LETTERS

PUBLISHED ONLINE: 3 APRIL 2017 | DOI: 10.1038/NNANO.2017.33

Joule-heated graphene-wrapped sponge enables

fast clean-up of viscous crude-oil spill
Jin Ge1†, Lu-An Shi1†, Yong-Chao Wang2†, Hao-Yu Zhao1, Hong-Bin Yao1, Yin-Bo Zhu2, Ye Zhang1,
Hong-Wu Zhu1, Heng-An Wu2 and Shu-Hong Yu1*

The clean-up of viscous crude-oil spills is a global challenge.
Hydrophobic and oleophilic oil sorbents have been demonstrated
as promising candidates for oil-spill remediation. However, the
sorption speeds of these oil sorbents for viscous crude oil are
rather limited. Herein we report a Joule-heated graphene-
wrapped sponge (GWS) to clean-up viscous crude oil at a high
sorption speed. The Joule heat of the GWS reduced in situ
the viscosity of the crude oil, which prominently increased
the oil-diffusion coefficient in the pores of the GWS and thus
speeded up the oil-sorption rate. The oil-sorption time was
reduced by 94.6% compared with that of non-heated GWS.
Besides, the oil-recovery speed was increased because of the vis-
cosity decrease of crude oil. This in situ Joule self-heated sorbent
design will promote the practical application of hydrophobic and
oleophilic oil sorbents in the clean-up of viscous crude-oil spills.
Frequent oil-spill accidents not only cause severe and long-term
damage to marine ecosystems, but also lead to a great loss of valuable
resources1,2. To eliminate the environmental pollution of oil spills
quickly, an efficient and environment-friendly oil-recovery approach
is in high demand. Here we summarize the criteria of an ideal
method for oil-spill remediation as: (1) clean-up the oil spills at a
high speed to alleviate the spreading and weathering of the oil,
(2) be able to recover the oil spill with a high oil/water separation effi-
ciency, (3) bring few adverse effects to the marine lives, (4) be compa-
tible with a large-area application and easily manipulated and (5) work
efficiently under harsh marine conditions. Unfortunately, traditional
oil-recovery technologies, such as dispersants3, solidifiers4, in situ
burning5 and skimmers6 cannot meet all the above requirements.
Recently, advanced sorbents with both hydrophobic and oleo-
philic properties have become potential candidates to realize an
ideal oil remediation that meets all the above criteria. For
example, carbon-based aerogels7–14, porous boron-nitride
nanosheets15, nanowire membranes16, modified commercial
sponges17,18 and organic silica aerogels19 have shown many
advantages, such as a high efficiency of oil/water separation,
environment-friendly characteristics, easy manipulation and a
self-adaption capability under harsh sea conditions. Especially, by
taking advantage of the self-controlled interfaces of the oil sorbent
under an external suction force, an in situ pumping device based
on a hydrophobic sponge can collect the oil from a water surface
in an efficient and continuous way20.
However, one crucial issue that hampers the practical application
of these advanced absorbent materials is that they show a low
capture performance for viscous crude oil. As is well known,
about 40% of the world’s oil reserve is heavy crude oil. Its viscosity
ranges from 103 to 105 mPa s at room temperature, which is much
higher than that of the model oils (below 500 mPa s) used in previous
reports7,11,14,18. Additionally, light crude-oil spills (1–100 mPa s) will
experience a remarkable increase in viscosity after the evaporation
of its light components2,21. The diffusion of such a viscous crude
oil into the inner pores of the aforementioned sorbents is very
slow, which results in a low oil-sorption speed and inefficient
usage of materials.
Here we report a Joule-heated graphene-wrapped sponge (GWS)
for the high-speed sorption of viscous crude oil from a water surface
(Fig. 1). The graphene coating uniformly wraps the skeletons of the
sponge substrate, which endows the GWS with hydrophobic and
conductive properties (Fig. 1, top left). When GWS contacts the
viscous crude oil on a water surface, the oil is absorbed selectively
into the pores because of the hydrophobic property of graphene,
but at a very limited oil-sorption speed. After applying a voltage
to the GWS, current flows through the graphene coating and
Joule heat is generated, which quickly heats up the GWS (Fig. 1,
middle). Then the hot GWS can heat up the surrounding crude
oil and thus the oil viscosity decreases, which then increases the
diffusion coefficient of the crude oil into the GWS. After cutting
off the applied voltage, the absorbed oil localized in the pores
of GWS is still hot and remains of low viscosity, which also
facilitates the subsequent oil-recovery and transportation processes
(Fig. 1, top right).
Fabrication of GWS by centrifugation-assisted dip coating
As shown in Fig. 2a, a porous substrate was firstly filled with gra-
phene oxide (GO) solution. Then the porous substrate was centri-
fuged to remove the excess GO solution away from the pores, to
leave only a residual of the GO nanosheets on the skeleton’s
surface. The centrifugation not only recycles the GO solution,
which reduces material consumption, but also makes a homo-
geneous GO coating on the skeleton of the porous substrate
without blocking the pores (Supplementary Fig. 1). The GWS was
obtained by reducing the GO coating with HI solution22.
Melamine sponge (MS) and mineral wool (MW) were selected as
typical porous substrates to fabricate GWS (hereafter, MS@RGO
and MW@RGO, respectively (RGO, reduced graphene oxide)).
Scanning electron microscopy (SEM) images of MS@RGO
(Supplementary Fig. 2) and MW@RGO (Supplementary Fig. 3)
show that the open porous systems of the substrates remained.
Some wrinkle stripes that appeared on the skeletons of MS and
MW indicate the existence of the RGO coating. In the Raman
spectra (Supplementary Figs 2 and 3), the D peak (1,356 cm−1)

1
Division of Nanomaterials and Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Suzhou
Nano Science and Technology, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Department of Chemistry, University of Science
and Technology of China, Hefei 230026, China. 2 CAS Key Laboratory of Mechanical Behavior and Design of Materials, Department of Modern Mechanics,
CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, Anhui 230027, China. †These authors contribute equally
to this work. *e-mail: shyu@ustc.edu.cn

434 NATURE NANOTECHNOLOGY | VOL 12 | MAY 2017 | www.nature.com/naturenanotechnology

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2017.33
App
ly vo
ltage
Graphene coating
Electrode
Sponge substrate
Viscous crude-oil spill
Improved oil-sorption speed
Figure 1 | Schematic illustration of Joule-heated GWS used to clean-up a viscous crude-oil spill. The red colour applied to the graphene coating represents
the temperature increase. The dark brown of the oil represents the original highly viscous crude oil, and the light brown of the oil represents the crude oil
with a decreased viscosity.
and G peak (1,594 cm−1) of GO and RGO appeared after the coating
processes, and the increased D/G intensity ratio demonstrated the
reduction of GO23. The GWS fabricated by the centrifugation-assisted
dip-coating method consumed very little GO. For example, the weight
content of graphene in MS@RGO was only 0.045 mg cm–3, which is
much less than that of ultralight graphene aerogels reported previously
(0.16 mg cm–3) (ref. 7). The fabrication of the GWS can be easily scaled
up by using industrial centrifuges (Supplementary Fig. 4). Figure 2b
shows a typical optical image of two pieces of the MS@RGO monolith.
The spherical water droplets on their surfaces (inset shows a water
contact angle of ∼131°) and the light-emitting diode (LED) lamp
between them indicate their good hydrophobic and electrical conduc-
tivity properties, respectively. When a voltage was applied across the
two sides of the MS@RGO monolith, the temperature of its surface
increased very quickly because of the Joule-heating effect of RGO
(Supplementary Movie 1).
Heat tolerance of the RGO coating
MW@RGO was selected as the model GWS because of the high
thermostability of the mineral wool (over 1,000 °C
(Supplementary Fig. 5)). The MW@RGO was gradually heated by
step-increased voltages, and the resistance and surface temperature
of the MW@RGO were recorded (Supplementary Fig. 6 illustrates
the measurement set-up). Figure 2c shows the curve of the
average surface temperatures (ASTs), maximum surface tempera-
tures (MSTs) and the resistance change of MW@RGO versus time
under different input voltages. The negative temperature coefficient
of the resistance of RGO24 means the resistance decrease of
MW@RGO at the initial stages of each voltage step resulted from
the increase of temperature. When the voltage was less than 50 V,
the MST was less than 350 °C (AST ≈ 285 °C) and the decrease of
R0 was caused by the reduction of residual oxygen-containing func-
tional groups on the RGO nanosheets25. At 55 V, the MST exceeded
400 °C, and R0 began to increase after the Joule-heating process,
which indicates oxidation of the RGO coating. The oxidation
might happen at the core of the MW@RGO because the inner temp-
erature of the MW@RGO was higher than that of its surface and
might have exceeded the breakdown temperature of graphene
(TBD ≈ 600 °C) (ref. 26) in air. Therefore, the MW@RGO monolith
might keep stable below the MST of 350 °C (AST ≈ 285 °C). In the
NATURE NANOTECHNOLOGY | VOL 12 | MAY 2017 | www.nature.com/naturenanotechnology
© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
LETTERS
Power supply
ed
Hot oil sorbent
bsorb
Oil a
Current flow through graphene
(to generate Joule heat)
Viscosity decrease Viscous crude-oil spill
Sea water
13.5 hour test of Joule heating under a constant power supply, the
AST of the MW@RGO monolith could be kept at around 285 °C
(Supplementary Fig. 7).
The effect of Joule heating on the oil-sorption process is reflected
clearly by the dynamic permeating behaviour of viscous crude-oil
droplets into the MW@RGO monolith. Figure 2d is a photograph
of a typical heavy crude oil used as the model viscous crude oil in
the following test. When an oil droplet (∼8 µl) was placed onto
the surface of MW@RGO (22 °C), it took eight minutes for the oil
droplet to penetrate entirely into the MW@RGO (Fig. 2e, upper
row). However, when the MW@RGO was heated to an AST of
90 °C by an electric current, the whole process completed in only
six seconds (Fig. 2e, lower row), which demonstrates an extensive
improvement in the oil-sorption speed under Joule heating of the
RGO coating (Supplementary Movie 2).
Influence of oil temperature on the oil-sorption speed
A quantitative evaluation of the oil sorption into MS@RGO was per-
formed based on the concept of the liquid sorption coefficient Ks.
The specific value of Ks can be obtained based on a wicking
method27–29 (Supplementary Fig. 8). The crude oil was heated to
different temperatures by a hot plate and then the wicking test
was performed. Figure 3a shows that the slopes of the curves at
the initial stage becomes steeper with an increase in the oil
temperature, whereas the curve at 91 °C matches well with that at
97 °C. Figure 3b (red squares) shows the Ks values derived from
the slopes of the curves at the initial stage, which reveals that
the oil-sorption speed increases sharply after exceeding an oil
temperature of 40 °C, and keeps constant when the oil temperature
exceeds 91 °C.
To shed light on the contribution of the oil-viscosity decrease to
the improvement of the oil-sorption speed, we evaluated all the par-
ameters that influence the liquid sorption coefficient Ks , which was
theoretically derived as in equation (1)30:
 










γ ε*√

cosθ
Ks = dl r (1)
μ λ 0 2
where dl , γ and μ are the density, surface tension and viscosity of
the oil, respectively, ε* is the effective sorption porosity of the
435
LETTERS NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2017.33

a GO RGO
Skeleton

Dip Take out, centrifuge Reduction

HI
Recycle GO solution

Sponge substrate GO solution GO-wrapped sponge RGO-wrapped sponge

b c 1,000 300
30 V 35 V 40 V 45 V 50 V 55 V
Water − +

Surface temperature (°C)

droplet 800 R0 Resistance of the MW@RGO monolith
200

Resistance (Ω)
600
LED 100
400 Average surface temperature
Maximum surface temperature
MS@RGO MS@RGO 200 0

0
0 1,000 2,000 3,000
Time (s)

d e
Viscous crude oil
2 min 4 min 6 min 8 min
Unheated (22 °C)

0s 1s 3s 6s
Heated (90 °C)

Figure 2 | Fabrication of the GWS and Joule-heating effect of the GWS. a, Schematic illustration of the fabrication processes of GWS. b, The photograph of
two MS@RGO monoliths demonstrates their good hydrophobic and electric conductivity properties. Inset shows the water contact angle of GWS, ∼131°.
c, The resistance and surface-temperature changes of the MW@RGO monolith (2.6 × 2.3 × 0.8 cm3) applied with multivoltage steps from 30 to 55 V. Before
the next voltage step, the former voltage was switched off and the MW@RGO monolith allowed to cool to room temperature. The resistance changes during
the cooling processes were not recorded. R0 is the original resistance of the MW@RGO monolith. d, Photograph of a typical viscous crude oil (provided by
the China University of Petroleum). e, Permeating behaviour of one oil droplet on the surface of MW@RGO monoliths with (lower row) or without (upper row)
a voltage applied.

sorbent, 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 sorbent. The second bracket
represents the parameters of the sorbent’s pore structure, which
does not change during the Joule-heating process. The changes of
dl, θ, γ and μ with an increase in oil temperature were measured
separately. Figure 3c shows that both dl and θ experienced a
small decrease during the heating process (only ∼0.05 kg m–3
variation for dl and ∼23° variation for θ). However, the value of
√










dl ( cos θ)/2 was almost constant (Fig.  3d).




Therefore, Ks is
mainly determined by the value of γ/μ. According to
the measured results of the surface tension (γ) and the viscosity (μ)
of the crudeoil



in the temperature range 10–97 °C (Fig. 3e), the
values of γ/μ at different temperatures were calculated
and plotted as a function of temperature(blue



circle in Fig. 3b).
The results show that the values of γ/μ increase with an
increase in the oil temperature and the trend of its variation with
oil temperature is consistent with that of Ks values obtained by
the wicking method. As the surface tension of oil (γ) decreases
with an increase of oil temperature (Fig. 3e), the increase of Ks is
mainly caused by the decrease in oil viscosity, which is the basis
of our Joule-heated sorbent design for the high-speed uptake of
viscous crude oil.
To evaluate quantitatively the impact of Joule heating on the oil-
sorption speed, the wicking method was combined with voltage-
triggered Joule heating to measure the Ks value for oil into GWS.
MS@RGO was chosen as the study object because of its low cost,
light weight, elasticity and mechanical robustness, which are impor-
tant for the practical applications of Joule-heated sorbents. Electric-
power densities of 0, 0.27 W cm–3 (20 V) and 0.58 W cm–3 (30 V)
were applied to MS@RGO, and the ASTs were 20, 98 and 148 °C,
respectively (Supplementary Fig. 9). Figure 3f shows that with an
increase of power density from 0 to 0.58 W cm–3, Ks improved
sixfold and the saturated oil-sorption time was reduced by 90%.
To show clearly the significance of Joule heating on the oil-sorption
speed of graphene-based sorbents, MW@RGO with an AST of
∼250 °C was used to absorb a crude-oil spill from a water surface
(Supplementary Movie 3 and Supplementary Fig. 10). With the
aid of Joule heating, the crude oil was quickly absorbed into
MW@RGO rather than adhering to its surface.
Optimization of heat-transfer efficiency
In a real scenario of oil clean-up by Joule-heated GWS (MS@RGO
(Supplementary Fig. 11)), the GWS will float on the oil surface at the
initial stage because of its light weight and the high viscosity of the
crude oil. Then, with the aid of Joule heat, the crude oil is gradually

436 NATURE NANOTECHNOLOGY | VOL 12 | MAY 2017 | www.nature.com/naturenanotechnology

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2017.33 LETTERS
a 10.0 b 10 0.6
Oil temperature (°C)
97 8 0.5
7.5
91

√γ/μ (m3/2 s−1/2)

Ks (kg m−2 s−1/2)
67 0.4
ms (kg m−2) 6
59
5.0 0.3
46
4
39
31 0.2
2.5 2
25
0.1

0.0 0

0 10 20 30 40 0 20 40 60 80 100
t1/2 (s1/2) Oil temperature (°C)

c 0.98 30 d 0.8

25

dl √(cos θ)/2 (kg m−3)

0.96 0.7
Oil density (kg m−3)

20

0.94 0.6

θ°
15

10
0.92 0.5
5

0.90 0 0.4
20 40 60 80 100 20 40 60 80 100
Oil temperature (°C) Oil temperature (°C)
e f 8
6.95 kg m−2 Power density (W cm−3)
10,000 ts = 130 s 0
24 0.27
6 K = 0.811 5.44 kg m−2
s 0.58
Viscosity (mPa s)

ts = 328 s
γ (mN m−1)

22 4.03 kg m−2
ms (kg m−2)

4
1,000 Ks = 0.313
ts = 1342 s
20
2
Ks = 0.135

100 18
0

0 20 40 60 80 100 0 10 20 30 40
Oil temperature (°C) t1/2 (s1/2)

Figure 3 | Effect of Joule heating on the oil-sorption kinetics. a,√
Weight of viscous crude oil at different temperatures absorbed into the GWS per unit
contact area (ms) versus the square root of the sorption time ( t ). The measurements were performed at room temperature (20 °C). b, Liquid sorption
√





coefficient (Ks) derived from a versus oil temperature, and the square root of the ratio of the oil surface tension to the oil viscosity ( γ/μ), derived from e
versus oil temperature.√
Ks could be derived from the slope of the linear relation between the mass of oil absorbed per unit area (ms) and the square root of
the absorption time ( t ). c, Plots of oil density (dl , purple squares) and θ (green circles) versus oil temperature. θ is the contact angle of the oil droplet
√












(∼1.6 ul) on a RGO film, which was approximated as the contact angle of the interface between the oil and pore wall. d, dl ( cos θ)/2, calculated according
to the values in c, versus oil temperature. e, The change of oil viscosity and surface tension as a function of oil temperature. f, The weight of viscous crude
oil absorbed into MS@RGO (2 × 2 × 1.5 cm−3) with a power density per unit contact area versus the square root of sorption time. ts is the saturated
oil-sorption time. The measurements were performed at room temperature (20 °C).

absorbed into the GWS. Meanwhile, the GWS gradually sinks into confining the heated region to the bottom part of GWS. Here, we
the oil until it reaches the oil–water interface. This clean-up pro- propose two designs to confine the heated region. As shown in
cedure is a complex dynamic process and its thermal transmission Fig. 4a, one is to coat only the bottom part of the GWS with a
cannot be measured exactly in the experiment. Therefore, we silver electrode (upper left, named as GWS-x, x denotes the thick-
performed simulations to investigate the heat transfer in the oil- ness of the silver electrode). The other is to coat only the bottom
sorption tests. As the core concept of our clean-up method is to part of the MS with RGO, with the GWS part coated with silver
reduce the viscosity of crude oil by Joule heating, the comparatively electrodes (lower left, named as GWS-MS-x, x denotes the thickness
ideal hypothesis is that as much as possible of the quantity of Joule of the silver electrode). The temperature distributions in GWS-18,
heat should be transferred to the oil. GWS-9, GWS-5 and GWS-MS-5 under the same electric-power
The simulation of heat transfer from GWS to the oil input were simulated (Supplementary Computational Methods 2).
(Supplementary Computational Methods 1 and Supplementary Fig. 12) Figure 4a shows that the average temperature in the bottom part
indicates that the heat-utilization efficiency can be improved by of the GWS-x (close to the oil–GWS interface) can be improved

NATURE NANOTECHNOLOGY | VOL 12 | MAY 2017 | www.nature.com/naturenanotechnology 437

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
LETTERS NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2017.33

°C °C
a 60 b 60
GWS-x GWS-18 GWS-9 GWS-18 GWS-9

18 mm GWS 50 50
x

GWS-MS-x GWS-5 GWS-MS-5 40 GWS-5 GWS-MS-5 40

MS
18 mm
x 30 30
GWS

5 cm

c d 500 e 0.5
Lifting arm
Electric power = 0.16 W cm−3 Maximum electric power

Electric power (W cm−3)

Force sensor

Oil-sorption time (s)

GWS-x GWS-x
400 0.4
Copper wire GWS-MS-x GWS-MS-x
Iron wire Laser-
displacement 300 0.3
GWS or Silver sensor
GWS-MS electrode
Viscous crude-oil Laser 200 0.2
Thermocouple
Sea water thermometers
100 0.1
Bottom platform 4 8 12 16 20 4 8 12 16 20
Electrode thickness (mm) Electrode thickness (mm)

f 200 g h 80
GWS-x-Pmax 500 GWS-x-Pmax 20 Water

Heat absorbtion ratio (%)

180 Air
Oil-sorption time (s)

GWS-MS-x-Pmax GWS-MS-x-Pmax 60 Oil

160 400 15
40
Q (J)

140
7.5 10
300
120 15 20
5
100 7.5 2.5 5
200 0
10 2.5
80
4 8 12 16 20 110 120 130 140 150 0 20 40 60 80 100
Electrode thickness (mm) Time (s) Time (s)

Figure 4 | Effects of heat distribution on the utilization efficiency of heat energy. a, Simulated temperature distribution on GWS-x and GWS-MS-x
(GWS here is MS@RGO) with different electrode structures. x denotes the height of the electrode. The sample thickness is 5 mm and the input electric power
is 0.094 W cm–3. The room temperature was 24 °C. b, Experimental results that correspond to the simulations in a. c, Schematic illustration of the set-up for
the measurement of the sinking speed of oil sorbents and temperature change of water below the oil/water interface. d, Oil-sorption time for GWS-x and
GWS-MS-x under the same input electric power density (0.16 W cm–3). x = 2.5, 5, 7.5, 10, 15 and 20 mm. e, Maximum electric power (Pmax) that could be
applied to GWS-x and GWS-MS-x. The maximum electric power was obtained by increasing the electric power on GWS-x and GWS-MS-x gradually, until they
emitted a scorched smell, which indicated the thermal degradation of the MS substrate. f, Oil-sorption time for GWS-x and GWS-MS-x under their maximum
electric power densities. g, Electric energy and oil-sorption time for GWS-x-Pmax and GWS-MS-x-Pmax. h, Simulated heat transfer of GWS-MS-10-Pmax during
the oil-sorption process. As the temperatures of the GWS or GWS-MS change during the oil-absorption test, we used the resistances of GWS or GWS-MS at
room temperature (R0) to calculate the power densities in d–g by U 2/R0. The real values are larger than the data we measured.

when the heat region is concentrated to the bottom part of the GWS best performance, the oil-sorption time cannot be improved further
by reducing x. Particularly, for the cases of GWS-x and GWS-MS-x by increasing the input power because of the limit to the stable temp-
with the same electrode size of 5 mm, the heated region in GWS-MS-5 erature (∼250 °C) of the MS substrate. Figure 4e shows that the
is focused more uniformly at the bottom, whereas that in GWS-5 is maximum electric power (Pmax) applied to GWS-x and GWS-MS-x
focused more in the vicinity of the electrodes. Moreover, the average increases with an increase of x, and Pmax of GWS-x is higher than
temperature of GWS-MS-5 is higher than that of GWS-5. The corre- that of the corresponding GWS-MS-x. As the total electric energy
sponding experimental results (Fig. 4b) match well with the simulated (Q) depends on the product of electric power (P) and oil-sorption
results in Fig. 4a, which indicates that these two designs can improve time (t), it is possible to reduce t by increasing the electrode
the utilization efficiency of Joule heating. thickness or using GWS-x rather than GWS-MS-x, without increas-
To optimize x for the highest energy-utilization efficiency, we ing Q dramatically. Figure 4f shows that the oil-sorption time of
designed a homemade set-up (Fig. 4c) to measure the sinking GWS-x-Pmax and GWS-MS-x-Pmax decreased with an increase
speed of GWS-x and GWS-MS-x under a very small hold force of x, and the oil-sorption time of GWS-x-Pmax is less than that
(<0.3 mN, downward direction), as well as the temperature change of GWS-MS-x-Pmax when x = 2.5 and 5 mm. When x increases
of the water below the oil/water interface. First, we studied the to a certain value, the oil-sorption times of GWS-x-Pmax and
relationship between the x and oil-sorption time under the same GWS-MS-x-Pmax begin to increase, and the oil-sorption time of
applied electric power (0.16 W cm–3). Figure 4d shows that the oil- GWS-x-Pmax becomes longer than that of GWS-MS-x-Pmax when
sorption times for both GWS-x and GWS-MS-x decrease with a x > 7.5 mm. The energy consumption and oil-sorption time
decrease of x, and the GWS-MS-x shows a faster oil adsorption of GWS-x-Pmax and GWS-MS-x-Pmax are plotted in Fig. 4g.
than the corresponding GWS-x. Although GWS-MS-2.5 shows the GWS-MS-2.5-Pmax (166 J) saved 65.6% of electric energy compared

438 NATURE NANOTECHNOLOGY | VOL 12 | MAY 2017 | www.nature.com/naturenanotechnology

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2017.33
a
0% 45%
25 °C
b
0% 45%
75 °C
c
Pump on
Voltage off
d Pump on
Voltage on
Figure 5 | Influence of Joule heat on the oil-recovery speed. a,b, Recovery of the viscous crude oil (25 and 75 °C, respectively) from GWS by compressing
GWS from 0 to 75% strain. c,d, Continuously collecting the viscous crude oil from the surface of sea water by in situ pumping through GWS under applied
voltages of 0 and 17 V, respectively.
with GWS-20-Pmax (482 J), which demonstrates the advantage
of a heating region at the bottom part of the GWS. Among all
the sorbents, GWS-MS-10-Pmax may be the best choice because
of the shortest oil-sorption time and relatively low energy
consumption. Compared with GWS-20, GWS-MS-10 also saved
50% of the GO consumption.
To determine the energy utilization efficiency of GWS-MS-10-Pmax
during the whole oil-sorption process, the dynamic process of thermal
diffusion was simulated according to the oil-sorption speed
(Supplementary Fig. 13, Supplementary Movie 4 and Supplementary
Computational Methods 3). Figure 4h shows that about 48.0, 37.8
and 4.8% of Joule heat transferred to the oil, air and water, respectively,
during the oil-absorbing process. Although the oil temperature near the
bottom surface of GWS-MS-10-Pmax only increased from 26.1 to 34 °C,
the viscosity of the crude oil decreased by 41.3% and the oil-sorption
time was reduced by 94.6% (Supplementary Fig. 14). The heat power
could be increased further if we use a sponge substrate with a
higher thermal stability than MS, and then the sorption time of
GWS-MS-10 could be reduced further. The size of GWS-MS-10
in the oil-absorbing experiment is very small, and considerable
Joule heat would transfer to air from the side surfaces. However,
for a larger GWS-MS-10, heat dissipation from the side surfaces
would be decreased, and thus the utilization efficiency of Joule
heat would increase (Supplementary Fig. 15). For the practical
application of large GWS sorbents in the future, GWS could be
embedded with dense electrodes and heated homogeneously
under a low applied voltage (Supplementary Figs 16 and 17, and
Supplementary Movie 5).
Performance of Joule-heated GWS for crude-oil recovery
Oil-recovery speed is significant for the reuse of the oil and also to
recycle the sorbent materials. Here mechanical compression
NATURE NANOTECHNOLOGY | VOL 12 | MAY 2017 | www.nature.com/naturenanotechnology
© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
LETTERS
60% 75% 75% 6s 6s
After
60% 75% 75% After 6 s
4 min 8 min
1.58 g
25 s 40 s
3.87 g
(Supplementary Fig. 18) and in situ pumping (Supplementary
Fig. 19) were applied to collect the oil and recycle the sorbents.
MS@RGO monoliths filled with the oil at 25 and 75 °C were com-
pressed up to a strain of 75% (Supplementary Movie 6). Figure 5a
shows that although the crude oil at 25 °C extruded out of the
surface of MS@RGO, the oil was too sticky to flow. By a compressive
strain of 75%, the oil began to flow slowly. However, for the oil at
75 °C, the oil began to flow quickly from the MS@RGO at a com-
pressive strain of 45% (Fig. 5b). The complete oil-recovery process
took only ten seconds, which saves 81.8% of oil-sorption time com-
pared with oil at 25 °C (Supplementary Fig. 20). In addition, the
percentage of oil recovered from the MS@RGO also improved by
22.8%. Furthermore, the increase of the oil temperature lowered
the pressure needed to compress the MS@RGO (Supplementary
Fig. 21). For the oil at 25 °C, 482 kPa is needed to compress the
MS@RGO to an 80% strain. However, the pressure decreased
dramatically to 234 kPa for the oil at 40 °C, and to 74 kPa for the
oil at 60 °C. Heating the oil in these experiments is to obtain a
precise oil temperature. In an actual oil-spill clean-up, the oil will
be heated by the Joule-heating effect. The elastic property of the
MS substrate and the flexibility of the RGO coating mean that
MS@RGO can be recycled repeatedly though compression-recovery
processes (Supplementary Fig. 22).
The in situ pumping of oil-spill sorbents has been demonstrated
as a promising approach to recover oil spills in an efficient and con-
tinuous way20. Nevertheless, this method is suited only to oil with a
low viscosity. By introducing Joule heating to decrease the oil vis-
cosity, an in situ pumping method (Supplementary Fig. 19) may
be able to collect viscous oil spills. Figure 5c shows that the oil
spill at room temperature was pumped out to the collecting vessel
very slowly. After four minutes of pumping, the oil was still in the
pipe. Finally, only ∼1.58 g of the oil spill was collected in eight
439
LETTERS NATURE NANOTECHNOLOGY
minutes, which reveals that the efficiency of the in situ pumping
method is too low for the collection of viscous crude-oil spills. In
contrast, when an electric power of 0.5 W cm–3 (17 V) was
applied to the MS@RGO to generate Joule heating, the in situ
pumping oil-recovery process became very fast (Supplementary
Movie 7). As shown in Fig. 5d, the crude oil can be pumped into
the collecting vessel in only 25 seconds. After 40 seconds of
pumping, 3.87 g of crude oil was collected. The calculated recovery
rate (2,320 kg h–1 per kg of MS@RGO) was 29 times higher than
that without applying an electric voltage to MS@RGO.
In conclusion, we demonstrate, for the first time, a Joule-heated
sorbent design to realize the clean-up of viscous crude-oil spills at a
high speed. This advance addresses the problem in oil-spill remedia-
tion that the traditional porous oil sorbents cannot absorb viscous
crude oil quickly. By concentrating the heated region of the sorbent
at the oil surface, the electric energy for the oil clean-up can be
decreased by 65.6% and the consumption of RGO can be reduced
by 50%. The heat energy transferred to oil can be saved for oil recov-
ery and, especially, oil transport by pipes. Although the fraction of
heat transferred to the air is still high, there is a large potential to
improve the energy efficiency further through air–GWS isolation.
With the development of a thermally stable polymer sponge, the
temperature of GWS could be improved further, which will lead to
a faster oil-adsorbing speed. This Joule self-heated sorbent design
will provide a new strategy for highly efficient remediation of
viscous crude oil-spills.
Methods
Methods and any associated references are available in the online
version of the paper.
Received 8 February 2016; accepted 2 February 2017;
published online 3 April 2017
References
1. Jernelov, A. How to defend against future oil spills. Nature 466, 182–183 (2010).
2. Peterson, C. H. et al. Long-term ecosystem response to the Exxon Valdez oil
spill. Science 302, 2082–2086 (2003).
3. Kujawinski, E. B. et al. Fate of dispersants associated with the Deepwater
Horizon oil spill. Environ. Sci. Technol. 45, 1298–1306 (2011).
4. Vidyasagar, A., Handore, K. & Sureshan, K. M. Soft optical devices from self-
healing gels formed by oil and sugar-based organogelators. Angew. Chem. Int.
Ed. 50, 8021–8024 (2011).
5. Buist, I., McCourt, J., Potter, S., Ross, S. & Trudel, K. In situ burning. Pure Appl.
Chem. 71, 43–65 (1999).
6. Broje, V. & Keller, A. A. Improved mechanical oil spill recovery using an
optimized geometry for the skimmer surface. Environ. Sci. Technol. 40,
7914–7918 (2006).
7. Sun, H., Xu, Z. & Gao, C. Multifunctional, ultra-flyweight, synergistically
assembled carbon aerogels. Adv. Mater. 25, 2554–2560 (2013).
8. Si, Y., Yu, J., Tang, X., Ge, J. & Ding, B. Ultralight nanofibre-assembled cellular
aerogels with superelasticity and multifunctionality. Nat. Commun. 5, 5802 (2014).
9. Barg, S. et al. Mesoscale assembly of chemically modified graphene into complex
cellular networks. Nat. Commun. 5, 4328 (2014).
10. Wu, C., Huang, X., Wu, X., Qian, R. & Jiang, P. Mechanically flexible and
multifunctional polymer-based graphene foams for elastic conductors and oil–
water separators. Adv. Mater. 25, 5658–5662 (2013).
11. Niu, Z., Chen, J., Hng, H. H., Ma, J. & Chen, X. A leavening strategy to prepare
reduced graphene oxide foams. Adv. Mater. 24, 4144–4150 (2012).
12. Wu, Z.-Y. et al. Carbon nanofiber aerogels for emergent cleanup of oil spillage
and chemical leakage under harsh conditions. Sci. Rep. 4, 4079 (2014).
13. Liang, H.-W. et al. Macroscopic-scale template synthesis of robust carbonaceous
nanofiber hydrogels and aerogels and their applications. Angew. Chem. Int. Ed.
51, 5101–5105 (2012).
440 NATURE NANOTECHNOLOGY | VOL 12 | MAY 2017 | www.nature.com/naturenanotechnology
© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
DOI: 10.1038/NNANO.2017.33
14. Bi, H. et al. Spongy graphene as a highly efficient and recyclable sorbent for oils
and organic solvents. Adv. Funct. Mater. 22, 4421–4425 (2012).
15. Lei, W. W., Portehault, D., Liu, D., Qin, S. & Chen, Y. Porous boron nitride
nanosheets for effective water cleaning. Nat. Commun. 4, 1777 (2013).
16. Yuan, J. et al. Superwetting nanowire membranes for selective absorption. Nat.
Nanotech. 3, 332–336 (2008).
17. Ruan, C., Ai, K., Li, X. & Lu, L. A superhydrophobic sponge with excellent
absorbency and flame retardancy. Angew. Chem. Int. Ed. 53, 5556–5560 (2014).
18. Nguyen, D. D., Tai, N.-H., Lee, S.-B. & Kuo, W.-S. Superhydrophobic and
superoleophilic properties of graphene-based sponges fabricated using a facile
dip coating method. Energy Environ. Sci. 5, 7908–7912 (2012).
19. Hayase, G., Kanamori, K., Fukuchi, M., Kaji, H. & Nakanishi, K. Facile synthesis
of marshmallow-like macroporous gels usable under harsh conditions for the
separation of oil and water. Angew. Chem. Int. Ed. 52, 1986–1989 (2013).
20. Ge, J. et al. Pumping through porous hydrophobic/oleophilic materials: an
alternative technology for oil spill remediation. Angew. Chem. Int. Ed. 53,
3612–3616 (2014).
21. Fingas, M. F. The evaporation of oil spills: development and implementation of
new prediction methodology. In Int. Oil Spill Conf. Proc. 281–287 (1999).
22. Pei, S., Zhao, J., Du, J., Ren, W. & Cheng, H.-M. Direct reduction of graphene
oxide films into highly conductive and flexible graphene films by hydrohalic
acids. Carbon 48, 4466–4474 (2010).
23. Stankovich, S. et al. Synthesis of graphene-based nanosheets via chemical
reduction of exfoliated graphite oxide. Carbon 45, 1558–1565 (2007).
24. Trung, T. Q. et al. High thermal responsiveness of a reduced graphene oxide
field-effect transistor. Adv. Mater. 24, 5254–5260 (2012).
25. Wang, Z.-L. et al. Facile, mild and fast thermal-decomposition reduction of
graphene oxide in air and its application in high-performance lithium batteries.
Chem. Commun. 48, 976–978 (2012).
26. Liao, A. D. et al. Thermally limited current carrying ability of graphene
nanoribbons. Phys. Rev. Lett. 106, 256801 (2011).
27. Aggarwal, R. K. Evaluation of relative wettability of carbon-fibers. Carbon 15,
291–293 (1977).
28. Nishi, Y., Dai, G. Z., Iwashita, N., Sawada, Y. & Inagaki, M. Evaluation of
sorption behavior of heavy oil into exfoliated graphite by wicking test. Mater. Sci.
Res. Int. 8, 243–248 (2002).
29. Nishi, Y., Iwashita, N., Sawada, Y. & Inagaki, M. Sorption kinetics of heavy oil
into porous carbons. Water Res. 36, 5029–5036 (2002).
30. Beltran, V., Escardino, A., Feliu, C. & Rodrigo, M. D. Liquid suction by porous
ceramic materials. Br. Ceram. Trans. 87, 64–69 (1988).
Acknowledgements
This work is supported by the Foundation for Innovative Research Groups of the National
Natural Science Foundation of China (Grant 21521001), the National Natural Science
Foundation of China (Grants 21431006, 21761132008 and 11525211), Key Research
Program of Frontier Sciences, CAS (Grant QYZDJ-SSW-SLH036), the Chinese Academy
of Sciences (Grants KFJ-EW-116, KJZD-EW-M01-1), the Strategic Priority Research
Program of the Chinese Academy of Sciences (XDB22040402), the Ministry of Science and
Technology of China (Grant 2014CB931800), the Users with Excellence and Scientific
Research Grant of Hefei Science Center of CAS (2015HSC-UE007) and the Fundamental
Research Funds for the Central Universities (WK6030000018). We thank H.-L. Jiang for
help in obtaining the crude oil provided by the China University of Petroleum (Huadong).
Author contributions
J.G. and S.-H.Y. conceived the idea and designed the experiments. J.G. planned the
experiments, performed the experiments, collected and analysed the data, and wrote the
paper. S.-H.Y. supervised the project, analysed the results and wrote the paper. L.-A.S.
designed and performed the experiments, and collected and analysed the data. H.-A.W.
supervised the simulations of heat transfer. Y.-C.W. and Y.-B.Z. performed the simulations
and wrote the paper, and contributed to the discussion of energy utilization and
optimization design. H.-Y.Z., Y.Z. and H.-W.Z. designed and performed the experiments.
H.-B.Y. analysed the results and wrote the paper. All authors discussed the results and
commented on the manuscript.
Additional information
Supplementary information is available in the online version of the paper. Reprints and
permissions information is available online at www.nature.com/reprints. Correspondence and
requests for materials should be addressed to S.H.Y.
Competing financial interests
The authors declare no competing financial interests.
NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2017.33
Methods
Materials. All the chemicals were obtained commercially and used without further
purification. The MS was purchased from Runde Trading. GO was fabricated
according to a modified Hummers method31. Crude oil was provided by the
China University of Petroleum. A self-priming pump (Mabuchi RS-360SH) was
obtained from Wisdom Paradise Diy Studio. Sea salt was bought from Asia Marine
Fantastic. Sea water was obtained by dissolving 37 g of sea salt into one litre of
deionized water (DIW).
Instruments and characterization. The surface structures of the samples were
investigated by SEM (Zeiss Supra 40, Carl Zeiss). The viscosity of the oil was
measured by a rotatory viscometer (NDJ-5S, Shanghai Ping Xuan Scientific
Instruments). The density of the oil was measured by a digital densitometer
(MDY-2, Shanghai Precision Instruments). Surface tension of the oil was measured
by a Langmuir–Blodgett trough (KN2002, KSV NIMA). Water contact angles were
measured by the CAST 2.0 contact-angle-analysis system (Solon Information
Technology). The surface temperatures of the samples were measured by a thermal
infrared camera (VarioCAM®hr head 680, InfraTec). Raman spectra were performed
on a LabRamHR with an excitation wavelength of 514.5 nm. Thermogravimetric
analysis was conducted on a DTG-60H in air at a temperature range from
20 to 1,200 °C. Heat conductivity and heat capacity were measured by a
Hot Dish 2500 (Hot Disk). The press–release cycle test was performed on a universal
mechanical testing machine (Instron 5565A). The weight of MS@GO during the
wicking test was measured by an Instron 5560A equipped with a 10 N load cell.
Preparation of GWS and MS-GWS. The hydrophobic and oleophilic MS@RGO
was produced by a dip coating and reduction process. The MS was immersed into a
GO solution (3 mg ml–1) until fully wetted. Then, the MS fully filled with GO
solution was pulled out and centrifuged at 3,000 revolutions per minute for 2 min to
remove unwanted GO solution. After this, the GO-coated MS (MS@GO) was dried
at 60 °C for 1 h. MS@RGO was obtained by immersing MS@GO in HI (≥45.0 wt%)
at 90 °C for 5 s. Then the MS@RGO was pulled out and immediately rinsed with
ethanol and DIW several times. Finally, the MS@RGO was dried in an oven at
200 °C for 2 h. The fabrication method for MW@RGO was the same as that for
MS@RGO, except the concentration of GO was 1.5 mg ml–1. For the fabrication of
GWS-MS, the GO solution was first placed in a vessel with a flat bottom, and the
depth of the GO solution could be tuned just by controlling the volume of it. Then
the MS was put into the GO solution and contacted with the bottom of the vessel.
The bottom surface should be kept parallel with the surface of the GO solution
during the dipping process. After a time, the MS was taken out and put onto a plate,
and turned upside down. Then the middle of the top surface of the MS was pressed
gently a few times to ensure the GO solution was absorbed into the middle of the
bottom part. The subsequent centrifugation and reduction processes were similar to
those for fabricating the GWS. The thickness of the GWS in GWS-MS depends on
the depth of the GO solution.
Measurement of θ. First, 3 mg ml–1 GO was sprayed onto a glass slide and dried in
an oven at 60 °C for 1 h. Then the GO film on the glass slide was reduced to an RGO
film by HI (≥45.0 wt%) at 90 °C. After this, the RGO film was connected to a power
NATURE NANOTECHNOLOGY | www.nature.com/naturenanotechnology
© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
LETTERS
supply by silver paste and copper wires. By using the Joule-heating effect of the RGO
film, the surface temperature of it could be tuned by the amount of voltage applied.
The surface temperature was measured by an infrared thermal camera. The oil
contact angle was measured by a CAST 2.0 contact-angle-analysis system (Solon
Information Technology). The volume of oil droplets was ∼1.6 µl. Before each
measurement, the oil droplets were left on the RGO film for 14 min (reduced to
4 min for the RGO film at 97 °C).
Measurement of the sinking speeds of GWS-x and GWS-MS-x. During the oil-
absorbing process, the weight of the oil absorbed by the sorbent cannot be measured
directly. Fortunately, the oil-sorption speed can be reflected by the sinking speed of
the sorbent, which can be obtained by recording the displacement of the sorbent.
However, because of the small size of the sorbents (2 × 2 × 2 cm−3) we used for the
oil-absorbing test, the posture of the sorbents tilts easily during the oil-absorbing
process, which makes it difficult to measure the displacement of the sorbent. This
posture-tilt mainly results from the inhomogeneous density and pore structure of
the sorbent. To settle this problem, we put forward a homemade system to measure
the sinking speed of the Joule-heated sponge (Fig. 4c). The sorbent (GWS or GWS-
MS) is fixed to the force sensor of a lifting arm (Instron 5565A) by four iron wires,
which avoids the sorbents tilting during the-oil-absorbing process. The movement of
the lifting arm can be controlled precisely (1 µm). As all the sorbents (GWS-x and
GWS-MS-x) have electrodes of different weights, the influence of the weights of the
electrodes is deducted. The force-sensor value is kept at a very small value
(<0.3 mN), during the oil-absorbing process. Therefore, all the sorbents sank into
the oil under the interaction force between the sorbents and the crude oil.
The displacement of the lifting arm was measured by a laser displacement sensor
(CD33, OPTEX). The temperatures of water at the oil/water interface under the
sorbent as well as that 4 and 8 mm below the oil/water interface were measured by a
thermoelectric thermometer during the oil-absorbing test.
Pumping recovery method. Sea water (30 ml) was added into a 100 ml beaker, and
then ∼20 ml of crude oil was added to the beaker to form a viscous crude-oil spill.
Two opposing side walls of MS@RGO (2 × 2 × 2.9 cm3) were coated with silver paste
(in a square loop) and were connected to a power supply by copper wires. The
MS@RGO was immersed into the water. Then one tip of a pipe was inserted into the
MS@RGO, and the other tip was connected to the inlet of the self-priming pump.
The pump’s outlet was connected to a collecting vessel by another pipe. An electric
power of 0.5 W cm–3 (17 V) was applied to the MS@RGO. After heating it for 1 min,
a voltage of 5.76 V was applied to the pump. Pumping through the unheated
MS@RGO was also performed at the same pump voltage. Before pumping, the
MS@RGO monoliths were filled with crude oil.
Data availability. The data that support the findings of this study are available
within the article and in the Supplementary Information.
References
31. Ge, J. et al. Facile dip coating processed graphene/MnO2 nanostructured
sponges as high performance supercapacitor electrodes. Nano Energy 2,
505–513 (2013).
Reproduced with permission of the copyright owner. Further reproduction prohibited without
permission.