Applied Surface Science 390 (2016) 190201

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Activated carbon-based magnetic TiO2 photocatalyst codoped with

iodine and nitrogen for organic pollution degradation
Xuejiang Wang , Jingke Song, Jiayu Huang, Jing Zhang, Xin Wang, RongRong Ma,
Jiayi Wang, Jianfu Zhao
College of Environmental Science and Engineering, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092, PR
China

a r t i c l e

i n f o

Article history:
Received 29 June 2016
Received in revised form 2 August 2016
Accepted 6 August 2016
Available online 9 August 2016
Keywords:
Magnetic photocatalyst
Activated carbon
Codoped
Water treatment
Reusability

a b s t r a c t
Magnetic photocatalyst iodine and nitrogen codoped TiO2 based on chitosan decorated magnetic
activated carbon (I-N-T/CMAC) was prepared via simple coprecipitation and sol-gel method. The characteristics of photocatalysts were investigated by X-ray diffraction (XRD), N2 adsorptiondesorption
isotherm, eld emission scanning electron microscopy (FESEM), energy dispersive spectrometry (EDS),
fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), UVvis diffuse reection
spectroscopy (UVvis DRS), photoluminescence (PL) spectroscopy and vibrating sample magnetometer (VSM). It turned out that the prepared material had large surface area, enhanced absorption of visible
light, and magnetically separable properties when mole ratio of I/Ti was 0.1. Iodine-nitrogen codoped
magnetic photocatalyst was used for the removal of salicylic acid (SA), and the rate of adsorption reaction
for SA by I0.1 -N-T/CMAC followed the pseudo second-order kinetic. Under visible light irradiation, 89.71%
SA with initial concentration = 30 mg/L could be removed by I0.1 -N-T/CMAC, and photodegradation rate
of SA on I0.1 -N-T/CMAC composites was 0.0084 min1 which is about 4 times higher than that of magnetic
photocatalyst with nitrogen doped only. The effects of SA initial concentration, pH, coexisting anions and
humic acid to the degradation of SA with the prepared material were also investigated. Main oxidative
species in the photodegradation process are OH and h+ .
2016 Elsevier B.V. All rights reserved.

1. Introduction
Photocatalysis oxidation have been proved to be a promising
path for the decomposition of contaminants which are too toxic
to be degraded through traditional biochemical approaches [1,2].
Titanium dioxide (TiO2 ), due to its chemical inertness and biological, powerful oxidizing power, high benet-to-cost ratios, and so
on, is widely used for the organic pollutants degradation in water
and wastewater [36]. However, TiO2 of anatase have a wide band
gap (3.2 eV), which could only be motivated by UV light to create
electronhole pairs [7]. However, only 5% of the solar light is UV
light, and this inhibited the use of TiO2 as an efcient photocatalyst [3,6,811]. In 2001, Asahi et al. found that through nitrogen
doping the band gap of TiO2 could be narrowed and hence the
absorption of visible light was enhanced [12]. From then on, there

Corresponding author. Tel. +86 021 65984268.

Corresponding author.
E-mail addresses: wangxj@tongji.edu.cn (X. Wang), zhaojianfu@tongji.edu.cn
(J. Zhao).
http://dx.doi.org/10.1016/j.apsusc.2016.08.040
0169-4332/ 2016 Elsevier B.V. All rights reserved.

were many investigations about the nonmetal elements (e.g., N, I,

C, B, S and F) doping of TiO2 to improve the visible light absorption [5,1315]. Comparing with other nonmetal dopants, iodine
was reported could substitute lattice titanium as I5+ and Ti4+ have
the approximate ionic radii, and then iodine doping may bring
about superior photocatalytic activity [16]. In recent years, many
authors report that iodine doped titania have highly efcient to
the decomposition of organic pollutants [4,13]. Furthermore, different from single nonmetal doping TiO2 materials, co-doped-TiO2
always exhibits excellent photocatalytic performance in visible
light region on account of the benets from each merits of dopant
[6,17,18], and it is known that nitrogen-doped TiO2 can achieve
band gap narrowing, and iodine doping could enhance charge separation [8,17].
However, the difculty in photocatalyst recycling of conventional powder photocatalyst also limits the practical application of
this technology [19,20]. Finding some practical ways to use this
technique in industrial-scale is urgently and signicantly. Many
technologies have been taken for the immobilizing of TiO2 catalysts
on different solid substrates, and it is thought that immobilization of TiO2 nano-particles is high efciently and money saving for

X. Wang et al. / Applied Surface Science 390 (2016) 190201

the utilization of nano-TiO2 [1924]. Until now, different kinds of

carriers have been investigated, such as y ash [25], perlite granules
[20], expanded graphite [26] and activated carbon [21,27]. While in
the wastewater treatment process, supported TiO2 which could be
separated easily and own higher adsorption capability is greatly
expected. Previously, Ao et al. [28] reported magnetic activated
carbon (MAC) which including highly dispersed magnetic nanoparticles, and then anatase TiO2 was coated onto MAC. The composite
material can be easily separated through an additional magnetic
eld and the activated carbon captures the pollutants by adsorption
is benecial to the enhancement of photocatalytic activity.
In the present work, iodine and nitrogen codoping was used
to make the band gap of TiO2 narrow, and codoped TiO2 was
deposited on MAC by a sol-gel process. While MAC was prepared
by co-precipitation method, and iron oxide nanoparticles was
encapsulated by cross-linked chitosan-glutaraldehyde. In aqueous solution, the prepared photocatalyst was applied to the
photocatalytic degradation of salicylic acid (SA). The adsorption
performance of the materials was investigated, and the inuence
of different mole ratios of I/Ti, SA initial concentration, pH, coexisting anions and humic acid on photocatalytic degradation efciency
was studied.

191

Fig. 1. XRD patterns of N-T/CMAC, I0.05 -N-T/CMAC, I0.1 -N-T/CMAC and I0.15 -NT/CMAC.

2. Experimental
2.1. Chemical and materials
All materials were bought from Sinopharm Chemical Reagent
Beijing Co., Ltd. (China), unless otherwise mentioned. They were
of reagent-grade or higher purity. Deionized water was used in all
cases for preparing solutions. The reagents were used as received
without further purication.
2.2. Catalysts preparation
Magnetic photocatalysts were prepared according to a convention method by three steps [29]. Firstly, the synthesis of MAC
following the coprecipitation method reported by Zhang et al. [30].
Typically, 8.25 g activated carbon (AC) was added into 250 mL iron
salt solution which is composed of FeCl3 6H2 O (9.45 g, 35 mmol)
and FeSO4 7H2 O (9.75 g, 35 mmol) at a mole ratio of 1:1, and the
compounds were vigorous stirred at room temperature for 1 h.
Then adding 100 mL solution of NaOH (2.5 M) into the iron salt
solution, and the formed solution was stirred and maintained at
100 C with a thermostatic water Bath for 2 h. The obtained precipitate was separated by a magnet, and to obtain a neutral pH the
material was washed with distilled deionized water many times.
Second stage, the synthesis of chitosan (Cts) encapsulated MAC
which is named as CMAC for short. In this process, a chemical
cross-linking method of chitosan-glutaraldehyde was use as the
encapsulated material. 1.0 g chitosan (Cts) was dissolved in 50 mL
glacial acetic acid (0.5 vol.%), then 2 mL glutaraldehyde (25%) was
added and sonication for 20 min. Afterwards, 10 g MAC was added
and vigorously stirred for 2 h and aged 10 h. Then obtained samples
were dried in a drying oven at 105 C for 12 h.
The nal stage was the preparation of iodine-nitrogen-codopedtitania coated onto chitosan encapsulated magnetic activated
carbon particles (I-N-T/CMAC). I-N-T/CMAC was obtained through
a simple solgel method under mild conditions. 2 g of CMAC was
dispersed in 61 mL TiO2 sol (15 mL tetrabutyl titanate, 40 mL anhydrous ethanol and 6 mL glacial acetic acid), then a certain amount of
potassium iodate (0.428 g, 0.856 g, 1.284 g) was added and the mole
ratio of I/Ti was 0.05, 0.1 and 0.15 respectively. The solutions was
stirred for 1 h at room temperature. Afterwards, 2 g urea dissolved
into 5 mL deionized water and added dropwise into the titania sol to

Fig. 2. N2 adsorptiondesorption isotherms of N-T/CMAC, I0.05 -N-T/CMAC, I0.1 -NT/CMAC and I0.15 -N-T/CMAC.

form gel. The compounds were aged at room temperature for 24 h,

and then dried at 105 C for 12 h. Catalysts were obtained with calcination temperature at 550 C for 2 h under nitrogen atmosphere
in a tubular furnace, and they were named as Ix -N-T/CMAC where
x corresponds to the mole ratios of I/Ti.
2.3. Characterization
The obtained materials were analyzed through X-ray diffraction
(XRD) experiments, which performed on a X-ray diffractometer
(Bruker D8 Advance, German) using Cu K radiation ( = 1.5406 )
to identify the crystalline phase. Each sample was detected at 40 kV
and 40 mA over a range of 1090 with a step time of 2.5 s and
a step size of 0.01 . The surface micromorphologies of prepared
materials were examined using Field-Emission Scanning Electron
Microscope (FESEM, Zeiss, Ultra55) with an energy dispersive
spectrometry (EDS) detector for spectrometry. A high resolution
transmission electron microscope (TEOL2010 (JEM), Japan) with a
eld emission-transmission gun at 200 kV was also used to detect
the morphology of materials. Fourier transform infrared (FTIR)
spectra were collected on a Nicolet 5700 FTIR spectrometer using
KBr pellets technique. XPS measurements were conducted using
a Thermo-VG Scientic ESCALAB 250 XPS system equipped with
Al K X-ray radiation. The XPS spectra of the samples were cali-

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X. Wang et al. / Applied Surface Science 390 (2016) 190201

Fig. 3. The SEM images and element maps: AC(a), low and high magnication images for I0.1 -N-T/CMAC (bd), element maps images for I0.1 -N-T/CMAC (eh), respectively.

X. Wang et al. / Applied Surface Science 390 (2016) 190201

193

Table 1
Effects of mole ratios of I/Ti on specic surface area, crystal size and band gap of Ix -N-T/CMAC .
Photocatalyst

Specic surface area (m2 g1 )

Average Pore size (nm)

Total pore volume (cm3 g1 )

Crystal size(nm)

Eg /eV

N-T/CMAC
I0.05 -N-T/CMAC
I0.1 -N-T/CMAC
I0.15 -N-T/CMAC

172.88
199.71
199.3
162.09

6.232
6.012
6.313
5.617

0.266
0.3
0.315
0.228

17.28
17.50
14.82
16.53

3.05
2.91
2.33
2.81

Table 2
Surface atomic concentrations of catalysts from XPS analyses.
Sample

Surface atomic concentration (%)

N-T/CMAC
I0.1 -N-T/CMAC

Ti

4.49
3.65

26.59
29

0.85
0.55

66.19
64.69

0.35

Table 3
Room temperature magnetic properties for synthesized Fe3 O4 , N-T/CMAC and I0.1 N-T/CMAC respectively.
Samples

Hc (Oe)

Mr (emu g1 )

Ms (emu g1 )

Fe3 O4
N-T/CMAC
I0.1 -N-T/CMAC

167.89
143.99
182.6

8.5906
0.98840
0.95012

37.535
4.6429
3.4642

brated by C 1s level from carbon samples at 284.6 eV, and the high
resolution XPS peaks were tted with mixed Lorentzian-Gaussian
curves after a Linear background subtraction. Optical property
was obtained in the range of 200700 nm on a Shimadzu UV2550
UVvis-spectrophotometer with BaSO4 as a reectance standard.
Photoluminescence (PL) spectra were measured at room temperature on a Steady state/Lifetime Fluorescence Spectrophotometer
(QM-40, PTI, USA). Nitrogen adsorption and desorption isotherms
were carried out using an ASAP 2020, Micrometritics analyzer to
obtain Brunauer-Emmett-Teller (BET) surface area. Magnetic properties (M-H curve) were collected at room temperature by using a
vibrating sample magnetometer (VSM).

Fig. 4. FTIR spectra of N-T/CMAC and I0.1 -N-T/CMAC.

tor. There was a cooling device to eliminate thermal effect and a

tube to supply air (0.1 L/min). During the photocatalytic reaction,
5 mL solution were sampled and ltered with 0.45 m membrane
lter at each time intervals for analysis. The concentration of
SA was detected by a Shimadzu UV-2700 spectrophotometer at
295 nm which corresponds to the characteristic absorption peak
of SA.

2.4. Adsorption experiments

3. Results and discussion

To investigate the adsorption characteristic of prepared materials, the adsorption kinetic for the removal of SA were evaluated.
Adsorption experiments were performed by adding 0.1 g assynthesis catalysts with 50 mL SA solution (30 mg/L) and pH = 5,
then stirring the solutions with a shaker under 25 C and 150 rpm
in the dark. The amount of SA adsorbed by Ix -N-T/CMAC qt (mg/g)
at certain time was analyzed following the equation:

3.1. Characteristics of photocatalysts

q t (mg/g) =

(C0 -Ct )V
m

(1)

where C0 and Ct are the initial concentration of SA (mg/L) and the

remaining concentration of SA at certain time (mg/L), respectively.
V is the volume of the SA solution (L), and m is the amount of Ix -NT/CMAC used (g).
2.5. Photocatalytic activity test
The photocatalytic processes were performed in a Phchem III
photo reactor manufactured by NBeT Instrument Co. Ltd. (Beijing,
China), under a 500 W Xe lamp (XE-JY500) irradiation equipped
with a 400 nm optical lter which only allows visible light to
pass through. The initial volume for salicylic acid (SA) was 50 mL,
and different concentrations of SA were used in the experiments.
The concentration of photocatalysts was 2 g L1 . Photocatalyst
and solution was added into the quartz glasstube set of reac-

The XRD patterns of as-prepared I-N-T/CMAC photocatalysts

with different doping ratios are shown in Fig. 1. Different characteristic peaks with 2 values of 25.2 (101), 37.9 (004), 47.9
(200), 54.2 (105), and 62.6 (204) are found and could be indexed
to anatase phase of TiO2 (JCPDS le No. 21-1272), which are consistent with the XRD results in the previous reports [9]. No peaks
assigned to other crystal phases of TiO2 (rutile and brookite) or TiI4
are observed. Based on Scherrers formula, the crystallite size of
all the prepared samples was obtained by using the peak width at
half the maximum intensity (FWHM) of (101) peak, and the results
are presented in Table 1. From Fig. 1 and Table 1, it can be seen
that compared with N-T/CMAC, Ix - N-T/CMAC powders are mainly
anatase phase, and the particle size of materials decrease when the
mole ratio of I/Ti is 0.1 (14.82 nm). This may be attributed to the
existence of KIO3 which could enhance the energy barrier mutual
diffusion between the grains, and the crystal particles growth are
hindered [1].
While the characteristic peaks at 2 = 30.2 and 35.6 are assigned
to Fe3 O4 , and they were corresponding to (220) and (311) reections agree well with JCDPS card# 19-0629 [31]. The peak appeared
at 32.8 was attributed to the existent of Fe2 O3 [32,33]. According to
the previous investigation [31], the overloading of activated carbon
with magnetite nanoparticles and their subsequent transforma-

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X. Wang et al. / Applied Surface Science 390 (2016) 190201

Fig. 5. XPS survey spectra of I0.1 -N-T/CMAC: (a) Ti 2p (b):N 1s, (c): C 1s, (d): I 3d.

tions may lead to the formation of this impurity phase. Moreover,

the rst small peak at 2 = 23.6 could assign to the existence of
few graphite which was from activated carbon [34,35]. When the
mole ratio of I/Ti is 0.1, the sample own the smallest crystallite size
and the photocatalyst could disperse much better than the other
samples, and hence the peak at 2 = 23.6 was weakened which
indicated MAC was coated much better.
Consequently, nitrogen adsorption-desorption isotherms of Ix N-T/CMAC samples are shown in Fig. 2. To all the samples, type IV
isotherms are detected, which indicate the presence of mesoporous
structure [1]. The average pore diameters of the samples (Table 1)
were 5.6176.313 nm, also conrmed the existence of mesoporous
structure. The pore channel allow light to scatter inside, and the
absorption of light can be enhanced [36]. I0.05 -N-T/CMAC and I0.1 N-T/CMAC have the higher specic surface area than N-T/CMAC,
which is 199.71 and 199.3 m2 g1 respectively. Further, Increasing the mole ratio of I/Ti to 0.15 reduce the specic surface area
to 162.09 m2 g1 . Meanwhile the average pore size and total pore
volume decreased as the increase of potassium iodate addition
amount. Excess potassium iodate may block the micropores of Ix N-T/CMAC. While the micropores nanostructure and larger specic
surface area are helpful for the reactant molecules approach to the
photo-active sites, which could improve the photocatalytic activ-

ity of materials [16,26]. In this way, the mole ratio of I/Ti = 0.1
is suitable to get higher specic surface area and photocatalytic
activity.
The morphologies of AC and I0.1 -N-T/CMAC composites are
shown in Fig. 3. Comparing Fig. 3(a) and (b), it can be seen that
nanometer-scale TiO2 particles were well dispersed on the surface
of AC. Furthermore, as shown in Fig. 3(c) and (d), the surface of AC
was covered by the agglomerates of many irregular size TiO2 crystallites. Element maps (Fig. 3(e)(h)) show the coexistence of large
amount titanium, oxygen and iodine on the surface of composites.
The distribution of Ti, O and I was similar, suggesting that TiO2
particles were well-dispersed on the support. Moreover, the morphology of I0.1 -N-T/CMAC sample was observed by TEM (Fig. S1),
which also indicated that the coated particle consisted of irregularshape nanoparticles.
Fig. 4 shows FTIR spectrum of N-T/CMAC and I0.1 -N-T/CMAC.
The bands at about 3415 cm1 and 1635 cm1 could be assigned
to the stretching vibrations of OH groups from hydroxyls and
the exural vibrations of H O H groups adsorbed on the surface and channel of TiO2 materials[37,38]. The peaks at 1529 cm1 ,
1593 cm1 and 1396 cm1 , were corresponding to the vibration
of C C and C O stretching vibrations, respectively, which
came from the used precursor and solution [39]. While the broad

X. Wang et al. / Applied Surface Science 390 (2016) 190201

band below 700 cm1 is attributed to the existence of Ti O Ti

bonds[40].
In order to investigate the nature of doped elements, the doped
TiO2 samples were analyzed by XPS (shown in Fig. 5). In Fig. 5(a),
XPS peak of Ti 2p appear at 466.1eV(Ti 2p1/2 ) is assigned to Ti4+ [8].
The peak at 460.4 eV (Ti 2p3/2 ) could be attributed to the existence
of Ti-N bond [41], which is correspond to the result of N 1 s spectrum. In Fig. 5(b), Nitrogen with two bonding states are detected at
398.4 and 402.1 eV, which is attributed to the substituted nitrogen
dopant in titania with the formation of Ti-O N and Ti-N O linkages respectively [42]. As shown in Fig. 5(c), two peaks were found
in C 1 s XPS spectrum, whereas the peak at 286.2 and 288.4 eV can
be attributed to C O bond and C O (or O C C) bond, respectively
[17,43], while this result agree with the result of FT-IR analysis.
From Fig. 5(d), I 3d region can be tted into four peaks in the
spectrum around 620.2, 621.6, 631.7 and 633.1 eV. The two peaks
about 631.7 eV (I 3d3/2 ) and 620.2 eV (I 3d5/2 ) show the existence
of I [8], while the other two weaker peaks at 621.6 (I 3d5/2 ) and
633.1 eV (I 3d3/2 ) which indicate the oxidation state of doped iodine
is I5+ [1,16]. The results show that I5+ /I pairs were observed for Idoped TiO2 and that I5+ ions substitute for Ti4+ which exist in the
IOTi bond. The I7+ peak at around 624.0 eV was not found, so TiO2
doped with multivalency iodine I7+ /I was not exist in this method
[16]. Furthermore, the existence of I5+ /I pairs is likely affect the
atomic ratio of Ti, N and C (Table 2). Comparing with the N-T/CMAC
sample, the surface atomic concentration of Ti, N and C slightly
decreased, which implies the doping of I5+ /I pairs happened.
Fig. 6 (a) displays UVvis absorption spectra of I-N-T/CMAC samples with different dosage of potassium iodate. It can be found
that when the mole ratio of I/Ti is 0.1 the absorption peak appear
from 550 to 600 nm shift to the visible regions of solar spectrum.
While this shift towards the longer wavelength derives from the
band gap narrowing of titanium dioxide by iodine and nitrogen codoping [1,42]. The effect of co-doping lead to the formation of the
hybridized states located in the band gap [44]. However, more or
less iodine dosage all lead to the absorption peaks reduces. The band
gap energies (Eg ) of catalysts are calculated by plotting (h)2 to
h in Fig. 6(b), where is the absorption coefcient, h is the photon energy and Eg is the energy of band gap [45]. The band gap
energies of N-T/CMAC, I0.05 -N-T/CMAC, I0.1 -N-T/CMAC and I0.15 N-T/CMAC are listed in Table 1 which were 3.05, 2.91, 2.33 and
2.81 eV respectively, and I0.1 -N-T/CMAC have lower band energy
than N-T/CMAC, therefore the photocatalysts are more likely to
be operated under visible light. Moreover, Fig. 6(b) shows the
Photoluminscence (PL) spectra of N-T/CMAC, I0.05 -N-T/CMAC, I0.1 N-T/CMAC and I0.15 -N-T/CMAC composites, and the PL spectra of
samples exhibited similar positions for most peaks, but with different PL intensity. I0.1 -N-T/CMAC own the lower PL intensity than the
other samples which implies the co-doping elements suppress the
photo-generated electron recombination from conduction band to
valence band in TiO2 [18,44].
Furthermore, the magnetic property of I0.1 -N-T/CMAC was measured using VSM system. Fig. 7. Show the magnetic hysteresis loop
of Fe3 O4 , N-T/CMAC and I0.1 -N-T/CMAC, and the associated magnetic parameters of coercive eld (Hc), remnant magnetization
(Mr) and saturation magnetization (Ms) are summarized in Table 3.
The magnetization saturation (Ms) value of I0.1 -N-T/CMAC is much
smaller than pure Fe3 O4 powder. Comparing with N-T/CMAC, the
doping of iodine made the materials Ms further reduce. However
it can be observed from the photograph (inset) that the prepared
I0.1 -N-T/CMAC could be easily separated.
3.2. Adsorption studies
To evaluate the adsorption characteristics of SA on N-T/CMAC
and I0.1 -N-T/CMAC, in the dark condition adsorption kinetics was

195

Fig. 6. UVvis absorption spectra (a); energy band gap (b) and Photoluminescence
spectra (c) for N-T/CMAC, I0.05 -N-T/CMAC, I0.1 -N-T/CMAC and I0.15 -N-T/CMAC.

observed with the initial concentration of SA = 30 mg/L (Fig. 8(a)).

It can be found that the adsorption of SA on the prepared photocatalysts reached to equilibrium in about 60 min. I0.1 -N-T/CMAC
has large number of adsorption sites because of its large surface
area and porous structure, as shown in Fig. 2. Moreover, the pseudo
rst-order and pseudo second-order equations were used to analyze the kinetics of the adsorption process of SA on N-T/CMAC and
I0.1 -N-T/CMAC, and the equations are expressed as follows [46,47]:
log (qe -qt ) = logqe -

k1 t
2.303

(2)

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X. Wang et al. / Applied Surface Science 390 (2016) 190201

Fig. 7. Magnetization curve of Fe3 O4 , N-T/CMAC and I0.1 -N-T/CMAC at room temperature.

t
1
t
=
+
qt
k2 q2e qe

(3)

where qt and qe are the amounts of SA adsorbed at time t (min) and

at equilibrium (mg/g), respectively, k1 (1/min) and k2 (g/mg/min)
are the kinetic parameters to be determined. Kinetic parameters
of these plots of log(qe -qt ) versus t and t/qt versus t are given in
Table 4. The results show that the values of k1 and qe which were
determined from the slope and the intercepts of the plots of log(qe
qt ) versus t (plots not shown). While the calculated qe did not
match well with the experimental data (qe,exp ) for the studied concentration, and the R2 values (Table 4) were relatively low, which
means this kinetic model did not suitable for the description of the
adsorption process. As shown in Fig. 8(b), the plots of t/qt versus t
showed linear regression. For the pseudo second-order kinetic, the
correlation coefcients (R2 ) were above 0.999 and the calculated
qe values were close to the experimental values (Table 4). Therefore, the adsorption of SA on I0.1 -N-T/CMAC followed the pseudo
second-order kinetic model. In the pseudo-second-order adsorption model, the parameter h = k2 qe 2 represent the initial adsorption
rate. In Table 4. The value h of I0.1 -N-T/CMAC is higher than that
of N-T/CMAC which indicate the catalyst own a faster adsorption
rate[48]. The adsorptivity of catalyst is related to the value of specic surface area.
3.3. Photocatalytic degradation of SA

Fig. 8. Adsorption kinetics of SA onto N-T/CMAC and I0.1 -N-T/CMAC (a); secondorder kinetic plots for SA removal(b).

3.3.1. Effect of I/Ti mole ratios

Photocatalytic decomposition of SA (30 mg/L) with Ix -NT/CMAC at pH 5.0 under visible light irradiation are shown in
Fig. 9(a). It is found that the amount of SA adsorbed onto I0.1 -NT/CMAC in dark is higher than that of other materials, which is
correspond to its larger surface area. With visible light irradiation,
the removal efciency of SA could reach to 89.71%. To evaluate the
photodegradation rate of I0.1 -N-T/CMAC, plots of ln(Ce /C) against
reaction time t follows pseudo-rst-order kinetics are shown in
Fig. 9(b), where Ce and C are the equilibrium concentration of SA
after adsorption and the remaining concentration of SA at certain time, respectively. The k obtained from slop of the plots were

X. Wang et al. / Applied Surface Science 390 (2016) 190201

197

Table 4
Pseudo-rst-order and pseudo-second-order kinetic parameters of SA adsorption onto N-T/CMAC and I0.1 -N-T/CMAC.
Catalyst

N-T/CMAC
I0.1 -N-T/CMAC

qe ,exp

(mg/g)

Pseudo-rst-order

Pseudo-second-order

Pseudo-second-order

qe (mg/g)

k1 (1/min)

R2

qe (mg/g)

k2 (g/mg/min)

h(mg/g/min)

R2

4.988
8.438

4.755
8.042

0.075
0.108

0.912
0.881

5.262
8.809

0.0197
0.0167

0.545
1.296

0.999
0.999

Table 5
photocatalytic kinetic parameters of SA solution by different photocatalysts.
Photocatalysts

k/min1

R2

N-T/CMAC
I0.05 -N-T/CMAC
I0.1 -N-T/CMAC
I0.15 -N-T/CMAC

0.0021
0.0058
0.0084
0.0038

0.9902
0.9789
0.9852
0.9830

Fig. 10. Photocatalytic degradation of SA with I0.1 -N-T/CMAC at different initial

concentration.

exhibited in Table 5, and the rate constant of SA removal with I0.1 N-T/CMAC was 0.0084 min1 which is four times higher than that
of N-T/CMAC (0.0021 min1 ). Therefore, the doping of iodine not
only enhance the adsorption of SA, but also enhance the absorption of visible light, and the increase of hydroxyl radicals generation
improve the photodegradaiton rate of SA. Moreover, total organic
carbon (TOC) was used as the mineralization index for the system
and the TOC removal efciency of I0.1 -N-T/CMAC for SA was investigated. In Fig. 9(c). It can be found that TOC removal efciency
increased as time went by. After 180 min irradiation under visible
light, 78.32% of TOC was eliminated. Then the degradation speed
of SA began to reduce and 86.17% of TOC was degraded at 480 min
which indicated that SA was effectively mineralized.

Fig. 9. Photocatalytic degradation of SA with Ix -N-T/CMAC (a); the pseudo-rstorder reaction kinetics of SA degradation under visible light irradiation by the
photocatalysts (b) and TOC removal efciency by I0.1 -N-T/CMAC (c).

3.3.2. Effect of initial SA concentration

The effect of the initial concentration of SA on the photodegradation was conducted and the results are shown in Fig. 10. It is shown
that the removal efciency of SA decreased with the SA concentration increase, and the k obtained from slope of the plot ln(Ce /C)
against reaction time t also decreased which was 0.00428 min1 ,
0.00355 min1 for 50 mg/L, 70 mg/L SA, respectively. When the initial concentration of SA increase, more SA molecules will cover
the photocatalytically active site of I0.1 -N-T/CMAC which may suppress the photons reach to the surface of photocatalyst. In this way,
the generation of hydroxyl radicals was reduced, and degradation
efciency of SA also decrease [46].

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X. Wang et al. / Applied Surface Science 390 (2016) 190201

Scheme 1. Diagram showing the photodegradation mechanism of prepared material.

3.3.3. Effect of pH, coexisting anion and humic acid (HA)

It is known that the pH of solution may have inuence on the
adsorption of SA and hence affect the efciency of photocatalysis
[49]. While in groundwater and surface water, there exist various kinds of negative ions with SA [50,51]. Furthermore, humic
acid (HA) mostly consists of natural organic matter, is also widely
exist in natural waters, and the concentration of HA is the range
of 0.1200 mg/L [46,49]. In the photodegradation process of pollutants, the changing of pH, presence of coexisting anions and HA
may have inuence on the photocatalytic degradation of SA. Hence,
the effects of pH, anions and HA were studied by adjusting pH
of the solutions, adding different concentration of NaCl, Na2 SO4
and HA for 50 mg/L initial concentration of SA with 2 g/L I0.1 -NT/CMAC. From Fig. 11(a), for I0.1 -N-T/CMAC, as the increase of pH
the removal efciency of SA rst decreases and then increases. At
pH = 9.0, the extent of degradation becomes the lowest for I0.1 -NT/CMAC. In acidic solution (about pH = 3.0), salicylic acid exists as
molecular form which is favorable for the adsorption, as the solution pH increasing, salicylic acid is ionized to a negative ion and
then the adsorption capacity of SA decreases rapidly which lower
the photodegradation process [52]. In addition, the production
of OH radicals could be enhanced under alkaline pH conditions,
which assists in the degradation of SA through OH radical oxidation mechanism[53]. In Fig. 11 (b), it is found that Cl and SO4 2
all deactivate the photocatalyst as the increase of concentration.
Some researchers reported that Cl anion could act as scavenger of
positive holes (h+ ) and OH especially in acidic pH [51,54], while
the reaction between sulfate with hydroxyl radical and/or positive
holes, leading to the formation of ionic radicals SO4 which is less

reactive than OH [46]. Hence the presence of Cl and SO4 2 all

have negative effect on the photodegradation of SA. Differently, in
Fig. 11(c), the photodegradation of SA was strengthened at a lower
concentration of HA (2, 4 and 6 mg/L), and weakened at 8 mg/L. It
is known that HA could serve as a photosensitizer under sunlight
or weak irradiation of simulated sunlight [26,50], and HA produces
reactive species which may enhance the degradation of pollutants
[50]. But, excessive HA will inhibited the photolysis process through
competitive photoabsorption [55].

3.4. Photocatalytic mechanism and reusability of catalyst

To further investigate the underlying photocatalytic mechanism, radical and hole trapping experiments were used to detect
the main oxidative species in the photocatalytic oxidation process. Tert butyl alcohol (TBA) was used as OH scavengers [56],
and benzoquinone (BQ) was adopted to quench O2 [57]. KI was
introduced as the scavenger of h+ [56]. From Fig. 12(a), it is clear
that the addition of scavengers all made the removal efciency
of SA decrease. Especially, the presence of TBA and KI made the
removal efciency of SA have much more reduce which is 40.6%
and 56.69% respectively. As a result, the oxidizing species OH
and h+ play more important roles in the degradation process of
SA with I0.1 -N-T/CMAC, and the photodegradation mechanism of
prepared material is shown in Scheme 1. The reusability of I0.1 -NT/CMAC was tested with ve times run and the results are shown in
Fig. 12(b). After ve times run, the degradation rate of SA still keeping high photocatalytic performance (75.78%), which is important
for the application in wastewater treatment.

X. Wang et al. / Applied Surface Science 390 (2016) 190201

199

Fig. 12. Effects of different reactive species scavengers on the photodegradation

of SA(30 mg/L) by I0.1 -N-T/CMAC under visible-light irradiation (a); reusability of
catalyst (b).

Fig. 11. Photodegradation of SA with initial concentration 50 mg/L by using I0.1 -NT/CMAC with different pH (a), in the presence of chloride, sulfate anions (b) and HA
(c).

4. Conclusions
Magnetically separable photocatalyst I0.1 -N-T/CMAC was prepared through coprecipitation and sol-gel method. Beneting from
the doping of iodine, I0.1 -N-T/CMAC presented better adsorption
and photocatalytic performance. XRD analysis conrmed that the
TiO2 supported on activated carbon are mainly anatase phases.

I0.1 -N-T/CMAC had high specic surface area of 199.3 m2 /g. SEMEDS and TEM analysis indicated that TiO2 was well coated on the
surface of magnetic activated carbon. FTIR, XPS, UVvis and PL
studies indicated the decorating of carbon and doping of iodine,
nitrogen happened, hence the prepared material had a better light
absorption in visible light region and the charge separation was
enhanced. Moreover, the prepared material could be easily separated by an additional magnetic eld. The photodegradation rate
of SA (30 mg/L) on I0.1 -N-T/CMAC composites was 0.0084 min1 ,
which is about 4 times higher than that of N-T/CMAC under visible light. Increase of SA initial concentration made the degradation
rate of SA decrease. As the increasing of pH, the removal efciency
of SA rst decreases and then increases. Coexisting anions such as
Cl and SO4 2 have negative inuence on the photo-degradation
of SA. But suitable concentration of humic acid could enhance the
photodegradation of SA. In the photodegradation process, OH and
h+ are the main oxidative species. I0.1 -N-T/CMAC still own good
photocatalytic activity after ve times run and it can be used in the
degradation of SA from surface water.

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X. Wang et al. / Applied Surface Science 390 (2016) 190201

Acknowledgement
This work was supported by National Natural Science Foundation of China (No. 21277097, 21377095).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2016.08.
040.
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