Q s
(2)
2
where Qs is incidence light power (1000w/m ) and Qe is the
energy consumed by heating oil. Qe can be estimated by eq 3:
Qe = ∭ (T − T0)Cpρ dV (3)
where T0, T, V, ρ, and Cp are the initial temperature, the
temperature at any time, the volume of the oil, the mass
density, and the heat capacity, respectively. The results are
shown in Table 1. Obviously, the simulation of heat transfer
from light to the oil indicated that heat-utilization efficiency was
relatively high at the initial stage and they showed a downward
trend after 2 min. Most likely, this is due to the high
temperature gradient between the PPy-PEG-PODS-MS and the
oil interface at the beginning of the heating, thus more heat was
transferred to the oil. Subsequently, as the oil temperature
increased, the temperature gradient decreased and the heat was
transferred more to the air. From the point of view of η, the
conversion efficiency of the photothermal sponge for the light
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energy to heat viscous oil was higher. The higher photothermal
conversion efficiency of the as-prepared sponge has provided
perfect evidence that we can utilize the advanced material can
be used to deal with the viscous oil spill.
The oil absorption capacities of MS, PODS-MS, PPy-PEG-
MS, and PPy-PEG-PODS-MS under xenon lamp radiation are
shown in Figure 5b. In Figure 5b, the oil absorption capacity
increased with time prolonged. The maximal absorption
quantity of MS, PPy-PEG-MS, PODS-MS, and PPy-PEG-
PODS-MS were 22.0, 21.0, 23.0, and 29.2 g/g, respectively.
Obviously, the maximal absorption quantity of PODS-MS was
higher than MS and PPy-PEG-MS. In theory, the fabrication
rough construction can make the hydrophobic surface to be
more hydrophobic and turn the oleophilic surface to be more
oleophilic.9 Sticking to this principle, in the present study, the
modification by OTS has fabricated a rough structure on the
surface of sponge substrates and hereby decreased the surface
energy, which in turn affects its oil affinity. Furthermore,
although the absorption capacity and absorption rate of PPy-
PEG-PODS-MS and PODS-MS were similar at the initial stage,
the absorption of PPy-PEG-PODS-MS on the oil gradually
accelerated and tended to balance with the change in time. The
possible reason for the phenomenon was that, with the increase
of the irradiation time, the oil temperature gradually rose and
led to the viscosity of oil decreased, which consequently
accelerated the oil diffusion and the absorption rate of the as-
prepared material. In other words, that is the core concept of
DOI: 10.1021/acs.iecr.8b00166
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Industrial & Engineering Chemistry Research
Figure 9. (a) Reusability of PPy-PEG-PODS-MS: A1−A7 = oil
absorption cycle condition; D1−D7 = oil desorption cycle condition.
(b) The water contact angle (WCA) after multiple absorption cycles
and the maximum temperature of PPy-PEG-PODS-MS after 20 min
with the xenon lamp irradiation.
our cleanup method to reduce the viscosity of the viscous oil
and increase the oil absorption capacity.
3.4. Influence of Oil Temperature on the Oil-
Absorption Speed. According to Nishi46 and Ge,14 the rate
of the oil-absorption into PPy-PEG-PODS-MS at different
temperatures was performed based on the concept of the liquid
absorption coefficient Ks. The viscous oil was heated at different
temperatures, and the viscosity of oil corresponding changed.
Thereby, the theory is the fundamental principle that we design
the advanced material. To shed light on the contribution of the
oil viscosity decrease to the improvement of the oil absorption
speed, the liquid absorption coefficient Ks was theoretically
derived as follows:14,47
⎡ γ ⎤⎡⎢ ε* ⎤⎡ cos θ ⎤
Ks = ⎢d1 ⎥ r0 ⎥⎢ ⎥
⎣ μ ⎦⎢⎣ λ ⎥⎦⎣ 2 ⎦ (4)
where dl, γ, and μ are the density, surface tension, and viscosity
of the oil, respectively, ε* is the effective absorption porosity of
the absorbent, λ is the average tortuosity factor of the capillaries
(λ > 1), r0 is the average pore radius, and θ is the contact angle
of the interface between the oil and the pore wall of the
absorbent. The effective absorption porosity ε* is the volume of
the macropores directly involved in the absorption per unit
volume of the sample. ε* is calculated from the ordinate ms*
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broken away from the linear relation of the experimental plots
of ms* versus t by means of eq 5:46
ms*
ε* =
Ld1 (5)
where L is the thickness of the specimen in the absorption
direction when the viscous oil was wicked up to the top of the
specimen and ms* is the weight of viscous oil at different
temperatures absorbed into the PPy-PEG-PODS-MS per unit
contact area.
From eq 4, d1 γ /μ is the parameter based on the liquid.
ε*/λ r0 represents the parameters of the absorbent’s pore
structure, which does not change during the photothermal
process. The oil density and contact angles at different
temperatures were exhibited in Figure 6a. However, as can be
seen from Figure 6b, the value of d1 cos θ /2 was almost
constant. Therefore, Ks is mainly determined by the value
of γ /μ . According to the value of the viscosity surface tension
(Figure 6c), the results showed that the values of γ /μ
increased with an increase in the oil temperature, and the trend
of its variation with oil temperature is consistent with Ks
(Figure 6d), which is the basis of our photothermal absorbent
design for the high-speed uptake and recovery of viscous oil.
3.5. Absorption Kinetics. The research of absorption
kinetics is important because it provides significant information
on the mechanism of the absorption process. In general, the
most common models for the absorption are pseudo-first-order
and pseudo-second-order, which can be expressed in the linear
form as the following equations,48,49 respectively:
ln(Q e − Q t) = ln Q e − k1t (6)
t 1 t
= 2
+
Qt k 2Q e Qe (7)
where Qe (g/g) and Qt (g/g) refer to the amount of oil
absorbed at equilibrium and at any time, t (min), respectively.
k1 (g g−1 min−1) and k2 (g g−1 min−1) are the rate constant of
the pseudo-first-order and pseudo-second-order absorption,
respectively. The linear regression coefficient, R2, and
parameters of kinetics models were calculated and are listed
in Table 2. It can be seen that the results of the pseudo-second
order model with the R2 values (0.9846, 0.9874, and 0.9853)
were higher than pseudo-first-order model with the R2 values
(0.8657, 0.8594, and 0.6930), respectively. In addition, the
values from the pseudo-second-order kinetic model were quite
consistent with the experimental values, whereas the values
from the pseudo-first-order kinetic model were more than
experimentally observed data (Qexp). Clearly, the absorption
behaviors of oil on PPy-PEG-PODS-MS do not follow the
pseudo-first-order kinetics model but predominantly fit the
pseudo-second-order kinetics model (Figure 7). The phenom-
enon is mainly due to the fact that the pseudo-first-order model
is only applicable to simple absorption processes, such as single
physical absorption and chemical absorption. However, the
pseudo-second-order model contains all of the processes of
absorption and is controlled by different factors, indicating that
pseudo-second-order absorption kinetics is more suitable to
describe the as-prepared sponge absorption process.50
3.6. Performance of the As-Prepared Sponge for
Viscous Oil Recovery. In view of practical applications, oil is
DOI: 10.1021/acs.iecr.8b00166
Ind. Eng. Chem. Res. 2018, 57, 4955−4966
Industrial & Engineering Chemistry Research
often recovered from the absorbents by squeezing51,52 or
distilling.53,54 To study the ability of oil recovery of as-obtained
samples, we used the traditional method of squeezing to
recover the oil, and the results are exhibited in Figure 8a. As can
be seen, the oil recovery increased with time in the absence of
xenon lamp, and the amount of recovery was lower than the
absorption capacity. This phenomenon indicates the oil was too
sticky to flow at room temperature, indicating that the
stickiness limits the recovery of oil from the sponge and the
reusability. Nevertheless, the oil temperature can reach 28 °C
under the xenon lamp irradiation. The higher temperature led
the viscosity of the oil to decreased rapidly, speeding up the
recovery time and increasing the desorption capacity. Hence,
the oil absorption capacity was increased by 32.6% and the oil
absorption time was reduced by 40.0%.
In theory, the rise of oil temperature was caused not only by
harvesting light energy through PPy but also by directly
irradiating oil from the xenon lamp during the process of
viscous oil recovery. In order to make comprehensive
investigations, the MS, PODS-MS, PPy-PEG-MS, and PPy-
PEG-PODS-MS were also irradiated under the xenon lamp and
the results of the absorption and desorption are shown in
Figure 8b. In Figure 8b, it is obvious that oil absorption and
desorption of PPy-PEG-MS and PPy-PEG-PODS-MS are
better than those for MS and PODS-MS. The recovery of
PPy-PEG-MS and PPy-PEG-PODS-MS was slightly lower
compared to its primitive absorption capacity. Such excellent
oil recovery ability of samples can be assigned to their
remarkable photothermal performance of PPy nanoparticles.
The lower recovery of MS and PODS-MS is attributed to the
fact that reducing the viscosity of the heat only comes from the
direct irradiation of the xenon lamp. More concretely, the
photothermal conversions from the attached PPy nanoparticles
have prominently decreased the viscosity of the oil, increased
the oil-diffusion coefficient within the pores of the as-prepared
sponge, and consequently sped up the oil desorption.
In past years, the complicated and time-consuming process
of oil recovery from the absorbents was often an obstacle to
their practical application. To conquer this dilemma, we
recommended a method of in situ pumping for oil recovery
and built up a bench-scale oil collection apparatus (Figure
8c).55,56 Compared to the classical method of squeezing, the oil
recovery by in situ pumping has great merits for the recovery of
the oil since the tedious processes of desorption after
absorption were avoided and the whole cleanup time was
prominently saved. The precise results of oil recovery by in situ
pumping were shown in Figure 8c. In Figure 8c, 20.2 and 40.0 g
of oil were recovered by in situ pumping in the absence and
existence of xenon lamp irradiation with 10 min, respectively.
Lower recovery capacity in the absence of the xenon lamp
irradiation stems from the high viscosity of oil at room
temperature.57 Nevertheless, the oil can be pumped into the
collecting vessel quickly with xenon lamp irradiation. The
possible reason for the phenomenon is the oil temperature
increased 10 °C and reached 28 °C with the xenon lamp
irradiation, which reduced the viscosity of the oil and
accelerates the oil recovery. Hence, the in situ pumping by
PPy-PEG-PODS-MS with the xenon lamp irradiation is
beneficial to recover the viscous oil. Especially, the self-
controlled oils collection system not only recovers a large
amount of PPy-PEG-PODS-MS but also makes the collection
of oil spills easier and faster.58
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3.7. Reusability. In general, the PPy-PEG-PODS-MS could
be reused and the oil could be recovered, which are significant
features in the practical application. Figure 9a shows the
reusability of the as-prepared sponge for absorption and
desorption of viscous oil with xenon lamp irradiation. It is
obvious that the overall trend in oil absorbency of the samples
is downward with the increase of the absorption cycles, and
each reduction content is almost negligible compared to the
original absorption capacity, suggesting that PPy-PEG-PODS-
MS has good reusability.
The illegal operation may deform the coating on the PPy-
PEG-PODS-MS.59,60 In order to further study whether the
coating has been destroyed in the actual application process, we
subsequently studied the alteration of the wettability and
photothermal property of the PPy-PEG-PODS-MS after
multiple absorption cycles to confirm the reusability of PPy-
PEG-PODS-MS.
Figure 9b shows the change of WCAs and maximum
temperature of the PPy-PEG-PODS-MS after seven absorption
cycles. The WCAs of the PPy-PEG-PODS-MS were slightly
decreased, indicating that the PODS nanoparticles firmly
attached on the sponge and cannot easily fall off even under
external forces. The photothermal property of PPy-PEG-
PODS-MS is another significant function to judge the
reusability of the photothermal material. When the PPy-PEG-
PODS-MS was further irradiated by xenon lamp, the maximum
temperature of the PPy-PEG-PODS-MS decreased 3.0 °C after
seven cycles of absorption and desorption. The reduction was
very small compared to the photothermal heating. Therefore, it
could be inferred that during the oil absorption and desorption
process, the majority of PPy nanoparticles were firmly adhered
to the sponge. Based on the data of WCAs and maximum
temperature, we can demonstrate that the basic structure and
properties of the PPy-PEG-PODS-MS were not damaged
during the reuse procedure, which have provided perfect
evidence for the reusability of PPy-PEG-PODS-MS.
4. CONCLUSION
In summary, we have demonstrated an advanced hydrophobic
photothermal sponge, which involves harvesting and converting
solar light to heat on oil surface, conducting to the decrease of
the oil viscosity. The concept was embodied by a rational
integration of surface hydrophobicity and light-to-heat
conversion nanoparticles onto the raw melamine sponge,
which exhibited significant photothermal conversion perform-
ance and hydrophobicity and thus decreased the viscosity of the
oil and improved the absorption. The experimental results have
shown that the oil absorption capacity was increased by 32.6%
and the absorption time was reduced by 40.0%. Moreover, by in
situ pumping, the oil recovery capacity was increased 47.0%
while the oil recovery time was reduced by 70.0% compared
with the squeezing method. Owning to the advantages of high
oil absorption capacity, low density, light-to-heat conversion,
excellent hydrophobicity, and reusability, we believe that the as-
prepared composite material is a promising candidate for the
replacement of traditional oil absorbents and can be applied in
the large-scale removal of spilled viscous oil on the water
surface.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: baibochina@163.com. Tel: +86 29 82339052. Fax:
+86 29 82339961.
DOI: 10.1021/acs.iecr.8b00166
Ind. Eng. Chem. Res. 2018, 57, 4955−4966
Industrial & Engineering Chemistry Research
ORCID
Bo Bai: 0000-0002-3958-9874
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Yulin Municipal Science and
Technology Bureau. This work was financially supported by
China Postdoctoral Science Special Foundation, Scientific
Research Foundation for the Returned Overseas Chinese
Scholars and Fundamental Research Funds for the Central
Universities (No. 2013G2291015)
■
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