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Article
A New Method to Synthesize S-Doped TiO2 with Highly Efficient
and Stable Indoor Sunlight Photocatalytic Performance
Mingshan Zhu, Chunyang Zhai, Liqun Qun, Cheng Lu, Andrew S Paton, Yukou Du, and M. Cynthia Goh
ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/
acssuschemeng.5b01137 • Publication Date (Web): 02 Nov 2015
Downloaded from http://pubs.acs.org on November 12, 2015

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8 A New Method to Synthesize S-Doped TiO2
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with Stable and Highly Efficient
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13 Photocatalytic Performance under Indoor
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16 Sunlight Irradiation
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Mingshan Zhu †, Chunyang Zhai ‡, Liqun Qiu †, Cheng Lu †,*, Andrew S. Paton †,
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22 Yukou Du ‡, and M. Cynthia Goh †,*
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25 † Department of Chemistry, University of Toronto, M5S3H6, Canada.
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28 ‡ College of Chemistry, Chemical Engineering and Materials Science, Soochow
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30 University, Suzhou 215123, China.
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33 ABSTRACT In this paper, we report a new, low-cost and facile solvothermal
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36 approach to synthesize visible-light-active S-doped TiO2 (S-TiO2) by using dimethyl
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38 sulfoxide (DMSO) as both the S source and the solvent. Energy-dispersive X-ray
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41 (EDX) and X-ray photoelectron spectroscopy (XPS) solidly confirmed the presence of
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44 S element in the final product. The as-prepared S-TiO2 nanoparticles exhibited
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46 excellent and long-term stable photocatalytic performance for the degradation of
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49 organic pollutants under visible and indoor sunlight illumination. The catalyst still
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52 kept high photoactivity even after several months of exposure to the indoor sunlight
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54 irradiation. This result suggests a new approach to achieve stable and highly efficient
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57 solar light driven photocatalysts for water purification.
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KEYWORDS: photocatalyst; S-doped TiO2; visible light; indoor sunlight; long-term

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8 INTRODUCTION
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11 To cope with the growing pollution of our hydrosphere, a variety of technologies,
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13 including heterogeneous semiconductor photocatalytic oxidation, have been
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16 developed for wastewater treatment.1-4 Titanium dioxide (TiO2), as the most widely
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19 studied semiconductor photocatalyst, has thus far been explored to meet the
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21 requirements of water purification.1-4 However, the band gap of pure TiO2 is ca. 3.2
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24 eV, which means that it can only show activity under UV irradiation. It is well known
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27 that UV light accounts for no more than 5% of the total solar energy, which is a small
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29 amount compared to the 45% of energy in the visible region.4 Hence, in order to
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32 effectively utilize solar radiation, it is desirable to develop efficient
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35 visible-light-driven photocatalysts for remediating the growing pollution in our
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37 hydrosphere.
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40 Since the Asahi group first reported the visible-light photocatalytic activity of
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43 nitrogen doped TiO2,5 more research has been focused on the modification of TiO2
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45 with non-metal or/and metal ion doping.3-5 In these cases, the dopant is often
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48 incorporated as an anion or cation to take the place of Ti or/and oxygen in the lattice
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51 of TiO2, resulting in bandgap narrowing in TiO2 nanostructures and showing high
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53 visible-light photocatalytic activity. Among these dopants, sulfur (S) doping has
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56 received particular attention, owing to its highly thermal stability and significant
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59 enhancement in visible light driven photocatalytic activity,6-13 where the TiS2, thiourea,
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CS2, etc. were often used as the S source.6-13 However, these precursors are either
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7 Dimethyl sulfoxide (DMSO), an important polar aprotic compound, is widely
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10 used as a solvent in various organic and inorganic syntheses. Recently, some
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12 researchers found that DMSO can slowly release S2– ions into solution for synthesis
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15 of S-based semiconductors under the facile one-pot solvothermal condition, resulting
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18 in highly crystalline structures of Cu2S, CdS, ZnS and NiS.14-17 Compared to the other
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20 S sources, DMSO is low-cost and easy to operate. We therefore are inspired to
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23 explore a new route to synthesize S-doped TiO2 (S-TiO2) by using DMSO as the S
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26 source.
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40 Scheme 1. Schematic illustration of the formation process of S-TiO2 powders.
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Specifically in this paper, we report a new, low-cost and facile method for the
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46 synthesis of S-TiO2 through a solvothermal method, as shown in Scheme 1. Titanium
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49 butoxide was used as the Ti source and DMSO served as both the S source and the
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solvent during the reaction. The resulting powders were then calcined at 500 °C to
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54 further crystallize the structure and to remove any surface attached organic species.
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57 Energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy
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(XPS) solidly confirmed the presence of the sulfur element in the final product,

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4 suggesting the generation of S-TiO2. More importantly, these S-TiO2 nanoparticles
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7 exhibited more excellent and long-term stable photocatalytic performance for the
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10 degradation of organic pollutants under indoor sunlight illumination than commercial
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12 P25 TiO2. The catalyst still kept high photoactivity even after several months of
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15 exposure to the indoor sunlight irradiation. This result suggests a new approach to
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18 achieve stable and highly efficient solar light driven photocatalysts for water
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20 purification.
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24 EXPERIMENTAL SECTION
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27 Materials. Dimethyl sulfoxide (DMSO, certified ACS, Fisher Scientific), Titanium
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29 (IV) butoxide (97%, Sigma-Aldrich), All other chemicals were purchased from
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32 Sigma-Aldrich without further purification before use. Milli-Q water was used
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35 throughout our experiments.
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37 Synthesis of the S doped TiO2 (S-TiO2) nanoparticles. To synthesize the S-doped
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40 TiO2 powders, titanium butoxide (5.1 g, 0.015 mol) was added into the 50 mL DMSO
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43 solvent under stirring. The solution was continuous stirred at room temperature for 30
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45 min, then transferred into a 100 mL Teflon autoclave and held at 180 °C for 18 h.
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48 After that, the precipitates were collected by centrifugation, washed with water and
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51 ethanol, and then dried in an oven at 60 °C for 12 h. After that, the powder was
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53 calcined at 500 °C for 4 h, resulting in a light yellow S-TiO2 sample.
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56 Photocatalytic performance. For catalytic experiments, 20 mg of samples were
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59 dispersed in a 10 mL rhodamine B (RhB, 22.5 mg L−1) or methylene blue (MB, 20 mg
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L−1) solution, wherein a 20 mL cuvette was used as the reactor. A 150 W xenon arc
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4 lamp installed in a laboratory lamp housing system (LS 150 Xenon Arc Lamp Source,
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7 Abet Technologies) was employed as the light source. The light passed through a
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10 polyester Lee type-226 cut off filter (400nm) before entering the reactor. The reaction
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12 system was kept for 30 min in dark to achieve an equilibrium adsorption state before
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15 visible-light irradiation. The photodegradation of RhB and MB was investigated by
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18 measuring the real-time UV−vis absorption of RhB and MB at 554 nm and 665 nm,
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20 respectively. Aliquot of the reaction solution (0.25 mL) was taken out from the
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23 reaction system for the real-time sampling. The pollutants relative concentrations
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26 (C/C0) variation were used to evaluate the photocatalytic activities, where C was the
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28 concentration of RhB or MB at a real-time t, and C0 was the concentration in the RhB
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31 or MB solution before it was kept in dark. The integrated light intensity was measured
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34 to be ca. 30 mW cm–2 by a visible–light radiometer (model: PM200, Thorlabs
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36 GmbH).
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39 In order to investigate the wavelength-dependent photocatalytic performance, the
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42 incident light was passed the assigned bandpass filter (365 ±15 nm, 400±15 nm and
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44 465 ±15 nm) before entering the reactor. In these cases, 50 mg of samples were
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47 dispersed into 40 mL of RhB or MB aqueous solution (10 mg L-1) for the catalytic
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50 experiments. The average intensity of the incident light was ca. 4.4 mW cm–2.
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52 To investigate the long term photocatalytic activity, 20 mg of S-TiO2 samples
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55 were dispersed in two cuvettes containing 10 mL RhB (13.5 mg L−1) and MB (15 mg
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58 L−1) solution, respectively. The reaction system was kept beside the laboratory
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4 9:00 am to 3:00 pm during a sunny day. The light intensity of the indoor sunlight was
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7 5 ~ 35 mW cm–2. When the dyes were degraded completely, the concentrated RhB
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10 and MB solutions were added in the reactor to reach the initial concentration for a
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12 new cycle. The cycling experiment was repeated for over three-month period to
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15 evaluate the long term photocatalytic stability under indoor sunlight irradiation. The
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18 recycled photocatalysts were then collected to further determine the photocatalytic
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20 activity. In details, 20 mg of catalyst powders were dispersed in two cuvettes
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23 containing 10 mL RhB (13.5 mg L−1) and MB (15 mg L−1) solution, respectively. The
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26 solutions were irradiated under simulate indoor sunlight (λ>350 nm, 50 mW cm-2) for
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31 Apparatus and measurements. Transmission electron microscopy (TEM) studies
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34 were conducted on a TECNAI-20 electron microscope operating at an accelerating
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36 voltage of 200 kV. Scanning electron microscope (SEM, S–4700) was used to
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39 determine the morphology of the as-prepared composite samples. The energy
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42 dispersive X-ray (EDX) analysis was conducted with a Horiba EMAX X-act energy
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44 dispersive spectroscope that was attached to the S-4700 system. The X–ray diffraction
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47 (XRD) measurements were performed on a PANalytical X' Pert PRO MRD system
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50 with Cu Ka radiation (k =1.54056 Å) operated at 40 kV and 30 mA. UV-vis diffuse
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52 reflectance spectra were obtained on an UV-vis spectrophotometer (Hitachi, Model
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55 U-3900) using BaSO4 as the reference. X-ray photoelectron spectroscopy (XPS) was
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58 performed on an ESCALab220i-XL electron spectrometer from VG Scientific using
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60 300 W Al Kα radiation. The binding energies were referenced to the C1s line at 284.8

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4 eV from adventitious carbon. All of these measurements were carried out at room
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7 temperature. BET surface areas were measured on Autosorb-1 (Quantachrome Inc.)
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13 RESULTS AND DISCUSSION
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16 The morphology of the as-synthesized S-TiO2 nanoparticles was analyzed by
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19 scanning electron microscope (SEM) and transmission electron microscope (TEM).
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21 As shown in Figure 1a and 1b the S-TiO2 nanoparticles appeared to be small
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24 spherical particles with the average size ca 9.1 nm (See insert of the Figure 1b, the
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27 corresponding size histogram of S-TiO2 nanoparticles counted from the TEM image).
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29 The X-ray powder diffraction (XRD) pattern of the S-TiO2 powders was carried out to
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32 investigate the crystalline phase of the as-prepared sample. Figure 2 clearly reveals
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35 the peaks at 25.5°, 38.0°, 48.1°, 54.2°, 55.2°, 62.8°, 69.1°, 70.3°, and 75.3° which
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37 were assigned to the diffraction of the (101), (004), (200), (105), (211), (204), (116),
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40 (220), and (215) crystal planes, respectively, of anatase TiO2 (JCPDS No. 21-1272).13
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43 As there are no diffraction peaks due to the rutile phase observed in the spectrum, we
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45 conclude that the as-prepared S-TiO2 was in a purely anatase structure. Furthermore,
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48 the average grain size determined from the Scherrer equation (D = 0.9λ/βcosθ) was
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51 about 9.5 nm based on (101) diffraction peak,13 which also consisted with the TEM
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16 Figure 1. (a) SEM and (b) TEM images of the as-prepared S-TiO2 nanoparticles. The
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19 insert in image b is S-TiO2 size distribution histogram deduced from the TEM image.
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22 The UV–Vis diffuse reflectance spectra are used to analyze the optical properties
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24 and the bandgap energy of the samples. Figure 3A shows the results from the
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27 reflectance measurements of S-TiO2 and commercial P25 TiO2 nanoparticles.
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30 Compared to the P25 TiO2 (curve b, the absorption edge at ca. 398 nm), the
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32 absorption edge of S-TiO2 red–shifted to ca. 435 nm (curve a), and the corresponding
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35 UV-Vis spectrum shows a trailing absorption from 400 nm to 550 nm. The
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38 photographic images (insets in Figure 3A) also show a distinct colour difference
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40 between the as-prepared S-TiO2 nanoparticles (light yellow) and commercial P25 TiO2
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43 nanoparticles (white). Extrapolation of the reflectance was used to obtain the band
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46 gap energy of the samples. The bandgap energy of S-TiO2 and P25 TiO2 were ca. 2.85
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48 eV and 3.1 eV, respectively, as shown in Figure 3B. The “tail-like” feature and
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51 bandgap narrowing were attributed to the introduction of S atoms in the lattice of TiO2.
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18 Figure 2. XRD pattern of the as-prepared S-TiO2 nanoparticles.
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35 Figure 3. (A) The UV–Vis diffuse reflectance spectra and (B) plots of (αhν)2 vs.
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38 photon energy of S-TiO2 (a) and P25 TiO2 (b) nanoparticles. The inserts in image A
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40 are the photographs of the S-TiO2 (a) and commercial P25 TiO2 (b) nanoparticles.
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43 Table 1. Ti, O and S contents of as-prepared S-TiO2 were determined by EDX and
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45 XPS study.
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47 Element EDX (atom %) XPS (atom %)
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49 Ti 32.07 31.17
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51 O 66.24 66.83
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53 S 1.69 2.00
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19 Figure 4. EDX elemental analysis of of the as-prepared S-TiO2 nanoparticles.
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22 To verify the existence of S, the EDX and XPS spectra of S-TiO2 were applied
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24 and shown in Figure 4 and Figure 5. First, from the EDX spectrum (Figure 4), Ti, O,
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27 and S elements were observed in the as-prepared samples, suggesting the formation of
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30 S-doped TiO2. Moreover, the XPS survey spectrum clearly shows the O 1s, Ti 2p, S
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32 2p and C 1s core levels (Figure 5). Specifically, the O 1s XPS spectrum can be
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35 resolved into two peaks at ca. 529.9 and 531.7 eV, which are ascribed to Ti–O and
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38 surface OH species, respectively.18 The Ti 2p in S-TiO2 displays two peaks centered at
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40 458.8 and 464.4 eV, which can be ascribed to the binding energy of Ti 2p3/2 and Ti
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43 2p1/2, respectively.18 The presence of S was confirmed by a peak at 168.5 eV. This
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46 peak can be further deconvoluted into two peaks at 168.5 eV and 169.7 eV, which can
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48 be assigned to S 2p3/2 and S 2p1/2 respectively.11,13 Generally, the peak at ~168.5 eV is
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54 area higher than that of S 2p1/2 peak.11 Hence, the S element might be S6+ in the lattice
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56 of S-TiO2. This is also similar to previous literature reports.7,11,12 The C 1s XPS
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59 spectrum showed one peak at 284.8 eV and a shoulder at around 288.8 eV, which are
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assigned to C-C bonds and C-O bonds19, respectively. This is possibly due to the
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4 environmental species detected during the measurement. However, we did not
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7 observe the formation of C-Ti bonds because of the missing of the bands at ~ 282 eV,
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10 suggesting element C was not doped into the crystalline lattice20. The semiquantitative
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12 analysis of the as-synthesized S-TiO2 by EDX and XPS are summarized in Table 1.
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15 First, the results indicate that the atomic ratio between O and Ti is similar to the
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18 theoretical stoichiometric atomic ratio, indicating the formation of TiO2. The S
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20 content in S-TiO2 is about 2 atom% determined by EDX and XPS (Table 1). All the
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44 Figure 5. (a) XPS survey spectrum of S-TiO2 nanoparticles, (b) Ti 2p, (c) O 1s, (d) S
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47 2p and (e) C 1s signals taken from S-TiO2.
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50 The above analyses of the S-TiO2 suggest that the S element was successfully
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52 introduced into the lattice of TiO2, resulting a distinct absorption in the visible light
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55 range. This visible light response enables the S–TiO2 nanoparticles a potential to
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58 utilize visible light in solar spectrum for catalytic degradation of organic pollutants.
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4 as targeting objects to evaluate the photocatalytic activities of the as-prepared S-TiO2.
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7 Figure 6 shows the molecular structure of the above two dyes molecules.
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10 Photo-degradations of RhB and MB under visible-light irradiation were performed as
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12 the photoreaction probes to evaluate the photocatalytic activity of S-TiO2, and the
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15 results are shown in Figure 7. For comparison, commercial P25 TiO2 was also used at
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18 the same experimental conditions. There was negligible degradation of RhB and MB
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20 pollutants when no catalysts were used after 120 min of visible-light irradiation.
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23 Around 82.8% and 63.8% of RhB and MB molecules degraded in 120 min when P25
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26 TiO2 was used. In contrast, when our S-TiO2 nanoparticles were used as the
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28 photocatalyst, the photoactivity was significantly improved, and the RhB and MB
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31 molecules were degraded nearly 97% and 100% under visible-light irradiation in 120
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34 minutes. Moreover, the BET surface area of the as-prepared S-TiO2 is ca. 124.24 m2
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39 The larger surface area might also play a role to improve the catalytic activity.
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42 Furthermore, we also synthesized S-doped TiO2 following the previously
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44 reported work by using thiourea as S source through the precipitation method (details
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47 see Supporting Information)7, and the obtained samples was named as S-TiO2-P.
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50 However, there were only 62.3% and 72.4% of RhB and MB molecules degraded
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52 respectively in 120 min over S-TiO2-P sample at the same experiment conditions.
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58 is a better method to fabricate high efficient visible-light active S-TiO2 photocatalyst
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39 curves for the degradation of RhB (a and b) and MB (d and e) pollutants without
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42 catalysts and with commercial P25 TiO2 and S-TiO2 catalysts under visible light
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44 (λ>400 nm) irradiation. The real-time absorption spectra of RhB (c) and MB (f)
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47 solution during the photodegradation process over S-TiO2 under visible-light
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50 illumination from 0 min to 120 min.
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55 and the reaction time (t), indicating that the decomposition of RhB and MB over TiO2
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58 photocatalysts follows the first-order kinetics. The rate constants of the catalytic
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4 respectively, while those of S-TiO2 were 0.028 min-1 and 0.043 min-1. The
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7 photocatalytic efficiency of S-TiO2 was improved ca. 2 and 5 times compared with
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10 the P25 TiO2 for the degradation of RhB and MB molecules, respectively. The reason
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12 of the improved catalytic performance of the as-prepared S-TiO2 is attributed to the S
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15 element introduced into the lattice of TiO2, which narrows the bandgap of the TiO2,
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18 resulting in enhanced visible light absorption of solar energy.
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20 The solvothermal temperature controls the DMSO decomposition, and further
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23 controls the S-doping ratio in the TiO2 crystalline lattice. As DMSO is non-degradable
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26 below 150 oC, and decomposes at boiling point 189 oC, possibly leading to the
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28 explosion,17 the solvothermal reaction was controlled between 140 oC and 180 oC. We
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31 did not observe S-doping at 140 0C possibly due to the DMSO non-degradation.
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34 Figure S2 shows the amount of S doping in TiO2 was ca. 0.73 when the solvothermal
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36 treatment temperature was 160 °C (S-TiO2-160). Figure S3 shows RhB and MB
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39 molecules were degraded nearly 71.6% and 87.3% under visible-light irradiation
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42 within 120 min by using S-TiO2-160 photocatalysts. S-TiO2-160 shows the poor
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44 photocatalytic activities compared with S-TiO2 synthesized at 180 °C solvothermal
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47 treatment, possibly due to the lower S-doping in the lattice.
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50 Calcination temperature determines the crystallinity of the formed TiO2, and the
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52 Figure S4 shows the XRD patterns of the as-prepared S-TiO2 calcined at 400 °C,
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55 500 °C and 600 °C. The S-TiO2 presented a pure anatase structure at 400 °C and
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58 500oC calcination, and a mixture of anatase and rutile phases at 600 oC. Figure 8
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4 calcined at different temperature. The catalytic performance for S-TiO2 calcined at
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15 temperature (600 oC) calcination promotes the transition from anatase to rutile
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18 structure, deteriorating the catalytic performance accordingly.
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38 Figure 8. Photocatalytic activities of various S-TiO2 by different calcinations
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40 temperature for the degradation of RhB and MB under visible light irradiation with
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43 120 min.
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46 Different bandpass filters were used to study the irradiation light wavelength
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48 dependence during the photocatalytic degradation of RhB and MB pollutants, and the
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51 results were shown in Figure 9. Commercial available P25 TiO2 was used as a
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54 reference for comparison. In UV band when 365±15 nm bandpass filter was used, the
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56 as-prepared S-TiO2 and P25 TiO2 showed the similar photocatalytic activities. In
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59 visible band 400±15 nm, the photocatalytic activity of S-TiO2 was more than two
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times higher than that of P25 TiO2. There was very weak dyes degradation on both
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4 S-TiO2 and P25 TiO2 when the longer wavelength bandpass filter 465±15 nm was
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7 used. These results first are consistent with the bandgap analyzation as discussed in
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10 Figure 3; furthermore, by comparing the photocatalytic activity of P25 TiO2 and
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12 S-TiO2, the activity similarity at 365±15 nm band and apparent increase at 400±15 nm
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15 for S-TiO2 suggest that the main reason for enhancing catalytic activities were
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18 attributed to S element introduced into the lattice of TiO2 other than the increased
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20 surface area. In summary, S-TiO2 has superior photocatalytic performance than P25
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23 TiO2 to degrade the organic pollutants.
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47 Figure 9. Wavelength dependence for photocatalytic degradation of RhB and MB by
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50 using commercial P25 TiO2 and S-TiO2 as photocatalysts. The light exposure time
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52 was 4 hours.
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55 Besides catalytic performance, stability is another important factor for high
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58 quality catalysts with practical applications. Moreover, in a real environment, sunlight
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4 photocatalysts. Considering the above issues, the stability of S–TiO2 photocatalyst
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7 was investigated by recycling degradation of RhB and MB pollutants under indoor
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10 sunlight (λ>350 nm) irradiation. At the end of each cycle, the organic pollutants were
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12 resupplied to the initial concentration for the next run. It should be noted that these
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15 experiments were carried out without stirring or extra light irradiation. Figure 10
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18 shows the catalyst still kept a high catalytic capability to degrade both RhB and MB
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20 over more than 40 cycles in a 3 month test span by using S-TiO2 as the photocatalyst.
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23 We estimated the number of the bonded surface hydroxyl group on S-TiO2 was the
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26 same as that of P25 TiO2, which is about 9.5 1019/g (equals 1.58 104 mol/g) as
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28 previously reported, 21 and all of surface bonded –OH groups acted as active sites for
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31 catalytic reaction. As a result, if we regard the target organic molecule as a catalysant,
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34 the turnover number for RhB and MB catalytic degradation is 3.66 and 6.08,
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36 respectively.
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39 To further compare the photocatalytic performance between S-TiO2 and P25
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42 TiO2, we investigated the catalytic activity for the degradation of RhB and MB
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44 pollutants before and after the long term irradiation. All the photodegradation
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47 reactions were carried out under simulated indoor sunlight (λ>350 nm) irradiation for
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50 24 min. As shown in Figure S5, the fresh catalysts S-TiO2 and P25 TiO2 used before
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52 the long-term irradiation treatment both exhibited a high photoactivity, and the RhB
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55 and MB were degraded nearly 98.5% and 100%, 94.6 % and 94.4 %, respectively.
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58 P25 TiO2 showed significant activity drop after cycling 20 times under simulate
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60 indoor sunlight irradiation, and the photocatalytic degradation of RhB and MB was

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4 reduced to 77.2 % and 75 %. On the other hand, the S-TiO2 still displayed high
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7 catalytic activity even after long-term indoor sunlight irradiation. Figure S5A shows
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10 that 96.2 % of RhB and and 93.1 % MB were degraded in 24 minutes after S-TiO2
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12 were recycled 40 times. These results solidly suggest that as-synthesized S-TiO2 could
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15 be employed as a long term stable and efficient catalyst for the water purification
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18 under solar light illumination in practical use.
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39 Figure 10. Long-term (3 months) continuous photocatalytic degradation of RhB and
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42 MB pollutants by using S-TiO2 catalysts (20 mg) under indoor sunlight (λ>350 nm)
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44 irradiation.
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47 The high photocatalytic performance of S-TiO2 is first owing to S doping in the
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50 Ti-O-Ti crystalline structure, resulting in a red-shift of the absorption edge and
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52 narrowed bandgap, and leading to the visible light photosensitivity. Furthermore, XPS
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55 results (Figure 5) suggest sulphur is in +6 state, hence when S atom takes the place of
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58 Ti, it forms SO4 tetrahedral unit in the lattice. Visible light illumination on the
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60 photocatalyst forms the photogenerated pairs. Compared with photogenerated holes

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4 (TiO2+), (SO2+) holes are expected to have higher oxidation potential and can easily
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7 decompose any unreacted intermediate species adsorbed on the surface. This strong
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10 surface self-cleaning property leads to long-term photocatlytic stability.
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12 CONCLUSION
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15 In conclusion, visible-light-sensitive S-doped TiO2 with high photocatalytic
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18 performance and long-term stability was synthesized through a facile solvothermal
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20 method, in which DMSO acted as both the solvent and the S source. The existence of
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23 S in the lattice of TiO2 resulted in a narrowing of the S-TiO2 bandgap and therefore
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26 providing a visible-light catalytic response. Compared with commercial P25 TiO2,
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28 S–TiO2 showed evidently enhanced photoactivity for the degradation of RhB and MB
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31 under visible light irradiation. Excitingly, S-TiO2 displayed excellent catalytic
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34 stability after long-term indoor sunlight irradiation. This work provides a new method
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36 for developing stable and efficient visible-light-driven photocatalysts to degrade
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39 organic pollutants. These materials would also be expected to have promising
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42 applications in solar cells, water splitting, and other light harvesting systems.
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45 ASSOCIATED CONTENT
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47
48 Supporting Information
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51 The Supporting Information is available free of charge on the ACS Publications
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53 website
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56 Preparation of S-doped TiO2 by using thiourea as S source (S-TiO2-P) and
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59 corresponding photocatalytic performance, EDX spectrum and photocatalytic
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4 activities of S-TiO2-160, XRD patterns of S-TiO2 annealed at different temperature,
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7 and photocatalytic stability of S-TiO2 and P25 TiO2
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11 AUTHOR INFORMATION
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13 Corresponding Author
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16 * Tel./Fax: +1-416-9784526. E-mail: clu@chem.utoronto.ca (C. Lu);
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19 cgoh@chem.utoronto.ca (M. C. Goh).
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21 Author Contributions
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24 The manuscript was written through contributions of all authors. All authors
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26
27 have given approval to the final version of the manuscript.
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29 Notes: The authors declare no competing financial interest.
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31
32
33 ACKNOWLEDGMENT
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36 Funding for this work was provided by the Natural Sciences and Engineering
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38 Research Council of Canada.
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40
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42 REFERENCES
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Title: A New Method to Synthesize S-Doped TiO2 with Stable and Highly Efficient
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Photocatalytic Performance under Indoor Sunlight Irradiation
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11 Authors: Mingshan Zhu, Chunyang Zhai, Liqun Qiu, Cheng Lu, Andrew Paton,
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13 Yukou Du, and M. Cynthia Goh
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35 A new facile method for the synthesis of S-doped TiO2 with excellent and long-term
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