TiO<Subscript>2</Subscript>@MgO core-shell film: Fabrication and application to dye-sensitized solar cells

In this study,TiO2@MgO core-shell film was obtained by using a simple chemical bath deposition method to coat a thin MgO film around TiO2 nanoparticles. The core-shell configuration was characterized by X-ray diffractometer (XRD),scanning elec-tron microscopy (SEM),energy dispersive X-ray spectroscopy (EDX),and high-resolution transmission electron microscopy (HRTEM). Lattice fringes were observed for the TiO2 particles,and the MgO shell showed an amorphous structure,revealing a clear distinction between the core and shell materials. Applying the core-shell film as photoanode to the dye-sensitized solar cells (DSSCs),it shows a superior performance compared to the pure TiO2 electrode. Under the illumination of simulated sunlight (75 mW-cm-2),the short circuit photocurrent (Jsc),the open circuit photovoltage (Voc),and the fill factor (fF) are 8.80 mA-cm-2,646 mV,and 0.69,respectively,and the conversion efficiency (η) in-creased by 21.8% (from 4.32% to 5.26%) when dipping for opti-mum condition.     

Catalysis of organic pollutant photodegradation by metal phthalocyanines immobilized on TiO<Subscript>2</Subscript>@SiO<Subscript>2</Subscript>

A TiO2@SiO2 hybrid support was prepared by the sol-precipitation method using n-octylamine as a template.The photocatalyst manganese phthalocyanine tetrasulfonic acid (MnPcS) was immobilized on the support to form MnPcS-TiO2@SiO2.X-ray diffraction (XRD) and UV-Visible diffuse reflectance spectra (UV-Vis DRS) were employed to characterize the catalyst.The photocatalytic degradation of rhodamine B (RhB) and the catalytic oxidation of o-phenylenediamine (OPDA) under visible light irradiation were used as probe reactions.The mineralization efficiency and the degradation mechanism were evaluated using chemical oxygen demand (COD Cr) assays and electron spin resonance (ESR),respectively.RhB was efficiently degraded by immobilized MnPcS-TiO2@SiO2 under visible light irradiation.Complete decolorization of RhB occurred after 240 min of irradiation and 64.02% COD Cr removal occurred after 24 h of irradiation.ESR results indicated that the oxidation process was dominated by the hydroxyl radical (·OH) and superoxide radical (O-·2) generated in the system.     

Preparation of Zn-doped TiO2 nanotubes electrode and its application in pentachlorophenol photoelectrocatalytic degradation

Zn-doped titanium oxide （TiO2） nanotubes electrode was prepared on a titanium plate by direct anodic oxidation and immersing method in sequence. Field emission scanning electron microscopy （FESEM） showed that the Zn-doped TiO2 nanotubes were well aligned and organized into high density uniform arrays with diameter ranging from 50 to 90 nm. The length and the thickness were about 200 and 15 nm respectively. TiO2 anatase phase was identified by X-ray diffraction （XRD）. X-ray photoelectronspectroscopy （XPS） indicated that Zn ions were mainly located on the surface of TiO2 nanotubes in form of ZnO clusters. Compared with TiO2 nanotubes electrode, about 20 nm red shift in the spectrum of UV-vis absorption was observed. The degradation of pentachlorophenol （PCP） in aqueous solution under the same condition （initial concentration of PCP： 20 mg/L; concentration of Na2SO4：0.01 mol/L and pH： 7.03） was carried out using Zn-doped TiO2 nanotubes electrode and TiO2 nanotubes electrode. The degradation rates of PCP using Zn-doped TiO2 nanotubes electrode were found to be twice and 5.8 times as high as that using TiO2 nanotubes electrode by UV radiation （400 μw/cm^2） and visible light radiation （4500 μw/cm^2）, respectively. 73.5% of PCP was removed using Zn-doped TiO2 nanotubes electrode against 45.5% removed using TiO2 nanotubes electrode in 120 min under UV radiation. While under visible light radiation, the degradation efficiency of PCP was 18.4% using Zn-doped TiO2 nanotubes electrode against 3.2% using TiO2 nanotubes electrode in 120 min. The optimum concentration of Zn doping was found to be 0.909%. The PCP degradation efficiencies of the 10 repeated experiments by Zn-doped TiO2 nanotubes electrode were rather stable with the deviation within 3.0%.     

Synthesis and characterization of Pt-MoO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>-TiO<Subscript>2</Subscript> electrodes for direct ethanol fuel cells

To enhance the CO-tolerance performance of anode catalysts for direct ethanol fuel cells, carbon nanotubes were modified by titanium dioxide (donated as CNTs@TiO₂) and subsequently served as the support for the preparation of Pt/CNTs@TiO₂ and Pt-Mo/CNTs@TiO₂ electrocatalysts via a UV-photoreduction method. The physicochemical characterizations of the catalysts were carried out by using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and infrared spectroscopy of adsorbed probe ammonia molecules. The electrocatalytic properties of the catalysts for methanol oxidation were investigated by the cyclic voltammetry technique. The results show that Pt-Mo/CNTs@TiO₂ electrode exhibits the highest performance in all the electrodes. It is explained that, the structure, the oxidation states, and the acid-base properties of the catalysts are influenced due to the strong interaction between Ti and Mo species by adding TiO₂ and MoO _x to the Pt-based catalysts.     

A review of TiO<Subscript>2</Subscript> nanoparticles

Climate change and the consumption of non-renewable resources are considered as the greatest problems facing humankind.Because of this,photocatalysis research has been rapidly expanding.TiO2 nanoparticles have been extensively investigated for photocatalytic applications including the decomposition of organic compounds and production of H2 as a fuel using solar energy. This article reviews the structure and electronic properties of TiO2,compares TiO2 with other common semiconductors used for photocatalytic applications and clarifies the advantages of using TiO2 nanoparticles.TiO2 is considered close to an ideal semi- conductor for photocatalysis but possesses certain limitations such as poor absorption of visible radiation and rapid recombination of photogenerated electron/hole pairs.In this review article,various methods used to enhance the photocatalytic characteristics of TiO2 including dye sensitization,doping,coupling and capping are discussed.Environmental and energy applications of TiO2, including photocatalytic treatment of wastewater,pesticide degradation and water splitting to produce hydrogen have been summarized.     

Preparation of porous nanoparticle TiO2 films for flexible dye-sensitized solar cells

A TiO2 paste was prepared by mixing commercial TiO2 (P25), ethanol, distilled water and a small amount of Ti (IV) tetrai-sopropoxide (TTIP), following by a hydrothermal treatment. Before hydrothermal treatment, a stirring for 48 h can prevent cracking TiO2 films. TTIP significantly promote the chemical connection between TiO2 particles and its adherence to the substrate, the TTIP amount of 6 mol% is suitable. UV irradiation can remove some impurities and water from the TiO2 film with an optimal time of 2 h. Transmission electron microscopy, X-ray diffraction, scanning electron microscopy and photovoltaic tests are charac- terized and measured. Shortcircuit current density, open-circuit voltage, fill factor and photoelectric conversion efficiencies for the fabricated flexible dye-sensitized solar cell are 7.20 mA cm-2, 0.769 V, 0.686 and 3.84%, respectively, under irradiation with a simulated solar light of 100 mW cm-2.     

Synthesis,characterization, and theoretical study of N,S-codoped nano-TiO<Subscript>2</Subscript> with photocatalytic activities

Nitrogen and sulfur doped titanium dioxide photocatalysts were prepared by the sol-gel method. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-visible diffuse reflectance spectra (DRS). Photocatalytic activities of the samples were investigated on the degradation of methyl orange (MO). The effect of the dopants on the electronic structure of TiO₂ was studied by the first-principles calculations based on the density functional theory (DFT). The orbital hybridization resulted in energy gap narrowing and electronic delocalization in the crystal of doped TiO₂. Mobile electrons of varied energetic states could offer enhanced electron transfer, together with optical absorption improvement. The results show that the doping elements of N and S play a cooperative role in the modification of electronic structure, which enhances the photocatalytic performance. The experimentally observed absorption edges of N-doped TiO₂, S-doped TiO₂, and N, S-codoped TiO₂ are 420, 413, and 429 nm, respectively, which can be explained by the theoretical calculation results.     

Preparation of transparent TiO2 nanocrystalline film for UV sensor

Nanocrystalline TiO2 is a very important inorganic semiconductor function material with a wild band gap of 3.0-3.2 eV. Owing to its characteristics of selectiveabsorption for UV light, it has been extensively applied in photocatalysts, dye-sensitized sola…     

Synthesis and Structure of Polypyrrole Derivatives／V2O5 Nanocomposites

Poly ( N, N, N-trimethyl ( 2-pyrrol-l-yl ) ethyl ammonium iodide )/V2O5 ( PTPAI/V2O5) nanocomposites were synthesized by sol-gel method. This method involved formation of vanadium pentoxide xerogel in the prcscnce of polypyrrole derivatives solution. X-ray diffraction(XRD) indicated that the polypyrrole derivative particles encapsulated in the fibrous V2O5 network and the layered distance significantly increased from 1. 077 39 to 1. 354 56 nm. The interaction between polypyrrole and V2O5 in the ‘nanocomposites‘ was characterized by IR spectroscopy. The Scanning Electron Microscope(SEM) micrographs reveal the structural contrasts between the hybrid materials and the pristine vanadium oxide xerogel.     

I-doping of anodized TiO<Subscript>2</Subscript> nanotubes using an electrochemical method

In order to obtain TiO2 with high photocatalytic activity, a cathode reduction was used to dope I⁷⁺ and I⁵⁺ into TiO₂ nanotubes of anodized Ti in C₂H₂O₄•2H₂O + NH₄F electrolyte. SEM images show that the anodization method integrated the preparation with the doping process, which for nonmetals-doping is advantageous to maintain the morphological integrity of TiO₂ nanotubes. I⁷⁺-I⁵⁺-doping enhances the UV response of TiO₂ and result in a red-shift. Under UV/visible irradiation, a I⁷⁺-I⁵⁺-doped sample (400°C) showed the highest I_ph and photocatalytic efficiency. A part of I^– in the I⁷⁺-I⁵⁺-doped sample is involved in the UV response, the red-shift and the higher I_ph.     

Fabrication of visible-light responsive S-F-codoped TiO<Subscript>2</Subscript> nanotubes

Fabrication and S-F-codoping of TiO2 nanotubes were carried out by a one-step electrochemical anodization process to extend the photoresponse of TiO2 to the visible-light region. The prepared samples were annealed in air and detected by SEM, XRD, XPS and UV-vis DRS spectrophotometer. The results showed that the average tube diameter of the nanotubes was 150 nm and the average tube length was 400 nm. The doped TiO2 nanotubes exhibited strong absorption in visible-light region. Photoelectrocatalytic degradation efficiency of 4-CP over S-F-codoped TiO2 nanotubes was 39.7% higher than that of only-F-doped sample. Moreover, sulfur and fluorine codoped into substitutional sites of TiO2 had been proven to be indispensable for strong response and high photocatalytic activity under visible light, as assessed by XPS.     

Photoelectrical performance of nanocrystalline TiO2 film electrode sensitized by Ru(II)-bipyridine complexes

Two kinds of Ru(II)-bipyridine complexes,cis-di(thiocyanate)bis(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium(II) andcis-di(thiocyanate)bis(2, 2′-bipyridyl-3, 3′-dicarboxylate) ruthenium(II), were utilized as the sensitizers to the nanocrystalline TiO₂ film electrodes. Study shows that the two dyes have quite different sensitization properties due to the strong steric effect of carboxyl groups. In addition, the pretreatment to nanocrystalline TiO₂ film electrodes with TiCl₄ was investigated, which is an effective way to improve the photoelectric conversion performances of sensitized TiO₂ electrodes.     

ZnO microsheet modified TiO<Subscript>2</Subscript> nanoparticle composite films for dye-sensitized solar cells

Randomly oriented ZnO microsheets were successfully self-assembled on TiO₂ nanoparticle (TN) film to act as the scattering layer via a cathodic electrodeposition process. The light scattering properties of ZnO microsheets were studied by UV-Vis spectrometer in the 400–800 nm wavelength range. It was found that ZnO microsheets exhibited excellent ability to scatter the incident light for ZnO microsheet-TiO₂ nanoparticle (ZT) composite films. The results showed that dye-sensitized solar cells (DSSCs) fabricated with ZT composite films showed higher short-circuit density (J_sc) and conversion efficiency than TN-based DSSCs, due to the light scattering properties of ZnO microsheets.     

Structure and photocatalytic properties of TiO<Subscript>2</Subscript>-Graphene Oxide intercalated composite

TiO2-Graphene Oxide intercalated composite (TiO2-Graphene Oxide) has been successfully prepared at low temperature (80°C) with graphite oxide (GO) and titanium sulfate (Ti(SO4)2) as initial reactants.GO was firstly exfoliated by NaOH and formed single and multi-layered graphite oxide mixture which can be defined as graphene oxide,[TiO]2+ induced by the hydrolysis of Ti(SO4)2 diffused into graphene oxide interlayer by electrostatic attraction.The nucleation and growth of TiO2 crystallites took place at low temperature and TiO2-Graphene Oxide composite was successfully synthesized.Furthermore,the photocatalytic properties of TiO2-Graphene Oxide under the irradiation of UV light were also studied.The results show that the degradation rate of methyl orange is 1.16 mg min-1 g-1(refer to the efficiency of the initial 15 min).Compared with P25 powder,this kind of intercalation composite owns much better efficiency.On the other hand,the reusable properties and stable properties of TiO2-Graphene Oxide intercalated composite are also discussed in this paper.At last,crystalline structure,interface status,thermal properties and microscopic structure of TiO2-Graphene Oxide were characterized by X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS),thermogravimetric analysis (TGA),field emission scanning electron microscopy (FESEM) and high-resolution Transmission Electron Microscopy (HRTEM).Also,we have analyzed major influencing factors and mechanism of the composite structures which evidently improve the photocatalytic properties.     

Preparation of narrow band gap V2O5/TiO2 composite films by micro-arc oxidation

V₂O₅/TiO₂ composite films were prepared on pure titanium substrates via micro-arc oxidation (MAO) in electrolytes consisting of NaVO₃. Their morphology and elements were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis. Phase composition and valence states of species in the films were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS) were also employed to evaluate the photophysical property of the films. The V₂O₅/TiO₂ composite films show a sheet-like morphology. Not only V₂O₅ phase appears in the films when the NaVO₃ concentration of the electrolyte is higher than 6.10 g/L and is loaded at the surface of anatase, but also V⁴⁺ is incorporated into the crystal lattice of anatase. In comparison with pure TiO₂ films the V₂O₅/TiO₂ composite films exhibit significantly narrow band gap energy. The film prepared in an electrolyte consisting of NaVO₃ with a concentration of 8.54 g/L exhibits the narrowest band gap energy, which is approximately 1.89 eV. The V₂O₅/TiO₂ composite films also have the significantly enhanced visible light photocatalytic activity. The film prepared in an electrolyte consisting of NaVO₃ with a concentration of 8.54 g/L exhibits the best photocatalytic activity and about 93% of rhodamine is degraded after 14 h visible light radiation.     

Electro-deoxidation of V<Subscript>2</Subscript>O<Subscript>3</Subscript> in molten CaCl<Subscript>2</Subscript>-NaCl-CaO

The electro-deoxidation of V₂O₃ precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl₂ and NaCl with additions of CaO, a cathode of compact V₂O₃, and a graphite anode under the potential of 3.0 V at 1173 K. The phase constitution and composition as well as the morphology of the samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). 3 g of V₂O₃ could be converted to vanadium metal powder within the processing time of 8 h. The kinetic pathway was investigated by analyzing the product phase in samples prepared at different reduction stages. CaO added in the reduction path of V₂O₃ formed the intermediate product CaV₂O₄.     

Research on C<Subscript>3</Subscript>N<Subscript>4</Subscript> superhard compound thin film and its application

By combination of DC reactive magnetron sputtering with multiple arcplating, the alternating C₃N₄/TiN compound film is deposited onto HSS. The core level binding energy and the contents of carbon and nitrogen are characterized by X-ray photoelectron spectrum. X-ray diffraction (XRD) shows that compound thin film contains hard crystalline phases of α-C₃N₄ and β-C₃N₄. The Knoop microhardness in the load range of 50, 5–54, 1 GPa is measured. According to acoustic emission scratch test, the critical load values for the coatings on HSS substrates are in the range of 40–80 N. The metal coated with C₃N₄/TiN compound films has a great improvement in the resistance against corrosion. Many tests show that such a coating has a very high wearability. Compared with the uncoated and TiN coated tools, the C₃N₄/TiN coated tools have a much longer cutting life. Foundation item: Supported by the National Natural Science Foundation of China (19875037) Biography: Wu Da-we( (1941-), male, Professor, research direction; thin film and its application.     

水热法制备TiO2-ZnO纳米棒分级结构及其光电性能研究

为了增加光电极光生电子传输通道并提高其光敏剂的负载能力,采用两步水热法制备了一种新颖的TiO_2-ZnO纳米棒分级结构。采用水热法在FTO导电玻璃基底上生长TiO_2纳米棒有序阵列膜,通过浸泡提拉在TiO_2纳米棒上包覆一层ZnO溶胶,经烧结形成ZnO种子层;再次采用水热法于TiO_2纳米棒上生长ZnO纳米棒,形成TiO_2-ZnO纳米棒分级结构,通过旋涂辅助连续离子反应分别在TiO_2纳米棒阵列和TiO_2-ZnO纳米棒分级结构中沉积光敏剂CdS纳米晶,形成CdS/TiO_2纳米棒复合膜和CdS/TiO_2-ZnO纳米分级结构复合膜。利用SEM,TEM,XRD、紫外-可见吸收光谱、瞬态光电流图谱等表征和测试手段,对样品的形貌、结构、光吸收和光电性能进行了表征和测试。结果表明,与单纯的TiO_2纳米棒阵列相比,TiO_2-ZnO分级结构可以沉积更多的CdS光敏剂,CdS/TiO_2-ZnO纳米分级结构复合膜的光吸收性能和瞬态光电流均明显优于CdS/TiO_2纳米复合薄膜。凭借优异的光电性能,TiO_2-ZnO分级结构在太阳电池光阳极材料中具有很好的应用前景。     

Photo-induced degradation of Ru（Ⅱ） complex absorbed on anatase TiO2 thin film electrode

Photo-induced degradation of a monolayer of Ru（Ⅱ） complex absorbed on anatase TiO2 thin film was studied by using resonant micro-Raman spectroscopy. Under intense light radiation of a laser and in the absence of a reducing agent, the dye decomposed quickly. When the dye-sensitized TiO2 thin film electrode was covered by a reducing agent, namely the I^-/I3^- redox couple, the photo-induced decomposing rate was slowed by a factor of -10^6. In both cases, the dye decomposed with time under an exponential law.     

Preparation and performance of dye-sensitized solar cells based on ZnO-modified TiO<Subscript>2</Subscript> electrodes

The ZnO-modified TiO₂ electrode was prepared by adding Zn(CH₃COO)₂·2H₂O to the TiO₂ colloid during the sol-gel production process, and was used in dye-sensitized solar cells (DSCs). The open circuit voltage (V _OC) and fill factor (ff) of the cells were improved significantly. The performances of the ZnO-modified TiO₂ electrode such as dark current, transient photocurrent, impedance, absorption spectra, and flat band potential (V _fb) were investigated. It is found that the interface charge recombination impedance increases and V _fb shifts about 200 mV toward the cathodic potential. The effect mechanism of ZnO modification on the performance of DSCs may be that ZnO occupies the surface states of the TiO₂ film.