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.     

Highly Active TiO2/Polyelectrolytes Hybrid Multilayered Hollow Nanofibrous Photocatalyst Prepared from Electrouspun Fibers Using Electrostatic Layer-by-Layer Technique

Compared to conventional film photocatalysts, fiber photocatalyst has a greater surface-to-volume ratio and a 3-D open structure that allows its surface active sites to be accessible for reactants more easily and effectively. However, TiO ₂ powder (Degussa P25), by itself, cannot be prepared in the form of fibers, but with the help of a polymer nanofiber, TiO ₂ particles can be immobilized in a fibrous network of polyelectrolyte. Here, hybrid multilayered hollow nanofibers (HMHNFs) composed of TiO ₂ /polyelectrolyte (PE) have been prepared by a combination of a electrospinning method and layer-by-layer (LBL) technology. The results show that both the average diameter and the wall thickness of the HMHNFs can be well controlled by the template, as well as the number of coating layers. The dried morphology of the obtained HMHNFs is dependent on the inner deposited numbers of the polyelectrolyte layers. When compared with other nanostructured TiO ₂ materials, such as commercial TiO ₂ nanoparticles (P25, Degussa) and TiO ₂ films, the hollow TiO ₂ /PE hybrid nanofibers exhibited higher photocatalytic activities.     

TiO2 thick films supported on reticulated macroporous Al2O3 foams and their photoactivity in phenol mineralization

TiO₂ thick films deposited on macroporous reticulated Al₂O₃ foams with pore size of 10 ppi and 15 ppi were prepared using dip coating from slurries of Aeroxide^® P25 nanopowder and precipitated titania. All prepared films have sufficiently good adhesion to the surface of the substrate also in case of strongly cracked films. No measurable release of deposited TiO₂ after repeated photocatalytic cycles was observed. The photocatalytic activity was characterized as the rate of mineralization of aqueous phenol solution under irradiation of UVA light by TOC technique. The best activity was obtained with Aeroxide^® P25 coated Al₂O₃ foam with the pore size of 10 ppi, annealed at 600 °C. The optimal annealing temperature for preparation of films from precipitated titania could be determined at 700 °C. Films prepared by sol-gel deposition technique were considerably thinner compared to coatings made of suspensions and their photocatalytic activity was significantly smaller.     

Low-temperature hydrothermal synthesis of highly photoactive mesoporous spherical TiO2 nanocrystalline

TiO₂ microspheres with mesoporous textural microstructures and high photocatalytic activity were prepared by hydrothermal treatment of mixed solution of titanium sulfate and urea with designed time. The prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N₂ adsorption-desorption measurements. The photocatalytic activity was evaluated via the photocatalytic oxidation of acetone in air at room temperature. The results show that the hydrothermal time significantly influences on the morphology, microstructure and photocatalytic activity of the as-prepared samples. With increasing hydrothermal time, specific surface areas and pore volumes decrease, contrarily, the crystallite size and relative anatase crystallinity increase. The photocatalytic efficiency of the as-prepared samples is obviously higher than that of commercial Degussa P25 (P25) powders. Especially, the as-prepared TiO₂ powders by hydrothermal treatment for 7 h shows the highest photocatalytic activity, which exceeds that of P25 by a factor of more than 2 times.     

Controlled synthesis of TiO2-B nanowires and nanoparticles for dye-sensitized solar cells

Controllable synthesis of the TiO₂-B nanowires (NWs) and nanoparticles (NPs) had been achieved via a facile hydrothermal route, respectively, only by tuning the solution volume. The dye-sensitized solar cells prototypes had been fabricated using TiO₂-B NW and NP electrodes, respectively. The TiO₂-B NP cells had higher photocurrent and photoelectrical conversion efficiency than the TiO₂-B NW cells though the latter exhibited larger photovoltage compared to the former. The key factors such as the photogenerated electron injection drive force, surface defects and the interfacial charge transfer, which determined the photoelectrical properties, had been systematically researched with the surface photovoltage spectra (SPS) and the electrochemical impedance spectra (EIS). The SPS proved that there was larger photoelectron injection drive force in TiO₂-B NP photoelectrode than that in NW photoelectrode. And the electrochemical impedance spectra (EIS) revealed that TiO₂-B NP cells had faster interface charge transfer compared to TiO₂-B NW cells. Both proved that NP cells had the higher photocurrents.     

A novel approach towards high-performance composite photocatalyst of TiO2 deposited on activated carbon

TiO₂ photocatalysts deposited on activated carbon (TiO₂/AC) were prepared by dip-hydrothermal method at 180 °C using peroxotitanate as a precursor, then calcinated at 300-800 °C. The samples were characterized by X-ray diffraction, scanning electron microscopy, Raman spectroscopy and the nitrogen absorption. Their photocatalytic activity was evaluated by degradation of methyl orange (MO). The results showed that TiO₂ particles of anatase type were well deposited on the activated carbon surface. TiO₂/AC calcinated at 600 °C exhibited the best photocatalytic performance. For the comparison, the same photocatalysis experiment was carried out for two mixtures of commercial TiO₂ (Degussa P25) with AC and synthetic TiO₂ with AC. It was found that the composite catalyst TiO₂/AC was better than the two mixtures. Besides, different from fine powdered TiO₂, the granular TiO₂/AC photocatalysts could be easily separated from the bulk solution and reused; indeed, its photocatalytic ability was hardly decreased after a five-cycle for MO degradation. The kinetics of the MO degradation fitted well the Langmuir-Hinshelwood model.     

Hydrothermal synthesis of well-dispersed ultrafine N-doped TiO2 nanoparticles with enhanced photocatalytic activity under visible light

Ultrafine nitrogen-doped TiO₂ nanoparticles with narrow particle size distribution, good dispersion, and high surface area were synthesized in the presence of urea and PEG-4000 via a hydrothermal procedure. TEM observation, N₂ adsorption, XRD, UV-vis spectroscopy, the Raman spectroscopy and XPS analysis were conducted to characterize the synthesized TiO₂ particles. The synthesized TiO₂ particles were a mixture of 49.5% anatase and 50.5% rutile with a size of around 5 nm. The photocatalytic activities were tested in the degradation of an aqueous solution of a reactive Brilliant Blue KN-R under both UV and visible light. The synthesized TiO₂ particles showed much higher photocatalytic activity than a commercial P25 TiO₂ powder under both UV and visible light irradiations. The high performance is associated to N doping, the reduced particle size, good dispersion, high surface area, and a quantum size effect.     

A study on photo-generated charges property in highly ordered TiO2 nanotube arrays

In this study TiO₂ nanotube arrays were fabricated by potentiostatic anodization of titanium sheet. The X-ray diffraction (XRD) pattern and field emission scanning electron microscopy (FE-SEM) image indicated the TiO₂ nanotube arrays were of pure anatase form and highly ordered. The properties of the photo-generated charges in the nanotube arrays were investigated by transient photovoltage (TPV) technique and surface photovoltage (SPV) technique based on lock-in amplifier with dc bias, in comparison with the commercial powder derived film. The separation processes of the photo-induced charges in the system of TiO₂ nanotubes on Ti have been demonstrated to be correlated with the incident light intensity, surface trapping states, and the interfacial electric field between Ti and TiO₂. The results also show that the highly ordered nanotube film could generate much stronger SPV responses under external electric field than the commercial powder derived film.     

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.     

Enhancement of photocatalytic degradation of polyethylene plastic with CuPc modified TiO2 photocatalyst under solar light irradiation

Solid-phase photocatalytic degradation of polyethylene (PE) plastic, one of the most common commercial plastic, over copper phthalocyanine (CuPc) modified TiO₂ (TiO₂/CuPc) photocatalyst was investigated in the ambient air under solar light irradiation. Higher PE weight loss rate, greater texture change; more amount of generated CO₂, which is the main product of the photocatalytic degradation of the composite PEC plastic can be achieved in the system of PE-(TiO₂/CuPc) in comparison with PE-TiO₂ system. The CuPc promoted charge separation of TiO₂ and enhanced the photocatalytic degradation of PE based on the analysis of surface photovoltage spectroscopy (SPS). During the photodegradation of PE plastic, the reactive oxygen species generated on TiO₂ or TiO₂/CuPc particle surfaces play important roles. The present study demonstrates that the combination of polymer plastic with TiO₂/CuPc composite photocatalyst in the form of thin film is a practical and useful way to photodegrade plastic contaminants under solar light irradiation.     

Titanium dioxide nanoparticles prepared by laser pyrolysis: Synthesis and photocatalytic properties

TiO₂ nanoparticles were synthesized via the laser pyrolysis of titanium tetrachloride-based gas-phase mixtures. In the obtained nanopowders, a mixture of anatase and rutile phases with mean particle size of about 14 nm was identified. Using the thermal heated laser nanopowders, mechanically stable films were produced by immobilizing titania nanopowders on glass substrates (the doctor blading method followed by compression). The photocatalytic activity of the prepared films was tested by the degradation of 4-chlorophenol in an aqueous solution under UV-illumination. By referring to known commercial samples (Degussa P25) similarly prepared, higher photocatalytic efficiency was found for the laser-prepared samples.     

Photocatalytic performance of silver TiO2: Role of electronic energy levels

Nano-sized silver deposits on the surface of Degussa P25 TiO₂ (Ag-DP25) particles act as sites of electron accumulation where the reduction of adsorbed species takes place. Electrons can be transferred from Degussa P25 TiO₂ (DP25) to Ag particles because of the difference in the work functions of the two materials. The efficiency of the electron transfer depends on the size and the distribution of metal deposits. A significant photocatalytic oxidation enhancement by metal deposit will only be observed if the metal deposits play a more dominant role than just increasing the life time of charge carriers. The properties of metal deposits like, loaded amount, oxidation state of the deposit and its size will influence the performance. Further, a decrease in band-gap in DP25 and Ag-DP25 was observed due to the carbide ion substitution for the oxide ion in TiO₂. Such unintentional carbon incorporation is expected mostly in combustion synthesized materials. Silver metal deposits and unintentional incorporation of the carbon shows the beneficial effect by specific mechanism in the photocatalytic degradation of Congo Red (CR).     

二氧化钛纳米晶/石墨烯复合物的制备及其光催化性能 (cited: 1)

以氧化石墨和TiO₂溶胶为前驱物,结合絮凝与水热技术制备了TiO₂纳米晶/石墨烯复合物,表征了产物的结构、形貌、孔隙率、光谱吸收性质. 结果表明：TiO₂纳米晶的存在一定程度上阻止了石墨烯片层的重组,TiO₂纳米晶/石墨烯复合物较单纯TiO₂材料具有更强的吸光性能、对亚甲基蓝分子更强的吸附性能以及更高的电荷分离效率. 在紫外光和太阳光下,TiO₂纳米晶/石墨烯复合物对亚甲基蓝的光催化降解效率均高于P25和纯TiO₂.     

Decomposition of gaseous toluene on thermally-excited titanium dioxide and its ESR study under high temperatures

Decomposition of gaseous toluene on thermally-excited activated titanium dioxide (TiO₂) was investigated using a simple flow system. The decomposition of toluene on the TiO₂ bead was 92% at 400 °C. The irregular phenomena in the toluene decomposition at around 300 °C seemed to be due to the coloration of the TiO₂ bead. Electron spin resonance (ESR) measurement at high temperatures was carried out using the heating unit. Since the g-value of the signal was 1.996, the existence of Ti³⁺ in TiO₂ material was confirmed. That is, oxygen vacancy generated by thermally-excitation of TiO₂, and the reaction activity of the TiO₂ bead for gaseous toluene must be due to spins on the material.     

Photocatalytic degradation of BTEX using W-doped TiO2 immobilized on fiberglass cloth under visible light

W-doped TiO₂ were immobilized on fiberglass cloth (FGC). The catalyst possessed small crystallite sizes with a red-shift on an absorption edge. Good dispersion was observed over the immobilized catalyst. The photocatalytic degradation of gaseous BTEX was conducted in a flow reactor under day-light fluorescent. Parameters including gas flowrate, catalyst loading, initial concentration and relative humidity (%RH) were investigated. The prepared catalysts showed higher efficiency than that of TiO₂ approximately 18, 3, 3 and 2.5× for benzene, toluene, ethylbenzene and o-xylene, respectively. The condition to achieve 100% BTEX removal was found at 20 min/ml, catalyst loading 0.1 mg/cm² and 30% RH.     

Low temperature synthesis of iodine-doped TiO2 nanocrystallites with enhanced visible-induced photocatalytic activity

Iodine-doped TiO₂ nanocrystallites (denoted as I-TNCs) were prepared via a newly developed triblock copolymer-mediated sol-gel method at a temperature of 393 K. I-doping, crystallization and the formation of porous structure have been simultaneously achieved. The obtained particles were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and UV-vis spectrophotometer. The results indicated that the as-prepared I-TNCs possessed a diameter of ca. 5 nm with anatase crystalline structure and a specific surface area of over 200 m² g⁻¹. The presence of iodine expanded the photoresponse in visible light range, and led to enrich in surface hydroxyl group on the TiO₂ surface. Compared with the commercial photocatalyst P25, the I-TNCs significantly enhanced the photocatalytic efficiency in the degradation of rhodamine B and 2,4-dichlorophenol, and the I-TNCs with 2.5 mol% doping ratio exhibited the best photocatalytic activity.     

Characterization and photocatalytic activity of Zn–TiO2/AC composite photocatalyst

Activated carbon (AC) supported Zn²⁺–TiO₂ photocatalyst was prepared by sol–gel method. The prepared samples were characterized by X-ray diffraction, scanning electron micrograph, nitrogen absorption, diffuse reflectance UV/VIS and X-ray photoelectron spectroscopy. Using toluene as a pollution target, the photocatalytic activity of photocatalyst was evaluated. The results showed that prepared photocatalyst was obviously helpful for the removal of toluene in air. The photocatalytic degradation of toluene by Zn²⁺–TiO₂/AC reached 100% for 40 min and remained 75% after 160 min, while degradation by TiO₂ was only 30%. It indicated that the photocatalytic activity of prepared photocatalyst was enhanced. It is due to Zn²⁺-doping increased the oxidation and reduction of hole–electron pairs, which was the important factor in heterogeneous photocatalysis.     

Enhancement of the photocatalytic activity of TiO2 nanoparticles by surface-capping DBS groups

TiO₂ nanoparticles capped with sodium dodecylbenzenesulfonate (DBS) are synthesized by a sol-hydrothermal process using tetrabutyl titanate and DBS as raw materials. The effects of surface-capping DBS on the surface photovoltage spectroscopy (SPS), photoluminescence (PL) and photocatalytic performance of TiO₂ nanoparticles are principally investigated together with their relationships. The results show that the surface of TiO₂ nanoparticles can be well capped by DBS groups while the pH value and added DBS amount are controlled at 5.0 and 2% of TiO₂ mass weight, respectively, and the linkage between DBS groups and TiO₂ surfaces is mainly by means of quasi-sulphonate bond. The intensities of SPS and PL spectra of TiO₂ obviously decrease after DBS-capping, while the activity can greatly increase during the photocatalytic degradation of Rhodamine B (RhB) solution, which are mainly attributed to the electron-withdrawing character of the DBS groups. Moreover, the enhancement of photocatalytic activity of DBS-capped TiO₂ is also related to the increase in the capability for adsorbing RhB.     

Porous TiO2 microspheres with tunable properties for photocatalytic air purification

The synthesis of highly-crystalline porous TiO₂ microspheres is reported using ultrasonic spray pyrolysis (USP) in the presence of colloidal silica as a template. We have exploited the interactions between hot SiO₂ template particles surface and TiO₂ precursor that occur during reaction inside the droplets, to control the physical and chemical properties of the resulting particles. Varying the SiO₂ to titanium precursor molar ratio and the colloidal silica dimension, we obtained porous titania microspheres with tunable morphology, porosity, BET surface area, crystallite size, band-gap, and phase composition. In this regard, we have also observed the preferential formation of anatase vs. rutile with increasing initial surface area of the silica template. The porous TiO₂ microspheres were tested in the photocatalytic degradation of nitrogen oxides (NO_x) in the gas phase. USP prepared nanostructured titania samples were found to have significantly superior specific activity per surface area compared to a commercial reference sample (P25 by Evonik-Degussa).     

Preparation of titania hollow spheres by catalyst-free hydrothermal method and their high thermal stabilities

TiO₂ hollow spheres have been prepared by hydrothermal method using carbon spheres as hard templates based on template-directed deposition and calcination in order to remove templates. The morphology and structure of samples were systematically characterized by using various techniques, including XRD, zeta analyzer, SEM, TEM, DRS and FTIR. In this approach, the anatase phase was retained for temperatures up to 900 °C. Moreover, negative charged titania is deposited onto the negative charged surface of carbon spheres, which is proved by nanoparticle size analyzer. Therefore, a possible formation mechanism of TiO₂ hollow spheres was proposed. TiO₂ hollow spheres calcined at 550 °C exhibited the superior photocatalytic activity for the degradation of Rhodamine B, 2.9 times greater than that of Degussa P25. Furthermore, thermal stability of TiO₂ hollow spheres was examined. Fortunately, we found that hollow structures could still be visible distinctly after calcining at 900 °C.