1 s2.0 S0959652620303231 Main
1 s2.0 S0959652620303231 Main
a r t i c l e i n f o a b s t r a c t
Article history: Eco-friendly and cost-effective designs of adsorbents are highly desirable to realize highly efficient
Received 19 July 2019 removal of heavy metals and organic pollutants from wastewater. Herein, the biomimetic co-deposition
Received in revised form from polyphenol-substance tannic acid induced the grafting of renewable cardanol-derived siloxane on a
18 January 2020
cellulose nanofiber (CNF) framework to form an eco-friendly and low-cost microporous aerogel to
Accepted 25 January 2020
Available online 30 January 2020
capture Cu(II) and organic contamination. Owing to the three-dimensional cellulosic porous structure
and easily accessible active sites, the as-prepared aerogel manifested a low density and favorable hy-
Handling Editor: Prof. S Alwi drophobicity, which were vital for highly efficient absorption toward Cu(II) and oil droplets. The satu-
rated adsorption capacity of modified aerogels for Cu(II) was found to be 45.6 mg/L, which is higher than
Keywords: the majority of reported biobased adsorbents. Based on thermodynamic and kinetic studies, the Cu(II)
Nanocellulose-based aerogel adsorption closely approximated that of a spontaneous and endothermic chemisorption process. In
Tannic acid addition, the modified aerogel effectively collected various oils and organic solvents from water, with
Contaminant maximum absorption capacities up to 108 g/g (chloroform); it also exhibited good stability in a Cu(II)/
Adsorption
chloroform binary system. The multiple separation efficiency indicated that the obtained aerogel is very
Hydrophilicity
suitable for application in practical water purification. It is particularly important that the whole syn-
thesis process of modified aerogels is green and economical without additional toxic agents; this allows
them to significantly reduce secondary pollution to the environment after use, contamination emissions
to the environment. These results demonstrated that the novel nanostructured composites with a
naturally functional polymer layer have unexpected potential as an ideal candidate for practical water
purification.
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2 Y. Ji et al. / Journal of Cleaner Production 255 (2020) 120276
Cellulose nanofiber (CNF), a one-dimensional (1D), netlike, sufficient hydrophobicity and high porosity for oil/water separa-
nanocellulose-based material, has attracted significant attention as tion. Its facile co-deposition coating process was conducted in an
a nano-sized building block for use in biobased aerogels owing to aqueous alkaline solution. The surface modification of TA@CNF-
its excellent mechanical properties, large surface area, and tunable CDA composites was evaluated, and the detailed effects of various
surface chemistry (Han et al., 2017). However, CNF is challenged by parameters on the removal of Cu(II) and the separation of oil/water
intrinsic hydrophilicity and inferior adsorption sites, which thus emulsion behavior were also investigated. This work provides a
affect its performance in oil-in-water separation and the extraction cost-effective approach not only for high value-add utilization of
of heavy-metal ions (He et al., 2018). The surface modification of forest biomass, but also for the treatment of heavy-metal-ion
CNFs has been investigated recently, aiming to improve the wastewater and oil contaminations.
chemical functionality and alter the wettability of CNF-based ma-
terials. For instance, Zhang et al. (2014) prepared ultra-lightweight
nanocellulose sponges via one-step silylation of methyltrimethox- 2. Experimental section
ysilane (MTMS) on a CNF framework. The obtained CNF aerogels
displayed a high absorption capacity of organic solvents, reaching 2.1. Materials
up to 100 times (dodecane) their own mass. In this respect, with
MTMS or octyltrichlorosilane as the silylating agent, the chemical CNF suspension (0.9 wt%, diameter: 5e20 nm, length: 2e7 mm)
vapor deposition (CVD) technique has been proposed as an alter- was supplied by Tianjin Haojia Cellulose Co., Ltd. (Tianjin, China).
native to fabricate hydrophobic nanocellulose-based aerogels. Tris (hydroxymethyl) aminomethane (Tris) and tannic acid (TA)
Although a considerable number of studies have recently been were purchased from Tianjin Heowns Biochem Co., Ltd. (Tianjin,
conducted for exploring the capability of hydrophobic CNF-based China). Sodium hydroxide (NaOH, 85%) and hydrogen chloride
aerogels in oil/water separation (Sai et al., 2015), very few efforts (HCl, 37.5%) were obtained from Beijing Chemical Reagents Co.,
have been made to improve their performance as adsorbents for Ltd. (Beijing, China). CDA was synthesized via the epoxy-opening
capturing organic solvents and heavy metals from various waste- between aminopropyltriethoxysilane (APTES, 98%) and carda-
waters simultaneously. In fact, the adsorption capacity of cellulose nol glycidyl ether based on a previously reported method (Wang
aerogel for heavy-metal ions relies strongly on its active sites and et al., 2019b). All chemicals were analytical grade and used as-
porous structure (Lam et al., 2018). For these reasons, CNF requires received.
rational modification to design an efficient aerogel with broad
applications in the separation of organic contaminants and heavy- 2.2. Preparation of TA@CNF-CDA aerogels
metal-containing wastewater.
Of particular interest, mussel-inspired catechol chemicals, such First, the CNF suspension (0.9 wt%) was dispersed into TrisHCl
as polydopamine (Yang et al., 2018), gallic acid (Zuorro et al., 2016), solution (pH ¼ 8.5, 0.5 wt%) and ultrasonicated for 30 min using a
and tannic acid (TA) (Lim et al., 2018), are regarded as emerging sonicator (VC-750, 750 W, Sonics and Materials Instruments). Then,
highly efficient, versatile platforms to realize material surface the suspension was divided into seven beakers, each containing
functionalization. Among them, TA is a natural polyphenol derived 80 g of solution, and one beaker was set aside to serve as the pure
from various edible plants and is particularly attractive in surface CNF sample. Next, 0.02 g of TA was introduced to five of the
hydrophilization engineering owing to its advantages of abundant remaining six samples (the CNF-CDA sample was omitted) and
functional groups, low cost, and biocompatibility (Xu et al., 2018). vigorously stirred until the solvent was completely dissolved in the
TA contains several pyrogallol functional groups, which possess an CNF suspension. Then, a certain amount of CDA was mixed with
excellent chemical reactivity with thiol or amine-terminal mono- 20 mL absolute ethanol. After the mixture was dispersed entirely, it
mers; thus, they provide an active intermediate layer to improve was introduced into the obtained TA-coated CNF suspension, and
the surface and adsorption efficiency. Wang et al. (2018a,b) pro- then stirred for 6 h at room temperature. Finally, the resulting
posed a one-step and general strategy to design multifunctional TA@CNF-CDA aerogels were obtained by freeze-drying (80 C) for
surfaces by co-depositing TA and 3-aminopropyltriethoxysilane 12 h. The names of the TA@CNF-CDA aerogels are listed in Table 1.
(APTES) on hydrophobic membranes. Further studies revealed
that TA induced siloxane hydrolysis/condensation reactions to form
polysiloxane hybrids under a weak alkaline environment and 2.3. Characterization
simultaneously served as an adherent layer for the in-situ silicifi-
cation of substrates. Note that TA as a hyperbranched polymer with The apparent density of the aerogels was calculated by
multi-phenolic hydroxyl groups can give rise to several active sites measuring the weight and physical dimensions of the samples.
owing to its strong coordination ability toward metallic species Fourier transform infrared spectra (FTIR, Nicolet 6700, USA) were
(Luo et al., 2016). It supplies a sufficient engineering platform and obtained using the spectrometer between 4000 and 650 cm1. X-
active points for the CNF-based aerogels to realize the effective ray photoelectron spectroscopy (XPS; Thermo Electron Corpora-
capture of organic pollutants and heavy-metal ions. tion, USA) was conducted to analyze the surface composition of the
Herein, considering the advantages of TA and silicification, a samples. Thermogravimetric analysis (TGA; Q50, TA instruments,
hybrid Cu(II) and oil/water adsorption coating was introduced on USA) was performed to examine the weight loss of samples at a
the framework of CNF aerogels by a green, one-step strategy heating rate of 10 C/min in nitrogen. The surface morphologies
(Scheme 1a). To endow their hydrophobicity, CNF was functional- were collected using a scanning electron microscope (FE-SEM,
ized by chemical deposition of the desired cardanol-derived Hitachi SU8010, Japan) with an accelerating voltage of 15 kV and a
siloxane (CDA). CDA as a siloxane derivative with rich, long transmission electron microscope (TEM, JEOL H-7650, USA). The
aliphatic chains (C15) was synthesized from the renewable resource specific surface areas of the aerogels were calculated according to
of cashew-nut-shell liquid, which facilitates the cost-effective the BarrettJoynerHalenda (BJH) method with an ASAP 2020
construction of a hydrophobic layer on the TA-functionalized CNF instrument (BET, Quantachrome, USA). The surface wettability was
surface. The as-prepared TA/CDA-functionalized CNF (TA@CNF- evaluated through the water-membrane contact surface and ob-
CDA) composite aerogels not only had abundant active adsorption tained using a contact angle instrument (OCA 20CA, Dataphysics,
sites arising from the resulting TA complex, but also supplied Germany) at room temperature.
Y. Ji et al. / Journal of Cleaner Production 255 (2020) 120276 3
Scheme 1. (a) The preparation procedure for TA@CNF-CDA; (b) the possible interaction mechanism between TA and CDA.
Table 1
Reagent dosage in the fabrication procedure. ðC0 Ct ÞV
qt ¼ (1)
Sample CNF (g, 0.5 wt%) TA (g) CDA (g) W
CNF 80 0 0
where C0 and Ct refer to the initial and equilibrium Cu(II) concen-
TA@CNF 80 0.02 0
CNF-CDA 80 0 0.6 trations (mg/L), respectively; V is the total volume (L) of the
[email protected] 80 0.02 0.2 adsorption solution; and W is the mass (g) of the adsorbent.
[email protected] 80 0.02 0.4
[email protected] 80 0.02 0.6
[email protected] 80 0.02 0.9
2.5. Organic pollutants absorption experiment
2.6. Both heavy metal ions and solvents removal experiments C]C and CeC aromatic groups, respectively (Wang et al., 2019a).
Moreover, the introduction of the TA molecules onto the CNF
Chloroform and Cu(II) were selected as organic pollutants to scaffolds was evidenced by the broadening of the stretching vi-
assess the simultaneous absorption performances of the TA@CNF- bration peak assigned to the eOH groups at 1689 cm1. With regard
CDA aerogels. Chloroform-in-water emulsions were prepared by to TA@CNF-CDA, the emergence of new peaks at 2923 and
adding chloroform to Cu(II)-containing solutions under 30 min of 2853 cm1, attributed to the asymmetric vibrations of eCH3 and
sonication (OP-10 served as the emulsifier); the solutions contained eCH2 (Wang et al., 2019e), strongly indicate successful grafting of
50 mg/L Cu(II) and 50 mL chloroform. TA@CNF-CDA composites of the long chains of CDA chains onto the CNF. Moreover, the
0.18 g were added into the as-prepared emulsions (100 mL). When stretching vibration peak observed at 1194 cm1 belongs to CeOeSi
the sample masses became constant with increasing time, these (Wang et al., 2019b), which demonstrates that the polysiloxane was
solutions were separated by centrifugation. Accordingly, the prac- decorated successfully on the TA@CNF interface.
tical adsorption capacity of TA@CNF-CDA toward chloroform and XPS analysis was employed to characterize the changes in
Cu(II) was calculated. element composition after chemical modification (Fig. 1b).
Compared with pure CNF, the Si 2s and Si 2p peaks were identified
3. Results and discussion clearly in the spectrum of TA@CNF-CDA. The O/C ratios of the CNF
and TA@CNF-CDA samples were compared (Table 2) and showed a
Scheme 1a illustrates the procedure and synthetic mechanism decreasing trend where CNF (0.8) > TA@CNF (0.78) > TA@CNF-CDA
of the multifunctional TA@CNF-CDA aerogel. The CDA was (0.37). The O/C value of TA@CNF-CDA decreased owing to the
employed as a hydrolysable organoalkoxysilane with long chains to higher carbon contents of the TA and CDA molecules. The C 1s
immobilize on the multi-aromatic ring structure of TA via hydro- spectrum of TA@CNF-CDA was resolved into four main component
lyzation/condensation reactions (Scheme 1b), thereby effectively peaks with binding energies at 285.0, 285.7, 286.3, and 288.4 eV,
forming adhesive polysiloxanes on the CNF surface. The TA/CDA related to the CeC, CeN, CeOH, and C]O moieties (Xiong et al.,
hybrid coating was expected to form strong interactions with CNF 2016), respectively (Fig. 1c). The occurrence of nitrous carbons
owing to the synergistic effects between excellent adhesion prop- (CeN) in TA@CNF-CDA was related to the co-condensation reaction
erty of the TA and polysiloxanes (Lee et al., 2007). The whole syn- between the hydroxyl groups from TA and CDA (Xu et al., 2016).
thesis process of TA@CNF-CDA needed no additional organic These results are consistent with the FTIR results, and further
agents, resulting in an eco-friendly and economical process. confirm that the TA-CDA hybrid coating was formed and success-
fully introduced onto the CNF scaffolds.
Fig. 1. (a) FTIR spectra and (b) wide-scan XPS spectra of CNF, TA@CNF and TA@CNF-CDA; (c) the deconvolution curves of C 1s XPS spectrum for TA@CNF-CDA; (d) TGA thermograms
of CNF, TA@CNF and TA@CNF-CDA.
Y. Ji et al. / Journal of Cleaner Production 255 (2020) 120276 5
Subsequently, Fig. 1d shows the TGA curves of CNF, TA@CNF, and honeycomb structures is believed to be conducive to the good
TA@CNF-CDA. Because the introduction of typical hydrophilic TA adsorption performance of target compounds.
macromolecules led to the evaporation of absorbed water, and
TA@CNF displayed only a slight weight loss at a low temperature 3.2. Cu (II) adsorption studies
(<120 C) (Li et al., 2017). For TA@CNF-CDA, the weight loss at
440 C was greater than that of CNF and TA@CNF, which further The lignocellulose-derived TA@CNF-CDA composite aerogels
proves the successful formation of a robust TA-CDA hybrid coating. were synthesized under optimized conditions and used to handle
In Fig. 2a, CNF exhibited a typical netlike structure with inter- wastewater containing Cu(II) to evaluate the heavy-metal adsorp-
twining of the fibrils. In comparison, TA@CNF-CDA displayed a tion performance. As shown in Fig. 3a, the removal capacity of the
porous network morphology with broadened fibrils, and several pure CNF aerogel reached as high as 36.7 mg/g, but only 24 mg/g
dark shadows tended to form on its surface (Hu et al., 2017), indi- was obtained for the CNF-CDA. This was mostly ascribed to its
cating a small amount of organic layer on the surface of CNF. lower surface area and decreased active sites after grafting CDA
Fig. 2bec shows that the well-defined 3D porous structure molecules on the CNF surface (Phan et al., 2019). In comparison, the
comprised more thin sheets than pure CNF and TA@CNF. Mean- TA-CDA coating comprises rich oxygen-containing functional
while, there are evident small honeycomb-like pores homoge- groups that are beneficial for Cu(II) adsorption. In addition, it
neously dispersed in the CNF network, suggesting the formation of exhibited an increased adsorption capability for Cu(II) (45.6 mg/g),
adherent TA-CDA. Thus, such changes are strongly indicative of the which was likely a result of the complexation/chelation in-
surface modification of CNF and the successful fabrication of teractions between the oxygen-containing groups of TA@CNF-CDA
TA@CNF-CDA aerogels. and cationic Cu(II) (Fig. 3d) (Gao et al., 2013; Li et al., 2014).
According to the N2 adsorptionedesorption (Table 3), the BET
surface area of the CNF, TA@CNF, and TA@CNF-CDA were 150.61,
134.41, and 75.66 m2/g, respectively. As CNF was further co- 3.2.1. Effects of pH, initial concentration, and temperature on
deposited by TA and CDA, the BET surface area and pore volume adsorption of Cu(II)
were decreased inversely. This could be due to the large number of In general, pH is an important factor that affects the Cu(II) ion
TA and CDA molecules on the CNF scaffolds, and thereby, the adsorption process. The results are depicted in Fig. 3b and
smaller pores were jammed by the irregularly coated layers (Gao demonstrate that the adsorption capacity of Cu(II) for TA@CNF-CDA
et al., 2018). In this case, the newly generated large pores with increased with the pH from 1 to 5. At low pH values, the removal of
Cu(II) was insignificant owing to the charge on the surface of the
Fig. 2. (a) TEM images of CNF and TA@CNF-CDA. The digital and SEM images of (b) CNF and (c) TA@CNF-CDA.
6 Y. Ji et al. / Journal of Cleaner Production 255 (2020) 120276
Table 3
Bulk density, specific surface area, and pore volume studies of the CNF, TA@CNF and TA@CNF-CDA composites.
Sample r aerogel (mg/cm3) BET specific surface area (m2/g) Pore diameter (nm) Pore volume (cc/g)
Fig. 3. (a) Removal capacity of CNF and hybrid aerogels for Cu(II) (initial concentration of Cu(II) ¼ 50 mg/L; pH ¼ 5.0; contact time ¼ 3 h); (b) effect of pH values on the percentage of
Cu(II) removal by TA@CNF-CDA (initial concentration of Cu(II) ¼ 50 mg/L; contact time ¼ 3 h); (c) effect of initial concentration and contact time on the percentage of Cu(II) removal
by TA@CNF-CDA (pH ¼ 5.0; T ¼ 25 C); (d) schematic illustration of the Cu(II) adsorption mechanism by TA@CNF-CDA aerogel; (e) effect of temperature on the percentage of Cu(II)
removal by TA@CNF-CDA (initial concentration of Cu(II) ¼ 50 mg/L; pH ¼ 5.0); (f) plot of ln KD versus 1/T for Cu(II) ions adsorption at different temperatures.
adsorbent and the form of metal ions in aqueous solution (Zhang maximum removal percentage for Cu(II) of 56.92% was observed at
et al., 2019). In this case, the protonation of the functional groups the optimal pH of 5.0, indicating that TA@CNF-CDA has a high
on the adsorbents was the main cause of electric repulsion of the coordinating capacity for Cu(II).
same positively charged Cu(II), thereby leading to a low adsorption In addition to the pH value, the initial concentration of the
capacity (Zhao et al., 2017). With an increase in the pH, the removal Cu(II)-containing solution is another key parameter for the per-
efficiencies for Cu(II) increased sharply, which could be explained formance of adsorbents. Accordingly, different initial concentra-
by the strengthening of electrostatic attraction between the nega- tions of Cu(II) were used to further investigate the adsorbents, as
tively charged TA@CNF-CDA surface and Cu(II) ions (Semercio €z illustrated in Fig. 3c. The results demonstrated that the Cu(II)
et al., 2017). The adsorption experiments at pH values (>5.0) removal efficiency decreased as Cu(II) concentration increased
were not evaluated because the predominant copper form is metal- from 10 to 150 mg/L (pH ¼ 5.0). This phenomenon could be
hydrolyzed substances (e.g., Cu(OH)2) for the consequent precipi- explained from two aspects: The decreased ionization degree
tation (Badruddoza et al., 2013). Based on this information, the arising from the TA@CNF-CDA surface, and the hindrance effect of
Y. Ji et al. / Journal of Cleaner Production 255 (2020) 120276 7
excessive ions in the adsorption process (Wang et al., 2017). In at equilibrium and at time t (h), respectively; and k1 and k2
contrast, the contact time strongly affected the adsorption perfor- represent the rate constants of the pseudo-first-order and pseudo-
mance of adsorbents TA@CNF-CDA, indicating that numerous second-order kinetic models, respectively.
active sites of TA@CNF-CDA were readily available for the initial The effects of the contact time on the adsorption of Cu(II) were
adsorption (Wen et al., 2019). Thus, a contact time of 360 min was investigated, with the results presented in Fig. 4a and b and Table 5;
selected to ensure the saturation of bounding Cu(II) ion in the these data demonstrated that the TA@CNF-CDA closely followed a
following experiments. pseudo-second-order model (R2 ¼ 0.994), indicating that the
The adsorption capacity of Cu(II) was found to increase with chemisorption was the dominant control step for the adsorption
temperature, suggesting that the higher temperature promoted the process of Cu(II) (Mo et al., 2019).
adsorption process of TA@CNF-CDA toward Cu(II) (Ain et al., 2019).
Thermodynamic parameters were considered to better understand 3.2.3. Adsorption isotherms
the inherent energetic changes during the adsorption process, as The absorption isotherms of Cu(II) on TA@CNF-CDA were fitted
calculated by the following formulas: separately using Langmuir and Freundlich models:
DS DH Ce Ce 1
ln KD ¼ (3) ¼ þ (9)
R RT qe qm KL qm
Table 4
Thermodynamic parameters of Cu(II) adsorption on the TA@CNF-CDA.
Fig. 4. (a) Data fit to pseudo-first-order kinetic model for Cu(II) adsorption; (b) data fit to pseudo-second-order kinetic model; (c) adsorption data fitted with the Langmuir model;
(d) adsorption data fitted with the Freundlich model.
Table 7
Comparison of Cu(II) adsorption on TA@CNF-CDA and other biobased adsorbents.
Fig. 5. (a) Water drop (blue) and diesel (red) on the surface of TA@CNF-CDA; (b) the WCA of different aerogels with different amounts of CDA; (c) images of the WCA of CNF,
TA@CNF and TA@CNF-CDA aerogels.
where kid and C are the intraparticle diffusion rate and the inter-
cept, respectively. In Fig. 7c, the plot of uptake versus time yielded
typical 3-linearity regions, implying that the adsorption of chlo-
roform and diesel onto TA@CNF-CDA contained mainly three con-
trolling process: i) boundary layer diffusion, ii) diffusion into the
mesopore, and iii) micropore diffusion (Cheung et al., 2007). From
Table 8, the slope ki1 in the first linear portion was greater than the
others, indicating the existence of a relatively speedy process dur-
ing the boundary layer diffusion. Moreover, the result showed that
all the slope values determined for the diesel were much higher
Fig. 6. Removal of diesel and chloroform (dyed with Sudan III) with TA@CNF-CDA from than that of chloroform, which is probably relative to the high
the surface and the bottom of water. viscosity of this liquid.
Fig. 7. (a) Absorption capacities of TA@CNF-CDA for various oils and organic solvents and comparison of density of the different liquid; (b) adsorption capacity of TA@CNF-CDA for
Cu(II) and chloroform under unitary/mixed systems; (c) adsorption data fit to intraparticle diffusion model of chloroform and diesel onto TA@CNF-CDA.
10 Y. Ji et al. / Journal of Cleaner Production 255 (2020) 120276
Table 8 Badruddoza, A.Z., Shawon, Z.B., Tay, W.J., Hidajat, K., Uddin, M.S., 2013. Fe3O4/
Diffusion model parameters for the adsorption of chloroform and diesel on TA@CNF- cyclodextrin polymer nanocomposites for selective heavy metals removal from
CDA. industrial wastewater. Carbohydr. Polym. 91 (1), 322e332.
Cao, N., Qian, L., Li, J., Wang, Y., Yang, B., Szunerits, S., Boukherroub, R., 2017. Facile
First stage Second stage Third stage synthesis of fluorinated polydopamine/chitosan/reduced graphene oxide
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ki1 C R2 ki2 C R2 ki3 C R2
Chen, S., Yue, Q., Gao, B., Li, Q., Xu, X., 2011. Removal of Cr (VI) from aqueous so-
Chloroform 23.36 0.48 0.984 6.10 65.71 0.976 1.12 97.20 0.947 lution using modified corn stalks: characteristic, equilibrium, kinetic and
Diesel 16.93 20.32 0.986 5.66 29.71 0.993 1.24 60.81 0.965 thermodynamic study. Chem. Eng. J. 168 (2), 909e917.
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4. Conclusions
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and cellulosic 3D porous aerogels for Cu(II) and organic-solvents
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removal by anchoring renewable cardanol-derived siloxane (CDA) nanocellulose on the structure and properties of poly(vinyl alcohol)-borax
on the TA-functionalized CNF skeleton, TA@CNF-CDA. The as- hybrid foams. Cellulose 24 (10), 4433e4448.
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Declaration of competing interest Liu, Y., Tu, W., Chen, M., Ma, L., Yang, B., Liang, Q., Chen, Y., 2018. A mussel-induced
method to fabricate reduced graphene oxide/halloysite nanotubes membranes
for multifunctional applications in water purification and oil/water separation.
The authors declare that they have no known competing Chem. Eng. J. 336, 263e277.
financial interests or personal relationships that could have Luo, J., Lai, J., Zhang, N., Liu, Y., Liu, R., Liu, X., 2016. Tannic acid induced self-
assembly of three-dimensional graphene with good adsorption and antibac-
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