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Constructing multifunctional MOF@rGO

Cite this: J. Mater. Chem. A, 2017, 5,
hydro-/aerogels by the self-assembly
11873 process for customized water remediation†
Jiajun Mao,a Mingzheng Ge,ab Jianying Huang,a Yuekun Lai, *a Changjian Lin,c
Keqin Zhang, a Kai Meng*a and Yuxin Tang *b

The development of scalable and reliable three-dimensional macroscopic functional aerogels is of remarkable
significance because of their wide applications in the energy and environmental fields. Although the metal–
organic frameworks (MOFs) have shown promising applications in water remediation, the construction of
MOFs-based aerogels is highly challenging. Herein, for the first time, we report a general strategy for one-
step fabrication of a ZIF-8 MOF/reduced graphene-oxide hydrogel in a short period via self-assembly, with
the synergistic effects of chemical reduction and cross-linking by metal ions; upon drying, the hydrogel
yields the ZIF-8/reduced graphene-oxide aerogel. The highly porous ZIF-8 hybrid aerogel displays high
absorption capacity and cycling stability for oils and organic solvents, due to its superhydrophobic
Received 13th February 2017
Accepted 18th April 2017
properties and high specific surface areas. In addition, the corresponding hydrogel demonstrates
photocatalytic dye degradation ability, as well as excellent water purification performance for removing
DOI: 10.1039/c7ta01343d
toxic dyes, heavy metal ions and benzo pollutants. Our synthetic strategy is proven to be versatile for
rsc.li/materials-a constructing a variety of functional nanocomposite hydro-/aerogels towards customized water remediation.

Water pollution has led to severe environmental problems, and stability and recyclability of MOFs in the presence of water are
threatens human health and sustainable development.1 Nor- a major challenge when considering them for applications in
mally, waste water is complex, with different kinds of pollutants separation, absorption and catalysis.7 Therefore, a mechanical
such as oil, organic solvents, heavy metal ions and dyes, and support with easy recovery for holding the MOFs in water is in
there are challenges associated with the traditional methods high demand. Recently, reduced graphene-oxide aerogels (rGA),
including burning, mechanical collection, photocatalysis and which are composed of three dimensional (3D) interconnected
ltration by membrane or dispersant, for water remediation in reduced graphene-oxide (rGO) frameworks, have been utilized
one-material systems for sustainable development.2 Therefore, in various elds such as capacitors,8 lithium-ion batteries,9
it is desirable to develop a multifunctional material for catalysts,10 sensing,11 and water purication,12 due to their
customized water remediation, which can not only separate oils outstanding photoelectric, mechanical and thermal properties
and organic solvents, but can also remove heavy metal ions and as well as low density and high specic surface area.12,13 This
degraded pollutants from water with easy recovery. renders them as ideal mechanical supports for the MOF mate-
From the perspective of materials, metal–organic frame- rials, and we foresee that MOFs decorated on a 3D ultra-light
works (MOFs), a type of porous crystalline material with merits graphene aerogels can have additional remarkable multifunc-
of ultra-large surface areas (>500 m2 g
1), well-ordered and tional properties such as superhydrophobicity, catalytic activity,
controllable pore sizes, have attracted great interest due to their oil/water separation and metal ion absorption, etc. Although
promising applications in gas storage3 and water purication,4 there are some reports on the hybrid structure of MOFs/gra-
catalysts5 and carbon dioxide capture, etc.6 However, the poor phene14 or MOF aerogels,15 one-step construction of a self-
assembled MOFs-based aerogel with free-standing properties
is rarely explored, especially with respect to catalytic ability and
a
National Engineering Laboratory for Modern Silk, College of Textile and Clothing contaminated water resource reclamation, which require the
Engineering, Soochow University, Suzhou 215123, P. R. China. E-mail: yklai@suda. candidate materials to be easily recovered from water. To this
edu.cn; [email protected]
end, compared to 2D graphene and other adsorbents, 3D rGA
b
School of Materials Science and Engineering, Nanyang Technological University, 50
can be recovered and easily tuned in terms of shape, volume
Nanyang Avenue, 639798, Singapore. E-mail: [email protected]
c
State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University,
and density, making it feasible for scale-up production. Nor-
Xiamen 361005, P. R. China mally, the self-assembly strategies of 3D GA from graphene
† Electronic supplementary information (ESI) available. See DOI: oxide (GO) can be classied as follows: chemical reduction
10.1039/c7ta01343d

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approach, cross-linking agent method, and template-directed KMnO4, then the mixture was constantly stirred in an ice bath.
method. For example, Shi et al. reported the preparation of Aerward, the mixture was kept at 35  C for 5 h, dropped in 150
self-assembled rGO hydrogel via a one-step hydrothermal mL deionized water and then heated to 90  C for 10 min.
process by means of a chemical reduction process.16 Another Finally, the resulting solution was ltered and washed several
self-assembly strategy is to use cross-linking agents, such as times with HCl, water and ethanol, respectively.
cellulose, carbon nanotubes, metal ions, and organic reagents,
to induce the assembly of graphene oxide nanostructures.17
Preparation of zeolitic imidazolate framework-8 (ZIF-8)
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Furthermore, a template-directed chemical vapor deposition

method was also reported for directly synthesizing 3D rGA.18 Herein, 0.256 g Zn(NO3)2$6H2O was dissolved in 25 mL meth-
However, these methods usually require long reaction times (6– anol (denoted as solution A) and 0.56 g 2-methylimidazole was
24 h) and high energy consumption (120–180  C), and induce dissolved in another 25 mL methanol (denoted as solution B),
incomplete reduction and impurities. Moreover, rGA exhibits then solution A was slowly poured into solution B under stir-
low efficiency in heavy metal absorption and photodegradation ring; aer 24 h at room temperature, the solution became
activities. These limitations have strongly motivated us to turbid and the product was washed with methanol three times.
develop a facile approach to prepare an integrated MOFs/rGO
material system with enhanced multifunctionality towards
customized water remediation. Synthesis of 3D rGA/nanoparticles
To address the above challenges, in this work, we report for 12 mL of 1 mg mL
1 GO aqueous solution and 12 mL hydrazine
the rst time, a rapid strategy for one-step construction of hydrate (or 120 mg vitamin C) were mixed in a cylindrical
stable, highly porous and multifunctional MOFs@reduced sample vial, and the solution of 0.8 mL MOFs or metal oxide
graphene-oxide hydrogel composites within a short time (<1 h), (mass ratio 1 : 2) earlier synthesized was poured into the
with synergistic effects of chemical reduction processes and mixture. The vessel was then placed into an electrical oven at
cross-linking by metal ions. Herein, graphene oxide (GO) sheets 95  C for 1 h. Ultimately, the 3D hydrogel was taken out and
act as frameworks and binding sites for the decoration of MOFs washed with deionized water and alcohol, then freeze-dried into
nanoparticles on GO walls. During the chemical reduction an aerogel. For comparison, rGA was fabricated by adding
process of GO, sheets of oxygen-containing groups (hydroxyl reductant or metal oxide only.
and carboxyl groups) are removed, pushing the self-assembly of
GO nanosheets due to the enhancement of p–p stacking
interactions. With the addition of ZIF-8 (Zn2+ source) into the Characterizations
above system with ultrasonic dispersion, free Zn2+ can coordi- The morphology of the aerogel surface was observed by eld
nate to the centers of carboxyl, hydroxyl and epoxy groups of GO emission scanning electron microscope (FESEM, HitachiS-
by metal–oxygen covalent bonding with strong electrostatic 4800) at 3.0 kV. An energy dispersive X-ray spectrometer (EDS)
interaction, and serve as linkers agglomerating GO nanosheets tted to the SEM was applied for elemental analysis. A Kratos
for fast self-assembly. The synergistic effects of chemical Axis-Ultra HSA X-ray photoelectron spectrometer (XPS) was used
reduction and cross-linking agents would signicantly promote to examine the chemical composition with a 100 W AlKa X-ray
the self-assembly process, shortening the reaction time. As source and a base pressure of about 4  10
9 mbar. The
a proof-of-concept study, compared to single rGA aerogel, ZIF-8/ wetting properties of water droplets on the sample surfaces
rGA displayed better mechanical properties and other new were characterized using an optical contact angle meter system
functions given by MOFs. ZIF-8@rGO aerogel frameworks dis- (Krüss DSA100, Germany). The volumes of droplets used for the
played excellent oil absorption and photocatalytic dye degra- static contact angle measurement were 6 mL. The crystal phases
dation ability due to their high specic surface areas. of the samples were characterized by an X-ray diffractometer
Furthermore, the hydro-/aerogel composites also exhibited with CuKa radiation (XRD, Philips, X'pert-Pro MRD). The
a high absorption capacity and cycling stability for oils and Raman spectra were analyzed by A Raman spectrometer
organic solvents, and excellent water resource reclamation (HORIBA JOBIN YVON, HR800). Fourier transform infrared
performance for the removal of toxic dyes, heavy metal ions and (FTIR) spectra were obtained on a Varian Scimitar 1000 spec-
benzo pollutants. More impressively, our approach can be trophotometer with a scan range of 4000–400 cm
1.
extended to a variety of MOFs or metal oxide aerogels, which are
promising for other potential applications; for example,
a Fe3O4/GA with magnetism will guide aerogel adsorbing Oil uptake
organic pollutants and help in recyclability. The absorption capacity of GA/nanoparticles was measured for
various organic liquids with different densities (including
Experimental tetrahydrofuran, dimethylformamide, chloroform, methanol,
acetone, chloromethane, hexane, hexadecane); weights were
Preparation of GO sheets determined before and aer absorption. The capacity was
GO sheets were prepared by a well-known, modied Hummers' calculated by the formula: (Ma
Mb)/Mb, where (Mb and Ma
method. Typically, graphite powder (3 g) was dispersed in 69 mL represent the weights of GA/nanoparticles before and aer
concentrated sulfuric acid, followed by the addition of 9 g absorption, respectively.)

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Photocatalytic measurements nanosheets, shortening the self-assembly time to less than 1 h.

For comparison, under the same conditions, without the addi-
The photocatalytic activity of ZIF-8/rGA was measured by the
tion of ZIF-8 (Zn2+ ion), it was found that nanosheets were
fading of an aqueous solution of methyl blue (MB) with
partially assembled and aggregated together, and the solution
a concentration of 25 mg L
1. A 300 W mercury lamp was used
remained black, indicating that GO nanosheets were still
as the simulated UV source. The distance between the UV
uniformly dispersed in the solution without the formation of
source and samples was 8 cm. Before light illumination, the GA
the 3D hydrogel. With the addition of ZIF-8, free Zn2+ could
was immersed in 15 mL of an aqueous solution of MB in
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a quartz container at room temperature for 6 h to establish coordinate to the –OH and –COOH groups of GO via the metal–
adsorption equilibrium. The concentration of MB was analyzed oxygen covalent or electrostatic interactions,19 and then serve as
linkers for the pre-assembly of GO nanosheets. Aer the reac-
using a UV-Vis spectrophotometer (Hitachi, UV-1080, Japan) at
tion, all graphene oxide nanosheets were reduced to rGO with
a wavelength of 463 nm.
the promotion of p–p stacking, then rGO and nanoparticles
were self-assembled layer-by-layer into the hydrogel. The brown
Water purication
uniform solution gradually turned into a black hydrogel
Pb2+ and Cd2+ were dissolved in deionized water to evaluate the suspension by heating at 95  C for 1 h. Finally, a macro-/
adsorption capacity of 3D porous ZIF-8/rGA aerogel. The aerogel microporous ZIF-8/rGA with high BET surface area (168 m2
was placed into a ask containing 50 mL aqueous solution, then g
1, Fig. S2†) was obtained by freeze drying of the hydrogel, and
removed aer 20, 40, 60, 90, 120, 150, 180, 240, 300, 360 min. the density of synthesized ZIF-8/rGA was around 14  5 mg
Inductively coupled plasma (ICP) spectroscopy was used to cm
3. This process directly decorated the functional ZIF-8 on
measure the concentrations of metal ions. Phthalic acid (H2– the GO and shortened the required duration of further self-
PA) solutions were dissolved in deionized water to obtain the assembly.
desired concentrations, and adsorbents (20 mg) were placed in The morphologies of GO nanosheets, ZIF-8 and the ZIF-8/
the aqueous solutions (50 mL) at pH ¼ 7. The H2–PA concen- rGA nanosheets were studied (Fig. 2). It was found that the
trations were measured based on the absorbance at 280 nm. GO was stacked layer by layer, and exhibited hydrophilicity due
to the abundant oxygen-containing groups (Fig. 2a). The as-
Results and discussion synthesized ZIF-8 with average particle size of about 100 nm
was well-ordered and uniformly dispersed (Fig. 2b), and it was
The rGA/nanoparticles were synthesized by a one-pot approach hydrophobic with a contact angle about 110 , due to the
via self-assembly of rGA and nanoparticles with the synergistic hydrophobic nature of the metal clusters (ZnN4), with imidazole
effects of the chemical reduction process and cross-linking by
metal ions. Here, ZIF-8 was chosen as the representative MOF
for the case study. The schematic illustration is shown in Fig. 1.
During the synthesis process, the prepared ZIF-8 (with the
formula of Zn(2-methylimidazole)2) was rstly dispersed in
methanol, and then added into the mixture of GO nanosheet
aqueous solution and hydrazine hydrate with ultrasonic
dispersion. During the reaction, layered GO nanosheets
(Fig. S1†) were self-assembled by removing hydrophilic groups
(OH, COOH, etc.), with the enhancement of p–p stacking under
reduction with hydrazine hydrate. The generation of free Zn2+
ions promoted the gelation process for self-assembled rGO

Fig. 2 FESEM images of (a) GO nanosheet powder and (b) ZIF-8

nanoparticles. Low-magnification FESEM images of (c, e) rGA, (d, f)
ZIF-8/rGA; (e, f) are the corresponding high-magnification SEM images
Fig. 1 Schematic of the self-assembly mechanism of the rGO and ZIF- of (c, d). The insets in (a, b, e, f) are the images of water drops on the
8 nanoparticles for the formation of ZIF-8/rGO composite hydrogels. surfaces of GO, ZIF-8, GA and ZIF-8/rGA aerogel, respectively.

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linkers and small pore size inhibiting the penetration of water groups bonded to the GO could be reduced by hydrazine
molecules into the pores.20 Aer reduction, rGA and ZIF-8/rGA hydrate.24 Aer reduction, the oxygen contents measured by
exhibited a 3D network structure containing a uniform distri- EDS before and aer the reduction were 26.3% and 8.7%,
bution of macro- and micropores, and ZIF-8 nanoparticles were respectively. These phenomena indicate the reduction of GO
uniformly distributed on the rGO wall (Fig. 2c, e and d, f). and the introduction of ZIF-8 into the rGA. The EDS map clearly
Besides, rGO aerogel became hydrophobic with a contact angle proves the uniform distribution of ZIF-8 nanoparticles on the
of 120 (Fig. 2e), due to the removed oxygen-containing groups, rGO walls (Fig. 3d). From the above result, it can be concluded
Published on 04 May 2017. Downloaded by Auckland University of Technology on 1/28/2019 1:38:26 PM.

while ZIF-8/rGA exhibited superhydrophobicity with a contact that the ZIF-8/rGA composites have been successfully synthe-
angle of about 153 , with the synergistic effects of rGO and ZIF- sized, and rGA has been self-assembled by removing some
8, with more robust micro/nanoscale hierarchical structure.7 hydrophilic groups (epoxy, carboxyl, etc.) with enhancement of
FTIR spectra of ZIF-8, GO, and ZIF-8/rGA are shown in p–p stacking.
Fig. 3a. In contrast to GO, aer reduction, the C]O at 1710 Fig. 4a shows the wide-scan XPS spectra of GO, ZIF-8, rGA
cm
1 disappeared, while Zn–N at 421 cm
1, C–N at 995 cm
1 and ZIF-8/rGA, and the binding energies corresponding to C, N,
and C]N at 1560 cm
1 appeared, illustrating that ZIF-8 was O are located at 285, 398 and 530 eV, respectively. Compared to
deposited on the rGO aerogel.21 Fig. 3b shows the XRD of ZIF-8/ GO, the C/O ratio of ZIF-8/rGA decreases due to the removal of
rGA and GO, and rGA. Due to the relatively low peak intensity of oxygen-groups, besides, the Zn 2p peak at 1023 eV is derived
the rGO at around 25 and overlapping with the ZIF-8, the ZIF-8/ from ZIF-8. In contrast to pure ZIF-8, Zn 3d and Zn 3p were not
rGA only exhibits the representative characteristic peaks of ZIF- detected, due to a relatively low peak intensity expression aer
8. Fig. 3c shows the Raman spectrum of ZIF-8/rGA, ZIF-8 and combining with rGA. Narrow spectra of GO, ZIF-8, ZIF-8/rGA are
GO. The D-band at 1335 cm
1 was lower than the G-band at displayed in Fig. 4b–d, respectively. The reduction of the C]O
1580 cm
1 before GO was reduced. Both the FT-IR and Raman (289 eV) bond is consistent with FTIR and Raman spectra
spectra with new characteristic peaks at 490 cm
1 and 390 (Fig. 3). For ZIF-8/rGA, the peak intensity of C–N was detected
cm
1, respectively, veried the formation of a chemical covalent owing to the ZIF-8 on the rGA framework.
bond of Zn–O between ZIF-8 and rGA.22 The G-band is a signif- Aerogels formed with and without reductant aer adding the
icant characteristic of sp2 hybridized carbon materials, while same amount of ZIF-8 at 95  C for 1 h are compared in the ESI
the D band reveals the sp3 defects within the hexagonal (Fig. S3†). The Raman spectra show that the intensity ID/IG of
graphitic structure. For the 1 h reaction with the metal nano- rGA with reductant is higher than the one without reductant,
particles and reductant, the intensity of the D-band increased while FTIR also shows that rGA was thoroughly reduced when
more than the G-band, where ID/IG increased from 0.87 to 1.10. reductant was added; besides, the peaks related to oxygen-
This is ascribed to the decrease in the mean size of the sp2 containing groups disappeared aer reduction (Fig. 4); these
domains upon the reduction of GO.23 According to a previous results are consistent with FTIR and Raman spectra (Fig. S3b
report,24 GO contains hydroxyl or epoxide groups lying above and d†). Hydrazine hydrate and other reductants cause the
and below the GO planes, and carbonyl groups at the edges. more effective reduction of GO, which will effectively improve
During the reduction process, hydrazine reacts with most the performance of the aerogel. TGA analysis (Fig. S3e†)
carbonyl groups to form C]N bonds of hydrazones and most revealed that thermo-stability was improved by adding reduc-
epoxide rings are opened to form hydrazino alcohols.23 Few –OH tant, while oxygen-containing groups were reduced by thermal

Fig. 3 (a) FTIR and (c) Raman spectra of the precursor ZIF-8, GO, rGA
and as-prepared ZIF-8/rGA composites. (b) XRD and (d) EDS spectra of Fig. 4 (a) Wide-scan XPS spectra of GO, ZIF-8, rGA and ZIF-8/rGA. (b–
ZIF-8/rGA composites. Inset of (b) shows the XRD spectrum of GO. d) Core-level C 1s spectra of GO, rGA, and ZIF-8/rGA respectively.

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decomposition without reductant. The hydrophobicity sharply on the water. When ZIF-8/rGA touches liquid, it separates oil
increased aer reductant addition, which is benecial for the from water faster. The adsorbed oil can be removed by burning,
efficiency of oil absorption from water. Electrical conductivity and the waste oil is released due to the re resistance of gra-
was also greatly improved with reductant (Fig. S4†). phene. Aer burning the oil, the intact aerogel could quickly
Fig. 5a shows the stress–strain comparison of GA, Zn2+/rGA and comprehensively adsorb organic liquid again (Fig. 6e–h),
and ZIF-8/rGA. ZIF-8/rGA can bear a wide range of strain (0– and ZIF-8/rGA can be directly reused as fuel through the
80%); in the range of 0–20%, it has lower modulus and higher combustion method. In reality, waste oil may be randomly
Published on 04 May 2017. Downloaded by Auckland University of Technology on 1/28/2019 1:38:26 PM.

deformation. At the second stage from 20–60%, the curve tends distributed in the water; a magnetic aerogel was also prepared
to be smooth. In the last strain range, the stress–strain curve by a similar method to guide the aerogel in adsorbing oil. As
climbs steeply, corresponding to a lower strain at higher stress. shown in Fig. 6i–k, the oil-polluted region is marked in red, and
However, the stress–strain curve of GA remained almost a magnetic bar was used to move Fe3O4/rGA easily (SEM and
unchanged. Aer coordination ionic bonding, the mechanical corresponding EDS mapping of Fe3O4/rGA are shown in
properties of the binary Zn2+/rGA nanoparticles were greatly Fig. S5†) from the oil–water mixture and adsorbed hexadecane.
enhanced due to the improved interfacial strength,19b,25 and can Precious volatile solvents can be extracted from the aerogel with
support up to 45 kPa load. Cyclic compressive properties of heating up to the boiling point of the adsorbents, followed by
rGA/ZIF-8 are shown in Fig. 5b. In the rst cycle of the curve, we the regeneration of the aerogel (Fig. S6†).
found a key point at the strain of 45%. When ZIF-8/rGA was Generally, ZIF-8/rGA can adsorb up to about 34 to 59 times
compressed ve times to 45% of its previous height, the height its weight, which is more effective than conventional sponge
of GA remained the same at every compression, indicating the and foam.19 The different densities and viscosities of organic
stable mechanical properties of the ZIF-8/rGA aerogel. solvents result in different absorption capacities. Oil–water
Oil–water separation can be achieved on hydrophobic/ separation requires that pollutants are adsorbed and prevented
oleophilic or hydrophilic/oleophobic materials/lms. ZIF-8/ from continuing to pollute the water. Some precious volatile
rGA with high superhydrophobic/oleophilic and porous struc- solvents could be collected by distillation (Fig. S4†), while other
ture showed excellent water repellency and oil adsorption. oils may be directly lit for rapid and easily recycling. Hex-
Fig. 6a displays 1 mL of hexadecane dyed with oil-red oating adecane was chosen to measure the recycling absorption ability
of ZIF-8/rGA by the repeated adsorption and burning processes.
The maximum oil absorption weight gain did not change by
much within the range of 3400–3600%, with the process
repeated up to 10 times (Fig. 6m). Moreover, the morphology
and structure of 3D porous ZIF-8/rGA adsorbent were not
obviously changed aer 10 cycles (insets of Fig. 6m), indicating
the excellent recyclability of the ZIF-8/rGA adsorbent. This may
be ascribed to the robust superhydrophobicity and excellent
binding force of porous ZIF-8/rGA.
The oil absorption ability can be determined as weight
change, which is dened as the weight of oil adsorbed per unit
weight of blank GA/nanoparticles. In this study, some classical
organic liquids were chosen for testing (Fig. 6l), such as ketones
with different carbon chain lengths, which are crucial compo-
nents of crude oil, and organic solvents like alcohols and
toluene. ZIF-8/rGA composites display superior adsorption
capacity toward these solvents, because of their higher specic
surface area than Zn2+/rGA, especially methanol and alcohol,
due to zeolitic imidazolate performing high ethanol uptakes.26
Generally, GA/nanoparticles can adsorb up to about 34 to 59
times their weight, which is more effective than conventional
sponge and foam.27 The different densities and viscosities of
organic solvents result in different absorption capacities. Oil–
water separation requires that pollutants are adsorbed and
prevented from continuing to pollute the water. Some precious
volatile solvents could be distilled and collected, while other
abandoned oil may be directly lit for rapid and easily recycling.
Fig. 5 (a) Stress–strain curve of ZIF-8/rGA, Zn2+/rGA, and rGA Hexadecane was chosen to measure the recycling absorption
synthesized only with reductants; insets show hydrogels of GO
ability of ZIF-8/rGA by the repeated adsorption and burning
without metal ions with hydrazine hydrate only, and GO with reductant
with ZIF-8 at 95  C for 1 h. (b) Cyclic compressive stress–strain curves processes. The maximum oil absorption weight gain has little
of ZIF-8/rGA; inset ZIF-8/rGA before and after supporting 100 g change within the range of 3400–3600%, with the process
weight. repeated up to 10 times (Fig. 6m). The ZIF-8 decorated aerogels,

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Fig. 6 (a–h) Repeated adsorption process of hexadecane (stained with oil-red, floating on water) by ZIF-8/rGA (by burning abandoned oil for
repeated absorption). (i–k) Illustration of oil–water separation with magnetic Fe3O4/rGA under a magnetic field (c, g, k: after adsorption for 2 s). (l)
Absorption capacities (wt%) of Zn2+/rGA and ZIF-8@rGO aerogel towards different organic liquids. (m) Absorption capacities (wt%) of ZIF-8@rGO
aerogel during the repeated absorption experiment with hexadecane; the regenerated aerogel was treated by oil burning.

aer repeated burning processes, could produce ZnO and reduced to 51.8% of the original when the ZIF-8/rGA catalyst
carbon to some extent under air, but they remain porous was added, suggesting a higher degradation efficiency. No
frameworks and highly hydrophobic (Fig. S7†).28 Moreover, the obvious adsorption intensity change in MB was found without
macro-morphology and structure of the 3D porous ZIF-8/rGA the presence of rGA or ZIF-8/rGA, indicating the stability of
adsorbent did not obviously change aer 10 cycles (insets of molecular MB under UV illumination. The p-conjugated and
Fig. 6m and S7†), indicating the excellent recyclability of the high electron mobility of the rGO can effectively prevent the
ZIF-8/rGA adsorbent. This may be ascribed to the robust recombination of electron–hole pairs. Thus, the degradation
superhydrophobicity and excellent binding force of porous ZIF- performance of ZIF-8/GA was higher than pure ZIF-8.29 The
8/rGA. pseudo-rst-order reaction kinetics rate constant of the photo-
Compared to the large number of reports on dye adsorption catalytic degradation for self-degradation, pristine rGA, ZIF-8
by graphene aerogels, the photocatalytic degradation of organic and ZIF-8/rGA were calculated to be 0.17, 1.16 and 4.32 
dyes is rarely reported. The photocatalytic performance 10
3 min
1, respectively, which means the photocatalytic
depends on the ability of the photocatalyst to create electron– performance of ZIF-8/rGA is 3.7 times higher than pure GA.
hole pairs, which generate free radicals (e.g. cOH radicals) that Fig. 7b displays the degradation mechanism of ZIF-8/rGA.
are able to degrade the organic molecular pollutants. In Hydroxyl radicals (cOH) have been widely accepted as the
contrast to traditional adsorption processes, the detoxication crucial active factor for photocatalytic degradation. The HOMO–
of sustainable photocatalytic degradation processes is more LUMO gap can explain the photocatalytic process of ZIF-8/rGA.
meaningful (Fig. S8†). MB represents the widely used organic In general, the highest occupied molecular orbital (HOMO) is
dyes that usually exist in waste water. In each experiment, the mainly contributed by the N 2p bonding orbitals in the ZIF-8,
conditions were kept constant (0.5 g L
1 specimen in 100 mL of while the lowest unoccupied molecular orbital (LUMO) results
10 mg L
1 MB). Fig. 7a illustrates the photodegradation rates from empty Zn orbitals. Under the irradiation of UV light, elec-
under UV light irradiation. The photocatalytic degradation of trons in the HOMO are excited to LUMO, leaving holes in the
the MB pollutant follows the rst-order reaction kinetics model HOMO of ZIF-8. The photo-excited electrons from ZIF-8 are
with R2 ¼ 0.999, R2 ¼ 0.996, R2 ¼ 0.993, respectively, which can quickly transferred through the conductive rGO sheets, due to
be described as ln(C0/Ct) ¼ kt, where C0, Ct, k, t are the initial MB the highly efficient link between rGA and ZIF-8, and react with
concentration, the concentration aer a xed reaction time, the the O2 and H2O soaked on the surface of 3D ZIF-8/rGA to
rate constant and reaction time, respectively. In the absence of produce active radicals of cO2
and OH
. The absorbed OH
and
catalyst, the pristine rGO aerogel and ZIF-8 were used as pho- H2O can react with the holes from the ZIF-8 to form cOH
. Due
tocatalysts and the concentration of MB was only reduced by to the formation of active radical groups, the dye is degraded by
2.0%, 14.1% and 37.6% aer 120 min irradiation, respectively. the photodegradation process. These synergistic effects of these
However, it was found that the concentration of MB was rapidly two routes resulted in the rapid decolourization of MB dye.

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Paper Journal of Materials Chemistry A

Ion exchange and electrostatic adsorption play key roles in

the removal of heavy metal ions by adsorbents.30 ZIF-8/rGA
adsorbents (Cd2+ or Pb2+) were further investigated for heavy
metal ion removal and the result is shown in Fig. 7c and d.
Adsorption was conducted at pH ¼ 6 because few negative ions
are generated from ZIF-8/rGA at lower pH, while at higher pH
(>9) these two metal ions will hydrolyse to settle down. On
Published on 04 May 2017. Downloaded by Auckland University of Technology on 1/28/2019 1:38:26 PM.

immersion in waste water, the rGA is converted to hydrogel and

can adsorb heavy metal ions and easily separate from the water.
The adsorbed amount of Pb2+ or Cd2+ on ZIF-8/rGA increases
sharply within the initial 90 min, followed by a slow increase,
and then reaches equilibrium at about 240 min. The adsorption
curves t the Langmuir isotherm model. The pseudo-rst order
kinetic models were approximated to the equations of ln(qe

qt) ¼ ln(qe)
k1t, which were adapted to t the experimental
data, where qe and qt are the containment (mg g
1) of heavy
metal ions adsorbed at equilibrium and time t (min), k1 is the
rate constant of the model (min
1). The valve of R2 was close to
1. The calculated maximum adsorption capacities of Cd2+ and
Pb2+ were 101.1 and 281.5 mg g
1, respectively, which demon-
strated superior adsorption capability, compared to Zn2+/rGA
with 72.4 and 240.8 mg g
1, respectively. The electrostatic
adsorption plays a key role in removing heavy metals for the ZIF-
8/rGA or rGA, since rGA containing the residual oxygen-groups
Fig. 7 (a) First-order reaction kinetics curves of the degradation of MB (–OH) exhibits negative charge, and heavy metal ions exhibit
for self-degradation, rGA, ZIF-8, and ZIF-8/rGA under UV irradiation positive charge. Besides, the uniform decoration of ZIF-8
(dark-adsorption 8 h before photodegradation). (b) Schematic diagrams nanoparticles on the composite aerogel provided extra active
of the electron transfer in the ZIF-8/rGA and photodegradation mech-
anism of MB under UV irradiation. (c) Adsorption rate plots of Zn2+/rGA
or binding sites for the improved absorption of heavy metal
and ZIF-8/rGA for Cd2+ and Pb2+ ions from water, with a concentration ions.31 More impressively, the aerogel not only displayed good
of 400 mg L
1 at room temperature at pH ¼ 6. (d) Scheme showing the adsorption capacity for metal ions, but also showed promising
mechanism of heavy metal ion exchange. (e) Effect of time on the H2–PA removal capability for benzene series pollutants. For compar-
absorption capacity of pristine rGA and ZIF-8/rGA at room temperature. ison, the amounts of phthalic acid (H2–PA) adsorbed by ZIF-8/
(f) Main absorption mechanism of H2–PA. The adsorption of phthalic acid
on ZIF-8/rGA occurred due to the electrostatic adsorption at pH ¼ 7.
rGA were much higher than for the pristine rGA sample

Fig. 8 FESEM images for the other MOFs/rGA or metal oxide/rGA. (a) MOF-5/rGA, (b) MOF-199/GA, (c) MIL-88-Fe/rGA, (d) ZnO/rGA, (e) TiO2/
rGA, (f) CuO/rGA. Inset: SEM images and photographs of the modified GA, with the addition of vitamin C at 95  C for 1 h.

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Journal of Materials Chemistry A Paper

(Fig. 7e and f). This enhancement of adsorption capacity is D. G. Gong, P. D. Kanhere, T. Lim, Z. L. Dong and Z. Chen,
mainly ascribed to the large surface area of ZIF-8. Since H2–PA J. Phys. Chem. C, 2012, 116, 2772–2780.
exists as negatively charged anions (PA2
) at pH ¼ 7, the posi- 2 (a) Y. X. Tang, Y. Y. Zhang, X. H. Rui, D. P. Qi, Y. F. Luo,
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the formation of ZIF-8/rGA, we foresee that this one-step S. H. Li, S. N. Zhang, Z. Chen, K. Q. Zhang, S. S. Al-Deyab
Published on 04 May 2017. Downloaded by Auckland University of Technology on 1/28/2019 1:38:26 PM.

approach can be extended to fabricate various functional and Y. K. Lai, Adv. Sci., 2017, 4, 1600152; (c) M. Z. Ge,
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