Study of the synergic effect of sulphate pre-treatment and platinisation on the highly improved photocatalytic activity of TiO2

An important improvement of the photocatalytic activity of sol–gel prepared TiO₂ has been achieved by sulphate pre-treatment, calcination at high temperature and further platinisation of the samples.

The presence of sulphuric acid clearly stabilised TiO₂ surface area against sintering, maintaining at the same time anatase phase until higher calcination temperatures than in non-sulphated samples. Platinisation of the samples with different nominal amounts of platinum (from 0.5 to 2.5 wt%) was performed and the influence of sulphate treatment on the dispersion and deposit size of platinum on the TiO₂ surface was studied.

Characterisation results and photocatalytic activity of these catalysts were compared with those of unmodified TiO₂. Simultaneously sulphated and platinised TiO₂ samples were highly active for phenol degradation, used as model reaction for the photocatalytic studies, having higher activities than only platinised or only sulphated samples. The activity of these samples were several orders of magnitude higher than that of the commercial TiO₂ Degussa P25 (platinised or unmodified) as well, with independence of the nominal amount of platinum of the samples.

A wide characterisation of the samples was performed and correlations between characterisation results and activity properties are reported.     

铋及钴掺杂TiO2陶瓷负载膜的制备及光催化性能

以钛酸四丁酯为钛源,Bi(NO₃)₃·5H₂O为铋源,Co(NO₃)₂·6H₂O为钴源,采用溶胶-凝胶法在陶瓷基片上分别制备了应用于固定式光催化反应器的Bi-TiO₂复合膜及Co-TiO₂复合膜。研究了涂膜方式及煅烧升温速率对膜表面形态的影响,并以甲基橙溶液为目标降解物,对比了旋涂法及浸渍提拉法制备的薄膜在不同升温速率下的光催化活性。通过热分析仪(TG-DSC)、X射线衍射仪(XRD)和扫描电镜(SEM)等测试手段分析了掺杂薄膜的结构。结果表明,采用旋涂法制备的薄膜与陶瓷基体结合较为紧密,而浸渍提拉法制备的薄膜催化活性较高。当煅烧温度为500 ℃,升温速率为10 ℃/min时,其对甲基橙的降解率较高。当摩尔比为0.010时Bi-TiO₂复合膜的催化活性较佳,100 min光降解甲基橙比率达到8.10%。钴或铋掺杂TiO₂均可提高TiO₂催化剂的光催化活性,Bi-TiO₂膜的催化活性优于Co-TiO₂膜。     

TiO2 optical coating layers for self-cleaning applications

TiO₂ films deposited by various coating techniques were investigated for self-cleaning applications. The optical coating layers of TiO₂ films prepared from a sol–gel precursor were deposited on glass substrates using spin coating, dip coating and screen printing techniques. Effects of film deposition techniques on crystal structure, microstructure, thickness, photocatalytic activity, hydrophilicity and optical properties of the films were investigated using XRD, AFM, SEM, surface profilometer, UV–vis spectrophotometer and contact angle measurement. Dip coating the TiO₂ optical film two and three times resulted in superhydrophilic surfaces. Increasing number of dipping times was found to increase the photocatalytic activity.     

SBA-15/Ni/TiO2/CNTs复合材料的制备及其光催化性能

通过溶胶凝胶法,经多次涂覆在SBA-15上负载掺杂镍的纳米TiO₂,得到SBA-15/NiO/TiO₂复合物;再以TiO₂中还原态金属镍为催化剂,通过化学气相沉积法（CVD）,在SBA-15/NiO/TiO₂表面原位生长碳纳米管,制得SBA-15/Ni/TiO₂/CNTs复合材料。通过XRD、SEM、TEM、UV-Vis和Raman等方法考察了SBA-15/Ni/TiO₂/CNTs复合材料的结构和性能,并通过降解亚甲基蓝溶液评价其光催化活性。结果表明,SBA-15/Ni/TiO₂/CNTs复合光催化剂的催化活性较SBA-15/NiO/TiO₂显著提高。 二次涂覆掺杂镍的二氧化钛制得的复合光催化剂的催化活性高于一次涂覆。     

微米级TiO2/AC催化剂在光催化-膜分离耦合反应装置中降解酸性红B废水

采用X射线衍射分析、扫描电镜分析和傅里叶红外光谱分析对溶胶-凝胶法制得的负载型微米级TiO₂/活性炭（AC）催化剂性能进行了表征,并对其在光催化-膜分离耦合反应装置中光催化降解酸性红B废水时的性能和膜通量的影响进行了研究。结果表明：在最佳煅烧温度400℃时负载的TiO₂以锐钛矿为主,与载体活性炭之间以Ti-O-C键结合,且分布较为均匀;微米级TiO₂/AC催化剂的光催化降解性能随其煅烧温度的升高和粒径的减小而均呈现为先增加、后降低的趋势,TiO₂/AC对膜通量的影响则随煅烧温度的升高和粒径的减小而呈先降低、后增加的趋势,且TiO₂/AC粒径以10.272μm为宜。椰壳活性炭为载体的TiO₂/AC催化剂的光催的化降解性能高于褐煤活性炭为载体的,且前者对膜通量的影响更小。微米级TiO₂/AC催化剂的光催化降解性能高于商业TiO₂的,且对膜通量的影响比商业TiO₂的低。     

活性炭纤维负载Pr3+:Y2SiO5/TiO2复合材料的制备与性能

为了提高纳米TiO₂对太阳光的利用率和实现光催化剂的回收再利用,采用溶胶-凝胶法将上转换荧光材料与纳米TiO₂复合,通过负载于活性炭纤维（ACF）表面制备了Pr³⁺：Y₂SiO₅/TiO₂/ACF复合材料。运用XRD、FT-IR、SEM、FS、UV-vis DRS等对材料的结构及性能进行了综合表征,并以亚甲基蓝为模拟污染物评价复合材料的可见光催化活性,考察了材料制备过程中煅烧温度、负载次数等制备条件对复合材料可见光下催化性能的影响。结果表明,在浸渍2次、800℃煅烧的制备条件下,复合材料中TiO₂为锐钛矿相（占34.1%）与金红石相（占65.9%）的混合相,亚甲基蓝（15 mg·L^-1）12 h内去除率高达93.8%,反应符合拟一级动力学,反应速率常数为0.2471 h^-1,回收再生利用4次后去除率仍保持在75%以上。     

Synthesis of nanosized TiO2/SiO2 particles in the microemulsion and their photocatalytic activity on the decomposition of p-nitrophenol

Nanosized pure TiO₂ particles were prepared by hydrolysis of TTIP in the sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles. TiO₂/SiO₂ nanoparticles were also prepared from TEOS as a silicon source and TTIP as a titanium source. These particles were characterized by TEM, XRD, FT-IR, BET, TGA and DTA. From thermal analysis and XRD analysis, the anatase structure of pure titania appeared in the 300–600 °C calcination temperature range and the rutile structure was showed above 700 °C. However, no rutile phase was observed for the TiO₂/SiO₂ particles up to 800 °C. The crystallite size decreased and the surface area of TiO₂/SiO₂ particles monotonically increased with an increase of the silica content. From FT-IR analysis, the band for Ti–O–Si vibration was observed and the band intensity for Si–O–Si vibration increased with an increase of the silica content. The micrographs of TEM showed that the TiO₂/SiO₂ nanoparticles had a spherical and a narrow size distribution. In addition, TiO₂/SiO₂ particles showed higher photocatalytic activity than pure TiO₂ and the TiO₂/SiO₂ (90/10) particles showed the highest activity on the photocatalytic decomposition of p-nitrophenol.     

Solvothermal syntheses of semiconductor photocatalysts of ultra-high activities

Thermal treatment of titanium(IV) butoxide dissolved in 2-butanol at 573 K under autogenous pressure (alcohothermal treatment) yielded microcrystalline anatase-type titanium(IV) oxide (TiO₂). Thermal treatment of oxobis(2,4-pentanedionato-O,O′)titanium (TiO(acac)₂) in ethylene glycol (EG) in the presence of sodium acetate and a small amount of water at 573 K yielded microcrystalline brookite-type TiO₂. Tungsten(VI) oxide (WO₃) powders of monoclinic crystal structure with high crystallinity were synthesized by hydrothermal treatment (HTT), at 523 or 573 K, of aqueous tungstic acid (H₂WO₄) solutions prepared from sodium tungstate by ion-exchange (IE) with a proton-type resin. Anatase and brookite TiO₂ products were calcined at various temperatures and then used for photocatalytic mineralization of acetic acid in aqueous solutions under aerated conditions and dehydrogenation of 2-propanol under deaerated conditions. Almost all the anatase-type TiO₂ samples showed the activities more than twice higher than those of representative active photocatalysts, Degussa P-25 and Ishihara ST-01 in both reactions. A brookite sample with improved crystallinity and sufficient surface area obtained by calcination at 973 K exhibited the hydrogen evolution rate almost equal to P-25. HTT WO₃ powders with various physical properties were used as photocatalyst for evolution of oxygen (O₂) from an aqueous silver sulfate solution. WO₃ powder of high crystallinity, e.g., IE-HTT-WO₃ synthesized at 573 K, gave much higher O₂ yield than commercially available WO₃ samples.     

Effect of external bias voltage and coating thickness on the photocatalytic activity of thermal sprayed TiO2 coating

TiO₂ coatings of different thickness were prepared by a thermal spray process. It was found that the external bias applied to the as-sprayed TiO₂ coating could significantly improve its photocatalytic performance, which was characterized by decomposition of methylene blue (MB) solution. The decomposition efficiency increased with increasing external bias voltage. However, for voltage greater than 15 V, the decomposition efficiency remained constant. The TiO₂ coating with a thickness of 6 μm showed the best photocatalytic performance under an external bias voltage of 15 V.     

Syntheses of TiO2 photocatalysts by the molten salts method: Application to the photocatalytic degradation of Prosulfuron

Titania photocatalysts were synthesised by the molten salts method by reaction of a titanium precursor with three different alkali metal nitrates (LiNO₃, NaNO₃, KNO₃). The titania powders obtained have been characterised using TEM, XRD, BET and UV-Vis absorption spectroscopy. Their photoactivities were evaluated by degrading a commercial sulfonylurea herbicide, Prosulfuron^®. It has been found that the rate constants increased in the following order: Li2 prepared in KNO₃, with a rate constant 1.4 times smaller than that of P25. The effect of calcination was also studied, especially for the sample prepared in NaNO₃ (TiO₂[Na]). An improvement in photocatalytic activity was observed when TiO₂[Na] was calcined in the region of 700–800 °C. Even though the photocatalytic activities obtained did not exceed or even equal to that of Degussa P25, nevertheless, this study constitutes the first attempt to synthesise titania photocatalysts by the molten salts method.     

色氨酸辅助合成光催化活性增强的球形纳米TiO2

以L-色氨酸（L-Trp）为生物模板,采用简单水解及煅烧后制备了球形结构TiO₂纳米光催化剂。通过X射线衍射、扫描电子显微镜、红外光谱、紫外-可见漫反射光谱、光致发光光谱和N₂吸附-解吸等方法对制得的TiO₂纳米材料进行表征。在催化剂合成过程中,L-Trp作为生物模板发挥至关重要的作用,能够指导球形结构纳米TiO₂的形成。考察了不同煅烧温度下制备的TiO₂样品光催化活性,结果表明550℃时制备的TiO₂样品具有优异的光催化活性,紫外光照射30min对甲基橙溶液的降解率达到95%左右,主要是由于较大比表面积和球形结构的协同效应。光催化剂稳定性实验表明,所制备的TiO₂纳米材料可作为一种实用有效的光催化剂用于紫外光照射下降解有机染料。同时,对L-Trp辅助下球形结构TiO₂纳米颗粒的可能生长机理进行讨论。     

纳米N掺杂TiO2的制备及可见光催化活性研究

N-doped TiO2 nanoparticle photocatalysts were prepared through a sol-gel procedure using NH4C1 as the nitrogen source and followed by calcination at certain temperature. Systematic studies for the preparation parameters and their impact on the structure and photocatalytic activity under ultraviolet （UV） and visible light irra-diation were carried out. Multiple techniques （XRD, TEM, DRIF, DSC, and XPS） were commanded to characterize the crystal structures and chemical binding of N-doped TiO2. Its photocatalytic activity was examined by the deg- radation of organic compounds. The catalytic activity of the prepared N-doped TiO2 nanoparticles under visible light （λ〉400nm） irradiation is evidenced by the decomposition of 4-chlorophenol, showing that nitrogen atoms in the N-doped TiO2 nanoparticle catalyst are responsible for the visible light catalytic activity. The N-doped TiO2 nanoparticle catalyst prepared with this modified route exhibits higher catalytic activity under UV irradiation in contrast to TiO2 without N-doping. It is suggested that the doped nitrogen here is located at the interstitial site of TiO2 lattice.     

不同水解抑制剂下Sr2+掺杂改性纳米TiO2的制备及可见光响应行为

采用溶胶-凝胶法,以钛酸丁酯为钛源,分别以三乙醇胺和亚氨基二乙酸为水解抑制剂,制备掺杂不同含量Sr²⁺的纳米TiO₂,并对其在可见光范围内对孔雀石绿的光催化降解活性进行评价。结果表明,Sr²⁺掺杂能够有效提高纳米TiO₂的光催化性能,并确定不同条件下合成的纳米TiO₂的最佳掺杂量和反应条件。对掺杂的TiO₂进行紫外可见漫反射光谱、X射线衍射、傅里叶变换红外光谱以及氮物理等温吸附等表征,揭示了表面性能、电子结构、脱水性能、吸附性能、结晶程度和晶相结构等多方面协同作用是Sr²⁺掺杂的TiO₂具有最高光催化活性的原因。这种新型光催化剂可能在环境净化和水处理方面具有一定的应用价值。     

Photoresponse and AC impedance characterization of TiO2–SiO2 mixed oxide for photocatalytic water decomposition

TiO₂–SiO₂ mixed oxides were prepared by sol–gel processes with one-stage (mix up fully hydrolyzed titania- and silica-sol), two-stage (with pre-hydrolysis) and modified two-stage synthesis routes. The photoresponse and AC impedance characterization of the derived catalysts are studied and correlated for the first time with the photocatalytic activities in water decomposition under UV illumination. Synergistic effects in terms of photocatalytic activity and electronic properties including band-gap energy, flat band potential and doping density were observed on atomically mixing TiO₂ and SiO₂ by the two-stage synthesis route. Meanwhile, the decline of photocurrent density were found on TiO₂–SiO₂ relative to bare TiO₂, which could be attributed to low quality crystalline structure of the former compared to that of the latter. The superior photocatalytic performance of TiO₂–SiO₂ is ascribed to the higher flat band potential, band-gap energy, and doping density than those of bare TiO₂.     

Application of pulsed chemical vapor deposition on the SiO2-coated TiO2 production within a rotary reactor at room temperature

Pulsed chemical vapor deposition (P-CVD) is a promising technology for the surface modification of TiO₂ particles. For the scale-up application of P-CVD, a custom-designed rotary reactor and corresponding coating process at room temperature was developed in the present work. The obtained SiO₂-coated TiO₂ particles were characterized by various measures including high-resolution transmission electron microscope, Fourier transform infrared spectroscopy, X-ray diffraction, etc. The results illustrated that the SiO₂ films with a thickness of (3.7 ±0.7) nm were successfully deposited onto the surface of TiO₂ particles. According to the dye degradation tests and acid solubility measurement, the deposited film can effectively inhibit the photocatalytic activity and enhance the weatherability of the TiO₂ particles. Zeta potential measurements showed that the SiO₂-coated TiO₂ is possible to be stably dispersed in the pH range of 6.9–11.6. The coating process made the whiteness of TiO₂ particles decreased slightly but still sufficient (97.3 ±0.1) for application. Furthermore, the properties of the TiO₂ particles coated by P-CVD were compared with the particles coated by traditional wet chemical deposition. It is shown that the P-CVD can produce thinner but denser films with better photoactivity suppression performance. The developed coating process within the rotary reactor was proved practically feasible and convenient for the scale-up production of SiO₂-coated TiO₂ via P-CVD.     

Antibacterial Activity of Photocatalytic Titanium Dioxide Thin Films with Photodeposited Silver on the Surface of Sanitary Ware

The antibacterial activity of photocatalytic titanium dioxide (TiO₂) thin films with photodeposited silver on the surface of sanitary ware was studied. Samples were prepared by coating a TiO₂ sol that was calcined at 880°–980°C and photodeposited with silver ions onto the glazed layer of the sanitary ware. The relationships between the antibacterial activity and the fabrication conditions were investigated by X-ray diffractometry, scanning electron microscopy, and colorimetry. The phase of TiO₂ identified in the thin films was a mixture of anatase and rutile. The amount of rutile phase increased as the calcination temperature increased, and grain growth of the TiO₂ particles was observed. The activity was dependent on the TiO₂ thickness, the calcination temperature, and the amount of silver. These results suggest that the antibacterial activity was strongly affected by the amount of anatase in the thin films.     

Synthesis of functionalized mesoporous TiO2 molecular sieves and their application in photocatalysis

Functionalized mesoporous TiO₂ molecular sieves were prepared by treating ordered mesoporous TiO₂ with phosphoric acid or ammonium sulfate at high temperature. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption–desorption measurement, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectrometer (FT-IR). The photocatalytic activity of the samples was evaluated by photocatalytic decomposition of bromomethane (CH₃Br) in air. Results revealed that the functionalized TiO₂ samples preserved ordered mesostructure and exhibited enhanced physicochemical properties. The photocatalytic activity of the functionalized mesoporous TiO₂ sample was about three times higher than that of the pure mesoporous TiO₂. The concentrations of phosphoric acid and ammonium sulfate solutions used for the functionalization of TiO₂ greatly influenced the photocatalytic activity of the resultants materials. The optimal concentrations of phosphoric acid and ammonium sulfate solutions were 0.05 and 0.10 M, respectively. The enhanced photocatalytic performance of the functionalized mesoporous TiO₂ could be attributed to large specific surface area, high hydroxyl density, and enhanced surface chemical state.     

纳米TiO2/沸石复合材料光催化降解苯酚的性能

苯酚是一种较难处理的有毒有机污染物。本文以TiOSO₄为钛源,尿素为沉淀剂,沸石为载体,采用均匀沉淀法制备了纳米TiO₂/沸石复合材料,并以苯酚作为降解对象,研究了不同TiO₂负载量、煅烧温度以及重复使用对纳米TiO₂/沸石复合材料的光催化降解苯酚性能的影响。结果表明:TiO₂负载量为30%、煅烧晶化温度为650℃时,经300W高压汞灯照射3.5h,纳米TiO₂/沸石复合材料对20mg/L苯酚溶液的光催化降解率达到91.6%;重复使用5次仍对苯酚溶液具有85%的光催化降解率。     

The effect of Pt on the photocatalytic degradation pathway of methylene blue over TiO2 under ambient conditions

The high performance photocatalytic TiO₂ films were successfully obtained by a galvanostatic anodization of metallic titanium using the optimum anodization condition, subsequent to pre-nitridation treatment. The optimized anodization parameters on the formation of high photocatalytic TiO₂ film were investigated. The pre-nitridation treatment was performed by annealing metallic Ti under a nitrogen atmosphere of 0.1 MPa. The anodized TiO₂ film showed the high photocatalytic activities to decompose not only gaseous acetaldehyde but also tetrachloroethylene, which revealed that the anodized TiO₂ film is a possible candidate of the photocatalyst for environmental purifications comparable to the best photocatalyst of fine crystalline powder.     

Crystallization and Photoactivity of Tio2 Films Formed on Soda Lime Glass by a Sol-Gel Dip-Coating Process

Transparent nanophase TiO₂ thin films on soda lime glass were prepared from titanium tetraisopropoxide (TTIP) by a sol-gel dip-coating method. The TiO₂ films had amorphous phase up to 400°C and anatase phase at 500°C. The amorphous TiO₂ films obtained at 300-400°C showed considerable photoactivity for the degradation of formic acid. The photoactivity of the TiO₂ films was enhanced with increasing calcination temperature from 300° to 500°C. The crystallinity of the anatase films at 500°C was improved with increasing calcination time up to 2 h and reduced with a further increase in calcination time to 4 h due to the significant formation of sodium titanate phase as a result of sodium diffusion. The four-time-dipping anatase films at 500°C exhibited the greatest photoactivity at the calcination time of 2 h. Sodium diffusion into TiO₂ films was retarded by a SiO₂ underlayer of 50 nm in thickness.