J O U RN A L OF E N V I RO N ME N TA L SC IE N CE S 6 0 (2 0 1 7) 4 3–5 2

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Preparation of Ag@AgCl-doped TiO2/sepiolite and its

photocatalytic mechanism under visible light

Shaomin Liu⁎, Dinglong Zhu, Jinglin Zhu, Qing Yang, Huijun Wu

School of Earth Science and Environmental Engineering, Anhui University of Science and Technology, Huainan 232001, China

AR TIC LE I N FO ABS TR ACT

Article history: A cube-like Ag@AgCl-doped TiO2/sepiolite (denoted Ag@AgCl–TiO2/sepiolite) was successfully

Received 18 August 2016 synthesized via a novel method. X-ray diffraction, scanning electron microscopy, energy
Revised 8 October 2016 dispersion X-ray fluorescence, X-ray photoelectron spectroscopy, Fourier transform infrared
Accepted 13 December 2016 spectroscopy, and diffuse reflectance ultraviolet–visible spectroscopy were performed to
Available online 29 March 2017 determine the structure and physicochemical properties of Ag@AgCl–TiO2/sepiolite. SEM
micrographs revealed that Ag@AgCl nanoparticles and TiO2 film are well deposited on the
Keywords: surface of tube-like sepiolite. As a result, Ag@AgCl–TiO2/sepiolite exhibits a red shift relative to
Ag@AgCl TiO2/sepiolite. Photocatalytic experiments demonstrated that the dosage of catalysts plays an
Sepiolite important role during photocatalysis. The photoelectrochemical activities of Ag@AgCl–TiO2/
Photocatalyst sepiolite and TiO2/sepiolite were also investigated. Photocurrent responses confirmed that the
Photocurrent ability of Ag@AgCl–TiO2/sepiolite to separate photo-generated electron–hole pairs is stronger
than that of TiO2/sepiolite. Methylene Blue degradation is also improved under alkaline
conditions and visible light irradiation because more UOH is produced by visible light excitation.
This excellent catalytic ability is mainly attributed to the formed Ag nanoparticles and the
Schottky barrier at the Ag/TiO2 interface. Active species analysis indicated that UO−2 and h+ are
implicated as active species in photocatalysis. Therefore, catalysts are excited to produce
abundant electron–hole pairs after they absorb photons in photocatalysis.
© 2017 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences.
Published by Elsevier B.V.

Introduction
TiO2 has been extensively investigated to remove various
organic pollutants because this substance is cost effective,
nontoxic, stable, and highly photocatalytic (Lee et al., 2013;
Ren et al., 2013; Yurdakal et al., 2008; Yu and Xu, 2007).
However, TiO2 with a large band gap can be activated under
ultraviolet (UV) light irradiation. As such, its practical appli-
cations are impeded. Therefore, other methods, such as
nonmetal doping (Li et al., 2008; Xu et al., 2008; Yu et al.,
2009), metal deposition (Lukac et al., 2007; Paramasivalm et
al., 2008; Teoh et al., 2007), and semiconductor coupling
(Akurati et al., 2008; Ho et al., 2004; Kansal et al., 2008), have
been developed to enhance TiO2 photocatalytic performance.
Ag@AgX have also been widely explored as plasmonic
resonance photocatalysts because nano-silver and silver
halide can polarize photo-induced charges. Polarization then
facilitates the separation of photoelectron–hole pairs, which
can broaden visible light absorption and provide efficient
plasmonic resonance through Ag nanoparticles deposited on
semiconductor surfaces (Begum et al., 2012; Ma et al., 2012;
Wang et al., 2013; Zhu et al., 2016a, 2016b). A new plasma
photocatalyst of Ag–AgCl@TiO2 with a highly efficient cata-
lytic activity to degrade 4-chlorophenol and reduce Cr (VI) has

⁎ Corresponding author. E-mail: shmliu1@163.com (Shaomin Liu).

http://dx.doi.org/10.1016/j.jes.2016.12.026
1001-0742/© 2017 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.
44 J O U RN A L OF E N V I RO N ME N TA L SC IE N CE S 6 0 (2 0 1 7) 43–5 2
also been successfully prepared with a one-step synthesis
method. This highly efficient photocatalytic activity can be
attributed to the surface plasma resonance effect of nanopar-
ticles, such as Ag nanoparticles, scattered on the Ag–AgCl@TiO2
surface (Guo et al., 2012). Novel visible light-driven plasma
photocatalyst Ag–AgCl@TiO2 nanotube arrays also possess a
high photocatalytic activity for the photocatalytic degradation
of Methyl Orange. This activity is contributed by the effect of
silver exposed to visible light and the rapid separation between
charges and electrons (Yu et al., 2009). Natural materials with a
large scale and a high cation exchange capacity have been used
as carriers (Mcevoy et al., 2014; Yang et al., 2012). Sepiolite is an
excellent catalytic support because of its fibrous structure and
open porous network. Microcosmic skeleton is a cage structure
composed of a nanoscale hollow fiber and characterized by a
molecular sieve, large internal channels, large specific surface
area (125–210 m2/g), and excellent adsorption, storage, and
assisted catalytic functions (Barrera et al., 2009). Modified
sepiolite contains numerous adsorption sites for pollutants
and causes the adsorbed pollutants to migrate to the degrada-
tion center located on a semiconductor surface. Therefore,
sepiolite has been used as an effective carrier. However, other
catalysts, such as modified sepiolite supported by Ag–AgCl,
have been rarely evaluated.
In this study, an acid-activated sepiolite was used as a
supporter for Ag–AgCl and sol–gel synthesis to deposit TiO2 on
the sepiolite surface. A visible-light-response Ag@AgCl-doped
TiO2/sepiolite (Ag@AgCl–TiO2/sepiolite) was synthesized suc-
cessfully and then characterized through X-ray diffraction
(XRD), scanning electron microscopy (SEM), energy dispersion
X-ray fluorescence (EDX), X-ray photoelectron spectroscopy
(XPS), Fourier transform infrared spectroscopy (FT-IR), and
ultraviolet–visible (UV–vis) diffuse reflectance spectroscopy
(DRS). The photocatalytic degradation activity of Ag@AgCl–
TiO2/sepiolite was evaluated on the basis of the photocatalytic
degradation of Methylene Blue solutions under visible light
irradiation. The photoelectrochemical properties and photo-
catalytic mechanism were also discussed.
1. Experiment
1.1. Chemicals
The following chemical reagents were used in this study:
butyl titanate (Tianjin Dengke Chemical Reagent Co., Ltd.,
China), absolute ethyl alcohol (Yantai City Double Chemical
Co., Ltd., China), acetone (Tianjin Dengke Chemical Reagent
Co., Ltd., China), acetylacetone (Tianjin Dengke Chemical
Reagent Co., Ltd., China), ethanol (Yantai City Double Chem-
ical Co., Ltd., China), polyethylene glycol (PEG, Tianjin Bodi
Chemical Industry Co., Ltd., China), silver nitrate (Sinopharm
Group Chemical Reagent Co., Ltd.,), polyvinylpyrrolidone (PVP,
Tianjin Dengke Chemical Reagent Co., Ltd., China), NaCl
(Yantai City Double Chemical Co., Ltd., China), HCl (Tianjin
Bodi Chemical Industry Co., Ltd., China), NaOH (Tianjin Bodi
Chemical Industry Co., Ltd., China), potassium iodide (KI,
Sinopharm Group Chemical Reagent Co., Ltd., China),
P-benzoquinone (PBQ, Sinopharm Group Chemical Reagent
Co., Ltd., China), tert-butanol (TBA, Sinopharm Group Chemical
Reagent Co., Ltd., China), TiO2 (Shanghai Susen Industrial Co.,
Ltd., China), HNO3 (Tianjin Bodi Chemical Industry Co., Ltd.,
China), and sepiolite (Neixiang County Xinglei sepiolite Co., Ltd.,
China). Solutions were prepared with deionized water.
1.2. TiO2/sepiolite preparation
TiO2 was deposited on the sepiolite surface via a sol–gel method,
as described in a previous study (Liu et al., 2016). Solution A with
absolute ethyl alcohol and deionized water was dripped into
solution B with ethanol, butyl titanate, and acetyl acetone. The
pH of the mixture was adjusted to 5 with 67% HNO3 and stirred for
1 hr at 25°C. In a water bath at 50°C, PEG was added to the mixture
as a surface surfactant before sepiolite was added under
continuous stirring for 1 hr. After 24 hr of activation at room
temperature, the solution was evaporated in a water bath at 80°C
to nearly dry. Solids were dried in an oven at 80°C. TiO2/sepiolite
was obtained after the solids were calcinated for 2 hr at 500°C to
eliminate organic matter.
1.3. Ag@AgCl–TiO2/sepiolite preparation
Ag@AgCl was deposited onto TiO2/sepiolite via a two-step
synthesis method. Sepiolite and PVP were added to 80 mL of
water–ethanol solution stirred for 30 min. AgNO3 was added
to form solution A and further stirred for 30 min. The solution
A was then transferred to a 100 mL Polytetrafluoroethylene
(PTFE-lined) stainless steel high-pressure reactor and then
heated for 3 hr in 130°C. After the solution A was cooled to
room temperature, 20 mL of solution B which contained NaCl,
was added into solution A drop by drop. The pH of the mixture
was adjusted to 2.5 with 36 wt.% HCl and the mixture was
continuously stirred in the dark for 24 hr. The obtained
mixture was irradiated for 30 min with a 500 W Xe lamp to
deoxidize Ag+ to Ag0. The solids were centrifuged, washed,
and dried for 8 hr at 80°C. The molar ratio of Ag+ is 1.18% and
metallic Ag is 2.11%.
For comparison, pure Ag@AgCl was synthesized with the
same method, but TiO2/sepiolite was not used.
1.4. Characterization
The XRD of the sample powder was obtained by using a Bruker
D8 (D8, Bruker, Germany) Cu-Kα X-ray single crystal diffrac-
tion tester. The 2θ ranged from 10 to 80°. The SEM images of
the samples were collected with a JSM-6700F scanning
electron microscope (Japanese Electronics Company JEOL,
Japan). FT-IR spectra (400–4000 cm−1) were obtained by using
a Magna-IR 750 (Nicolet, America) infrared-performing testing
device. XPS spectrum was carried on a ESCALAB 250 X-ray
photoelectron spectrometer (Thermo-VG Scientific, America)
with Al Kɑ (hυ = 1486.6 eV) source. A DRS spectrum was
recorded by utilizing a duv-3700 spectrophotometer (Japanese
Shimadzu, Japan) from 220 to 800 nm and barium sulfate was
used as the control group. Photoelectric measurement was
conducted on an electrochemical workstation (LK2006a,
Tianjin Lanlike Chemical Electronic High Technology Co.,
Ltd., China) under visible light irradiation. A glass film
composed of the as-prepared catalyst samples, a platinum
 J O U RN A L OF E N V I RO N ME N TA L SC IE N CE S 6 0 (2 0 1 7) 4 3–5 2
Fig. 1 – XRD patterns of sepiolite, TiO2/sepiolite, pure
Ag@AgCl, and Ag@AgCl–TiO2/sepiolite. XRD: X-ray diffraction.
sheet, and Ag/AgCl (saturated KCl) were employed as a working
electrode, a counter electrode, and a reference electrode,
respectively.
1.5. Photocatalytic experiment
The photocatalytic activity of Ag@AgCl–TiO2/sepiolite was eval-
uated on the basis of the degradation of Methylene blue (MB)
solution at room temperature. Photocatalysis was carried out in a
photocatalytic reactor (GXH500W; Beijing NBET Technology Co.,
Ltd., China). In this experiment, 100 mg of Ag@AgCl–TiO2/
sepiolite was suspended in 250 mL of MB solution (6 mg/L). The
suspension was stirred magnetically in the dark for 30 min to
maintain adsorption–desorption balance and then exposed to
light. The reaction solution sample was collected every 20 min
and centrifuged to examine the absorbance at 662 nm with a
spectrophotometer (UV2550, Shimadzu, Japan). The photocata-
lytic degradation rate (r, %) was calculated as follows:
r ¼ ð1−Ai =A0 Þ  100% ð1Þ
where, A0 is the initial absorbance of the MB solution that reached
absorption equilibrium and Ai is the absorbance of the MB
solution at reaction time i.
1.6. Re-use of the photocatalyst
Recycle experiment on photocatalytic degradation of MB by Ag@
AgCl–TiO2/sepiolite was performed to examine its recycling
property. After finishing a cycle, the solution was filtrated and
the catalyst particles were purified for 120 min. Then the catalyst
Fig. 2 – SEM images of the as-prepared sample: (a) sepiolite, (b) TiO2/sepiolite, and (c) Ag@AgCl–TiO2/sepiolite. SEM: scanning
electron microscopy.
45
Energy (×103 eV)
Fig. 3 – EDX spectrum of the Ag@AgCl–TiO2/sepiolite
composite. EDX: energy dispersion X-ray fluorescence.
particles were dried in an oven at 80°C for 2 hr. And then the next
cycle began. Each cycle lasted 120 min under visible light. The
re-use experiment was conducted for three cycles.
2. Results and discussion
2.1. XRD analysis
The XRD spectra of sepiolite, TiO2/sepiolite, pure Ag@AgCl, and
Ag@AgCl–TiO2/sepiolite are shown in Fig. 1. The diffraction peaks
of TiO2/sepiolite and Ag@AgCl–TiO2/sepiolite were at 25.30, 37.79,
48.03, 55.05, and 62.68° corresponding to (101), (004), (200), (211),
and (204) crystal faces, respectively. These peaks originated from
the standard spectra of TiO2 anatase type (JCPDS no. 21-1272). The
diffraction peaks of Ag@AgCl/sepiolite were evident and consis-
tent with those of Ag@AgCl. The peak positions were 27.82, 23.34,
46.23, 54.82, 57.48, 67.45, 74.46, and 76.74° that matched with (111),
(200), (220), (311), (222), (400), (331), and (420) crystal faces. These
peaks were from the chlorargyrite standard spectra (JCPDS no.
31-1238). In addition, a very weak diffraction peak of located at
38.11° attributed to the cubic phase Ag (JCPDS no. 65-2871) has
also been observed. This finding indicated that nano-silver is
formed during catalyst preparation under exposure to visible
light.
2.2. SEM analysis
The morphological characteristics of the as-prepared photo-
catalysts were represented by SEM. The SEM images of sepiolite,
TiO2/sepiolite and Ag@AgCl–TiO2/sepiolite are shown in Fig. 2.
46 J O U RN A L OF E N V I RO N ME N TA L SC IE N CE S 6 0 (2 0 1 7) 43–5 2
Fig. 4 – XPS spectrum of Ag@AgCl–TiO2/sepiolite: (a) survey scan, (b) Ag 3d, (c) Cl 2p, and (d) Ti 2p. XPS: X-ray photoelectron
spectroscopy.
The photocatalysts used in this study were needle tubes with a
diameter of 1 μm. A large morphological difference was observed
from the images of sepiolite, TiO2/sepiolite, and Ag@AgCl–TiO2/
sepiolite. A thin film layer was coated onto the sepiolite surface
(Fig. 2b). Consequently, the surface became rough. A number of
Ag@AgCl cubic structures were deposited onto the TiO2/sepiolite
surface (Fig. 2c). Therefore, sol–gel method and two-step
Fig. 5 – FT-IR spectrum of photocatalysts: (a) sepiolite, (b)
TiO2/sepiolite, and (c) Ag@AgCl–TiO2/sepiolite. FT-IR: Fourier
transform infrared spectroscopy.
synthesis can be applied to deposit TiO2 thin film and Ag@AgCl
particles onto the sepiolite surface efficiently.
2.3. EDX analysis
The EDX of Ag@AgCl–TiO2/sepiolite is shown in Fig. 3, which
shows O, Si, Ti, Ag, C, Ca, Cl, F, and Mg. Ag and Cl came from
AgCl. The EDX peaks of Ti, O, Si, C, Ca, Mg, and F were from
sepiolite. The EDX spectral peaks were detected at 3 and
2.7 keV. Therefore, these peaks are attributed to Ag and Cl
(Devi et al., 2016).
2.4. XPS analysis
The chemical compositions of Ag@AgCl-doped TiO2/sepiolite
were determined through XPS (Fig. 4). O, Si, and Ti, together
with Ag, C, Cl, and Mg, are the main elements of Ag@AgCl–
TiO2/sepiolite (Fig. 4a). The components of the Ag 3d peak
were found at 366.98 and 372.98 eV, which corresponded to
the binding energies of Ag 3d5/2 and Ag 3d3/2, respectively. The
double separation was 6 eV (Fig. 4b). The pairs of peaks at
366.64, 372.61 eV and at 367.50, 373.41 eV belonged to Ag+ and
Ag0, respectively (Liang et al., 2015). The peaks at 366.98 and
372.98 eV are mostly attributed to the metallic silver and Ag+
(Zheng et al., 2007; Lu et al., 2008), respectively. It shows that
 J O U RN A L OF E N V I RO N ME N TA L SC IE N CE S 6 0 (2 0 1 7) 4 3–5 2
Fig. 6 – (a) UV–vis diffuse reflectance spectra of TiO2/sepiolite, Ag@AgCl–TiO2/sepiolite and Ag@AgCl; (b) Plots of (αhυ)2 versus
energy (hυ) for the band gap energy of TiO2/sepiolite, Ag@AgCl–TiO2/sepiolite and Ag@AgCl. UV–vis: ultraviolet–visible.
Ag has been successfully synthetized. The Cl 2p peak
components were observed at 197.28 and 198.88 eV, which
matched with the binding energies of Cl 2p3/2 and Cl 2p1/2 and
thus represented the double peak separation of 1.6 eV. The
binding energy of 458.76 eV was from Ti 2p.
Fig. 7 – (a) The influence of dosage of catalysts on
photocatalytic degradation of Methylene Blue (MB); (b) The
fitting curve of pseudo-first-order kinetic equation.
47
2.5. FT-IR analysis
The FT-IR spectra of sepiolite, TiO2/sepiolite, and Ag@AgCl–
TiO2/sepiolite significantly differed from one another (Fig. 5).
The peaks within 400–600 cm−1 corresponded to the typical
absorption peaks of the Ti–O bond (Liu et al., 2016). The peak
at approximately 1430 and 1010 cm−1 belonged to the
characteristic peak of Si–O–Si base of sepiolite and the peaks
at approximately 3430 and 3680 cm−1 were the characteristic
–OH stretching vibrations, which could be attributed to the
polar group of sepiolite (Qiu et al., 2013; Zhu et al., 2012). A
new component was also observed in Ag@AgCl–TiO2/sepiolite,
and strong absorption peaks at 666, 1640, and 2900 cm−1 were
presented. These peaks were contributed by C–Cl stretching
vibration and C_O stretching vibration. The FT-IR peaks of
several groups of modified Ag@AgCl–TiO2/sepiolite disap-
peared, and this observation was related to the deposited
Ag@AgCl. The occurrence of new peaks was caused by Ag@
AgCl deposited on the TiO2/sepiolite surface. These results
indicated that Ag@AgCl and TiO2 are well deposited onto the
sepiolite surface.
2.6. UV–vis absorption spectroscopy
Fig. 6a illustrates the UV–vis diffuse reflectance spectra of TiO2/
sepiolite, Ag@AgCl–TiO2/sepiolite, and Ag@AgCl. Ag@AgCl–TiO2/
sepiolite and Ag@AgCl photocatalysts exhibited stronger absorp-
tion in the visible light region. The absorption edge of Ag@AgCl–
TiO2/sepiolite was estimated at 420 nm. Thus, the modified
photocatalyst rather than TiO2/sepiolite is red shifted. Fig. 4b
presents the plots of (αhυ)2 versus energy (hυ) for the band gap
energies of TiO2/sepiolite, Ag@AgCl–TiO2/sepiolite, and Ag@AgCl.
These energies were calculated on the basis of the optical
absorption edge obtained from UV–vis DRS spectra:

n
Αhυ ¼ k hυ−Eg ð2Þ
where, α is the absorption coefficient, k is the parameter related
to the effective masses associated with valence and conduction
bands, n is 1/2 of the direct transition, hυ (eV) is the absorption
energy, and Eg (eV) is the band gap energy (Li et al., 2007; Wang,
2008; Xu et al., 2008). The curve tangents revealed that the band
48 J O U RN A L OF E N V I RO N ME N TA L SC IE N CE S 6 0 (2 0 1 7) 43–5 2
gap energies of TiO2/sepiolite, Ag@AgCl–TiO2/sepiolite, and Ag@
AgCl were approximately 3.12, 3.08, and 2.51 eV, respectively.
This trend may be caused by the formed plasmon resonance of
(Ag-NP) nanoparticles on the TiO2/sepiolite surface under visible
light irradiation.
2.7. Photocatalytic experiment
2.7.1. Influence of catalyst dosage on the photocatalytic degradation
of MB
The dosage of catalysts plays an important role in the photo-
catalytic degradation of MB (Fig. 7a). The MB concentration
was 6 mg/L and the photocatalytic time was 2 hr. Other
reaction conditions were held constant during the photocat-
alytic experiment. The degradation ratio increased as the
catalyst dosage was increased under visible light irradiation.
The degradation ratio of MB was 19.44% when a low dosage of
catalysts was added. MB was decomposed by 82.72% under
visible light irradiation for 2 hr when the catalyst dosage
reached 0.15 g. MB was rapidly decomposed at high dosage.
Therefore, the availability of more absorption sites for
pollutants caused the rapid photocatalytic decomposition of
MB. This trend was also attributed to the effect of Ag-NP on
the surface of TiO2/sepiolite and the formed Schottky barrier
at the Ag/TiO2 interface (Kawahara et al., 2005). The results of
fitting are shown in Fig. 7b. The MB concentration was 6 mg/L,
and the photocatalytic time was 2 hr. Other reaction condi-
tions were held constant in the photocatalytic experiment.
The effect of catalyst on the rate constant of photocatalysis
was examined by varying the dosage of Ag@AgCl–TiO2/
sepiolite. The MB concentration can be quantified on the
basis of its absorbance at 662 nm according to Beer's law (Ma
et al., 2016). The photocatalytic degradation of MB is in
accordance with pseudo-first-order kinetic equation by fitting
in the following (Eq. (3)):
ln ðC=C0 Þ ¼ −kðt−ti Þ
where, C (mg/L) is the concentration of MB at reaction time i,
C0 (mg/L) is the initial concentration of MB, k is the reaction
rate constant, and t (min) is the reaction time.
Fig. 8 – Influence of initial pH on photocatalytic degradation
of Methylene Blue (MB).
The reaction rate constant increases from 0.001 to 0.014 min−1
when the dosage of Ag@AgCl–TiO2/sepiolite increases from 0.01
to 0.15 g. Therefore, the reaction site increased as the catalyst
dosage increased; consequently, more free radicals are likely
produced and reaction efficiency is improved.
2.7.2. Influence of initial pH on photocatalytic degradation of MB
Fig. 8 shows the influence of the initial pH on the photocat-
alytic degradation of MB. The physicochemical properties of
catalysts and pollutants are affected by pH. Consequently, the
initial pH of the MB solution was also examined in this work.
Before this experiment, the pH of the dye solution was
controlled to the corresponding pH with the 10% NaOH and
10% HCl solution. The other experimental conditions were
0.1 g of Ag@AgCl–TiO2/sepiolite and an initial MB concentra-
tion of 6 mg/L. In Fig. 8, the degradation ratios of MB were
72.16%, 84.52%, 67.71%, 85.92%, and 91.39% when the initial pH
was set from 3 to 11. The lowest degradation ratio was
observed under neutral conditions, whereas a higher degra-
dation ratio was observed at pH 11.
At the acidic pH range, the degradation ratios are less and
this is because of dissolution of TiO2/sepiolite. In other word, H+
in MB solution can react with the impurity of TiO2/sepiolite gap
to produce the corresponding salt at low acidic pH values
(Subash et al., 2013). With the increase of pH, the concentration
of H+ decreases and H+ can only be attached to the surface of the
catalyst. In this way, the catalyst surface is positively charged
and it makes the fast migration and transformation of the
photoelectrons. When pH of MB is at the range of 7–11, the
higher degradation ratios can be observed. This trend was
attributed to the production of more UOH, which produced from
the oxidation reaction of OH− and holes in the catalyst surface
through visible light excitation. When pH of solution is at 5–7,
there are less H+ and OH− in MB solution thus the degradation
ratios decrease.
ð3Þ
2.7.3. Degradation ratios of different catalysts on the photocat-
alytic degradation of MB
The degradation ratios of Ag@AgCl–TiO2/sepiolite, Ag@AgCl–
TiO2, and TiO2/sepiolite composites were measured (Fig. 9). The
Fig. 9 – Influence of different catalysts on photocatalytic
degradation of Methylene Blue (MB).
 J O U RN A L OF E N V I RO N ME N TA L SC IE N CE S 6 0 (2 0 1 7) 4 3–5 2
Fig. 10 – Total Organic Carbon (TOC) content with time in
Methylene Blue (MB) solution.
MB concentration was 6 mg/L, the catalyst dosage was 0.15 g,
and the photocatalysis was conducted under visible light
irradiation for 2 hr. Other reaction conditions were the same
as the photocatalytic experiments. The degradation ratios of
the Ag@AgCl–TiO2/sepiolite, Ag@AgCl–TiO2, and TiO2/sepiolite
composites increased with time. At 120 min, their degradation
ratios reached the maximum: 82.72%, 76%, and 58%, separately.
Therefore, the catalytic performance of Ag@AgCl–TiO2/sepiolite
was higher than those of Ag@AgCl–TiO2 and TiO2/sepiolite.
2.7.4. TOC content with time in a MB solution of Ag@AgCl–TiO2/
sepiolite for photocatalytic degradation
Changes in the Total Organic Carbon (TOC) content with time
were determined in the MB solution of Ag@AgCl–TiO2/
sepiolite for photocatalytic degradation (Fig. 10). The concen-
tration of the MB solution was 6 mg/L and the dosage of Ag@
AgCl–TiO2/sepiolite was 0.1 g. Photocatalysis was conducted
under visible light irradiation for 2 hr. Other reaction condi-
tions were held constant in the photocatalytic experiments.
The TOC content of MB decreased with time. At 0–40 and
80–100 min, the TOC content in MB decreased sharply. At
40–80 min, the TOC content decreased slowly from 27.28 to
Fig. 11 – Photocatalytic performances of Ag@AgCl–TiO2/
sepiolite in the first three re-use cycle.
49
21.78 mg/L. At 100–120 min, the TOC content absorbed in
Ag@AgCl–TiO2/sepiolite reached saturation, and the mini-
mum value was 3.52 mg/L. The results showed that organic
matter was formed in the MB solution after the reaction
decreased. The MB solution after the photocatalysis is not
more hazardous than the original solution.
2.7.5. Re-use property
The stability of a photocatalyst is a very important factor in
practical applications. Photocatalytic performances of Ag@
AgCl–TiO2/sepiolite in the first three re-use cycles in Fig. 11.
The photocatalytic degradation rate decreased from 82.72% in
the first run to 76.21% in the third run, and this is because
some catalyst has been washed off in the re-use cycles.
However, the results indicated that Ag@AgCl–TiO2/sepiolite
have an excellent stability of the photocatalytic performance.
2.7.6. Photoelectrochemical property
The photoelectric currents of TiO2/sepiolite and Ag@AgCl–
TiO2/sepiolite used as working electrodes under visible light
irradiation are presented in Fig. 12. The plots of periodic on/
off photocurrent responses showed that the transient pho-
toelectric current produced by Ag@AgCl–TiO2/sepiolite was
approximately twice that of TiO2/sepiolite. The generation
mechanism of photoelectric current involves the separation
and transfer of photon-generated carriers, such as electrons
and holes, in the photocatalytic structure under visible light
irradiation. Therefore, the working electrode of Ag@AgCl–
TiO2/sepiolite can produce higher-strength photoelectric
current. This finding indicates that the highly efficient
transfer of the electrode/electrolyte interface is caused by
photon-generated carriers in the conduction band of Ag in
the catalyst; this highly efficient transfer and the few
combinations of photo-induced electron–hole pairs effec-
tively prolong the service life of carriers (She et al., 2015). High
photocurrents correspond to enhanced electron and hole
separation efficiencies and photocatalytic activities.
Electrochemical impedance spectra (EIS) were obtained to
investigate the charge transfer and interface reaction character-
istic of photocatalysts and to evaluate the separation efficiency of
photo-generated electron–hole pairs and the property of carriers
in accordance with a previously described method (Liu et al.,
2000). The EIS of Ag@AgCl–TiO2/sepiolite and pure sepiolite are
shown in Fig. 13. The Nyquist arc corresponds to the charge
transfer between an electrode surface and an electrolyte. A small
arc represents a high efficient charge transfer and a low charge
transfer impedance. Ag@AgCl–TiO2/sepiolite contains a small
Nyquist arc and thus possesses a smaller impedance and a higher
charge transfer on the interface. This finding indicated that Ag@
AgCl–TiO2/sepiolite exhibits a good heterostructure to provide
an enhanced effective transfer between electrode surfaces and
electrolytes.
2.7.7. Possible photocatalytic mechanism
The main active substances during photocatalysis were analyzed
by adding different trapping agents to explore the photocatalytic
mechanism of Ag@AgCl–TiO2/sepiolite. In this experiment, Tert
Butanol (TB), Benzoquinone (BQ), and KI were used as the
respective trapping agents of UOH, UO−2, and h+ (Li et al., 2011;
Yoon and Lee, 2005). The effects of different trapping agents on
50 J O U RN A L OF E N V I RO N ME N TA L SC IE N CE S 6 0 (2 0 1 7) 43–5 2
Fig. 12 – Photocurrent responses: (a) Ag@AgCl–TiO2/sepiolite
and (b) TiO2/sepiolite under visible light irradiation.
photocatalysis are illustrated in Fig. 14. After the samples were
exposed to visible light for 120 min, the catalytic degradation rate
of Methylene Blue without a trapping agent was 77.68%. The
degradation rates of Methylene Blue in the presence of 2 mmol/L
TBA, PBQ, and KI were 58.52%, 29.64%, and 7.99%, respectively.
In this experiment, TBA captured UOH produced during
photocatalysis, and this observation indicated that few UOH
were produced. Therefore, UOH is the main active substance in
photocatalysis. After PBQ was added to the reaction solution, the
photocatalysis was significantly inhibited, and the degradation
rate of Methylene Blue exposed to visible light was 29.64%. PBQ
captured UO−2. This observation showed that abundant UO−2 were
produced and implicated in photocatalysis. Thus, UO−2 is the main
active substance in photocatalysis. KI also inhibited photo-
catalysis, and the photocatalytic degradation rate was 7.99%
when the samples were exposed to visible light for 120 min. This
phenomenon demonstrated that catalysts in photocatalysis are
excited to produce abundant electron–hole pairs after photons
are absorbed. The holes on the valence band directly participated
in degrading Methylene Blue and occupied the dominant role in
photocatalysis. Hence, the free radical capture experiment
revealed that UO−2 and holes are the main active substances in
photocatalysis, and these substances play a dominant role in this
Fig. 13 – Electrochemical impedance spectroscopy of Ag@
AgCl–TiO2/sepiolite and TiO2/sepiolite.
Fig. 14 – Photocatalytic degradation of Methylene Blue (MB)
over the Ag@AgCl-doped TiO2/sepiolite under different
conditions with exposure to visible light.
reaction. Active sepiolite is characterized by a large specific
surface area because of its strong adsorption ability. This material
can provide more adsorption sites for pollutants. The adsorbed
Methylene Blue can be transferred to the degradation center on
the catalyst surface and thus degrade pollutants.
When exposed to visible light, Ag nanotube and TiO2 absorbed
photons were excited to produce photo-induced electron–hole
pairs (Fig. 15). The photo-induced electrons on the valence band
of TiO2 transferred to Ag nanoparticles under the action of the
Schottky barrier and recombined with photo-induced holes,
which were retained on Ag nanoparticles. The energy gap of
TiO2 was 3.2 eV. The electrons injected to the valence band of
AgCl were captured by O2 adsorbed on the AgCl surface because
AgCl was not excited by visible light; consequently, UO−2 is
produced (Xu et al., 2011). The energy gap of AgCl was 3.25 eV.
AgCl could not be excited by visible light, but the low valence
band produces band potentials (0.06 vs. Normal Hydrogen
Electrode (NHE)) to transfer photo-induced electrons from Ag to
CB in AgCl. The photo-induced holes on the valence band of Ag
nanoparticles were transferred and injected onto the AgCl
surface and consequently reduced Cl− to Cl0; thus, Cl−/Cl0 redox
couples are formed (Wang et al., 2010). These active species can
help induce MB on the composite surface.
3. Conclusions
A novel visible light-responsive Ag@AgCl–TiO2/sepiolite plas-
monic composite was successfully synthesized through sol–
gel and two-step synthesis methods. A typical SEM micro-
graph of Ag@AgCl–TiO2/sepiolite showed that the cube-like
Ag@AgCl was well deposited on the surface of TiO2/sepiolite.
Photocatalytic degradation experiments demonstrated that
the degradation ratio increased as the dosage of Ag@AgCl–
TiO2/sepiolite exposed to visible light irradiation was in-
creased. The photoelectrochemical properties of TiO2/sepiolite
and Ag@AgCl–TiO2/sepiolite electrodes confirmed that the ability
of Ag@AgCl–TiO2/sepiolite to separate photo-generated electron–
hole pairs was stronger than that of TiO2/sepiolite. The excellent
catalytic ability is mainly attributed to the effects of Ag-NP on the
surface of TiO2/sepiolite and the formed Schottky barrier at the
Ag/TiO2 interface. The main active species, such as UO−2 and h+,
 J O U RN A L OF E N V I RO N ME N TA L SC IE N CE S 6 0 (2 0 1 7) 4 3–5 2
Fig. 15 – Proposed mechanism of photocatalytic degradation for Ag@AgCl-doped TiO2/sepiolite under visible light.
play a key role in MB degradation. This study provides a basis for
the investigation of plasmon photocatalysts activated by visible
light.
Acknowledgments
This work was supported by the Young and Middle-aged
Academic Key Members of Anhui University of Science and
Technology, the Doctor's degree Innovation Training Program
(No. 2013bj1105), and the International Cooperative Project of
Anhui Province (No. 12030-603003).
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