Room temperature visible light oxidation of CO by high surface area rutile TiO2-supported metal photocatalyst

Visible light-active rutile TiO₂ with a high surface area of 200 m²/g was obtained by a low-temperature sol–gel synthesis, based on a long aging duration of a titania sol to stabilize the rutile phase. Decorated by an adequate amount of metallic nanoparticles, this non-doped TiO₂ displays high and stable performances for the on-stream room temperature oxidation of CO by visible light photocatalysis.     

Hydrothermal doping method for preparation of Cr-TiO2 photocatalysts with concentration gradient distribution of Cr

Cr³⁺-doped anatase titanium dioxide photocatalysts were prepared by the combination of sol–gel process with hydrothermal treatment. The samples were characterized by UV–vis diffuse reflectance spectroscopy, X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) specific surface area (S_BET), transmission electron microscopy (TEM), atomic absorption flame emission spectroscopy (AAS), electron paramagnetic resonance (EPR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was confirmed that Cr substitutes Ti⁴⁺ in TiO₂ lattice in trivalent ionic state, and the concentrations of dopants Cr³⁺ decrease from the exterior to the interior of doped TiO₂. The photocatalytic activity of Cr-TiO₂ was investigated for the photocatalytic degradation of XRG aqueous solution both under UV and visible light irradiation. Due to the excitation of 3d electron of Cr³⁺ to the conduction band of TiO₂, Cr-TiO₂ shows a good ability for absorbing the visible light to degrade XRG. Doping of chromium ions effectively improves the photocatalytic activity under both UV light irradiation and visible light irradiation with an optimal doping concentration of 0.15% and 0.2%, respectively. The special distribution of dopants Cr³⁺ seems having a good effect on enhancing the photocatalytic activity of Cr-TiO₂.     

Dye sensitized artificial photosynthesis in the gas phase over thin and thick TiO2 films under UV and visible light irradiation

Perylene diimide based organic sensitizers capable of electron generation under illumination were used to initiate gas phase photo reduction reactions on TiO₂ thin and thick film surfaces. For comparison [Ru(Bpy)₃]²⁺ dye sensitizers were also studied. The photo reduction of CO₂ was carried out under static conditions in the gas phase. TiO₂ films were coated on hollow glass beads via a sol–gel procedure. Pt was incorporated on the films either by adding the precursor salt in the sol, Pt(in), or by wet impregnation of calcined film with an aqueous solution of the precursor salt, Pt(on). Organic sensitizers were incorporated on the films by wet impregnation of the film from an aqueous solution. Under UV illumination, the methane yields of platinized TiO₂ thin films decreased in the following order: Pt(on)·TiO₂ > Pt(in)·TiO₂ > TiO₂. The presence of organic sensitizers inhibited the catalytic activity of pure and platinized TiO₂ thick films under UV illumination. The relative enhancement of the reaction yields in the presence of the organic sensitizer under visible light illumination depended on the presence of Pt as well as the incorporation method of Pt in the TiO₂ structure. The reaction yields were better when Pt was impregnated on the TiO₂ film than when Pt was incorporated in the Ti sol. On the other hand, pure or platinized TiO₂ under visible light illumination was totally inactive indicating the role of the organic dye in generating catalytically active electrons under visible light.     

Effects of Sn dopant on the photoinduced charge property and photocatalytic activity of TiO2 nanoparticles

In this paper, Sn-doped TiO₂ nanoparticles were prepared by a sol–gel method, and also were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared spectrum (IR), ultraviolet–visible diffuse reflection spectrum (UV–vis DRS), photoluminescence spectrum (PL), surface photovoltage spectroscopy (SPS) and electrical field induced surface photovoltage spectroscopy (EFISPS). The sample activity was evaluated by photocatalytic oxidation reactions of phenol solution. The effects of thermal treatment temperature and Sn amount on photoinduced charge property, mainly involving charge separation and bound excitons resulting from surface states, and photocatalytic activity of TiO₂ nanoparticles were principally investigated. The results show that an appropriate calcination temperature and Sn dopant amount can greatly enhance the SPS responses of TiO₂ nanoparticles related not only to the band–band transitions but also to the bound excitons, and obviously weaken the PL signal, while the photocatalytic activity remarkably raises. These demonstrate that the separation rate of photoinduced charges of TiO₂ nanoparticles can be effectively improved by doping Sn, which is responsible for the obvious increase in the photocatalytic activity. Moreover, the existence of bound excitons related to surface states also favor the photocatalytic activity. In addition, it can be found that the SPS responses related to the bound excitons could easily exhibit in the TiO₂ sample consisting of much of anatase and little of rutile, which is possibly ascribed to the heterojunction between the anatase and rutile phase.     

Preparation of rough anatase films and the evaluation of their photocatalytic efficiencies

Sol–gel derived rough anatase films without controlled particle sizes were prepared by surfactant templating. The coating sol–gel was obtained by hydrolysis of Ti(OC₃H₇)₄ in ethanol/HNO₃ solution. The gel films, prepared by dipping glass substrates in surfactant solutions, were dried after immersion under an atmospheric pressure. The rough films of TiO₂ anatase were obtained after calcining at 500 °C. The resultant films were transparent, semitransparent or opaque and 136–402 nm thick. It was found that the TiO₂ films prepared from the sol–gel with surfactant showed a granular nanostructure, and they were composed of regular particles, for example; between 50 and 70 nm. The roughness of the films was found to depend on the surfactant concentration in the sol–gel solution and can show a roughness between 0.82 and near of 17 nm. The photocatalytic activity of the films for the degradation and mineralization of phenol, an industrial pollutant, in water and under 365 nm irradiation was improved by the surfactant modification. Kinetic analysis of degradation and mineralization of phenol in water were employed to evaluate the different TiO₂ films under the same experimental conditions. The global photonic efficiency for degradation and mineralization of phenol ξ_g, was calculated to facilitate comparison with a TiO₂ standard photocatalyst named Degussa P-25.     

Sn掺杂TiO2/ACF复合材料的制备、表征及光催化性能

以Ti(OC₄H₉)₄为前体,SnCl₄为Sn源,采用胶溶-回流法制备了Sn掺杂的TiO₂,利用浸渍提拉法将其负载到活性炭纤维(ACF)表面,并运用SEM、XRD、XPS、DRS等手段对TiO₂/ACF复合材料进行表征,考察了复合材料光催化降解气相甲醛的性能。研究结果表明,Sn元素掺入TiO₂晶格中,有利于抑制TiO₂晶粒的生长,促进TiO₂由锐钛矿型向金红石型的转化,光吸收范围发生一定程度红移;HNO₃的用量为0.015mol、掺锡量为6%、负载两层的TiO₂/ACF-50复合材料在紫外光照射下对甲醛的去除率复合材料可达85.2%,而在可见光下仅为65.3%。     

Catalytic activation of ceramic filter elements for combined particle separation, NOx removal and VOC total oxidation

The development of a catalytically active filter element for combined particle separation and NO_x removal or VOC total oxidation, respectively, is presented. For NO_x removal by selective catalytic reduction (SCR) a catalytic coating based on a TiO₂–V₂O₅–WO₃ catalyst system was developed on a ceramic filter element. Different TiO₂ sols of tailor-made mean particle size between 40 and 190 nm were prepared by the sol–gel process and used for the impregnation of filter element cylinders by the incipient wetness technique. The obtained TiO₂-impregnated sintered filter element cylinders exhibit BET surface areas in the range between 0.5 and 1.3 m²/g. Selected TiO₂-impregnated filter element cylinders of high BET surface area were catalytically activated by impregnation with a V₂O₅ and WO₃ precursor solution. The obtained catalytic filter element cylinders show high SCR activity leading to 96% NO conversion at 300 °C, a filtration velocity of 2 cm/s and an NO inlet concentration of 500 vol.-ppm. The corresponding differential pressures fulfill the requirements for typical hot gas filtration applications. For VOC total oxidation, a TiO₂-impregnated filter element support was catalytically activated with a Pt/V₂O₅ system. Complete oxidation of propene with 100% selectivity to CO₂ was achieved at 300 °C, a filtration velocity of 2 cm/s and a propene inlet concentration of 300 vol.-ppm.     

The preparation of coupled WO3/TiO2 photocatalyst by ball milling

The coupled photocatalyst WO₃/TiO₂ is prepared by ball milling by doping WO₃ into TiO₂ and using H₂O solution as disperser. The coupled photocatalyst WO₃/TiO₂ is characterized by UV–VIS diffuse reflection spectrum, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and Transmission electron microscopy (TEM). The results show that the optimum percentage of WO₃ doped is 3% and that the photocatalytic activity of the coupled WO₃/TiO₂ photocatalyst is much higher than that of TiO₂ and WO₃–TiO₂ with no ball milling. Compared with TiO₂, the photoexcited wavelength range of the WO₃/TiO₂ photocatalyst red-shifts about 50 nm, and the light absorption intensity is also improved. The crystal phase of TiO₂ is not changed and new crystal phases are not found during the process of ball milling. WO₃ and TiO₂ coupled highly, forming the WO₃/TiO₂ photocatalyst. The increased photocatalytic activity of the coupled photocatalyst may be attributed to the enhance charge separation efficiency and the extend wavelength range of photoexcitation.     

Characterization and photocatalytic activity of N-doped TiO2 prepared by thermal decomposition of Ti–melamine complex

Nitrogen doped spherical TiO₂ has been prepared by thermal decomposition of Ti–melamine complex in air atmosphere. A clear shift in the onset light absorption from UV region (<400) to visible region (>520 nm) has been observed for the N-doped samples. It has been deduced from the optical absorption spectra that the higher calcination temperature results in the decrease in the amount of N-doping. The XRD results revealed the phase transition of TiO₂ from anatase to rutile crystalline phase, starting at calcination temperature ≥600 °C. The electron microscopic images reveal the formation of spherical and flakes of TiO₂ nanocrystals (25 nm). The chemical nature of N in the N-TiO₂ has been evolved through X-ray photoelectron spectroscopy. The presence of different types of N species have been observed corresponding to different oxidation states and the presence of Ti–N and O–Ti–N have been confirmed from the observed binding energy values. Photocatalytic decomposition of methylene blue has been carried out both in the visible region and UV + visible region. In the visible region, N-TiO₂ showed higher activity compared to the undoped commercial TiO₂ (Degussa P25).     

Photocatalytic decomposition of 4-nitrophenol on Ti-containing MCM-41

A series of Ti-containing MCM-41 samples, such as Ti-MCM-41 with variable Si/Ti ratios and Cr–Ti-substituted TiO₂-loaded MCM-41 having different TiO₂ loading, were prepared and studied for the photocatalytic decomposition of 4-nitrophenol in UV and visible light. The samples were characterized using surface area measurement, XRD, FT-IR, and UV–vis DRS techniques. In the case of the Ti-MCM-41 samples with Si/Ti ratios higher than 20 which were found to have typical mesoporous structure, the framework incorporation of Ti into MCM-41 increased with decreasing Si/Ti ratio. On the contrary, the Ti-MCM-41 with lower Si/Ti ratio (Si/Ti = 10) shows low structural integrity and the formation of Ti-oxide species, leading to a considerable decrease in surface area. In the case of Cr–Ti-substituted TiO₂-loaded MCM-41 samples, significant absorption occurs in visible light and the absorption in both UV and visible region increases with increasing TiO₂ loading. However, when the amount of TiO₂ loaded on Cr–Ti-MCM-41 increased above 33 wt.%, the absorption in visible light increased slightly. Thus, it seems that, at higher TiO₂ loading, some TiO₂ particles are not closely bound to the wall of Cr–Ti-MCM-41. The photocatalytic activities of Ti-containing MCM-41 samples were strongly influenced by the amount of Ti. Under UV illumination, the highest photocatalytic activity for photocatalytic decomposition of 4-NP was observed for the Ti-MCM-41 having Si/Ti ratio of 20. Among various Ti-containing MCM-41 materials prepared in this work, only Cr–Ti-substituted TiO₂-loaded MCM-41 catalysts exhibited discernable photocatalytic activities in visible light, and their photocatalytic activities increased considerably with increasing TiO₂ loading up to 33 wt.%. Further increase in TiO₂ loading enhanced photocatalytic activity slightly.     

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.     

Effect of sulfate ions for sol–gel synthesis of titania photocatalyst

We have found that the use of sulfuric acid in the peptization process of sol–gel method produced SO₄²⁻-incorporated TiO₂ which is mechanically strong by firing at low temperature such as 200°C. The synthesized TiO₂ has larger specific surface area and retards the phase transition from anatase to rutile compared with that prepared from the peptization with nitric acid. The S-content of the TiO₂ fired at 200°C was 1.52 wt.%; the value has a maximum of 2.74 wt.% at 400°C. The XPS measurements indicate that S exists mainly as SO₄²⁻. The TiO₂ fired at 400°C showed the highest photocatalytic activity for ethylene degradation. Especially, we would like to emphasize the TiO₂ sintered at 200°C because they are extremely hard in spite of such a low sintering temperature. This photocatalyst may provide a great opportunity for extensive applications as self-supporting membranes.     

B掺杂对负载型TiO_2光催化剂脱硝性能的影响

采用超声辅助溶胶-凝胶法制备活化半焦负载B掺杂TiO_2光催化剂,即B-TiO_2/ASC。在相同实验条件下,分别在紫外和可见光下研究其对模拟烟气的光催化氧化脱硝性能。结果表明,在紫外和可见光下,B掺杂光催化剂的活性得到提高,在可见光下的活性增加更加显著,反应180 min后仍可保持80%以上的脱硝率。结合XRD和FT-IR分析,可以看出B以取代掺杂的方式存在于TiO_2中并且导致TiO_2表面缺陷。表面缺陷有助于光生载流子的分离,从而延长光生电子的寿命并增加参与光催化反应的光生电子数量,从而产生更多的羟基自由基氧化NO,最终提高光催化脱硝率。     

Preparation of freestanding and crack-free titania–silica aerogels and their performance for gas phase, photocatalytic oxidation of VOCs

Freestanding and crack-free titania–silica aerogels with high titanium content (i.e., Ti/Si = 1) were successfully prepared by adjusting the hydrolysis of the two alkoxide precursors to a comparable rate during the sol–gel processing. Two titania–silica aerogels were prepared by ethanol and CO₂ supercritical drying methods. Well-dispersed, nanometer-sized anatase crystal domains (ca. 10 nm) were crystallized by high temperature, ethanol supercritical drying. The crystalline domains were solidly anchored to the aerogel network by Ti–O–Si bonds. Titania–silica aerogels prepared by CO₂ supercritical drying method were devoid of TiO₂ crystals. A molecular-level mixing was achieved and anatase TiO₂ was only crystallized with difficulty by high temperature calcination (1073 K). Both aerogels were mesoporous and displayed similar open pore structure that is readily accessible to reactant molecules. However, only the titania–silica aerogel with anatase TiO₂ prepared by ethanol supercritical drying was active for the gas phase, photocatalytic oxidation of volatile organic compounds (i.e., isopropanol and trichloroethylene). Catalysts prepared from Degussa P25 TiO₂ displayed lower activity under similar reaction conditions.     

Structure and photocatalytic performance of TiO2/clay nanocomposites for the degradation of dimethachlor

In the present study TiO₂/clay composites were synthesized by dispersion of TiO₂ on the surfaces of a natural montmorillonite and a synthetic hectorite in order to increase the sorption ability of TiO₂ and therefore its photocatalytic action. Six materials with different loading in TiO₂ (15, 30 and 55 wt%) were prepared and characterized by several analytical techniques including XRD, BET and SEM analysis. The synthetic procedure allows the development of delaminated layers for hectorite–TiO₂ samples, while in the case of montmorillonite–TiO₂ composites we have the formation of a more lamellar-like aggregation. It was found that, the greater the percentage of TiO₂, the greater the pore volume and the specific surface area of the montmorillonite–TiO₂ samples. On the contrary, in the case of hectorite–TiO₂ samples, as the content of TiO₂ increases, the surface area and pore volume decreases. The photocatalytic efficiency of the nanocomposite catalysts was evaluated using a chloroacetanilide herbicide (dimethachlor) in water as model compound. The primary degradation of dimethachlor followed pseudo-first-order kinetics according to the Langmuir–Hinshelwood model. All supported catalysts exhibit good photodegradation efficiency and their overall removal efficiency per mass of TiO₂ was better than that of bare TiO₂ produced by the sol–gel method. In conclusion, together with their good sedimentation ability the composite materials could be considered as a promising alternative for the removal of organic water contaminants.     

A novel preparation of high surface area TiO2 nanoparticles from alkoxide precursor and using active carbon as additive

TiO₂ nanoparticles have been prepared by a novel alkoxide sol–gel precipitation. The presence of active carbon in different percentages could act as an interesting template. Upon calcination, carbon is eliminated leaving surface features significantly different from TiO₂ prepared in the absence of carbon. Wide surface and structural characterisation of samples have been carried out. Correlations with carbon percentage is pointed out from this characterisation. Interesting spherical aggregates of nanosized TiO₂ are observed from TEM images probably stabilised by the presence of carbon. Physicochemical correlations made will be very useful in further application of these TiO₂ to be used as potential high surface area photocatalyst.     

静电纺丝制备银修饰二氧化钛纳米纤维应用于光降解亚甲基蓝

采用静电纺丝法制备银修饰二氧化钛纳米纤维,通过XRD、TEM及UV-Vis等分析其基本物性,且在UV光与泛光波照射下探讨其对亚甲基蓝溶液的光降解效果。物性分析显示银修饰二氧化钛纳米纤维呈锐钛矿与金红石并存的多晶结构,且其在400~800 nm的吸光度峰值增强约50%,表明经银修饰后二氧化钛纤维的光吸收范围大大扩展。光降解分析显示经UV照射120 min后银修饰二氧化钛纳米纤维可将MB溶液的吸光度峰值降至0,经泛光波照射120 min后亦可将MB溶液的吸光度峰值降至0.1以下,说明经银修饰后二氧化钛纤维对MB具有较好的UV与泛光波光降解效能。     

Synthesis and Antimicrobial Activity of Boron-doped Titania Nano-materlals

Antibacterial activity of boron-doped TiO2 （B/TiO2） nano-materials under visible light irradiation and in the dark was investigated. A simple sol-gel method was used to synthesize TiO2 nano-materials. X-ray diffraction pattern of B/TiO2 nano-materials represents the diffraction peaks relating to the crystal planes of TiO2 （anatase and rutile）. X-ray photoelectron spectroscopy result shows that part of boron ions incorporates into TiO2 lattice to form a possible chemical environment like Ti-O-B and the rest exist in the form of B2O3. The study on antibacterial effect of B/TiO2 nano-materials on fungal Candida albicans （ATCC10231）, Gram-negative Escherichia coli （ATCC25922） and Gram-positive Staphylococcus aureus （ATCC6538） shows that the antibacterial action is more significant on Candida albicans than on Escherichia coli and Staphylococcus aureus. Under visible light irradiation, the antibacterial activity is superior to that in the dark.     

Au/TiO2复合物的制备、表征及其增强光催化灭菌活性

为提升TiO₂光催化活性克服其可见光响应能力差的问题，采用沉积-沉淀法制备了Au/TiO₂复合物光催化剂，利用X射线衍射（XRD）、傅里叶红外光谱（FTIR）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-vis DRS）、荧光发射光谱等对样品进行了表征。XRD、FTIR和XPS结果表明，Au/TiO₂中TiO₂为锐钛矿相且Au成功沉积至TiO₂。UV-vis DRS和荧光发射光谱结果表明，适量Au修饰不仅能提高TiO₂对可见光的吸收，还可促进TiO₂光生电子-空穴对分离，有利于增强其光催化活性。自由基捕获实验证实，形成?OH的数量与光照时间成正比且?OH生成量越多，光催化活性越高。对比考察了Au/TiO₂和TiO₂在氙灯光源照射下对大肠杆菌的光催化杀灭作用，并探讨了Au负载量、光照时间、光照强度、光催化剂浓度等因素对灭菌性能的影响。结果表明：Au/TiO₂的光催化灭菌活性优于TiO₂，且与光照时间和光照强度均成正比；Au的适宜负载量为3%（质量分数）；3%Au/TiO₂在光照时间60min、光照强度7mW/cm²、光催化剂浓度100μg/mL的条件下，对大肠杆菌的杀灭效率高达91.3%。     

Fabrication and characterization of Ag–TiO2 multiphase nanocomposite thin films with enhanced photocatalytic activity

Ag–TiO₂ multiphase nanocomposite thin films were prepared on quartz substrates by the liquid phase deposition (LPD) method from a mixed aqueous solution of ammonium hexafluouotitanate, silver nitrate and boric acid under ambient temperature and atmosphere followed by calcination at 500 °C for 1 h. The grain growth of anatase was depressed upon Ag⁺ doping. However, silver ions not only promoted (or catalyzed) the formation of brookite phase but also reduced the phase transformation temperature of anatase to rutile. With increasing AgNO₃ concentration, the transmittance and band gap of the composite thin films decreased; however, the intensity of surface plasmon absorption (SPA) peaks increased and their peak position shifted to a longer wavelength range. When AgNO₃ concentration was higher than 0.03 M, the prepared samples consisted of anatase, brookite, rutile and metal silver nanocrystal particles, and their grain size ranges were 5–30 nm. The photocatalytic activity of the Ag–TiO₂ multiphase nanocrystal composite thin films prepared by this method exceeded that of pure TiO₂ thin films by a factor of more than 6.3 when AgNO₃ concentration was kept in the range of 0.03–0.05. This was attributed to the fact that there were many hetero-junctions, such as anatase/rutile, anatase/brookite, Ag/anatase, Ag/rutile and so on, existed in the Ag–TiO₂ multiphase nanocomposite films.