Visible light induced electron transfer process over nitrogen doped TiO(2) nanocrystals prepared by oxidation of titanium nitride

Nitrogen doped TiO(2) nanocrystals with anatase and rutile mixed phases were prepared by incomplete oxidation of titanium nitride at different temperatures. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), core level X-ray photoelectron spectroscopy (CL XPS), valence band X-ray photoelectron spectroscopy (VB XPS), UV-vis diffuse reflectance spectra (UV-vis DRS), and visible light excited photoluminescence (PL). The photocatalytic activity was evaluated for photocatalytic degradation of toluene in gas phase under visible light irradiation. The visible light absorption and photoactivities of these nitrogen doped TiO(2) nanocrystals can be clearly attributed to the change of the additional electronic (N(-)) states above the valence band of TiO(2) modified by N dopant as revealed by the VB XPS and visible light induced PL. A band gap structure model was established to explain the electron transfer process over nitrogen doped TiO(2) nanocrystals under visible light irradiation, which was consistent with the previous theoretical and experimental results. This model can also be applied to understand visible light induced photocatalysis over other nonmetal doped TiO(2).     

Microwave assisted rapid and complete degradation of atrazine using TiO(2) nanotube photocatalyst suspensions

A technology, microwave-assisted photocatalysis on TiO(2) nanotubes, which can be applied to degrade atrazine rapidly and completely, was investigated. TiO(2) nanotubes were prepared, and confirmed by XRD, TEM and ESR. Microwave-assisted photocatalytic degradation of atrazine in aqueous solution was investigated. The result indicates that atrazine is completely degraded in 5min and the mineralization efficiency is 98.5% in 20min, which is obviously more efficient than that by the traditional photocatalytic degradation methods. It may be attributed to the intense UV radiation generated by electrodeless discharge lamps under microwave irradiation, the increased number of OH, additional defect sites on TiO(2) under the irradiation of microwave and larger specific surface area of TiO(2) nanotubes which could adsorb more organic substances to degrade than TiO(2) nanoparticles. Along with the degradation of atrazine, the concentrations of Cl(-) and NO(3)(-) increase gradually. In 20min [Cl(-)] and [NO(3)(-)] are 3, 27.8mg/L, respectively, which are close to their stoichiometric values. The major intermediates of atrazine were identified by HPLC/MS and possible degradation pathways of atrazine in microwave-assisted photocatalysis on TiO(2) nanotubes were proposed.     

Photocatalytic ozonation of dimethyl phthalate with TiO2 prepared by a hydrothermal method

TiO(2) was prepared by a hydrothermal method at a low temperature and used to degrade and mineralize dimethyl phthalate (DMP). TiO(2) was characterized by XRD, TEM, BET and UV-vis techniques. The characteristics of TiO(2) prepared by a hydrothermal method (h-t TiO(2)) included a good crystalline anatase phase, greater surface area, stronger absorption to UV light wavelength and lower agglomeration than TiO(2) prepared by a classic sol-gel method (s-g TiO(2)). The photocatalytic activity of h-t TiO(2) prepared under optimal hydrothermal condition (180°C for 10h) was 2.5 times higher than that of s-g TiO(2) in degrading DMP. The process of photocatalysis combined with UV irradiation and ozonation (TiO(2)/UV/O(3)) considerably improved the mineralization and degradation of DMP compared to photocatalysis combined with UV irradiation (TiO(2)/UV), ozonation combined with UV irradiation (UV/O(3)), and ozonation alone (O(3)). A kinetic study showed the mineralization in TiO(2)/UV/O(3) followed the Langmuir-Hinshelwood model.     

Ag-Si Co-doped TiO2 photocatalyst synthesized via a nonaqueous method

Ag-Si/TiO2 photocatalysts were synthesized in a nonaqueous system at 140 degrees C, and then annealed at different temperatures. The obtained photocatalysts were characterized by XRD, TEM, BET, TG-DTA, XPS, as well as UV-vis DRS. The results showed that All Ag-Si/TiO2 held an anatase phase and high thermal stability and the phase transformation from anatase to rutile was retarded to about 900 degrees C. The Ag-Si/TiO2 particles were highly mono-dispersed and the particles size became smaller compared to TiO2. Additionally, UV-vis light absorption shifted to visible region after Ag doping. Si weaved into the matrix of TiO2, while Ag dispersed on the surface of TiO2 particles. The visible light photocatalytic activity was evaluated by Rhodamine B (RhB) degradation in an aqueous solution under visible light irradiation. It was found that the photccatalytic activities of the obtained Ag-Si/TiO2 samples were all higher than those of pure TiO2 and Ag/TiO2, reaching the maximum at the Ag and Si content of 0.5 mol% and 20.0 mol%, respectively. The enhanced visible photocatalytic activity may be attributed to the simultaneous effects of silver and silicon co-doping.     

Synthesis of nano titania particles embedded in mesoporous SBA-15: characterization and photocatalytic activity

Supported nanocrystalline titanium dioxide (TiO2) has been prepared by a post-synthesis step via Ti-alkoxide hydrolysis through the use of mesoporous SBA-15 silica. TiO2/SBA-15 composites with various TiO2 loading have been prepared and characterized by X-ray diffraction, nitrogen adsorption, Fourier transform infrared spectroscopy and diffusive reflective UV-vis spectroscopy. The addition of mesoporous SBA-15 prevents the anatase to rutile phase transformation and the growth of crystal grain. TiO2 did not block the SBA-15 pores, and their surface was fully accessible for nitrogen adsorption. Calcination in air of the composites up to 800 degrees C did not change the nanocrystal phase and slightly increased the domain size from 5.0 to 7.5 nm, indicating that the anatase TiO2 grains in the mesostructures have a relatively high thermal stability and proper pore diameter allows controlling the size of obtained titania particles. The TiO2/SBA-15 composites prepared by this study showed much higher photodegradation ability for methylene blue (MB) than commercial pure TiO2 nanoparticles P-25. Experimental results indicate that the photocatalytic activity of titania/silica mixed materials depends on the adsorption ability of composite and the photocatalytic activity of the titania, and there is an optimal ratio of Ti:Si, too high or low Ti:Si ratio will lower the photodegradation ability of the composites.     

Preparation and characterization of N-S-codoped TiO(2) photocatalyst and its photocatalytic activity

N-S-codoped anatase nanosized TiO(2) photocatalyst (NSTO) was successfully prepared by one-step hydrothermal method from a mixed aqueous solution of Ti(SO(4))(2) and thiourea. The samples were characterized by XRD, UV-vis, XPS, FT-IR and EA. From results of UV-vis, a red shift of the absorption edge was brought out owing to N and S codoping, and the extension for photoabsorption range of NSTO occurred. XRD, XPS, EA and FT-IR studies revealed that N and S were in situ codoped in the lattice of TiO(2) and N concentration decreased from the surface to the center of NSTO. Especially, the photocatalytic tests indicated that NSTO exhibited a high activity for decompositions of methyl orange both under UV-light and vis-light irradiation comparing to S-doped TiO(2) (STO) and undoped TiO(2) (TO). The high activity of NSTO can be related to the results of the synergetic effects of strong absorption in the UV-vis region, red shift in adsorption edge, oxygen vacancies and the enhancement of surface acidity induced by N and S codoping.     

Application of a microbial toxicity assay for monitoring treatment effectiveness of pentachlorophenol in water using UV photolysis and TiO2 photocatalysis

Conventional approaches for monitoring the effectiveness of wastewater treatment processes include evaluating the degradation of the target compound and/or generation of its nontoxic byproducts. These approaches are, however, limited because routine chemical analyses alone are neither able to fully address potential hazard to biological receptors nor characterize potential synergistic interactions. This study was carried out to investigate the degradation effectiveness of pentachlorophenol (PCP) by treatment with UV-A, UV-B photolysis, sunlight, TiO(2) photocatalysis, and/or their combinations. Chemical analyses of the parent compound and its selected byproducts, as well as acute toxicity assessment using the luminescent bacteria Vibrio fischeri (Microtox), were conducted during and after the various photolytic and photocatalytic treatments. In general, the toxicity reduction pattern observed after treatment corresponded well with the chemical degradation data. However, it should be noted that there were occasions that acute microbial toxicity was observed even from the treated water samples, some of which showed complete removal of the parent compound. This post-treatment toxicity might be due to toxic PCP byproducts, which may include polychlorinated dibenzodioxins/furans, tetrachloro-p-benzoquinone, and other intermediates. The TiO(2) photocatalysis with UV-B photolysis was the most effective method to remove both PCP and its toxic derivatives in the water. The Microtox assay is an easy to use and promising approach for evaluating the effectiveness of wastewater treatment processes.     

Degradation of nitrobenzene using titania photocatalyst co-doped with nitrogen and cerium under visible light illumination

A type of nitrogen and cerium co-doped titania photocatalyst, which could degrade nitrobenzene under visible light irradiation, was prepared by the sol-gel route. Titanium isopropoxide, ammonium nitrate, and cerium nitrate were used as the sources of titanium, nitrogen, and cerium, respectively. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffusive reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and N(2) adsorption-desorption isotherm were employed to characterize the as-prepared photocatalyst. The degradation of nitrobenzene under visible light illumination was taken as probe reaction to evaluate the photoactivity of the co-doped photocatalyst. The commercial TiO(2) photocatalyst (Degussa P25), which was thought as a high active photocatalyst, was chosen as standard photocatalyst to contrast the photoactivity of the nitrogen and cerium co-doped titania photocatalyst. The results showed that the photocatalytic performance of the nitrogen and cerium co-doped titania was related with the calcination temperature and the component. The nitrogen atoms were incorporated into the crystal of titania and could narrow the band gap energy. The doping cerium atoms existed in the forms of Ce(2)O(3) and dispersed on the surface of TiO(2). The improvement of the photocatalytic activity was ascribed to the synergistic effects of the nitrogen and cerium co-doping.     

Photocatalytic activity of La, Y Co-doped TiO2 nanoparticles synthesized by ultrasonic assisted sol-gel method

Bare TiO2 (T), La-doped TiO2 (LT), Y-doped TiO2 (YT), La, Y co-doped TiO2 (LYT) were successfully prepared by facile ultrasonic assisted sol-gel synthesis using Ti(OC4H9)4 as the precursor. The products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-visible diffuse reflectance spectra (DRS), and X-ray photoelectron spectroscopy (XPS), respectively. The photocatalytic activities of anatase samples, with the average particle diameters ranging from 14 nm to 21 nm, were evaluated for photodegradation of methyl orange (MO). The XPS results indicated that Y atoms were incorporated into titania lattice, while La atoms existed on the crystal surface. Due to doping, the optical absorption edges of LT, YT, and LYT shifted to the visible light region by 21 nm, 29 nm and 35 nm, respectively. The photocatalytic performances of the doped samples, such as LT, YT and LYT, were much higher than that of bare TiO2 under UV-visible light irradiation. And the photoreactivity efficiency of the LYT was the highest. It indicated that a strong La-Y synergistic interaction appeared to play a decisive role in driving the excellent photocatalytic performance of titania.     

The direct synthesis of mesoporous structured MnO(2)/TiO(2) nanocomposite: a novel visible-light active photocatalyst with large pore size

A series of visible-light-driven mesoporous structured MnO(2)/TiO(2) nanocrystal photocatalysts have been synthesized through a modified sol-gel method, and the N(2) adsorption-desorption isotherm confirms that the mesoporous materials possess large pore size (up to 9.2?nm) and a narrow pore size distribution. X-ray powder diffraction (XRD) analyses and complementary x-ray photoelectron spectroscopy (XPS) measurements reveal that the doping of the transition metal Mn inhibits the growth of TiO(2) anatase nanocrystals and the Mn species are highly dispersed on the surface of TiO(2). The ultraviolet (UV)-vis spectrum demonstrates the excellent adsorption properties of MnO(2)/TiO(2) over the whole region of visible light, which enables this novel photocatalysis material to possess remarkable activity in the photocatalytic degradation of methylene blue under visible light radiation. Moreover, a 'coating mechanism' based on the nucleation of titania nanocrystals along with the interaction between the dopant precursors and titania clusters has been suggested.     

Nitrogen-doped TiO2 nanotube array films with enhanced photocatalytic activity under various light sources

Highly ordered nitrogen-doped titanium dioxide (N-doped TiO(2)) nanotube array films with enhanced photocatalytic activity were fabricated by electrochemical anodization, followed by a wet immersion and annealing post-treatment. The morphology, structure and composition of the N-doped TiO(2) nanotube array films were investigated by FESEM, XPS, UV-vis and XRD. The effect of annealing temperature on the morphology, structures, photoelectrochemical property and photo-absorption of the N-doped TiO(2) nanotube array films was investigated. Liquid chromatography and mass spectrometry were applied to the analysis of the intermediates coming from the photocatalytic degradation of MO. The experimental results showed that there were four primary intermediates existing in the photocatalytic reaction. Compared with the pure TiO(2) nanotube array film, the N-doped TiO(2) nanotubes exhibited higher photocatalytic activity in degradating methyl orange into non-toxic inorganic products under both UV and simulated sunlight irradiation.     

Enhancing the photoelectric conversion of dye-sensitized solar cell via nitrogen-doped nanocrystalline titania electrode

A high efficient dye-sensitized solar cell (DSC) was fabricated using nitrogen-doped nanocrystalline titania(TiO2) photoanode. X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), X-ray powder diffraction (XRD), zeta potentials, nitrogen adsorption-desorption and elemental analysis experiments were employed to characterize the nitrogen-doped nanocrystalline TiO2 photoanode. An obvious enhancement of the optical absorption in the range of 380-550 nm was observed for nitrogen-doped TiO2, which was attributed to both the substitutional N and the chemisorbed N2 molecules. A conversion efficiency of 9.04% was obtained on the DSC based on nitrogen-doped TiO2 photoanode annealed in a flow of NH3 at 550 degrees C, with an increase of 15.6% improvement in comparison with pure TiO2 (7.82%). The mechanism for the enhanced photovoltaic performance was discussed.     

Visible light active photocatalytic degradation of bisphenol-A using nitrogen doped TiO2

Nitrogen doped titania was prepared by low temperature sol-gel method using titanium precursor and nitrogen containing bases like triethylamine and tetramethyl ammonium hydroxide compounds. The materials were characterized by XRD, BET, SEM, XPS, DRS-UV, and FT-IR techniques. DRS-UV study substantially indicates shift of the absorption edge of TiO2 to lower energy region. The phase composition, crystallinity, specific surface area, and visible light activity of nitrogen doped titania depend upon the preparation conditions. Photocatalytic degradation of bisphenol-A in aqueous medium was investigated by TiO2 and nitrogen doped TiO2 under visible light irradiation in a batch photocatalytic reactor. The results indicate higher visible light activity for nitrogen doped TiO2 than commercial TiO2 (Degussa P25) for bisphenol-A degradation. The influence of various parameters such as initial concentration of bisphenol-A, catalyst loading and pH was examined for maximum degradation efficiency.     

Photocatalytic degradation of gaseous benzene over TiO2/Sr2CeO4: kinetic model and degradation mechanisms

Photocatalytic oxidation of benzene in air was carried out over TiO2/Sr2CeO4 catalysts. The prepared photocatalyst was characterized by SBET, UV-vis diffuse reflectance and XPS. TiO2/Sr2CeO4 absorbs much more visible light than TiO2 in the visible light region. The XPS spectrum shows that the binding energy value of Ti 2p3/2 transfers to a lower value. The main purpose was to investigate the kinetic model and degradation mechanisms. The kinetic data matched well with the Langmuir-Hinshelwood (L-H) kinetic model with the limiting rate constant and the adsorption constant in this case were 0.0064 mg l-1 min-1 and 9.2078 l mg-1, respectively. No gas-phase intermediates were detected by direct GC/FID analysis under the conditions despite the high benzene concentration. Ethyl acetate and (3-methyl-oxiran-2-yl)-methanol were two major identified intermediates which were accompanied by butylated hydroxytoluene, 2,6-bis(1,1-dimethylethyl)-4,4-dimethylycyclohe, 2,5-cyclohexadiene-1,4,dione,2,6-bis(1,1-dim). It is plausible that at least one of these less-reactive intermediates caused the deactivation of the photocatalyst. Finally, the photocatalytic oxidation mechanisms were speculated.     

High-efficiency dye-sensitized solar cell based on a nitrogen-doped nanostructured titania electrode

A highly efficient dye-sensitized solar cell (DSC) was fabricated using a nanocrystalline nitrogen-doped titania electrode. The properties of the nitrogen-doped titania powder, film, and solar cell were investigated. The substitution of oxygen sites with nitrogen atoms in the titania structure was confirmed by X-ray photoemission spectroscopy (XPS). The UV-vis spectrum of the nitrogen-doped powder and film showed a visible light absorption in the wavelength range from 400 to 535 nm. An enhancement of the incident photon-to-current conversion efficiency (IPCE) in the range of 380-520 nm and 550-750 nm was observed. An 8% overall conversion efficiency has been achieved. The results of the stability test indicated that the solar cell fabricated by the nitrogen-doped titania exhibited great stability.     

Syntheses of titania and poly(3,4-ethylenedioxythiophene) bilayer nanotubes

Synthesis of bilayer tubes of poly(3,4-ethylenedioxythiophene) (PEDT) and titania by electrochemical polymerization of PEDT and chemical deposition of titania in the pores of anodic alumina was reported. Electron diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and fourier transformed infrared spectroscopy (FTIR) were used to characterize these bilayer tubes. SEM photographs show the tubes of uniform diameters around 200 nm. TEM photographs confirm the formation of titania and PEDT bilayer tubes of 230 nm and 100 nm diameter, the thickness of outside TiO2 layer and inner PEDT layer are around 20 nm under the experimental condition. The XPS spectra of the bilayer tubes show that the Ti2p peak shifts to a lower binding energy and S2p peak shifts to a higher binding energy. Electron diffraction patterns show that TiO2 nanotubes formed was single crystals of anatase phase. I-V characteristic curves were measured for samples prepared under various conditions.     

微波辅助制备掺铁纳米TiO2溶胶及其性能研究

为了进一步提高纳米二氧化钛溶胶的光催化活性,采用微波辅助胶溶的方法制备了不同铁掺杂量的纳米二氧化钛(Fe-TiO2)溶胶,并以偶氮染料活性艳红X-3B为目标物,分别考察不同铁掺杂量对纳米Fe-TiO2溶胶光催化活性的影响,研究表明原子数分数为0.05%的Fe3+掺杂量最佳;对Fe-TiO2溶胶、TiO2溶胶及P25(Degussa纳米TiO2)悬浮液的光催化活性进行对比,结果表明:TiO2溶胶与P25悬浮液光催化活性相当,而Fe-TiO2溶胶较前两者具有更高的光催化活性.采用XRD、DLS、AFM和DRS的分析方法对溶胶进行表征,结果表明:微量铁掺杂对纳米TiO2的晶型及粒径分布无显著影响;但铁掺杂可以使纳米TiO2对紫外光的吸收有较大程度的增强,同时吸收边带发生了较明显的红移.铁掺杂对于提高纳米TiO2溶胶的光催化活性和拓展其光吸收范围均具有显著的积极的作用.     

微波掺氮有序多孔TiO2材料的制备与性能

采用晶胶模板法制备了有序多孔TiO<,2>材料,在微波辐照条件下对其掺氮改性,利用扫描电镜(SEM)、X射线衍射(XRD)、光电子能谱(XPS)方法对掺氮TiO<,2>材料进行表征,并研究掺氮前后TiO<,2>材料光催化性能.实验结果显示,通过晶胶模板法所制备的有序多孔TiO<,2>材料的整体比较致密,但局部有孔洞的塌...     

Synthesis, characterization, and photocatalytic activity of TiO(2-x)N(x) nanocatalyst

Nitrogen-doped titanium dioxide powders were prepared by wet method, that is, the hydrolysis of acidic tetra-butyl titanate using aqueous ammonia solution, followed by calcination at temperatures about 350 degrees C. The catalysts exhibited photocatalytic activity in the visible light region owing to N-doping. The light absorption onset of TiO(2-x)N(x) was shifted to the visible region at 459 nm compared to 330 nm of pure TiO(2). An obvious decrease in the band gap was observed by the optical absorption spectroscopy, which resulted from N2p localized states above the valence band of TiO(2-x)N(x) (compared to TiO(2)). The TiO(2-x)N(x) catalyst was characterized to be anatase with oxygen-deficient stoichiometry by X-ray diffraction (XRD), surface photovoltage spectroscopy (SPS) and X-ray photoelectron spectroscopy (XPS). The binding energy of N1s measured by XPS characterization was 396.6 eV (TiN bonds, beta-N) and 400.9 eV (NN bonds, gamma-N(2)), respectively. The photocatalytic activity of TiO(2-x)N(x) under visible light was induced by the formation of beta-N in the structure. Photocatalytic decomposition of benzoic acid solutions was carried out in the ultraviolet and visible (UV-vis) light region, and the TiO(2-x)N(x) catalyst showed higher activity than pure TiO(2).     

Preparation and Characterization of Nucleus/Shell TiO2/HAP Complex Nanophotocatalyst

A rapid and more efficient method was developed to prepare nucleus/shell titania/hydroxyapatite （TiO2/HAP） complex nanophotocatalyst. Hydroxyapatite （5 μm） which had been dissolved with 0.1 mol/L HCI was formed on the surface of the nanosized anatase titania powders by increasing the pH value of the solution at 90℃ in the water bath for only several hours .The microstructure and morphology of the resulting sample were investigated by X-ray diffraction （XRD）, Fourier-transform infrared spectroscopy （FT-IR）, scanning electron microscopy （SEM）, energy dispersive spectrum （EDS） and atomic force microscope （AFM）. The results indicated that nucleus/shell structural TiO2/HAP was formed in our experiments, and the thickness of the coating layer was about 5 nm. Photocatalytic decomposition of methyl orange was utilized to test the photocatalysis of the resulting samples and the result was compared with that of pure anatase titania powders （about 20 nm）. It was shown that the photocatalytic activity of the sample was not decreased due to the coating of HAP.