Photodegradation of methyl orange by BiOI-sensitized TiO2

BiOI-sensitized titanium dioxide (TiO2) photocatalysts were prepared by a deposition method at room temperature and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller surface area measurements. The photocatalytic activities of the catalysts were evaluated for the degradation of methyl orange (MO) solution under UV and visible light irradiation. The effects of catalyst amount, initial pH value, initial concentration of MO, as well as KI amount were investigated. ...     

热喷涂法制备的La3+掺杂纳米TiO2粉末的表征

采用等离子热喷涂法以钛酸四丁酯为主要原料制备出稀土离子掺杂的纳米TiO2光催化剂.通过XRD,XPS,TEM,UV-Vis等检测手段对样品进行表征,同时检测了其光催化性能,并分析了掺杂对TiO2的影响机理.结果表明,所制备的La3 掺杂纳米TiO2是锐钛矿相和金红石相混晶结构,粒径分布在10～50nm之间;La3 掺杂能够促进锐钛矿向金红石的转变,同时抑制TiO2晶粒的长大;La3 掺杂使TiO2紫外-可见吸收光谱发生红移;适量La3 掺杂能显著提高TiO2的光催化活性,最佳掺杂浓度为0.5%(与Ti原子摩尔比),甲基橙降解率在90min内可达到82.4%.比纯TiO2高出13.2%.     

Preparation and properties of a nano TiO<Subscript>2</Subscript>/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> composite superparamagnetic photocatalyst

Nano TiO₂/Fe₃O₄ composite particles with different molar ratios of TiO₂ to Fe₃O₄ were prepared via sol-gel method. X-ray diffraction, transmission electron microscopy, and vibration sample magnetometry were used to characterize the TiO₂/Fe₃O₄ particles. The photocatalytic activity of the particles was tested by degrading methyl blue solution under UV illumination (254 nm). The results indicate that with the content of TiO₂ increasing, the photocatalytic activity of the composite particles enhances, while the magnetism of the particles decreases. When the molar ratio of TiO₂ to Fe₃O₄ is about 8, both the photocatalytic activity and magnetism of the TiO₂/Fe₃O₄ particles are relatively high, and their photocatalytic activity remains well after repeated use.     

CC/PANI/TiO2复合材料的制备及其光催化性能研究

先采用原位聚合的方法在碳布上负载聚苯胺,然后利用溶剂热法在制备的碳布/聚苯胺(CC/PANI)复合材料上生长二氧化钛纳米片,得到了可便捷分离的CC/PANI/TiO₂复合光催化材料。通过SEM、XRD、UV、FTIR、XPS等手段对所制备的样品进行了形貌和结构表征,并比较了CC/PANI/TiO₂复合材料和纯TiO₂紫外-可见光条件下催化降解RhB的活性差异,结果表明CC/PANI/TiO₂复合材料具有比TiO₂更优异的光催化活性。光致发光光谱说明CC/PANI/TiO₂复合材料的发光强度比纯TiO₂的弱,有效抑制了光生载流子的复合;瞬态光电流响应和电化学阻抗谱(EIS)证明CC/PANI/TiO₂纳米复合材料更有效促进电子-空穴对分离和提高转移效率;活性物质捕捉实验证实?OH和?O_2^-是复合材料光催化降解RhB过程中的主要活性物质。CC/PANI/TiO₂复合材料循环利用6次后,仍然具有较高的催化活性,显示了其在污水处理领域中的良好应用前景。     

Fabrication of Dy2Ti2O7 nanocrystalline at 700 °C and its photocatalytic activity

Dy₂Ti₂O₇ nanocrystalline was fabricated by a soft-chemistry route named as citric acid sol–gel method (CAM). The fabricating process was monitored by XRD, FT-IR and TG-DTA methods. It was found that compared with traditional solid state reaction (SSR), Dy₂Ti₂O₇ was synthesized at a relatively low temperature (700 °C) and with shortened reaction time (2 h). The morphology and surface composition of obtained products were determined by TEM and SEM-EDX experiments. Results showed that the obtained Dy₂Ti₂O₇ with good dispersibility were all square-like; the average size was about 50 nm and there was ample oxygen-deficient (40%) on the product interfaces. Also, the obtained products had higher BET surface area (25.10 m²/g). These properties are very helpful for a catalyst to achieve excellent photocatalytic activity. Photodecomposition of methyl orange was used as the model system to evaluate its photocatalytic property. It was found that Dy₂Ti₂O₇ showed good photocatalytic activity and the decomposition rate of methyl orange was about 99% within 60 min.     

Development of UV-LED/TiO2 Device and Their Application for Photocatalytic Degradation of Methylene Blue

The determination of design and operational conditions of ultraviolet light-emitting diode (UV-LED)/TiO₂ device is the major concern for the development and potential application of the photocatalytic process. In this article, development of UV-LED/TiO₂ device and their applications for photocatalytic degradation of methylene blue (MB) are reported. The UV-LED with an output wavelength of 376 nm was applied as the UV light source for the photocatalytic decomposition of because of. The photocatalytic behavior of the photocatalytic decomposition of because of in aqueous solution operated by the UV-LED/TiO₂ device was studied under various conditions including initial dye concentration, the mass of catalyst, light power, and pH value. The decomposition of because of in aqueous solution by TiO₂ photocatalytic process with the UV-LED was found to be technically and actually feasible. Besides, our results show a promising technique for organic waste-water treatment by the UV-LED/TiO₂ method.     

~ ~ 3＋ Sol-gel synthesis and photoluminescence characterization of La2Ti2O7.EU3＋nanocrystals

Eu³⁺ doped La₂Ti₂O₇ nanocrystals with pure monoclinic phase and size of about 100 nm were prepared by a citric acid (CA) assisted sol-gel method. Techniques of thermo-gravimetric (TG) and differential scanning calorimetry (DSC), X-ray diffraction (XRD), as well as transmission electron microscopy (TEM) were employed to characterize the as-synthesized nanoparticles. Furthermore, photoluminescence (PL) performances of the Eu³⁺ doped La₂Ti₂O₇ nanocrystals were evaluated with focus on the effects of calcination temperature and Eu³⁺ doping concentration on the photoluminescence properties.     

Preparation and characterization of platinum doped porous titania nanoparticles for photocatalytic oxidation of carbon monoxide

TiO₂ samples doped with platinum oxide were obtained by using a sol-gel low temperature approach. The photocatalytic oxidation of CO in the presence of O₂ was monitored to study the influence of the Pt doping on the photocatalytic degradation performance of TiO₂. The obtained results were compared with those obtained with TiO₂ Degussa (P-25). Photocatalytic studies of the prepared mesoporous Pt/TiO₂ nanoparticles for the photooxidation of CO revealed notable photocatalytic activity, which was 3 times higher than that of Pt photodeposited onto commercial TiO₂ Degussa P-25. Also quantum yield for CO₂ formation for mesoporous Pt/TiO₂ calcined at 500 °C is higher than that of Pt photodeposited onto commercial TiO₂ Degussa P-25 by about three times. The structure and textural properties Pt/TiO₂ were studied by X-ray powder diffraction (XRD), N₂ adsorption (BET), Transmission electron microscopy (TEM) and UV.     

Effect of Nd2O3 addition on the surface phase of TiO2 and photocatalytic activity studied by UV Raman spectroscopy

TiO₂ modified with Nd₂O₃ (Nd-TiO₂) nanoparticles were prepared by a co-precipitation method and utilized as the photocatalysts for the degradation of Rhodamine B (RhB). The influence of Nd₂O₃ on the bulk and surface phase, surface area, particle size, and optical response of TiO₂ was investigated by X-ray diffraction (XRD), UV Raman spectroscopy, transmission electron microscopy (TEM), BET, and UV-visible diffuse reflectance spectra. It is found that the crystalline phase and phase composition in the bulk and surface region of Nd-TiO₂ calcined at high temperatures can be tuned by changing the amount of Nd₂O₃. Based on the results from XPS, EDX, XRD, and UV Raman spectra, it is assumed that Nd³⁺ ions do not enter the TiO₂ lattice, but highly disperse onto the Nd-TiO₂ particle surface in the form of Nd₂O₃ crystallites. These crystallites inhibit the agglomeration, growth in crystal size, and anatase-to-rutile phase transformation of TiO₂. In the photocatalytic degradation of RhB reaction, Nd-TiO₂ nanoparticles with higher surface area and wider optical response are more reactive in case of the same surface anatase phase. When the mixed phases of anatase and rutile exist in the surface region of Nd-TiO₂, the synergetic effect over surface area and optical response is the important parameter which determines optimal photocatalytic activity.     

TiO2/膨润土复合光催化材料的常温制备及性能研究

采用改进的溶胶-凝胶法,在以水为主要溶剂的反应体系中,控制钛酸四丁酯充分水解、缓慢聚合,在 常压、低温(70℃)的温和条件下制备出稳定的TiO₂纳米晶溶胶,并利用TiO₂纳米晶溶胶在膨润土表面负载,获得TiO₂/膨润土复合光催化材料。采用 X 射线衍射、扫描电镜、比表面积测定等研究手段对样品的结构形貌进行了表征,并考察了其光催化活性。结果表明：较高的水用量有利于TiO₂晶体形成,当去离子水:钛酸四丁酯摩尔比大于167:1时,在溶胶体系中出现了锐钛矿型TiO₂纳米晶体;TiO₂纳米晶主要负载于膨润土表面,并未嵌入到膨润土层间结构,但相对于单一膨润土,TiO₂负载显著提高了材料比表面积;当去离子水:钛酸四丁酯摩尔比=192:1时,在紫外光照射下,复合光催化材料表现出最高的光催化活性,对亚甲基蓝的降解率达到93.8%。     

Catalytic reduction of SO2 by CO over CeO2–TiO2 mixed oxides

The structure and catalytic desulfurization characteristics of CeO₂–TiO₂ mixed oxides were investigated by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and catalytic activity tests. According to the results, a CeO₂–TiO₂ solid solution is formed when the mole ratio of cerium to titanium n(Ce):n(Ti) is 5:5 or greater, and the most suitable n(Ce):n(Ti) is determined as 7:3, over which the conversion rate of SO₂ and the yield of sulfur at 500 °C reach 93% and 99%, respectively. According to the activity testing curve, Ce_0.7Ti_0.3O₂ (n(Ce):n(Ti)=7:3) without any pretreatment can be gradually activated by reagent gas after about 10 min, and reaches a steady activation status 60 min later. The XPS results of Ce_0.7Ti_0.3O₂ after different time of SO₂+CO reaction show that CeO₂ is the active component that offers the redox couple Ce⁴⁺/Ce³⁺ and the labile oxygen vacancies, and TiO₂ only functions as a catalyst structure stabilizer during the catalytic reaction process. After 48 h of catalytic reaction at 500 °C, Ce_0.7Ti_0.3O₂ still maintains a stable structure without being vulcanized, demonstrating its good anti-sulfur poisoning performance.     

Phase Relations in the System TiO<Subscript>2</Subscript>-V<Subscript>2</Subscript>O<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> under Oxidizing and Reducing Conditions

The target of this work was to investigate the phase development in the catalyst system consisting of TiO₂ (Anatase) and V₂O₅ (Shcherbinaite) under several gas atmospheres. Thus a set of V₂O₅/TiO₂ specimens was prepared by ball milling and exposed to subsequent annealing in air and feed gas in the temperature range from 400 to 700 °C. The XRD-results showed that the initial phases Anatase and Shcherbinaite remain stable for all atmospheres containing oxygen. In the temperature range above 525 °C the formation of a Rutile solid solution (Rutile-ss) containing VO _x species takes place. However, under reducing conditions (lower oxygen partial pressure) the reduction of V₂O₅ to V₂O₃ was found by X-ray diffraction measurements. There is no miscibility up to 1300 °C followed by the formation of V₂TiO₅ (Berdesinskiite). SEM images underline the reduction by monitoring the change in morphology with respect to the V-containing phases. TiO₂ remains without much alteration. The two phases V₂Ti₇O₁₇ and V₂Ti₃O₉ (Schreyerite) as described in mineralogy have not been observed in these experiments. The knowledge of phase relations helps to find the appropriate processing conditions and to understand the aging phenomena of catalysts.     

Structure and dielectric characterization of xNd(Mg1/2Ti1/2)O3-(1 − x)Ca0.6La0.8/3TiO3 in the microwave frequency range

The crystal structures, phase compositions and the microwave dielectric properties of the xLa(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.8Sr_0.2TiO₃ composites prepared by the conventional solid state route have been investigated. The formation of solid solution is confirmed by the XRD patterns. Doping with B₂O₃ (0.5 wt.%) can effectively promote the densification and the dielectric properties of xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. It is found that xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics can be sintered at 1375 °C, due to the liquid phase effect of B₂O₃ addition observed by Scanning Electronic Microscopy. At 1375 °C, 0.4Nd(Mg_1/2Ti_1/2)O₃-0.6Ca_0.6La_0.8/3TiO₃ ceramics with 1 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 49, a Q × f value of 13,000 (at 8 GHz) and a temperature coefficients of resonant frequency (τ_f) of 1 ppm/°C. As the content of Nd(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 20,000 GHz for x = 0.9 is achieved at the sintering temperature 1400 °C.     

Fabrication of patterned TiO2 thin film by a wet process

Hydrophobic/hydrophilic patterned TiO₂ thin film was successfully fabricated on a glass substrate by a wet process. A micro-nano complex structure with a high roughness was fabricated by a layer-by-layer selfassembly and liquid phase deposition (LPD) method. To fabricate superhydrophobic TiO₂ thin films, TiO₂ nanoparticles were deposited on the surface of (PAH/PAA) thin film by a LPD method and the surface of TiO₂ was modified by a hydrophobic treatment using fluoroalkyltrimethoxysilane. The RMS roughness and water contact angle of the prepared TiO₂ thin film were ca. 65.6 nm and ca. 155°. The superhydrophobic surface exposed to UV light changed to a hydrophilic surface by the photocatalytic property of TiO₂ to decompose a hydrophobic group. Finally, hydrophobic/hydrophilic patterned TiO₂ thin film with a 300 ??m dot size was fabricated. The surface morphology, transmittance, surface roughness and water contact angle of the prepared thin films were measured by a field emission scanning electron microscope, an atomic force microscope, a UV-Vis spectrophotometer and a contact angle meter.     

Photocatalytic performance of nano-photocatalyst from TiO2 and Fe2O3 by mechanochemical synthesis

Nano-particles of homogeneous solid solution between TiO₂ and Fe₂O₃ (up to 10 mol%) have been prepared by mechanochemical milling of TiO₂ and yellow Fe₂O₃/red Fe₂O₃/precipitated Fe (OH)₃ using a planetary ball mill. Such novel solid solution cannot be prepared by conventional co-precipitation technique. A preliminary investigation of photocatalytic activity of mixed oxide (TiO₂/Fe₂O₃) on photo-oxidation of different organic dyes like Rhodamine B (RB), Methyl orange (MO), Thymol blue (TB) and Bromocresol green (BG) under visible light (300-W Xe lamp; λ > 420 nm) showed that TiO₂ having 5 mol% of Fe₂O₃ (YFT1) is 3-5 times higher photoactive than that of P25 TiO₂. The XRD result did not show the peaks assigned to the Fe components (for example Fe₂O₃, Fe₃O₄, FeO₃, and Fe metal) on the external surface of the anatase structure in the Fe₂O₃/TiO₂ attained through mechanochemical treatment. This meant that Fe components were well incorporated into the TiO₂ anatase structure. The average crystallite size and particle size of YFT1 were found to be 12 nm and 30 ± 5 nm respectively measured from XRD and TEM conforming to nanodimensions. Together with the Fe component, they absorbed wavelength of above 387 nm. The band slightly shifted to the right without tail broadness, which was the UV absorption of Fe oxide in the Fe₂O₃/TiO₂ particle attained through mechanochemical method. This meant that Fe components were well inserted into the framework of the TiO₂ anatase structure. EPR and magnetic susceptibility show that Fe³⁺ is in low spin state corresponding to μ_B = 1.8 BM. The temperature variation of μ_B shows that Fe³⁺ is well separated from each other and does not have any antiferromagnetic or ferromagnetic interaction. The evidence of Fe³⁺ in TiO₂/Fe₂O₃ alloy is also proved by a new method that is redox titration which is again support by the XPS spectrum.     

Enhanced photocatalytic activity of TiO2 nanoparticles using WS2/g-C3N4 hybrid as co-catalyst

TiO₂/WS₂/g-C₃N₄ composite photocatalysts were synthesized by a liquid-exfoliation-solvothermal method. In this process, the WS₂/g-C₃N₄ nano-sheets were prepared by liquid-exfoliation method from the bulk WS₂ and C₃N₄ in the alcohol system, and then the TiO₂ nanoparticles (NPs) grew on the WS₂/g-C₃N₄ nano-sheets by in-situ synthesized technique. The photocatalytic activity of the as-prepared samples was evaluated by photocatalytic degradation of methyl orange (MO). The results showed that the as-prepared samples exhibited higher photocatalytic activities as compared to the pure TiO₂, g-C₃N₄ and TiO₂/g-C₃N₄ composite. The enhanced photocatalytic activities of TiO₂/WS₂/g-C₃N₄ photocatalysts could be attributed to the synergistic effect of heterostructure between TiO₂ NPs and WS₂/g-C₃N₄ nano-sheets, which could efficiently improve the separation of photogenerated electron/hole pairs and utilization efficiency of photons. The quenching tests of radicals indicated that ·O^?₂ had crucial effect on degradation of MO, which demonstrated that ·O^?₂ was the main active radical in photocatalytic reaction process.     

Mechanical Properties of Layered La<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> Thermal Barrier Coatings

Lanthanum zirconate (La₂Zr₂O₇) has been proposed as a promising thermal barrier coating (TBC) material due to its low thermal conductivity and high stability at high temperatures. In this work, both single and double-ceramic-layer (DCL) TBC systems of La₂Zr₂O₇ and 8 wt.% yttria-stabilized zirconia (8YSZ) were prepared using air plasma spray (APS) technique. The thermomechanical properties and microstructure were investigated. Thermal gradient mechanical fatigue (TGMF) tests were applied to investigate the thermal cycling performance. The results showed that DCL La₂Zr₂O₇ + 8YSZ TBC samples lasted fewer cycles compared with single-layered 8YSZ TBC samples in TGMF tests. This is because DCL La₂Zr₂O₇ TBC samples had higher residual stress during the thermal cycling process, and their fracture toughness was lower than that of 8YSZ. Bond strength test results showed that 8YSZ TBC samples had higher bond strength compared with La₂Zr₂O₇. The erosion rate of La₂Zr₂O₇ TBC samples was higher than that of 8YSZ samples, due to the lower critical erodent velocity and fracture toughness of La₂Zr₂O₇. DCL porous 8YSZ + La₂Zr₂O₇ had a lower erosion rate than other SCL and DCL La₂Zr₂O₇ coatings, suggesting that porous 8YSZ serves as a stress-relief buffer layer.     

Photocatalytic activity and kinetics for acid yellow degradation over surface composites of TiO2-coated activated carbon under different photocatalytic conditions

TiO₂-coated activated carbon surface (TAs) composites were prepared by a sol–gel method with supercritical pretreatment. The photocatalytic degradation of acid yellow (AY) was investigated under UV radiation to estimate activity of catalysts and determine the kinetics. And the effects of parameters including the initial concentration of AY, light intensity and TiO₂ content in catalysts were examined. The results indicate that TAs has a higher efficiency in decomposition of AY than P25, pure TiO₂ particles as well as the mixture of TiO₂ powder and active carbon. The photocatalytic degradation rate is found to follow the pseudo-first order kinetics with respect to the AY concentration. The new kinetic model fairly resembles the classic Langmuir-Hinshelwood equation, and the rate constant is proportional to the square root of the light intensity in a wide range. However, its absorption performance depends on the surface areas of catalysts. The model fits quite well with the experimental data and elucidates phenomena about the effects of the TiO₂ content in TAs on the degradation rate.     

SnO2@TiO2核-壳纳米线的制备及其光催化性能研究

本文通过固-液-气(VLS)生长机制,利用化学气相沉积法(CVD)制备SnO₂纳米线。利用原子层沉积(ALD)以钛酸四异丙酯为前驱体在SnO₂纳米线表面沉积不同厚度的TiO₂壳层,形成SnO₂@TiO₂核-壳纳米线结构。通过中间Al₂O₃插层,分别制备出金红石和锐钛矿两种不同晶型的TiO₂,从而制备出两种不同复合结构的SnO₂@TiO₂核-壳纳米线。实验研究该复合结构中TiO₂的厚度与晶型对紫外光下光催化降解甲基橙溶液活性的影响。     

Photocathodic protection properties of TiO2–V2O5 composite coatings

TiO₂/vanadium pentoxide (V₂O₅) and TiO₂–V₂O₅ coatings were prepared on type 304 stainless steel substrates via a sol–gel method, respectively. The TiO₂/V₂O₅ coating is compared with the TiO₂–V₂O₅ coating in terms of the photo‐electrochemical performance. The two coatings can be stored with photogenerated electrons under UV irradiation in 3 wt% aqueous NaCl. The self‐discharging time of the TiO₂/V₂O₅ coating is slower than that of the TiO₂–V₂O₅ coating. The slow discharging may be suitable for an anti‐corrosion application for stainless steel. In the case while the two coatings are electrochemically charged under UV irradiation for 1 h, the TiO₂/V₂O₅ coating can maintain a good cathodic protection for type 304 stainless steel for 6 h in the dark, while the TiO₂–V₂O₅ coating can only maintain a good cathode protection for 0.5 h in the dark.