Interfacial sol–gel processing for preparation of porous titania particles using a piezoelectric inkjet nozzle

The aim of the present work is to apply the liquid–liquid interfacial crystallization using a piezoelectric inkjet nozzle to the sol–gel processing. The instillation process was compared with the batch process to elucidate the effectiveness of the inkjet technique on the liquid–liquid interfacial sol–gel processing. The effect of frequency and water concentration in titanium tetraisopoxide (TTIP) solution on titania particle properties was investigated for sol–gel processing with a piezoelectric inkjet nozzle. Titania particles produced by each process were calcined at 500 °C. The crystal structure, morphology, pore size distribution and specific surface area of titania particles were evaluated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen physisorption measurement. The photocatalytic activity of titania particles was evaluated by the photodegradation of methylene blue solution under UVC light irradiation.     

工业钛液水热合成多孔二氧化钛

以工业钛液为原料,水热合成高活性多孔TiO2,采用XRD、SEM、粒度分布、FT - IR和比表面分析对样品进行表征,并以亚甲基蓝光催化降解体系评价其光催化活性.结果表明,随着水热时间延长,样品的晶粒尺寸逐步增大,比表面积先增大后减小,光催化活性也呈现先增大后减小趋势;随着水热温度增高,样品晶粒尺寸逐步增大,光催化活性...     

Influences of heat-treatment on the microstructure and properties of silica–titania composite aerogels

Silica–titania composite aerogels were synthesized via ambient pressure drying by using water glass and titanium tetrachloride as raw materials. The influences of heat-treatment at different temperature with different heating rate on the microstructure and properties of the composite aerogels were investigated by differential thermal analyzer, Fourier transform infrared spectrometer, X-ray diffraction, nitrogen adsorption–desorption, scanning electron microscope and transmission electron microscope analysis. The results indicate that the silica–titania composite aerogels heat-treated at 250 °C exhibited highest specific surface area, pore volume and average pore diameter. When the heat-treatment temperature was higher than 450 °C, the –CH₃ groups on the surface of silica–titania composite aerogels would transform into –OH groups gradually, and in the meantime, the composite aerogels network structure would be destroyed gradually and the crystallinity of TiO₂ would be improved with the increase of heat-treatment temperature. Particularly, heat-treatment at temperatures above 750 °C would cause serious damage to the network structure of the composite aerogels. The adsorption/photocatalytic activity experiments showed that the composite aerogels heat-treated at 550 °C exhibit highest darkroom adsorption efficiency, and the 650 °C-heat-treated samples exhibited highest efficiency for removing the Rhodamine B from water.     

Photocatalytic study of polymorphic titania synthesized by ambient condition sol process

Nanocrystalline titania of different phases were produced by ambient condition sol process with phase control originating from alterations in experimental variables. The produced titania photocatalysts were characterized by use of x-ray diffraction, BET surface area, transmission electron microscopy and related to methyl orange degradation. The results showed that the photocatalytic activity of brookite and anatase phase titania samples to be greater than that of Degussa P-25 and rutile phase titania sample. In addition, brookite, due to surface area considerations, appears to be the most photocatalytically active phase of titania.     

Solvothermal preparation of TiO2/saponite nanocomposites and photocatalytic activity

A saponite-rich clay sample from western Macedonia, Greece was used for the preparation of TiO₂–saponite nanocomposites by solvothermal reaction of a mixture of water and ethanol as the solvent, hexamethylene tetramine as the precipitant and titanium trichloride as the TiO₂ precursor. Phase composition was determined by X-ray diffraction (XRD) and particle morphology and elemental content was characterized by scanning electron microscopy and energy dispersive spectroscopy (SEM–EDS). These samples were also characterized by attenuated total reflection using Fourier transform infrared spectroscopy (ATR–FTIR). Particle-size analysis was carried out using dynamic light scattering method (DLS) and specific surface area and pore-size distribution analyses using BET N₂ adsorption–desorption isotherms. The composite photocatalysts showed a mesoporous structure with the distribution of pore diameters centered at 3.8 and at 5.7–9.8 nm, with high specific surface areas. The photocatalytic activities of titania–saponite nanocomposites in decomposing NOx gas were measured as a function of two different TiCl₃–saponite ratios. TiO₂:saponite with a mass ratio of 0.2:1 (Ti-Sap1) showed the highest photocatalytic activity because of its relatively large specific surface area and higher TiO₂ content. Both the TiO₂–saponite nanocomposites showed higher photocatalytic activity than the standard titania (Degussa P25) based on TiO₂ content because the titania was well dispersed on saponite.     

Synthesizing and Comparing the Photocatalytic Properties of High Surface Area Rutile and Anatase Titania Nanoparticles

Rutile titania nanocrystalline particles with high specific surface areas were directly prepared by thermal hydrolysis of titanium tetrachloride aqueous solution. The as-prepared rutile titania powder was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer–Emmett–Teller surface area analysis, and Fourier transform Raman and IR spectroscopies. Neither anatase nor amorphous titania could be detected in this titania powder by XRD, Raman spectroscopy, and high-resolution TEM. In the phenol degradation reaction, the rutile titania powder with an initial crystalline size of 7 nm was found to have higher photocatalytic activity than that of anatase titania with the same specific surface area. The rutile titania powders calcined at 300° and 450°C also showed a relatively high photocatalytic property. The high activity of the as-prepared rutile titania was attributed to the abundance of hydroxy groups in the powder, as was proven by thermogravimetric analysis data, which provided more active sites for the degradation reaction.     

Influence of titania content on mechanosynthesis of chlorapatite–titania composite nanopowders

The effect of titania content on mechanochemical synthesis of chlorapatite–titania composite nanopowders was studied for the first time. According to the obtained data, the phase compositions, structural features as well as morphological characteristics of the composites were influenced by the titania content. In the presence of 3–5 wt% titania, milling for 5 h resulted in the formation of chlorapatite–titania composite nanopowders. The crystallite size of the samples was around 25±1 and 23±1 nm in the presence of 3 and 5 wt% titania, respectively. With increasing the titania content to 7 wt%, no chemical reaction happened during the milling. The composite nanopowders showed high volume fraction of grain boundaries. Based on the FT-IR results, the products had high chemical purity which is very important in biomedical applications. The TEM images indicated that the composite nanopowder was composed of spheroidal particles with a mean size of around 35 nm. The proposed synthesis strategy provides a facile pathway to obtain novel chlorapatite-based composite nanopowders with high purity and optimal properties.     

Effect of hydrodynamics during sol–gel synthesis of TiO2 nanoparticles: From morphology to photocatalytic properties

In this study, the role of mixing hydrodynamics during the sol–gel synthesis of titania nanoparticles and the consequences on their photocatalytic properties were investigated. For the first time three different T-mixer geometries were tested. Alcoholic solutions of titanium tetra-isopropoxide and water were mixed in three different T-mixers with turbulence promoters and thus different mixing characteristics. The changes of nanoparticle sizes during the induction time of the sol–gel process were followed by dynamic light scattering and velocity and turbulence fields were simulated by Computational Fluid Dynamics (CFD) for the three T-mixer geometries. The results indicated that macro-mixing is crucial during the first step as it determines the nucleation rate and then the primary particle size. The micro-mixing has an influence on particle properties, especially on particle stability. Titanium dioxide nanoparticles synthesized by the sol–gel process were deposited on alumina supports. A homogeneous film of about 200 nm was deposited in all cases. Degradation of Acid Orange 7 (AO7) was used to evaluate the photocatalytic activity of TiO₂ coatings. No difference was observed between the photoactivity of synthesized TiO₂. Total mineralization of the dye occurred after 24 h irradiation.     

Effect of the status of Sm on the properties of Sm contained N doped TiO2 photocatalysts

Nitrogen-doped TiO₂ (TiO_2?xN_y) nanoparticles with and without adding Sm³⁺ were synthesized by thermohydrolysis of TiCl₃. The samples were characterized by X-ray diffraction, specific surface area determination, UV–Vis diffuse reflectance spectroscopy. The photocatalytic activity of the sample was investigated by employing the oxidative destruction of nitric oxide as a probe reaction using a flow reactor. Although the doping of Sm³⁺ in the lattice of titania was not useful to improve the photocatalytic activity, loading of samarium oxides on the surface of titania resulted in an improvement of the photocatalytic activity of the nitrogen-doped TiO₂. The beneficial effect was explained by an increased separation efficiency of the photogenerated electron–hole pairs.     

Photocatalytic performance of highly transparent and mesoporous molybdenum-doped titania films fabricated by templating cellulose nanocrystals

In this paper, the synthesis of mesoporous Mo-doped titania films templated by cellulose nanocrystals (CNCs) and their photocatalytic performance are reported for the first time. The prepared titania composite precursors containing the CNCs and molybdenum chloride were spin-coated on indium tin oxide (ITO) glass substrate, followed by calcining at 400?°C for 1?h. X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscope (SEM), and UV–vis spectrometer were employed to characterize the phase composition, pore structure, morphology, and optical property of the titania films in relation to CNCs templating and Mo doping. Photocatalytic performances of the titania films were also evaluated on the photodegradation of trichloroethylene under a fluorescent light source. The Mo-doped titania films with CNCs templating were highly transparent and mesoporous, exhibiting only anatase phase, high specific surface areas ranging in 135.4 – 149.0?m²/g, and small crystallite sizes of 9.5 – 11.1?nm. The results indicate that Mo ions were successfully doped by substituting for Ti ions in the titania lattice. The Mo doping stabilized the anatase phase and also increased the surface area of the CNCs-templated titania film while decreasing the mean pore width. Notably, the visible light absorption capacity and photocatalytic activity of the CNCs-templated titania films doped with Mo were dramatically greater than those of the pure and the CNCs-templated titania films, which is ascribed to the decreased recombination rate of photoexcited charges and the increased surface area with aids of the CNCs templating and the Mo doping.     

煅烧温度对工业钛液制备多孔二氧化钛的影响

以工业硫酸钛液为前驱体,采用水热法制备多孔二氧化钛,考察了煅烧温度对多孔二氧化钛结构和性能的影响。采用XRD、SEM、BET对样品进行表征,并以亚甲基蓝光催化降解体系评价其光催化活性。随着煅烧温度的延长多孔二氧化钛的比表面积逐渐降低,晶粒尺寸逐渐增大,光催化活性先增加后降低,其中以450℃煅烧1h所得样品催化活性最佳,1h对亚甲基蓝的降解率为80．19％,其比表面积93．3m2／g,晶粒尺寸16．48nm。     

Synthesis,analysis and characterization of ordered mesoporous TiO2/SBA-15 matrix: Effect of calcination temperature

Mesoporous TiO₂/SBA-15 matrix was prepared by the sol–gel synthesis of TiO₂ in previously prepared SBA-15 particles. Nonionic surfactant was used as liquid template and Na₂SiO₄ as SiO₂ precursor for the synthesis of mesoporous silica SBA-15 with high specific surface area. Different calcination temperature was used for the synthesis and analysis of TiO₂/SBA-15 matrix. The synthesized titania/silica composites were characterized by X-ray diffraction, FTIR, TEM, UV–vis spectroscopy, etc. TEM micrographs showed titania is successfully embedded in SBA-15 channel. Different calcination temperature indicates different size of particle formation and different photocatalytic properties. The activity test indicated that TiO₂/SBA-15 composite prepared by this method had better photocatalytic performance than pure TiO₂. The preparation method and the textural characteristics of mesoporous materials have great influence for the photocatalytic activity.     

TiO2粉末纳米尺寸效应对光催化性能的影响

用溶胶一凝胶法制备了TiO2纳米粉晶。对TiO2干凝胶粉进行了差热-热重(DTA/TG)分析；对不同温度处理的粉末用X射线衍射(XRD)进行了研究，并进行了比表面积测试。研究发现随着热处理温度的升高，纳米粉末的粒径逐渐增大，比表面积逐渐减小：晶型由锐钛矿变为金红石相。本实验通过光催化降解甲基橙来表征粉末的光催化活性。结果表明，TiO2纳米粉末的粒径、比表面积及晶型严重影响其光催化活性。另外，实验还发现TiO2纳米粉末对于光催化活性存在一个临界尺寸(约lOnm),当粉末的粒径小于这个临界尺寸时,其比表面积和光催化活性急剧增大。     

Solvothermal synthesis and photocatalytic activity of Al-doped BiOBr microspheres

A series of Al-doped BiOBr microspheres with different Al contents were synthesized via a facile solvothermal method. The as-prepared samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), energy dispersive spectrometry(EDS), X-ray photoelectron spectroscopy(XPS), N₂ adsorption–desorption and UV–visible diffuse reflectance spectroscopy(UV–vis DRS). The photocatalytic activity was evaluated by the photocatalytic degradation of methyl orange in an aqueous solution under visible light irradiation. The results revealed that Al doping could greatly improve photocatalytic performance of BiOBr and different Al contents resulted in different photocatalytic activities. The highest activity was achieved by 4 at%Al-BiOBr. The enhanced photocatalytic activity was attributed to efficient separation of photogenerated electron–hole pairs and large BET surface area.     

镍掺杂对二氧化钛光催化性能影响的研究

采用溶胶-凝胶法制备了纳米二氧化钛以及不同掺镍量的TiO₂纳米粒子(原料中Ni∶TiO₂的摩尔分数为1%、3%、5%、7%、9%)。用紫外光照射甲基橙溶液的光催化降解实验研究了掺镍对二氧化钛光催化剂催化效率的影响，试验结果表明,当用n（Ni）∶n（TiO₂）＝5%的Ni(NO₃)₂溶液进行镍掺杂时，制得的TiO₂催化剂光催化效率最高，但与纯TiO₂相比，镍掺杂会减弱TiO₂的光催化效率。X射线衍射分析表明，未掺杂的TiO₂以锐钛矿和金红石两种晶型混合存在，镍掺杂后TiO₂的晶型几乎全为锐钛矿。镍掺杂后会减小TiO₂粒子的尺寸，增大其比表面积。     

TiO2掺杂粉体的溶胶-凝胶和水热合成及其光降解甲醛

为了研究不同掺杂对二氧化钛光化学活性的影响,采用溶胶-凝胶,水热法,由TiOCl2成功制备了掺杂氮原子的二氧化钛样品,并制备了掺杂0.5%(摩尔分数)Fe3 ,Gu2 ,V5 ,Pd2 等金属离子的可见光响应型介孔材料.样品经由X射线衍射,透射电镜,Brunauer-Emmett-Teller(BET)比表面积,Barrett-Joyner-Halenda孔径分布,紫外可见光谱,光电子能谱和荧光光谱等表征;以荧光灯为光源(入射光波长λ≥410 nm),光催化降解甲醛为模式,评价了样品的催化活性.结果表明:掺杂Fe3 ,Cu2 ,V5 ,Pd2 的二氧化钛和单一掺氮的二氧化钛样品的粒径均为10 nm左右,BET比表面积为130 m2/g左右,均为锐钛矿相二氧化钛;Fe/TiO2,Cu/TiO2,V/TiO2,Pd/TiO2和TiO2/N样品的带隙能依次为:2.99,2.93,2.36,2.92 eV和2.87 eV,其在可见光下的光催化降解速率常数分别为:0.006 3,0.008 6,0.004 9,0.003 l/min和0.003 3/min.Cu/TiO2较高的荧光强度和较大的比表面积,导致了其较高的可见光光解活性.     

Photocatalytic degradation of methanol on titania and titania–silica aerogels prepared by non-alkoxide sol–gel route

Titania and titania–silica aerogels were prepared by alkoxide or non-alkoxide sol–gel route and subsequent supercritical drying with carbon dioxide at low temperature. The resulting aerogels having high surface area and mesoporosity were used as photocatalysts for gas phase methanol degradation reaction. Photocatalytic degradation reactions were carried out on titania and titania–silica aerogels, and commercial Degussa P-25 titania. The photocatalytic activities of titania and titania–silica aerogels were higher than that of the P-25. While the conversion of methanol degradation over the P-25 catalyst was only 50–60%, that for the titania aerogel was observed to be above 98% due to the higher specific surface area and the well developed mesoporous structure. In spite of lower titania contents, much higher surface area and high dispersion of titania of titania–silica aerogel gave rise to the high photocatalytic activity in comparison to those of titania aerogels. Moreover, titania–silica aerogel was also used for the photodegradation and adsorption hybrid system. It was observed that the high removal efficiency for methanol was caused by the combination of higher catalytic activity and adsorption capacity.     

Fine Control of Nitrogen Content in N-doped Titania Photocatalysts Prepared from Layered Titania/Isostearate Nanocomposites for High Visible-Light Photocatalytic Activity

In this contribution, high photocatalytic activity under visible-light irradiation realized by means of the fine control of the nitrogen content in doped titania photocatalysts is reported. The photocatalyst samples were prepared from a layered titania/isostearate nanocomposite as precursor, and the fine control of nitrogen content was achieved by the adjustment of the amount of hybridized isostearate in the nanocomposite, preserving the crystallinity and specific surface area of the final samples. Photocatalytic activity under the UV-light irradiation (290 and 350 nm) decreases with nitrogen content. Under visible-light irradiation (470 nm), a maximum value of photocatalytic activity was observed at [N]/[Ti] = 0.0145, whereas the absorbance in the visible-light region increases with nitrogen content. Fine control of the doped-nitrogen content provides a possible route to achieving high visible-light photocatalytic activity where the maximum value of the apparent quantum yield under 470 nm light irradiation exceeds 2%.     

Sol–gel preparation of titania multilayer membrane for photocatalytic applications

The main goal of the present study is to prepare a titania membrane with high permeability and photocatalytic activity for environmental applications. In this investigation a mesoporous titania multilayer membrane on alumina substrate is successfully fabricated via the sol–gel processing method. The prepared titania polymeric sol for the membrane top layer has an average particle size of 11.7 nm with a narrow distribution. The resulting TiO₂ multilayer membrane exhibits homogeneity with no cracks or pinholes, small pore size (4 nm), large specific surface area (83 m²/g), and small crystallite size (10.3 nm).The permeability and photocatalytic properties of the titania membrane were measured. The photoactivity of the titania membrane was examined to be 41.9% after 9 h UV irradiation based on methyl orange degradation. This measurement indicates high photocatalytic activity per unit mass of the catalyst. Through multilayer coating procedure, the photocatalytic activity of the membrane improved by 60% without sacrificing the membrane permeation. The prepared TiO₂ photocatalytic membrane has a great potential in developing high efficient water treatment and reuse systems due to its multifunctional capability such as decomposition of organic pollutants and physical separation of contaminants.     

Microwave-hydrothermal synthesis of extremely high specific surface area anatase for decomposing NOx

Apparently C-doped and undoped or pure nanoparticles of anatase were synthesized using a microwave hydrothermal process in the temperature range of 140–180 °C for 1 h from several Ti precursors, such as Ti ethoxide, Ti isopropoxide and Ti oxysulfate. Nanoparticles of anatase samples were characterized by powder X-ray diffraction, transmission electron microscopy (TEM) and photocatalytic activity measurements. Results showed that nanoparticles in the size range of 4–17 nm of anatase were obtained in all cases with surface areas in the range of 151–267 m²/g. The photocatalytic activity of the prepared titanias was measured using methylene blue (MB) and NO_x molecules. Because MB has very strong adsorption on the samples, photocatalytic degradation under either solar light or black light irradiation was found to be very limited. However, the DeNO_x abilities of carbon-doped titanias were higher than those of Degussa P25 commercial titania sample and undoped or pure titanias especially under irradiation by long wavelength or visible light (>500 nm).