Separation and Purification Technology 251 (2020) 117308

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Separation and Purification Technology

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

Functionalized carbon fiber felts with selective superwettability and fire T

retardancy: Designed for efficient oil/water separation
Ning Cao, Jingyu Guo, Kunpeng Cai, Qingzhong Xue, Lei Zhu, Qingguo Shao, Xinxiu Gu,
⁎
Xiaobei Zang
Key Laboratory of Unconventional Oil & Gas Development, Ministry of Education, School of Materials Science and Engineering, China University of Petroleum (East China),
Qingdao 266580, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Advanced materials with special wettability have attracted wide attention for their potential application in
Carbon fiber felt environmental remediation, catalysis or superfluid now. This contribution reports a straightforward and low-cost
Diazonium chemistry high-performance methodology for the preparation of carbon fiber felt with selective superwettability and fire
Oil/water separation resistance. The functionalized carbon fiber felt (UV-CFF) is prepared by a simple UV-O3 treatment process for the
Selective superwettability
enhancement of its superamphiphilicity in air and superoleophobicity underwater, the underwater contact an-
Flame retardancy
gles of the organics is over 155°. Subsequently, surface functionalization of UV-CFF with 4-tri-
fluoromethyldiazobenzene hydrochloride is carried out. Its surface could be effectively modified with aryl and
carbon–fluorine groups through diazonium chemistry to obtain a superhydrophobic carbon fiber felt (f-CFF)
with water contact angle of 152.5 ± 0.8°. Both of the UV-CFF and f-CFF samples exhibits effective oil/water
separation behavior. Benefiting from the selective superwettability, the two samples provide the potential to
selectively eliminate underwater oily phases and emulsions under different hydraulic pressures. For UV-CFF, its
rejection of oil reaches 100%, and the rejection of water for f-CFF reaches 98.21 ± 0.7%. The adsorption
capacities of different types of organic solvents for f-CFF is 4–14 g g−1, and its demulsification capacity can
reach to 99.9%. Due to its corrosion resistance, facile fabrication technique, cycle stability and flame retardancy,
the carbon felts hold great promise for potential applications in environmental remediation of water.

1. Introduction divided into two types according to their differences of wettabilities:

As a by-product of the expanding industrial and transportation de-
velopment, oily water results in heavy pollution in rivers, oceans and
other water body, which eventually damages the ecosystem and
threatens the human health [1–4]. Therefore, it becomes an urgent task
for human beings to have a rapid and efficient control of oily waste-
water emissions and oil spills [5,6]. Meanwhile, most of the spilled oil
and organic pollutant are highly inflammable and their leakage is po-
tentially accompanied by fire and explosion. Unfortunately, the tradi-
tional methods, such as mechanical collection, conglomeration/en-
trapment and in-situ incineration, are difficult to implement and
normally less efficient [7,8].
In recent years, the novel superwettable porous materials with se-
lective oil/water separation have attracted increasing attention due to
their low cost, high adsorption efficacy, environmental and chemical
stability [9], such as superhydrophobic aerogels [10,11], modified
sponges [12,13], metal grids [14,15].These materials are mainly
superhydrophobic and superoleophilic materials, superhydrophilic and
underwater superoleophobic ones. Both of them have been used in the
field of oil/water separation for either immiscible oil/water mixture or
stable emulsion. For the superhydrophobic materials, their surface en-
ergy is normally lower than that of water but higher than that of or-
ganic solvents. Meanwhile, they own ideal surface hierarchical struc-
ture. Thus, the special wettability enables these materials to repel water
and be effectively wetted by most of organic solvents. Benefiting from
the intrinsic liquid storage space and liquid transportation channels, the
porous superhydrophobic materials can easily achieve oil/water se-
paration. For the preparation of these functionalized porous materials,
many methods are available, including dip-dry process, solvent
thermal, chemical vapor deposition and sol–gel approach with various
substrates such as graphene aerogel, polyurethane sponge, stainless
steel mesh and cotton felts [13–16]. However, the application scenario
of this porous materials is only limited to oily phase direct contact such
as oil contamination scavenge on the water, gravity-driven separation

⁎
Corresponding author.
E-mail address: xiaobeizang@upc.edu.cn (X. Zang).

https://doi.org/10.1016/j.seppur.2020.117308
Received 7 May 2020; Received in revised form 18 June 2020; Accepted 23 June 2020
Available online 29 June 2020
1383-5866/ © 2020 Elsevier B.V. All rights reserved.
N. Cao, et al.
of immiscible high-density organic chemical/ water mixture, water-in-
oil emulsion and crude oil dehydration [17]. In the scenario of aqueous
phase direct contact, the functionalized porous materials, featuring
underwater anti-oil-wetting ability, can play a decisive role in efficient
oil/water separation. Therefore, the superhydrophilic and underwater
superoleophobic porous materials are widely researched, and the in-
spiration comes from the special surface structure of both mussel shell
and fish scales [18–20]. Wang et al, prepared an underwater super-
oleophobic mesh with natural attapulgite nanorods coating via an
ecofriendly bioadhesion method. The decorated mesh prewetted with
water was able to filtrate a series of light oil/water mixtures with the
separation efficiency over 97.5%. And the mesh exhibited anti-corro-
sion behavior and good recyclability [21]. In this case, the oil re-
pellency behavior is mainly controlled by the hierarchal structure and
chemical status of the surface which can regularly trap water droplets
in micro-nano regions, and this can be explained by the classic Wenzel-
Cassie equations,
cosθW = rcosθOW ,
cosθCB = rf fso cosθOW + fso − 1,
where, θW is the contact angle in Wenzel state. θCB means the apparent
oil contact angle in Cassie state. rf represents the ratio of the real
contact line to the projected contact line of the portion of solid that is in
contact with the oil. fSO represents the area fraction of the solid surface
in contact with oil [22,23].
Recently, several kinds of porous carbon-based materials and their
composites are exhibiting potential as alternative materials for efficient
oil/water separation due to their low cost, easy access, rich surface
chemistry and environmental stability. Yuan et al. prepared a com-
pressible, superhydrophobic and multifunctional hierarchical biomass
carbon@SiO2@MnO2 aerogel with large absorption capacity
(60–120 g g−1) and great recyclability [24]. Yue et al. fabricated a
biomass-derived banana peel/waste paper hybrid aerogel (BPWP) with
hierarchical porous structure. BPWP possessed high oil sorption capa-
city of 35–115 times and could effectively separate various water-in-oil
emulsion with separation efficiency above 99.6% [25]. Jing et al. fab-
ricated porous superhydrophobic biomass carbon (BC) aerogel with
high selectivity and excellent absorption capacities (77.67–143.63 g g-
1). At the same time, BC aerogels have excellent oil recoverability and
reusability properties [26]. Ge et al. prepared MOF-derived-Co2+
modified carbon fiber foams with outstanding oil/water separation
ability, including high adsorption efficiency (up to 200 times its own
weight), low density, remarkable recyclability and fire retardancy [27].
Yi et al. employed the carbon nanotube (CNTs) to enhance the super-
hydrophilic and under-water superoleophobic behavior of polyvinyl
alcohol (PVA) membranes and develop a novel CNTS-PVA composites
for filtration of n-hexadecane/water emulsion. Due to the excellent
electrical conductivity of CNTs, the composites also exhibited anti-oil-
fouling performance in a low voltage alternating current electric field
[28]. Our previous papers showed that the nanodiamond particles re-
inforced polyurethane (PU) sponge, reduced graphene oxide (rGO) re-
inforced PU sponge and rGO/Chitosan aerogel have adjustable super-
wettability and potential application for oil/ water separation and
crude oil dehydration [10,13,17].
Moreover, the diazonium chemistry functionalization is an essential
method for the construction of the superhydrophobic surface on carbon
substrates [29,30]. In the past few years, diazonium salts have been
proven to be a very important chemical in surface modification, novel
catalyst and sensor material synthesis [30–32]. In the diazonium re-
action, covalent bonds are attainable between functional groups and
the carbon fiber surface. Compared with the physical bonding mode,
the covalent bonding is much more reliable [32]. Although derivati-
zation of carbon via diazonium chemistry has been widely studied,
there are few researches on the diazonium modified porous carbon
materials with superwettability targeted to oil/water separation.
Separation and Purification Technology 251 (2020) 117308
Meanwhile, it is easy to decompose the as-prepared diazonium salts by
using the classic diazonium chemistry for material surface modification.
These modification procedures seem to be complex and low-efficient
[33]. In this sense, it is meaningful to develop an in-situ diazonium
chemistry for surface modification. Indeed, this strategy is user-
friendly, efficient and promising for mass production.
Herein, porous carbon fiber felts, consisting of random poly-
acrylonitrile (PAN) based carbon fibers, are selected as the substrates.
By means of UV-O3 treatment with UV-ozone clean system, abundant
hydrophilic groups are introduced onto the surface of the initial hy-
drophobic felts and they are changed into superhydrophilic and un-
derwater superoleophobic materials (UV-CFF). Meanwhile, the 4-tri-
fluoromethyl azobenzene hydrochloride solution is synthesized and the
in-situ diazonium chemistry modification of UV-CFF is carried out
through a direct immersion process at below 5 °C. The as-prepared
carbon fiber felt (f-CFF) exhibits superhydrophobic and superoleophilic.
Due to having different superwettabiliy, UV-CFF and f-CFF show ex-
cellent separation performance for various immiscible oil/water -
(1)
mixtures and emulsions with high speed, efficiency and hydraulic
pressure resistance. At the same time, both of them own good corrosion
(2)
resistance and thermal stability. The fire retardancy of the felts will
expand their application in emergency disposal of oil spill accidents and
industrial oily wastewater treatment. Additionally, carbon fiber felt is
widely used as a water proof medium in the field of civil engineering
field for its reduced price [34], the UV-ozone clean process and dia-
zonium salt reaction are facile. Based on the above factors, the total
availability cost of UV-CFF and f-CFF is low, and they are promising to
be commercialized.
2. Experimental parts
2.1. Materials
CFF was purchased from Yantai Luhang Carbon Material
Technology Co., Ltd. Sodium nitrite (analytical grade), hydrochloric
acid (analytical grade), Sudan III and Methylene blue were supplied by
Sinopharm Group Chemical Reagent Co., Ltd. Ammonium hydroxide
(analytical grade) and sodium hydroxide (analytical grade) were
bought from Xilong Chemical Co., Ltd. Sodium chloride (≥99.5%) and
Ethyl alcohol absolute (Analytic pure) were purchased from Tianjin
Bodi Chemical Co., Ltd. Trichloromethane (analytical grade) and
Toluene (analytical grade) were bought from Tianjin Fuyu Fine
Chemical Co., Ltd. Hexane (analytical grade) and acetone (analytical
grade) were purchased from Shanghai Jinjinle Industrial Co., Ltd.
Gasoline (90 #) and Diesel (0 #) were collected from China Petroleum
and Chemical Corporation.
2.2. Preparations of UV-CFF and f-CFF
After being ultrasonically cleaned with acetone and deionized water
and dried in the oven at 50 °C, CFF was treated by UV-O3 for 15, 30 and
45 min to obtain a series of UV-CFF including UV-CFF-15, UV-CFF-30
and UV-CFF-45 respectively. Then UV-CFF was divided into several
cubes and put into the as-prepared diazonium salt solution at the
temperature below 5 °C for 6 h. At last, f-CFF was obtained as shown in
Fig. 1a. Briefly, diazonium salts were prepared as follows: 6.4 g 4-tri-
fluoromethylaniline, 13.24 mL concentrated hydrochloric acid and
13.33 mL deionized water were mixed in a three-necked flask. 4-tri-
fluoromethylaniline agent dissolved completely when the temperature
raised to 60 °C. After cooling to below 5 °C in an ice-water bath, sodium
nitrite solution was added drop-wise until the potassium iodide-starch
test paper turned blue.
2.3. Characterizations
The microscopic analysis of CFF was observed using a field emission
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N. Cao, et al. Separation and Purification Technology 251 (2020) 117308

CF3 CF CF3 CF3

3
UV-O3

HCl
5ȭ
NaNO2

NH2 CF3 CF3 N2Cl

CF3 CF3
C-C/C-H

C 1s
F 1s
1332

O 1s
1165
284.6
f-CFF
Transmittance /%

1740

f-CFF

Intensity /a.u.
Intensity /a.u.
1252

UV-CFF C=O
UV-CFF 288.5 C-O/C-N
285.8
CFF
1070
1620

CFF

4000 3600 3200 2800 2400 2000 1600 1200 800 700 600 500 400 300 200 100 0 296 294 292 290 288 286 284 282 280
Wavenumbers/cm-1 Binding energy/eV Binding energy/eV
D-band G-band
C-C/C-H
284.6 C-C/C-H
284.6
Intensity /a.u.

Intensity /a.u.

Intensity /a.u.
f-CFF

CF3 C-O/C-N
C=O C-O/C-N C=O 285.4
285.5 292.4 287.8 UV-CFF
288.6

1355

1594
CFF

296 294 292 290 288 286 284 282 280 296 294 292 290 288 286 284 282 280 600 800 1000 1200 1400 1600 1800
Binding energy/eV Binding energy/eV Raman shift/cm-1

Fig. 1. The preparation and characterizations of CFF, UV-CFF and f-CFF. (a) Illustration of fabrication process of f-CFF; (b) FTIR spectra of CFF, UV-CFF and f-CFF; (c)
XPS spectra and high resolution C 1s peaks of CFF (d), UV-CFF (e) and f-CFF (f); (g) Raman spectra of CFF, UV-CFF, f-CFF.

scanning electron microscope (JSM-7800LV, JEOL, Japan). A Fourier
transform infrared spectrometer (FTIR, Nicolet 8700, USA) was used to
confirm the functional groups of UV-CFF and f-CFF. The elemental
composition analysis of UV-CFF and f-CFF was carried out using X-ray
photoelectron spectroscopy (ESCALAB 250Xi, USA) with AL Kα radia-
tion (hv = 1486.6 eV). The Raman spectra were collected by a Raman
spectrometer (Renishaw, Britain) with the laser excitation of 532 nm.
Thermogravimetric analysis (TGA) was used to check the stability of
UV-CFF and f-CFF, performed in a N2 atmosphere under the tempera-
ture ranging from 30 to 850 °C on a thermal analyzer (STA-449, China).
The three-dimensional hole diameter of UV-CFF and f-CFF was mea-
sured by mercury pressure porosimeter (9500 IV pore, USA) with the
external pressure was 0-30Mpa. The contact angles of UV-CFF and f-CFF
were measured with 2 droplets of different liquids using a contact angle
apparatus (OCA100, Germany) at room temperature. Particle size dis-
tribution of after demulsification of oil in water emulsion using nano
particle size analyzer (SZ-100, China). The concentration of emulsion
measurement by UV–vis spectrophotometer (UV-1800, 190 ~ 1100 nm,
China). The UV-O3 treatment of CFF with UV-ozone clean system (PSD-
UV4T, USA), the UV light wavelength is 185 nm.
3. Results and discussions
3.1. Chemical composition and surface morphology analysis
The f-CFF was prepared through UV-O3 treatment and diazonium
salt solution reaction, as illustrated in Fig. 1a. After the combined
modifications, the chemical states on the CFF surface changed, as
shown in Fig. 1b. In FTIR spectra, the characteristic absorption peaks of
CFF appeared at 1070 cm−1 and 1620 cm−1, which are attributed to
the stretching vibration of the C-O functional group in the epoxy group
and the C = C skeleton of the carbon fiber respectively. After radiation
by UV-O3, a new characteristic absorption peak appeared at
1740 cm−1, which is attributed to C = O in the carboxyl group or
carbonyl group [35]. By comparison, the intensity of the C-O absorption
peak at 1070 cm−1 in UV-CFF is significantly greater than that in CFF,
indicating that UV-CFF contains more oxygen-containing groups.
Macroscopically, UV-CFF is hydrophilic. After reacting with diazonium
salt, new characteristic peaks appeared at 1165, 1252, and 1332 cm−1,
of which 1165 cm−1 is attributed to the vibration of the CF2 group and
1252 and 1332 cm−1 are attributed to the stretching vibration of the
-CF3 group. It is definitely indicated that -CF3 functional groups have
been introduced to UV-CFF by reacting with the diazonium salt suc-
cessfully.
The chemical structure and element content were analyzed by XPS.
According to the total spectrum of CFF (Fig. 1c), the main peaks of C1s
and O1s were observed at 284.6 eV and 532.1 eV. After UV-O3 treat-
ment, the oxygen/carbon content ratio altered significantly from 0.11
to 0.15 (Table 1), which means that a large amount of oxygen-con-
taining functional groups has been introduced to the carbon fiber sur-
face. As a result, the hydrophilicity of CFF is improved effectively. Then
after reacting with diazonium salt, f-CFF exhibits an F1s peak located at
685.7 eV, indicating that CFF has successfully reacted with the diazo-
nium salt. For further analysis, C1s fine spectrums of CFF, UV-CFF and

3
N. Cao, et al. Separation and Purification Technology 251 (2020) 117308

Table 1 3.2. Micromorphology analysis

Atomic percentages of different elements.
Sample C 1s (at%) O 1s (at%) F 1s (at%) O 1s/C 1s SEM images of CFF show typical three-dimensional porous network
of carbon fibers, as shown in Fig. 2a. High-magnification SEM images in
CFF 90.12 9.88 – 0.11 Fig. 2b display that CFF consists of carbon fibers roughly 20 µm in
UV-CFF 86.92 13.08 – 0.15
diameter with some narrow and shallow grooves and a small amount of
f-CFF 86.19 0.52 13.29 0.01
granular impurities. That mainly comes from the carbonization of
carbon fibers and the preparation of carbon fiber felts. Upon treat-
f-CFF were fitted in Fig. 1d-fed. The carbon of CFF and UV-CFF mainly ments, the groove on the surface was retained and the structure did not
exists in three states: C-C/C-H (near 284.6 eV), C-O/C-N (near change significantly, as shown in Fig. 2c and d.
285.5 eV) and C = O (near 288.0 eV). According to the fitted data, the
proportion of C-O/C-N and C = O on the surface of UV-CFF increases to
3.3. Wettability
45.22% from 34.85% of CFF, which is completely consistent with FTIR
results. The reason is that the number of oxygen-containing functional
It is known that wettability is characterized by the contact angles
groups on the carbon fiber surface increases significantly after UV-O3
between water and organics. The uncreated carbon fiber felt is hydro-
treatment. Additional fitted peak at 292.4 eV for -CF3 shows the -CF3
phobic surface with water contact angle of 135 ± 0.2°, after UV-O3
group has been successfully introduced to the surface of UV-CFF after
treatment, it would become a hydrophilic surface. Within a certain
reacting with the diazonium salt in accordance with the FTIR results.
time, the hydrophilicity of CFF in air is improved with the extension of
To obtain better confirmation, Raman spectroscopy was carried out.
the UV-O3 treatment time, as shown in Fig. 3a. When water droplets
As can be seen in Fig. 1g, there are two distinct characteristic peaks at
(3 μL) contact with UV-CFF-15 and UV-CFF-30, some of the water
1590 ~ 1600 cm−1 and 1350 ~ 1360 cm−1, corresponding to the G
droplets are quickly adsorbed. Unfavorably, the water droplets in the
and D peaks of the carbon fiber. Among them, the G peak represents the
UV-CFF increase the immersion resistance and burden the water’s
sp2 bond of the planar structure and the D peak represents the sp3 bond
spread. As a result, the final water droplets are completely adsorbed in
of the tetrahedral structure or the hybrid sp2 bond [36]. ID/IG is used to
1 ± 0.1 s and 0.4 ± 0.1 s. For UV-CFF-45, the droplet adsorption
indicate the graphitization degree of the carbon materials and the in-
speed is too high to be captured by the contact angle apparatus, so UV-
tegrity of the graphite structure. The larger the ID/IG, the higher the
CFF-45 has the best superhydrophilicity, and it is proved that the op-
disorder of the material structure, and the more defects and disorders.
timal treatment time is 45 m.
The ID/IG ratios of UV-CFF (1.01) and f-CFF (1.03) are higher than that
Besides, the underwater oil contact angle of the UV-CFF surface is
of CFF (0.97). It is demonstrated that there are more unsaturated
governed by the organic solvent. As shown in Fig. 2b, chloroform has
carbon atoms along with the functional groups on the surface of carbon
the largest underwater contact angle exceeding 160° and the other four
fibers and some carbon atoms changed from sp2 to sp3 hybrids after UV-
organics also have the underwater contact angles exceeding 155°, and
O3 treatment and diazonium salt reaction [37].
they are all superoleophobic underwater. Hydrophilic groups increased

(a) (b)

100 μm 20 μm

(c) (d)

20 μm 20 μm

Fig. 2. The SEM image of CFF (a) and the high-magnification SEM images of CFF, UV-CFF, f-CFF.

4
N. Cao, et al. Separation and Purification Technology 251 (2020) 117308

(a)

15 min

30 min

45 min

(b) 170 (c) 160

155

Water contact angle /°

165
150
Contact angle /°

160
145
155 140

150 135
130
145
125
140 120
l el e e
oi s n in rm 0.4 0.5 0.6 0.7
p ie ue ol fo UV-CFF quantity /g
m D ol as
or
o
Pu T G hl
C
Fig. 3. (a) The spreading process of water on the UV-CFF surface at different processing times; (b) Contact angles of various organic liquids under water on the UV-
CFF surface; (c) The effect of UV-CFF quality on surface wettability of f-CFF.

significantly on the surface after UV-O3 treatment, such as epoxy where M0 and M1 are the weight of CFF before and after oil absorption,
groups, hydroxyl groups, and carboxyl groups. As a result, UV-CFF is respectively [10].
superhydrophilic in the air, and once UV-CFF is immersed in water, a From another perspective, the separation capacity (S) is a useful
water film forms on the surface to prevent it contacting with organics, indicator. The separation capacity of CFF is calculated by the following
so UV-CFF exhibits underwater superoleophobic characteristics. formula (2):
Based on the UV-CFF, a superhydrophobic f-CFF was fabricated. The
Wb
hydrophobic behavior of f-CFF varies depending on the mass ratio be- S= × 100%
Wa (2)
tween the diazonium salt and the UV-CFF, as shown in Fig. 3c. When
the mass of UV-CFF was 0.3 g and 0.4 g, f-CFF exhibited super- where Wa and Wb are the weight of liquid staying on the CFF before and
hydrophobicity with the water contact angles of 154 ± 0.6° and after separation, respectively [10].
152.5 ± 0.8°, respectively. As the mass of UV-CFF continued to in- The cyclic stability (R) of CFF is calculated by the following formula
crease to 0.5 g and 0.6 g, the f-CFF hydrophobicity deteriorated with (3):
the contact angle less than 150°. Comprehensively considering the cost
Wmax − Wmin
and superhydrophobic ability, f-CFF prepared by 0.5 g UV-CFF and R=1− × 100%
W1 (3)
diazonium salt was used in subsequent experiments. When the f-CFF
was immersed in water under external force, the air film between f-CFF where W1 is the adsorption capacity of CFF during the first cycle; Wmax
and water prevented it from wetting, and this is called “Silver Mirror and Wmin are the maximum and minimum oil adsorption capacity of
Phenomenon” [38]. When the external force as removed, the f-CFF CFF in 10 cycles, respectively [10].
surfaced quickly without any water droplets. All the above investiga- The flux (F) of CFF is calculated by the following formula (4):
tions demonstrate that f-CFF has superhydrophobic properties.
V
F=
t ·S (4)
3.4. Oil/water separation ability
where V indicates the volume of liquid passed, t represents time, S is the
Adsorption capacity and cyclic stability are important parameters to area of separation membrane [39].
evaluate the oil/water separation ability. According to the formula (1), The rejection (J) of CFF is calculated by the following formula (5):
the f-CFF's oil absorption capacity (K) is estimated: V1
J= × 100%
M − M0 V2 (5)
K= 1
M0 (1) Where V1 represents the volume of liquid remaining on the

5
N. Cao, et al. Separation and Purification Technology 251 (2020) 117308

(a)

Toluene

UV-CFF

Water

(b) (d)
Water

(c)
f-CFF

Chloroform

(e) UV-CFF (f) 100

6000 f-CFF 99
98
97
Rejection(%)
Flux(L/m ·h)

4500
96
2

95
3000 UV-CFF
94
f-CFF
93
1500 92
91
0 90
4 6 8 4 5 6 7 8
Thickness(mm) (h) Thickness(mm)
(g) 8.0
Oil adsorption capacity /wt/wt

13.62 Ethanol
Oil adsorption capacity /wt/wt

14 7.5 Gasoilne
12 Hexane
7.0
10 6.5
8 6.0
6.65
5.88 5.56
6 5.12 5.5
4.72
4 5.0
2 4.5
0 4.0
r m ol ne in
e ne an
e 0 1 2 3 4 5 6 7 8 9 10 11
fo an lue sol eto x Cycles
ro Et
h e
hl
o To G a Ac H
C
Fig. 4. The oil/water separation ability of UV-CFF (a), f-CFF (b) and (d); The flux(e) and rejection(f) of UV-CFF and f-CFF; (g) Adsorption capacity test of f-CFF for
different organic solvent; (h) Cycle tests of adsorption of ethanol, gasoline and hexane by f-CFF.

separation membrane, V2 represents the volume of liquid before se- UV-CFF were studied. Firstly, the UV-CFF was wetted by water and put
paration [39]. into the bottom of the homemade oil–water separation device; sec-
The demulsification capacity (D) of f-CFF is calculated by the fol- ondly, the mixture of toluene (dyed by Sudan III) and water (volume
lowing formula (6): ratio) with the ratio of 1:1 was poured into the device. Under the effect
of gravity, water flows through UV-CFF, while toluene stays above UV-
C1 − C2
D= × 100% CFF, as shown in Fig. 4a. After 5 min, the water didn’t drip, indicating
C1 (6)
that UV-CFF has great oil/water separation performance. After 10 cy-
where C1 represents the initial oil concentration, C2 represents the oil cles, water still didn’t drip, indicating that UV-CFF has excellent re-
concentration of demulsification [40]. cycling performance.
In light of the unique super-amphiphilicity in air and super- According to the superhydrophobic and superlipophilic character-
oleophobicity underwater, the oil/water separation characteristics of istics of f-CFF, the oil/water separation was studied. As shown in

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N. Cao, et al. Separation and Purification Technology 251 (2020) 117308

Table 2 demulsification process and characterization. The as-prepared f-CFF

Comparison of flux of different separation membrane. was immersed into the oil-in-water emulsion, and the entire demulsi-
Separation membrane Water flux(L/m2·h) Refs fication process was performed with stirring. As shown in Fig. 5, many
small oil droplets appeared in the microscopic image before demulsi-
Cellulose sponge 91 [41] fication, with a diameter of 100 nm to 1 μm. After the demulsification,
Mineral-coated membrane 90 [42]
these small oil droplets almost completely disappeared. It can be seen
Electrospun fibrous membrane 3106 ± 100 [43]
Electro-responsive carbon membrane 190 [44]
from the macro image that the liquid turned to be clear from a turbid
Tri-layer composite membrane 502 ± 92 [45] state after demulsification. Further, the particle size distribution of oil
UV-CFF 3767 ± 17 This work in water emulsion after demulsfication was analyzed by nano particle
Nanofibrous membrane 3311 [46] size analyzer. As showed in Fig. 5d, the particle size distribution of
Carbon-silica membrane 3032.4 ± 234.6 [47]
three emulsions after demulsfication was 5–350 nm. The average par-
Copolymers membrane 4200 [48]
Electrospun frogspawn structured membrane ≥4400 [49] ticle size of toluene in water emulsion, cyclohexane in water emulsion
Polycaprolactone/beeswax electrospun 1599 [50] and cetane in water emulsion were 197.90 nm, 67.49 nm and
membrane 132.08 nm. It shows that f-CFF has great demulsification ability for oil-
f-CFF 6205 ± 42 This work
in-water emulsions. In order to test the demulsification capacity, we
measured the concentration of emulsion after demulsfication by UV–vis
spectrophotometer. As showed in Fig. 5e, the highest absorbance of
Fig. 4b, toluene is immediately adsorbed within 2 s from the moment
three emulsions were around 350 nm. After measurement, the con-
that f-CFF contacts with toluene dyed with Sudan III. As shown in
centration of toluene in water emulsion, cyclohexane in water emulsion
Fig. 4c, when f-CFF is exposed to chloroform dyed by bright methyl
and cetane in water emulsion after demulsfication were 80 ppm,
blue in water, chloroform was quickly adsorbed within 1 s. The ex-
30 ppm and 60 ppm. The demulsification capacity of f-CFF to toluene in
perimental results prove that f-CFF is superhydrophobic and super-
water emulsion, cyclohexane in water emulsion and cetane in water
lipophilic, which is mainly attributed to its low surface energy and
emulsion were 99.92%, 99.97% and 99.94%.
porous structure. With the same oil/water separation device, f-CFF was
used to separate oil organic solvent/water mixture. As shown in Fig. 4d,
3.5. Durability and reusability
chloroform falls through the pores of f-CFF under the effect of gravity,
while water stays on the surface of W-CFF because of “air cushion ef-
Durability and reusability are both important for the oil/water se-
fect”. After 10 cycles, the mixture is successfully separated by f-CFF,
paration materials in practical application. Firstly, we separately mea-
indicating that the good cycle stability.
sured the oil and water pressure resistance, which directly influences
In the process of oil/water separation, in order to determine the
the useful life of UV-CFF and f-CFF. In the oil/water separation process,
separation rate and efficiency of separation membrane, it is usually
the liquid (oil or water) staying on the CFF creates a certain pressure to
necessary to determine its flux and rejection. As shown in Fig. 4e-f, the
the separation membrane. The test was carried out by sealing the
water flux decreases as the thickness of the UV-CFF increases, but the
oil–water separator, adding a pressure gauge, and increasing the pres-
rejection for oil has no significant change, reaching almost 100%. In
sure by filling argon. When oil droplets (or water droplets) flowed
practical applications, if there is no special requirement, the UV-CFF
through the CFF, the pressure was the oil pressure resistance (water
with a thickness of 4 mm is the best separation membrane. With the
pressure resistance). The theoretical oil/water pressure resistances
decrease of the thickness of separation membrane, the oil flux of f-CFF
(Ptheo) of UV-CFF and f-CFF are calculated by the following formula
to toluene increases significantly. When the thickness of f-CFF is 4 mm,
(4):
the rejection to water is 94.69 ± 0.5%. When the thickness is 8 mm,
the rejection reaches 98.21 ± 0.7%, showing a slight change. In 2R 0 cosθ
Ptheo =
practical applications, f-CFF of different thicknesses can be selected rmax (7)
according to the situation. The water flux of UV-CFF [41–45] and the
where R0 is the oil/water interface tension or water surface tension, and
oil flux of f-CFF [46–50] are comparable to or even higher than those
rmax is the maximum pore diameter of CFF [55]. After measurement, the
previously reported, as shown in Table2.
maximum pore diameter of CFF is 89.97 μm, the interfacial tension of
Moreover, the adsorption rate of f-CFF was measured, which is the
toluene/water is 3.57 × 10−2 N/M, and the surface tension of water is
mass ratio of oil absorption and original f-CFF. After standing for 30 s,
7.28 × 10−2 N/M. According to formula (7), the theoretical oil pres-
the three-dimensional holes of f-CFF were filled with organics. The
sure resistance (toluene) of UV-CFF is 0.74 kPa, and the theoretical
adsorption rates of f-CFF for various organic substances differ due to the
water pressure resistance of f-CFF is 1.42 kPa. As can be seen from
difference in the density of organics. It is shown that the adsorption
Fig. 6a, the oil pressure / water pressure resistance ratio of the CFF and
mass of f-CFF in chloroform is almost 14 times, and others (ethanol,
f-CFF are slightly higher than the theoretical value, and it increases
toluene, gasoline, acetone and hexane) are nearly 6 times of its own
with the increase of the thickness. This is because that the buffering
weight (Fig. 4g), which is comparable to or higher than previous reports
effect of penetration can increase the pressure value under constant
[51–54]. More importantly, f-CFF has better stability in those solvents.
pressure. This situation occurs at intermediate stages when the pressure
After f-CFF absorbed organic, it would be dried by electric thermostatic
value reaches the theoretical value, but the oil droplets (water droplets)
drying oven. Then, it would continue to adsorb organic matter, and its
cannot instantly pass through the separation membrane and drip. The
adsorption capacity was calculated. The above process loops ten times.
oil pressure on the UV-CFF [56–59] and the water pressure on the f-CFF
Finally, we used the formula (3) to calculate its cycle stability. Fig. 4h
[15,60–62] are not lower than that on the previously reported mate-
shows the cycle adsorption property of f-CFF for ethanol, gasoline and
rials.
hexane. The adsorption capacity of f-CFF fluctuates within a small
Secondly, the thermal stability was measured. As shown in Fig. 6b,
range, and the cycle stability for ethanol, gasoline and hexane can reach
CFF, UV-CFF, and f-CFF have significant weight loss between 30 ~ 300
96.67%, 95.95% and 91.78%.
°C, mainly due to the decomposition and volatilization of residues and
At last, the demulsification of f-CFF was tested. First, the mixture
coatings on the surface of the carbon fiber during preparation and
was made of oil (toluene, cyclohexane and cetane) and water with the
processing. At a temperature above 300 °C, CFF has almost no weight
volume ratio of 9:1. After the mixture was ultrasonically shaken for 1 h
loss with the residual mass being 96.77%. At 500 ~ 700 °C, UV-CFF and
and stirred for 1 h, oil-in-water emulsion was obtained successfully. The
f-CFF have a slight weight loss, which may be caused by the thermal
emulsion was stable for 5 h, which is long enough for the
oxidation and decomposition of amorphous carbon on the carbon fiber

7
N. Cao, et al. Separation and Purification Technology 251 (2020) 117308

16 12 12
d
14
10 10
12
Intensity(%)
Intensity(%)

Intensity(%)

8 8
10
8 6 6
6
4 4
4
2 2
2
0 0 0
1 10 100 1000 10000 1 10 100 1000 10000 1 10 100 1000 10000
Size(nm) Size(nm) Size(nm)
e
Absorbance(a.u.)

Absorbance(a.u.)
Absorbance(a.u.)

300 350 400 450 500 550 600 300 350 400 450 500 550 600 300 350 400 450 500 550 600
Wavelength(nm) Wavelength(nm) Wavelength(nm)
Fig. 5. Optical and macro images before and after demulsification of toluene in water emulsion (a), cyclohexane in water emulsion (b) and cetane in water emulsion
(c); (f) Particle size distribution of after demulsification of toluene in water emulsion, cyclohexane in water emulsion and cetane in water emulsion; (e) UV–vis
spectrum of toluene in water emulsion, cyclohexane in water emulsion and cetane in water emulsion.

8
N. Cao, et al. Separation and Purification Technology 251 (2020) 117308

(a) (b)
2.0 UV-CFF 1.87 100 CFF

Oil/water intrusion pressure /kPa

f-CFF UV-CFF
99 f-CFF
1.8
1.63 98
1.6 1.49
97

Mass /%
1.4 96
1.2 95
1.03
1.0 94
0.89
0.81 93
0.8
92
4 6 8 100 200 300 400 500 600 700 800
Thickness /mm Temperature/Ԩ

(c) (d)

(e) (f)
160
underwater oil contact angle /°

160
Water contact angle /°

150

140
150

130

140 120
HCl NaOH NaCl 0 2 4 6 8 10 12 14
pH values
Fig. 6. The durability and reusability. (a) Oil /water intrusion pressure of modified carbon fiber felts with different thicknesses; (b) TGA curves of CFF, UV-CFF and f-
CFF; (c) and (d) Burning an ethanol soaked UV-CFF (Inset is the contact angle of diesel under water on UV-CFF after Burning), f-CFF (Inset is the water contact angle
on f-CFF after burning); (e) Optical images of a diesel droplet on the UV-CFF surface in HCl, NaOH, NaCl aqueous solutions; (f) The water contact angle of f-CFF at
different pH values.

surface, the residual masses of UV-CFF and f-CFF are 94.36% and
93.03% respectively. CFF, UV-CFF and f-CFF all have good temperature
tolerance and applicability.
In addition, UV-CFF and f-CFF have strong flame retardancy prop-
erties. As shown in Fig. 6c and d, UV-CFF and f-CFF lifted from alcohol
are ignited and retain the original macroscopic morphology after
burning. Both the UV-CFF's underwater diesel contact angle and f-CFF's
water contact angle are more than 150°, indicating that the combustion
process did not destroy the chemical composition and internal struc-
ture. The flame retardancy properties of UV-CFF and f-CFF comes from
the original great temperature tolerance of untreated carbon fiber felt.
Meanwhile, the burning test results indicates that the bonding between
functional groups and carbon fiber surface would not be destroyed by
combustion (Fig. 6c, d). UV-CFF and f-CFF could be the candidate for
thermal insulation materials.
At last, in order to best mimic the real situation involving various
corrosive environments during the processing of dealing with crude oil
spills and organic pollutants, the corrosion resistances of UV-CFF and f-
CFF was tested. The corrosive solutions include hydrochloric acid
(1 mol/L), sodium hydroxide solution (1 mol/L) and sodium chloride
solution (10 mol/ L). The underwater diesel contact angle of UV-CFF in
acid, alkaline, and salt solution are shown in Fig. 6e. The results show
that in harsh corrosive environments, the underwater oil contact angles
of UV-CFF remain to be more than 150°, exhibiting the characteristics
of underwater superoleophobicity. Besides, f-CFF durability test was
measured under corrosive environment. First, a solution with a pH
value of 1–13 was prepared with hydrochloric acid and ammonium
hydroxide. The f-CFF was immersed in the above solution for 30 min by
an external force, lifted out, ultrasonically cleaned with pure water for
10 min, and dried in an oven. Subsequently, the water contact angles of
each f-CFF surface were tested. The water contact angle corresponding
to different pH values is shown in Fig. 6f. After immersing in a solution
with a pH value of 5 to 9, the water contact angle of f-CFF was still more
than 150°, showing super-hydrophobic characteristics. After being

9
N. Cao, et al.
soaked in solutions with pH values other than 5 to 9, the water contact
angle decreased. This is because that the corrosive environment de-
stroys the connection between the -CF3-containing functional group and
the carbon fiber. Even so, the water contact angle was still more than
140°, showing relatively good corrosion resistance.
4. Conclusion
Benefiting from the abundant surface chemistry and fire resistance,
the carbon fiber felts with selective superwettability were fabricated by
UV-O3 treatment and diazonium chemistry. After the carbon fiber felts
were treated with UV-O3, the UV-CFF exhibited excellent oil/water
separation ability with the oil pressure resistance of 1.03 kPa and good
cycle stability. It also maintained underwater superoleophobic proper-
ties in acid, alkali and salt solutions with good corrosion resistance,
high temperature stability and flame retardancy properties. After re-
acting with diazonium salt, the functional group containing -CF3 is
connected to the surface of UV-CFF, leading to the decrease of its sur-
face energy. The resultant f-CFF with superhydrophobic / super-
lipophilic properties can be employed for the effective separation of oil
/ water mixtures with the water pressure resistance of 1.87 kPa.
Besides, f-CFF has adsorption capacity of 4–14 for organics and exhibits
great cycle adsorption stability. And the demulsification capacity of f-
CFF to oil in water emulsion could reach more than 99.90%. In addi-
tion, f-CFF also has good corrosion resistance, high temperature stabi-
lity, and flame retardancy properties. In the process of wastewater
treatment, a variety of harsh corrosive environments are often en-
countered, even fire and explosions may occur. The corrosion resistance
and flame retardancy properties of UV-CFF and f-CFF were very im-
portant. Due to having different superwettability, the corresponding
oil–water separation materials can be selected according to the density
of oil in the actual application process. In conclusion, the f-CFF holds
great promise in practical oil/water separation applications in various
environments.
CRediT authorship contribution statement
Ning Cao: Conceptualization, Writing - original draft, Supervision.
Jingyu Guo: Investigation, Writing - original draft. Kunpeng Cai:
Writing - review & editing. Qingzhong Xue: Visualization. Lei Zhu:
Visualization. Qingguo Shao: Methodology, Funding acquisition.
Xinxiu Gu: Writing - review & editing. Xiaobei Zang: Project admin-
istration, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work was supported by National Natural Science Foundation of
China (No. 21905304), Natural Science Foundation of Shandong
Province (No. ZR2019BEM031), the Fundamental Research Funds for
the Central Universities (No. 19CX05001A).
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