Solar active nano-TiO2 for mineralization of Reactive Red 120 and Trypan Blue: 1st Nano Update

Nano-TiO₂ was synthesized by sol–gel method. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) images, transmission electron microscope (TEM), BET surface area measurement and DRS analysis. The formation of anatase phase nano-TiO₂ was confirmed by XRD measurements and its crystalline size is found to be 15.2 nm. SEM images depict the crystalline nature of prepared TiO₂. The BET surface area of prepared TiO₂ is found to be 86.5 m² g^?1 which is higher than that of commercially available TiO₂–P25. The photocatalytic activity of prepared anatase phase TiO₂ has been tested for the degradation of two azo dyes: Reactive Red 120 (RR 120) and Trypan Blue (TB) using solar light. The photocatalytic activity of nano-TiO₂ is higher than TiO₂–P25 under solar light. The mineralization of dyes has been confirmed by chemical oxygen demand (COD) measurements.     

Photocatalytic effect of nano-TiO<Subscript>2</Subscript> loaded cement on dye decolorization and <Emphasis Type="Italic">Escherichia coli</Emphasis> inactivation under UV irradiation

In the present study, titanium dioxide (TiO₂) nano-particles were synthesized by sol–gel technique and then used to provide nano-TiO₂ loaded cement samples at 1, 5, and 10 wt% for investigation of Malachite green pigment decomposition and Escherichia coli inactivation under UV irradiation. Surveys conducted on the synthesized TiO₂ nano-particles showed a 100 % anatase phase with a mean particle size of 66.5 nm, surface area of 64.352 m² g^?1, and a porosity volume of 0.1278 cm³ g^?1. Cement samples containing this catalyst exhibited stronger photocatalytic properties as compared to the same amount of pure catalyst. Considering both photocatalytic performance and cost of catalyst, 5 wt% titanium dioxide was suggested to be added to cement. By addition of 1 wt% polycarboxylic copolymer as super-plasticizer to the cement paste, the photocatalytic sample activities were reinforced so that a similar performance could be obtained at 1 wt% catalyst as compared to 5 wt% catalyst without super-plasticizer.     

Fabrication and characterization of TiO2 photocatalytic thin film prepared from peroxo titanic acid sol

A novel sol–gel technique using the PTA (peroxo titanic acid) sol as precursor for the fabrication of TiO₂ photocatalytic thin film is introduced in this paper. The peroxo titanic acid sol was synthesized from titanyl sulfate (TiOSO₄), ammonia and peroxide solution (H₂O₂). The transparent and porous TiO₂ thin film was prepared via a sol–gel technique using PTA sol and polyethylene glycol (PEG) as precursor and template, respectively. The TiO₂ thin film samples were characterized by the X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–visible spectrophotometry (UV–vis), X-ray photoelectron spectrum (XPS) and thermogravimetry and differential thermal analysis (TG-DTA) technique. The PTA sol displayed amorphous TiO₂ below 100 °C. The anatase phase formed at 200 °C to 700 °C. The crystallinity of anatase phase was improved with increasing temperature. The anatase crystals on the surface of TiO₂ film were strip-like, the size being about 100 nm in length and 40 nm in diameter. Addition of PEG to the PTA sol developed porous structures in the film and changed the size and shape of the particles. The surface of the film contained Ti, O and C elements and Na element that diffused into the film from the glass substrate. The photocatalytic performance of TiO₂ film was tested for the degradation of 10 mg/L methyl orange. The degradation of methyl orange solution reached 98.9% after irradiated for 180 min under UV light. The porous TiO₂ thin film exhibited high photocatalytic activity towards degrading methyl orange.     

Synthesis and Comparative Study of Nano-TiO2 Over Degussa P-25 in Disinfection of Water

Nanostructured TiO₂ crystals were synthesized by gel to crystalline conversion. The crystals obtained were anatase form of titania averaging in 30 nm particles with an intrinsic band gap of 3.1 eV. The photocatalytic behavior was evaluated for the bactericidal effect in water, contaminated with the indicator organism Escherichia coli. The 100% photoinactivation of E. coli was achieved within 60 min with suspended nano-TiO₂. The catalytic activity of synthesized nanosample was observed to be 2.6 times more than that of commercial TiO₂ sample referred to as Degussa P-25. The photoinactivation of E. coli was tested with irradiation source of different wavelengths to substantiate the influence of particle size and nano crystallinity on electronic band structure. The photoactivity of nano titania enhanced to 1.625 times when the source of irradiation shifted from 360 to 400 nm while Degussa P-25 showed no change.     

Preparation and photocatalytic antibacterial property of nitrogen doped TiO2 nanoparticles

Nitrogen doped TiO₂ (N-TiO₂) nanoparticles with about 30 nm in size were produced by a sol–gel method and characterized respectively by UV–vis, X-ray diffraction (XRD), Transmission electron microscopy, X-ray photoelectron spectroscopy (XPS). Their photocatalytic antibacterial properties were evaluated by the antibacterial ratio against Escherichia coli in dark and under simulated sunlight respectively. The XRD pattern showed that the doped nano-TiO₂ was mainly composed of anatase phase. The XPS spectra of the N-TiO₂ sample indicated that TiO₂ was doped by nitrogen atom. The nitrogen doping created a new N 2p state slightly above the valence band top consists of O 2p state, and this pushes up the valence band top and decreased the band gap. Which leaded to the absorption edge was red-shifted to the visible light region of UV–vis spectra of nitrogen doped nano-TiO₂ comparing with pure nano-TiO₂. The antibacterial percentage of N-TiO₂ against E. coli reached to 90 % under simulated sunlight for 2 h, which was much better than that in dark, also than that of pure nano-TiO₂. The photo-catalytic antibacterial activity was activated under visible light. The structure and integrity of cell wall and cell membrane were destructed, and even caused the bacteria death.     

硼铈共掺杂纳米TiO2光催化降解三氯杀螨醇和菊酯类农药

采用溶胶-凝胶法在钛酸丁酯水解过程引入硼酸、硝酸铈,制备具有光催化活性的硼铈共掺杂纳米二氧化钛（TiO2）,经XRD、TEM、FT-IR、UV-Vis-DRS表征晶体结构,在日光灯照射下,光催化降解三氯杀螨醇、高氟氯氰菊酯、氟戊菊酯农药。结果表明：硼铈共掺杂的TiO2只有锐钛矿型,而纯的或掺铈的TiO2有含有锐钛矿型、金红石相和少量板钛矿型,UV-Vis-DRS测定结果表明硼铈共掺杂的TiO2禁带宽度变小,硼铈共掺杂的TiO2在可见光区吸光度高于掺杂铈和不掺杂的TiO2,在420nm~850nm有强的吸收;在同样光照下对三氯杀螨醇、高氟氯氰菊酯、氟戊菊酯的降解试验证明硼铈共掺杂纳米TiO2的光催化活性高于不掺杂或只掺杂铈的TiO2。     

CO2在纳米SiO2/TiO2悬浮体系中的光催化还原

用水热法合成了氧化硅改性的具有高比表面积、高催化活性的锐钛型二氧化钛, 并在其悬浮体系中将CO₂光催化还原合成甲醇. 采用XRD, TEM, 物理吸附, UV-Vis吸收光谱和FTIR等表征手段对催化剂结构特征进行了研究. 结果表明: 添加氧化硅后, 氧化硅和二氧化钛之间形成Si—O—Ti键, 抑制了TiO₂晶粒生长, 提高了锐钛型TiO₂的比表面积, 且随着含硅量的增加, SiO₂/TiO₂的UV吸收逐步蓝移, 禁带宽度增加. 还原反应结果表明: SiO₂/TiO₂具有光催化还原活性, 且随着含硅量的增加先增加后减小, 当SiO₂质量分数为3.5%时, SiO₂/TiO₂复合催化剂反应活性最强, 5 h内甲醇产量可达到21.0 mg/L, 并有少量甲醛生成.     

Fabrication and photocatalytic property of TiO<Subscript>2</Subscript> nanofibers

TiO₂ nanofibers were prepared from tetrabutyl titanate sol precursors by using electrospun method. X-ray diffraction (XRD) and atomic force microscope (AFM) were used to characterize their crystal structure and morphology feature. The results demonstrated that TiO₂ nanofibers possessed anatase phase and the average diameter of TiO₂ nanofibers was about 150 nm. The photocatalytic property of TiO₂ nanofibers was evaluated for the photodecomposition of methyl orange solution. And TiO₂ nanofibers exhibited high photocatalytic activities with transfer efficiency about 100% after 20 min.     

Catalytic degradation of gaseous benzene by using TiO2/goethite immobilized on palygorskite: Preparation,characterization and mechanism

The nano-TiO₂/goethite/palygorskite catalysts were prepared by sol–gel method. The morphology and structure of the catalysts were analyzed by X-ray diffraction (XRD), UV–Vis reflection spectrometer, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and N₂ adsorption-desorption measurement. The results indicated that the self-made catalysts had excellent catalytic performance on gaseous benzene degradation. In the case of benzene concentration at 30 mg/m³, the degradation efficiency, over TiO₂/goethite/palygorskite composite with mass ratio of 10:5:5, reached 70.4% after 180 min 254 nm UV irradiation. The reaction mechanism and kinetics study showed that palygorskite/goethite/TiO₂ composites photocatalytic degradation benzene was mainly caused by oxidizing property of electron–holes and oxygen synergy effect.     

Enhanced photocatalytic activities of TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> nanohybrids immobilized on cement-based materials for dye degradation

Using cement-based material as a matrix for photocatalytic hybrids is an important development for the large-scale application of photocatalytic technologies. In this work, photocatalytic activity of nanosized hybrids of TiO₂/SiO₂ (nano-TiO₂–SiO₂) for degradation of some organic dyes on cementitious materials was highlighted. For this purpose, an optimal inorganic sol–gel precursor was firstly applied to prepare the composites of nano-TiO₂–SiO₂ which was characterized by XRD, SEM and UV–Vis. Then, a thin layer was successfully coated on white Portland cement (WPC) blocks using a dipping process in a nano-TiO₂–SiO₂ solution. The effect of nano-TiO₂–SiO₂-coated WPC blocks on photocatalytic decomposition of three dyes, including Malachite green oxalate (MG), Methylene blue (MB) and Methyl orange (MO) were studied under UV irradiation and monitored by chemical oxygen demand tests. The results showed an increase in photocatalytic effects which depends on the structure and pH of the applied cement.     

Synthesis and photocatalytic activity of nanocrystalline TiO2 co-doped with nitrogen and cobalt(II)

Nitrogen-modified cobalt-doped TiO₂ materials were successfully prepared via a modified sol–gel method. The structure and properties of the catalysts were characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM, ultraviolet–visible light diffuse reflectance spectra (UV–Vis DRS), N₂ adsorption–desorption isotherms, and energy-dispersive X-ray spectroscopy. The XRD patterns of the pure and co-doped TiO₂ samples indicate that the predominant phase was anatase. The average grain size obtained from TEM was approximately 10 nm. The Brunauer–Emmett–Teller analysis results indicate that the specific surface area was 77.7 m² g^?1. The UV–Vis DRS results for the co-doped sample reveal an absorption edge that had been red-shifted to 500 nm. The photocatalytic activities of the samples were evaluated through photodegradation of papermaking wastewater under UV and visible light irradiation. Compared with the cobalt-doped TiO₂ sample and Degussa P25, the 3 mol% N-doped mesoporous N/Co-TiO₂ photocatalyst exhibited the highest photocatalytic activity, which can be ascribed to the synergistic effect of the N and Co co-doping.     

Nano Pt–TiO2 for an efficient one-pot photocatalytic synthesis of quinaldines from anilines and ethanol

Nanosized platinum particles loaded on the TiO₂ nanoparticles were prepared to assess its photocatalytic activity in simple one-pot synthesis of quinaldines from anilines in ethanol using UV light. The catalyst was characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy, X-ray photoelectron spectra (XPS), Brunauer?CEmmer?CTeller surface area, atomic force microscope and diffuse reflectance spectra. XRD patterns revealed that the crystal structure of Pt?CTiO₂ resembled anatase phase of TiO₂. The UV?CVis spectra indicated an increase in absorption of visible light when compared to TiO₂. XPS analysis reveals that platinum particles are present mainly in metallic form. Furthermore, TEM analysis showed non-spherical-shaped Pt?CTiO₂ nanoparticles of the diameter 10?C30?nm. Upon irradiation in the presence of Pt?CTiO₂, aniline and oxidation products derived from ethanol undergo condensation?Ccyclization to afford quinaldines. Higher efficiency of Pt?CTiO₂ than Au?CTiO₂ in the conversion of aniline to quinaldines is due to the higher work function of Pt.     

Preparation of nanocrystalline TiO<Subscript>2</Subscript> powders for photocatalytic oxidation of phenol

Nanocrystalline TiO₂ powders in the anatase, rutile, and mixed phases prepared by hydrolysis of TiCl₄ solution were of ultrafine size (<7.2 nm) with high specific surface areas in the range 167 to 388 m²/g. In the photocatalytic degradation of phenol as model reaction, the photocatalytic properties of TiO₂ nanoparticles were evaluated by use of UV–vis absorption spectroscopy and total organic carbon (TOC) content. The synthetic mixed-phase TiO₂ powder calcined at 400 °C had higher activity than pure anatase or rutile; it degraded more than 90% phenol to CO₂ (evaluated by TOC) after irradiation with near UV light for 90 min at a catalyst loading of 0.4 g/L. The TOC results indicated that rutile TiO₂ crystallites of particle size 7.2 nm resulted in much better photocatalytic performance than particles of larger size. This result suggested that some intermediates, not determined by UV–vis absorption spectroscopy, existed in the solution after the photocatalytic process over the rutile TiO₂ photocatalysts of larger crystallite size.     

Photocatalytic Oxidation of Aniline in the Gas Phase Using Porous TiO2 Thin Films

The gas-phase photocatalytic oxidation of aniline on a new kind of porous nano-TiO₂ composite films is investigated. The composite film was prepared on glass fiber with the water glass as binders and dilute H₂SO₄ solution as solidifying reagent. The surface characters were observed by scanning electron microscope. The photocatalytic degradation of aniline on the composite films was carried out in a TiO₂/UV system. Some important factors affecting the photodegradation, such as the concentration of TiO₂, the initial concentration of aniline, and the existing water vapor, are also studied. The product of photocatalytic oxidation was detected by Fourier transform-Infrared. The partial intermediate products were absorbed on TiO₂ surface, which resulted in catalyst deactivation. But when it was irradiated under UV illumination or solar irradiation for some time, the catalyst could be reused without loss of catalytic activity. Translated from the Journal of Wuhan University (Natural Science Edition), 2005, 51(2) (in Chinese)     

Effect of amines on the peroxo-titanates and photoactivity of annealed TiO2

The aim of this study was to explore the influence of various n-propylamines (mono, di, and tri) and tert-butylamine on the properties of prepared peroxo-titanates and annealed TiO₂. Detailed structural characterization (SEM, TEM with EDX, XRD) confirmed the 2D-foil morphology of TiO₂ nanocrystals and the CHNS analysis together with XPS showed presence of carbon (under 1 wt%). The annealed TiO₂ showed excellent photocatalytic activity and up to four times higher decomposition rate constant upon UV irradiation than the P25. Favourable growth of TiO₂ crystals was observed especially when propylamine and tert-butylamine were used (as precursors for the peroxo-titanates). Increased photocatalytic efficiency of the highly crystalline nano-TiO₂ was confirmed due to high-reactive anatase facets and the morphology composed of microsheets formed by interconnected nanocrystals. The photoinduced electron transfer was confirmed via EPR spectroscopy. This synthesis’ procedure offers a novel preparation method of highly photoactive C-doped TiO₂ achieved relatively easily after annealing of lyophilized amino-peroxo-titanate.     

Cooperation among N,F and Fe in tri-doped TiO<Subscript>2</Subscript> photocatalyst

TiO₂ photocatalysts tri-doped with N, F and Fe were synthesized by a sol–gel method. The cooperation of N, F and Fe in tri-doped TiO₂ was verified by monitoring NH₃ decomposition, X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible (UV–Vis) absorption spectroscopy, and by the simulation based on the density functional theory (DFT). The results from NH₃ decomposition revealed that the cooperation of N, F and Fe broadened the optical response of TiO₂ to the visible light range and also enhanced the photocatalytic activity of TiO₂ under UV light. The reusability of the tri-doped TiO₂ sample after three cycles under UV and visible light irradiation was very good. XRD patterns and SEM and HRTEM images indicated that the tri-doped sample was nanometric anatase with a small amount of rutile with an average particle size of 18 nm. Tri-doping with N, F and Fe suppressed the phase transition from anatase to rutile and also resulted in some more lattice defects. XPS analysis showed that the N, F and Fe atoms were doped into the TiO₂ lattice. UV–Vis absorption spectra of the tri-doped TiO₂ showed that its optical absorption edge was moved up to 640 nm and its UV absorption was also enhanced. The DFT results confirmed that the cooperation of Fe 3d and N 2p orbits narrowed the band gap of TiO₂ and the F 2p orbit broadened the upper valence bands. The synergistic electron density around N, F and Fe in tri-doped TiO₂ was capable of enhancing the photochemical stability and reusability of TiO₂.     

Direct synthesis of Nd3+ doped mesoporous TiO2 and investigation of its photocatalytic performance

Nd³⁺ doped mesoporous TiO₂ samples with different molar ratio of Nd/Ti were synthesized by a sol?Cgel method. The textural and optical properties of the samples were systematical characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption?Cdesorption isotherms, Fourier transform infrared spectroscopy and UV?CVisible absorbance spectroscopy. It was revealed that Nd³⁺ doping inhibited the phase transformation from anatase to rutile after calcination, and the mesoporous structure of doped samples was still retained with the increase of Nd/Ti molar ratio. The surface area of the samples varied from 137 to 210 m²g^?1 and the average pore size of them ranged between 5.7 and 8.2?nm. The photocatalytic activities of all the samples were evaluated by degradation methyl orange (MO) in aqueous solution as a model reaction under UV light irradiation. The results showed that the doped samples demonstrated a higher photocatalytic activity than the mesoporous TiO₂, and the 3?mol% Nd³⁺ doped mesoporous TiO₂ exhibited the best photocatalytic performance. Meanwhile, a promotion effect of the H₂O₂ added was verified in the degradation of MO.     

Optimal TiO2–Graphene Oxide Nanocomposite for Photocatalytic Activity under Sunlight Condition: Synthesis,Characterization, and Kinetics

TiO₂–graphene oxide nanocomposites have been fabricated by the sol–gel technique for degradation of a typical cationic dye solution. The prepared photocatalysts were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric‐differential analyses, Brunauer–Emmett–Teller surface area measurement, and scanning and transmission electron microscopy. In addition, the photocatalytic activities of samples were evaluated by degradation of methylene blue aqueous solution under the sunlight irradiation. The change in color of solution was evaluated by the UV–vis spectroscopy, and the maximum photocatalytic decoloration (94%) was achieved within 60 min, which exceeded that of pure anatase under the same conditions. The results show that the nanocomposite containing 9.0 wt% of graphene oxide has the superior photocatalytic performance to either single‐phase anatase or other composites containing different amounts of graphene oxide. The experimental degradation data obtained from the batch tests were analyzed by a modified kinetic model, which predicted the performance with higher regression coefficients and lower relative errors. The distribution of TiO₂ nanoparticles (<20 nm) on graphene oxide sheets is proposed to be the efficient factor in the homogeneous degradation of dye which can concomitantly improve the photocatalytic activity.     

铁、铈共掺杂纳米TiO2溶胶的制备及抗菌性能

采用微波辅助胶溶工艺,在常压条件下,制备了可用于室内杀菌的铁、铈共掺杂纳米TiO₂水溶胶,通过X-射线衍射(XRD)、等离子体发射光谱(ICP)、动态光散射(DLS)、透射电镜(TEM)和X射线光电子能谱(XPS)对产物结构进行了表征,并选用白色葡萄球菌、大肠杆菌和枯草芽孢杆菌为受试菌种,分别在无光照、自然光照条件下,采用菌落计数法对水溶胶抗菌性能进行了检测。结果表明,用微波辅助胶溶工艺制备的Fe/Ce共掺杂纳米TiO₂为锐钛矿型,其平均粒径为10 nm。Fe/Ce的掺杂改性能有效提高纳米TiO₂水溶胶的抗菌性能,尤其是在自然光照条件下,Fe/Ce共掺杂纳米TiO₂溶胶在6 h内对各测试菌种的杀菌率均为95%以上,表明Fe/Ce共掺杂纳米TiO₂水溶胶具有很高的广谱杀菌性。采用透射电镜(TEM)对杀菌过程中的大肠杆菌菌体形态进行观测,探讨了Fe/Ce共掺杂纳米TiO₂水溶胶的抗菌机理。     

Synthesis of anatase TiO2 in a vinyl-containing ionic liquid and its enhanced photocatalytic activity

TiO₂ microspheres were synthesized by the sol–gel method using the ionic liquid (IL) 1-vinyl-3-propylimidazolium iodide (VPIM⁺I^?) as a reaction medium, then calcined at 500 °C. The samples were characterized by X-ray diffraction, scanning electron microscopy, and ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy. The phase of TiO₂ microspheres is anatase, and VPIM⁺I^? is able to favor the growth of anatase phase and prevents the collapse of small pores. The photocatalytic activity of TiO₂-IL was tested by degradation of 2-nitrophenol under UV light illumination. The photocatalytic activity of TiO₂-IL was higher than that of samples prepared in the reaction medium without VPIM⁺I^?.