Microporous and Mesoporous Materials 226 (2016) 79e87

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Microporous and Mesoporous Materials

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

Mesoporous silica-based carbon dot/TiO2 photocatalyst for efcient

organic pollutant degradation
Chen Cheng a, b, Deli Lu c, Bin Shen b, Yongdi Liu a, Juying Lei a, *, Lingzhi Wang b, **,
Jinlong Zhang b, Masaya Matsuoka d
a

State Environmental Protection, Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, School of Resources and
Environmental Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, PR China
Key Lab for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237,
PR China
c
School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418, PR China
d
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan
b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 14 October 2015
Received in revised form
5 December 2015
Accepted 22 December 2015
Available online 30 December 2015

Carbon dots (CD) and Ti species were assembled in the mesoporous silica matrix by a one-pot cocondensation strategy. The CD and Ti in the silica matrix were demonstrated to interact in two ways: on
the one hand, part of the carbon in CD was doped into the Ti species; on the other hand, CD worked as
photosensitizers for Ti species. The synergy effect between CD and Ti in the silica matrix along with the
unique physical properties of the composite including ordered pore channels, large surface area and
wide-range light absorption from UV to near IR made this composite be an excellent photocatalyst, as
demonstrated by the photocatalytic degradation of azo dye acid orange 7. In addition to the degradation
of organic pollutant, this newly developed mesoporous composite is expected to have promising applications in various areas related to environment and energy such as photoreduction of CO2 and photocatalytic H2 production.
2016 Elsevier Inc. All rights reserved.

Keywords:
Carbon dot
TiO2
Mesoporous silica
Photocatalytic degradation
Organic pollutant

1. Introduction
Mesoporous silica materials based on SieO framework have
attracted widespread interests in applications of catalysts [1e3],
biolabels [4,5], adsorbents [6e8], and sensor devices [4,9,10] due to
their unique structural features like exceptionally high surface area,
uniform and well-dened pore topology, since the rst synthesis of
MCM-41 in 1992 [11]. However, it is also known that mesoporous
silica materials composing of only Si and O atoms do not possess
any oxidation capacity and any ability for absorption of UV or
visible light [12], which greatly limit their applications in the eld
of catalysis, in particular for photocatalysis. In order to expand their
applications for photocatalysis, many efforts have been carried out.
For instance, nanoparticles of semiconductors have been dispersed
into the mesopores to form mesoporous composites with efcient
photocatalytic activity [13e19]. This kind of composites has been

* Corresponding author.
** Corresponding author.
E-mail addresses: leijuying@ecust.edu.cn (J. Lei), wlz@ecust.edu.cn (L. Wang).
http://dx.doi.org/10.1016/j.micromeso.2015.12.043
1387-1811/ 2016 Elsevier Inc. All rights reserved.

commonly reported for TiO2 [2,16,17,19], Bi2WO6 [13], WOx

[14,15,18] and so on. On one hand, the mesopores help to prevent
the agglomeration of semiconductor nanoparticles, thus acquiring
relatively better catalytic activity. On the other hand, however, the
nanoparticles in the pore channels inevitably sacrice the pore
volume and even lead to the pore blockage, which hinder further
improvement of the photocatalytic activity. Nevertheless, this
shortcoming can be well resolved by introducing the species with
photocatalytic activity into the mesoporous framework rather than
into the mesopores. As it has attracted a great deal of attention
recently, transition metal species (e.g., titanium, cerium [20],
chromium [21], vanadium [22], and molybdenum [23]) were
incorporated as photoactive sites into the frameworks of mesoporous materials. By dispersing the photoactive sites in the silica
matrix, the mesopores were well maintained and considerable
catalytic activity was obtained for specic catalytic and photocatalytic reactions. However, this advantage was actually achieved
at the expense of light-absorption range of photocatalyst. For
example, the high dispersion of Ti species in silica framework
increased splitting degree of energy level, leading to wider

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C. Cheng et al. / Microporous and Mesoporous Materials 226 (2016) 79e87

forbidden band than that of common TiO2, therefore resulting in

the blue-shift of absorption spectrum [24].
Recently, carbon dots (CD) have attracted great attention due to
its non-toxicity, good chemical stability and excellent optical
properties. It has been applied to couple with various semiconductors to extend their light absorption to visible or even NIR
range for better photocatalytic performance. For example, Li et al.
reported the design of TiO2/CD photocatalysts that harnessed the
full solar spectrum [25]. Liu and coworkers developed hematite/CD
nanocomposites with a quasi-cube morphology and a single crystal
structure around 600 nm in size. They investigated the effective
photocatalytic activity towards the degradation of benzene and
methanol under the visible-light irradiation [26]. More recently,
Guo et al. explored a novel CD/carbon nitride hybrid photocatalyst
that responded to infrared light irradiation [27]. However, up to
now, there are still few reports about the combination of CD and
photocatalytically active species in the mesoporous silica matrix to
simultaneously utilize the advantages of CD and mesoporous
materials.
Herein, we assembled CD and Ti species in the mesoporous silica
matrix by a one-pot co-condensation of tetraethyl orthosilicate
(TEOS), silylated carbon dot (Si-CD) and tetrabutyltitanate (TBOT).
Mesoporous silica SBA-15 was chosen in consideration of its uniform and ordered pore structure and large surface area. The
resultant CD and Ti co-incorporated mesoporous composite
possessed excellent light absorption from UV to NIR. Experimental
results demonstrated that this mesoporous composite had relatively high photocatalytic activity towards degradation of organic
pollutant acid orange 7. Moreover, the composite containing both
CD and Ti had greatly enhanced catalytic capability, compared to
those materials containing only either CD or Ti. The mechanism for
the improved photocatalytic activity was nally proposed based on
the XPS analysis, the electrochemical and photophysical
measurements.
2. Experimental
2.1. Synthesis of silylated carbon-dots (Si-CDs)
Si-CDs were obtained with a novel one-step synthetic route
following the method described previously [28]. The reaction
proceeded through pyrolysis of anhydrous citric acid. N-(b-aminoethyl)-g-aminopropylmethyldimethoxysilane (AEAPMS) (10 mL)
was put into a 50 mL three-necked ask, and raised the temperature to 240
C with stirring under the nitrogen atmosphere. Then
anhydrous citric acid (0.5 g) was added into the ask quickly. After
1 min, the heating was stopped and the reaction mixture was
cooled to the room temperature. The oily liquid product was obtained after being washed with hexane twice, sealed with hexane
and stored in the refrigerator.
2.2. Synthesis of the mesoporous silica (MS) composites
incorporated with CD and Ti
The MS composites were prepared using Pluronic P123 as the
template by a method similar to that described before [30]. Typically, Pluronic P123 (EO20PO70EO20, Mav 5800, Aldrich) (0.5 g)
was dissolved into 2.0 M HCl solution (120 mL) to get a homogeneous solution by vigorous stirring at 38
C. Then, TEOS (9 mL) and
appropriate volume of Si-CDs were added and the mixture was
stirred continually for 24 h at 38
C. The volume ratio of TEOS and
Si-CDs was controlled as 20, 15, 10 and 5. Subsequently, the mixture
was transferred into an autoclave and hydrothermal at 100
C for
24 h. Then the samples were ltered, washed with deionized water
for three times, dried at 60
C under vacuum condition. To protect

the CDs in the framework, we used a facile extraction method to

remove the P123 template. The as-prepared samples (50 mg) were
added into a solution of sodium acetate (60 mg) in ethanol (5 mL).
The mixture was stirred under reux for 1 h at 92
C, then centrifuged and washed with water for at least three times, dried and
calcinated at 450
C for 4 h under nitrogen atmosphere. The heating
rate was 1
C min1. The obtained samples with TEOS/Si-CDs ratios
of 20, 15, 10, and 5 were named as CD-MS-20, CD-MS-15, CD-MS-10,
CD-MS-5, respectively.
The above samples contained only CDs in the framework. The
samples simultaneously incorporated with CD and Ti were prepared by a similar method. The volume ratio of TEOS and Si-CDs
was set at 15 and different volumes of TBOT were added after the
addition of TEOS and Si-CDs. The obtained samples were named as
CTi-MS-15-X, where X represented the volume ratio of TEOS and
TBOT which was 100,150 or 200.
As a comparison, we also synthesized CD incorporated silica
ber method [31]
nanoparticles without mesopores by a Sto
described as follows. Deionized water (7 mL), ethanol (25 mL)
and ammonia (5 mL) were mixed in a ask by magnetic stirring
while TEOS (3 mL) and ethanol (35 mL) were mixed in another
ask. After 30 min, the two solutions were merged, and Si-CDs
(150 mL) were soon added. The solution was then stirred for 3 h
at room temperature. Then the sample was centrifuged and washed
with deionized water for several times, dried and calcinated at
450
C for 4 h under nitrogen atmosphere. And the rate was
1
C min1. The nally obtained sample was named as SiO2-CDs-20.
2.3. Evaluation of photocatalytic activities
The photocatalytic activities were evaluated by the decomposition of the aqueous solution of Acid Orange 7 (AO7, 10 mg L1). A
300-W high-pressure Xe lamp for which the emission wavelength
is about 200e800 nm was used as a light source of the home-made
photo reactor, cooled with owing water in a quartz cylindrical
jacket around the lamp. For a typical photocatalytic experiment, a
total of 50 mg of catalyst powders was added 50 mL of the above
simulating pollutants solution in the quartz tube. Prior to irradiation, the suspensions were magnetically stirred in the dark for
30 min to ensure the establishment of an adsorption/desorption
equilibrium. The above suspensions were kept under constant air
equilibrate conditions before and during the irradiation. At given
time intervals, about 4 mL aliquots were sampled, immediately
centrifuged and ltered through syringe lters (cellulose acetate
membranes) with the size of 0.22 mm to remove the photocatalysts.
The ltrates were analyzed by recording variations in the absorption in UVevis spectra with using a Shimadzu UV-2450 ultraviolet
visible spectrometer.
2.4. Catalyst characterization
The morphology of as-made CD-MS and CTi-MS-15 series
samples was characterized by transmission electron microscopy
(TEM, JEM2000EX) and scanning electron microscopy (SEM, JEOL
JSM-6360LV microscope at an accelerating voltage of 15 kV). Small
angle XRD patterns which were conducted to identify the samples'
microstructure characteristics, were collected in the range of
0.5e5
(2q) and recorded on a Rigaku D/MAX-2550 diffract meter
using Cu Ka radiation of wavelength 1.5406 , typically running at a
voltage of 40 kV and current of 100 mA. UVevisible absorbance
spectra were achieved for the dry-pressed disk samples using a
Scan UVevisible spectrophotometer (SHIMADZU, uv-2450), and
using BaSO4 as a reectance sample. BET surface area measurements were carried out by N2 adsorption at 77 K using an ASAP2020
instrument. By utilizing the BarretteJoynereHalenda (BJH) model,

C. Cheng et al. / Microporous and Mesoporous Materials 226 (2016) 79e87

the pore volumes and pore size distributions were got from the
adsorption branches of isotherms. Electrochemical Impedance
Spectroscopy (EIS) was carried on the classical three-electrode
system, using Zahner electrochemical station to test the electrochemical property of the samples. The supporting electrolyte is the
mixed solution of 2.5 mmol L1 K3Fe(CN)6 and K4Fe(CN)3 and
0.1 mol L1 KCl. The counter, reference and working electrode are Pt
electrode, saturated calomel electrode (SCE) and FTO glass coated
with thin lm sample, respectively. The electrode potential was
0.2 V versus SCE. The frequency range was from 0.1 to 106 Hz.
During the rest, we used the standard FTO conductive glass as the
sample-base, then created a 10 mm * 15 mm region by scotch tape.
10 mg sample was dispersed into 1 mL isopropanol by ultrasonic,
drop wise added 20 mL onto the glass, and made statically leveled.
Finally, the scotch tape was teared away after it was dried at 70
C.
X-ray photoelectron spectroscopy (XPS) studies were taken by a
PerkineElmer PHI 5000CESCA system with Al Ka radiation operated at 250 W. The vacuum level was lower than 1  108 Torr.
Samples were pre-treated as vacuum dried for 2 h, and then coated
on the test-base uniformly in N2 atmosphere.
3. Results and discussion
3.1. Synthesis and structural properties
In this work, the successful fabrication of CDs and Ti coincorporated mesoporous composites were achieved using a
modied method for typical mesoporous silica SBA-15 [32,33]
under acidic aqueous conditions in the presence of Pluronic
P123 tri-block copolymer as a pore structure-directing agent. In
the process of the synthesis, the silica source TEOS, Si-CDs and
titanium source TBOT were successively added into the reaction
solution and conducted a co-condensation, leading to homogeneous incorporation of CDs and Ti in the silica framework. Here
the acidic reaction condition could slow down the hydrolysis rate
of TBOT and beneted for the uniform dispersion of Ti in the silica
skeleton. In addition, Si-CDs possessed amino groups on the surface [28,29]. These amino groups could complex with Ti during
the synthesis process which was also benecial for the uniform
dispersion of Ti and, moreover, could lead to close contact between CD and Ti in the silica framework. It's worth being noted
that, before the preparation of these CD and Ti co-incorporated
samples, a series of MS composites with different doping
amounts of CDs in the absence of Ti were prepared by using
different TEOS/Si-CDs volume ratios to obtain an optimal doping
amount of CD.
The mesoporous structures of the mesoporous composites
incorporated with only CD and co-incorporated with CD and Ti
were examined by a combination of XRD, TEM and nitrogen sorption measurements. Fig. 1a exhibits the small-angle XRD patterns of
the as-prepared mesoporous composites with only CD incorporation synthesized with different TEOS/Si-CDs volume ratios,
respectively. As shown in the gure, CD-MS-20 with the lowest CD
doping amount exhibited diffraction peaks, quite similar to the
blank MS with three peaks in the range of 0.7e1.0
and 1.5e2.0
,
which corresponded to the (100), (110) and (200) reections,
respectively, indicating the presence of uniformly hexagonal pores
with good ordering in the material. With the decrease of TEOS/SiCD volume ratios, which meant an increase of CD in the framework, the three characteristic peaks were diminished and no
observable peak remained when the ratio of TEOS/Si-CDs was
decreased to 10. The results suggested that the ordering of the
mesopores decreased with the increasing amount of CD, which was
due to the fact that the Si-CDs were integrated into the silica
framework with multiple althoxysilyl groups through exible N-(b-

81

aminoethyl)-g-aminopropyl chains, so that when its amount

increased, the degree of cross-linking decreased, thus resulting in
disorder of the mesopores. The same trend had been observed by
TEM images shown in Fig. 2aed. Ordered mesoporous channels
were exhibited in CD-MS-20 and CD-MS-15, while amorphous
nature was observed for CD-MS-10 and CD-MS-5 which have more
CD amounts. The nitrogen adsorptionedesorption isotherms of
different samples (Fig. 1b) and the corresponding textual and
structure parameters (Table 1) demonstrated a similar conclusion
as discussed above. The isotherms of MS, CD-MS-20 and CD-MS-15
presented typical type IV isotherm curves with a well-dened step
at relative pressure P/P0 0.6e0.8, which clearly illustrated that
these samples possessed mesoporous structure. As the amount of
CD increased, the N2 adsorption isotherms exhibited a tendency to
change from type IV to I, which was already reported for other
periodic mesoporous organosilicas [34,35] and constitutes(ed) a
typical behavior for materials with gradually decreasing pore
diameter on the borderline between mesopore and micropore
ranges (barrier at 2 nm) [36]. From the above results, it can be
concluded that ordered mesoporous structure could maintain in
the composites unless the ratio of TEOS/Si-CDs decreased to lower
than 15. In addition, the photocatalytic experiments which would
be discussed later showed that CD-MS-15 exhibited the best photocatalytic activity. Therefore, the optimum CD doping amount was
determined to be TEOS/Si-CDs volume ratio at 15, which corresponded to the sample CD-MS-15. Then a series of CD and Ti coincorporated samples were prepared with 3 different TEOS/TBOT
ratios, while keeping and the ratio of TEOS/Si-CDs constant was
kept at 15 according to the above results. The samples were named
as CTi-MS-15-X, where X represented the volume ratio of TEOS and
TBOT and its value was equal to 100,150 or 200, respectively. Fig. 3b
shows nitrogen adsorptionedesorption isotherms of the three
samples. The isotherms exhibited type IV behavior, indicating the
preservation of mesopores in the samples with the coincorporation of Ti. The XRD pattern in Fig. 3a demonstrated that
the ordering of the mesoporous structure decreased with the increase of the Ti doping amount, but the diffraction peaks also
showed that all the three samples still remained ordered mesopores. Fig. 2e and f shows typical TEM and SEM image(s) of CTi-MS15-150 prepared with the TEOS/TBOT ratio of 150 as a representative. A rod-like surface morphology was exhibited by both the
SEM and TEM images, and ordered mesopores could be clearly
observed from the TEM image. The ordered mesopores proved by
TEM, XRD and nitrogen adsorption/desorption isotherms, combing
with the large specic surface area up to 430.52 m2 g1 obtained
from BET measurement results (Table 1), demonstrated that the
composites co-incorporated with CDs and Ti developed by this
research well maintained the advantages of mesoporous silica
materials.
3.2. UVevis diffuse reection spectra
The UVeVis absorption spectra of CD-MS series samples were
recorded, as shown in Fig. 4a. From the gure, we could nd the
obvious presence of absorption band in visible light region, and the
absorption intensity varied with increase of the CD doping amount.
Fig. 4b presents spectra of CTi-MS-15 series samples. It's shown
that, in addition to the absorption of CDs, all samples featured a
narrow and intense ultra-violet absorption band around about
227 nm. Generally, the band with a maximum at about
200e220 nm was attributed to a ligand-to-metal charge-transfer
transition (LMCT) in isolated TiO4 or HOTiO3 units. It usually
believed to connect directly with the framework Ti4 in tetrahedral
coordination. Commonly, this band was used as direct proof to
demonstrate that titanium atoms have been incorporated into the

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C. Cheng et al. / Microporous and Mesoporous Materials 226 (2016) 79e87

Fig. 1. Small angle XRD patterns (a), N2 sorption isotherms (b), and the corresponding pore distribution curves (c) of CD-MS-X series samples.

framework of a molecular sieve. The intense peak at 227 nm

showed increase location and red-shift of this band, attributed to a
distorted tetrahedral coordination environment or the existence of
some titanium species in an octahedral coordination environment
[37,38]. In addition, it's worth mentioning that, from the UVevis
spectroscopy results it could be found that both series of samples
whether only CD incorporated or CD and Ti co-incorporated had
very broad light absorption from UV region up to near infrared
region (800 nm). This wide absorption spectra indicated high lightharvesting capabilities of the catalysts which was benecial for
improved photocatalytic activity.

high resolution O1s spectrum as shown in Fig. 5b. Two peaks at

529.4 and 532 eV could be clearly observed, which represented the
TieOeTi [42e44] and TieOeC [45,46], respectively. The existence
of TieOeC suggested that the CDs also connected with Ti through
the CeO bond. The big peaks around 534.8e536.4 eV were related
to OeH which came from the oxygen and/or water adsorbed onto
the surface of mesoporous silica [47,48]. Collectively, the XPS results showed that there was a close integration between CD and Ti
in the silica matrix, which was expected to result in a synergistic
effect between CD and Ti for the improvement of the photocatalytic
activity.

3.3. X-ray photoelectron spectroscopy (XPS) analysis

3.4. Photocatalytic activity

To investigate the interaction between CD and Ti species in the

silica matrix, XPS measurement was performed. Fig. 5a shows the
high resolution C1s spectra of CTi-MS-15-150 and CD-MS-15. For
CD-MS-15, the C1s XPS spectra can be tted into two peaks at 285.7
and 288.5eV, corresponding to CeO and C]O (or OeC]O) [39,40],
respectively. While for CTi-MS-15-150, in addition to the peaks for
CeO and C]O, a new peak at 281.8 eV arised. This peak was
associated with the bond of TieC [41], indicating that part of carbon
in CD formed chemical bond with titanium in the composite, which
meant part of carbon existed as a dopant in the Ti species. And the
peak at 285.7 eV of CD-MS-15 had relatively difference with
286.5 eV of CTi-MS-15-150, which was mainly due to the introduction of highly distributed Ti. However, the amount of Ti moiety
was so little that the XPS spectrum of Ti could not be obtained.
Nevertheless, the existing form of Ti could be investigated by the

The photocatalytic activities of the prepared CD-MS series and

CTi-MS-15 series samples were evaluated by the degradation reaction of organic pollutant AO7. Fig. 6a shows the degradation rates
of AO7 dye over CD-MS series samples. It was found that, the
samples incorporated with CDs all worked as effective photocatalysts for AO7 degradation. The photocatalytic activity was
increased with increasing CDs, which indicated that introducing a
suitable amount of CDs could effectively improve the photocatalytic
activity for the degradation of AO7. Further increasing the amount
of CDs, the photocatalytic activity was decreased, which may be
due to that overdose CDs resulted in damage of mesoporous
structure, thus reducing the surface area. CD-MS-15 with the
property of ordered mesoporous microstructure, and loaded with
relative much CDs, was found to have the best photocatalytic activity. Therefore, the optimum CD doping amount was determined

C. Cheng et al. / Microporous and Mesoporous Materials 226 (2016) 79e87

83

Fig. 2. TEM images of CD-MS-20 (a), CD-MS-15 (b), CD-MS-10 (c), CD-MS-5 (d), CTi-MS-15-150 (e) and SEM image of CTi-MS-15-150 (f).

to be TEOS/Si-CDs at 15:1. Also, control experiments for the

degradation of AO7 were done by employing CD-doped composites
without mesopores which was named as SiO2-CDs-20 and synber method. The results in Fig. 6a show
thesized with classical Sto

that the sample had almost no photocatalytic activity with 3 h

irradiation, demonstrating that the mesopores play an important
role in the efcient photocatalytic activity, which was mainly due to
two aspects: (1) the ordered mesoporous channels provided

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C. Cheng et al. / Microporous and Mesoporous Materials 226 (2016) 79e87

Table 1
The structural and textural parameters of the CTi-MS-15-X series samples.
Samples

SBET (m2 g1)

Vpore (cm3 g1)

dpore (nm)

a0 (nm)

d (nm)

dwall (nm)

MS
CD-MS-5
CD-MS-10
CD-MS-15
CD-MS-20
CTi-MS-15-100
CTi-MS-15-150
CTi-MS-15-200

584.87
388.07
435.41
478.36
570.99
359.30
430.52
455.71

0.884
0.235
0.333
0.767
0.785
0.500
0.812
0.839

7.78
2.42
3.06
5.53
6.46
5.56
7.55
7.36

10.02
e
e
11.76
10.88
9.76
10.77
11.25

8.68
e
e
10.19
9.42
8.45
9.33
9.74

2.24
e
e
6.23
4.42
4.20
3.23
3.92

Fig. 3. Low angle XRD patterns (a), N2 sorption isotherms (b) and the corresponding pore distribution curves (insert) of CTi-MS-15-X series samples.

Fig. 4. DRUVevis spectra of CD-MS series samples (a) and CTi-MS-15 series samples (b).

unobstructed paths for the diffusion of organic pollutant molecules

to reach the active sites; (2) the large surface area resulting from
the mesopores provided plenty of active sites and had better
adsorption ability of the pollutant molecules.
Possessing likewise ordered mesopores, large surface area and
optimum CD doping amount at TEOS/Si-CDs ratio of 15:1, the CTiMS-15 series of samples also exhibited efcient photocatalytic
degradation to AO7 which are presented in Fig. 6b. In addition, the
results were compared with those of CD-MS-15 incorporated with
only CD and Ti-MS-150 incorporated with only Ti. From both gures, it can be found that the CTi-MS-15 series of samples all
exhibited higher photocatalytic activities than CD-MS-15 and TiMS-150. And among them, CTi-MS-15-150 had the highest

photocatalytic activity which was much higher than those of CDMS-15 and Ti-MS-150. More specically, for the degradation of
AO7, the dye could be completely decomposed over CTi-MS-15-150
in 1.5 h, while over CD-MS-15 the complete degradation took more
than 3 h and over Ti-MS-150 little AO7 dye were degraded. We
further compared the photocatalytic properties of the above
different photocatalysts by the photocatalytic degradation rate
constants determined by the rst-order kinetic equation ln(C0/
C) kt, shown in Fig. 6c. Remarkably, the average value of rate
constant k of CTi-MS-15-150 was about twice that of CD-MS-15 and
nine times that of Ti-MS-150. These results clearly demonstrated
that simultaneous introduction of CD and Ti into the framework of
MS results in highly effective mesoporous silica-based

C. Cheng et al. / Microporous and Mesoporous Materials 226 (2016) 79e87

85

Fig. 5. XPS spectra of CTi-MS-15-150 and CD-MS-15: (a) C1s and (b) O1s.

Fig. 6. The photocatalysis performance of CD-MS series samples (a) and CTi-MS-15 series samples (b) for the degradation of AO7; and a comparison of degradation kinetic rates of
different samples (c).

photocatalyst, and the photocatalytic activity was much more

efcient than that of the single CD or single Ti incorporated.
3.5. Photocatalytic mechanism
To investigate the mechanism for the enhancement of the
photocatalytic activity by the combination of CD and Ti species in
the mesoporous silica matrix, photoluminescence (PL) spectra
were measured. Fig. 7a is the results of PL spectra of CD-MS and
CTi-MS-15-150. PL emission measurement has been widely used

to investigate the fate of electronehole pairs in photocatalyst

because PL emission is known to result from the recombination of
photo-generated charges [49,50]. The higher the PL emission intensity is, the higher the recombination efciency of the photogenerated carriers is. As evident in Fig. 7a, the CD-MS sample
exhibited strong photoluminescence at room temperature
centered at 450 nm originated from the CD in the composite. In
comparison, the intensity of this emission band dropped signicantly for CTi-MS-15-150. This indicated the co-incorporation of
CD and Ti could inhibit the recombination of the photo-generated

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C. Cheng et al. / Microporous and Mesoporous Materials 226 (2016) 79e87

Fig. 7. (a) Fluorescence spectra of CD-MS-15 and CTi-MS-15-150; (b) Electrochemical Impedance Spectroscopy of CTi-MS-15-150, CD-MS-15 and Ti-MS-150.

electronehole pairs of CD and improved their separation efciency, leading to an enhancement of the photocatalytic
performance.
Besides the photoluminescence measurement, electrochemical
impedance spectroscopy (EIS) was applied to investigate the charge
transfer resistance of the catalysts [51e53]. The EIS results of TiMS-150, CD-MS-15 and CTi-MS-15-150 are presented in Fig. 7b in
the form of Nyquist plots. From the gure we could see that Ti-MS150 with highly dispersed Ti species in the silica framework had
large arc radius, indicating a very high charge transport resistance
of the material, which meant that the photo-induced charges were
difcult to transfer from the Ti moieties to the surface and the
photocatalytic activity was greatly restricted. The charge transport
resistance of the CD-MS-15 with CD in the framework was much
smaller, because CD as a kind of carbon material, provided the
excellent property of high electrical conductivity, and mesoporous
silica itself had the property of large surface area, making it become
a high charge-carrier transport medium [54]. The spectra of CTiMS-15-150 showed that simultaneously introducing of CD and Ti
further lowered the resistance of the material, promoting the
transfer of the charges to the catalyst surface and so improving the
photocatalytic performance.
Based on the above results, we suggested that the underlying
causes for the excellent photocatalytic performance of the CD and
Ti co-incorporated mesoporous composites could be concluded as
follows and the possible mechanism is shown in Fig. 8. Firstly, the

abundant mesopores and large surface area were benecial to the

adsorption of reactants as soon and much as possible. Secondly, the
co-incorporation of CD and Ti made the composite combining the
light absorption of CD and Ti species. In addition, the carbon doping
(as supported by the formation of TieC linkages from the XPS
analysis) could create an intragap localized states of C 2p located
above the valence band edge of TiO2 [55]. Therefore, the highly
dispersed Ti species could also be excited by the visible light,
making both CDs and TiO2 be excited by the UVevis light to produce electronehole pairs and generate active species $O
2 and $OH.
Thirdly, CDs could work as photosensitizes to TiO2 and injected
photo-generated electrons to TiO2 [56,57]. And then the electron
was transferred to surface-absorbed O2, leading to the formation of
active specie: O
2 . Consequently, the electronehole pair of the CD
could be separated more efciently, as demonstrated by the PL
analysis. Lastly, the tight integration of CDs and Ti could help for the
transfer of photo-generated electrons efciently as proved by the
EIS result, and then further reduced the recombination rate of
electronehole pairs as well as greatly promoted the generate of
active species on the surface. All the above contributed to the nal
excellent photocatalytic activity.
4. Conclusion
In summary, we have successfully prepared CD and Ti coincorporated mesoporous silica composites by a facile cocondensation of TEOS, Si-CDs and TBOT in the presence of surfactant. The incorporation of CD and Ti made the inert silica framework light-harvesting and photocatalytical active toward the
degradation of organic pollutant AO7. Moreover, control experiments demonstrated that the mesopores of the composites played
an important role in the efcient photocatalysis. The coincorporation of CD and Ti further improved the photocatalytic
activity mainly due to the high charge separation efciency and the
good charge-carrier transport capability resulting from the combination of CD and Ti in the silica framework. In addition to the
degradation of organic pollutant, these newly developed mesoporous composites are expected to nd potential applications in
photocatalytic water splitting, photoreduction of carbon dioxide
and so on.
Acknowledgments

Fig. 8. Schematic description of possible photocatalytic mechanism of CD and Ti coincorporated photocatalysts under UVevis light irradiation.

This work was nancially supported by National Natural Science

Foundation of China (U1407102, 21407049), the Science and

C. Cheng et al. / Microporous and Mesoporous Materials 226 (2016) 79e87

Technology Commission of Shanghai Municipality (14ZR1410700,

14230710500), the Fundamental Research Funds for the Central
Universities (222201314045), China Postdoctoral Science Foundation (2015T80409), Shanghai Pujiang Program (14PJ1402100).
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