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Capacitive deionization (CDI) devices with low energy consumption and high salt removal efficiencies have
Published on 18 January 2016. Downloaded on 06/03/2016 13:19:17.
attracted much attention. Recently, graphene has been proved to be one of the most promising materials
for CDI electrodes. However, pristine graphene is far from desirable due to its low removal efficiency and
unavoidable decays in performance. In this study, a reduced graphene oxide/Fe3O4 nanoparticle
(RGO@Fe3O4) hybrid is proposed and synthesized via a hydrothermal approach for enhanced CDI.
Electrochemical analysis of this nanocomposite material has revealed typical electrical double layer
capacitive behaviour and an improved specific capacitance. Furthermore, the electrosorption capacity
Received 4th November 2015
Accepted 14th January 2016
and current efficiency of RGO@Fe3O4 were found to be nearly two folds higher than that of RGO. This
huge improvement is attributed to the hydroxylation of the Fe3O4 surface. In addition, the maximum
DOI: 10.1039/c5ra23151e
electrosorption capacity predicted from the Langmuir isotherm was 8.33 and 4.63 mg g1,
www.rsc.org/advances corresponding to the RGO@Fe3O4 and RGO electrode, respectively.
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inorganic materials with high loading amounts.20,21 In partic- tometer (Bruker, D8 Advance-Eco) equipped with a Ka radiation
ular, the incorporation of metal oxides will signicantly (l z 1.54 A) source. Thermogravimetric analysis (TGA) was
improve the capacitance of graphene-based materials.22 Fe3O4
carried out using Shimadzu DTG-60 under compressed air ow
for example, is environmentally benign, chemically stable and
gas at a rate of 5 C min1. X-Ray photoelectron spectroscopy
has high pseudocapacitance through redox reactions. Poten-
(XPS, Thermo ESCALAC250Xi) spectra was collected on a mon-
tially, Fe3O4 is a choice material for the synthesis of graphene/
ochromatized Al Ka X-ray source (1486.6 eV).
metal oxide nanocomposites for energy storage and related
technologies.23
2.3 Electrochemical test
In this work, reduced graphene oxide and Fe3O4
(RGO@Fe3O4) hybrids were prepared by a facile hydrothermal The RGO@Fe3O4 electrodes were fabricated as follows:
method and fabricated as electrodes for symmetrical CDI. The RGO@Fe3O4, carbon black and polyvinylidene uoride were
cyclic voltammetry (CV) curve of RGO@Fe3O4 exhibits a typical mixed in a mass ratio of 80 : 10 : 10 and dispersed in ethanol
electrical double layer capacitive behaviour. Compared to RGO, with the addition of a few drops of dimethylformamide. The
the enhanced capacitance of RGO@Fe3O4 may arise from an resulting mixture was coated onto the graphite paper with
exchange activity between the hydrated Fe3O4 and Na+. Subse- a spatula, followed by drying at 60 C for 12 h. The electro-
quently, the electrosorption performance of RGO@Fe3O4 and chemical measurements were performed in a typical three-
RGO were comparatively investigated. It is found that the electrode setup composed of either RGO or RGO@Fe3O4 as
removal capacity, electrosorption rate constant and charge working electrodes, Pt foil as the counter electrode and a satu-
efficiency of RGO@Fe3O4 is nearly twice as high as that of RGO. rated calomel electrode (SCE) as the reference electrode. CV
Additionally, the maximum removal capacity of RGO@Fe3O4 is measurements were performed at various scan rates from 1 to
predicted by the Langmuir model, which shows a high value of 100 mV s1 on an electrochemical workstation (VMP3, Bio-logic,
8.33 mg g1. France) in 1 M NaCl solutions.
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Fe3O4(H2O)n ¼ Fe3O4(OH)
n + nH
+
(2)
Fe3O4(OH)
n + nNa ¼ Fe3O4(OH)nNan
+
(3)
the same transient (inset). Fig. 4(d) shows the conductivity and
Fe2+ and Fe3+ in the Fe2p3/2 spectrum is expected to be 709.4 eV current transition (inset) of RGO@Fe3O4 at electrical voltages of
and 710.8 eV, respectively, the asymmetric broadband centered 1.0, 1.2, 1.4 and 1.6 V respectively. Clearly, the higher voltage is,
at around 710 eV manifests the coexistence of Fe3+ and Fe2+. the higher salt removal capacity is.
CV measurements were extensively employed to study the In order to make reasonable comparisons, the normalized
electrochemical behavior and to determine the specic capaci- removal capacity (mg g1) of the RGO/RGO@Fe3O4 electrode
tance of the electrodes. Fig. 4(a) displays the representative CV under different cell voltages (V) is plotted in Fig. 5(a). For both
curves of RGO/RGO@Fe3O4 at a scanning rate of 10 mV s1 in 1 electrodes, an increase in electrical voltage results in higher
M NaCl solution while Fig. 4(b) depicts the corresponding removal capacity due to higher electrostatic force. At a certain
specic capacitance at scanning rates ranging from 1 to 100 mV voltage, the removal capacity of RGO@Fe3O4 is nearly two folds
s1. The curves of both RGO and RGO@Fe3O4 demonstrate an higher than RGO. The current efficiency is also calculated and
almost rectangular shape without presenting any peaks, sug- shown in Fig. 6(a). It is dened as:
gesting double layer capacitive behavior. Compared to that of
GF
RGO electrode, the CV curve of RGO@Fe3O4 has a larger inte- L¼ 103 (4)
grated CV area, implying a higher specic capacity. The 58:5 S
improvement of the specic capacity from RGO to RGO@Fe3O4 where F is the Faraday constant (96 485 s A mol1), G (removal
is mainly ascribed to the hydroxylation of Fe3O4 surface.28 Thus, capacity, mg g1) and S (specic charge which is obtained by
diffusion and adsorption of ions become facile on the hybrid integrating the current (A) with time (s), C g1). In the case of an
electrode. The mechanism of this process is probably as follows: ideal CDI process, each electron charge is fully charge-balanced
by a counter ion adsorption and the transfer of an electron from
one electrode to another is accompanied by the removal of
precisely one salt molecule from the bulk solution. However,
due to co-ions impaction caused by simultaneous adsorption,
the current efficiency is oen less than 1 which means that the
11970 | RSC Adv., 2016, 6, 11967–11972 This journal is © The Royal Society of Chemistry 2016
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1.0 V 1.2 V
1.4 V 1.6 V
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and shows a higher specic capacity which is probably due to 10 D. R. Dreyer, S. J. Park, C. W. Bielawski and R. S. Ruoff, Chem.
the hydroxylation of Fe3O4 surface. Compared to RGO, the Soc. Rev., 2010, 39, 228.
electrosorption capacity and current efficiency of RGO@Fe3O4 11 D. S. Zhang, X. R. Wen, L. Y. Shi, T. T. Yan and J. P. Zhang,
is nearly two folds higher than that of RGO regardless of applied Nanoscale, 2012, 4, 5440.
voltage. The kinetics and isotherm results also illustrate 12 H. B. Li, S. Liang, J. Li and L. J. He, J. Mater. Chem. A, 2013, 1,
a higher electrosorption rate of RGO@Fe3O4 electrode. The 6335.
maximum electrosorption capacity predicted from the Lang- 13 Z. Wang, B. J. Dou, L. Zheng, G. Zhang, Z. H. Liu and
muir isotherm is 8.33 mg g1 whereas the corresponding value Z. P. Hao, Desalination, 2012, 299, 96.
for RGO is 4.63, indicating the great potential of RGO@Fe3O4 in 14 H. Wang, D. S. Zhang, T. T. Yan, X. R. Wen, J. P. Zhang and
application to CDI. L. Y. Shi, J. Mater. Chem. A, 2013, 1, 6335.
15 X. T. Xu, L. K. Pan, Y. Liu, T. Lu, Z. Sun and D. H. C. Chua,
Sci. Rep., 2015, 5, 8458.
Acknowledgements 16 X. T. Xu, L. K. Pan, Y. Liu, T. Lu and Z. Sun, J. Colloid Interface
Sci., 2015, 445, 143.
The research project is supported by the Singapore National
17 Y. Liu, X. T. Xu, T. Lu, Z. Sun, D. H. C. Chua and L. K. Pan,
Research Foundation under its Environmental & Water Tech-
Published on 18 January 2016. Downloaded on 06/03/2016 13:19:17.
11972 | RSC Adv., 2016, 6, 11967–11972 This journal is © The Royal Society of Chemistry 2016