Applied Catalysis A: General 524 (2016) 163172

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Applied Catalysis A: General

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

Efcient photocatalytic degradation of acid orange 7 over N-doped

ordered mesoporous titania on carbon bers under visible-light
irradiation based on three synergistic effects
Youji Li , Ming Li, Peng Xu, Shaohua Tang, Chen Liu
College of Chemistry and Chemical Engineering, Jishou University, Hunan 416000, China

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

Article history: N-Doped ordered mesoporous titania on carbon bers (NOMT/CFs) has been prepared by a liquid-crystal
Received 5 October 2014 template (LCT) method with the aid of supercritical deposition. The NOMT/CFs product has been char-
Received in revised form 18 January 2015 acterized by X-ray diffraction analysis, scanning electron and transmission electron microscopies, X-ray
Accepted 31 January 2015
photoelectron spectroscopy, N2 sorption, UV/Vis diffuse reectance spectrophotometry, and photolumi-
Available online 7 June 2016
nescence. The photoactivity of the obtained product in the degradation of acid orange 7 (AO7) solution
under visible-light irradiation has been evaluated. A photocatalytic mechanism involving three syner-
Keywords:
gistic effects of NOMT/CFs is proposed, whereby the titania acts as an electron/hole generator with its
N-doped ordered mesoporous titania
Carbon ber
ordered mesostructure facilitating electronhole separation, N-doping enhances visible-light adsorption,
Synergy and the CFs serve to concentrate the pollutant around the active sites, favor electron transfer, and facil-
Supercritical deposition itate convenient recycling. Gas chromatography and mass spectrometry have been used to analyze the
Visible-light photoactivity intermediates generated in the conversion of AO7, allowing a tentative decomposition pathway to be
proposed. The effects of catalyst amount, pH, and initial AO7 concentration have been examined as oper-
ational parameters. The photocatalytic reactions follow pseudo-rst-order kinetics and are discussed in
terms of a modied LangmuirHinshelwood model.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Titanium dioxide, a chemically stable, highly efcient, and
nontoxic photocatalyst, has been widely used for water and air
purication [13]. However, conventional TiO2 photocatalyst can
only utilize light of wavelengths shorter than 388 nm (UV range)
due to its wide band gap (Eg 3.2 eV for anatase), which lim-
its its practical application with solar light [47]. Many efforts
have been made in the last two decades with a view to over-
coming this limitation. The two main approaches have been dye
sensitization [4] and doping with impurities [57]. It has been
reported that the incorporation of nitrogen into the titania crys-
tal lattice can shift the activation energy of the TiO2 photocatalyst
into the visible light region [6,8]. Thus, researchers have found
that nitrogen-doping technology is important for the application
of visible-light-induced photocatalytic TiO2 [9,10]. On the other
hand, photo-induced electronhole pairs have a short recombi-
nation time of the order of 109 s, whereas the reaction time for
Corresponding author.
E-mail address: bcclyj@163.com (Y. Li).
TiO2 with pollutants is in the range 108 103 s [1]. Thus, the
rapid recombination of electrons and holes is one of the major
reasons for the low photocatalytic activity. To solve this short-
coming, some researchers have recently developed pore-structured
titania to provide a high content of activated centers for the
adsorbed pollutants, because the efcient oxidation of organics
is a surface-orientated process in photocatalysis [11,12]. Since its
rst preparation through a modied solgel process using a phos-
phate surfactant by David and Jackie [13] in 1995, mesoporous TiO2
has received increasing attention because of its porous structure.
This property facilitates photocatalytic degradation of contami-
nants such as humic substances, phenolic compounds, pesticides,
chlorinated compounds, and dyes [1419]. It has also been found
that a porous support serves to concentrate the pollutant around
the active sites on mesoporous titania, and is effective in facili-
tating the separation of electronhole pairs [20]. In addition, the
separation of TiO2 powder from treated wastewater prior to dis-
charge is a time-consuming and expensive process, which has
limited the development and application of TiO2 photocatalysis in
water treatment. To provide high pollutant concentrations in the
vicinity of catalytic centers and to permit convenient separation
of the photocatalysts from the catalytic system, many efforts have

http://dx.doi.org/10.1016/j.apcata.2015.01.050
0926-860X/ 2016 Elsevier B.V. All rights reserved.
164 Y. Li et al. / Applied Catalysis A: General 524 (2016) 163172
been made to immobilize photocatalysts on porous supports, such
as activated carbon [21], zeolites [22], ceramics [23], glass bers
[24], optical bers [25], and steel bers [26]. Compared to pow-
der and particulate supports, ber supports are more amenable to
convenient recycling of composite catalysts [24,26]. Among such
ber supports, carbon bers (CFs) are ideal substrate materials
for applications in the photocatalysis of pollutants because they
are long, thin strand materials composed mostly of carbon atoms,
which endows them with advantages such as light weight, high
tensile strength, manufacturing exibility, heat resistance, and sta-
bility under corrosive conditions [2729]. Although CFs have been
used as substrates for the preparation of photocatalysts, most cases
have been limited to the immobilization of TiO2 particles without
ordered mesostructure or doping [27,28,30].
In this work, with the goals of effectively utilizing visible
light, high catalytic performance, and convenient separation of
the photocatalysts from the water treatment system, NOMT with
an ordered mesostructure and visible-light photoactivity has been
supported on CFs by a liquid-crystal template (LCT) method with
the aid of supercritical deposition. To explore the possible syn-
ergy between N-doping, the ordered mesostructure, and the CF
support on the photoactivity of TiO2 , the as-prepared photocata-
lysts have been characterized by various analytical techniques. The
performances of these new materials have been tested in the pho-
tocatalytic degradation of a dye under visible-light irradiation. The
dye under consideration is acid orange 7 (AO7; C16 H11 N2 O4 SNa),
which is a highly water-soluble, acid orange dye of the anionic
monoazo class. It is widely used as a colorant in textiles, leather,
and paper. Hence, the photodegradation of AO7 is important with
regard to the purication of dye efuents [3].
2. Experimental
2.1. Reagents
Raw carbon bers used as supports, prepared by activation
of polyacrylonitrile, were obtained from Henan (surface area:
1280 m2 /g, total pore volume: 0.19 cm3 /g). Tetrabutyl titanate,
cetyltrimethylammonium bromide, hydrochloric acid, urea, and
absolute ethanol were all analytical grade and were purchased from
Beijing Zhonglian Chemical Reagent company. The chemical struc-
ture of AO7 and its absorption spectrum are given in Supporting
Information Fig. S1. Deionized water, puried with an Elga-Pure
water purication system, was used to prepare all solutions for the
experiments.
2.2. Preparation of photocatalysts
NOMT/CFs was prepared by deposition in supercritical CO2 ,
using tetra-n-butyl titanate, a liquid crystal, and urea as the
precursor, soft template, and nitrogen source, respectively. First,
cetyltrimethylammonium bromide (5 g) was accurately weighed
and then completely dissolved in distilled water with stirring for a
specied period of time to form the liquid-crystal template (LCT) by
a similar methodology to that described elsewhere [18]. Next, tetra-
butyl titanate (25 mL) and urea (2 g) were dissolved in ethanol, and
the mixture was magnetically stirred (100 rpm) for 2 h. Ambient
laboratory temperature was maintained while stirring. A solution
containing HCl (3.3 mL) and the obtained liquid crystal was added
dropwise over 1 h until a liquid-crystal sol was obtained. After
aging the sol for 12 h at room temperature, it was deposited on CFs
in supercritical CO2 (at 7.6 MPa and 50 C). Subsequently, organic
material in the resulting composite was extracted in a soxhlet appa-
ratus for 48 h. The composite was dried for 30 min at 100 C in an
oven and then calcined at 500 C for 1 h in a nitrogen atmosphere to
synthesize NOMT/CFs. Simultaneously, another portion of the aged
sol was calcined at 500 C for 1 h to synthesize pure NOMT pow-
der for comparison. To further evaluate the synergistic relationship
between NOMT and CFs, and to determine the effect of NOMT on
the synergy, N-doped nanostructured TiO2 on CFs (NNT/CFs) was
also prepared by deposition in supercritical CO2 . The synthetic pro-
cesses used to obtain the NNT and NNT/CFs were similar to those
used for NOMT and NOMT/CFs, respectively, but without the LCT.
2.3. Characterization of the composite photocatalyst
The prole of the NOMT/CF photocatalyst was observed by
scanning electron microscopy (SEM) (Hitachi S3400N, Japan).
High-resolution transmission electron microscopy/selected-area
electron diffraction (HRTEM/SAED) was performed with a JEOL
(JEM 2100F) microscope. Small-angle X-ray scattering (SAXS) mea-
surements were made on a Nanostar U small-angle X-ray scattering
system (Bruker, Germany) using Cu-K radiation (40 kV, 35 mA).
Wide-angle X-ray diffraction (WAXRD) patterns were recorded on
a Bruker D4 X-ray diffractometer with Ni-ltered Cu K radia-
tion (40 kV, 40 mA). Nitrogen adsorptiondesorption isotherms
were used to determine the BrunauerEmmettTeller (BET) sur-
face area and pore size distribution (ASAP2010, Micromeritics Co.,
USA) at 77 K. UV/Vis absorption spectra were recorded at 298 K
on a UV/Vis diffuse reectance spectrophotometer (Shimadzu UV-
2100). X-ray photoelectron spectroscopy (XPS) data were obtained
with an ESCALab220i-XL electron spectrometer from VG Scien-
tic using 300 W Al K radiation. Photoluminescence (PL) emission
spectra were measured using a Spex 500 uorescence spectropho-
tometer with 325 nm radiation for excitation. The CF-supported
composite was ignited at 900 C and the TiO2 loading was calculated
in terms of ash weight by thermogravimetric analysis (WCT-2C,
Optical Instrument Factory, Beijing).
2.4. Photocatalytic reactor and light source
To examine the degradation of AO7 in aqueous solution under
visible light, experiments were carried out using a cylindrical batch
reactor tted with a water-cooled quartz jacket and an air-sparging
motor. A 500 W high-pressure Hg lamp with a UV lter was placed
about 20 cm from the reactor. The photon ow entering the reactor
was 6 mW cm2 for visible light irradiation.
2.5. Photocatalytic activity test
The experimental procedure involved placing 500 mL of a l-
tered suspension in the photocatalytic reactor. Air was bubbled
through the reaction solution at a rate of 560 mL min1 to ensure
a constant concentration of dissolved oxygen. Thereafter, samples
of about 5 mL were withdrawn at specied time intervals dur-
ing illumination and ltered through 0.45 mm lters. The AO7
concentration in the reaction mixture was monitored by a TU-
1810 spectrophotometer by measuring the absorption intensity
at max = 480 nm in a 10 mm quartz cell to evaluate decoloriza-
tion. The photocatalysis was tested in triplicate and the results are
reported as mean values, with an error of less than 5%. The total
organic contents (TOC) of the suspensions containing the photo-
catalyst and the corresponding initial solutions of the dyes were
directly analyzed using a TOC analyzer (model 820, Sievers, USA) to
evaluate mineralization. Dye degradation products were identied
by GCMS (Agilent 7890A5973N).
 Y. Li et al. / Applied Catalysis A: General 524 (2016) 163172
3. Results and discussion
3.1. Characterization of catalysts
3.1.1. Morphological and textural properties of NOMT/CFs
The morphology of the obtained product was rst examined
by SEM and TEM. Compared with the smooth surface of pure CFs
(Fig. 1a), an image of NOMT/CFs (Fig. 1b) revealed that a titania
layer had been immobilized on almost each ber. Although the
titania layer had been extensively deposited on the bers, the
same spatial distribution of CFs was retained in the composite.
Therefore, adequate UV irradiation could penetrate the felt-form
photocatalyst to a certain depth to reach a three-dimensional envi-
ronment for the photocatalytic reaction. This feature differentiates
the present photocatalyst from current immobilized photocata-
lysts such as TiO2 immobilized on the surfaces of glass [31], steel
plate [32], and ceramic membranes [33], which only provide a
two-dimensional surface for photodegradation. Additionally, the
CF substrates are uniformly and compactly covered by a large num-
ber of irregular-shaped aggregates with dimensions of 0.51 m
to form a rough surface, as shown in Fig. 1c. The thickness of the
titania layer is around 200 nm (Fig. 1d). However, the aggrega-
tion size of NOMT in the composites is smaller than that of pure
NOMT, at about 2 3 m according to the observed morphology
(Fig. S2). TEM characterization provided additional information
regarding the interior structure of these architectures. A typical
TEM image is shown in Fig. 1e; the NOMT/CFs exhibited a well-
ordered channel arrangement in large domains, corresponding to
the SAXS pattern (see discussion below). The inset in Fig. 1e shows
the SAED pattern, which also displays a well-resolved diffraction
ring and many diffraction spots, indicating high crystallinity of
the pure anatase phase. An HRTEM image (Fig. 1f) shows a 2D
mesostructure, containing ordered mesopores of about 3 nm in
diameter, and randomly oriented anatase nanocrystals with well-
dened crystallinity with a lattice spacing of 0.35 nm, consistent
with the d-spacing of the (101) reections of pure anatase [14].
3.1.2. Crystalline structure of samples
For NOMT and its composites calcined at 500 C, the ordered
pore structure was characterized on the basis of SAXS measure-
ments in the 2 range 0.21.5 (Fig. 2a). The SAXS patterns of
both NOMT and NOMT/CFs show characteristic Bragg peaks [(100)
reections] indicative of ordered pores in the samples. NNT and
its composites do not show any diffraction peaks in the 2 range
0.21.5 in their SAXS patterns because of their extremely large
pore dimensions and lack of an ordered mesoporous structure
[19]. The characteristic (100) reection of pure NOMT shifted to
a 2 angle larger than that for NOMT/CFs, indicating a decrease
in the unit-cell parameter and shrinkage of the framework. This
change may be attributed to the close contact of the thin NOMT
layers to the CF surfaces, which exhibit hinder effect for titania
crystallization. The WAXRD pattern for the NOMT/CFs obtained
at a calcination temperature of 500 C indicated only the anatase
phase (Fig. 2b), whereas anatase and rutile phases can coexist in
pure NOMT obtained at the same calcination temperature. Gen-
erally speaking, the mesoporous TiO2 show low crystal transition
temperature from the anatase to the rutile possible due to crys-
tal size, mesoporous morphology, doping, calcination time and so
on [3]. At the same calcination condition, crystal transition tem-
perature of pure NOMT is lower than composite NOMT/CFs. This
can be attributed to the CFs suppressing the phase transformation
of mesoporous TiO2 from anatase to rutile form at high temper-
atures. which is good agreent with reports[30,34]. Additionally,
compared with pure NNT without rutile, the dual-phase nature of
NOMT endows it with low thermal stability due to
165
the mesostructure, as described elsewhere [19]. Although the
patterns of NOMT/CFs exhibit narrower and more intense diffrac-
tion peaks than those of raw CFs, the coexisting TiO2 peaks for
NNT/CFs are more distinct. Enhanced anatase diffraction peaks of
the (101), (004), (200), (105), (211), and (204) planes for NNT/CFs
were observed at 2 = 25.48, 37.98, 48.28, 54.28, 55.38, and 64.37 ,
respectively (JCPDS No. 211272). Meanwhile, there were obvious
decreases in the intensity of the distinct diffraction peaks of the
CFs for the G(002) (2 = 24.47 ) and G(101) (2 = 44.29 ) planes,
suggesting the presence of numerous titania layers on the sur-
face of the support. The crystallite sizes, as calculated from the
broadening of the (101) anatase peak by the Scherrer equation,
were found to be 10.1 nm (NOMT/CFs), 16.3 nm (NOMT), 14.7 nm
(NNT/CFs), and 19.7 nm (NNT) (Table 1). The crystallite sizes of
NOMT/CFs and NOMT are thus smaller than those of NNT/CFs and
NNT, respectively. This may be attributed to hindering effects of
carbon adsorption and LCT decomposition on the growth of the
anatase nanocrystals.
3.1.3. Chemical composition of NOMT/CFs
XPS analysis provided valuable insight into the chemical compo-
sition of the carbon-ber-supported N-doped OMT photocatalyst.
An XPS survey spectrum of the photocatalyst exhibited prominent
peaks of carbon, oxygen, and titanium, but a relatively feeble peak
due to nitrogen, as shown in Fig. 3a. The O1 s spectrum can be
resolved into two peaks, one at 530.6 eV and the other at 529.1 eV
(Fig. 3b). The former can be attributed to surface hydroxyl groups
and the latter to the Ti-O-Ti lattice oxygen of TiO2 [35]. A high-
resolution XPS spectrum of C1 s on the composite photocatalyst
is shown in Fig. 3c, which can be tted by three peaks at bind-
ing energies of 281.5, 284.1 and 285.9 eV, respectively. This implies
that three different chemical environments of carbon existed in
the products. The weak peaks at 281.5 and 284.1 eV are usually
assigned to the C-Ti and C-C, and the strong peak at 284.6 eV is
ascribed to oxygen-bound species C-O [30,36,37]. Due to surface
oxidation during the preparation process, the oxidized active sites
on the CF surface can contribute to the deposition and growth of
N-doped OMT. The presence of nitride dopant is conrmed by the
N1 s core level peaks. Two peaks at binding energies of 399.6 and
401.6 eV are observed, as shown in Fig. 3d. The rst major peak can
be attributed to the nitrogen introduced into the OTiN structure
[38], indicating that some O atoms were substituted by N atoms,
consistent with the visible-light activity of doped TiO2 .
The latter peak can be assigned to the presence of intersti-
tial N, being characteristic of NO or NO2 in the N-doped TiO2
sample [39,40]. The molar ratio of N to Ti in all N-doped sam-
ples was about 2.3% based on XPS analysis. Additionally, nitrogen
adsorption desorption isotherms and the corresponding pore size
distribution curves were measured to investigate the porous struc-
ture of the as-prepared samples (see Fig. S3). The obtained samples
exhibited type IV isotherms characteristic of mesoporosity. The
NOMT/CFs products showed higher surface area (778 m2 /g) than
that of NNT/CFs (195 m2 /g) due to the covering N-doped OMT on the
surface of the CFs. Although the mean pore diameter of NOMT/CFs
(1.3 nm) was lower than that of NNT/CFs (1.7 nm), the total pore
volume of NOMT/CFs (0.08 mL/g) was larger than that of NNT/CFs
(0.04 mL/g) owing to the generation of more pores by the associa-
tion of the titania layers with ordered mesoporous structure.
3.1.4. Optical absorption properties
The absorption edge and band-gap energies of the as-prepared
samples were determined by UV/Vis diffuse reectance spec-
troscopy. Diffuse reectance spectra of the N-doped samples are
illustrated in Fig. 4a. All spectra clearly show a red-shift of the
absorption edge towards the visible region due to the lower energy
between the valence band and conduction band of TiO2 . Notably,
166 Y. Li et al. / Applied Catalysis A: General 524 (2016) 163172

Fig. 1. SEM image of carbon bers (a), SEM images of NOMT/CFs at low and high magnications (bd), TEM image of NOMT/CFs at low magnication (e) with selected-area
electron diffraction (SAED) pattern and its high-magnication TEM image with the d-spacing (f).

Fig. 2. SAXS (a) and WAXRD (b) patterns of samples.

the absorption intensities of the composites were higher than that cating that a small-particle quantum size effect was absent in the
of pure N-doped titania at UV and visible wavelengths. This dif- composites. The pure NOMT showed a small shift toward longer
ference can mainly be attributed to the black hue of CFs, and wavelengths in comparison with NNT. This behavior of NOMT is
therefore their strong absorption over the entire range of wave- presumably due to its mesoporous structure and the signicant sur-
lengths employed. The absorption intensities of the NOMT/CFs face effects. The band gaps Eg were calculated using the following
were higher than those of NNT/CFs at UV and visible wavelengths, equation:
which may be attributed to the mesoporous morphology. There
was no shift toward longer wavelengths for the absorption band of
the composites in comparison with that of N-doped titania, indi- 1/2
(Ah) = h Eg (1)
 Y. Li et al. / Applied Catalysis A: General 524 (2016) 163172 167

Table 1
An overview of the texture parameters of NOMT and NNT supported on CFs in comparison with those of pure NOMT and NNT and their physical mixtures with CFs.

Samples Content of TiO2 Surface area Total pore Average pore Crystallite size Band-gap energy
(wt.%)a (m2 /g)b volume (cm3 /g)c diameter (nm)c (nm)d (eV)e

NOMT/CFs 6.5 778 0.08 1.3 10.1 2.84

NNT + CFs 6.5 1127 19.7
NOMT 100 137 0.03 2.5 16.3 2. 84
NNT/CFs 6.5 195 0.04 1.7 14.7 2.90
NOMT + CFs 6.5 1263 16.3
NNT 100 61 19.7 2.90
a
TiO2 content was calculated by TG with an error of less than 1%.
b
The BET surface area was determined by the multipoint BET method.
c
The total pore volume and average pore size were calculated by the Barrett Joyner Halenda method (adsorption branch).
d
The average crystallite size of TiO2 was determined by XRD using the Scherrer equation.
e
The band-gap energies were calculated using the equation: (Ahv)1/2 = hv-Eg .

Fig. 3. XPS spectrum of the as-prepared NOMT/CFs (a) and its high-resolution XPS spectra of O1 s (b), C1 s (c), and N1 s (d).

where A is the absorption intensity and h is the photon energy.
Band gaps Eg were obtained from the intersection of the tangents
to the straight portions of plots of (Ahv)1/2 against the energy of
exciting light (hv), as shown in Fig. 4b. Band gaps of the obtained
samples are listed in Table 1. The anatase form of the N-doped sam-
ple exhibited a relatively low band gap compared with that of pure
TiO2 , which has a band-gap energy of 3.2 eV [4]. This observation
clearly indicates that the TiO2 doped with urea could generate addi-
tional energy levels above or below the valence band of TiO2 [35].
Although Ti C bonds were formed, as indicated by XPS analysis
(Fig. 3c), which is benecial for band-gap narrowing as in the case
of carbon-doped TiO2 [10,41], the CF support did not further narrow
the band gap of the as-prepared N-doped TiO2 .
3.2. Photocatalysis
3.2.1. Photocatalytic degradation of AO7 under visible-light
irradiation
Prior to detailed evaluation of the photocatalytic activities of
the obtained products, it was noted that the concentration of AO7
in aqueous solution decreased even without illumination because
of adsorption. However, the decrease with each catalyst was only
8 26% of the original AO7 concentration (Fig. S4). For comparison,
it can be seen in Fig. 5a that AO7 self-photodegradation was almost
negligible under visible-light irradiation in the absence of any cata-
lyst. Evidently, P25 showed negligible photocatalytic activity in the
degradation of AO7. However, all of the N-doped samples exhibited
good catalytic efciency for AO7 degradation due to the enhanced
168 Y. Li et al. / Applied Catalysis A: General 524 (2016) 163172

Fig. 4. UV/Vis diffuse reectance spectra of samples (a) and plots of (Ahv)1/2 versus photon energy (b).

1.0 Photolysis
b
P25 Visible light
CB
0.8 NNT e- e-
EC O2
UVlight e-

2.8eV
0.6 NOMT
A/A0

NNT-CFs CFs O2
0.4 EV
3.2eV
NOMT-CFs
NOMT, O2p h+
OH--
0.2 a NNT/CFs
EV
Anatase, O2p h+
NOMT/CFs OH
VB
0.0
0 30 60 90 120 150 180 210 240
Time (min)
1.0 3.5
y = 0.0092 x, R2 = 0.98
1st cycle 2nd cycle 3rd cycle 4th cycle 5th cycle
y = 0.0041x, R2= 0.99
d
3.0 NOMT/CFs
0.8 y = 0.0024x , R2= 0.98
c
Ln (TOC0/TOC)

2.5 y = 0.0013x, R2= 0.98

0.6 y = 0.0011x, R2= 0.99
2.0 NNT/CFs
y = 0.0005x, R2 = 0.99
A/A0

0.4 1.5

1.0 NOMT-CFs
0.2 NNT-CFs
0.5 NOMT
NNT
0.0 0.0
0 2 4 6 8 10 12 14 16 18 20 0 70 140 210 280 350 420
Time (hr) Time (min)

Fig. 5. The photocatalytic degradation of AO7 aqueous solution under visible light; its color removal rates (a), catalytic mechanism (b), cycling runs (c), and mineralization
degree (d) over NOMT/CFs; catalyst content = 1 g/L, pH 7, AO7 content = 1 mg/L.

visible-light adsorption. This is consistent with the photocatalytic
mechanism of N-doped anatase under visible light reported in the
literature [9,10]. Although pure NNT showed a certain photocat-
alytic effect (25%) for AO7 degradation, the photocatalytic activity
(44%) of NOMT was greater than that of NNT because of its porous
structure with a great number of activated centers, providing
effective separation of electronhole pairs [16]. The rate of AO7
decolorization was further accelerated by NOMT-CFs and NNT-CFs
due to extensive adsorption of the dye molecules on the CFs, facili-
tating their photocatalytic decomposition by TiO2 . Additionally, the
photocatalytic activity of NNT-CFs was evidently lower than that
of NOMT-CFs, mainly due to the mesostructured titania of the lat-
ter. Furthermore, the photocatalytic activity of the composite was
higher than that of a simple mixture of the components because of
the intimate contact between the CFs and NOMT, which is benecial
for electron transfer [42]. The suppression of exciton recombina-
 Y. Li et al. / Applied Catalysis A: General 524 (2016) 163172
Fig. 6. A possible pathway for the degradation of AO7 in the visible-light photocatalysis system by using NOMT/CFs as catalyst.
tion in the presence of CFs is evidently also an important factor in
the improved activity of titania besides the high adsorptivity of dye
molecules, which showed good agreement with their PL intensities
(see Fig. S5). On the basis of the above analysis and the relevant band
positions of pure and N-doped TiO2 , a photocatalytic mechanism
for the action of NOMT/CFs is proposed, as illustrated in Fig. 5b. As
mentioned above, the band gap of pure TiO2 is 3.2 eV, and excita-
tion can only be achieved with UV light of wavelengths less than
388 nm. After N-doping, the band gap was obviously decreased and
new impurity levels were introduced between the conduction and
valence bands of TiO2 . Therefore, NOMT/CFs has a narrower band
gap with a change in the light absorption band from the near-UV to
the visible-light range. The process of visible-light photocatalytic
oxidation of AO7 is described as follows:
NTiO2 + h hVB + + eCB (2)
O2 + eCB O2 (3)
O2 + H2 O OH + OH (4)
+ OH
hVB + OH (5)
OH + AO7 CO2 + H2 O (6)
Firstly, electrons and holes are generated under visible light
irradiation. The electrons can then react with molecular O2 on the
surface of TiO2 to form a superoxide anion radical (O2 ). This O2
can then interact with adsorbed H2 O to produce OH radicals, the
main species responsible for the degradation of pollutants, such as
AO7 in the present case. Meanwhile, holes can be captured by the
surface OH to also form OH radicals. From the above equations, it
can be inferred that OMT played an important role in preventing the
recombination of photogenerated electron and hole pairs, because
its ordered mesoporous structure provides a large number of acti-
vated centers. This increases the likelihood of electron-hole pairs
on the surface of the catalyst reacting with adsorbed O2 and H2 O,
respectively, to form O2 and OH. Additionally, CFs also facilitate
channeling of electrons due to their graphite structure [5]. Hence,
the separation rates of photogenerated charge carriers are effec-
169
tively improved. Meanwhile, many dye molecules are adsorbed on
the CF support, leaving them suitably predisposed in the photocat-
alytic environment, thereby enhancing the photocatalytic activity.
To verify the practical applicability of NOMT/CFs, recycling exper-
iments on the photocatalytic decoloration of AO7 solution were
carried out under visible-light irradiation. As shown in Fig. 5c, the
efciency of photocatalytic decoloration was maintained without
any signicant decline after ve cycles. Thus, NOMT/CFs displayed
great potential for practical application in wastewater treatment
using solar light. The excellent reusability of NOMT/CFs may stem
from the good binding property between the NOMT layer and CFs.
As shown in Fig. S6, two SEM images of NOMT/CFs after ve cycles
show no detectable differences in comparison with those of the
corresponding fresh samples (Fig. 1b and c), which is benecial for
the stability of the photocatalytic performance. Additionally, the
brous structure of the catalyst is very benecial for its separation
from the treated wastewater. To further examine the photoactivity
of the obtained samples under visible light, the degree of AO7 min-
eralization was analyzed in the presence of various photocatalysts,
as shown in Fig. 5d. Photodegradation of AO7 roughly followed
pseudo-rst-order kinetics. The rate constants for AO7 degradation
with NOMT/CFs, NNT/CFs, NOMT-CFs, NNT-CFs, NOMT, and NNT
were found to be 9.2, 4.1, 2.4, 1.3, 1.1, and 0.5 103 min1 , respec-
tively. Among all of these catalysts, NOMT/CFs show the highest
photocatalytic activity for AO7 degradation under visible-light irra-
diation. This can be attributed to three synergistic effects between
enhanced visible-light absorption of N-doping, high adsorptivity
of dye molecules, and fast electron transport in CFs and effective
separation of electronhole pairs in OMT.
3.2.2. Possible pathways for conversion of AO7
In general, for TiO2 under UV irradiation, the oxidative activity
of TiO2 particles is mostly
attributed to species formed through reactions initiated by
photogenerated electronhole pairs, such as OH, other peroxyl rad-
icals, and valence-band holes [42]. The intermediates generated in
170 Y. Li et al. / Applied Catalysis A: General 524 (2016) 163172

Table 2
Reaction intermediates of AO7 degradation identied by GCMS.

Compound Identied reaction Photocatalytic time Compound Identied reaction Photocatalytic time
intermediates (min) intermediates (min)

sulfanilic acid 25 1,2-naphthalenedione 125

1-amino-2-naphthol 50 ninhydrin 150

p-benzoquinone 75 2-formylbenzoic acid 175

2-naphthalenol 100 hexylacetic acid 200

10

9
Rate constant K103 (min)

5 [AO7] = 1mg/L
4 pH = 7

3
0.5 1 2 3

NOMT/CFs (g/L) Fig. 8. Effect of pH on the degradation rate constant of AO7.

Fig. 7. Effect of NOMT/CFs dosage on the degradation rate constant of AO7.

vation of activated molecules through collision with ground-state

the conversion of AO7 using NOMT/CFs under visible light were
identied by GCMS, as illustrated in Table 2.
Additionally, a possible pathway for AO7 photocatalytic degra-
dation by NOMT/CFs is proposed in Fig. 6. A representative GCMS
trace is also presented in Fig. S7. Overall, the photocatalytic degra-
dation of AO7 by NOMT/CFs can be described in terms of a series
of consecutive degradation steps. AO7 is rstly decomposed to aro-
matic intermediates, further oxidized to ring-opened products, and
nally mineralized to CO2 , H2 O, and inorganic salts [43].
3.2.3. Effects of the NOMT/CFs dosage
The reaction rate, which is a function of catalyst content, is an
important parameter [44]. It is well known that the absorption
of light and adsorption of the reactant on the titania surface are
limiting factors in such photocatalysis. For a certain light inten-
sity, the amount of photons impinging on the photocatalyst is
nite. At contents up to about 1 g L1 (or saturated adsorption
of photons), the degradation rate increases with increasing cata-
lyst content simply because more catalyst provides more activated
centers and can adsorb more of the reactant. However, a further
increase in catalyst dosage beyond 1 g L1 may result in deacti-
molecules. At dosages higher than 1 g L1 , NOMT/CF aggregation
(particleparticle interactions) may commence, thereby lowering
the effective surface area of the catalyst and thus the adsorption of
the reactant. Additionally, the turbidity of the mixture is increased,
which greatly reduces the amount of light transmitted through the
solution.
3.2.4. Effects of pH
Fig. 8 shows the variation in rate constant of AO7 mineraliza-
tion with pH. Interestingly, the order of reaction rates was pH
7 > pH 9 > pH 5 > pH 11 > pH 3. Strong acid or alkali was not appro-
priate for decomposing AO7 because the amount of hydroxyl ion
adsorbed on TiO2 is inuenced by the pH [45]. At various pH val-
ues, the main pathways for producing OH are probably different;
therefore, the rates of OH production are different. An increase
in pH can be expected to increase the number of OH ions on the
TiO2 surface, and OH could be formed when OH combines with
photogenerated holes [Eqs. (5) and (7)] [40]:
+
hVB
+ + H2 O(ads) OH + H (7)
 Y. Li et al. / Applied Catalysis A: General 524 (2016) 163172
Fig. 9. Effect of initial AO7 concentration on kapp and 1/kapp (a) and the ks and kr values of different samples (b).
In acidic solution, the photocatalytic degradation of AO7 is
probably due to the formation of OH according to the following
reactions [Eqs. (3), (8)(10)]:
O tures are obviously increased and are much higher than those of
2(ads)
+ H+ HO2
2HO2 O2 + H2 O2
H2 O2 + O
2(ads)
OH + OH + O2
More efcient formation of hydroxyl radicals occurs in alkaline
solution via the shorter route
[Eq. (7)]. On the other hand, AO7 has a sulfonate group in its
structure, which is negatively charged under alkaline conditions;
therefore, AO7 may not be effectively adsorbed on the photocata-
lyst surface in alkaline solution [46]. The above ndings indicated
that the most efcient photodegradation of AO7 probably occurred
at neutral pH.
3.2.5. Effects of the initial AO7 concentration and kinetics of
photocatalytic mineralization
The efciency of the mineralization process was found to
decrease with increasing concentration of AO7 (Fig. 9). This may
have been a result of blocking of the photocatalytically active
sites [47]. The modied LangmuirHinshelwood kinetic model [37]
is generally utilized for such photo-oxidation processes, and the
degradation rate is expressed by the following equation:
1 1 C0
= +
Kapp kr kS kr
where C0 is the initial concentration of the reactant (mg L1 ), kr is
the reaction rate constant (mg L1 min1 ), ks is the adsorption coef-
cient of the reactant (L mg1 ), and Kapp is the observed apparent
pseudo-rst-order rate constant (min1 ).
It was found that the LangmuirHinshelwood kinetic model [Eq.
(11)] adequately describes the
kinetic behavior of AO7 degradation by NOMT/CFs, because a
linear plot of reciprocal of rate (1/kapp ) against initial AO7 concen-
tration (C0 ) showed a high R2 of 0.98. The LangmuirHinshelwood
equation could also be applied for the degradation of AO7 by other
catalysts, as shown in Fig. 9b. As indicated in Fig. 9b, all of the sam-
ples showed photocatalytic activity, and the rate constants kr and
absorption equilibrium constants ks determined in this way were
dependent on the nature of the N-doped titania and the synergy
between CFs and titania. Values of kr with NOMT were higher than
those with NNT. This can be attributed to the fact that more pores
are formed and more activated centers are located on the external
surface of the catalyst, making them more accessible to the target
171
substrate. Therefore, the better dye removal performance may be
attributed to the porous structure of the titania, which is consistent
with the variation in ks . By addition of CFs, both K and kr of mix-
(8)
pure N-doped titania. This may be due to the fact that the CFs serve
(9) to concentrate the AO7 molecules around the active sites and facil-
itate electron transfer. However, the positive impact of CFs on the
(10) photocatalytic efciency greatly depends on the combined char-
acteristics of CFs and titania. Although ks of composites is lower
than that of mixtures, K and kr of the former were higher than
those of the latter because close contact between CFs and titania is
more benecial to electron transfer and migration of the adsorbed
AO7 to the active sites of titania. Additionally, the high photoactiv-
ity (K = 9.2 103 min1 , kr = 0.015 mg L1 min1 ) and adsorption
capacity (ks = 4.26 L mg1 ) of NOMT/CFs can be attributed to more
activated centers, faster electron transfer, and easier migration of
the adsorbed AO7 as a result of the mesostructure and close contact.
4. Conclusions
With the aim of effectively utilizing visible light and conve-
nient application of the photocatalyst in water treatment systems,
(11) NOMT/CFs has been successfully fabricated by a combined method
of supercritical deposition and liquid-crystal templating. The
NOMT/CF composite showed high photocatalytic activity for AO7
degradation under visible-light irradiation due to three synergis-
tic effects arising from effective separation of electronhole pairs,
enhanced visible-light adsorption, and high adsorptivity of dye
molecules. Meanwhile, the strong binding between the NOMT layer
and the CFs leads to excellent recyclability of NOMT/CFs in practical
applications for wastewater treatment using solar light. A photo-
catalytic mechanism for the action of NOMT/CFs and a degradation
pathway for AO7 have been proposed. Conditions of 1 mg L1 AO7,
pH 7, and 1 g L1 NOMT/CFs were identied as optimal for AO7
degradation. The NOMT/CFs system has good potential for com-
mercial application. The photocatalytic degradation processes can
be described in terms of a modied LangmuirHinshelwood model
for the surface reaction between the dyestuff and the oxidizing
agent. The values of the adsorption equilibrium constants, ks , and
the rate constants, kr , were certainly dependent on the catalyst por-
perties. For NOMT/CFs with the highest rate constant, kr and ks were
0.015 mg L1 min1 and 4.26 L mg1 , respectively.
172 Y. Li et al. / Applied Catalysis A: General 524 (2016) 163172
Acknowledgements
This work was supported by Natural Science Foundation of
China (21476095,51172092) and Hunan Provincial Natural Science
Fund for Distinguished Young (13JJ1023). In addition, we appre-
ciate the constructive suggestions of the anonymous reviewers,
which are invaluable in improving the quality of the manuscript.
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.apcata.2015.01.
050.
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