Environmental Pollution xxx (2017) 1e11

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Biochar composite membrane for high performance pollutant

management: Fabrication, structural characteristics and synergistic
mechanisms*
Abdul Ghaffar a, b, Xiaoying Zhu a, b, **, Baoliang Chen a, b, *
a
Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310058, China
b
Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou 310058, China

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

Article history: Biochar, a natural sourced carbon-rich material, has been used commonly in particle shape for carbon
Received 6 August 2017 sequestration, soil fertility and environmental remediation. Here, we report a facile approach to fabricate
Received in revised form freestanding biochar composite membranes for the first time. Wood biochars pyrolyzed at 300
C and
20 September 2017
700
C were blended with polyvinylidene fluoride (PVdF) in three percentages (10%, 30% and 50%) to
Accepted 30 September 2017
Available online xxx
construct membranes through thermal phase inversion process. The resultant biochar composite
membranes possess high mechanical strength and porous structure with uniform distribution of biochar
particles throughout the membrane surface and cross-section. The membrane pure water flux was
Keywords:
Biochar
increased with B300 content (4825e5411 ± 21 L m2 h1) and B700 content (5823e6895 ± 72 L m2
Membrane h1). The membranes with B300 were more hydrophilic with higher surface free energy (58.84
Adsorption e60.31 mJ m2) in comparison to B700 (56.32e51.91 mJ m2). The biochar composite membranes
Filtration indicated promising adsorption capacities (47e187 mg g1) to Rhodamine B (RhB) dye. The biochar
Regeneration membranes also exhibited high retention (74e93%) for E. coli bacterial suspensions through filtration.
Synergistic mechanism After simple physical cleaning, both the adsorption and sieving capabilities of the biochar composite
membranes could be effectively recovered. Synergistic mechanisms of biochar/PVdF in the composite
membrane are proposed to elucidate the high performance of the membrane in pollutant management.
The multifunctional biochar composite membrane not only effectively prevent the problems caused by
directly using biochar particle as sorbent but also can be produced in large scale, indicating great po-
tential for practical applications.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction of environmental remediation, carbon sequestration, soil fertility,

Biochar is verified to be black carbon produced from thermal
treatment of naturally abundant biomass and can be obtained from
different types of feedstock materials such as wood, plant residue
and solid waste, to name a few (Chen et al., 2012a,b; Qian and Chen,
2013; Zhang et al., 2014). This “green carbon” has attracted great
interest in recent years because of its fascinating features in terms
*
This paper has been recommended for acceptance by Dr. Yong Sik Ok.
* Corresponding author. Department of Environmental Science, Zhejiang Uni-
versity, Hangzhou, Zhejiang 310058, China.
** Corresponding author. Department of Environmental Science, Zhejiang Uni-
versity, Hangzhou, Zhejiang 310058, China.
E-mail addresses: aghaffar@zju.edu.cn (A. Ghaffar), zhux@zju.edu.cn (X. Zhu),
blchen@zju.edu.cn (B. Chen).
waste management and bioenergy production (Lian et al., 2011;
Ghaffar et al., 2015; Ghaffar et al., 2017). Biochar applications
such as carbon sequestration and environmental contaminant
remediation including poly aromatic hydrocarbons (PAHs), organic
pesticides, phenolic compounds, heavy metals and inorganic con-
taminants have been reported earlier (Beesley et al., 2011; Ahmad
et al., 2014; Mohan et al., 2014; Inyang et al., 2016; Tan et al.,
2015; Xie et al., 2015). Nonetheless, the promising adsorption
ability of biochars for decontamination of pollutants depends on its
interconnected mesostructures, heterogeneous surface chemistry,
high surface area (SA) and porous structure, which vary greatly
with raw material and proposed pyrolysis conditions (Ghaffar et al.,
2017). However, all this considerable progress and research
regarding applications of biochar is still in the form of solid particle
resulting easy loss or release in natural environments, which may

https://doi.org/10.1016/j.envpol.2017.09.099
0269-7491/© 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Ghaffar, A., et al., Biochar composite membrane for high performance pollutant management: Fabrication,
structural characteristics and synergistic mechanisms, Environmental Pollution (2017), https://doi.org/10.1016/j.envpol.2017.09.099
2 A. Ghaffar et al. / Environmental Pollution xxx (2017) 1e11
put possible difficulties during application especially in case of
recycling or recovery process. Therefore, the practical applications
of biochar in waste water treatment or soil remediation were
greatly inhibited by the troublesome biochar particle recovery
processes.
Once biochar was introduced in environmental media such as
water, soil or landfill leachate, the stability of biochar depends on
water chemistry, chemical reactivity or physical binding, oxidation
(aging) and reduction (redox) (Keiluweit et al., 2010; Klupfel et al.,
2014; Yang et al., 2016). Biochar tends to accumulate or adsorb
available pollutants in its surroundings immediately upon contact
because of high reactivity, specific SA to volume ratio and physi-
ochemically dynamic nature, thus losing its original shape and
properties. In addition, there have been recent advancements for
the modification of biochar surface, so called “designed” or “engi-
neered” biochar either by chemical or physical route resulting an
increase in adsorption capacity to facilitate the application of bio-
char into commercial applications (Zhang et al., 2013; Inyang et al.,
2014; Liu et al., 2015; Tang et al., 2015; Wu et al., 2017; Ghaffar et al.,
2017; Reguyal et al., 2017). The presence of hazardous organic
contaminants (e.g., PAHs, dioxins and furans) and inorganic ones
(heavy metals) poses a question mark over the common use of
biochars. The potential release of such contaminants from biochar
to groundwater or soil and uptake by plants may have negative
effects on living organisms and humans (Koltowski and Oleszczuk,
2015; Hale et al., 2012; Oleszczuk et al., 2013). All these factors
simultaneously drive immobilization and toxicity level of biochar,
resulting in potential risks upon their release in environmental
media. Therefore, we must design a system to extend our knowl-
edge for safe applications of biochar to avoid distribution and
transport with effective recovery to control the potential environ-
mental risks associated to biochar.
One promising strategy to minimize the distribution and
transport of biochar would be the fabrication of biochar based
macrostructures or device such as membrane, without sacrificing
its powerful adsorption capability during waste water treatment or
soil remediation. In particular, biochar properties are far from
uniform structure with energetic un-homogeneities, defects and
unsaturated sites owing to its complex nature and disordered car-
bon. In comparison to graphene and carbon nanotubes, biochar is
sustainable and cost effective, thus could achieve simultaneously
the advantage of unique properties and cost reduction. Currently,
some membranes composite carbon based materials such as carbon
nanotubes (CNTs), graphene and graphene oxide (GO) with poly-
mers such as poly acrylonitrile (PAN) and polyvinylidene fluoride
(PVdF), which were used for separation and purification processes
(You et al., 2012; Yang et al., 2013; Joshi et al., 2014). To date, the
application of biochar has not been focused on continuous
adsorption-desorption systems such as in membrane matrix.
Scalable, efficient and topical production of biochar membranes
with tunable properties is essential for industrial applications to be
feasible (Jyothi et al., 2017). This ability remains a critical challenge.
Therefore, the facile fabrication of biochar into membrane profile
would be of both technological and scientific importance.
Herein, we report a sustainable design for fabrication of porous
biochar membrane with PVdF in a controlled composition with
uniform loading. The premise of our strategy is that biochar is
sustainably constructed into freestanding thin membrane with
tunable pore size and desirable adsorption capacity. The surface
and cross-sectional morphology of membranes was examined by
scanning electron microscopy (SEM). The Brunauer-Emmett-Teller
(BET) method was used to quantify SA of membranes from N2 gas
physisorption isotherms. The surface functionalities were quanti-
tatively investigated by Fourier Transformed Infrared-Attenuated
Total Reflectance spectroscopy (FTIR-ATR). The mechanical
Please cite this article in press as: Ghaffar, A., et al., Biochar composite membrane for high performance pollutant management: Fabrication,
structural characteristics and synergistic mechanisms, Environmental Pollution (2017), https://doi.org/10.1016/j.envpol.2017.09.099
properties of membranes were obtained in terms of tensile stress
and strain. The streaming potentials of membrane surface were
obtained through an electro-kinetic analyzer. The contact angles
were used to gain insight to characterize hydrophobic or hydro-
philic nature of membranes. As a prototypical application, aqueous
RhB solution and E. coli bacterial suspension were used as artificial
waste water to access the performance of membranes. Moreover,
the biochar/PVdF composite membranes had excellent sorption,
sieving performance and antibiofouling property simultaneously,
in contrast to control membrane. Given that the biochar membrane
features sustainable application in environmental pollution man-
agement, highlighting the multifunctionality of biochar particles.
2. Materials and methods
2.1. Materials
Polyvinylidene fluoride (PVdF) (Mw ~ 180000 by GPC) was ob-
tained from Sigma Aldrich. Polyvinylpyrrolidone (PVP) and
analytical grade dimethylacetamide (DMAc > 99%), were obtained
from Aladdin Chemicals Reagent Company (Shanghai, China). All
chemicals were used as received without further purification.
Deionized water was used for all experiments. For the preparation
of biochars, wood biomass was obtained from the local field,
Hangzhou, China. Two biochars, at two different temperatures
were prepared by the pyrolysis of wood biomass. Briefly, the ob-
tained wood chips were washed with fresh water and air-dried for
2 days following oven-drying overnight at 105
C. Then the biomass
feedstock was ground by a high speed rotary machine to obtain
milled biomass and passed through a 100 mesh sieve. The
powdered sieved wood biomass was placed in a ceramic pot, and
covered tightly with a lid. The pyrolysis was carried out at desired
temperatures (300 and 700
C), in a muffle furnace (1100-40,
Shanghai HAOYUE Instrument and Equipment Co. Ltd., China) un-
der N2 environment for 6 h, to avoid the calcination of the biomass
in the presence of oxygen. The heating rate was controlled at 5
C
min1 for slow pyrolysis to produce more solid residue (biochar).
The biochar samples were washed with deionized water continu-
ously under magnetic stirring for 24 h to remove the water-soluble
inorganic materials. The washing process was repeated until pH
was stabilized and biochar was obtained through 0.22 mm filter
following oven-drying for 2 days at 65
C. To control the size of
biochar, the charred solids were passed through a 500 mesh sieve
to produce the final biochar samples. Biochars were referred to as
B300 and B700; with numbers referring to the pyrolysis
temperatures.
2.2. Preparation of biochar/PVdF membranes
Biochar based blended PVdF membranes were fabricated by the
thermal phase inversion (TPI) process. In particular, 17% PVdF and
1% PVP were dissolved in 82% DMAc under continuous stirring at
70
C to get a homogeneous solution. The PVdF/biochar ratio was
introduced as 9:1, 7:3 and 5:5 into the above prepared solution. The
solution was stirred for 24 h at 70
C and followed by degassing
under vacuum to release the bubbles. The resultant solutions were
uniformly casted with a thickness of 200 mm on glass plates with an
automatic BEVS1811 film applicator and a BEVS 1806/150 doctor
blade (BEVS industrial Co., Ltd., Guangzhou, China) at 0.5 m min1.
The glass plates were dried at 40
C in an oven and immersed in a
coagulation bath containing ethanol/H2O (1:1 v/v) at room tem-
perature to further solidify the membranes for 90 min. The formed
membranes were peeled off and transferred into the pure water
bath for 24 h to remove the residual PVP completely. The mem-
branes with different biochar addition were named as M31, M33,
 A. Ghaffar et al. / Environmental Pollution xxx (2017) 1e11
M35, M71, M73 and M75, where M31, M33, M35 contains B300 and
M71, M73, M75 contains B700, respectively. The mass percentile of
biochars were different i.e., 10 (M31 and M71), 30 (M33 and M73)
and 50% (M35 and M75), respectively. The pure PVdF (M) and PVdF
with PVP but without biochar (M0) were also prepared following
the same procedure.
2.3. Characterization of biochars and membranes
The structural and surface morphologies of biochars and
membranes were characterized by SEM. The BETeN2 was used to
measure SA and pore volume (PV). The surface functional groups
were observed by FTIR-ATR. The tensile stress and strain parame-
ters were used for mechanical strength with dry membrane sam-
ples. The surface properties were further characterized by zeta
potential (z) and contact angles (CA). More details about charac-
terization are presented in the supplementary information (SI).
2.4. Static and dynamic adsorption of RhB
RhB was selected as model pollutant to test the adsorption ca-
pacity of the biochar membranes. In brief, the sorption kinetic
studies were conducted with an initial concentration of 10 mg L1
RhB (pH ¼ 7.0 ± 1). The solidetoeliquid ratios for biochars were
different and calculated as an average value incorporated in same
type of membrane (i.e., M) from three different pieces (Mi, Mii, Miii).
The solid to liquid ratios for membrane pieces were also taken as an
average weight of three membrane pieces per 500 mL, respectively.
The remaining concentrations in a series of independent samples
were measured from 0 min to 96 h. Each point, either the blank or
calibration control, was evaluated in triplicate. The dynamic
adsorption (filtration) experiment was conducted with an initial
concentration 2 mg L1 of RhB, with a mechanical pump at a flow
rate of 1 mL min1. The effluent was collected after 2 mL, each
point. RhB concentration was measured using an UV/Vis spec-
trometer (UV-2550, Shimadzu) and calculated by the absorbance at
554 nm.
2.5. Bacteria filtration tests
Escherichia coli (E. coli) was used to assure the sieving effect and
anti-biofouling performance of the membranes via filtration pro-
cess at 0.5 bar. The bacterial suspension was cultivated in LB broth
(10 g of tryptone, 5 g of yeast extract, and 10 g of NaCl) at 37
C for
24 h before harvest as reported earlier (Zhu et al., 2013). Then the
bacterial suspension was centrifuged at 4000 rpm for 10 min, and
supernatant was discarded. The bacterial pellets were washed
thrice and re-suspended with PBS for a final concentration of  105
CFU mL1. The retention % of final bacterial suspensions was
measured at a wavelength of 600 nm by UV-Vis spectrophotometer.
The experiment was repeated three times.
2.6. Regeneration of membranes
Regeneration stability of the membranes was evaluated by a
continuous RhB adsorption-desorption under same peristaltic
pump. For the membrane regeneration, a mixture solution of
ethanol and water (1:1 v/v) was used as the eluent. The membrane
was regenerated by backwash, i.e., after each permeation cycle of
RhB feed solution, the prepared eluent (20% effluent volume), was
passed through the membrane module at the same flow rate
(1 mL min1) to elute the RhB molecules adsorbed on the mem-
branes. Effluents from the outlet were consecutively collected at
same time intervals and analyzed using a spectrophotometer at
554 nm. Whereas in case of bacterial suspensions, the membranes
Please cite this article in press as: Ghaffar, A., et al., Biochar composite membrane for high performance pollutant management: Fabrication,
structural characteristics and synergistic mechanisms, Environmental Pollution (2017), https://doi.org/10.1016/j.envpol.2017.09.099
3
were regenerated by simple pure water wash. The membranes with
retained E. coli after filtration were rinsed with DI water continu-
ously for 5 min and dried in open atmosphere. The regeneration
cycles (for RhB and E. coli) were repeated for three consecutive runs
to assure the membrane performance.
2.7. Data analysis
Pseudo-first-order and pseudo-second-order kinetic models
were used to analyze the static adsorption capacity of biochars and
membranes. The dynamic adsorption capacity was calculated by
totaling the each interval. Water flux of the membrane samples
were measured by a Millipore filtration device equipped with N2
cylinder providing the pressure, a digital balance and computer.
The membrane samples were initially compacted for 15 min at
0.5 bar to get a steady flux. The flux was recorded at 0.5 bar every
0.5 min and the average values are reported based on 3 cycles.
Water flux was calculated by:
Q
J¼ (1)
ADt
where J is the water permeation flux, L m2 h1; Q is the perme-
ation volume of the water, L; A is the effective area of the mem-
brane, m2; and Dt is the total operating time, h. More details about
data analysis equations for CA, work of adhesion between solid-
liquid surface, surface free energy (SFE), relative flux decay (RFD)
and relative flux recovery (RFR) are presented in the SI.
3. Results and discussion
3.1. Fabrication and structure of the biochar composite membranes
The biochar/PVdF membranes were constructed by introducing
biochar particles into bulk PVdF solution. The schematic illustration
of the current study to design biochar membrane is presented in
Fig. 1. The detailed properties and composition of membranes are
summarized in Table 1. The color of membrane was found to be
darker with an increase in biochar ratio and optical images are
presented in Fig. S1. The existence of biochar may influence the
structure of the constructed membrane as well. To study structure
of the biochar/PVdF membranes, membrane surface and cross
section were observed with SEM.
The typical surface morphologies of all prepared membranes is
presented in Fig. 2. For comparison, SEM images of membranes
without biochars (M and M0) are presented in SI (Fig. S2). The SEM
images of membrane backside are presented in Fig. S3. The M
membrane was found to be less porous with rough surface in
comparison to M0. The difference between M and M0 is related to
PVP which is commonly practiced as pore forming agent. The
morphologies of resultant biochar membranes were remarkably
changed, demonstrating porous structure with close distribution of
biochar throughout the membrane granular surface. Interestingly,
the M33 was found to be crumpled and bearing caves on surface.
The different ratio of biochar in PVdF membrane matrix clearly
Fig. 1. Scheme of the biochar membrane fabrication.
4 A. Ghaffar et al. / Environmental Pollution xxx (2017) 1e11

Table 1
The structural characteristics and properties of biochar composite membranes with different composition.

Parameter Membrane name

M0 M31 M33 M35 M71 M73 M75

a
Additive None B300 B300 B300 B700 B700 B700
PVdF: biochar (mass ratio) 10:0 9:1 7:3 5:5 9:1 7:3 5:5
Surface pore size (mm)b 0.509 ± 0.05 0.57 ± 0.012 0.553 ± 0.016 0.536 ± 0.02 0.508 ± 0.006 0.494 ± 0.008 0.468 ± 0.004
Surface area (m2 g1)c 2.85 19.35 28.66 29.73 31.39 50.71 55.30
Pore volume (cc g1)d 0.018 0.023 0.024 0.026 0.033 0.041 0.048
Water contact angle (
) 110.3 ± 2.2 80.5 ± 3.4 83.4 ± 2.7 72.1 ± 1.5 91.9 ± 1.8 93.1 ± 2.6 97.1 ± 4.3
Surface free energy (mJ m2)e 47.62 58.84 59.73 60.31 56.32 54.28 51.91
Isoelectric point 3.01 3.24 3.63 3.68 3.59 3.69 2.96
Tensile strength (MPa) 76.06 ± 13.32 65.4 ± 10.88 52.96 ± 5.95 35.25 ± 0.07 102.73 ± 8.4 81.03 ± 4.28 48.5 ± 0.28
Tensile strain (%) 10.4 ± 1.58 3.45 ± 1.62 2.3 ± 0.14 2.09 ± 0.007 4.73 ± 1.59 2.03 ± 0.32 2.01 ± 0.014
a
PVP was constant in all membrane by 1 wt%.
b
Based on 10 SEM images measurements.
c
Brunauer-Emmett-Teller (BET) method.
d
Barrett-Joyner-Halenda (BJH) method.
e
Neumann's method.

Fig. 2. Scanning Electron Microscope (SEM) images of membrane surface of M31 (a), M33 (b), M35 (c), M71 (d), M73 (e), and M75 (f). The biochars (B300 and B700) in membrane
surface are marked by red arrows, respectively. The scale bar is 100 mm.

changed the morphology during biochar/PVdF interaction followed
by TPI, resulting in coarse and smaller pores. The backside of M33
and M73 was also crumpled suggesting that biochar was mixed
more homogenously.
The M35 and M75 membranes exhibited small pores, inter-
connected with each other throughout membrane matrix. The
higher ratio of biochar tends to agglomerate with each other, thus
could form suppressed pores. The cross sectional images (Fig. 3)
clearly showed the presence of biochar exhibiting spongy structure
with uniform biochar distribution resembling to voids, macro-voids
and pore channels with a top dense layer, especially in M35. The
presence of PVP exhibited a slight change in the cross section of M0
membrane and was denser than M membrane (Fig. S4). The cross
sections of membranes became thicker with biochar ratio and
membrane with B300 biochar was found to be more abundant in
comparison with B700 biochar, thus providing longer pore chan-
nels. This sponge like structure could ensure the physical strength
and uniform flow distribution. The membrane without biochar
(M0) is typically flat and homogenous with macropores. However,
biochar type could induce agglomeration leading to more com-
pressed and non-interpenetrating constitution.
To probe the possible interaction between the biochar and PVdF
in suspensions, the SA of biochar, solid concentration, interparticle
forces and PVdF structure could be taken into consideration. The
pronounced increase in SA was observed for B700, suggesting
increased micropores as compared to B300 biochar, which in turn
may result in increased adsorption of PVdF through extensive
interaction between biochar and PVdF. In a previous study, it was
found that the interaction between graphite and PVdF through the
hydroxyl (eOH) functional group leads to different slurry micro-
structures, despite different viscosities which does not originate
solely from the physical characteristics of the graphite particles
(Yoo et al., 2003). The interaction between biochar and PVdF could
lead to a considerable particleeparticle interaction rather than
those between particle and polymer. Also, the concentrated solu-
tion tends to increase interparticle attraction. The primary van der
Waals interaction becomes the major dominant force in absence of
repulsive forces, thereby responsible for the coordinated network
of considerable mechanical strength. Hence, B700 biochar having
high SA comparatively to B300 biochar (Table S1) can favor high
interaction and thus believed to be more interactive with PVdF.
However, the role of PVdF should not be ruled out in mixed biochar-

Please cite this article in press as: Ghaffar, A., et al., Biochar composite membrane for high performance pollutant management: Fabrication,
structural characteristics and synergistic mechanisms, Environmental Pollution (2017), https://doi.org/10.1016/j.envpol.2017.09.099
 A. Ghaffar et al. / Environmental Pollution xxx (2017) 1e11
Fig. 3. Scanning Electron Microscope (SEM) images of membrane crossesections of M33 (a), M35 (b), M73 (c), and M75 (d). The biochars (B300 and B700) in membrane cross-
sections are marked by red arrows, respectively.
PVdF solution since PVdF can easily react with biochar through
hydrogen bonding because of its fluorine atoms consequently
capable to physisorb to biochar surface. The electronegative ele-
ments such as fluorine, nitrogen or oxygen could form covalent
bonding thereby leading to electron distribution. Moreover, a sig-
nificant fraction of polymer projects away causing loops and trails
providing surfaces interaction, and the range of interaction pre-
scribes the overall thickness of the adsorbed layers (Yoo et al.,
2003). Hence, the main interaction between biochar and PVdF
could be considered as physisorption and hydrogen bonding, onto
the surfaces of biochars, leading to aggregated particles.
3.2. Mechanical properties of the biochar composite membranes
The mechanical properties of free-standing biochar/PVdF
membranes in terms of tensile stress and strain were probed to
measure the ability to stand the transmembrane pressure during
filtration (Table 1). As expected, the tensile stress of membranes
was decreased following the biochar ratio. The M35 membrane had
the lowest tensile strength which is related to the aggregation of
biochar within polymer matrix. These phenomena could be
attributed to rapid deterioration as aggregation or stacking of bio-
char occurs, indicating the weak adhesion and poor compatibility
between the biochar and the polymer matrix. Nevertheless, the
lowest tensile stress of 35 MPa for the M35 membrane is still much
greater than the earlier reported tensile stress of a commercially
available PVdF membrane being at 3.5 MPa (Shi et al., 2007; Zhu
et al., 2013). Additionally, the membranes with B700 at 10 and
30% ratio had the highest tensile strength corresponding to a ten-
sile stress of 102 and 81 MPa. The stronger interfacial interaction of
B700 may cause higher load transfer efficiencies at the interface,
thus leading to higher tensile stress. The strain at break (ductile
behavior) of prepared membranes dropped continuously, following
biochar ratio as compared to M0 membrane (Table 1). This sug-
gested that the biochars could link the PVdF network and increase
the rigidity while became brittle. Overall, the membranes showed
enhanced rigidity but weaker ductile properties following biochar
ratio.
Please cite this article in press as: Ghaffar, A., et al., Biochar composite membrane for high performance pollutant management: Fabrication,
structural characteristics and synergistic mechanisms, Environmental Pollution (2017), https://doi.org/10.1016/j.envpol.2017.09.099
5
3.3. Surface composition and properties of the biochar composite
membranes
The BETeSA and PSD (by Barrett-Joyner-Halenda (BJH) method)
of membranes as determined by N2 gas adsorption-desorption are
shown in Fig. 4a and b. The measured SA and PV of B700 was
451.38 m2 g1 and 0.089 cc g1, with maximum adsorption as high
as 197 cc g1 STP with pressure approaching saturation (P/
P0 ¼ 0.99), respectively, confirming higher aromatic and carbon-
ization degree, which is consistent with previous studies. The
distinct PSD for B700 biochar is in good agreement with its higher
SA and PV as compared to SA and PV of B300 biochar (16.36 m2 g1
and 0.024 cc g1) (Table S1 and Figs. S5a and S5b).
For membrane samples, M0 had the lowest SA 2.85 m2 g1 with
0.018 cc g1 PV, while there was no data obtained for M, which
indicated the role of PVP as pore forming agent in membrane
matrix. Following the biochar membranes, the SA and PV was
significantly increased with biochar ratio and temperature. The SA
of M75, M73 and M71 was 55, 50, and 31 m2 g1, with a total PV of
0.048, 0.041 and 0.033 cc g1, respectively. There was no substantial
difference between M35 and M33, almost both had similar SA and
PV (Table 1). The increased SA of membranes is due to biochar ratio
indicating rapid diffusion of N2 molecules into inner micropores, as
confirmed from PSD hysteresis (Fig. 4a and b). Hence, biochar can
additionally increase the SA, thereby increasing the N2 gas pene-
tration, with hierarchical architectures providing active sites. Those
large meso and micropores can form three-dimensional inter-
connected networks with high accessibility and may serve as
transport path to accelerate the mass diffusion.
The changes in surface functional groups of membranes were
analyzed by ATR-FTIR spectra and the results are shown in Fig. 4c.
Firstly, for biochars, several bands at 3371 cm1 for aliphatic eOH
stretching, at 2850 cm1 for eCH stretching, at 1719 cm1 and
1044 cm1 for C]C, C]O stretching were observed (Fig. S5c)
(Smith, 2011). The peak intensities at 3371 cm1 and 2850 cm1
were progressively decreased for B700, indicating a reduction of
eOH and aliphatic eCH bonds favoring decomposition and dehy-
dration process. In membranes, the representative peak at
6 A. Ghaffar et al. / Environmental Pollution xxx (2017) 1e11

Fig. 4. a) N2 adsorptiondesorption isotherms of the wood derived biochar-PVdF membranes. b) Pore size distributions constructed by analyzing N2 adsorption-desorption data
points using BJH method. c) ATR-FTIR spectra of biochar composite membranes.

1400 cm1 corresponds to eCH2 scissoring, wagging and vibrating
of vinyldine. The observed peak intensities at 1275, 1181, 1070, 883
and 840 cm1 represents eCF2 stretching, symmetrical stretching
of eCF, bending of eCH bond, eCH2 wagging of vinyldine and eCH2
rocking. The peak at 1070 cm1 became progressive due to cross-
linking of carboxylic acid functional group (eCOOH) and asym-
metric stretch of carboxylate (eCOOe) originated from biochar. In
addition, the band at 3300 cm1 was assigned to aliphatic eOH
stretching, corroboratively from biochars. The observed peak at
1665 cm1 confirmed the presence of PVP in the membrane matrix
(Chen and Hong, 2002).
The water contact angle (CA) of each membrane was measured
to characterize the surface wettability following static drop
method. The M0 membrane exhibited hydrophobic nature and had
the highest average water CA of 110.3
. PVdF does not have sig-
nificant polar groups; therefore it tends to be hydrophobic. The
membranes made from B300 (M31, M33 and M35) had static CA of
80.5
, 83.4
and 72.1
, all lower than 90
, respectively. The surface
functional moieties such as eOH and eCH (3371 and 2850 cm1)
were prevalent on B300 biochar, as indicated in the ATR-FTIR
spectra. Hence, B300 membranes suggest a moderate shift to hy-
drophilic surface following biochar ratio. The membranes with
B700 (M71, M73 and M75) had water CA of 91.9
, 93.1
and 97.1
,
respectively. B700 biochar also had some polar functional groups,
but progressively decreased because of higher pyrolytic tempera-
ture resulting more decomposition and carbonization.
Additionally, different organic solvents such as formamide,
diiodomethane, ethylene glycol and glycerol were used to charac-
terize membrane surface wetting behavior, thus different polarity
depending upon surface polar group could be obtained (Table S2).
The representative plots of ln((gl (1þcosq)/2)2) versus gl for
different organic solvents results in parabolic curve and are pre-
sented in Fig. 5a. The fitting with second order polynomial equation
will help to determine the constant coefficient related to specific
solid surface (b) and solid-liquid surface free energy (g) parameters.
The M0 membrane was wettable to formamide, diiodomethane
and ethylene glycol and was non-wettable to glycerol, because CA
was found to be less than 90
(Yuan and Lee, 2013). The membranes
with biochar were wettable to all tested organic polar solvents,
suggesting some polar groups were present on membrane surface.
The membranes with biochars were less wettable to glycerol in
comparison to formamide, diiodomethane and ethylene glycol. The
M75 membrane had generally lower surface wettability among
other membranes, because all of the corresponding CA of M75 for
formamide, ethylene glycol and glycerol were larger. The Neu-
mann's method was used to determine surface free energy (SFE) of
the prepared membranes. The M0 membrane had the lowest SFE at
room temperature 47.62 mJ m2. The SFE was increased for M31,
M33 and M35 membranes following B300 biochar ratio as 58.84,
59.73 and 60.31 mJ m2, because of eOH group existence, which
were originally initiated from biochar interaction. On the contrary,
the SFE was decreased following B700 ratio and came down from
56.32 to 51.91 mJ m2, for M71, M73 and M75 in comparison to
M31, M33 and M35. These observed SFE further support the work of
adhesion (Table S3) for the solid-liquid interface. In other words,
the higher SFE is probably attributed to increased surface polarity,
which is efficient by offering more polar interactions for the
membrane. The influence of biochar type and ratio on membrane
flux is presented in Fig. 5b. The pure water flux of M0 was 4634
LMH. The pure water flux of the membrane containing biochar was
increasing with the biochar content, regardless biochar type. The
pure water flux was also compared based on biochar type with

Fig. 5. a) Membrane wettability plots of ln((g1(1þcosq)/2)2) versus g1 for different solvents (water, formamide, diiodomethane, ethylene glycol and glycerol), b) Comparison of pure
water flux based on biochars % and biochar type, and c) Zeta potential curves of membranes.

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 A. Ghaffar et al. / Environmental Pollution xxx (2017) 1e11
same ratio (Fig. 5b). The pure water flux for M71, M73 and M75 was
dominant comparatively to M31, M33 and M35 following biochar
ratio and type (B700 and B300). The lower flux could be explained
by the increase in the entire membrane resistance, a greater
thickness of the membrane cross section and suppression of pore
channels in case of M33 and M35 (Zhang et al., 2016).
The zeta (z) potential curves of the membranes were obtained
from streaming potential and current measurements (Fig. 5c). A
membrane prepared with B300 had a more negative value than the
B700 membranes resulting from increased oxygen-containing
functional moieties on the membrane surface, which were preva-
lent in B300 biochar. The isoelectric point (pI) of M0 membrane was
approximately 3.01 and mostly negatively charged throughout the
pH range (9e2), as resulted from the adsorption of hydroxide ions
originating from the self-ionization of water (Zimmermann et al.,
2001, 2010). The pI for M31, M33 and M35 was found to be 3.24,
3.63 and 3.68 following B300 ratio. There was a strange difference
for M75 (2.96) when compared to M73 (3.69) and M71 (3.59),
respectively, possibly more PVdF dominated the surface of M75. As
observed in the results, M31 and M71 showed almost similar z
curves as compared to M0 (Fig. 5c), which indicated that the surface
properties of M31 and M71 were controlled by PVdF or biochar
particles were completely entrapped in PVdF phases. However, the
membrane was showing z potential contributed by both biochar
and PVdF with increased content of biochar. On the other hand,
M73 and M75 were less negative as compared to M33 and M35.
This might be contributed by the decomposition of carboxylic
groups in high temperature biochar.
3.4. Pollutant removal via membrane adsorption
To investigate the efficacy of biochar membranes, we carried out
the static and dynamic adsorption evaluation with a model
pollutant - RhB dye. Pseudoefirsteorder and Pseudoeseconde-
order kinetic models were used to investigate static adsorption
capacity of membranes (Fig. S6). The relative parameters and cor-
relation coefficient for static adsorption capacity of RhB on biochars
and membranes are presented in Table S4. The pseudoeseconde-
order model provided a better fit to kinetics as suggested by their
higher correlation coefficients (r2) than that of pseudoefirsteorder
model and showed higher adsorption capacity. The biochar (B700 ~
95% carbon, Table S1 and Fig. S7) showed a remarkably higher
adsorption capacity of 237 mg g1, comparatively to B300
(124 mg g1) which can be attributed to its completely carbonized
region and graphitic structure (Fig. 6a and 6 b). Biochar prepared at
higher temperature is considered to be of graphitic structure
stacked together with multiple interconnected pores (meso and
micro), and stirring van der Waals attractive forces along with in-
tegrated carbon layers. Nevertheless, the excellent adsorption ca-
pacity could be related to high SA (451 m2 g1) and carbonization
degree of B700 biochar. The M0 membrane had the lowest
adsorption capacity in both static and dynamic adsorption experi-
ments (22 and 0.77 mg g1). In contrast to M0, the static and dy-
namic adsorption capacities of membranes with biochars were
gradually increased following biochar ratio and pyrolytic temper-
ature. Notably, the static adsorption capacity of biochar membranes
was increased greatly from 47 for M31 to 187 mg g1 for M75
(Table S4) suggesting that membrane structure, biochar type, SA
and PV had obvious influence in adsorption process when loaded
with aqueous RhB, respectively. This clearly shows that the biochar
had active interaction with RhB while being inside the membrane.
The adsorption capacity range for biochar membranes during
dynamic experiments were 3.28e73.93 mg g1, and M75 had the
highest dynamic adsorption capacity, whereas M0 had the lowest
i.e., 0.77 mg g1 (Fig. 6b). It is obvious that the static and dynamic
Please cite this article in press as: Ghaffar, A., et al., Biochar composite membrane for high performance pollutant management: Fabrication,
structural characteristics and synergistic mechanisms, Environmental Pollution (2017), https://doi.org/10.1016/j.envpol.2017.09.099
7
adsorption capacities are totally different for the prepared mem-
branes, implying the importance of contact time, texture and pore
structure of membranes (Table S4). The adequate contact time
(96 h) causes the complete adsorption equilibrium within pore
channels during static adsorption. Whereas, adsorption equilib-
rium remains incomplete during dynamic experiments (Fig. 6b),
because of a very short contact time. RhB molecules are driven
easier through the basic pore channels, thereby causing incomplete
diffusion into inner or secondary pores and adsorbed by biochar to
continue dynamic adsorption within multiple interconnected pores
containing biochars. Therefore, the rapid diffusion and adequate
adsorption of RhB is not possible during dynamic adsorption ex-
periments because of continuous flow and short contact time
resulting in lower adsorption capacity in comparison to static
adsorption.
The potential stability and reusability of membrane (M75) was
assessed by monitoring the continuous adsorption-desorption ex-
periments (Fig. 6d). The membrane was backwashed by using a
mixture of 10 mL ethanol and water (1:1 by volume) as the eluent.
RhB molecules adsorbed on membranes can be easily eluted with
the permeation of the eluent with a gradual decrease in RhB con-
centration. Furthermore, the membrane retains almost original
adsorption efficiency after three consecutive regeneration cycles
and reuse, suggesting that the membrane is stable and effective for
further adsorption of RhB molecules from aqueous media. These
results are desirable for large scale practical application in indus-
trial waste-water treatment plants. Additionally, the ethanol from
the eluent can be recovered easily by distillation process, which
could be reused for next regeneration cycle of membrane.
3.5. Pollutant removal via membrane sieving
The biochar membranes sieving performance was evaluated by
dead end filtration of E. coli bacterial suspensions (Fig. 7a). The
sieving performance was compared as a function of biochar type
and ratio (Fig. 7b, c and d). As shown in Fig. 7a, the M0 membrane
retained approximately 77% of E. coli bacteria and was the lowest
among tested membranes. The M31 < M 33 < M35 retained E. coli
as 74 < 80 < 82%, whereas M71 < M73 < M75 retained E. coli
bacteria as 86 < 90 < 93%, respectively. The retention of E. coli
bacteria was found to be higher for B700 when compared to B300
biochar. The retention of bacterial suspensions could be attributed
to surface pore size of membranes (Table 1), which was found to be
0.57 > 0.553 > 0.536 mm following M31, M33 and M35. The M71,
M73 and M75 membranes had the smaller pore size
(0.508 > 0.494 > 0.468) in comparison to M31, M33 and M35
following biochar ratio, thus resulting in higher sieving
performance.
It can be observed that the flux of M0 membrane decreased
rapidly to a steady-state value after very short period of filtration.
This suggests rapid bacterial accumulation and adhesion on M0
membrane surface, thus leading to biofouling causing pore
blockage. However, biochar membranes demonstrated an
improved performance for bacteria filtration thereby exhibiting a
slower rate of flux decline. The better performance during bacteria
filtration could be linked to improved hydrophilicity and antibac-
terial property originated from biochar. The antifouling property of
the membranes was also indicated by the RFR and RFD after
filtration of bacterial suspensions. The RFD and RFR are listed in
Table S5. There was no significant difference in RFD values i.e., 90%
for all membranes. By contrast, the RFR was significantly improved
for all biochar membranes following biochar ratio in comparison to
M0. The RFR for M0 was approximately 78%, and improved up to
90% for M35. The highest RFR was observed for M75 approximately
at 97%, suggesting that B700 biochar performed better recovery in
8 A. Ghaffar et al. / Environmental Pollution xxx (2017) 1e11

Fig. 6. Static (a) and dynamic (b) adsorption capacity for RhB by the biochars/PVdF membranes. The breakthrough curves for RhB solutions by the biochar/PVdF membranes (c).
Regeneration of M75 membrane for three consecutive cycles, using a mixture solution of ethanol and water (1:1 v/v) as the eluent (d).

contrast to B300 biochar. Clearly, the flux was recovered effectively
in presence of biochar, again confirming more resistivity to
biofouling. Generally, the bacteria retained on membrane surfaces
could be washed away easily by simple physical washing. These
results indicate that the biochar membranes were highly resistant
to biofouling compared to the control membrane (M0). This phe-
nomenon could be clearly attributed to the presence of biochar
which resulted in antibacterial effects thereby preventing the
attachment (Mohanty and Boehm, 2014; Mohanty et al., 2014). In
short, the constructed biochar composite membrane provided
promising bacteria retention effect. More important, the existence
of biochar not only boosted the hydrophilicity of the membrane but
also introduced antibacterial effect, resulting enhanced anti-
biofouling performance of the membrane.
3.6. Synergistic effects of biochars and PVdF in membrane for high
performance pollutant management
The multifunctional performance of the prepared membranes
could be taken as synergistic effects of biochar and PVdF well-
organized structure. Biochars were acting as strong active sites,
while the PVdF was functioning as the support to reinforce the
mechanical strength of the membrane. Due to the strong phys-
isorption of PVdF onto biochar, biochars may be embedded with in
polymer matrix like cross-linkers, thus forming a continuous
connection among PVdF network. The biochar was actively
involved in RhB adsorption whereas surface pore size prevents the
permeation of E. coli bacteria i.e., the sieving effect, thus could
achieve the simultaneous multi-functionality. In this study, the
developed membranes indicated promising adsorption perfor-
mances and antifouling property. This could be attributed to the
synergistic effects of biochar and PVdF within membrane matrix by
(a) internal structure, (b) enhanced adsorption capacity, (c) sieving
effect and antibiofouling property, (d) regeneration and stability.
(a) Internal structure: The biochar in the membrane matrix was
evenly distributed and existed at surface and cross section
area. The membrane exhibited porous morphology and
porosity was increased as compared to control M0 mem-
brane, providing fast permeation to water molecule. The
fabrication of biochar membrane is an effective approach in
waste water remediation and soil treatment, ensuring
controlled porosity.
(b) Enhanced adsorption: The high SA and oxygen containing
functional moieties of biochar could ensure the effective
removal for heavy metals and organic pollutants thereby
providing consequent mass transfer during adsorption.
During the fabrication process, high SA took response for the
interaction between the biochar and PVdF; thus providing
facile interaction and eventually retained for RhB pollutant
and the adsorption of RhB should be attributed to the aro-
matic structure of biochar with active sites. Since the amount
of RhB sorbed on pure PVdF was lower than the biochars and
biochar/PVdF composite could take the advantage of syner-
gistic effects (Kim and Van der Bruggen, 2010). To probe the
possible synergistic effect in between biochar/PVdF, the
adsorption capacity of the constructed membrane was pre-
dicted based on the adsorption capacity of pure biochar
(Qbiochar) and PVdF (QPVdF) and their composition (x% refers
to the percentage of biochar), i.e.,
predicted
Qtotal ¼ Qbiochar  x% þ QPVdF  ð1  x%Þ. The predicted
adsorption capacity differences became more obvious and

Please cite this article in press as: Ghaffar, A., et al., Biochar composite membrane for high performance pollutant management: Fabrication,
structural characteristics and synergistic mechanisms, Environmental Pollution (2017), https://doi.org/10.1016/j.envpol.2017.09.099
 A. Ghaffar et al. / Environmental Pollution xxx (2017) 1e11 9

Fig. 7. Permeate flux variation of the membranes during the filtration of bacteria suspension (a). The comparison of flux variation during filtration of bacteria suspension based on
biochar type and ratio. The letters b, c and d are 10, 30 and 50% of biochars, respectively.

indicate that biochar was actively involved in adsorption
process and also changed the properties of PVdF (Table S4).
The predicted adsorption capacities for M31, M33 and M35
were 32.67, 53.10 and 73.53 mg g1; whereas M71, M73 and
M75 had the 43.91, 86.83 and 129.75 mg g1 predicted
adsorption capacities. The predicted adsorption capacity for
each membrane was always lower than the experimental
adsorption result. Therefore, it is reasonable to speculate
inhibition of RhB adsorption by steric constraint of hydration
shells to some pores of biochars (Chen et al., 2007). Upon
hydration, water may create new sorption sites via disrup-
tion of polar contacts, but RhB molecules were unable to
compete with water for newly created sites (Borisover and
Graber, 2002). Whereas, in biochar/PVdF composites, the
hydration shells became less active or diminished, thereby
providing more active path for RhB molecule, thus resulting
in increased adsorption capacity. Presumably, the promoted
adsorption capacity of biochar in the membrane matrix over
biochar particle could be attributed to the synergistic effects.
(c) Antibiofouling property: The biochar membranes also resulted
in improved antibiofouling performance. Besides the elec-
trostatic repulsion, the presence of biochar contributed two
additional anti-biofouling effects including hydrophilicity
improvement and antibacterial effect of the membrane.
(d) Regeneration and stability: Considering the practical appli-
cation, the regeneration and stability of biochar membrane
was also improved significantly. As indicated in Fig. 6d, the
regeneration was performed up to three consecutive cycles
and the M75 membrane had the same performance as the
primary cycle. Meanwhile, for bacterial suspensions, mem-
branes could be regenerated easily by simple pure water
wash (Fig. 7). The stable performance throughout the system
indicates the effective role of biochar particles for environ-
mental pollutant management, thus might be effective for
field specific applications.
The biochar membranes were designed based on three basic
criteria: (1) the biochar-PVdF solution must be homogenized
physically with overall dispersion, (2) the biochar and PVdF must be
isotropically bonded with each other to form uniform inter-
connected networks and (3) the membrane structure must not
break or crumple during regular processing such as filtration or
back-wash. The first requirement was satisfied by a versatile and
readily accessible high speed continuous stirring method, which
involved the homogenization of biochar-PVdF, and the final in situ
crosslinking. By controlling the mass ratio between biochar and
PVdF, we can change the adsorption ability and pore structure of
individual biochar membranes. The PVdF network is hoped to serve
as a support during the fabrication process. The homogenous so-
lution and controlled ratio of biochar can ensure a strong interac-
tion between them, resulting in improved strength of the biochar
membranes. During the fabrication process, uniform synthesis and
defect free membranes can thus be alleviated.
4. Conclusions
In summary, we have proposed a facile fabrication of free-
standing biochar membrane with PVdF in this study. The biochar

Please cite this article in press as: Ghaffar, A., et al., Biochar composite membrane for high performance pollutant management: Fabrication,
structural characteristics and synergistic mechanisms, Environmental Pollution (2017), https://doi.org/10.1016/j.envpol.2017.09.099
10 A. Ghaffar et al. / Environmental Pollution xxx (2017) 1e11
membranes have shown excellent mechanical stability and water
permeation overwhelming the dispersibility in environment, and
thus are of great potential for application in soil and water reme-
diation with safe recovery solution. Biochar was preserved well in
the membrane matrix with uniform distribution and resulted as
extreme potential active sites. The proposed methodology could
achieve the advantage of simultaneous adsorption and filtration in
waste water treatment applications. The results accomplished from
biochar membranes have the potential to be used for feasible
environmental remediation process and possibly for other organic
pollutants thereby regulating the biochar ratio accordingly to field
application. Furthermore, the simple fabrication method, the
mimetic structure, the unique properties and the existence of
different biochars, will enable more fundamental research and real
applications of the biochar in the near future.
Author disclosure statement
The authors declare that no competing financial conflicts exist.
Acknowledgments
This project was supported by the National Natural Science
Foundation of China (21425730, 21537005, 21621005, and
21607124), the National Key Technology Support Program of China
(2015BAC02B01), and National Basic Research Program of China
(2014CB441106). Abdul Ghaffar also acknowledges the financial
support for doctoral study from Zhejiang University.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.envpol.2017.09.099.
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Please cite this article in press as: Ghaffar, A., et al., Biochar composite membrane for high performance pollutant management: Fabrication,
structural characteristics and synergistic mechanisms, Environmental Pollution (2017), https://doi.org/10.1016/j.envpol.2017.09.099