Accepted Manuscript

Title: Magnetic graphene sponge for the removal of methylene

blue

Author: Baowei Yu Xiaoliang Zhang Jingru Xie Ruihan Wu

Xiaoyang Liu Hongliang Li Fang Chen Hua Yang Zhu Ming
Sheng-Tao Yang

PII: S0169-4332(15)01326-4
DOI: http://dx.doi.org/doi:10.1016/j.apsusc.2015.05.185
Reference: APSUSC 30511

To appear in: APSUSC

Received date: 9-2-2015

Revised date: 25-5-2015
Accepted date: 31-5-2015

Please cite this article as: B. Yu, X. Zhang, J. Xie, R. Wu, X. Liu, H. Li, F. Chen, H.
Yang, Z. Ming, S.-T. Yang, Magnetic graphene sponge for the removal of methylene
blue, Applied Surface Science (2015), http://dx.doi.org/10.1016/j.apsusc.2015.05.185

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 Highlights

► Magnetic graphene sponge is prepared for dye removal in aqueous solution.

► Magnetic graphene sponge has an adsorption capacity of 526 mg/g for methylene

blue.

t
ip
► Adsorption behaviors of methylene blue on magnetic graphene sponge are

cr
investigated.

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► Magnetic graphene sponge could be partially regenerated by washing with acidic

ethanol.

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M
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p te
ce
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Page 1 of 26
 Revised-No. APSUSC-D-15-01015

Magnetic graphene sponge for the removal of methylene blue

Baowei Yu, Xiaoliang Zhang, Jingru Xie, Ruihan Wu, Xiaoyang Liu, Hongliang Li,

t
ip
Fang Chen, Hua Yang, Zhu Ming, Sheng-Tao Yang*

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College of Chemistry and Environment Protection Engineering, Southwest University

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for Nationalities, Chengdu 610041, China.

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Corresponding author: Tel: +86-28-85522269; E-mail address: yangst@pku.edu.cn
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Page 2 of 26
 Abstract

Magnetic carbon nanomaterials have been widely adopted as adsorbents in water

treatment, but the low adsorption capacities largely limit their practical applications.

In this study, magnetic graphene sponge (Fe3O4-GS) was prepared by lyophilization

t
ip
for the adsorption of dye pollutant. The incorporation of Fe3O4 enabled the magnetic

cr
separation of Fe3O4-GS after the adsorption of methylene blue (MB). The adsorption

us
capacity of Fe3O4-GS for MB was 526 mg/g, much higher than those of the magnetic

carbon nanoadsorbents in the literature. The adsorption kinetics of MB on Fe3O4-GS

an
was moderately fast, which could be analyzed by the pseudo-second-order model and

intraparticle diffusion model. The thermodynamics study revealed that the adsorption
M
was driven by the increased randomness on the interface. The pH and ionic strength

had meaningful influences on the adsorption capacity of Fe3O4-GS. The facile

d
te

regeneration of Fe3O4-GS would definitely reduce its operating cost. The implications

to the environmental applications of magnetic carbon nanoadsorbents are discussed.

p
ce

Keywords: graphene sponge; adsorption; methylene blue; water treatment;

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nanotechnology

Page 3 of 26
 1. Introduction

Water pollution is one of the most serious environmental problems nowadays,

which hinder the development of human society [1, 2]. In particular, dye pollutants

have attracted the wide concerns from the scientific community and the public,

t
ip
because dyes are highly visible and usually toxic [3, 4]. To decontaminate the dye

cr
pollutants, various technologies are developed and applied, such as adsorption,

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electrolysis, advanced oxidation and active sludge method [5-7]. Among these widely

adopted solutions, adsorption is regarded as the fast, efficient and general technology

an
[7, 8]. Many categories of adsorbent materials are evaluated in dye removal [7, 8].

However, the adsorption capacities of these common adsorbents are generally low.
M
Recently, graphene and its composites are found to be highly effective

adsorbents for water treatment [9, 10]. For instance, we developed a series of
d
te

graphene adsorbents that could be used for the decontamination of heavy metals, dyes

and antibiotics [11-18]. The adsorption capacity of S-doped graphene sponge for Cu2+
p

was 40 times higher than that of active carbon [17]. Similarly, many other groups also
ce

dedicated their efforts to graphene adsorbents [19-21]. Among those attempts,

Ac

magnetic graphene adsorbents aroused the great interest, due to the easy magnetic

separation after the adsorption [22-25]. Unfortunately, upon the combination to

magnetic nanoparticles (NPs), the adsorption performance of graphene decreased

significantly. For example, the adsorption capacity of graphene oxide is 714 mg/g for

methylene blue (MB) [13], and the value decreased to 167 mg/g after the coupling to

Fe3O4 NPs [24].

Page 4 of 26
 Herein, we reported a facile method based on lyophilization for the preparation

of magnetic graphene sponge (Fe3O4-GS), which showed high adsorption capacity for

MB. Well dispersed Fe3O4 NPs were mixed with graphene oxide (GO) by stirring and

then lyophilized to produce porous Fe3O4-GS. Fe3O4-GS was characterized carefully

t
ip
by infrared (IR) spectrometer, transmission electron microscopy (TEM), X-ray

cr
photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and magnetometer. The

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isothermal adsorption was performed, giving an adsorption capacity of 526 mg/g. The

adsorption behaviors of MB on Fe3O4-GS were investigated and the influencing

an
factors were concerned. The regeneration of Fe3O4-GS was partially achieved by

washing with acidic ethanol. The implications to the environmental applications of

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Fe3O4-GS are discussed.
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2. Materials and methods

2.1 Preparation of Fe3O4-GS

p

Graphite and MB were purchased from Sinopharm Chemical Reagent Co. Ltd.,
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China. FeCl2·4H2O was purchased from Damao Chemical Reagent Co., Ltd, China.
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FeCl3·6H2O was bought from Bodi Chemical Engineering Co., Ltd, China. The rest

were of analytical grade.

FeCl2·4H2O (0.21 g) and FeCl3·6H2O (0.45 g) and were dissolved in 10 mL of

deionized water and 6.6 g sodium citrate was added under stirring. Then, the pH value

was adjusted to 12. After stirring for another 30 min, the Fe3O4 cores were separated

with a magnet and washed to neutral. Then, the Fe3O4 cores were dispersed again in

Page 5 of 26
 deionized water.

GO was prepared by the modified Hummers method as described in our previous

reports [11]. The aforementioned Fe3O4 dispersion was added dropwise to 300 mL of

GO (17.4 mg/mL) under stirring. The pH value of the mixture was adjusted to neutral.

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The mixture was stirred for another 1 h and lyophilized to obtain Fe3O4-GS.

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Fe3O4-GS was characterized by TEM (JEM-200CX, JEOL, Japan), IR

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(Magna-IR 750, Nicolet, USA), X-ray photoelectron spectroscopy (XPS, Kratos, UK),

XRD (D/MAX 2000, Rigaku, Japan), and magnetometer (MPMS XL-7Tesla,

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Quautum Design, USA). M
2.2 Adsorption isotherm

The adsorption isotherm of MB on Fe3O4-GS was evaluated in batch

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te

experiments. MB (8.0 mL, 50~400 mg/L, pH 6) was added to 5.0 mg of Fe3O4-GS.

The mixture was shaken on a thermostat at 308 K (CHA-S, Jintan Hankang Electronic
p

Co., China) at 100 rpm for 24 h to reach the equilibrium. Then, the supernatants were
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collected after the magnetic separation for the determination of the MB concentration,
Ac

which was achieved by measuring the absorbance at 664 nm. The equilibrium

concentration (Ce) was calculated referring to the standard curve of MB and the

equilibrium adsorption capacity (qe) could be calculated by (C0-Ce)/CFe3O4-GS. The

adsorption data were fitted to Langmuir model, Freundlich model and Temkin model

[14]. Similarly, the adsorption capacities of Fe3O4-GS for Cu2+ and 2-naphthylamine

were measured following the same protocol. Cu2+ concentrations were determined by

Page 6 of 26
 acetaldehyde-bis(cyclohexanone) oxaldihydrazone (BCO) method as described in our

previous study [11]. The 2-naphthylamine concentrations were determined by

measuring the absorbance at 341 nm.

To visualize the decontamination, the MB solutions (80 mg/L) before the

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treatment were placed in small cuvette as the positive control. The deionized water

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was placed in another cuvette as the negative control. The MB solution after

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adsorption was placed in the cuvette and a magnet was placed in the outside of

cuvette to separate the Fe3O4-GS. The photograph was taken. The visible absorbance

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spectra of the supernatants were recorded.
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2.3 Adsorption kinetics and thermodynamics

To investigate the adsorption kinetics, Fe3O4-GS (5.0 mg) was mixed with 8.0
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mL of MB (175 mg/L, pH 6), shaken for different time intervals (5~420 min) and then

magnetically separated. The MB concentration (Ct) was measured and the adsorption
p

capacity (qt) was calculated by (C0-Ct)/ CFe3O4-GS. The data was analyzed by
ce

pseudo-first-order model, pseudo-second-order model and intraparticle diffusion

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model [15].

To study the thermodynamics, the mixture of Fe3O4-GS (5.0 mg) and 8.0 mL of

MB (175 mg/L, pH 6) were incubated at different temperatures (273~328 K) for 5 h.

The adsorption data were fitted to calculate the thermodynamics parameters [15]. The

distribution coefficient Kd was calculated by qe/ce. The ΔH was determined from the

slope of the regression line after plotting lnKd against 1/T. The ΔG was calculated

Page 7 of 26
 accordingly.

2.4 Influence of pH and ionic strength

To investigate the influence of pH, the initial pH of MB was adjusted from 2 to

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12 with HCl or NaOH aqueous solution (PB-10, Sartorius, Germany). At each initial

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pH condition, Fe3O4-GS (5.0 mg) was mixed with 8.0 mL of MB (175 mg/L) for the

us
determination of qe.

To investigate the influence of ionic strength, MB was mixed with NaCl aqueous

an
solution at different initial concentrations. Fe3O4-GS (5.0 mg) was mixed 8.0 mL of

MB (175 mg/L, pH 6, Na+ concentration: 0~100mM) for the determination of qe.

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2.4 Recycling
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To regenerate the Fe3O4-GS, the used Fe3O4-GS was washed with acidic ethanol

(pH 2). Then the sample was lyophilized. The adsorption capacity was measured as
p

described above. The recycling was performed again to the circle number of 10. The
ce

relative capacity was calculated by qe,n/qe,0, where n was the recycling number.
Ac

3. Results and discussion

3.1 Characterization of Fe3O4-GS

Fe3O4-GS was dark brown sponge, which could magnetically adsorb on magnet

(Fig. 1a). The magnetic property of Fe3O4-GS was evaluated on a magnetometer (Fig.

1b). The magnetic hystersis loop suggested that Fe3O4-GS was ferromagnetic. The

Page 8 of 26
 saturated magnetization was 4.4 emu/g, which was very small comparing to bulk

Fe3O4 (92.8 emu/g) [26]. The low saturated magnetization of Fe3O4-GS should be due

to the low Fe3O4 content (16.7 wt%) and nanosize of Fe3O4 particles [27]. The

magnetic property of Fe3O4-GS indicated that Fe3O4-GS could be magnetically

t
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separated after the adsorption.

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Fig. 1. Photograph (a) and magnetic hystersis loop (b) of Fe3O4-GS.

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The TEM investigation confirmed that Fe3O4 particles were of nanosizes. As

shown in Fig. 2a, small NPs were located on the graphene sheets. The diameters of

Fe3O4 NPs were in the range of 5~20 nm. The XRD spectrum showed very low

intensity (Fig. 2b), which was consistent with the small particle sizes of Fe3O4 and the

Page 9 of 26
 few-layered graphene in Fe3O4-GS. The IR spectrum suggested that there were

oxygen containing groups on Fe3O4-GS (Fig. 3a). The peak at 3420 cm-1 should be

attributed to –OH/–COOH on both Fe3O4 particles and graphene sheets. The small

peak at 1720 cm-1 was assigned to –C=O. The peak at 2380 cm-1 referred to –CH2–,

t
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which should be the remnant citrate residues on Fe3O4. The presence of oxygen

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containing groups were also confirmed by the XPS spectrum. As shown in Fig. 3b,

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the majority of carbon atoms were in the form of C-C (52.4 at%). Another part of

carbon atoms were in the form of C-O (42.2 at%). The rest were in the form of C=O

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(5.4 at%). M
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Fig. 2. Representative TEM image (a) and XRD spectrum (b) of Fe3O4-GS.

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Page 10 of 26
 t
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cr
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Fig. 3. IR (a) and XPS (b) spectra of Fe3O4-GS.

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3.2 Adsorption behaviors

p

The adsorption capacity of Fe3O4-GS was evaluated by using MB as the model

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pollutant. The cationic dye MB is positively charged, thus, would interact strongly

with the oxygen containing groups on Fe3O4-GS. The adsorption isotherm of MB on

Ac

GO-CS was shown in Fig. 4. When the Ce values were lower than 15 mg/L, the

adsorption capacities (qe) increased quickly. Thereafter, the capacity increase slowed

down and reached 526 mg/g at Ce of 71 mg/L. The adsorption isotherm could be fitted

to Temkin model (R = 0.994). The b value was 0.038 kJ/mol, indicating that the

binding strength was moderate. The adsorption capacity of Fe3O4-GS was lower than

that of free GO (714 mg/g) [13], because Fe3O4 might bind to the adsorptive sites.

11

Page 11 of 26
 The low Fe3O4 content and porous structure of Fe3O4-GS were the main reasons of the

retaining capacity. The adsorption capacity of Fe3O4-GS was already much higher

than those magnetic carbon adsorbents in the literature (Table 1) [24, 28-32]. The

adsorption capacity of Fe3O4-GS was also higher than that of GO-chitosan (468 mg/g)

t
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[12], indicating that Fe3O4-GS retained more capacity of GO than GO-chitosan. In

cr
addition, it is worth to note that Fe3O4-GS could be used in treating other pollutants,

us
such as heavy metals and persistent organic pollutants (POP). In our preliminary

evaluations, Fe3O4-GS showed competitive performance in treating Cu2+ (59.6 mg/g)

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and 2-naphthylamine (628 mg/g). M
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Fig. 4. Adsorption of MB on Fe3O4-GS. (a) adsorption isotherm; (b) Temkin model.

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Page 12 of 26
 Table 1. Adsorption capacity of different magnetic adsorbents for MB.

Adsorbent qm (mg/g) Ref.

t
GO- β-cyclodextrin-chitosan@Fe3O4 84 [28]

ip
Graphene-Fe3O4/SiO2 97 [29]

cr
GO-CS-Fe3O4 95 [30]

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GO-Fe3O4 167 [24]

MWCNT-starch-iron oxide 136 [31]

Fe3O4@C NPs

Fe 3 O 4 -GS an117

526
[32]

This study
M
d

To visualize the decoloration, we placed the MB solution before and after the
te

treatment together to photograph. As shown in Fig. 5a, the blue solution turned
p

colorless and transparent after the adsorption. Fe3O4-GS stuck to the side wall of the
ce

cuvette due to the magnetic field, suggesting the efficient separation. To quantify the

decoloration, we recorded the absorbance spectra of MB (diluted by 16 times to 5

Ac

mg/L) and the decolorized solution (Fig. 5b). The typical peak at 664 nm was

observed in both solutions, while the intensity of the decolorized solution was very

low. Quantitatively, the decoloration efficiency was 98%.

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Page 13 of 26
 t
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Fig. 5. Magnetic separation of Fe3O4-GS after the adsorption of MB. (a) photograph;
d

(b) visible absorbance spectra of the supernatants before and after the adsorption.
p te

3.3 Kinetics and thermodynamics

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The adsorption kinetics of MB onto Fe3O4-GS was shown in Fig. 6. The

adsorption capacities increased fast in the first 3 h and became nearly constant
Ac

thereafter. The adsorption kinetics had moderate speed comparing to the novel

adsorbents [33], suggesting that Fe3O4-GS was hopeful from the kinetic perspective.

Comparing to GO dispersion, the adsorption kinetics was much slower [13]. This

should be due to the spongy structure, which required the diffusion of MB toward the

adsorptive sites. Similar phenomenon was reported by Liu et al. in their study of 3-D

GO [34]. The adsorption data were analyzed by the pseudo-first-order and

14

Page 14 of 26
 pseudo-second-order models. The qe calculated from the pseudo-first-order model was

162 mg/g, lower than the experimental qe by 41%. The R value was 0.979. These

collectively suggested that the pseudo-first-order model was not applicable in

describing the adsorption process of MB on Fe3O4-GS. The data were better fitted

t
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with the pseudo-second-order model (R=0.998). The experimental (5% higher) and

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calculated qe values also showed very good consistence. The rate constant of

adsorption (k2) was small (1.5 × 10-4 g/mg∙min-1), which was consistent with the

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moderate adsorption kinetics.

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Fig. 6. Adsorption kinetics of MB on Fe3O4-GS. (a) adsorption as a function of time;

(b) pseudo-first-order model; (c) pseudo-second-order model; (d) intraparticle

diffusion model.

15

Page 15 of 26
 The intraparticle diffusion model was adopted to reveal the diffusion mechanism

(Fig. 6d). The data were easily divided into two stages. In the first stage, the ki value

was 15.3 mg/g·min-0.5 and the C value was 67.6 mg/g (Table 2). In the second stage,

the C value increased to 253 mg/g, which implied that the boundary effect was very

t
ip
huge. The huge boundary effect inhibited the diffusion of MB toward the adsorptive

cr
sites, therefore the adsorption equilibrium was achieved. Both plots did not pass

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through the origin, so the adsorption involved the intraparticle diffusion and surface

diffusion.

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Table 2. Coefficients of the pseudo-first and second-order adsorption kinetic models
M
and the intraparticle diffusion model.

pseudo-first-order qe,exp (mg/g) k1 (min-1) qe,cal (mg/g) R

d

1.17 × 10-2
te

model 275 162 0.979

pseudo-second-order qe,exp (mg/g) k2 (g/mg∙min-1) qe,cal (mg/g) R

p

model 275 1.5 × 10-4 290 0.998

ce

intraparticle diffusion ki (mg/g·min-0.5) C (mg/g) R

Ac

model (stage 1) 15.3 67.6 0.994

intraparticle diffusion ki (mg/g·min-0.5) C (mg/g) R

model (stage 2) 1.04 253 0.897

Thermodynamics data are important to the parameter optimization and in-depth

understanding of the adsorption process. As demonstrated in Fig. 7a, the adsorption

16

Page 16 of 26
 capacity increased with the growth of temperature. This demonstrated that the

adsorption was endothermic in nature. Higher adsorption capacity of Fe3O4-GS could

be obtained at higher temperature. Higher temperature reduced the viscosity of the

solution and increased the diffusion rate of MB molecules [35].

t
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cr
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M
d
p te
ce
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Fig. 7. Adsorption thermodynamics of MB on Fe3O4-GS. (a) influence of temperature;

(b) thermodynamics analysis.

Based on the adsorption capacities at different temperature, we calculated the

thermodynamics parameters for the adsorption of MB on Fe3O4-GS (Table 3). All ΔG

values were negative in the temperature range of 273~328 K, indicating that the

17

Page 17 of 26
 adsorption was spontaneous. ΔG value decreased toward negative at higher

temperature, consistent with the larger adsorption capacity. The absolute values of ΔG

were very small, implying that the adsorption was physisorption. The adsorption

process was endothermic according to the positive ΔH value. The driven force for the

t
ip
adsorption was the increase of the randomness at the solid/solution interface, because

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the ΔS value was positive [15]. The thermodynamics parameters suggested that the

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adsorption of MB on Fe3O4-GS should be performed at higher temperature when

possible.

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Table 3. Thermodynamics parameters for the adsorption of MB on Fe3O4-GS.
M
T (K) ΔG (kJ·mol -1 ) ΔH (kJ·mol -1 ) ΔS (J·mol -1 ·K -1 )

273 -3.14
d
te

298 -6.99

308 -8.53 38.9 154

p

318 -10.1
ce

328 -11.6
Ac

3.4 Influence of pH and ionic strength

The pH influences the adsorption process of many charged pollutants since it

converts charge species as well as the surface properties of the adsorbent. Our results

suggested that pH had minor influence on the adsorption of MB on Fe3O4-GS. As

shown in Fig. 8a, the adsorption was promoted slightly along with the increase of pH

18

Page 18 of 26
 values. Electrostatic interaction was a major contributor of the total interaction

between MB and Fe3O4-GS [9]. The pH regulated adsorption should be attributed to

the protonation stages of both MB and Fe3O4-GS. The hydroxyl groups and carboxyl

groups on Fe3O4-GS were deprotonated at higher pH values to obtain more negative

t
ip
charges. Thus, the electrostatic interaction between MB and Fe3O4-GS would be

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strengthened. Nevertheless, the minor influence of pH suggested that Fe3O4-GS could

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be used under various pH values without serious capacity loss.

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Fig. 8. Influence of pH (a) and ionic strength (b) on the adsorption performance of

Fe3O4-GS.

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Page 19 of 26
 Ionic strength had meaningful influence on the adsorption of MB on Fe3O4-GS

(Fig. 8b). At the initial MB concentration of 175 mg/L, the adsorption capacity ranged

from 254 mg/g at 0 mM Na+ to 157 mg/g at 100 mM Na+. The inhibition of

adsorption was significant at high ionic strength. Electrostatic protection might be

t
ip
emerged after added NaCl, which could inhibit the immediate electrostatic interaction

cr
between adsorbent and adsorbate. The weakened interaction between MB and

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Fe3O4-GS led to the lower adsorption capacity. Beyond that, the increase of ionic

strength promoted the competitive adsorption between MB and Na+ on the adsorptive

an
sites of Fe3O4-GS. Such competitive adsorption was widely reported in the literature

[9]. Therefore, Fe3O4-GS should be used at low ionic strength to get better
M
performance.
d
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3.4 Recycling

The regeneration of adsorbent will reduce the operating cost, thus should be
p

evaluated for Fe3O4-GS. As shown in Fig. 9, the adsorption capacity showed a

ce

decrease trend during the recycling. The loss of adsorption capacity might be due to
Ac

the collapse of porous structure of Fe3O4-GS. It might also be related to the strong

interaction between GO sheets and MB molecules. In the literature, it was reported

that only 37% of MB could desorb from GO sheets upon the washing with acetic acid

in methanol [36]. After three cycles, the adsorption capacity did not change much.

The results here clearly indicated that Fe3O4-GS could be partially regenerated after

20

Page 20 of 26
 the adsorption of MB. The regeneration protocol was very simple. In the future, better

regeneration protocols and stable porous structure of Fe3O4-GS are highly demanded.

t
ip
cr
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an
Fig. 9. The relative adsorption capacities of recycled Fe3O4-GS.
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4. Conclusions

In summary, magnetic graphene sponge was prepared by lyophilization for the

d

adsorption of dye pollutant, where the adsorption capacity of Fe3O4-GS was much
te

higher than those of other carbon nanoadsorbents. The high adsorption capacity was
p

mainly due to the porous structure of graphene sponge. Thermodynamically, the

ce

adsorption was driven by the increased randomness on the interface. The fast

adsorption kinetics, magnetic separation and easy regeneration enabled the facile
Ac

applications in future. It is hoped that our results would benefit the ongoing

exploration of graphene based environmental nanotechnology.

Acknowledgements

We acknowledge financial support from the Science and Technology

Department of Sichuan Province (Pillar Program No. 20134FZ0060), Education

21

Page 21 of 26
 Department of Sichuan Province (No. 15ZA0392), the China Natural Science

Foundation (No. 201307101), and the Innovation Scientific Research Program for

Graduates in Southwest University for Nationalities (No. CX2015SZ041).

t
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