Materials Chemistry and Physics 199 (2017) 424e434

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Materials Chemistry and Physics

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Preparation of supported catalyst by adsorption of polyoxometalate on

graphene oxide/reduced graphene oxide
Azam Khodadadi Dizaji, Hamid Reza Mortaheb*, Babak Mokhtarani**
Chemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186, Tehran, Iran

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The produced graphene oxides were

characterized and applied to support
POM.

Graphene oxide showed a better
POM adsorption capacity than that of
reduced ones.

The highest adsorption was obtained
in pHs below isoelectric point of
graphene oxide.

The highest adsorption capacity was
acquired in suspension containing
water-methanol.

The kinetics of POM uptake process
was best fitted by a second-order
model.

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

Article history: Adsorption of tungstophosphoric acid (H3PW12O40) as a polyoxometalate (POM) on graphene oxide (GO)
Received 5 April 2017 and two reduced graphene oxide supports (RGO-a/RGO-b) for producing supported catalysts was studied
Received in revised form using an equilibrium adsorption technique by ultravioletevisible spectroscopy analysis. The surface
1 July 2017
properties of supports were analyzed by XPS to interpret their different adsorption properties. The
Accepted 4 July 2017
Available online 4 July 2017
samples were characterized by XRD, RAMAN, FTIR, SEM-EDX, and TEM analyses. The three most
determinant parameters in adsorption phenomena are presence of oxygen functional groups on the
support, the polarization of surface functional groups in accordance to the suspension pH, and the sol-
Keywords:
Polyoxometalate (POM)
vent type. The supported polyoxometalate on GO (GO/POM) prepared by adsorption in a suspension of
Adsorption 1:1 water/methanol mixture with pH ¼ 3.5 yielded the highest adsorption capacity of 427 mg/g while
Graphene/graphene oxide the adsorption capacities of supported polyoxometalate on reduced samples were 74 mg/g and 54 mg/g,
Equilibrium adsorption technique respectively. The pH-dependent behavior of ionizable surface oxygen functional groups was investigated
Ultravioletevisible spectroscopy and results revealed that also played a key role in the adsorption capacity. The highest POM adsorption
was obtained in the pHs below isoelectric point of GO where POM anions can establish chemical bonds
with the positive net surface charge. The highest adsorption capacity was obtained in the water-
methanol mixture. The kinetics of adsorption mechanism was best described by a pseudo-second-
order model.
© 2017 Elsevier B.V. All rights reserved.

* Corresponding author. 1. Introduction

** Corresponding author.
E-mail addresses: mortaheb@ccerci.ac.ir (H.R. Mortaheb), mokhtaranib@ccerci.
ac.ir (B. Mokhtarani).
Polyoxometalates (POMs) represent a diverse family of nanosize

http://dx.doi.org/10.1016/j.matchemphys.2017.07.016
0254-0584/© 2017 Elsevier B.V. All rights reserved.
 A. Khodadadi Dizaji et al. / Materials Chemistry and Physics 199 (2017) 424e434
polynuclear species containing transition metals (mainly vana-
dium, molybdenum, tungsten) and oxygen atoms with various
applications in both fundamental and applied sciences [1e5]. The
diversity of researches on polyoxometalates is significant due to the
variability of their size, structure, elemental composition, and
hence their chemical and electronic properties [6e8]. Keggin-type
POMs, known also as heteropolyacids (HPAs), have been receiving
continuous attentions because of their numerous advantages such
as strong Brønsted acidity and interesting redox properties that
make them appropriate for electrochemistry [8e10], photochem-
istry [11], energy storage [12e16], environmental protection [17],
and catalysis [18e28]. However, the most wide-ranging research on
polyoxometalates have been performed in the field of catalysis, in
which their applications as oxidation catalysts and Brønsted acid
catalysts have been going on since the late 1970s [1,6]. However, the
application range of these active spices is limited due to their low
surface area (1e5 m2g1) and problematic separation and recycling
processes [22,24]. Dispersing POMs on appropriate supports can
improve the availability of their active sites and actual activity, and
hence solve their separation problems [23,29e31]. These signifi-
cant aspects have prompted researchers to anchor POM on a sup-
port material by various methods such as sol-gel techniques
[31,32], electrostatic interactions [33], ion exchange [4,22], cova-
lent grafting [4], and impregnation [8,17,22,25,29,31,34e36]. The
most studied strategy consists of dispersing POMs on support
surfaces using the classical impregnation technique. However,
improper impregnation might led to losing deposited POMs due to
leaching [37]. The most common supports are mesoporous silica
[20,26,38,39], MOFs [3,4], polymers [16], metal oxides [33], mag-
netic nanoparticles [32], and carbon materials
[15,21,24,25,34,40,41]. Nowadays, graphene with exceptionally
unique properties such as high surface area, and high electrical,
thermal and mechanical properties has attracted great attentions
[8,18,23,42e45]. On the other hand, graphene oxide (GO, decorated
graphene sheets mostly by oxygen functional groups) is an ideal
processable form of graphene that can yield stable dispersions in
various solvents and serves as a promising support [23,43].
The HPAs are present in water and polar organic solutions in
their anionic forms. Therefore, the pH-dependence positive charge
of abundant oxygen functional groups on the graphene oxide sur-
face can adsorb anionic HPAs [34,36,43,44]. In addition to electro-
static interactions, proton donor functional groups of graphene
oxide can be associated with POMs by hydrogen bonding [4]. Bru-
nelle investigated surface polarization of supporting oxides versus
pH and adsorption of counter ions by electrostatic attraction [29].
Vissers reported the pH dependency of carbon samples with
different surface properties (oxygen functionality) in adsorption of
molybdate [36]. Although it has been found that charge properties
of the surface groups can affect the immobilization of POMs on
oxide surfaces [21,25,29,34,37], these effects have not been
addressed in detail for immobilization of POMs on graphene or
graphene oxide. Recently, Tessonnier et al. and Kim et al. deposited
POMs on reduced GO (RGO) and observed that the electrostatic
interactions were more than the electron transfer interaction of
POMs with graphene surface because of large content of oxygen
functional groups [8,23].
Up to now different support materials have been used for
dispersion of POMs. Although the effects of some properties of the
supports such as pH dependence of the surface functional groups
on their adsorption properties have been discussed in literature,
such effects have not been investigated in details for immobiliza-
tion of POMs on GO and RGO.
The present study focuses on the effects of functional groups of
the support surface, type of solvent, and the pH of solution on
immobilization of POMs on GO and RGO and their effects on the
425
adsorption. The findings of present study about POM immobiliza-
tion may provide new insights into preparation of graphene sup-
ported POMs and can be generalized to various POMs for a variety
of applications.
2. Experimental
2.1. Materials
The applied materials in current research, their purities, and
suppliers are as follows: pristine graphite powder, 325 mesh
(99.9%, Timcal), sulfuric acid (98%, Merck), phosphoric acid (99%,
Sigma-Aldrcih), hydrochloric acid (37%, Merck), hydrogen peroxide
(30% in H2O, Merck), sodium borohydride (98%, Merck), hydrazine
solution (80% in H2O, Merck), potassium permanganate and sodium
nitrate (99.5%, Merck), methanol (99.8%, Sigma-Aldrich), ethanol
(99.5%, Sigma-Aldrich). All materials were used without further
purifications.
2.2. Synthesis of graphene oxide
Graphene oxide (GO) was prepared according to the modified
Hummer method [42]. Briefly, 3 g graphite flakes and 18.0 g KMnO4
were loaded into a three-neck round bottom flask. Then, a mixture
of H2SO4/H3PO4 (360:40 mL) was slowly added to the mixture. The
reaction was stirred in an oil bath at 50  C for 12 h. The reaction
vessel was cooled to room temperature and placed into an ice bath.
400 mL of deionized water with 3 mL of 30% H2O2 was added to the
flask dropwise. The mixture was centrifuged (15000 rpm, 10min),
and the supernatant was decanted away. The remained solids were
washed with 200 mL of water, 200 mL of 30% HCl, and 200 mL of
ethanol. The solids were vacuum-dried overnight at 85  C and then
crushed to a fine powder in an agate mortar.
2.3. Preparation of reduced graphene oxide
- Production of RGO-a:
A colloidal suspension of 1 mg/mL graphene oxide was prepared
by sonication in an ultrasonic bath for 1 h. Hydrazine hydrate (1 mL,
80%, Merck) was then added to 100 mL of as prepared suspension
and the mixture was heated in an oil bath at 80  C for 12 h. The
product was washed with water and filtered after cooling to room
temperature. It was then dried at 80  C in a vacuum oven for 12 h
[46].
- Production of RGO-b:
100 mg colloidal suspension of graphene oxide (1 mg/mL) was
prepared by an ultrasonic bath. 200 mg of NaBH4 was then added to
the mixture and heated in an oil bath at 80  C for 4 h. The as-
prepared graphene sheets were separated by centrifuging, and
dried for 12 h at 80  C in the vacuum oven after washing well with
water [47].
2.4. Adsorption and preparation of supported polyoxometalate
Batch experiments were performed at 298 K to investigate the
POM adsorption on different supports. For each experimental run,
the colloidal suspension of 0.011 g of each support in 5 mL of the
solvent (1:1 water/methanol, water, or methanol) was prepared by
sonication in a 50-mL vial. 25 mL of POM solution in the corre-
sponding solvent (1:1 water/methanol, water, or methanol) with
the initial concentration of 300 ppm was poured into the vial. The
support loading was set to 365 mg/l. The pH of solution was
426 A. Khodadadi Dizaji et al. / Materials Chemistry and Physics 199 (2017) 424e434

adjusted in the range of 2.5e4.5 by adding dilute HCl and was kinetics models were used. The linearized equations of pseudo-
measured using a lab pH-Meter (827Metrohm, Swiss made). After first-order and pseudo-second-order models can be described as
taking the first sample from the suspension, the vial was removed follows:
from the ultrasonic bath and kept under constant stirring  
(500 rpm) for one day using a magnetic stirrer. The samples were Pseudo  first  order model : log qe;1  qt ¼ logqe;1  k1 t
taken at specified time intervals from the mixture, filtered through
a syringe filter (Whatman, 25 mm, pore size of 0.2 mm), and (2)
analyzed using UVeVis technique (PerkinElmer, USA, at
240e270 nm, with concentrations of POM in the range of 0.01e5 g/ t 1 t
Pseudo  second  order model : ¼ þ (3)
L). The adsorbed amounts, q, is calculated using the following qt k2 q2e;2 qe;2
equation:
where qt (mg/g) is the amount of POM adsorbed per unit mass of
Q ¼ V (C0-C)/W (mg/g) (1) the support at time t (min); qe,1 and qe,2 (mg/g) are the adsorption
capacities calculated by pseudo-first-order and pseudo-second-
where C0 and C are the initial and final POM concentrations (mg/L), order models with rate constants of k1 (1/min) and k2 (g/mg
respectively, V is the solution volume (mL), and W is the mass of the min), respectively [48].
support (g). Finally, the solid particles were collected from the
suspension for further physiochemical analysis using a filter paper,
washed with distilled water, and dried at 90  C. For studying the 2.5. Characterization analyses
POM leaching from the GO support, 0.01 g of sample was sus-
pended in 10 mL of the solvent and stirred for several hours, and The structures of different supports were characterized using a
after filtration the UVevis spectra of the filtrate were recorded. powder X-ray diffractometer (XRD, Bruker, D8-advance, 2q ¼ 4e70,
To assess the mechanism of adsorption and test the fitness of the 40 kV/30 mA with monochromatized Cu Ka radiation, k ¼ 1.54 Å).
experimental data, pseudo-first order and pseudo-second order Raman spectra were carried out with a 532 nm laser source Raman

(a) C1s
O1s RGO-b

RGO-a
Intensity (a.u. )

GO

Binding Energy (eV)

286.7 eV 284.8 eV
(b) 284.8 eV C-O C-C/C=C 284.8 eV
C-C/C=C C-C/C=C

GO 287.8 eV RGO-a RGO-b

C=O 286.7 eV
286.7 eV
289.2 eV C-O O 289.2 eV C-O
O-C=O 287.8 eV
O-C=O
C=O 289.2 eV
O-C=O

Fig. 1. (a) XP spectra of GO, RGO-a, and RGO-b; (b) High-resolution XP spectra of C1s peaks for GO, RGO-a, and RGO-b.
 A. Khodadadi Dizaji et al. / Materials Chemistry and Physics 199 (2017) 424e434 427

Table 1 microscope (Teksan, Takram P50C0R10). Molecular vibration

Analyses of C1s peaks and relative percentages of different functional groups ob- characterization of the samples was carried out by Fourier trans-
tained from XP spectra.
form infrared spectroscopy (FTIR; Perkin-Elmer spectrum 65). The
Sample CeC/C]C CeO/CeOeC C]O OeC]O Elemental Ratio (C/O) XP spectra of the samples were measured using a Gamma Data-
GO 56.1% 22.9% 15.5% 5.5% 1.79 Scienta ESCA 200 hemispherical analyzer equipped with an Al Ka
RGO-a 77.8% 19% 0% 3.2% 8.09 (1486.6 eV) X-ray source. The morphologies of samples were
RGO-b 83.6% 14.4% 0.3% 1.7% 29.33 examined by a scanning electron microscope (SEM, TESCAN,
Vega3). Transmission electron microscopy (TEM) images were
taken using a CM200 FEG TEM Philips-M.E.R.C.

POM 3. Results and discussion

3.1. X-ray photoelectron spectroscopy (XPS)

X-ray photoelectron spectroscopy analysis was carried out from

the binding energy of 1200 eVe0 eV to investigate the overall
Intensity (%)

composition of available elements on different supports as shown in

GO/POM Fig. 1a and b. The XP spectra of the samples in Fig. 1a show oxygen
peaks (533.4 eV) and carbon peaks (284.5 eV) [49]. Fig. 1 b dem-
onstrates the high resolution XP spectra for C1s peaks of GO, RGO-a,
RGO-a/POM
and RGO-b and their deconvolution peaks. The relative percentages
of different functional groups obtained from the deconvoluted
peaks in Fig. 1b are represented in Table 1. The survey scans provide
percentages of various oxygen functional groups in each sample.
RGO-b/POM According to data in Table 1, a lower C/O ratio for graphene oxide
(1.79) indicates the presence of higher amounts of oxygen con-
taining functional groups. Due to existence of hydroxyl, carboxyl,
carbonyl, and epoxide functional groups attached to the surface
Wavenumber (cm-1) [43]. RGO-b with the highest C/O ratio (29.33) has the lowest oxygen
containing functional groups while RGO-a stands somewhere in
Fig. 2. FT-IR spectra of POM, GO/POM, RGO-a/POM, and RGO-b/POM.
between GO and RGO-b with C/O ratio of 8.09 [50,51].

(a) (b)
POM

RGO-b
Intensity (a.u.)

Intensity(a.u.)

RGO-b/POM
RGO-a
RGO-a/POM

GO GO/POM

2 theta (degree) 2 theta (degree)

Fig. 3. XRD spectra of (a) GO, RGO-a and RGO-b, and (b) GO/POM, RGO-a/POM, and RGO-b/POM.

(a) (b)

Raman shift (cm-1) Raman shift (cm-1)

Fig. 4. Raman spectra of samples (a) GO, RGO-a, and RGO-b, (b) GO/POM, RGO-a/POM, and RGO-b/POM.
428 A. Khodadadi Dizaji et al. / Materials Chemistry and Physics 199 (2017) 424e434

3.2. Fourier transform infrared spectroscopy (FTIR)
The infrared spectra of POM and supported POM on GO, RGO-a,
and RGO-b are shown in Fig. 2. For unsupported H3PW12O40, four
characteristic bands denoting heteropolyacids of Keggin structure
are observed. These characteristic bands appear at 1108 cm1
(stretching frequency of P-O in the central PO4), 985 cm1 (ter-
minal bands for W¼O in the exterior WO6), 889 cm1 (band for
WeObeW bridge), and 805 cm1 (bands for the WeOceW bridge)
[52]. These features of H3PW12O40 in all samples indicate immo-
bilizing of H3PW12O40 on the surface of the support without
structure damaging. However, major differences in the spectra of
the GO/POM sample are observed compared to those of unsup-
ported POM. In particular, all characteristic bands of POM shifted
to higher wavenumbers when the POM is supported on GO. This
may be ascribed to the strong electrostatic interaction between
the POM anion and protonated surface functional groups of GO as
counterions [8,53]. The counterion (Hþ) may be partially delo-
calized between the cluster and the GO surface, and thus taking
part in the electrostatic bond. The induced polarization of coun-
terion changes the electron density or delocalizes the charge of
the POM. These alterations would also have a measurable effect on
the frequencies of IR spectrum [8]. In a similar study, Tessonnier
reported a large band shift for the GO/POM although he believed

(a) 2μm (d) 2μm

1500
C C W
1000
1000
O
500
O 500 O
P
0 W
0 1 2 3 4 5 0
0 5 10

(b) 2μm (e) 2μm

C
2000
3000 C

2000
1000

O 1000
W
0 O P
0 1 2 3 4 5 0
0 1 2 3 4 5

(c) 2μm (f) 2μm

5000 C
5000 4000
C
4000
3000
3000
2000
2000
1000 O 1000
O W P
0 0
0 1 2 3 4 5 0 1 2 3 4 5

Fig. 5. SEM and EDX characterizations of supports and their corresponding composite materials after POM immobilization: (a) GO, (b) RGO-a, (c) RGO-b, (d) GO/POM, (e) RGO-a/
POM, and (f) RGO-b/POM.
 A. Khodadadi Dizaji et al. / Materials Chemistry and Physics 199 (2017) 424e434 429

(a) (b)

30nm 30nm

Fig. 6. TEM images of (a) GO and (b) GO/POM.

that any change in the characteristic band of supported POMs

depends on the synthesis method that may cause different band
shifts [8].
In the present study, with the aid of favorable polarization of
surface functional groups in GO-POM, the observed shifts of about
85 cm1, 60 cm1, 99 cm1, and 34 cm1 for WeOceW, WeObeW,
W¼O, and P-O, respectively, indicate strong interactions whereas in
the case of RGO-a/POM and RGO-b/POM, smaller band shifts are
observed. This indicates restricted electrostatic interactions via
protonation of remained unreduced oxygen functional groups on
the reduced samples in addition to the electron transfer interaction
between the graphene surface and POM ions.

3.3. X-ray diffraction pattern (XRD)

The X-ray diffraction spectra of supports, POM, and composite

materials after POM immobilization are shown in Fig. 3. The lower
angle reflection peak (2q ¼ 11.82) of GO in Fig. 3 a indicates for-
mation of oxygen-containing groups between the layers during the
preparation of GO while the shift of the peak in RGO-a and RGO-b to
a higher value (2q ¼ 26.4) reflects the decrease in the interlayer
spacing after reduction process and verifies removal of surface
oxygen functional groups [17]. From the XRD analysis, the inter-
layer spacing of GO, RGO-a, and RGO-b are determined as 0.748,
0.338, and 0.336 nm, respectively, that are proportional to the de-
grees of oxidation and reflect the presence of oxygen functional
groups between the structural layers [10].
The XRD characteristic peaks of POM can be clearly seen in
Fig. 3b. However, the characteristic peaks of POM are not observed
in the XRD spectra of GO/POM, RGO-a/POM, and RGO-b/POM. This
may indicate that the POM crystals are in a high dispersed state on
the surface. It suggests that POM anions are immobilized on the
surface via a chemical bonding interaction [18].

3.4. Raman analysis

The Raman spectra of the synthesized samples are shown in

Fig. 4. Two intense peaks at 1592 cm1 (G band) and 1351 cm1 (D
band) corresponding to the breathing mode of k-point phonons of
A1g symmetry and the E2g vibration mode for the hexagonal sp2
carbon domains, respectively, are observed. The intensity ratio of
these bands (ID/IG) provides the degree of disorder and is
inversely proportional to the average size of sp2 domains in the Fig. 7. (a) Concentrations of POM in suspensions containing different supports as a
function of time, (b) UVevis spectra of POM solutions after contacting with GO, RGO-a,
samples. It can be used to confirm the reduction process. The ID/IG and RGO-b (inset shows equilibrium adsorption capacities). Experimental conditions:
intensity ratio of GO is increased after reduction indicating that Support loading ¼ 365 mg/l, POM concentration ¼ 250 ppm in 1:1 water/methanol,
the reduction process removes the oxygen moieties and alters the pH ¼ 3.5, and T ¼ 25  C.
430 A. Khodadadi Dizaji et al. / Materials Chemistry and Physics 199 (2017) 424e434
structure of GO with increasing the number of sp2 domains [9].
The decrease of the average size of sp2 domains might be attrib-
uted to the creation of new graphitic domains, which are smaller
in size but abounded in the number. The Raman spectra of GO/
POM, RGO-a-/POM and RGO-b/POM also contain both D and G
bands similar to those of GO, RGO-a, and RGO-b indicating that the
POM adsorption do not disrupt the graphitic structure of the
supports. The slight observed increment in the ID/IG ratio after
POM deposition may indicate that deposition of POM results in
increasing of defects and disorders [23].
3.5. Scanning electron microscopy (SEM) combined with energy
dispersive X-ray (EDX) analyses
The morphologies of the raw supports and composite materials
after POM immobilization are shown in SEM images of Fig. 5
(a)e(f). The overall composition of the samples are also deter-
mined by EDX analysis and shown as the insets in the figures. The
ruffled appearance and tulle-like structure of GO layers are evident
in Fig. 5a. The SEM images of reduced samples (RGO-a and RGO-b)
in Fig. 5b and c indicate agglomeration of loose and rippled silk-like
GO structure after reduction. The EDX spectra of the raw supports
(insets of Fig. 5 aec) show only carbon and oxygen. The lower O/C
ratios of RGO-a and RGO-b compared to that for GO provide evi-
dence that the oxidation method removes considerable amounts of
oxygen functional groups.
(a)
H+
- +
H+
(b)
H+
+
-
H+
Fig. 8. Polarization of some surface oxide-containing functional groups of graphene oxide in an acidic medium: (a) carboxylic acid, (b) phenolic hydroxyl.
The SEM images and the EDX spectra of corresponded samples
after POM immobilization confirm the same morphological
structure and presence of P and W (as representatives for POM). It
is also evident from the EDX spectra that the intensities of W and P
peaks are higher for GO/POM than those for RGO-a/POM and RGO-
b/POM.
3.6. Transmission electron microscopy (TEM) analysis
The TEM images of GO and GO/POM are shown in Fig. 6. The
flake-like structure of GO is clearly observed in Fig. 6a. The TEM
image of GO/POM sample (Fig. 4b) shows that the clusters of POM
are presents uniformly on the surface and between the GO layers as
dark points. From the figure, the average size of spherical POM
clusters is in the range of about 5e15 nm.
3.7. Effect of different supports
The surface chemistry of support plays a decisive role during
impregnation process in contact with an impregnating solution
[29,35,37,54]. The adsorption of POM on GO, RGO-a, and RGO-b was
investigated by UVevis spectroscopy. As seen in Fig. 7a, the POM
concentration is decreased significantly after contacting with GO
compared to that with RGO-a and RGO-b. The results indicate that
the abundant amount of GO’s surface oxygen functional groups
makes a large adsorption capacity for it in comparison to the
+
2
H2O
+
2
-
+ H2O
 A. Khodadadi Dizaji et al. / Materials Chemistry and Physics 199 (2017) 424e434 431

reduced samples. In other words, the electrostatic interactions 3.8. Effect of pH

between oxygen functional groups on the GO surface and POM
contribute more than the electron transfer interactions from the
POM to the graphene sheet [23]. The suddenly induced enhance-
ment in the POM adsorption for all experiments during the initial
five minutes is probably due to intensive stirring in the ultrasonic
environment in comparison to the next intervals using simple
stirring [55]. Fig. 7b shows the absorption spectra of 250-ppm POM
solutions after contacting with GO, RGO-a, and RGO-b for 24 h.
Since any change in the UV spectra of HPA solutions can be
attributed to the changes in the structure of the individual HPA, the
spectrum with a maximum absorption at 262.6 nm in all the
samples shows that HPA is stable in the in the experimental con-
ditions. The maximum POM adsorption capacities of the two
reduced samples (RGO-a and RGO-b), as shown in the inset of
Fig. 7b, are 75 mg/g and 55 mg/g, respectively, while the adsorption
capacity of POM on GO is as much as 427 mg/g. This is in agreement
with the finding by Schwegler who reported that the interaction of
POM with carbon materials depends on the support surface char-
acteristics [25].
The pH of solution can influence surface charging of the adsor-
bent as well as dissociation degree of the adsorbate
[25,29,34,35,41]. At the pH of isoelectric point (IEP), the amount of
negative and positive charges on the surface are exactly balanced
leading to a zero net charge [56]. In the case of GO, depending on
the solution pH, the oxygen functional groups on the surface can
undergo acid-base reactions, creating positive or negative surface
[54]. Fig. 8 depicts the reaction mechanism for polarization of
carboxyl and hydroxyl functional groups in different pHs. As seen in
the figure, increasing or decreasing pH will cause a positive or
negative charging of the surface functional groups.
IEP of GO is typically reported near pH ¼ 3.8 in literature [54,57].
The pH values of the experiments were chosen in the range of
2.5e4.5, in which POMs are stable. As seen in Fig. 9a, the concen-
tration of POM in the solution decreases steadily during the
experimental time and attains to the equilibrium conditions. In pHs
of 3.5 and 2.5, adding POM anions to the solution results in elec-
trostatic bonding with positive GO functional groups [29]. In

Fig. 9. (a) Concentrations of POM in suspensions containing GO with different pH as a function of time, (b) UVevis spectra of POM solutions in equilibrium time (inset shows
equilibrium adsorption capacities). Experimental conditions: support loading ¼ 365 mg/l, POM solution ¼ 250 ppm in 1:1 water/methanol, T ¼ 25  C.
432 A. Khodadadi Dizaji et al. / Materials Chemistry and Physics 199 (2017) 424e434

pH ¼ 4.5, the adsorption is significantly decreased due to major

barrier of electrostatic repulsions between negative ionized oxygen
functional groups on the GO surface and POM anions [44]. UV ab-
sorption spectra of the solutions in equilibrium conditions
(700 min) in Fig. 9b indicate that the HPA is stable in the whole pH
range with a maximum absorption at 262.6 nm. Also, a significant
increase in equilibrium adsorption capacity of GO in pH ¼ 3.5 is
observed in comparison to that for the solution with pH ¼ 4.5 and
pH ¼ 2.5. Godfride also reported the pH dependent behavior of
carbon for adsorption of molybdenum ions where positively
charged surface below IEP enhanced the adsorption capacity [34].
In addition, Komiyama believes that both adsorption characteristics
of the support oxide surfaces and the chemical species of the liquid
phase depend vastly on the pH of the impregnating solution [58].
Brunelle and Wang discussed the pH dependence of adsorption
characteristics of oxide surfaces in terms of IEP and positive/
negative polarization of the surface and hence different tendencies
to cations or onions in the solution [29,59].

3.9. Effect of solvent

In order to determine the effect of solvent on the POM adsorp-

Fig. 10. (a) Concentrations of POM in different suspensions containing GO as a function
of time, (b) UVevis spectra of POM solutions in equilibrium time (inset shows equi-
librium adsorption capacities). Experimental conditions: GO loading ¼ 365 mg/l, POM
solution ¼ 250 ppm in water, 1:1 water/methanol, and methanol, pH ¼ 3.5, and
T ¼ 25  C.
tion, methanol as an organic solvents, water, and mixture of 1:1
water/methanol were used. Methanol was selected since a Keggin
type HPA is not decomposed in alcoholic solutions. In addition,
methanol does not interfere with the UV detection. As seen in
Fig. 10a, the adsorption rate for water solution is higher than that
for methanol or the mixed solution and the equilibrium adsorption
is attained at 200 min thereafter POM is desorbed from the GO
support because of high solubility of POMs in water as a polar
solvent. In agreement with the above results, Wang believes that
the anion adsorption on the support surface is a reversible elec-
trostatic process with a desorption possibility [59]. According to
Fig. 10b, the amount of POM in methanol solution at equilibrium is
much lower than that in water or mixed solution. This is in
agreement with previous studies, in which the weaker POM
adsorption in alcohol solution was reported [25].
The desorption amounts of POM from the supported and dried
samples were tested in either polar protic (water) or polar aprotic
(acetonitrile) media. Less than 1 wt% of the POM was lost when

16
GOiii RGO-b ii RGO-a ii GOiii RGO-b ii RGO-a ii
14
GOi GOii GOi
GOii
12

10
(a) (b)
t/q

0
0 200 400 600 800
t (min)
Fig. 11. (a) Pseudo-first-order and (b) pseudo-second-order kinetic models for adsorption of POM on GO and RGOs. Experimental conditions: i) Support loading ¼ 365 mg/l, POM
solution ¼ 250 ppm in 1:1 water/methanol, pH ¼ 2.5, and T ¼ 25  C. ii) Support loading: 365 mg/l, POM solution: 250 ppm in 1:1 water/methanol, pH ¼ 3.5, and T ¼ 25  C. iii)
Support loading: 365 mg/l, POM solution: 250 ppm in 1:1 water/methanol, pH ¼ 4.5, and T ¼ 25  C.
 A. Khodadadi Dizaji et al. / Materials Chemistry and Physics 199 (2017) 424e434 433

Table 2
Kinetic parameters for adsorption of POM on different supports.

Samples qexp (mg/g) Pseudo first order Pseudo second order

k1  102 (1/min) qe,1 (mg/g) R2 k2  103 (g/mg min) qe,2 (mg/g) R2

a
GO 314.65 1.2 413.81 0.9826 0.003 359.14 0.9976
GOb 427.27 0.32 502 0.9966 0.003 444.26 0.9999
GOc 54.59 0.71 66.19 0.9978 0.002 62.13 0.9884
RGO-ab 72.78 0.39 31.01 0.8646 0.274 78.92 0.9975
RGO-bb 54.54 0.34 17.79 0.7659 0.335 55.98 0.9985

Experimental conditions:
a
Support loading ¼ 365 mg/l, POM solution ¼ 250 ppm in 1:1 water/methanol, pH ¼ 2.5, and T ¼ 25  C.
b
Support loading: 365 mg/l, POM solution: 250 ppm in 1:1 water/methanol, pH ¼ 3.5, and T ¼ 25  C.
c
Support loading: 365 mg/l, POM solution: 250 ppm in 1:1 water/methanol, pH ¼ 4.5, and T ¼ 25  C.

GO/POM was washed by acetonitrile even after 6 h stirring while
about 9 wt% of POM was lost from GO/POM in case of water. The
possibility of HPA to be leached out from the support should be
taken into account when using the supported POM in an aqueous
phase.
3.10. Kinetic analysis
In order to investigate the kinetics of sorption process, the
pseudo-first/second order models were applied to the experi-
mental data for different supports [60]. The kinetic parameters for
the two models were calculated from the slopes and intercepts of
linear fittings to the plots of log (qeqt) in Fig. 11a and t/qt in Fig. 11b
versus time. According to the values of correlation coefficients in
Table 2, the pseudo-second-order kinetic model provides a better
fitting and the experimental and theoretical uptakes are in good
consistency. This indicates that the POM uptake process might be
controlled by the chemical reaction step because of existence of
functional groups on the support surface i.e. according to the
assumption in the pseudo-second order model, the rate limiting
step is the chemisorption between the adsorbate and the adsorbent
[61].
4. Conclusion
Three different supports (GO and reduced GO) were used for
preparation of supported POM catalysts. The surface properties of
the prepared catalysts were characterized by different character-
ization methods. The profound parameters including support type,
suspension pH, and solvent were considered for immobilization of
POM through anion adsorption from precursor solution on the
support. GO with the highest amount of surface oxygen functional
groups showed the highest equilibrium adsorption capacity
(427 mg/g) compared to the other reduced samples (74 and 54 mg/
g for RGO-a and RGO-b, respectively). The pH dependence of the GO
surface charge was confirmed so that the effective POM adsorption
was obtained in a pH value below the isoelectric point (IEP) of the
support, in which the POM anions can form electrostatic bonds
with the positive charges of the surface functional groups. The
maximum equilibrium adsorption amount of POM was observed in
water/ethanol mixture. The kinetics of POM uptake process follows
a second-order kinetic model so that the chemisorption between
the adsorbate and the adsorbent process might control the
adsorption process.
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