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TiO2
NEW JOURNAL OF CHEMISTRY · 2013 ·Vol. 37 ·期 4 ·1115-1121 · IF 2.966

The fabrication and characterization of TiO2 nanospheres with high visible light photocatalytic activity by direct carbonization of block copolymer templates

Yuhui Chen,Tingting Xu,Xiaoyan Li,Qiaoling Zhao,Jin Huang,Yongsheng Li,Liuhe Wei,Zhi Ma

Titanium dioxide nanospheres with visible light photocatalytic activity were synthesized via a sol–gel approach using an amphiphilic diblock copolymer, polystyrene-block-polyacrylic acid (PS-b-PAA), as template at room temperature in toluene. The morphology and crystal structure of synthesized TiO2 nanospheres were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The XRD pattern of TiO2 nanospheres revealed the crystal transformation, resulting in the change of photocatalytic activity. The XPS pattern revealed the formation of Ti–O–C bonds upon carbonization, as a result of visible light absorption. The TiO2 nanospheres had diameters ranging from 200 to 500 nm. The photodegradation experiments showed that such TiO2 nanospheres had pronounced visible-light photocatalytic activity.

CAS / MDL: 546-68-9
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MATERIALS RESEARCH BULLETIN · 2012 · IF 2.105

Effects of hydrochloric acid treatment of TiO2 nanoparticles/nanofibers bilayer film on the photovoltaic properties of dye-sensitized solar cells

Lixin Song,Pingfan Du,Xiaoli Shao,Houbao Cao,Quan Hui,Jie Xiong

The TiO 2 nanoparticles/nanofibers bilayer film has been fabricated via spin coating and electrospinning followed by calcination. The TiO 2 bilayer film with thickness of about 6.0   μm is composed of anatase TiO 2 phase. Dye-sensitized solar cells (DSSC) were assembled by hydrochloric acid (HCl) treated TiO 2 film. The results of the photocurrent action spectra, electrochemical impedance spectroscopy (EIS), and I – V curves showed that each photovoltaic parameter of DSSC increased with the concentration of HCl increasing, and reached a maximum value and afterwards decreased. The maximum incident monochromatic photo-to-electron conversion efficiency (at 350   nm) and maximum overall conversion efficiency ( η ) of 0.05   M HCl treated TiO 2 based DSSC were enhanced to 48.0% and 4.75%, which were respectively increased by 14% and 6.3% than those of DSSC based on untreated TiO 2 film.

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CRYSTENGCOMM · 2013 ·Vol. 16 ·期 12 ·2384-2394 · IF 3.879

In situ synthesis of bimetallic Ag/Pt loaded single-crystalline anatase TiO2 hollow nano-hemispheres and their improved photocatalytic properties

Zhifeng Jiang,Jianjun Zhu,Dong Liu,Wei Wei,Jimin Xie,Min Chen

Considering that the reduction of particle size can increase the number of active sites, particle size is accepted to be the key factor in the design of photocatalysts. However, serious agglomeration of nanosized particles may cause not only a decreased surface area but also increase grain boundary recombination. Forming a hollow nano-hemisphere in single crystals with reactive sites could be a good method to overcome this drawback. In this work, we report the synthesis of novel anatase TiO2 hollow nano-hemispheres by using a mixture of CH3COO− and F− as size and morphology controlling co-agents that prevent aggregation and increase the number of active sites. Furthermore, bimetallic Ag/Pt nanoparticles (NPs) are uniformly loaded on both interior and exterior of the nano-hemispheres in situ. The Ag/Pt@TiO2 NPs with improved visible-light-harvesting ability, high charge–hole mobility, and low electron–hole recombination exhibited improved photocatalytic performance in the degradation of rhodamine B/ciprofloxacin (RhB/CIP) and hydrogen generation. The results presented here give a promising way toward the development of delicate bimetal@semiconductor composites for board applications in photocatalysis.

CAS / MDL: 85721-33-1
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CHEMICAL ENGINEERING JOURNAL · 2013 · IF 3.473

Selective photodegradation of 1-methylimidazole-2-thiol by the magnetic and dual conductive imprinted photocatalysts based on TiO2/Fe3O4/MWCNTs

Yingying Luo,Ziyang Lu,Yinhua Jiang,Dandan Wang,Lili Yang,Pengwei Huo,Zulin Da,Xuliang Bai,Xulan Xie,Pengyi Yang

The magnetic and dual conductive imprinted photocatalysts (MCIPs) were synthesized through the suspension polymerization method. TiO 2 /Fe 3 O 4 /MWCNTs, 1-methylimidazole-2-thiol and pyrrole were used as supports, template molecule and functional monomer, respectively. The MCIPs were further characterized by X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), scanning electron microscopy (SEM), transmission electron microscope (TEM), UV–visible diffuse reflectance spectra (UV–vis DRS), thermogravimetric analysis (TGA) and vibrating sample magnetometer (VSM). The result revealed that polypyrrole (PPy) was formed and well embedded in the surface imprinted layer of TiO 2 /Fe 3 O 4 /MWCNTs. Owing to PPy and MWCNTs, the MCIPs was equipped with dual conductivity which was particularly useful for photodegradation of 1-methylimidazole-2-thiol in aqueous solution under ultraviolet irradiation. Through a series investigation of factors, it was obvious that when the polymerization time was 24   h and the adding dose of pyrrole was 8   mmol, the resulting MCIPs obtained the highest photocatalytic ability. In addition, the photodegradation process obeyed the pseudo-first-order kinetic reaction and exhibited an excellent selective degradation ability of 1-methylimidazole-2-thiol. The degradation intermediate products and mechanism of 1-methylimidazole-2-thiol were further discussed.

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APPLIED SURFACE SCIENCE · 2015 · IF 2.711

Mesoporous anatase TiO2 microspheres with interconnected nanoparticles delivering enhanced dye-loading and charge transport for efficient dye-sensitized solar cells

Liang Chu,Zhengfei Qin,Qiaoxia Zhang,Wei Chen,Jian Yang,Jianping Yang,Xing⿿ao Li

Mesoporous anatase TiO 2 microspheres with interconnected nanostructures meet both large surface area and connected-structure for electron transfer as ideal nano/micromaterials for application in solar cells, energy storage, catalysis, water splitting and gas sensing. In this work, mesoporous anatase TiO 2 microspheres consisting of interconnected nanoparticles were synthesized by template-free, one-step fast solvothermal process, where urea was used as capping agent to control phase and promote oriented growth. The morphology was assembled by nucleation-growth-assembly-mechanism. The mesoporous anatase TiO 2 microspheres with interconnected nanoparticles were further utilized as efficient photoelectrodes of dye-sensitized solar cells (DSSCs), which were beneficial to capacity of dye loading and charge transfer. The power conversion efficiency (PCE) based on the optimized thickness of TiO 2 photoelectrodes was up to 7.13% under standard AM 1.5   G illumination (100   mW/cm 2 ).

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Journal of Materials Chemistry A · 2014 ·Vol. 2 ·期 20 ·7313-7318 · IF 0

Stable ZnO@TiO2 core/shell nanorod arrays with exposed high energy facets for self-cleaning coatings with anti-reflective properties

Ruosong Wang,Huaqiao Tan,Zhao Zhao,Guoqiang Zhang,Laiwen Song,Wenfei Dong,Zaicheng Sun

Nanostructured metal oxides such as ZnO and TiO2 have been extensively employed as self-cleaning coatings due to their large band gaps as well as their hydrophilic and photocatalytic properties. We have developed a simple hydrothermal method to coat thin TiO2 nanosheets with exposed (001) facets onto a ZnO nanorod array. The chemical stability of the ZnO nanorods was great improved due to the existence of the TiO2 layer. Owing to the porous structure of the ZnO@TiO2 nanorod arrays, this thin coating layer possesses anti-reflective properties. A transmittance improvement of ∼5% was observed for one-side coated FTO glass. This coating also exhibits good hydrophilic properties, after addition of the TiO2 nanosheets. More importantly, these ZnO@TiO2 nanorod arrays display excellent photocatalytic properties for the degradation of dye molecules, due to the heterojunction between the ZnO nanorods and TiO2 nanosheets. This heterojunction facilitates the charge separation of photo generated carriers. Based on the above features, the ZnO@TiO2 core/shell nanorod array film has many advantages as a self-cleaning coating.

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Nanoscale · 2015 ·Vol. 7 ·期 30 ·12979-12989 · IF 7.394

Hierarchical nanosheet-constructed yolk–shell TiO2 porous microspheres for lithium batteries with high capacity, superior rate and long cycle capability

Jun Jin,Shao-Zhuan Huang,Yu Li,He Tian,Hong-En Wang,Yong Yu,Li-Hua Chen,Tawfique Hasan,Bao-Lian Su

A hierarchical nanosheet-constructed yolk–shell TiO2 (NYTiO2) porous microsphere is synthesized through a well-designed, one-pot, template-free solvothermal alcoholysis process using tetraethylenepentamine (TEPA) as the structure directing reagent. Such a yolk–shell structure with a highly porous shell and dense mesoporous core is quite advantageous as an anode material for lithium ion batteries (LIBs). The outer, 2D nanosheet-based porous (15 nm) shell and the nanocrystal-based inner mesoporous (3 nm) core provide a stable, porous framework, effective grain boundaries and a short diffusion pathway for Li+ and electron transport, facilitating lithium insertion/extraction. The voids between the core and the shell can not only store the electrolyte due to capillary and facilitate charge transfer across the electrode/electrolyte interface but also buffer the volume change during the Li+ insertion/extraction. As a result, NYTiO2 demonstrates excellent Li+ capacity with outstanding cycle performance and superior rate capability at different rates for >700 cycles, retaining a 225 mA h g−1 reversible capacity after 100 cycles at 1 C. In particular, the reversible capacity can still be maintained at 113 mA h g−1 after 100 cycles at 10 C. We also observe the formation of homogeneously distributed 5–10 nm Li2Ti2O4 nanocrystallites on the surface of the nanosheets during the discharge–charge process. The synergy of the yolk–shell structure with dual mesopores in the shell and core and the Li2Ti2O4 nanocrystallites endow the hierarchical NYTiO2 with high reversible capacity, excellent rate capability and outstanding cycle performance.

CAS / MDL: 112-57-2
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Nanoscale · 2015 ·Vol. 8 ·期 9 ·4976-4983 · IF 7.394

Light-controlled propulsion, aggregation and separation of water-fuelled TiO2/Pt Janus submicromotors and their “on-the-fly” photocatalytic activities

Fangzhi Mou,Lei Kong,Chuanrui Chen,Zhihong Chen,Leilei Xu,Jianguo Guan

In this work, water-fuelled TiO2/Pt Janus submicromotors with light-controlled motions have been developed by utilizing the asymmetrical photocatalytic water redox reaction over TiO2/Pt Janus submicrospheres under UV irradiation. The motion state, speed, aggregation and separation behaviors of the TiO2/Pt Janus submicromotor can be reversibly, wirelessly and remotely controlled at will by regulating the “on/off” switch, intensity and pulsed/continuous irradiation mode of UV light. The motion of the water-fuelled TiO2/Pt Janus submicromotor is governed by light-induced self-electrophoresis under the local electrical field generated by the asymmetrical water oxidation and reduction reactions on its surface. The TiO2/Pt Janus submicromotors can interact with each other through the light-switchable electrostatic forces, and hence continuous and pulsed UV irradiation can make the TiO2/Pt Janus submicromotors aggregate and separate at will, respectively. Because of the enhanced mass exchange between the environment and active submicromotors, the separated TiO2/Pt Janus submicromotors powered by the pulsed UV irradiation show a much higher activity for the photocatalytic degradation of the organic dye than the aggregated TiO2/Pt submicromotors. The water-fuelled TiO2/Pt Janus submicromotors developed here have some outstanding advantages as “swimming” photocatalysts for organic pollutant remediation in the macro or microenvironment (microchannels and microwells in microchips) because of their small size, long-term stability, wirelessly controllable motion behaviors and long life span.

CAS / MDL: 7631-86-9
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ANALYTICAL CHEMISTRY · 2015 · IF 5.636

New Photocathodic Analysis Platform with Quasi-Core/Shell-Structured TiO2@Cu2O for Sensitive Detection of H2O2 Release from Living Cells

Zhenzhen Li,Yanmei Xin,Zhonghai Zhang

In this work, we clearly demonstrate for the first time the use of a p-type semiconductor, Cu2O, as the core unit of a photocathode to set up a new photocathodic analysis platform. With the help of a facile protection strategy, the Cu2O photocathode presented efficient photoelectrochemical performance for H2O2 sensing with a detection limit of 0.15 μM, which allowed the new photocathodic analysis platform to detect H2O2 released from living tumorigenic cells, thus demonstrating its potential application as a sensitive cancer detection probe. The protected TiO2 layer was coated on Cu2O to form a quasi-core/shell structure (TiO2@Cu2O) through a facile sol–gel method, which significantly enhanced the photostability, comparable to the TiO2@Cu2O samples prepared by a complicated atomic layer deposition method. In this new photocathodic analysis platform, the semiconductive metal oxides accomplish a job usually completed by conductive noble metals in an electroanalysis process. We believe that this photocathodic detection strategy opens up a new detection approach, extends the application range of semiconductor materials, and thus sheds light on the further fusing of photoelectrochemical technique with analytical methods.

CAS / MDL: 546-68-9
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Journal of Materials Chemistry A · 2014 ·Vol. 2 ·期 25 ·9699-9708 · IF 0

Design of new anode materials based on hierarchical, three dimensional ordered macro-mesoporous TiO2 for high performance lithium ion batteries

Jun Jin,Shao-Zhuan Huang,Jing Liu,Yu Li,Dai-Song Chen,Hong-En Wang,Yong Yu,Li-Hua Chen,Bao-Lian Su

As anode materials for lithium ion batteries, two three dimensionally ordered macroporous TiO2, one with disordered inter-particle mesopores formed by the aggregation of nanoparticles (3DOM) and another with inner-particle mesopores generated by a surfactant templating strategy (3DOMM), have been synthesized using poly(styrene-methyl methacrylate-3-sulfopropyl methacrylate potassium) (P(St-MMA-SPMAP)) spheres as a hard template and their electrochemical properties are compared. SEM and TEM observations reveal that both 3DOM TiO2 and 3DOMM TiO2 have well-ordered macropores and interconnected macropore walls with a regular periodicity. 3DOMM TiO2 demonstrates a specific surface area of 139 m2 g−1, which is higher than that of 3DOM TiO2 (99 m2 g−1) due to the smaller crystallite size and inner-particle mesopores. The electrolyte adsorption results show that both 3DOM TiO2 and 3DOMM TiO2 have similar adsorption capacities despite a difference in the surface area. Electrochemical impendence spectroscopy analysis shows that 3DOMM TiO2 has a lower charge transfer resistance and faster Li+ diffusion coefficient than 3DOM TiO2. Moreover, both 3DOM TiO2 and 3DOMM TiO2 possess excellent initial capacity of 248 mA h g−1 and 235 mA h g−1 at 0.2 C and 208 mA h g−1 and 202 mA h g−1 at 1 C, respectively. The reversibility study demonstrates that the 3DOMM TiO2 displays higher cycling capacity, superior rate behavior and higher Coulombic efficiency because the higher surface area provides more active sites and the presence of the inner-particle mesopores in the walls of macropores serve as a bicontinuous transport path and affords a shorter path length for diffusion of Li ions compared with the 3DOM TiO2 and its crystallite aggregated mesopores. The reversible capacity of 106 mA h g−1 observed for the 3DOMM TiO2 can be retained after 200 charge–discharge cycles at a relatively high current rate of 4 C. This cycle stability performance can be equally attributed to the crystallite size and inner-particle mesopores in the 3DOMM TiO2. Moreover, the existence of a bicontinuous porous structure in the 3DOMM TiO2 can further enhance the lithium insertion/extraction capacity at high rates. We believe that this study can shed light on the 3DOMM structure as a promising material for highly enhanced performance in lithium ion batteries.

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CHEMICAL ENGINEERING JOURNAL · 2014 · IF 4.058

Microwave synthesis of a novel magnetic imprinted TiO2 photocatalyst with excellent transparency for selective photodegradation of enrofloxacin hydrochloride residues solution

Ziyang Lu,Fei Chen,Ming He,Minshan Song,Zhongfei Ma,Weidong Shi,Yongsheng Yan,Jinze Lan,Fang Li,Peng Xiao

Magnetic imprinted TiO 2 photocatalyst (MITP) with excellent transparency was prepared via a microwave heating method based on enrofloxacin hydrochloride (ENRH) as the template molecule, methyl methacrylate (MMA) as the functional monomer, and TiO 2 @SiO 2 @Fe 3 O 4 (TSF) as the matrix material. TSF was synthesized by a mild sol–gel method. The results indicated that MITP possessed hierarchical spherical structure, good monodispersity, superior magnetic properties (Ms   =   11.59   emu/g), the average diameter was approximately 410   nm, and the surface-imprinted layer was composed of the imprinted polymer and poly (methyl methacrylate). Moreover, MITP was proved to exhibit an excellent photochemical stability and a higher photocatalytic efficiency than other photocatalysts, the apparent rate constant ( k ) for degradation of ENRH with MITP in 90   min under the visible light irradiation was 1.08   min −1 . The coefficient of selectivity ( k selectivity ) of MITP relative to TSF and magnetic non-imprinted TiO 2 photocatalyst (MNITP) was 2.14 and 2.08, respectively, indicating that MITP also possessed the strong ability to selective recognition and photodegradation of ENRH in the binary antibiotic residues solution containing ENRH and tetracycline (TC). In addition, the mechanism and intermediate products of selective photodegradation of the binary antibiotic residues solution with MITP were further discussed.

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TALANTA · 2014 · IF 3.511

A derivative photoelectrochemical sensing platform for herbicide acetochlor based on TiO2–poly (3-hexylthiophene)–ionic liquid nanocomposite film modified electrodes

Dangqin Jin,Qin Xu,Yanjuan Wang,Xiaoya Hu

Nonelectroactive acetochlor can be indirectly determined through the photocatalytical degradation of acetochlor. A derivative visible light photoelectrochemical sensor for indirect detection of the herbicide acetochlor using TiO 2 –poly(3-hexylthiophene)–ionic liquid nanocomposite is constructed. Poly(3-hexylthiophene) (P3HT) was synthesized via chemical oxidative polymerization with anhydrous FeCl 3 as oxidant, 3-hexylthiophene as monomer , chloroform as solvent, and the functional TiO 2 nanoparticles were facilely prepared by blending TiO 2 nanoparticles and P3HT at room temperature ionic liquid , 1-Butyl-3-methylimidazolium hexafluorophosphate solution. Operational parameters, including the photolysis time, ratios of TiO 2 to P3HT, bias voltage and pH of buffer solution have been optimized. Under optimal conditions, the proposed photoelectrochemical method could detect acetochlor ranging from 0.5 to 20   μmol   L −1 with a detection limit of 0.2   nmol   L −1 at a signal-to-noise ratio of 3. The assay results of acetochlor in water samples with the proposed method were in acceptable agreement with those of the gas chromatograph–mass spectrometer (GC–MS) method. The promising sensor opens a new opportunity for fast, portable, and sensitive analysis of acetochlor in environmental samples.

CAS / MDL: 174501-64-5
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