纳米二氧化钛的杀菌性能测试

采用新工艺制备出具有光催化性的纳米二氧化钛。为了验证其杀菌性，以工业循环冷却水中的异养菌为实验对象进行杀菌实验，结果表明：自制纳米二氧化钛具有良好的杀菌性，杀菌率可达99．2％，而且可以回收，循环使用，产品有广阔的应用前景。     

Atomically dispersed Pd on nanostructured TiO2 for NO removal by solar light

Reducing the particle size of noble metals on ceramic supports can maximize noble metal performance and minimize its use. Here Pd clusters onto nanostructured TiO₂ particles are prepared in one step by scalable flame aerosol technology while controlling the Pd cluster size from a few nanometers to that of single atoms. Annealing such materials at appropriate temperatures leads to solar photocatalytic NO_x removal in a standard ISO reactor up to 10 times faster than that of commercial TiO₂ (P25, Evonik). Such superior performance can be attained by only 0.1 wt.% Pd loading on TiO₂. Annealing these flame‐made powders in air up to 600 °C decreases the amorphous TiO₂ fraction and increases its crystal and particle sizes as observed by x‐ray diffraction (XRD) and N₂ adsorption. The growth of single Pd atoms to Pd clusters on TiO₂ prepared at different Pd loading and annealing conditions was investigated by scanning transmission electron microscopy and XRD. The single Pd atoms and clusters on TiO₂ are stable up to, at least, 600 °C for 2 h in air but at 800 °C they grow into PdO nanoparticles whose fraction is comparable with the nominal Pd loading. Hence, most of Pd atoms are on the TiO₂ surface where at 800 °C they diffuse and coalesce. Diffuse reflectance infrared Fourier transform spectroscopy reveals NO adsorption on single, double, three and fourfold coordinated Pd atoms depending on their synthesis and annealing conditions. The peak intensity of NO adsorption sites involving multiple Pd atoms is substantially lower in TiO₂ containing 0.1 wt.% than 1 wt.% Pd but that intensity from single Pd atoms is comparable. This indicates the dominance of isolated Pd atoms compared to clusters in Pd/TiO₂ containing 0.1 wt.% Pd that match or exceed the photocatalytic NO_x removal of Pd/TiO₂ of higher Pd contents. © 2016 American Institute of Chemical Engineers AIChE J, 63: 139–146, 2017     

载银TiO2薄膜制备及其光催化灭菌性能

在硫酸电解液中,用阳极氧化法在纯钛表面制备了纳米多孔TiO₂薄膜,并通过光沉积法进行了载银修饰。采用XRD、SEM对薄膜的形貌与相结构进行了表征,并考察了电流密度、电压和电解液浓度等对生成的TiO₂薄膜光催化灭菌性能的影响。结果表明：TiO₂薄膜由锐钛矿型和金红石型组成。随电压升高,金红石型的含量逐渐增多,微孔孔径增大,在电流密度为150 mA•cm^-2时,分别由120 V时的19%和93 nm增加到180 V时的96%和283 nm。电流密度的适当增大和适量的载银修饰有助于提高TiO₂薄膜光催化灭菌性能。在1 mol•L^-1硫酸溶液中,140 V/150 mA•cm^-2条件下制备的TiO₂薄膜,经3 g•L^-1硝酸银溶液中载银修饰后灭菌效果最佳。     

Preparation of nanostructured TiO2 thin films by aerosol flame deposition process

Titania thin films were prepared by using aerosol flame deposition process via the pyrolysis of titanium tetra-isopropoxide (TTIP) precursor. We analyzed the specific surface area, primary and secondary particle sizes, crystal structure, thin film morphology and thickness by BET method, electrophoretic light scattering, X-ray diffraction and scanning electron microscopy, respectively. The specific surface area of TiO₂ particles deposited is over three-times larger than that of commercial Degussa P25. Crystallite structure of TiO₂ particles can be controlled by changing the ratio of CH₄/O₂ flow rates. We could prepare TiO₂ thin films with single anatase phase by keeping the ratio of CH₄/O₂ flow rates at 200 ml/min: 1,000ml/min. As N₂ carrier gas flow rate to bubbler increases, the primary and secondary particle sizes increase, but decrease with increasing total N₂ gas flow rate through the central tube. The shorter the deposition height is, the smaller the deposition area is, but the thin film becomes thicker in the central region.     

多层纳米结构蓝色TiO2的电化学氧化性能和稳定性

蓝色TiO₂具有出色的电催化活性,被认为是降解有机污染物的最有潜力的阳极材料之一。然而蓝色TiO₂的电催化活性受表面形貌和界面性质的影响较大。本文采用冰水浴阳极氧化和阴极还原制备了由纳米颗粒、多孔层、纳米管阵列依次堆叠的多层纳米结构蓝色TiO₂,并探究了其电化学氧化性能。与无冰水浴辅助制备的相比,该方法制备的蓝色TiO₂具有更多的Ti³⁺含量、更大的活性面积和良好的电子传输能力,可有效降解亚甲基蓝（97.7%,120min,20mA/cm²）和实际废水（COD在180min内被完全去除）。自由基淬灭实验结果表明,添加Na₂SO₄能促进蓝色TiO₂产生羟基自由基和硫酸根自由基,而污染物的降解主要依赖于羟基自由基的氧化作用,硫酸根自由基仅在高Na₂SO₄浓度、低电流密度和高初始pH条件下有较大贡献。通过冰水浴阳极氧化制备的蓝色TiO₂的使用寿命是无冰水浴制备的2.4倍,表明这种多层纳米结构有利于提高蓝色TiO₂的稳定性。     

Direct synthesis of nanostructured TiO2 films with controlled morphologies by stagnation swirl flames

A novel premixed swirl flame in stagnation point geometry is used to synthesize uniform, high-quality nanostructured TiO₂ films at growth rates of 20–200 nm/s in a single step. The roles of precursor concentration and substrate temperature in controlling film morphology and characteristics are investigated. Increasing precursor concentration, for a given substrate temperature, significantly increases the packing density of the nanoporous film. The specific surface area of the film is mainly dependent on substrate temperature, where two distinct regimes, i.e. in-flame-agglomeration at low temperature and on-substrate-sintering at high temperature, specify film properties. A simplified deposition model for the formation of the nanoporous film structure is proposed, correlating penetration distance of thermophoretically-driven Brownian particles into the film with the resultant morphology. The model predicts the packing density in excellent agreement with experiments, thereby clarifying the complex roles of precursor concentration and substrate temperature. Finally, increasing substrate temperature, at fixed precursor concentration, changes the packing density little, but considerably decreases specific surface area, as sintering becomes dominant among controlling mechanisms.     

Bi@Bi4Ti3O12/TiO2 films on glass with photocatalytic and self-cleaning performance

A stable and translucent Bi@Bi₄Ti₃O₁₂/TiO₂ film was fabricated on conventional glass substrates for the first time. The film exhibited a good photocatalytic performance and efficient self-cleaning capability against organic dyes under full spectral irradiation and visible light irradiation. Bi₄Ti₃O₁₂/TiO₂ film was first prepared on a glass substrate with colloidal silica as a high temperature binder, followed by implantation of nanoscale Bi in it by an in-situ partially reduction of Bi₄Ti₃O₁₂ to generate Bi@Bi₄Ti₃O₁₂/TiO₂ films. The improved photocatalytic ability is probably attributed to the surface plasmon resonance of Bi atom as well as the enhanced electron transfer efficiency and synergistic effect of Bi₄Ti₃O₁₂ and TiO₂. According to trapping experiments, hydroxyl radicals (OH) were active species in the photocatalytic degradation of dyes under full spectral light irradiation and possible photocatalytic mechanism was proposed. The film prepared in this work may well have potential practical applications in many aspects, such as cleansing treatments for high building external decorative panels and also systematic characterization of the film suggests that the in-situ reduction is an effective and simple way to produce nanoscale Bi@Bi₄Ti₃O₁₂.     

Inclusion of low cost activated carbon for improving hydrogen production performance of TiO2 nanoparticles under natural solar light irradiation

Photocatalytic studies are primarily focused on the low cost and sustainable materials with suitable bandgap and high surface area. The ultra-fast electron-hole pair recombination and limited light absorptions affect the efficiency of photocatalyst in an adverse manner, which can be unravelled by choosing an efficient combination of photocatalysts and suitable co-catalyst/support materials. The present work explores the combination of low-cost and high potential activated carbon and TiO₂ as a nanocomposite, prepared through a one-pot hydrothermal process for hydrogen production under natural solar light irradiation. Among the synthesized photocatalysts, the one calcined at 400 °C for 2 h was found to be the best catalyst, which exhibited 3.5 times higher hydrogen production rate than the pristine TiO₂ while tested with water containing 5 vol.% glycerol. Importantly, the optimized nanocomposite was also tested for hydrogen production from simulated seawater under same conditions and it showed a hydrogen production rate of 20,383 μmol g^?1 h^?1, which is 2.4 times higher than the glycerol water solution. The enhanced hydrogen production rate is due to the reduced bandgap of AC-TiO₂ nanocomposite which offered more light absorption in the visible region compared to the pristine TiO₂. The XRD, Raman spectroscopy, TEM, and PL analysis were also examined to investigate the crystallinity, purity, morphology, and charge carrier recombination life time of the synthesized catalysts.     

玉米淀粉/TiO2纳米复合薄膜制备与性能

以玉米淀粉为基质,结合纳米Ti O₂,通过超声分散采用流延法制备了可生物降解的淀粉/Ti O₂纳米复合薄膜,研究了纳米Ti O₂对薄膜拉伸性能、阻隔性能及抗菌活性的影响,采用扫描电子显微镜(SEM)、红外光谱仪(FTIR)和X射线衍射仪(XRD)对复合膜的微观形貌和结构进行了表征。结果表明,淀粉/Ti O₂纳米复合膜中Ti O₂与淀粉分子间存在缔合作用,含适量Ti O₂的复合膜组分之间有良好的相容性,与淀粉膜相比,纳米复合膜的拉伸性能和水蒸气阻隔性能得到有效改善,含0.8%Ti O₂(质量分数,下同)的纳米复合膜拉伸强度为7.54 MPa,比淀粉膜提高了53.9%,水蒸气透过系数为5.50×10^-5 g/(mm·d),较淀粉膜降低了23.5%,该复合膜同时表现出较好的紫外线隔离性能及抗菌活性。     

One-step fabrication of N-doped TiO2 inverse opal films with visible light photocatalytic activity

N-doped TiO₂ inverse opal films were fabricated by a novel method through one-step coassembly of polymer colloidal spheres and titania precursor. This coassembly approach removed the need of preassembled colloidal crystal for precursor solution infiltration and respective chemicals for titania formation and nitrogen doping. Less crack films with well ordered inverse opal structure could be produced by adding appropriate amount of TiBALDH (titanium(IV)-bis-lactato-bis-ammonium dihydroxide) into the precursor solution. The films prepared at the optimized condition showed enhanced visible light photocatalytic activity, which could be attributed to both the N doping effect and their unique inverse opal structure.     

Enhanced performance of g-C3N4/TiO2 photocatalysts for degradation of organic pollutants under visible light☆

Photocatalytic degradation is one of the most promising remediation technologies in terms of advanced oxida-tion processes (AOPs) for water treatment. In this study, novel graphitic carbon nitride/titanium dioxide (g-C3N4/TiO2) composites were synthesized by a facile sonication method. The physicochemical properties of the photocatalyst with different mass ratios of g-C3N4 to TiO2 were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), N2 sorption, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and UV–vis DRS. The photocatalytic performances were evaluated by degradation of methylene blue. It was found that g-C3N4/TiO2 with a mass ratio of 1.5:1 exhib-ited the best degradation performance. Under UV, the degradation rate of g-C3N4/TiO2 was 6.92 and 2.65 times higher than g-C3N4 and TiO2, respectively. While under visible light, the enhancement factors became 9.27 (to g-C3N4) and 7.03 (to TiO2). The improved photocatalytic activity was ascribed to the interfacial charge transfer between g-C3N4 and TiO2. This work suggests that hybridization can produce promising solar materials for envi-ronmental remediation.     

Enhancement of the photocatalytic performance of Ag-modified TiO2 photocatalyst under visible light

A highly visible-light photocatalytic active Ag-modified TiO₂ (Ag–TiO₂) was prepared by a simple sol–gel process using TiOSO₄ as the starting material, AgNO₃ as a silver doping source, and hydrazine as a reducing agent. The prepared Ag–TiO₂ samples were characterized by several techniques such as X-ray powder diffraction (XRD), BET surface area measurement, scanning electron microscopy (SEM), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP-OES), energy dispersive X-ray spectrometry (EDX), X-ray absorption spectroscopy (XAS) and UV–vis diffuse reflectance spectroscopy (DRS). The Ag–TiO₂ photocatalyst, a mixture of amorphous and anatase phases, has a high surface area. The silver contents in the Ag–TiO₂ samples were determined by ICP measurements. The diffused reflectance UV–vis spectra indicated that the Ag–TiO₂ samples exhibited higher red shifts compared with the undoped TiO₂ sample. Indigo carmine degradation under visible irradiation indicated that the Ag–TiO₂ catalyst gave higher photocatalytic efficiency than those of commercial P25-TiO₂ and undoped-TiO₂ samples. The Ag–TiO₂ catalyst can be reused many times without any additional treatment.     

Visible light induced self-cleaning performance of iron-doped TiO2 nanoparticles for surface applications

This study aimed to enhance the visible light photosensitivity of TiO₂ nanoparticles for self-cleaning applications by doping with Fe³⁺. Nanocrystalline undoped and Fe-doped TiO₂ (Ti_1 − xFe_xO₂, x = .01–.04) were synthesized via sol–gel method. The results demonstrated that Fe-doped TiO₂ nanoparticles exhibited visible light sensitivity and self-cleaning properties. An increased Fe concentration resulted in a red shift in the absorption band edge. Fe_0.03-doped TiO₂ with an average particle size of ∼21 nm, a crystallite size of ∼12 nm, and a band gap of ∼2.86 eV showed the highest photocatalytic activity (60% methylene blue degradation) and super-hydrophilicity (water droplet contact angle 9°) under visible light radiation. These findings highlight the potential of Fe-doped TiO₂ nanoparticles as a promising material for self-cleaning applications.     

Photocatalytic performance of plasma sprayed Pt-modified TiO2 coatings under visible light irradiation

Plasma sprayed Pt/TiO₂ coatings were prepared by Atmospheric Plasma Spraying process. As-sprayed coatings were characterized by TEM, XRD and XPS. The photocatalytic performance was evaluated through the photo mineralization of methylene blue. All the Pt modified titanium dioxide coatings show significant absorption in the visible light range, while the pure titania coating reflects almost all the visible light. The photocatalytic efficiencies of as-sprayed pure TiO₂ coating and Pt/TiO₂ coatings are almost same under the irradiation of visible light. However, the efficiencies of all Pt/TiO₂ coating are greatly improved comparing with that of pure TiO₂ coating by applying 15 V external bias under the irradiation of visible light.     

Photodegradation behavior of the polycarbonate/TiO2 composite films under the UV irradiation in ambient air condition

Photocatalytic degradation mechanism of the polycarbonate(PC)/TiO₂ composite films was studied under the ambient air condition in order to investigate the feasibility of the PC/TiO₂ composite as a photodegradable polymer. TiO₂ composition in the PC/TiO₂ composite was changed from 0 wt% to 4 wt%. Photodegradation behaviors of the composite films were compared with that of the pure PC films by performing the weight loss monitoring under UV irradiation, FTIR spectroscopy, color measurement analysis, SEM, and XPS analysis. The weight loss rate of the PC/TiO₂ composite film (33% weight loss after 300 h) with 4 wt% TiO₂ was twice as high as the pure PC films (14% weight loss after 300 h). The increase in the FTIR hydroxyl peak, and carbonyl peak intensity and the yellowing observation during the photodegradation were due to the formation of the photoproducts (aliphatic, aromatic chain‐ketones, aromatic, and OH radical) and the structural modification of polycarbonate. XPS analysis of composite film showed the photodegradation of the polymer surface and TiO₂ particles exposure on the surface of the composite films matrix. POLYM. COMPOS., 36:1462–1468, 2015. © 2014 Society of Plastics Engineers     

Fabrication and deodorizing efficiency of nanostructured core-sheath TiO2 nanofibers

In this work, we report the fabrication and deodorizing efficiency of nanostructured core-sheath TiO₂ nanofibers prepared by a combined technique of electrospinning and metallization. The morphologies and crystal structures of the resultant nanofibers were investigated by emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), and wide angle X-ray diffraction (WAXD), respectively. The influence of annealing conditions, such as annealing temperature and time, various titanium isopropoxide (TTIP) weight fractions, which are based on the weight of the poly(vinyl acetate) (PVAc), on morphologies and crystal structures was evaluated for the nanostructured core-sheath TiO₂ nanofibers. UV blocking properties and deodorizing efficiency were also measured by UV-visible spectrometer and formaldehyde detector tube at room temperature, respectively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrophoretic deposition of nanostructured TiO2/alginate and TiO2-bioactive glass/alginate composite coatings on stainless steel

Abstract

Two alginate (Alg) based composite coatings on stainless steel AISI 316L substrates, one containing titania nanoparticles (n-TiO₂) and another one a mixture (50/50 wt-%) of n-TiO₂ and bioactive glass (BG), intended for biomedical applications, were developed by electrophoretic deposition (EPD) from ethanol/water suspensions. Different n-TiO₂ (2–10 g L^?1) and BG (1–5 g L^?1) contents were studied for a fixed alginate concentration (2 g L^?1), and the properties of the electrophoretically obtained coatings were characterised. Coatings with high ceramic content (up to 67 vol.-%) were obtained. The presence of BG particles improves the mechanical properties of the coatings by increasing the adhesion to the substrate and also accelerates the formation of hydroxyapatite after immersion of the coatings in simulated body fluid. The electrochemical behaviour of the coated substrates, evaluated by polarisation curves in Dulbecco’s modified eagle medium at 37°C, confirmed the corrosion protection function of the novel EPD coatings. The present polymer–ceramic composite coatings belong to an emerging family of bioactive, compliant coatings that are promising for a range of biomedical applications.     

有机玻璃基底镀TiO2/Au/TiO2膜用底涂层的制备

以溶液聚合工艺制备了数均分子量在20000左右、羟基值为40～48mgKOH/g的丙烯酸树脂,将该树脂与固化剂N-75按适宜的比例混合为底涂层,淋涂于800mm×400mm的洁净有机玻璃(PMMA)表面,在真空镀膜机中依次沉积TiO2膜和Au膜,获得了PMMA/底涂/TiO2/Au/TiO2膜。研究了不同配方的丙烯酸树脂合成工艺和混合溶剂的选择及配比对PMMA/底涂/TiO2/Au/TiO2膜性能的影响,讨论了"形变"的原因。研究发现,当乙酸丁酯和丙二醇甲醚醋酸酯以1∶1的质量比为混合溶剂,树脂和混合溶剂的质量比为1∶3时,所得涂膜具有良好的附着力。以Tego270为助剂,其质量分数为0.2%时能有效减少薄膜的"形变"缺陷。     

A unique Cu2O/TiO2 nanocomposite with enhanced photocatalytic performance under visible light irradiation

A unique Cu₂O/TiO₂ nanocomposite with high photocatalytic activity was synthesized via a two-step chemical solution method and used for the photocatalytic degradation of organic dye. The structure, morphology, composition, optical and photocatalytic properties of the as-prepared samples were investigated in detail. The results suggested that the Cu₂O/TiO₂ nanocomposite is composed of hierarchical TiO₂ hollow microstructure coated by a great many Cu₂O nanoparticles. The photocatalytic performance of Cu₂O/TiO₂ nanocomposite was evaluated by the photodegradation of methylene blue (MB) under visible light, and compared with those of the pure TiO₂ and Cu₂O photocatalysts synthesized by the identical synthetic route. Within 120 min of reaction time, nearly 100% decolorization efficiency of MB was achieved by Cu₂O/TiO₂ photocatalyst, which is much higher than that of pure TiO₂ (26%) or Cu₂O (32%). The outstanding photocatalytic efficiency was mainly ascribed to the unique architecture, the extended photoresponse range and efficient separation of the electron-hole pairs in the Cu₂O/TiO₂ heterojunction. In addition, the Cu₂O/TiO₂ nanocomposite also retains good cycling stability in the photodegradation of MB.