Photocatalytic reduction of oxygen molecules at the (1 0 0) TiO2 anatase surface

The adsorption, photoreduction and chemical activity of oxygen molecules on the (1 0 0) anatase surface have been investigated here together with the effects that surface oxygen vacancies (V_O) can have on these O₂-related processes. We use an original approach by treating molecules on the TiO₂ surface like surface defects in the same framework successfully used for defects in semiconductors. The achieved results: (i) give the first theoretical evidence of an acceptor behaviour of an adsorbed O₂ molecule, which is at the origin of its photoreduction; (ii) show that the V_O donor character is strongly affected by the interaction with O₂; and (iii) suggest that the release of radicals as well as the formation of O₂-related radicals may be favoured by photogenerated electrons in presence of surface V_O’s.     

Gallium- and iodine-co-doped titanium dioxide for photocatalytic degradation of 2-chlorophenol in aqueous solution: Role of gallium

Visible-light-driven TiO₂-based catalysts for the degradation of pollutants have become the focus of attention. In the present work, iodine-doped titania photocatalysts (I-TiO₂) were improved by doping with gallium (Ga,I-TiO₂) and the resulting physicochemical properties and photocatalytic activity were investigated. The structural properties of the catalysts were determined by X-ray diffraction, UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller analysis and transmission electron microscopy. We found that Ga probably enters the TiO₂ framework for doping levels <0.5 mol%. A further increase in Ga content probably leads to dispersal of excess Ga on the TiO₂ surface. The photocatalytic activity of Ga,I-TiO₂ catalysts was evaluated using 2-chlorophenol (2-CP) as a model compound under visible and UV-vis light irradiation. The results indicate that 0.5 mol% Ga loading and calcination at 400 °C represent optimal conditions in the calcining temperature range 400-600 °C and with doping levels from 0.1% to 1 mol%. The effective enhancement of 2-CP degradation might be attributed to the formation of oxygen vacancies by Ga doping, which could decrease the recombination of electron-hole pairs.     

Effects of native defects on the electronic structure and photocatalytic activity in anatase TiO2 by first principles calculations

The crystal structure, electronic structure, optical properties and photocatalytic activity of the native defects in anatase TiO₂ were investigated based on the density-functional theory (DFT). The results show that oxygen vacancies (V_O) have the lowest formation energy, and thus are easiest to form in the bulk structure. The conduction and valence band moves to the high or low energy region, and the energy gap becomes narrower for the native point defect models. In particular, oxygen interstitials (O_i) have a direct band gap, and new gap states appear in the band gap, which can be responsible for the high photocatalytic efficiency in anatase TiO₂. The phenomenon of “impurity compensation” takes place for the oxygen and titanium interstitials. Ti vacancy (V_Ti) can promote the utilization of solar light by analyzing the absorption spectra. All the calculated results show that O_i and V_Ti are beneficial in improving the photocatalytic activity of TiO₂ in the UV–visible light range.     

Fabrication and characterization of Fe-doped titania semiconductor electrodes with p-n homojunction devices

The nano-TiO₂ electrode with a p-n homojunction device was designed and fabricated by coating of the Fe³⁺-doped TiO₂ (p-type) film on top of the nano-TiO₂ (n-type) film. These films were prepared from synthesized sol-gel TiO₂ samples which were verified as anatase with nano-size particles. The semiconductor characteristics of the p-type and n-type films were demonstrated by current-voltage (I-V) measurements. Results show that the rectifying curves of undoped TiO₂ and Fe³⁺-doped TiO₂ sample films were observed from the I-V data illustration for both the n-type and p-type films. In addition, the shapes of the rectifying curves were influenced by the fabrication conditions of the sample films, such as the doping concentration of the metal ions, and thermal treatments. Moreover, the p-n homojunction films heating at different temperatures were produced and analyzed by the I-V measurements. From the I-V data analysis, the rectifying current of this p-n junction diode has a 10 mA order higher than the current of the n-type film. The p-n homojunction TiO₂ electrode demonstrated greater performance of electronic properties than the n-type TiO₂ electrode.     

Thermogravimetric and electrical study of non-stoichiometric titanium dioxide TiO2−x, between 800 and 1100°C

By means of thermogravimetrie and electrical measurements, it has been possible to give accurate informations on the nature of the defects produced by reduction of TiO₂ between 800 and 1100°C. For small partial pressures of oxygen P_o2. interstitial titanium Ti⁴_i prevails at temperature higher than 900°C. When P_O2 increases, oxygen vacancies are produced at first in the doubly ionized form V″_o and a progressive transition to singly ionized vacancies V″_o can be assumed. The formation enthalpies associated with these defects as calculated from our experimental results are 10.1 eV for Ti⁴_i, 4.6 eV for V″_o and 3.6–4.0 eV for V′_o. The electronic drift mobility μ is independent both of nature and concentration of the defects. The shape of its temperature dependence leads to conclude that the conduction in spite of the low μ value (0.06 cm² V^?1 s^?1 at 1100°C) is of the classical type for wide band semiconductors and not a hopping process.     

Thermodynamic properties of titanium dioxide,niobium dioxide and their solid solutions at high temperature

By means of thermogravimetric measurements, it has been possible to obtain information on the nature of the intrinsic and extrinsic defects of TiO₂, NbO₂ and solid solutions Nb_yTi_1?yO_2±x Pure TiO₂ is an oxygen-deficient oxide The main defects are oxygen vacancies, doubly ionized V^.._o or singly ionized V^._o, and interstitial titanium Ti³_i NbO₂ is a metal-deficient oxide The main defects are neutral niobium vacancies. The solid solutions Nb_yTi_1?yO_2±x may be divided into two groups If y > 0 04, the behavior is analogous to that of NbO₂; with the same defects, but the width of the homogeneity range decreases with the titanium content and Nb_{0 04}Ti_{0 96}O₂ is a stoichiometnc oxide If y < 004, the oxides are both metal deficient and oxygen deficient according to the oxygen partial pressure. We have particularly studied the solution Ti_{0 995}Nb_{0 005}O₂ In the oxygen-deficient domain, the main defects are assumed to be neutral or singly ionized oxygen vacancies In the metal-deficient domain, the main defects are metal vacancies V⁴_Ti From these results we have deduced the nature of intrinsic defects in TiO₂ to be Schottky defects: 2V^.._O + V⁴_T1.     

Tribological Properties of Thermosetting Polyimide/TiO2 Nanocomposites Under Dry Sliding and Water-Lubricated Conditions

Thermosetting polyimide(PI)-based nanocomposites containing various contents of nano-TiO₂ were fabricated via an in situ polymerization of monomer reactants (PMR) process. Under dry sliding and water-lubricated conditions the friction and wear behaviors of the PMR PI and its nanocomposites were evaluated and compared. The addition of nano-TiO₂ in PI contributed to improving the friction and wear behavior considerably under dry sliding. The highest change ratio of wear rate was 61% with the optimum nano-TiO₂ content of 3%, while the highest change of friction coefficient was 60% with the optimum nano-TiO₂ content of 9%. Under water-lubricated condition, contrarily, the addition of nano-TiO₂ in PI does harm to the tribological properties. Namely, the friction coefficient of the nanocomposites increased with increasing the nano-TiO₂ content. These results may be caused by the following facts: the hardness of the PI matrix would be increased by adding the nano-TiO₂ reducing the ability of elastic deformation of the nanocomposites; accordingly, the poor elastic deformation hindered the formation of a water-lubrication film on the surface. An investigation on the wear tracks indicated that the wear mechanism of PI/TiO₂ nanocomposites under dry sliding condition proceeded from fatigue wear to a combination of fatigue wear and abrasive wear with increasing the mass fraction of nano-TiO₂.     

First-principles study of native defects in rutile TiO2

Native point defects in the rutile TiO₂ are studied via first-principles pseudopotential calculations. Except for the two antisite defects, all the native point defects have low formation energies. Under the Ti-rich growth condition, high concentrations of titanium interstitials and oxygen vacancies would form spontaneously in p-type samples; whereas high concentrations of titanium vacancies would form spontaneously in n-type samples regardless of the oxygen partial pressure.     

Preparation of nanocrystalline Sn-TiO2−X via a rapid and simple stannous chemical reducing route

The Sn-TiO_2−X nanoparticles have been prepared via a rapid and simple stannous chemical reducing method. The as-prepared Sn-TiO_2−X nanoparticles were investigated by means of surface photovoltage spectroscopy (SPS), XPS, and DRS technology as well as photocatalytic degradation of RhB were studied under illumination. The experiment results revealed that the reduction of the TiO₂ particles raised their Fermi level, which can enhance the driven force of photoinduced electrons transferring from TiO₂ to adsorbed O₂ and SnO₂ on the surface of TiO₂. On the other hand, the amount of oxygen vacancies of the Sn-TiO_2−X increased after the stannous chemical reduction. The oxygen vacancies can also effectively inhibit the recombination of photoinduced electrons and holes pairs. These factors are favorable to the photocatalytic reaction.     

Synthesis of efficient TiO2-based photocatalysts by phosphate surface modification and the activity-enhanced mechanisms

A simple strategy to greatly increase the thermal stability of nanocrystalline anatase has been put forward to fabricate efficient TiO₂-based photocatalysts under ultraviolet irradiation, via the surface modification with phosphate anions. The results show that the increased anatase thermal stability is attributed to the roles of the phosphate modification effectively inhibiting the contacts among anatase nanocrystals. Compared to un-modified TiO₂, the modified TiO₂ calcined at high temperature (over 700 °C) exhibits much high photocatalytic activity for degrading Rhodamine B (or phenol) solution, even superior to the commercial P25 TiO₂. The activity enhancement is mainly attributed to the increased separation rate of photogenerated charge carriers on the basis of the measurements of steady state- and transient state-surface photovoltage spectroscopy. This work would provide a practical route to reasonably design and synthesize high-performance TiO₂-based nanostructured photocatalysts with high anatase thermal stability.     

Visible-light photocatalytic behavior of two different N-doped TiO2

The visible-light photocatalytic behavior of two different N-doped TiO₂ correlated with their physicochemical properties was investigated. The results show that N-TiO₂-1, prepared by a novel TiO₂ with unique defect structure, is more active in visible-light photocatalytic oxidation of C₃H₆ than N-TiO₂-2, prepared by standard P25-TiO₂ (Degussa). The specific rate constant of the former is ca. 5 times that of the latter. One model of photoactive center (V_o-NO-Ti) in anatase phase responsible for the visible-light photocatalytic activity is proposed. The higher the V_o-NO-Ti concentration is, the better the visible-light photocatalytic activity is.     

Visible light sensitization effect of polyaminobenzoate adsorbed on TiO2 nanocrystal surface

Poly-o-aminobenzoate (POA) was prepared by oxidizing o-aminobenzoic acid with (NH₄)₂S₂O₈ in an acidic solution. POA was adsorbed on TiO₂ nanocrystal surface to obtain a POA-TiO₂ nanocomposite. The polymerization reaction, structure, adsorption reaction on TiO₂ surface, and visible light sensitization effect of the polymer adsorbed on TiO₂ surface were studied by FT-IR and UV-visible spectra, cyclic voltammetry, and measurements of visible light photoelectrochemical and photocatalytic activities. Three kinds of POA with different long conjugate structures can be formed. These polymers have large absorbance in wide visible light region. POA molecules can be adsorbed on TiO₂ surface by anchoring their carboxylate groups to the TiO₂ surface with a multi-bridging chelating mode, which causes formation of the POA-TiO₂ nanocomposite with a high stability. POA adsorbed on the TiO₂ nanocrystal showed high visible light sensitization effect in the photocatalytic reaction.     

硼(氮、氟)掺杂对TiO2纳米颗粒光学性能的影响

利用X射线衍射谱、拉曼光谱和紫外-可见光吸收光谱研究了硼(氮、氟)掺杂对TiO₂纳米颗粒光学性能的影响.X射线衍射谱和拉曼光谱结果表明,掺硼(氮、氟)对TiO₂纳米颗粒的锐钛矿相晶体结构无明显影响,而其锐钛矿晶格出现畸变(c/a值增大),这被归因于掺杂原子对TiO₂纳米颗粒表面氧原子缺位沿晶格c轴方向的占据.另外,掺硼(氮、氟)TiO₂纳米颗粒吸收带红移与TiO相似文献   

Enhanced photocatalytic activity of graphene–TiO2 composite under visible light irradiation

Novel graphene–TiO₂ (GR–TiO₂) composite photocatalysts were synthesized by hydrothermal method. During the hydrothermal process, both the reduction of graphene oxide and loading of TiO₂ nanoparticles on graphene were achieved. The structure, surface morphology, chemical composition and optical properties of composites were studied using XRD, TEM, XPS, DRS and PL spectroscopy. The absorption edge of TiO₂ shifted to visible-light region with increasing amount of graphene in the composite samples. The photocatalytic degradation of methyl orange (MO) was carried out using graphene–TiO₂ composite catalysts in order to study the photocatalytic efficiency. The results showed that GR–TiO₂ composites can efficiently photodegrade MO, showing an enhanced photocatalytic activity over pure TiO₂ under visible-light irradiation. The enhanced photocatalytic activity of the composite catalysts might be attributed to great adsorptivity of dyes, extended light absorption range and efficient charge separation due to giant π-conjugation system and two-dimensional planar structure of graphene.     

Control of Tisurface defect on TiO2 nanocrystal using various calcination atmospheres as the first step for surface defect creation and its application in photocatalysis

A new development to create the surface defect (Ti³⁺) on TiO₂ was reported in this paper and compared to the common methods which must prepare the crystalline TiO₂ in the first step prior, and then create the surface defect in the second step. In this work, the surface defect creation was performed in the first step coinciding with the crystalline TiO₂ preparation using the sol-gel method. The creation was performed by varying the amounts of oxygen fed during calcination. Based on the CO₂-temperature programmed desorption (CO₂-TPD) and electron spin resonance (ESR) results, the surface defect (Ti³⁺) substantially increased with the amount of oxygen fed. Moreover, the samples resulting from calcination were used as photocatalysts for ethylene decomposition. The reactivity of those samples was also discussed.     

One-step synthesis of black TiO2-x microspheres by ultrasonic spray pyrolysis process and their visible-light-driven photocatalytic activities

Black TiO_2-x has recently emerged as one of the most promising visible-light-driven photocatalysts, but current synthesis routes that require a reduction step are not compatible with cost-effective mass production and a relatively large particle such as microspheres. Herein, we demonstrate a simple, fast, cost-effective and scalable one-step process based on an ultrasonic spray pyrolysis for the synthesis of black TiO_2-x microspheres. The process utilizes an oxygen-deficient environment during the pyrolysis of titanium precursors to directly introduce oxygen vacancies into synthesized TiO₂ products, and thus a reduction step is not required. Droplets of a titanium precursor solution were generated by ultrasound energy and dragged with continuous N₂ flow into a furnace for the decomposition of the precursor and crystallization to TiO₂ and through such a process spherical black TiO_2-x microspheres were obtained at 900 °C. The synthesized black TiO_2-x microsphere with trivalent titanium/oxygen vacancy clearly showed the variation of physicochemical properties compared with those of white TiO₂. In addition, the synthesized microspheres presented the superior photocatalytic activity for degradation of methylene blue under visible light irradiation. This work presents a new methodology for a simple one-step synthesis of black metal oxides microspheres with oxygen vacancies for visible-light-driven photocatalysts with a higher efficiency.     

阳离子空位和吸附氧的协同作用对Na0.5Bi0.5TiO3(100)表面磁性影响的第一性原理研究

The combination effect of cation vacancies and O₂ adsorption on ferromagnetism of Na_0.5Bi_0.5TiO₃(100) surface is studied by using density functional theory.An ideal Na_0.5Bi_0.5TiO₃(100) surface is non-magnetic and the cation vacancy could induce the magnetism.By comparing the formation energies for Na,Bi and Ti vacancy,the Na vacancy is more stable than the others.Therefore,we focus on the configuration and electric structure for the system of O₂ molecule adsorption on the Na_0.5Bi_0.5TiO₃(100) surface with a Na vacancy.Among the five physisorption configurations we considered,the most likely adsorption position is Na vacancy.The O₂ adsorption enhances the magnetism of the system.The contribution of spin polarization is mainly from the O 2p orbitals.The characteristics of exchange coupling are also calculated,which show that the ferromagnetic coupling is favorable.Compared with the previous calculation results,our calculations could explain the room-temperature ferromagnetism of Na_0.5Bi_0.5TiO₃ nanocrytalline powders more reasonably,because of taking into account adsorbed oxygen and cation vacancies.Moreover,our results also show that adsorption of O₂ molecule as well as introduction of cation vacancies may be a promising approach to improve multiferroic materials.     

Highly enhanced luminescence of ZnO green phosphors by calcining ZnS with NH4Br as additive

Zinc oxide (ZnO) phosphors with highly efficient green emission have been prepared by calcining ZnS with NH₄Br as additive in air atmosphere. The luminescent properties of as-prepared ZnO phosphors were characterized by X-ray photoelectron spectroscopy and photoluminescence. Our results reveal that the green emission is ascribed to a transition of a photo-generated electron from the localized defect centers (V_o⁺) to a deeply trapped hole (V_Zn⁻) within the band gap. The addition of NH₄Br enhances the luminescent emission of ZnO by promoting the formation of vacancies of both oxygen and zinc.     

Multiple nano-TiO2 layers to prevent dye/nano-TiO2 from photodegradation under a UV-exposure environment

A device of multiple nano-TiO₂ layers was proposed and fabricated to prevent a dye/nano-TiO₂ region from serious photo-degradation. In this device, the top of the dye/TiO₂ region was designed to be coated using sol-gel nano-TiO₂ thin films to shield UV irradiation from the photo-degradation effect. The sol-gel TiO₂ was prepared in a low temperature (75 °C) and verified as nano-sized particles and an anatase crystalline structure. Different devices of the multi-layer samples fabricated using different compositions of nano-TiO₂ were produced and exposed for UV irradiation tests. Results show that the presence of the sol-gel TiO₂ films coated on top of the dye/TiO₂ region can significantly alleviate the dye photo-degradation under UV irradiation. This multi-layer device can effectively improve the photo-stability of the dye/TiO₂ region in a UV-exposure environment.     

Photoluminescence and persistent luminescence properties of non-doped and Ti4+-doped Mg2SnO4 phosphors

Mg₂SnO₄ exhibits green photoluminescence and persistent luminescence, which originate from oxygen vacancies. When Ti⁴⁺ ions were doped, an interesting Mg₂SnO₄:Ti⁴⁺ phosphor with bluish white photoluminescence under ultraviolet irradiation and with green persistent luminescence was first obtained. Our investigation reveals that two emission centres exist in Mg₂SnO₄:Ti⁴⁺. The centres responsible for the green emission are considered to be the F centres (oxygen vacancies) and the blue centres are the TiO₆ complex. Trap clusters in the band gap with different depths, such as [Sn_Mg^‥—O_i^″], [Sn_Mg^‥—V_O^·], [Sn_Mg^‥—V_O^×] and Mg_Sn^″, correspond to the components at 85 ℃, 146 ℃ and 213 ℃ of the thermoluminescence curve.