Dubey 2014
Dubey 2014
Dubey 2014
h i g h l i g h t s
a r t i c l e i n f o a b s t r a c t
Article history: In this study, we report the fabrication of a graphene–carbon sphere hybridaerogel decorated with silver
Received 20 November 2013 nanoparticles (G/AgCS). Graphene oxide (GO) and carbon spheres doped with silver nanoparticles (AgCS)
Received in revised form 19 January 2014 were prepared separately. G/AgCS hydrogel was then synthesized by induced reduction and gelation of a
Accepted 21 January 2014
mixture of GO and AgCS in an oil bath. The G/AgCS aerogel was obtained by freeze drying the hydrogel.
Available online 30 January 2014
The synthesized G/AgCS aerogel was characterized using field-emission scanning electron microscopy,
transmission electron microscopy, X-ray diffraction, and Raman and infra-red spectroscopy. The G/AgCS
Keywords:
showed promising efficacy for the catalytic reduction of 4-nitrophenol in the presence of NaBH4. The cat-
Aerogel
Carbon sphere
alytic activity did not significantly decrease during more than 10 cycles of the catalytic reaction. The
Catalytic reduction adsorption capability of chromium(VI), uranium(VI), and methylene blue on the G/AgCS aerogel was also
Graphene evaluated using a Langmuir isotherm model in comparison to commercial activated carbons.
Adsorption Ó 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2014.01.042
1385-8947/Ó 2014 Elsevier B.V. All rights reserved.
S.P. Dubey et al. / Chemical Engineering Journal 244 (2014) 160–167 161
fullerene [21], carbon sphere (CS) [22], and graphene [23,24] have water was added to the above mixture, followed by the addition
been exploited as high capacity adsorbents for water purification. of 300 ml of water. Finally, 18 ml of H2O2 solution was added and
Various types of chemical and biological contaminants exist in nat- the solution changed color from brown to yellow, indicating a high
ural water; carbon derived materials usually exhibit an adsorption oxidation level of graphite to graphite oxide. The graphite oxide
capacity for some contaminants but are not efficient for others. A was washed three times via simple centrifugation and decantation
broad-spectrum adsorbent is desirable for environmental remedi- of the supernatant with 1 M HCl solution, and was then washed
ation processes. with deionized water. This viscous solution was diluted with water
A hierarchical nanostructure that consists of various types of car- and ultrasonicated for 1 h to make a GO suspension.
bon with different structural dimensions and/or porous structures,
such as graphene, CNT, CS, and chitosan may greatly improve the 2.3. Synthesis of AgCS
adsorptive and catalytic performance of a candidate material
through an advanced synergistic effect. Guo et al. have synthesized To date, many authors have used the hydrothermal method for
nanostructures composed of graphene and CS, and have found an CS synthesis. Most authors have used > 85–100% filling carbohy-
excellent application in supercapacitors, providing proof that drate solution for the synthesis of CS using hydrothermal synthesis
assemblies of various carbon types into hierarchical structures can [31–34]. Recently, Li et al. used 66% glucose solution for the syn-
give better alternatives to science and society [25]. Recently, a few thesis of CS by hydrothermal method [35]. We used a 50% filling
reports were published on the combination of different carbon dextrose solution for the synthesis of CS. To synthesize CS, we
based 3D macroscopic structures, such as graphene–CNTs aerogels, placed 100 ml of a 0.35 M dextrose solution in a 200-ml Teflon
[26,27] and chitosan–graphene hydrogels [28] as new materials for cup, then maintained the vessel at 175 °C for 5 h and allowed the
the degradation of water contaminants including organic dyes and solution to cool naturally to room temperature. The CS was collected
heavy metals. Graphene-based hydro- and aerogels incorporated after being washed with three cycles of centrifugation at 15000 rpm
with iron oxide nanoparticles also have been demonstrated for for 20 min, redispersed in water/alcohol/water, and dried in air.
the contaminant removal [8]. These composite materials exhibit Freshly prepared CS was well dispersed in 10 ml of water to
superior capacity for the adsorption of organic and inorganic com- prepare a 0.3% wt suspension, and AgNO3 was added slowly to
pounds than the single material graphene. In addition, the metal make a 1 M silver ion solution. The solution was vigorously shaken
doping on these hydro- and aerogels [29] can impart additional cat- for 15 min and stirred overnight (200 rpm) at room temperature to
alytic activity to the material. In spite of several previous studies on make a homogenous mixture. This mixture was then centrifuged at
the graphene-based hydro- and aerogels, the synthesis of graphene- 3000 rpm for 15 min to remove any remaining silver ions in the
based carbon–carbon composite with metal doping and its catalytic solution, and the silver nanoparticle (AgNPs)-decorated CS (AgCS)
and adsorption applications were rarely reported. was washed three times with water and alcohol. The resulting fil-
Herein, we report a novel self-assembly approach to prepare a trate was redispersed in 10 ml of water and ultrasonicated for 1 h
hierarchical nanostructured aerogel, composed of zero-dimen- to make a homogenous solution.
sional (0-D) CS decorated with silver nanoparticles (AgCS) and
two-dimensional (2-D) GO sheets using induced reduction and 2.4. Synthesis of G/AgCS hybrid hydrogel and aerogel
gelation with cysteine. The hierarchical nanostructure composed
of graphene and CS may improve the adsorption efficacy of the car- Eight milliliters of GO dispersion (3 mg/ml) was mixed with
bon material (compared to the single graphene-based material), 10 ml of AgCS solution. After 1 h of ultrasonication, a suitable
and the metallic silver can catalyze the reductive degradation of amount of cysteine was added and mixed well to chemically re-
nitroaromatic compounds. The synthesized graphene/AgCS duce and gelate the 2D GO sheets into a 3D graphene hybrid hydro-
(G/AgCS) were tested for the catalytic reduction of 4-nitrophenol, gel. Then, this mixture was left undisturbed in an oil bath at 80 °C
and the adsorption amelioration of methylene blue (MB) dye, for 9 h. Finally, the 3D structure was removed and washed with
Cr(VI), and U(VI) has been explored. ultrapure water. This black monolith was freeze-dried to convert
it into an aerogel for further catalytic and adsorption applications.
For the synthesis of graphene and graphene/CS (G/CS) hydrogel,
2. Materials and methods
10 ml of water and 10 ml of CS solution were added in 10 ml of
AgCS solution, keeping all the other conditions constant.
2.1. Reagents
2.5. Characterizations
Graphite flakes (100 mesh size), concentrated sulfuric acid,
sodium nitrate, potassium permanganate, hydrogen peroxide,
Electron microscope images were recorded using a Hitachi Cold
silver nitrate, L-cysteine, sodium borohydride, 4-nitrophenol
field emission scanning electron microscope (FE-SEM) at 10 kV.
(4-NP), potassium di-chromate, and MB were obtained from
Transmission electron microscope (TEM) images were collected
Sigma–Aldrich Co. Dextrose, PAC, and GAC were purchased from
using a JEOL high-resolution transmission electron microscope
Daejung Chemical Co. All the chemicals were used as received
with an acceleration voltage of 200 kV. Raman scattering was per-
without further purification. All solutions were prepared using
formed on a WITec Micro-Raman system using a 532 nm Helium
18 MX Milli-Q water from a Millipore system.
Neon laser source. Diffraction data were acquired on a Rigaku High
Power X-ray diffractometer (XRD). Powder diffraction data were
2.2. GO synthesis recorded for 2h angles between 5° and 80° with a scanning speed
of 0.05°/s. The various functional groups present in the hybrid
GO was synthesized from graphite flakes using a modified Hum- aerogels were measured using a Nicolet 6700 infra-red (IR) spec-
mer’s method [30]. Briefly, 3 g of natural graphite was placed in a trometer over the spectral range of 4000–400 cm1. The silver con-
1 L flask. Seventy milliliters of concentrated H2SO4 was added to tent in G/AgCS was calculated by acidifying the material and
the flask, followed by the addition of 1.5 g of NaNO3. Next, 9 g of measuring the concentration of released silver ion on an atomic
KMnO4 was slowly added with constant stirring in an ice bath with absorption spectrophotometer (AAS, AAnalyst 700, Perkin Elmer
the temperature maintained below 4 °C for 30 min. The mixture Co). The surface area and the pore size of PAC and G/AgCS were
was then stirred for 24 h for complete oxidation. Then, 150 ml of analyzed by a Micromeritics Gemini V system.
162 S.P. Dubey et al. / Chemical Engineering Journal 244 (2014) 160–167
2.6. Experiments for the removal of water contaminants pre-dispersed GO and AgCS were mixed and ultrasonicated to
obtain GO/AgCS complexes. This step was followed by the addition
For the catalytic reduction of 4-NP, 3 ml (0.03 M) of the fresh of a suitable amount of cysteine, and the solution was mixed well
NaBH4 solution was added to 30 lL of a 10 mM aqueous 4-NP solu- with high-speed stirring. The addition of cysteine results in the
tion in a quartz cuvette. Next, 3 mg of the G/AgCS aerogel was simultaneous reduction and gelation of GO to graphene hydrogel.
added to this mixture, and the concentration of 4-NP was deter- Hybrid G/AgCS hydrogel was obtained by heating the complex
mined by ultraviolet/visible (UV/Vis) spectroscopy at a wavelength mixture at 80 °C in an oil bath for 9 h. When the reaction time
of 400 nm using a Shimadzu UV-1800 spectrometer. was increased from 0 to 2 h, the hybrid monolith started floating
To determine the adsorption efficacy, 10 mg of aerogel was towards the surface of the water. With a further increase in reac-
added to 20 ml of the contaminant solution and slowly stirred tion time, the aggregate shrank, and a columnar-shaped hydrogel
for 18 h at room temperature. The solution pH was not controlled was obtained after 9 h. Graphene and G/CS hydrogels were synthe-
(typically 5–6). A 15 mg/L aliquot of MB, 10 mg/L of Cr(VI), and sized in a similar way. The resulting monoliths were freeze dried to
5 mg/L of U(VI) were used for the adsorption experiment. PAC obtain the corresponding aerogels. Cysteine serves as an environ-
and GAC were simultaneously tested for their efficacies towards mentally friendly reducing agent for the simultaneous reduction
the similar contaminants, with all other parameters kept constant. and gelation of GO to a graphene hydrogel. Two-milliliter aliquots
Isotherm studies by G/AgCS and PAC were performed at different of 0.02, 0.041, 0.082, and 0.123 M cysteine solutions were utilized
initial concentrations of MB, Cr(VI), and U(VI) to determine the to optimize the development of firm hydrogels (Fig. 2a–d). Gela-
maximum adsorption capacity of the synthesized hybrid G/AgCS tion did not occur with the 0.02 and 0.041 M cysteine solutions.
aerogel in comparison to PAC. The remaining concentrations of Although the gelatinous yellow solution of GO and GO/AgCS did
MB, Cr(VI), and U(VI) were analyzed using UV/Vis spectroscopy. gradually thicken and darken to a black color, a firm hydrogel
could not be formed, which can be clearly seen in Figs. 2a–b and
S1a–b (Supplementary data). By further increasing the concentra-
3. Results and discussion
tion of cysteine to 0.082 M (Fig. 2c), a hydrogel was obtained; how-
ever, this gel was easily broken (Fig. S1c in Supplementary data).
3.1. Synthesis parameters
By increasing the concentration of cysteine to 0.123 M, a very firm
hydrogel was produced (Fig. S1d in Supplementary data). Excess
The synthesis of graphene, G/CS, and G/AgCS hydrogels is de-
cysteine (0.165 M) will have a ten dency to remain and adhere to
scribed in Fig. 1. The GO used here was synthesized using a modi-
the surface of the hydrogel, which can be observed as white parti-
fied Hummer’s method. The CS was hydrothermally synthesized
cles on the surface of the hydrogel (Fig. S1e in Supplementary
from an aqueous dextrose solution and used to grow AgNPs on
data). We found an increase in the size of the hybrid G/AgCS hydro-
the surfaces of the spheres. To form the hybrid G/AgCS hydrogel,
gel (12 mm diameter and 14 mm height) relative to the graphene
hydrogel (10 mm diameter and 12 mm height). The sizes of the
G/CS and G/AgCS hydrogels remain almost constant. This synthetic
protocol can be utilized to develop different shapes and sizes of hy-
brid hydrogels by using the same reaction mixture in reaction ves-
sels of different shapes and sizes with the same temperature and
reaction time, as shown in the photograph (Fig. S2a–d in Supple-
mentary data). Importantly, the process is easy to scale up
(Fig. 2e); a hydrogel of approximately 40 50 mm size was formed
via the successful self-assembly of 100 ml of GO, 125 ml of water,
and 25 ml of a 0.123 M cysteine solution (Fig. S3a and b in Supple-
mentary data). The other physical parameters, such as the temper-
ature and reaction time, were not changed.
Fig. 2. Photographs of the cysteine concentration-dependent synthesis of the hydrogel with cysteine concentrations of (a) 0.02 M, (b) 0.041 M, (c) 0.082 M, and (d) 0.123 M.
(e) Photograph of the scaled-up synthesis of hydrogels using 100 ml of a GO suspension, 125 ml of water, and 25 ml of 0.123 M cysteine solution.
Fig. 3. Microscopic images of the different aerogels; (a–c) SEM images of graphene, G/CS, and G/AgCS; (d–f) TEM images of graphene, G/CS, and G/AgCS aerogels; inset: high
magnification of G/AgCS.
sp3 bonded carbon at approximately 1347–1351 cm1 and derives gradually decreased from 1.12 (G) to 1.06 for G/CS and even to
from a breathing mode of K-point phonons of A1 g symmetry, and 0.86 in the case of G/AgCS, indicating a significant decrease in
the G band near 1576–1588 cm1 signifies a plane vibration of an the number of defects present in the original GO solution [38]
E2g mode, mainly due to sp2 bonded carbon [36]. The intensity ra- and the successful recovery of sp2 bonded carbon in the G/AgCS
tio of the D and G peaks, ID/IG, is utilized to characterize the quan- aerogel.
tities of defects in graphene-based materials [37]. As shown in The FTIR spectra of graphene, G/CS, and G/AgCS aerogels are
Fig. 4b, as the reaction progresses from G to G/AgCS aerogel, the presented in Fig. 4c. The FTIR spectrum of the graphene hydrogel
intensity ratio of the well-documented D and G bands (ID/IG) shows major intensity bands at 1621.15, 1580.99, 1484.54, and
164 S.P. Dubey et al. / Chemical Engineering Journal 244 (2014) 160–167
Fig. 4. (a) Powder diffraction pattern; (b) Raman spectra; (c) IR spectra of the synthesized aerogels.
1406.43 cm1. The IR bands at 1621.15 cm1 are due to the reaction. A strong absorbance peak has been found for 4-NP at
stretching mode of the C@O unit. The 1580.99 and 1484.54 cm1 317 nm that shifted to 400 nm in the presence of NaBH4 due to
bands are due to ring deformations and confirm the presence of the deprotonation of 4-NP (pKa of 4-NP = 7.16) [40]. The addition
aromatic rings. The band at 1406.43 cm1 results from the stretch- of NaBH4 increased the solution pH to 10.5. Almost no change in
ing vibrations of the CAOH bonds in the carboxyl group. The other the absorbance of 4-NP at 400 nm was observed after 1 week in
intense bands observed are due to the aromatic CAH stretch the NaBH4 solution, indicating that no reduction reaction occurred
(2916.67 cm1), the CAOAC stretch (1297.08 and 1090.24 cm1), in the absence of the material. To accelerate the reduction of 4-NP
and the aromatic CAH bending (1193.40, 1041.50 cm1). The by NaBH4, metal nanoparticles have been used as a catalyst. Metal
bands near 1698.73 and 1620.46 cm1 in the G/CS hybrid surface nanoparticles, such as silver, copper, gold, and platinum, are
are attributed to C@O and C@C stretches, of which the intensity re- known to expedite electron transfer from donors (in this case
duces in the G/AgCS hybrid due to involvement in the reduction of BH4 ) to acceptors (in this case 4-NP) [41]. When G/AgCS was added
metal ions to metal nanoparticles. The band intensity correlated to the freshly prepared mixture of NaBH4 and 4-NP, the intensity of
mainly to the oxygenic groups in the graphene hydrogel and de- the absorbance peak at 400 nm decreased, and this was accompa-
creased significantly in their respective hybrid hydrogels, indicat- nied by the growth of a new absorption peak at 300 nm (Fig. 5a).
ing that the new hybrid aerogels were formed after the removal The absorption peak at 300 nm is due to the evolution of 4-amino-
of the oxygenic groups [39], while simultaneously restoring the phenol (4-AP) as the reduced product. The visible disappearance of
sp2-C network, supporting the Raman measurements [36]. the bright yellow color of 4-NP to the colorless 4-AP is captured
and presented in the inset of Fig. 5a.
3.3. Catalytic and adsorption applications The catalytic decomposition of 4-NP was completed in 10 min
(Fig. 5b). No catalytic activity was observed for the graphene and
To evaluate the catalytic activity of G/AgCS aerogel, the reduc- G/CS aerogels, indicating that the reduction reaction proceeds
tion of 4-NP in the presence of NaBH4 was examined as a model mainly due to the presence of AgNPs on the surface of the hybrid
S.P. Dubey et al. / Chemical Engineering Journal 244 (2014) 160–167 165
Fig. 5. (a) Catalytic reduction of 4-NP by NaBH4 in the presence of G/AgCS, inset: disappearance of bright yellow color of 4-NP; (b) plot of C/C0 versus time for the different
aerogels; (c) the reusability of the G/AgCS aerogel as a catalyst for the reduction reaction ([G/AgCS]0 = 1 g/L, [NaBH4]0 = 30 mM, [4-NP]0 = 0.1 mM). (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)
G/AgCS aerogel. NaBH4 is a hydrogen source that liberates hydro- materials reported). With further increases in the number of cycles,
gen gas by hydrolysis at room temperature, and this process can the conversion efficacy decreases; only 50% conversion can be ob-
be catalytically accelerated by metals [42]. It has been suggested tained after 23 cycles. It should be noted that until 11 cycles were
that the catalytic decomposition of BH 4 by AgNPs produces H-Ag completed, 15 min was sufficient for the catalytic reduction, but
and AgBH 3 as reactive intermediates (reaction (1)) [43], and these the time increased to 20 min for the12th–17th cycles and to more
species are believed to be responsible for the reduction of 4-NP to than 30 min for subsequent cycles. No loss of silver was observed
4-AP (reactions (2) and (3); stoichiometrically six-electron reduc- during all of the repeated runs, and the gradual decrease of the cat-
tion is required to transform 4-NP to 4-AP). alytic activity may be due to the blockage of active sites by byprod-
ucts from the catalytic reactions (possibly originated from 4-NP
2Ag þ BH4 ¡ Ag BH3 þ Ag H ð1Þ
and NaBH4 or their redox byproducts; further study is needed to
clarify this).
6H Ag þ 4 NP ! 4 AP þ 6Ag þ 6Hþ ð2Þ
To test the adsorption capability of the synthesized hybrid aero-
gel, the aerogels were stirred for 18 h in solutions containing
6Ag BH3 þ 4 NP ! 4 AP þ 6Ag þ 6BH3 ð3Þ
15 mg/L MB dye, 10 mg/L Cr(VI), and 5 mg/L of U(VI) concentration.
The recyclability of hybrid G/AgCS aerogel for the catalytic Commercial sources of AC (PAC and GAC) were also tested for com-
reduction of 4-NP was tested. After the reaction, the aerogel was parison. As presented in Fig. 6, the G, hybrid G/CS, and G/AgCS
removed using tweezers and blotted with filter paper to remove aerogels show 79.67%, 85.87%, and 83.96% adsorption efficacy for
the surface-adsorbed solution; this material was then used for fur- Cr(VI), respectively, in comparison to PAC (57.52%) and GAC
ther catalytic reactions. As shown in Fig. 5c, the catalytic efficacy of (47%). Meanwhile, for MB adsorption, hybrid G/CS, G/AgCS, and
this material remained remarkably stable even after 11 cycles for PAC have 100% adsorption efficacy, whereas G and GAC have
4-NP degradation, and this material can be successfully utilized 91.35% and 63.77% adsorption efficacy, respectively. Synthesized
for 17 successive cycles of catalytic reaction (up to 90%), which aerogels show comparatively higher adsorption efficacy for U(VI)
is valuable for recycling the synthesized material (refer to than commercial ACs. G/AgCS have the greatest efficacy of 84.5%
Table S1 in Supplementary data for the performances of similar in comparison to 66.9% for PAC. The metal and dye removal
166 S.P. Dubey et al. / Chemical Engineering Journal 244 (2014) 160–167
Table 1
Langmuir isotherm parameters evaluated for contaminants adsorption on PAC and
GAgCS.
results indicate that the high adsorption capacity of G/AgCS for dif-
ferent contaminants may be attributed to the facilitated diffusion
of contaminants into the large pores of the material. Similar obser-
vations have been reported in literatures [29,44]. The specific func-
Fig. 6. Adsorption efficacy of different aerogels and AC for Cr (VI) and MB removal tional groups on the G/AgCS surface can be also important. The
([G/AgCS]0 = 0.5 g/L, [U(VI)]0 = 5 mg/L, [Cr(VI)]0 = 10 mg/L, [MB]0 = 15 mg/L, reac- functionalization of G/AgCS material removes the hydrophobicity
tion time = 18 h). problem of the non-functionalized G aerogel which is very hydro-
phobic due to the enhanced hydrophobic and p–p interactions be-
tween the graphene nanosheets [29], and enhances the interaction
efficiency of G/AgCS and PAC were investigated with different ini-
between the metal ions and the adsorbent surface.
tial concentrations (1–20 mg/L) of Cr(VI) and U(VI). MB’s initial
concentration of (10–40 mg/L) was used for the isotherm study.
A Langmuir isotherm model was fitted to the obtained data of 4. Conclusions
the amount of adsorbed quantity (qe) and their equilibrium con-
centration (Ce) in solution (Fig 7). Results obtained from nonlinear In this study, an easy and scalable approach for the synthesis of
fitting are presented in Table 1 and show the Langmuir isotherm a hybrid G/AgCS aerogel was demonstrated. Using this method, the
constant (k), maximum adsorption capacity (Qm), and correlation shape and size of the aerogel can be readily controlled. G/AgCS was
coefficient (r2) of PAC and G/AgCS. It can be observed that G/AgCS found to be an efficient catalyst for the reduction of 4-NP into 4-AP,
has a better removal efficiency for Cr(VI) and U(VI) adsorption at using NaBH4 as a reducing agent. The hybrid aerogel can be easily
the experimented conditions, compared to PAC. Also Qm for Cr(VI) removed (using tweezers) from the reaction solution due to its
and U(VI) adsorption by G/AgCS is found to be the highest at 12.69 macroscopic nature, and it can be used many times while main-
and 13.31 mg/g, respectively, in comparison to 7.53 and 5.78 mg/g taining its catalytic activity. In addition, G/AgCS exhibited a higher
by PAC. PAC has the highest Qm for MB adsorption, which is adsorption capacity for Cr(VI) and U(VI) removal than PAC and a
69.75 mg/g compared to G/AgCS (65.83 mg/g). comparable adsorption capacity for MB removal based on the
The surface area and the average pore size of PAC and G/AgCS Langmuir isotherm model. The hybrid G/AgCS aerogel has shown
were analyzed (Table S2 in Supplementary data). Interestingly, promise as a multifunctional material for the treatment of contam-
G/AgCS (61 m2/g) exhibited much lower surface area than the com- inated water.
mercial PAC (792 m2/g). On the contrary, the average pore size of
G/AgCS (7.99 nm) was greater than that of PAC (3.38 nm). These Acknowledgments
References
[1] X.-L. Sheng, Q.-B. Yan, F. Ye, Q.-R. Zheng, G. Su, T-carbon: a novel carbon
allotrope, Phys. Rev. Lett. 106 (2011) 155703.
[2] C.H. Lu, H.H. Yang, C.L. Zhu, X. Chen, G.N. Chen, A graphene platform for
sensing biomolecules, Angew. Chem. Int. Edit. 121 (2009) 4879–4881.
[3] Z. Sun, T. Hasan, F. Torrisi, D. Popa, G. Privitera, F. Wang, F. Bonaccorso, D.M.
Basko, A.C. Ferrari, Graphene mode-locked ultrafast laser, Acs Nano 4 (2010)
803–810.
[4] C. Shan, H. Yang, J. Song, D. Han, A. Ivaska, L. Niu, Direct electrochemistry of
glucose oxidase and biosensing for glucose based on graphene, Anal. Chem. 81
Fig. 7. Isotherm plot for MB adsorption (adsorbate concentration, 10–40 mg/L) and (2009) 2378–2382.
Cr(VI) and U(VI) adsorption (adsorbate concentration, 1–20 mg/L); contact time, [5] Y. Wang, Z. Shi, Y. Huang, Y. Ma, C. Wang, M. Chen, Y. Chen, Supercapacitor
18 h; agitation speed, 200 rpm; temperature, 25 °C; adsorbent quantity, 10 mg; devices based on graphene materials, J. Phys. Chem. C 113 (2009) 13103–
adsorbate quantity, 20 mL. 13107.
S.P. Dubey et al. / Chemical Engineering Journal 244 (2014) 160–167 167
[6] Y. Xu, W. Hong, H. Bai, C. Li, G. Shi, Strong and ductile poly (vinyl alcohol)/ [25] C.X. Guo, C.M. Li, A self-assembled hierarchical nanostructure comprising
graphene oxide composite films with a layered structure, Carbon 47 (2009) carbon spheres and graphene nanosheets for enhanced supercapacitor
3538–3543. performance, Energy Environ. Sci. 4 (2011) 4504–4507.
[7] Y. Xu, K. Sheng, C. Li, G. Shi, Self-assembled graphene hydrogel via a one-step [26] Z. Sui, Q. Meng, X. Zhang, R. Ma, B. Cao, Green synthesis of carbon nanotube–
hydrothermal process, Acs Nano 4 (2010) 4324–4330. graphene hybrid aerogels and their use as versatile agents for water
[8] H.-P. Cong, X.-C. Ren, P. Wang, S.-H. Yu, Macroscopic multifunctional purification, J. Mater. Chem. 22 (2012) 8767–8771.
graphene-based hydrogels and aerogels by a metal ion induced self- [27] M. Zhang, B. Gao, X.D. Cao, L.Y. Yang, Synthesis of a multifunctional graphene–
assembly process, ACS Nano 6 (2012) 2693–2703. carbon nanotube aerogel and its strong adsorption of lead from aqueous
[9] O.C. Compton, Z. An, K.W. Putz, B.J. Hong, B.G. Hauser, L. Catherine Brinson, S.T. solution, RSC Adv. 3 (2013) 21099–21105.
Nguyen, Additive-free hydrogelation of graphene oxide by ultrasonication, [28] Y. Chen, L. Chen, H. Bai, L. Li, Graphene oxide–chitosan composite hydrogels as
Carbon 50 (2012) 3399–3406. broad-spectrum adsorbents for water purification, J. Mater. Chem. A 1 (2013)
[10] H.N. Lim, N.M. Huang, S.S. Lim, I. Harrison, C.H. Chia, Fabrication and 1992–2001.
characterization of graphene hydrogel via hydrothermal approach as a [29] T. Wu, M. Chen, L. Zhang, X. Xu, Y. Liu, J Yan, W. Wang, J. Gao, Three-
scaffold for preliminary study of cell growth, Int. J. Nanomed. 6 (2011) dimensional graphene-based aerogels prepared by a self-assembly process
1817–1823. and its excellent catalytic and absorbing performance, J. Mater. Chem. A 1
[11] H. Bai, C. Li, X. Wang, G. Shi, On the gelation of graphene oxide, J. Phys. Chem. C (2013) 7612–7621.
115 (2011) 5545–5551. [30] W.S. Hummers Jr., R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem.
[12] Y. Xu, Q. Wu, Y. Sun, H. Bai, G. Shi, Three-dimensional self-assembly of Soc. 80 (1958) 1339.
graphene oxide and DNA into multifunctional hydrogels, ACS Nano 4 (2010) [31] X. Sun, Y. Li, Hollow carbonaceous capsules from glucose solution, J. Colloid
7358–7362. Interface Sci. 291 (2005) 7–12.
[13] Y. Zhang, Y. Kuang, Y. Gao, B. Xu, Versatile small-molecule motifs for self- [32] Q. Wang, H. Li, L. Chen, X. Huang, Monodispersed hard carbon spherules with
assembly in water and the formation of biofunctional supramolecular uniform nanopores, Carbon 39 (2001) 2211–2214.
hydrogels, Langmuir 27 (2010) 529–537. [33] X. Sun, Y. Li, Colloidal carbon spheres and their core/shell structures with
[14] X. Jiang, Y. Ma, J. Li, Q. Fan, W. Huang, Self-assembly of reduced graphene oxide noble-metal nanoparticles, Angew. Chem. Int. Edit. 43 (2004) 597–601.
into three-dimensional architecture by divalent ion linkage, J. Phys. Chem. [34] L. Kong, X. Lu, X. Bian, W. Zhang, C. Wang, Accurately tuning the dispersity and
C114 (2010) 22462–22465. size of palladium particles on carbon spheres and using carbon spheres/
[15] Z. Tang, S. Shen, J. Zhuang, X. Wang, Noble-metal-promoted three-dimensional palladium composite as support for polyaniline in H2O2 electrochemical
macroassembly of single-layered graphene oxide, Angew. Chem. Int. Edit. 122 sensing, Langmuir 26 (2010) 5985–5990.
(2010) 4707–4711. [35] M. Li, W. Li, S. Liu, Control of the morphology and chemical properties of
[16] H. Bai, C. Li, X. Wang, G. Shi, A pH-sensitive graphene oxide composite carbon spheres prepared from glucose by a hydrothermal method, J. Mater.
hydrogel, Chem. Comm. 46 (2010) 2376–2378. Res. 27 (2012) 1117–1123.
[17] Z. Li, J. Shen, H. Ma, X. Lu, M. Shi, N. Li, M. Ye, Preparation and characterization [36] X. Zhou, J. Zhang, H. Wu, H. Yang, J. Zhang, S. Guo, Reducing graphene oxide via
of pH-and temperature-responsive hydrogels with surface-functionalized hydroxylamine: a simple and efficient route to graphene, J. Phys. Chem. C 115
graphene oxide as the crosslinker, Soft Matter 8 (2012) 3139–3145. (2011) 11957–11961.
[18] J. Rivera-Utrilla, M. Sánchez-Polo, V. Gómez-Serrano, P. Alvarez, M. Alvim- [37] D. Yang, A. Velamakanni, G. Bozoklu, S. Park, M. Stoller, R.D. Piner, S.
Ferraz, J. Dias, Activated carbon modifications to enhance its water treatment Stankovich, I. Jung, D.A. Field, C.A. Ventrice Jr., Chemical analysis of
applications. An overview, J. Hazard. Mater. 187 (2011) 1–23. graphene oxide films after heat and chemical treatments by X-ray
[19] S. Wang, C.W. Ng, W. Wang, Q. Li, L. Li, A comparative study on the adsorption photoelectron and micro-Raman spectroscopy, Carbon 47 (2009) 145–152.
of acid and reactive dyes on multiwall carbon nanotubes in single and binary [38] W. HoáShin, J. WookáChoi, A bifunctional approach for the preparation of
dye systems, J. Chem. Eng. Data 57 (2012) 1563–1569. graphene and ionic liquid-based hybrid gels, J. Mater. Chem. A 1 (2013) 43–48.
[20] Y. Si, T. Ren, Y. Li, B. Ding, J. Yu, Fabrication of magnetic polybenzoxazine-based [39] Q. Zhuo, Y. Ma, J. Gao, P. Zhang, Y. Xia, Y. Tian, X. Sun, J. Zhong, X. Sun, Facile
carbon nanofibers with Fe3O4 inclusions with a hierarchical porous structure synthesis of graphene/metal nanoparticle composites via self-catalysis
for water treatment, Carbon 50 (2012) 5176–5185. reduction at room temperature, Inorg. Chem. 52 (2013) 3141–3147.
[21] D.Y. Lyon, L.K. Adams, J.C. Falkner, P.J. Alvarez, Antibacterial activity of [40] N. Pradhan, A. Pal, T. Pal, Silver nanoparticle catalyzed reduction of aromatic
fullerene water suspensions: effects of preparation method and particle size, nitro compounds, Colloid Surf. A-Physicochem. Eng. Asp. 196 (2002) 247–257.
Environ. Sci. Technol. 40 (2006) 4360–4366. [41] A. Gangula, R. Podila, L. Karanam, C. Janardhana, A.M. Rao, Catalytic reduction
[22] X. Wang, J. Liu, W. Xu, One-step hydrothermal preparation of amino- of 4-nitrophenol using biogenic gold and silver nanoparticles derived from
functionalized carbon spheres at low temperature and their enhanced Breynia rhamnoides, Langmuir 27 (2011) 15268–15274.
adsorption performance towards Cr (VI) for water purification, Colloid Surf. [42] M. Rakap, S. Özkar, Hydroxyapatite-supported cobalt (0) nanoclusters as
A-Physicochem. Eng. Asp. 415 (2012) 288–294. efficient and cost-effective catalyst for hydrogen generation from the
[23] S.S. Gupta, T.S. Sreeprasad, S.M. Maliyekkal, S.K. Das, T. Pradeep, Graphene hydrolysis of both sodium borohydride and ammonia–borane, Catal. Today
from sugar and its application in water purification, ACS Appl. Mater. 183 (2012) 17–25.
Interfaces 4 (2012) 4156–4163. [43] K. Holbrook, P. Twist, Hydrolysis of the borohydride ion catalysed by metal–
[24] L. Liu, J. Liu, D.D. Sun, Graphene oxide enwrapped Ag3PO4 composite: towards boron alloys, J. Chem. Soc. A (1971) 890–894.
a highly efficient and stable visible-light-induced photocatalyst for water [44] S.M. Solberg, C.C. Landry, Adsorption of DNA into mesoporous silica, J. Phys.
purification, Catal. Sci. Technol. 2 (2012) 2525–2532. Chem. B 110 (2006) 15261–15268.
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