Materials and Design 107 (2016) 187–197

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Materials and Design

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High structure stability and outstanding adsorption performance of graphene

oxide aerogel supported by polyvinyl alcohol for waste water treatment
Jian Dai, Ting Huang, Su-qi Tian, Yan-jun Xiao, Jing-hui Yang, Nan Zhang, Yong Wang ⁎, Zuo-wan Zhou
School of Materials Science and Engineering, Southwest Jiaotong University, Key Laboratory of Advanced Technologies of Materials, Ministry of Education of China, Chengdu 610031, PR China

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

Article history: In this work, we developed a new kind of aerogel consisting of graphene oxide (GO) and polyvinyl alcohol (PVA),
Received 23 April 2016 in which PVA exhibited a role to stabilize the 3D porous structure of GO. The PVA-supported GO aerogels were
Received in revised form 9 June 2016 prepared through an environmentally friendly freeze-drying technique. The microstructure, the structure stabil-
Accepted 10 June 2016
ity, the adsorption ability for different dyestuffs, and the oil/water separation of the aerogels were systematically
Available online 11 June 2016
investigated. The results demonstrated that the PVA-supported GO aerogels exhibited outstanding performances.
Keywords:
First, the PVA-supported GO aerogels exhibited high structure stability, especially in the non-polar solvent, which
PVA-supported GO aerogel was apparently different from the widely reported GO aerogels in the literatures which experienced structure
Structure stability collapse in the solvent, especially in water. Second, the aerogels also exhibited high absorption selectivity for
Mechanical stability dyes, especially for the dyes with positive charges; the adsorption efficiency was over 96%. Third, the PVA-sup-
Adsorption ported GO aerogels still exhibited excellent oil/water separation ability and they can completely adsorb Sudan
Oil/water separation red/cyclohexane solution that floats on the water within 5 s. This work provides a simple and environmentally
friendly method to obtain the versatile GO aerogel, which really has a great potential in the field of waste
water treatment.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction (GO)-based aerogel is regarded as the proper candidate material for

waste water treatment due to its excellent mechanical properties and
The growing water pollution problems, relating to the emission of intrinsic adsorptive ability [16–19]. Graphene aerogel is well known as
various organic dyestuffs and heavy metal ions and the leakage of the hydrophobic and oleophilic aerogel due to the hydrophobicity of
crude oil and petroleum products, have become the most serious global graphene layers [20] and therefore, it exhibits excellent adsorption abil-
concerns because they greatly affect not only the health of human be- ity for oil. This indicates that the graphene aerogel can be used for oil/
ings but also the sustainable development of society. Many strategies water separation [21,22]. However, it should be noticed that, compared
or new materials have been developed to treat waste water. Among to graphene, the higher adsorption efficiency for organic pollutants is
these materials, aerogel materials have come into notice. Aerogels are expected for GO due to the presence of functional groups on the surface
lightweight materials that exhibit extremely low density, high specific of the GO layer, which provides more opportunities for GO layers to in-
surface area and high porosity. They have drawn significant attention teract with adsorbates. And also, the large aspect ratio and good me-
in the past decades. The potential application fields of aerogels are var- chanical properties can be obtained through the oxidation of graphite
ious, including catalyst supports, sorption materials, thermal super-in- layers, which result in a good structure stability for the aerogel. In addi-
sulators, and electrical and insulating materials [1–6]. To date, tion, a certain thermal or electrical conductivity is maintained for GO
different kinds of aerogels, including silica-based aerogels [7,8], metal after oxidation, which makes the GO-based aerogel sensitive to the cer-
oxides-based aerogels [9], carbon-based aerogels [10,11] and polymeric tain stimulus. Consequently, the properties of GO-based aerogels can be
aerogels [12], have been developed, and some of them have been com- well controlled [16–20].
mercially used. Recently, it has been proposed that aerogels are possibly Generally, the organic dyestuffs can be adsorbed on GO layers main-
the most appropriate material in waste water treatment due to their ly through a hydrogen bonding, charge attraction or π-π interaction be-
structural characteristics, especially the porous structure [13–15]. tween the functional groups of dyestuffs and the polar groups of GO
Among all kinds of aerogel materials, graphene or graphene oxide layers, including carboxyl, hydroxyl, and epoxy groups [23–25]. The
heavy metal ions, which are positively charged, can be adsorbed on
⁎ Corresponding author. the negatively charged GO layers through the charge attraction and
E-mail address: yongwang1976@[Link] (Y. Wang). complexation effect between them [26,27]. The adsorption mechanism

[Link]
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188 J. Dai et al. / Materials and Design 107 (2016) 187–197

of GO aerogel for oils is mainly related to the siphoning effect caused by 2. Experimental section
the porous structure of the aerogel and the good compatibility between
chains of oils and hydrophobic C\\C structure of GO layers [18,28]. 2.1. Material
However, during the waste water treatment, there is an inevitable prob-
lem that the three dimensional (3D) porous structure of the GO aerogel Graphite was obtained from Qingdao Heilong Graphite Co., Ltd.
could collapse due to the intrinsic fragility characteristic of the GO Poly(vinyl alcohol) (97%, n = 1788 ± 50) was purchased from Kelong
aerogel and the strong interaction between GO layers and solvent mol- chemicals, Chengdu. All the dyes and solvents are analytical reagents.
ecules [29,30]. This problem limits the cyclic utilization of GO aerogel to
a great degree and even causes the secondary pollution to the water en- 2.2. Preparation of PVA-supported GO aerogels
vironment. Therefore, the structure stability in solvents and the me-
chanical strength are important issues for the practical application of Graphene oxide was prepared through the oxidation of graphite in
GO aerogels. Many chemical and physical strategies have been devel- our lab according to the modified Hummer's method [37]. The corre-
oped to enhance the stability and mechanical strength of the GO aerogel sponding data of the GO can be seen in our previous work and the con-
[16,23,29,31–34], including introducing cross-linking agents [29,31], tent of functional groups was about 34.59% [38]. PVA-supported GO
metal or metal oxide nanoparticles [32], layered double hydroxides aerogels were prepared through solution blending and subsequent
[23], nano-fibrillated celluloses [33], carbon nanotubes [16,34], etc. freeze drying. Firstly, PVA powders with different masses of 0.2 g,
Among which adding the cross-linking agent is a relatively simple and 0.5 g and 1 g were dissolved into 50 mL distilled water at 50 °C to
efficient method. The cross-linking agent can adhere on the GO layers form an homogeneous solution. Then GO/water solutions with different
and connect GO layers with adjacent ones, while the aggregation of volumes (containing 0.5 g GO and 0.1 g GO) were poured into PVA/
cross-linking agent endows them with relatively high strength and sta- water solutions with violent stirring to obtain the GO/PVA mixing solu-
bility. Therefore, the 3D porous structure of the GO aerogel can be stabi- tions with different PVA contents and GO concentrations at room tem-
lized or strengthened to a great degree [29]. However, it should be perature. The mixing solutions were casted into the culture dishes and
noticed that GO layers are partially covered by cross-linking agent, pre-frozen in the refrigerator at − 7 °C for 24 h. Finally, the freezing
which might discount the adsorption efficiency of the GO aerogel, espe- GO/PVA hybrids were transferred to the freeze drying machine FD-1A-
cially when the cross-linking agent doesn't exhibit any adsorption abil- 50 (Boyikang, China) for 36 h, which leaded to the formation of the po-
ity. And also, the preparation process is not environmentally friendly rous structure through the sublimation of water. Finally, PVA-supported
with high cost, which limits the practical production to a great degree. GO aerogels can be obtained. In addition, for comparison, GO aerogels
So, it is of important significance to find a novel method to prepare without PVA were also prepared through the same process. According
an efficiently adsorptive and highly solvent-stable GO aerogel to sat- to the incorporating mass of GO and PVA, aerogels were named 0.1GO,
isfy the application demands. Specifically, although the structure sta- 0.1GO/0.2PVA, 0.1GO/0.5PVA, 0.1GO/1PVA, 0.5GO, 0.5GO/0.2PVA,
bility of the GO-based aerogel in solvents has aroused some 0.5GO/0.5PVA and 0.5GO/1PVA.
researchers' interest, the corresponding research is relatively little.
So far, there is a lack of comprehensive investigations about the 2.3. Wide angle X-ray diffraction (WAXD)
structure stability of GO-based aerogel in different solvents. Factual-
ly, this is a very important issue that needs to be considered before The microstructures of GO aerogels were investigated using a wide
the application of GO-based aerogel in waste water treatment be- angle X-ray diffraction (WAXD, PANalytical X'pert PRO diffractometer
cause the structure collapse may lead to the second contamination with Ni-filtered Cu Kα radiation, the Netherlands). The continuous
to the water environment. scanning angle range was set from 5° to 35° and the measurement
In this work, a few amount of poly(vinyl alcohol) (PVA) is intro- was carried out at 40 kV and 40 mA. The layer spacing GO layers was de-
duced into the solution of GO and it is expected that PVA could ex- duced through Bragg equation according to the variations of character-
hibit the role of the cross-linking agent, supporting the 3D porous istic diffraction peaks.
structure of GO aerogel in the solvent. The use of PVA is based on
the following aspects. First, PVA is a kind of water-soluble polymer 2.4. Scanning electron microscopy (SEM)
and it can be homogeneously mixed with GO in water. Therefore,
the preparation process for the GO aerogel is relatively simple and The morphologies of GO aerogels before and after adsorption were
environmentally friendly. Second, amounts of hydroxyl groups on characterized using a scanning electron microscope (SEM) Fei Inspect
PVA chains may interact with polar groups on GO layers, which re- (FEI, the Netherlands) with an accelerating voltage of 20.0 kV. Before
sults in the strong adhesion of PVA chains on GO layers. Consequent- SEM characterization, all the samples were sputter-coated with a thin
ly, it can be expected that PVA chains may have a stabilizing and layer of gold.
separating effect on the GO network structure. Third, ample hydrox-
yl groups on PVA chains might provide extra adsorption sites for con- 2.5. Fourier Transform infrared spectroscopy (FTIR)
tainments, which possibly compensate the negative effect on the
adsorption efficiency caused by the physical coverage of PVA chains A Fourier transform infrared spectroscope (FTIR) spectrometer iS50
on GO layers. So far, many researchers have been carried out to pre- (Thermo Nicolet, USA) was used to investigate the interaction between
pare the PVA/GO hydrogel and the main attention is focused on the dye molecules and aerogels. Allowing for absorption coefficient differ-
strengthening effect of GO on PVA hydrogel [35,36]. However, less ences with respect to various FTIR bands, a transmission mode with a
work is focused on the PVA/GO aerogel, especially for the GO aerogel resolution of 4 cm−1 was used. Before characterization, PVA/MB, PVA/
supported by PVA. With advantages above, different contents of PVA CR, GO/MB, GO/CR, pure PVA and pure GO mixtures were prepared
are incorporated into GO/water solution and PVA-supported GO with the solution method and then dried at 70 °C for 24 h. The obtained
aerogels are obtained through the environmentally friendly freeze- membranes were used for FTIR measurements to investigate the inter-
drying process. The structure stability in different solvents, the ad- action between the corresponding components.
sorption abilities for different dyestuffs and the oil/water separation
ability of the PVA-supported GO aerogels are systematically investi- 2.6. Measurement of solvent stability
gated. Specifically, to the best of our knowledge, this is the first work
that focuses on systematically investigating the structure stability of In this work, three kinds of solvents were selected as the probing sol-
GO-based aerogel in different solvents. vents including ethanol, water and cyclohexane. The as-prepared
 J. Dai et al. / Materials and Design 107 (2016) 187–197 189

aerogels were cut into a square block with the size of about 2 cm porosities are successfully prepared in our work. And also, the mean
(length) × 2 cm (width) × 0.8 cm (height). The square aerogels were pore sizes and pore size distributions of certain samples are measured
then immersed into the solvent with slight stirring and maintained in and shown in Fig. S1 (a), (b) and (c). It can be concluded that the
the solvent for 5 min. Photographs of macrostructures of aerogels in sol- PVA-supported GO aerogels have smaller pore sizes (71–75 μm) than
vents were taken and compared. After immersing, the aerogels were that of GO aerogels (86 μm), which indicates that denser structures
dried at room temperature and the final macrostructures of aerogels can be obtained for PVA-supported GO aerogels due to the connecting
were also recorded by taking photographs. effect of adsorbed PVA chains on GO layers. As shown in Fig. S1 (d),
the weak interaction through hydrogen bond between GO and PVA
2.7. Measurement of adsorbability for different dyes can be found due to the shift of the peak at 3378 cm−1(\\OH stretching
vibration) [39]. Meanwhile, the disappearance of the peak at 1641
Congo red (CR) and Methylene blue (MB) were selected for the in- (C_C stretching vibration) [39] for GO indicates that the GO layers
vestigations on the adsorbability of aerogels. The aerogels were cut can be covered by PVA chains during the sample preparation. In order
into a square block with the size of around 1 cm (length) × 1 cm to illustrate the microstructures of different aerogel.
(width) × 0.8 cm (height) and weighed carefully. Then the aerogel materials, wide angle X-ray diffraction (WAXD) was used to demon-
blocks were immersed into the 4 mL CR/ethanol and MB/ethanol solu- strate the effect of PVA on the exfoliation of GO layers. As is shown in Fig.
tions with the concentrations of 40 mg/L and 25 mg/L and maintained 1a, the 0.1GO and 0.5GO aerogels show the apparent diffraction peaks at
in solutions for 48 h. Then aerogels were taken out and the residue 2θ of 9.0° and 9.4°, and the interlayer spacing is calculated as 0.99 nm
amount of dye molecules in the solution was detected using a UV–Vis and 0.95 nm according to the Bragg equation, respectively. For the
Spectroscope UV-1800PC (SPECTROPHOTOMETER, Japan). The detect- PVA-supported GO aerogels, the variation of the GO microstructure is
ing wavelength range was 400 to 700 nm. Moreover, the pure solutions dependent upon GO concentration and PVA content. The 0.1GO/
with different concentrations were also detected in order to obtain the 0.2PVA aerogel exhibits no characteristic peak in the WAXD profile
standard curves of adsorption intensity versus solution concentration, while the 0.5GO/0.2PVA aerogel exhibits the characteristic peak at
which was used to calculate the adsorption efficiency and adsorption 7.0°, representing the interlayer spacing of 1.26 nm. Further increasing
amount. The adsorption efficiency (AE) was calculated according to the content of PVA leads to the shift of characteristic peak of GO to
the following equation: lower 2θ values and the characteristic peak completely disappears for
the 0.5GO/1PVA aerogel. This indicates that PVA exhibits a role to exfo-
C 0 −C A liate GO layers possibly due to the interaction between PVA and GO
AE ¼  100% ð1Þ
C0 layers and the diffusion of the chains of PVA into the layers of GO during
the sample preparation process, which can also verified by the FTIR re-
where C0 and CA represented the concentration of dye before and sults (Fig. S1(d)). Chem MX et al. prepared GO aerogel from an aqueous
after adsorption, respectively. The adsorption amount can be deter- solution and the result demonstrated that the interlayer spacing of GO
mined according to the following equation: was 0.74 nm [40]. It can be seen that the physical blending with
water-soluble polymers in aqueous solution is an efficient way to exfo-
ðC 0 −C A ÞV liate GO layers in the aerogel. This is very significant since it can greatly
AA ¼ ð2Þ
Mg increase the specific surface area of GO aerogels.
The morphologies of aerogels were characterized by scanning elec-
where V represented the volume of dye solution and Mg is the mass tron microscopy (SEM) measurements. As shown in Fig. 1b, the 0.1GO
of the aerogel. For the investigations on the adsorption selectivity, six aerogel exhibits a loose and porous morphology. However, in the
kinds of dye/water solutions with the concentration of 40 mg/L (MB, 0.1GO/0.2PVA aerogel, the GO layers are connected due to the adhesion
MG, NR, CR, ES and ABK) were selected for measurements. The measur- of PVA molecular chains on the surface of GO layers (Fig. 1c), which can
ing process is in accordance with the process above. The selected six be verified by morphologies obtained at relatively higher magnifica-
kinds of dyes are Congo red (CR), Methylene blue (MB), Malachite tions (Fig. 1d), in which one can clearly observe a thin layer of PVA
green (MG), Neutral Red (NR), Acid chrome blue k (ABK) and Eosin film on the GO surface. Meanwhile, SEM images of the 0.5GO/0.2PVA
(ES). aerogel are shown in Fig. S2. The porosity of the 0.5GO/0.2PVA aerogel
becomes smaller compared with the 0.1GO/0.2PVA aerogel, and partial
2.8. Oil/water separation GO layers assemble to a certain degree possibly due to the high content
of GO. Similarly, the deposition of PVA film on GO surface can be clearly
Cyclohexane was used as the probing solvent for oil/water separa- observed. Due to the deposition of PVA film on GO surface, one can also
tion. Firstly, the Sudan red/cyclohexane solution was pure into the see that although the interlayer spacing is increased and the exfoliated
water in a beaker and the stratification happens with the Sudan red/cy- GO structure is achieved, the GO layers become less transparent in the
clohexane solution on the water surface. Then the aerogel block was put PVA-supported GO aerogel compared with the pure GO aerogel.
into the beaker and absorbed the solution on the water surface. The ab-
sorption process was recorded by taking photographs and videos. In ad- 3.2. Structure stability and mechanical stability
dition, the adsorbability for different solvents was also measured. The
weighed aerogel blocks were put into different solvents and maintained As an adsorptive material that is expected to apply in the waste
for 5 min. After complete absorption, the wet aerogel blocks were water treatment, the stability of GO aerogel in different solvents is an
weighed again and the absorption amount can be calculated. important criteria to assess its practical application value. In this work,
three different solvents, including ethanol, water and cyclohexane,
3. Results and discussion were chosen to test the stability of all the aerogel materials. Fig. 2 and
Fig. S3 show the macrostructure changes of GO aerogels before and
3.1. Microstructures and morphologies of aerogels after being immersed into different solvents. Fig. 2a shows the initial
square shape of GO aerogels and PVA-supported GO aerogels before im-
The measured densities are ranged from 0.009 g/cm3 to 0.034 g/cm3 mersing into solvents. After being immersed into ethanol for 5 min (Fig.
and the porosities are above 95% for PVA-supported GO aerogels with 2b and Fig. S3a), severe structure collapse and volume shrinkage are ob-
different PVA contents and GO concentrations as shown in Table S1. served for the 0.1GO and 0.5GO aerogels, which indicates that the stabil-
This demonstrates that the ultra-light aerogels with ultra-high ity of pure GO aerogel in ethanol is rather poor. However, only a slight
190 J. Dai et al. / Materials and Design 107 (2016) 187–197

Fig. 1. (a) WAXD profiles showing the microstructure of different GO aerogels as indicated in the graph, (b, c) SEM images showing the morphologies of the 0.1GO and 0.1GO/0.2PVA
aerogels, respectively, and (d) morphology of the 0.1GO/0.2PVA aerogel obtained at relatively higher magnifications.

structure shrinkage happens for all the PVA-supported 0.1GO aerogels solvents. Moreover, Fe3O4/graphene [41], reduced GO [40], rGO/Poly(-
and nearly no changes are observed for PVA-supported 0.5GO aerogels. acrylic acid) [29], Poly(vinyl alcohol)/Cellulose nanofibrils/GO [33],
This demonstrates the good stability of PVA-supported GO aerogel in GO/layered double hydroxides [23] and graphene/Cellulose [42]
ethanol. Furthermore, one can see that increasing PVA content and/or aerogels are less stable in water, and Graphene/polystyrene/Fe3O4
GO concentration facilitate the enhancement of stability. After being im- [43], functionalized-rGO [44] and nitrogen-doped graphene [45]
mersed into water (Fig. 2c and Fig. S3b), the structures of 0.1GO and aerogels are stable in organic solvents with no detailing researches
0.5GO aerogels collapse severely and they cannot be taken out from about their stabilities in water carried out. Therefore, it can be conclud-
water. This can be attributed to the high hydrophilicity of GO layers ed that, compared to the reported works, the highest stability in differ-
and consequently, the GO layers of the aerogel easily disperse into ent solvents endows the obtained PVA-supported GO aerogel with the
water again. Meanwhile, the PVA-supported 0.1GO aerogels shrink highest application value in the field of waste water treatment.
into thin planes and the PVA-supported 0.5GO aerogels deform severely To further illustrate the stability of GO aerogels in different solvents,
except the 0.5GO/0.2PVA aerogel, which still exhibits an excellent sta- schematic diagrams are proposed and shown in Fig. 2e and 2f. For pure
bility in water. It should be noticed that all the PVA-supported GO GO aerogels, the molecules of polar solvents (water or ethanol) can in-
aerogels are less stable in water than in ethanol due to the presence of teract with the polar groups on the surface of GO layers through the hy-
water-soluble PVA. Finally, the stability of all the GO aerogels in cyclo- drogen bonding interaction, which leads to the destruction of the GO
hexane is investigated (Fig. 2d and Fig. S3c). One can see that the struc- network structure that formed through the weak Van der Waals' force
tures of all the GO aerogels are more stable in cyclohexane than in other and physical assembling. Therefore, the 0.1GO and 0.5GO aerogels are
solvents. The results demonstrate that the proper incorporation of PVA not stable in these polar solvents. For the PVA-supported GO aerogels
and higher GO concentration are in favor of stabilizing the 3D porous (Fig. 2f), the deposition of PVA film on the surface of GO layers connects
structure of the GO aerogel materials. the adjacent GO layers on one hand. On the other hand, the functional
To better understand the structure stability of the PVA-supported groups of GO layers interact with the polar groups of PVA chains,
GO aerogels, a series of typical graphene or GO-based aerogels that which reduces the probability of interaction between functional groups
have been reported in literatures are chosen and their stabilities in of GO layers and solvent molecules. However, more or less PVA is unfa-
water and organic solvents are analyzed according to photographs and vorable for the stability of the PVA-supported GO aerogels due to the
experimental data provided by researchers. As shown in Table 1, the water-soluble characteristic of PVA. At an appropriate concentration
PVA-supported GO aerogel developed in this work exhibits the highest ratio, the interaction between GO and PVA exceeds the interactions be-
structure stability in both water and organic solvents, while the neat GO tween GO and solvent and between PVA and solvent. Moreover, when
aerogel exhibits the lowest structure stability. Factually, the neat GO GO aerogels are immersed into the non-polar solvent (cyclohexane),
aerogel cannot keep stable in water and organic solvents. Consequently, only the weak interaction exists between the non-polar solvent mole-
the 3D structure is completely destroyed and GO layers disperse into the cules and GO layers due to the weak compatibility between GO and
 J. Dai et al. / Materials and Design 107 (2016) 187–197 191

Fig. 2. (a–d) The photographs showing the macro-morphologies of all the aerogels before (a) and after immersing in (b) ethanol; (c) water; (d) cyclohexane; (e) and (f) the schematic
diagrams showing the microstructure changes of GO aerogels and PVA-supported GO aerogels in solvents.

non-polar solvent molecules, while there is nearly no interaction be- compressed, demonstrating the compressible characteristic of GO
tween non-polar solvent molecules and PVA chains. Therefore, pure aerogel as widely reported in the literatures [19,47,48]. After removing
GO aerogel exhibits a slight shrinkage in the non-polar solvent due to the load, the shape of the 0.5GO aerogel is partially recovered. Further-
the intrinsic amphiphilic characteristic [45,46], while all the PVA-sup- more, one can observe the peeling of some GO layers from the aerogel.
ported GO aerogels exhibit higher stability than that in the polar sol- The results demonstrate that the 3D porous structure of pure GO aerogel
vent, such as water and ethanol. It is worth noting that the higher GO is partially destroyed under the loading condition. However, for the
concentration can enhance the stability of the GO aerogel in both 0.5GO/0.5PVA aerogel, at the same loading condition, the degree of
polar and non-polar solvents. compression is smaller than that of the 0.5GO aerogel, which demon-
In addition, a compressing experiment was carried out to further strates the reinforcing effect of PVA on GO aerogel. Specifically, after re-
confirm the reinforcing and stabilizing effects of PVA on GO aerogels. moving the load, the shape of the aerogel is completely recovered.
As shown in Fig. 3, at the load of 600 N, the 0.5GO aerogel is completely Obviously, the 3D porous structure of GO aerogel is supported and
192 J. Dai et al. / Materials and Design 107 (2016) 187–197

Table 1 adsorption efficiency, which is shown in Fig. S6, can be calculated ac-
Comparison of solvent resistance in water and organic solvent between the PVA-support- cording to the UV–Vis curves (Fig. S4a) and standard curve of solution
ed GO aerogel and other GO-based or graphene-based aerogels reported in literatures.
(++) the highest structure stability, (+) the moderate structure stability, (−) the low
concentration (Fig. S5). It can be seen that pure GO aerogel exhibits ad-
structure stability, and (−−) the lowest structure stability. sorption efficiency of about 88%. Although PVA-supported GO aerogels
exhibit relatively lower adsorption efficiency compared with the pure
Aerogel Water Organic solvent
GO aerogel, increasing GO content enhances the adsorption efficiency
This work of the PVA-supported GO aerogels. For example, the 0.5GO/0.5PVA
(0.5G/0.2PVA) ++ ++
aerogel still exhibits the adsorption efficiency of 75%. Third, according
GO − −
Graphene/Fe3O40 − Not reported to the calculating results (Fig. S6), for the PVA-supported GO aerogels
4
Reduced GO (rGO)41 − Not reported with same GO concentration, the CR adsorption efficiency increases
rGO/poly(acrylic acid)29 − Not reported with increasing PVA content. The adsorption mechanism of the PVA-
Poly(vinyl alcohol)/cellulose supported GO aerogel for CR can be explained as follows. On one
Nanofibrils/GO33 − Not reported
GO/layered double hydroxides23 + Not reported
hand, CR molecules can be adsorbed on GO layers due to the hydrogen
Graphene/cellulose42 + ++ bonding interaction and π-π conjugation interaction between them,
Graphene/polystyrene/Fe3O43 4 Not reported + which can be confirmed by the results obtained through Fourier trans-
Functionalized-rGO44 Not reported ++ form infrared spectroscopy (FTIR) measurements as shown in Fig. 4b.
Nitrogen-doped graphene45 Not reported ++
The peaks at 3392 cm−1 and 3464 cm−1 represent O\\H stretching vi-
bration for GO and N\\H stretching vibration for CR. [49,50] The corre-
sponding peak for GO/CR shifts to 3370 cm−1, which indicates the
stabilized by PVA. Therefore, it can be concluded that PVA-supported hydrogen bonding interaction between them. Meanwhile, the peaks at
0.5GO aerogels are more stable both in various solvents and under load- 1607 cm−1(N_N stretching vibration) [50] for CR and 1641 cm− 1
ing and can be regarded as good candidates for the waste water (C_C stretching vibration) [51] for GO overlap and shift to
treatment. 1593 cm− 1 for GO/CR. Also, the peaks ranged from 690 cm− 1 to
830 cm−1 (out-of-plane deformation of aromatic ring) [51] for CR dis-
3.3. Absorption performance for organic dyes appear. These changes indicate that the π-π conjugation interaction ex-
ists between CR and GO. In addition, previous WAXD profiles
For materials applied in the field of waste water treatment, the demonstrate that the incorporation of PVA exfoliates the GO layers,
adsorbability or the adsorption efficiency is the most important proper- which increases the aspect surface area of the aerogels. Consequently,
ty that should be paid attention to. In this work, the adsorbability of CR molecules have more chances to approach the GO layers of the
pure GO and PVA-supported GO aerogels for different dyes was investi- aerogel and can be adsorbed more efficiently. On the other hand, the
gated and the corresponding adsorption mechanisms were proposed. charge repulsion between GO and CR is weakened because the nega-
From Fig. 4a it can be seen that the 0.1GO and 0.5GO aerogels can ad- tively charged surfaces of GO aerogels are covered by PVA chains,
sorb the CR more efficiently, but the structures of both aerogels cannot which makes it easier for CR molecules to be adsorbed on the aerogel.
keep stable in the solution, which greatly discounts their application Meanwhile, PVA chains adhered on the GO layers can also adsorb
value in waste water treatment. In terms of PVA-supported GO aerogels, some CR particles through the hydrogen bonding interaction between
at least three conclusions can be obtained. First, all the PVA-supported S-containing groups of CR and C\\OH groups on PVA chains, which
GO aerogels can keep stable in solutions as shown in Fig. 4a. Second, can be demonstrated by the disappearance of the absorption peak at
higher GO concentration leads to higher CR adsorption efficiency due 1123 cm−1 (S_O stretching vibration) [49,51] for CR and peaks at
to more adsorption sites in the aerogels, which can be verified through 1256 cm−1 and 1050 cm−1 (C\\OH stretching vibration) for PVA [52,
the variations of solution color as shown in Fig. 4a and the UV–Vis ab- 53]. To further confirm the results, the surface morphology of the
sorption intensity of solution as shown in Fig. S4. Moreover, the 0.5GO/0.2PVA aerogel after adsorption was characterized using SEM.

Fig. 3. Photographs showing the original shape (a, d), compressed states (b, e), and shapes after removing load (c, f) of the 0.5GO aerogel (a, b, and c) and the 0.5GO/0.5PVA aerogel (d, e
and f). The load is 600 N.
 J. Dai et al. / Materials and Design 107 (2016) 187–197 193

Fig. 4. (a) Photographs showing the color changes of CR/ethanol solution 1: before adsorption and after absorbed by 2: 0.1GO, 3: 0.1GO/0.2PVA, 4: 0.1GO/0.5PVA, 5: 0.5GO, 6: 0.5GO/
0.2PVA, 7: 0.5GO/0.5PVA, and 8: 0.5GO/1PVA aerogels; (b) FTIR spectrums indicating the interaction between CR and aerogels; (c) and (d) SEM images showing the adsorption and
dispersion of CR particles on the surface of GO.

As shown in Fig. 4c and d, besides the homogeneous dispersion of most shift of the absorption peak at 1330 cm− 1 (–CH3 stretching vibra-
CR particles on the surface of GO layers (Fig. 4c), some CR aggregates, tion) to 1282 cm− 1 [54], and the strong π-π conjugation interaction,
which are formed through the adsorption of CR on PVA film, can be which can be deduced by the disappearance of the absorption peak
also differentiated (Fig. 4d). The results above demonstrate that both at 1599 cm− 1 (aromatic ring stretching vibration) [54] and absorp-
GO layers and PVA chains can interact with CR molecules and conse- tion peaks from 790 cm− 1 to 884 cm− 1 (aromatic plane vibration)
quently, good adsorbability for CR molecules is obtained for the PVA- [55] as shown in Fig. 5b. Meanwhile, only weak hydrogen bonding
supported GO aerogels, among which PVA-supported 0.5GO aerogels interaction between MB and PVA chains exists, which is deduced
have relatively high adsorption efficiency around 75% and good struc- by the slight changes of absorption peaks at 1050 cm− 1 and
ture stability. 1256 cm − 1 (C\\OH stretching vibration) [52,53]. On the other
Different from CR, the positively charged MB can be adsorbed on hand, the charge attraction between GO layers and MB molecules is
negatively charged GO layers more easily due to the charge attrac- weakened due to the coverage effect of PVA chains on the GO layers.
tion between them. From Fig. 5a it can be seen that the 0.1GO and Consequently, the deposition of PVA film on the GO layers reduces
0.5GO aerogels can adsorb MB more efficiently through the compar- the adsorbability of GO aerogel for MB to a great degree, although
ison of solution colors, but the structure collapse still happens for GO layers can be exfoliated by PVA chains. With the results above,
both aerogels. Meanwhile, two similar tendencies are obtained for it can be concluded that good adsorbability for MB is obtained for
MB comparing to CR. First, good structure stability in the solution is all the GO aerogels, among which the 0.5GO/0.2PVA aerogel is the
obtained for all the PVA-supported GO aerogels. Second, higher GO most proper candidate for waste water treatment with the relatively
concentration leads to higher MB adsorption efficiency, which can high adsorption efficiency over 90% and good structure stability.
also be further verified according to the UV–Vis curves (Fig. S3b) Furthermore, the adsorption thermodynamics is investigated with
and the calculation results of the adsorption efficiency (Fig. S5 and the 0.5GO/0.2PVA aerogel and MB as the adsorbent and adsorbates, re-
Fig. S6). The adsorption efficiency of pure GO aerogel for MB is as spectively. The Langmuir adsorption constant band the maximum ad-
high as 96%. However, for PVA-supported GO aerogels with the sorption amount xm (mg/g) can be estimated from the linear fitting
same GO concentration, the increase of PVA content leads to the de- curve (Fig. 5d) of 1/qe vs. 1/Ce according to the Langmuir adsorption
crease of adsorption efficiency for MB, which is extremely different model [56,57]:
from CR. For example, the adsorption efficiency is decreased from
90% of the 0.5GO/0.2PVA aerogel to 61% of the 0.5GO/1PVA aerogel. 1 b 1
¼ þ ð3Þ
On one hand, MB molecules can be adsorbed on GO layers through qe C e xm xm
hydrogen bonding interaction, which can be deduced by the red
194 J. Dai et al. / Materials and Design 107 (2016) 187–197

Fig. 5. (a) Photographs showing the color changes of MB/ethanol solution 1: before adsorption and after absorbed by 2: 0.1GO, 3: 0.1GO/0.2PVA, 4: 0.1GO/0.5PVA, 5: 0.5GO, 6: 0.5GO/
0.2PVA, 7: 0.5GO/0.5PVA, and 8: 0.5GO/1PVA aerogels; (b) FTIR spectrums indicating the interaction between MB and aerogels; (c) SEM image showing the adsorption and dispersion
of MB particles on the surface of GO layers; and (d) Langmuir fitting curves for MB adsorbed by the 0.5GO/0.2PVA aerogel.

where qe is the equilibrium adsorption amount of dyes (mg/g), Ce is mainly through two ways: the hydrogen bonding interaction between
the equilibrium concentration in the aqueous solution (mg/mL). And CR molecules and GO layers or PVA chains, and the π-π conjugation in-
then, the free energy of adsorption ΔGθ (kJ/mol) can be estimated ac- teraction between CR molecules and GO layers. Meanwhile, MB mole-
cording to the following equation [58]: cules can be adsorbed on the GO aerogel mainly through the
hydrogen bonding interaction, π-π conjugation interaction and charge
ΔGθ attraction between MB molecules and GO layers, and also PVA chains
logb ¼ þ 1:74 ð4Þ
2:3RT can weakly interact with MB molecules. Consequently, CR molecules
can be adsorbed on both GO layers and PVA chains, while MB molecules
where R is the gas constant, and T is the experimental temperature are mainly adsorbed on the GO layers. And also, different adsorption ef-
(K). Consequently, xm and ΔGθ are estimated to be 127.5 mg/g and ficiencies are obtained due to the different degrees of interactions.
− 3.82 kJ/mol, respectively. The negative low value of ΔGθ indicates To further investigate the role of PVA-supported GO aerogels in
that the adsorption for dyes is a spontaneous process and it is controlled waste water treatment, other dyes were chosen to measure the selec-
by relatively weak physical interaction between the aerogel and dye tive adsorption of aerogel as prepared. Here, the 0.5GO/0.2PVA aerogel
molecules [56]. Moreover, the adsorption amount (mg/g) of different was selected because of its relatively higher adsorption efficiency
aerogels for CR and MB at a certain dye solution concentration are calcu- among all the PVA-supported GO aerogels. As is shown in Fig. 7a, differ-
lated and shown in Fig. S7. Considering the structure stability, it can be ent color changes can be obtained for different dyes. For the NR, MB and
deduced that the 0.5GO/0.2PVA aerogel has the highest adsorption MG, colors of solutions become lighter obviously after adsorption. While
amount. There are at least two points that need to be noticed. First, all for ABK and ES, less obvious color variations can be observed after ad-
the aerogels exhibit relatively higher adsorption mass for CR possibly sorption. Specially, the color of CR solution shifts from red to light blue
due to the higher molecular weight of CR compared with MB. Second, after adsorption, which can be attributed to the decreasing pH value
PVA-supported GO aerogels exhibit relatively lower adsorption ability caused by \\COOH groups on the surface of GO layers [59]. According
compared with the pure GO aerogels. to UV–Vis measurements (Fig. S7), the adsorption efficiencies for differ-
To better understand the different adsorption mechanisms of GO ent dyes were calculated as shown in Fig. 7b. It can be seen that higher
aerogels for CR and MB, different schematic representations are pro- adsorption efficiencies of over 96% are obtained for NR, MB and MG,
posed according to the results above, which are shown in Fig. 6. In the while relatively lower efficiencies of 81.6%, 8.1% and 36.7% for ES, ABK
present work, PVA-supported GO aerogels consist of the GO skeleton and CR, respectively. Through the comparison of the chemical structures
and the deposited PVA film, which exhibits the reinforcement effect of different dye molecules as shown in Fig. S8, it can be deduced that the
for GO skeleton structure. Both GO and PVA exhibit adsorption behav- adsorption selectivity of the PVA-supported GO aerogel is mainly relat-
iors for CR and MB. CR molecules can be adsorbed on the GO aerogel ed to the static electrical property of the dye molecules. NR, MB and MG
 J. Dai et al. / Materials and Design 107 (2016) 187–197 195

Fig. 6. Schematic diagrams showing the interactions between dye molecules (CR and MB) and the PVA-supported GO aerogels.

molecules are positively charged and ABK and CR molecules are nega- 3.4. Oil/water separation performance
tively charged, while positive and negative charges coexist on the ES
molecules. For the reason that GO layers are negatively charged, the ad- Although the hydrophobic and oleophilic characteristics of GO is less
sorption efficiencies of GO aerogels are in the order of NR, MB and apparent compared with graphene, the residue hydrophobic structure
MG N ES N ABK and CR. Especially for ABK, a large amount of negative still endows GO with excellent adsorption ability for oils and organic
charges on the ABK molecules provide the strong charge repulsion solvents and therefore, GO aerogels still can be used in oil/water separa-
against the GO layers, which leads to the extremely lower adsorption ef- tion [18,28]. For example, the oil contaminants on the sea water surface
ficiency of aerogel. In addition, the adsorption efficiency for different can be absorbed by GO aerogels, which makes them an ideal candidate
dyes is also influenced by the hydrogen bonding interaction, π-π conju- material for eliminating spilled oils and other organic pollutants. In this
gation interaction and so on, which have been investigated above. work, GO aerogels is partially covered by the hydrophilic PVA film,

Fig. 7. (a) The photograph showing the adsorbability of the representative 0.5GO/0.2PVA aerogel for different dye solutions and (b) their corresponding adsorption amounts.
196 J. Dai et al. / Materials and Design 107 (2016) 187–197

Fig. 8. Photographs showing the process that cyclohexane is absorbed into the 0.1GO/0.2PVA aerogel in a short time.

which possibly reduces the hydrophobic characteristic of GO aerogels obtain the versatile GO aerogel, which has a great potential in the field
and therefore, it is interesting to ask whether the PVA-supported GO of waste water treatment.
aerogels still exhibit high efficiency in oil/water separation or not. To Supplementary data to this article can be found online at [Link]
clarify the doubt, the oil/water separation measurement was also car- [Link]/10.1016/[Link].2016.06.039.
ried out with the stable PVA-supported GO aerogels. Firstly, the absorp-
tion masses of the representative 0.1GO/0.2PVA aerogel for different
solvents, including ethanol, cyclohexane, N,N-dimethylformamide Acknowledgments
(DMF) and dichloroethane, were measured and the mass ratio of
absorbed solvents to aerogel are shown in Fig. S9. It can be seen that Authors express their sincere thanks to the National Natural Science
the PVA-supported GO aerogel exhibits excellent adsorption ability for Foundation of China (51473137 and 51203129). Prof. Jin Wang (South-
different solvents as investigated. The masses of adsorbed solvents are west Jiaotong University) was greatly appreciated for the useful
about 120–200 times higher than the mass of aerogel. And then, the discussion.
representative 0.1GO/0.2PVA aerogel was used to adsorb the Sudan
red/cyclohexane solution on the water surface. It can be seen from Fig.
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