Fabrication of ideally ordered anodic porous TiO2 by anodization of pretextured two-layered metals

Ideally ordered anodic porous TiO₂ was fabricated by anodizing an Al/Ti layered specimen. A two-layered specimen composed of an Al top layer and a Ti underlying layer was prepared and then processed by nanoimprinting. The Al top layer was easily pretextured by nanoimprinting owing to its softness and it was straightforward to introduce an ideally ordered pore arrangement by anodization. This pore arrangement was transferred to the underlying Ti layer, resulting in ideally ordered porous structures in TiO₂. This process can be applied to the high-throughput fabrication of ideally ordered anodic porous oxides other than TiO₂ and also to other metals with high hardness.     

The evolution of morphology of ordered porous TiO2 films fabricated from sol-gel method assisted ZnO nanorod template

Ordered porous TiO₂ films, including TiO₂ nanotube arrays, are fabricated by a sol-gel dip-coating approach via ZnO nanorod templates obtained from aqueous solution approach. The results indicate that the morphologies of ordered porous TiO₂ films have been great affected by the sol-gel dip-coating cycle number. Open-ended TiO₂ nanotube arrays can be obtained in optimum dip-coating cycle numbers. The TiO₂ nanotubes with the inner diameter matching well with the diameters of ZnO nanorods, are well assembled and separate each other. When the cycle number is less than this optimum value, no intact porous TiO₂ film can be obtained. As the cycle number is larger than this optimum value, an ordered porous TiO₂ film with many throughout holes is formed. The evolutive mechanism of ordered porous TiO₂ films is proposed.     

Fabrication of Ordered TiO2 Porous Thin Films by Sol-Dipping PS Template Method

Monolayer polystyrene spheres (∼400 nm) array templates were assembled orderly on clean glass substrates by dip-drawing method from emulsion of PS and porous TiO₂ thin films were prepared by using sol-dipping template method to fill TiO₂ sol into the interstices among the close-packed PS templates and then annealing to remove the PS templates. The effects of TiO₂ precursor sol concentration and dipping time in sol on the porous structure of the thin films were studied. The results showed pore size of the ordered TiO₂ porous thin film depended mainly on PS size and partly on TiO₂ sol concentration. The shrinkage of pore diameter was about 10% for 0.2 M and 20% for 0.4 M TiO₂ sol concentrations. X-ray diffraction (XRD) spectra indicated the porous thin film was anatase structure. The transmittance spectrum showed that optical transmittance of the porous thin film kept above 70% beyond the wavelength of 430 nm. Optical band-gap of the porous TiO₂ thin film (fired at 550^∘;C) was 3.12 eV.     

阳极氧化法制备TiO2多孔薄膜

本文综述了制备TiO₂薄膜的各种方法,详细介绍了阳极氧化法制备TiO₂多孔膜的进展,在非含氟电解液体系中,对纯钛进行阳极氧化处理可制得表面呈无规则生长的多孔膜结构;在含氟电解液体系中,则可自组织形成高度有序的TiO₂纳米管阵列,并指出阳极氧化法是可在常温低压下进行、操作工艺简单、薄膜性能稳定、再现性好的一种最具工业化应用潜力的制备方法。     

Template‐free Fabrication of ZnS/TiO2 Photocatalyst with Macrochannels

Constructing a porous structure in photocatalysts is an effective strategy for improving the photocatalytic activity because of its enhanced molecule transfer capability and light capturing efficiency. In this work, a hierarchical macro‐/mesoporous ZnS/TiO₂ composite with macrochannels was successfully synthesized without using templates by the simple dropwise addition of an ethanol solution of tetrabutyl titanate and zinc acetate into a sodium sulfide aqueous solution, which was then calcined at 450°C. Compared with pure TiO₂, the ordered porous ZnS/TiO₂ composite exhibited an enhanced photocatalytic activity on methylene blue removal under UV‐light irradiation. The results indicate that the macro‐/mesoporous structure, the large specific surface area, and the heterostructure combination between ZnS and TiO₂ play a synergistic effect on the enhanced photocatalytic activity via improving the light absorption and the diffusion of organic molecules, providing more reactive sites for the photocatalytic reaction and improving the separation of photogenerated electron–hole pairs, respectively. Radical trapping experiments demonstrated that holes (h⁺) and superoxide anion radicals (O₂⁻) play an important role in the photocatalytic oxidation process.     

A simple approach to porous low-temperature-sintering BaTiO3

Porous tetragonal BaTiO 3 ceramic was successfully prepared by a combination of hydrothermal and low-temperature-sintering method.The hollow TiO2@BaCO 3 as the sintering precursor was synthesized via a simple hydrothermal method,and then porous BaTiO 3 was generated by calcining the hollow TiO2@BaCO 3 precursor at 900 ℃ without additive.The hollow TiO2@BaCO 3 structure plays two important roles in the preparing of the porous BaTiO 3 ceramic.First,the TiO2@BaCO 3 hollow structure provides high surface areas and increases the contact points between BaCO 3 and TiO2,which can reduce the sintering temperature of the BaTiO 3 ceramic.Second,the cavity of the ordered arranged TiO2@BaCO 3 hollow sphere shows important influence on the porous structure,and the pore size of the as-prepared porous BaTiO 3 ceramic can be tuned from several nanometers to hundreds nanomters by changing the sintering temperature.The formation mechanism of the porous BaTiO 3 ceramic was proposed.     

CdSe electrodeposition on anodic, barrier or porous Ti oxides. A sensitization effect

A variety of oxide layers, from passive amorphous TiO_x of few nanometer thicknesses to micrometer-thick porous with different anatase to rutile ratios, were prepared by potentiostatic or galvanostatic anodization of Ti metal in H₂SO₄ and HF/H₃PO₄ solutions and used as substrates for electrodeposition of cadmium selenide from acidic selenite baths. The substrate and CdSe microstructures were investigated by X-ray diffraction and electron microscopy techniques. Barrier TiO_x and heterogeneously structured oxide substrates induced growth of zinc blend/wurtzite CdSe, whereas highly ordered porous titanium dioxide (TiO₂) accommodated growth of (10.0) oriented hexagonal CdSe thin layers. Pulsed potential plating was employed to control pore-filling during electrodeposition of CdSe. Photoelectrochemical evaluation of the produced electrodes in polysulfide cell under green light illumination implied a TiO₂ sensitization effect in the case of CdSe/(porous TiO₂)/Ti system, as evidenced by a negative shift in flat band potential and an increase in open circuit potential. The sensitization effect was observed even with CdSe deposited by a single potential pulse signifying the importance of contacting the TiO₂ surface to the electrolytic solution via a very thin layer of CdSe.     

Unique Ordered TiO2 Superstructures with Tunable Morphology and Crystalline Phase for Improved Lithium Storage Properties

Unique ordered TiO₂ superstructures with tunable morphology and crystalline phase were successfully prepared by the use of different counterions. Dumbbell‐shaped rutile TiO₂ and nanorod‐like rutile mesocrystals constructed from ultrathin nanowires, and quasi‐octahedral anatase TiO₂ mesocrystals built from tiny nanoparticle subunits were achieved. Interestingly, the obtained anatase mesocrystals have a fine microporous structure and a large surface area. The influence of the counterions in the reaction system is discussed and possible mechanisms responsible for the formation of the unique ordered TiO₂ superstructures with different morphologies and crystalline phases are also proposed based on a series of experimental results. The obtained TiO₂ superstructures were used as anode materials in lithium ion batteries, and exhibited higher capacity and improved rate performance; this is attributed to the intrinsic characteristics of the mesoscopic TiO₂ superstructures, which have a single‐crystal‐like and porous nature.     

Porous TiO2 Nanotubes with Spatially Separated Platinum and CoOx Cocatalysts Produced by Atomic Layer Deposition for Photocatalytic Hydrogen Production

Efficient separation of photogenerated electrons and holes, and associated surface reactions, is a crucial aspect of efficient semiconductor photocatalytic systems employed for photocatalytic hydrogen production. A new CoO_x/TiO₂/Pt photocatalyst produced by template‐assisted atomic layer deposition is reported for photocatalytic hydrogen production on Pt and CoO_x dual cocatalysts. Pt nanoclusters acting as electron collectors and active sites for the reduction reaction are deposited on the inner surface of porous TiO₂ nanotubes, while CoO_x nanoclusters acting as hole collectors and active sites for oxidation reaction are deposited on the outer surface of porous TiO₂ nanotubes. A CoO_x/TiO₂/Pt photocatalyst, comprising ultra‐low concentrations of noble Pt (0.046 wt %) and CoO_x (0.019 wt %) deposited simultaneously with one atomic layer deposition cycle, achieves remarkably high photocatalytic efficiency (275.9 μmol h⁻¹), which is nearly five times as high as that of pristine TiO₂ nanotubes (56.5 μmol h⁻¹). The highly dispersed Pt and CoO_x nanoclusters, porous structure of TiO₂ nanotubes with large specific surface area, and the synergetic effect of the spatially separated Pt and CoO_x dual cocatalysts contribute to the excellent photocatalytic activity.     

Preparation and properties of nanostructured TiO2 electrode by a polymer organic-medium screen-printing technique

An organic-medium screen-printing technique was developed for making porous TiO₂ electrodes. The TiO₂ pastes were prepared by mixing only 100% polyalkylene glycol and commercial nanocrystalline TiO₂ powders. The obtained paste is highly printable and hard to evaporate during printing. The TiO₂ electrodes have a very porous structure with large cavities. The dye-sensitized solar cell based on these meso-macroporous TiO₂ electrodes exhibits high overall conversion efficiency of 4.3–5.8%, which is comparable to those of prepared by water or terpineol medium.     

锐钛矿型多孔TiO2薄膜的溶解法制备及性能表征

在具有锐钛矿晶粒的TiO₂溶胶中加入苯丙乳液粒子，使用该混合液浸渍提拉涂膜，然后利用甲苯将薄膜中的苯丙乳液粒子溶解去除，并通过重复涂膜，在室温下获得了具有良好多孔性的锐钛矿型TiO₂薄膜。考察了多孔薄膜的表面形貌、光学性能、吸附性能和光催化性能。结果表明：随薄膜涂膜次数的增加，TiO₂多孔薄膜的吸光度增大，透光率减小，光吸收边波长向长波方向移动。罗丹明B在TiO₂多孔薄膜上的吸附量随涂膜次数的增加先升高，后降低；多次涂膜会在薄膜中产生半封闭的孔洞，经过长时间的毛细渗透等作用能进一步增加薄膜对罗丹明B的吸附。TiO₂多孔薄膜通过吸附+光催化氧化的模式快速分解罗丹明B，其活性主要受到薄膜在光催化反应初期的吸附能力的影响。此外，TiO₂的负载量、光的利用效率、以及光生电荷迁移及其分离等也是影响薄膜光催化活性的因素。     

Controllable Synthesis of Inverse Opal TiO2‐x Photonic Crystals and Their Photoelectric Properties

In this study, inverse opal TiO_2‐x photonic crystals (IO‐TiO_2‐x) have been successfully synthesized by a two‐step calcination. The whole synthesis is safe and feasible. Additionly, the reduction degree and the structure of IO‐TiO_2‐x can be precisely controlled. A series of IO‐TiO_2‐x samples with different reduction degree were prepared and characterized. The TEM images show that the obtained samples possess a 3D‐ordered macroporous inverse opal structure. The reduced Ti atoms/oxygen vacancies were confirmed by Raman and XPS spectroscopy. All IO‐TiO_2‐x samples showed better photoelectric properties than those of common TiO₂ which indicates their great potential to be applied to photoelectric fields. The improvement of photoelectric properties is attributed to the efficient electron‐hole separation efficiency induced by moderately reduced Ti atoms/oxygen vacancies. Meanwhile, the 3D‐ordered macroporous inverse opal structure and the band gap are regulated to “capture” more solar energy. This new approach is proven to be a meaningful method to synthesize high‐performance TiO₂ materials.     

Highly ordered combined structure of anodic TiO2 nanotubes and TiO2 nanoparticles prepared by a novel route for dye-sensitized solar cells

Combined structure of anodic TiO₂ nanotubes and TiO₂ nanoparticles (TiNTs-TiNPs) has been synthesized by a facile combination of hydrothermal and chemical vapor deposition methods. Ordered TiO₂ nanotubes with smooth walls were fabricated by two step anodization method in ethylene glycol containing NH₄F at 50 V. This nanotubular array after annealing at 450 °C was subjected to the hydrothermally produced gaseous environment in an autoclave with diluted TiCl₄ solution at its bottom. Vapors of TiCl₄ were allowed to react chemically with water vapors for predefined time durations at 180 °C that resulted in the deposition of TiO₂ nanoparticles on tubes’ surface and side walls. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirmed that for one hour reaction duration, nanoparticles were evenly coated on the walls of nanotubes, whereas, longer durations tend to deteriorate the tubular structure. Consequently, the ordered TiNTs-TiNPs array produced after one hour coating has shown better performance for dye-sensitized solar cell DSSC) in back illumination mode with 130% increase in efficiency as compared to the device based on bare TiO₂ nanotubes. The same photoanode has higher reflective properties with higher scattering ability. The solar cell based on this photoanode exhibits higher external quantum efficiency and effective charge transport properties. This study shows that porous ordered 1D structures based on TiO₂ are of crucial importance for the high performance of DSSCs.     

Enhanced photo-efficiency of immobilized TiO2 catalyst via intense anodic bias

Global environmental pollution is recognized as a serious problem that motivates the development of new technologies and mitigation of emissions from current ones. The civilian, commercial, and defense sectors of most advanced industrialized nations are facing problems related to remediation of hazardous wastes, contaminated soils and groundwater. In this communication, we describe results of a study indicating that the photo-efficiency of electrochemically grown porous TiO₂-catalyst can be dramatically enhanced by an electrochemical approach that enables the development of a highly efficient water purification system. The dramatic efficiency enhancement of this process arises from deep understanding of the nature of TiO₂-catalyst; intense and extreme electrochemical polarization would totally eliminates electron/hole pair recombination process, which is primary factor affecting photo-catalysis efficiency. Elimination of more than 99.9999% of E.coli bacteria (5–6 orders of magnitudes of inactivation) within 6 h was achieved by the use of this approach. It was found that immobilized grown porous TiO₂-catalyst can repeatedly be used, achieving extremely high efficiency, without any need for regeneration or highly advanced filtration techniques for the removal of the TiO₂ such as in the powder technology.     

Enhanced Visible‐Light‐Induced Photoelectrocatalytic Degradation of Methyl Orange by CdS Sensitized TiO2 Nanotube Arrays Electrode

In this work, CdS sensitized TiO₂ nanotube arrays (CdS/TiO₂NTs) electrode was synthesized with the CdS deposition on the highly ordered titanium dioxide nanotube arrays (TiO₂NTs) by sequential chemical bath deposition method (S‐CBD). The as‐prepared CdS/TiO₂NTs was characterized by field‐emission scanning electron microscopy (FE‐SEM) and X‐ray diffraction (XRD). The results indicated that the CdS nanoparticles were effectively deposited on the surface of TiO₂NTs. The amperometric I‐t curve on the CdS/TiO₂NTs electrode was also presented. It was found that the photocurrent density was enhanced significantly from 0.5 to 1.85 mA/cm² upon illumination with applied potential of 0.5 V at the central wavelength of 253.7 nm. The photoelectrocatalytic (PEC) activity of the CdS/TiO₂NTs electrode was investigated by degradation of methyl orange (MO) in aqueous solution. Compared with TiO₂NTs electrode, the degradation efficiencies of CdS/TiO₂NTs electrode increased from 78% to 99.2% under UV light in 2 h, and from 14% to 99.2% under visible light in 3 h, which was caused by effective separation of the electrons and holes due to the effect of CdS, hence inhibiting the recombination of electron/hole pairs of TiO₂NTs.     

A comparative study on photoelectrochemical performance of TiO2 photoanodes enhanced by different polyoxometalates

Based on the incorporation of polyoxometalates (POMs) into TiO₂ film, the photoelectrochemical performance of POMs/TiO₂ anode was elucidated by comparative investigation on the electron transport and electron–hole recombination in POMs/TiO₂ anode. The photoelectrochemical performance of the POMs/TiO₂ anode was clearly dependent on the type and content of POMs. Compared to the TiO₂ anode, the POMs/TiO₂ anode with low POMs loadings (0.75%) displayed the enhanced photoelectrochemical performance, while the excessive content (7.5%) of POMs could almost cause a negative effect. Thus, POMs could act as either “shallow electron trap” or “deep electron trap” depending on the different types and contents of POMs. This study reveals that the introduction of POMs into TiO₂ anode could facilitate photogenerated electron transfer and reduce electron–hole recombination, which is urgently desired to develop advanced composite materials of POMs/TiO₂ for application in photoelectrochemical catalysis and solar cells.     

Porous Si/TiO2 nanowire photoanode for photoelectric catalysis under simulated solar light irradiation

Porous Si/TiO₂ nanowire photoanodes were prepared by a combination of hydrothermal synthesis and metal‐assisted chemical etching. Characterization of samples was conducted using scanning electron microscopy and X‐ray diffraction, the results showing that a porous Si/TiO₂ heterojunction structure was synthesized. Diffuse reflection spectra show that the porous Si/TiO₂ nanowire photoanodes have a strong absorption. Photocurrent measurement shows that the photocurrent of the porous Si/TiO₂ nanowire photoanodes at 6 h is higher than that of others in the measuring region. The photoelectric catalysis (PEC) activities of porous Si/TiO₂ nanowire photoanodes were evaluated in degradation experiments of methylene blue under simulated solar light irradiation, and the sample at 6 h shows the highest PEC activity. Meanwhile, the PEC activity of the porous Si/TiO₂ nanowire photoanode is higher than that of the single direct photocatalysis process or electric catalysis. The mechanism of the PEC of the porous Si/TiO₂ nanowire photoanodes has been explained.     

Three-dimensionally ordered macro-porous Pt/TiO2 catalyst used for water-gas shift reaction

Three-dimensionally ordered macro-porous （3DOM） Pt/TiO2 catalysts were prepared by template and impregnation methods, and the resultant samples were characterized by using TG-DTA, XRD, SEM, TEM, and TPR techniques. The catalytic performance for water-gas shift （WGS） reaction was tested, and the influences of some conditions, such as reduction temperature of catalysts, the amount of Pt loadings and space velocity on catalytic performance were investigated. It was shown that Pt particles were homogeneously dispersed on 3DOM TiO2. The reduction of TiO2 surface was important for the catalytic performance. The activity test results showed that the 3DOM Pt/TiO2 catalysts exhibited very good catalytic performance for WGS reaction even at high space velocity, which was owing to the better mass transfer of 3DOM porous structure besides the high intrinsic activity of Pt/TiO2.     

Highly ordered nanoporous TiO2 and its photocatalytic properties

Hexagonally packed nanoporous TiO₂ has been developed by a self-templating electrochemical anodization method on titanium foil. The template is made by a two-step anodization process, where highly ordered hexagonally packed dimples are formed on titanium surface through self-organization. The template is then subjected to a third anodization process with a fast voltage ramp rate, from which a highly ordered porous structure is obtained. Such a material with an ordered structure shows enhanced photocatalytic activity as compared to titania nanotube.     

Self‐Organization of Honeycomb‐like Porous TiO2 Films by means of the Breath‐Figure Method for Surface Modification of Titanium Implants

This study describes a facile breath‐figure method for the preparation of honeycomb‐like porous TiO₂ films with an organometallic small‐molecule precursor. Multiple characterization techniques have been used to investigate the porous films and a mechanism for the formation process of porous TiO₂ films through the breath‐figure method is proposed. The pore size of the TiO₂ films could be modulated by varying the experimental parameters, such as the concentration of titanium n‐butoxide (TBT) solution, the content of cosolvent, and the air flow rate. In vitro cell‐culture experiments indicate that NIH 3T3 fibroblast cells seeded on the honeycomb‐like porous TiO₂ films show good adhesion, spreading, and proliferation behaviors, which suggests that honeycomb‐like porous TiO₂ films are an attractive biomaterial for surface modification of titanium and its alloys implants in tissue engineering to enhance their biocompatibility and bioactivity.