Hydrogenated Anatase: Strong Photocatalytic Dihydrogen Evolution without the Use of a Co‐Catalyst

The high‐pressure hydrogenation of commercially available anatase or anatase/rutile TiO₂ powder can create a photocatalyst for H₂ evolution that is highly effective and stable without the need for any additional co‐catalyst. This activation effect cannot be observed for rutile; however, for anatase/rutile mixtures, a strong synergistic effect can be found (similar to results commonly observed for noble‐metal‐decorated TiO₂). EPR and PL measurements indicated the intrinsic co‐catalytic activation of anatase TiO₂ to be due to specific defect centers formed during hydrogenation. These active centers can be observed specifically for high‐pressure hydrogenation; other common reduction treatments do not result in this effect.     

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.     

Hydrothermal Synthesis of a Crystalline Rutile TiO2 Nanorod Based Network for Efficient Dye‐Sensitized Solar Cells

One‐dimensional (1D) TiO₂ nanostructures are desirable as photoanodes in dye‐sensitized solar cells (DSSCs) due to their superior electron‐transport capability. However, making use of the DSSC performance of 1D rutile TiO₂ photoanodes remains challenging, mainly due to the small surface area and consequently low dye loading. Herein, a new type of photoanode with a three‐dimensional (3D) rutile‐nanorod‐based network structure directly grown on fluorine‐doped tin oxide (FTO) substrates was developed by using a facile two‐step hydrothermal process. The resultant photoanode possesses oriented rutile nanorod arrays for fast electron transport as the bottom layer and radially packed rutile head‐caps with an improved large surface area for efficient dye adsorption. The diffuse reflectance spectra showed that with the radially packed top layer, the light‐harvesting efficiency was increased due to an enhanced light‐scattering effect. A combination of electrochemical impedance spectroscopy (EIS), dark current, and open‐circuit voltage decay (OCVD) analyses confirmed that the electron‐recombiantion rate was reduced on formation of the nanorod‐based 3D network for fast electron transport. As a resut, a light‐to‐electricity conversion efficiency of 6.31 % was achieved with this photoanode in DSSCs, which is comparable to the best DSSC efficiencies that have been reported to date for 1D rutile TiO₂.     

Fluorine‐Doped Porous Single‐Crystal Rutile TiO2 Nanorods for Enhancing Photoelectrochemical Water Splitting

Fluorine‐doped hierarchical porous single‐crystal rutile TiO₂ nanorods have been synthesized through a silica template method, in which F^? ions acts as both n‐type dopants and capping agents to make the isotropic growth of the nanorods. The combination of high crystallinity, abundant surface reactive sites, large porosity, and improved electronic conductivity leads to an excellent photoelectrochemical activity. The photoanode made of F‐doped porous single crystals displays a remarkably enhanced solar‐to‐hydrogen conversion efficiency (≈0.35 % at ?0.33 V vs. Ag/AgCl) under 100 mW cm^?2 of AM=1.5 solar simulator illumination that is ten times of the pristine solid TiO₂ single crystals.     

掺杂二氧化锡的二氧化钛的光学性质及其光催化特性

二氧化钛多相催化是一种极具前途的环境污染深度净化技术。 本文以钛酸四丁酯和四氯化锡为原料,无水乙醇为溶剂,采用溶胶-凝胶法制备了掺杂二氧化锡的二氧化钛薄膜和复合氧化物粉体。通过测量薄膜的吸收光谱推算光学能隙,结果发现掺杂样品的光学能隙比纯二氧化钛样品有所变小。随着热处理温度的提高,掺杂和纯二氧化钛样品的光学能隙都略微降低。X-射线衍射分析表明,复合氧化物粉体的热处理温度对样品的晶体结构和光催化性能有重要影响。以掺杂二氧化锡5 % 摩尔比的样品与纯二氧化钛对照,500 ℃以下热处理样品以锐钛矿结构为主,600 ℃热处理样品为锐钛矿与金红石相共存,并显示了较好的光催化性能。透射电子显微镜观察显示,同样600 ℃热处理,掺杂样品要比纯二氧化钛具有更小的颗粒尺寸。在700 ℃热处理的样品中,掺杂样品只存在金红石相而纯二氧化钛样品中仍存有锐钛矿相。用阿伦尼乌斯经验关系式推测的晶粒生长的活化能,纯二氧化钛47.486 kJ.mol, 掺杂5 % 摩尔比的复合氧化物样品33.103 kJ.mol。以亚甲基蓝为降解物质,考察了掺杂量和热处理温度对样品的光催化性能。     

Expanding the Applications of the Ilmenite Mineral to the Preparation of Nanostructures: TiO2 Nanorods and their Photocatalytic Properties in the Degradation of Oxalic Acid

The mineral ilmenite is one of the most abundant ores in the Earth′s crust and it is the main source for the industrial production of bulk titanium oxide. At the same time, methods to convert ilmenite into nanostructures of TiO₂ (which are required for new advanced applications, such as solar cells, batteries, and photocatalysts) have not been explored to any significant extent. Herein, we describe a simple and effective method for the preparation of rutile TiO₂ nanorods from ball‐milled ilmenite. These nanorods have small dimensions (width: 5–20 nm, length: 50–100 nm, thickness: 2–5 nm) and possess large specific surface areas (up to 97 m² g^?1). Dissolution/hydrolysis/precipitation is proposed as a growth mechanism. The nanorods were found to have attractive photocatalytic properties in the degradation of oxalic acid. Their photocatalytic activity is close to that of the benchmark Degussa P25 material and better than that of a commercial high‐surface‐area rutile powder.     

The Virtue of Defects: Stable Bromine Production by Catalytic Oxidation of Hydrogen Bromide on Titanium Oxide

Rutile TiO₂ is a heavily investigated oxide with, to date, scarce applications in industrial catalysis. The inactivity of this material in oxidations has been related to its inability to dissociate molecular oxygen. Herein we show how rutile catalyzes the oxidation of HBr to Br₂ through defect states that are introduced during the reaction. The identification of active, stable, and abundant materials for bromine production is key to the future implementation of Br₂‐mediated alkane functionalization processes. The catalytic properties of TiO₂ are discussed in comparison to expensive rutile‐type oxides, such as RuO₂ and IrO₂, on the basis of surface characterization and molecular modeling.     

Exposed crystal surface-controlled TiO2 nanorods having rutile phase from TiCl3 under hydrothermal conditions

Size-, shape-, and phase structure-controlled synthesis of TiO₂ nanocrystallites has long been one of the main themes in TiO₂ research. Many synthetic techniques have been utilized in the preparation of TiO₂ nanocrystals, among which hydrothermal treatment has been drawing much attention because it directly produces well-crystallized nanocrystallities of a wide range of compositions of crystal phases within a short reaction time. In this study, we carried out hydrothermal growth of rutile TiO₂ rods by using aqueous titanium trichloride (TiCl₃) solutions containing NaCl. Uniform ultrafine rutile TiO₂ particles were obtained, and developed crystal faces were observed by TEM, SEM, XRD, and specific surface area measurements. The obtained rutile fine particles showed high levels of activity for degradation of 2-propanol and acetaldehyde under UV irradiation compared to the activity levels of anatase fine particles (ST-01) developed for environmental clean-up. The surface chemistry of the rutile TiO₂ particles was also investigated. From photodeposition of Pt and PbO₂, we suggest that the (1 1 0) face provides reductive sites and that the (1 1 1) face provides oxidative sites. These results indicate that the crystal faces facilitate the separation of electrons and holes, resulting in improvement of photocatalytic activity.     

Photocatalytic Activity of TiO2 Nanofibers with Doped La Prepared by Electrospinning Method

La‐TiO₂ nanofibers are prepared by a sol‐gel assisted electrospinning method. The structure and morphology of La‐TiO₂ nanofibers are characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). XRD analysis shows that the weight percentage of anatase and rutile in the 1.5 mol% La‐TiO₂ nanofibers calcined at 600 °C is about 8:2, which is similar to P‐25. The XRD data of La‐TiO₂ nanofibers with different La content shows that La³⁺ dopant has a great inhibition on TiO₂ phase transformation. The photocatalytic activity of the as‐prepared La‐TiO₂ nanofibers is evaluated by photocatalytic decolorization of Methylene Blue (MB) aqueous solution. The results show that the 1.5 mol% La‐TiO₂ nanofibers calcined at 600 °C exhibit high photocatalytic activity, indicating that 600 °C and 1.5 mol% are the appropriate calcination temperature and optimal molar ratio of La to Ti, respectively.     

The Critical Effect of Niobium Doping on the Formation of Mesostructured TiO2: Single‐Crystalline Ordered Mesoporous Nb‐TiO2 and Plate‐like Nb‐TiO2 with Ordered Mesoscale Dimples

Highly ordered mesoporous niobium‐doped TiO₂ with a single‐crystalline framework was prepared by using silica colloidal crystals with ca. 30 nm in diameter as templates. The preparation of colloidal crystals composed of uniform silica nanoparticles is a key to obtain highly ordered mesoporous Nb‐doped TiO₂. The XPS measurements of Nb‐doped TiO₂ showed the presence of Nb⁵⁺ and correspondingly Ti³⁺. With the increase in the amount of doped Nb, the crystalline phase of the product was converted from rutile into anatase, and the lattice spacings of both rutile and anatase phases increased. Surprisingly, the increase in the amount of Nb led to the formation of plate‐like TiO₂ with dimpled surfaces on one side, which was directly replicated from the surfaces of the colloidal silica crystals.     

Size‐ and Interface‐Modulated Metal–Insulator Transition in Solution‐Synthesized Nanoscale VO2‐TiO2‐VO2 Heterostructures

The M1 form of vanadium dioxide, which exhibits a reversible insulator–metal transition above room temperature, has been incorporated into nanoscale heterostructures through solution‐phase epitaxial growth on the tips of rutile TiO₂ nanorods. Four distinct classes of VO₂‐TiO₂‐VO₂ nanorod heterostructures are accessible by modulating the growth conditions. Each type of VO₂‐TiO₂‐VO₂ nanostructure has a different insulator–metal transition temperature that depends on the VO₂ domain sizes and the TiO₂‐VO₂ interfacial strain characteristics.     

Fabrication of nanoporous polymeric crystalline TiO2 composite for photocatalytic degradation of aqueous organic pollutants under visible light irradiation

A nanoporous polymeric crystalline TiO₂ composite (TiO₂/PDVB‐MA) has been successfully synthesized through an in situ synthesis method using divinylbenzene (DVB), methacrylic acid (MA) and tetrabutyl titanate. The experimental results showed that TiO₂ nanoparticles composed of the mixture phases of anatase and rutile were homogeneously dispersed into the PDVB‐MA support. The TiO₂/PDVB‐MA composite was used as photocatalyst for Rhodamine B (RhB), bisphenol A and 2,4,6‐trichlorophenol degradation under visible light irradiation. More interestingly, the excellent photocatalytic performance of the composite was observed with regard to RhB and bisphenol A, which might be ascribed to the synergistic effect between TiO₂ nanoparticles and PDVB‐MA. Moreover, TiO₂/PDVB‐MA composite could be recycled at least four times in the removal of RhB, suggesting that it is a promising photocatalyst to catalyze the degradation of organic pollutants under visible light irradiation.     

Synthesis of nanosized TiO2/SiO2 particles using microwave processes and their photocatalytic activity on the decomposition of orange II

The nanosized titania and TiO₂/SiO₂ particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination temperature has been investigated. The major phase of the pure TiO₂ particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO₂/SiO₂ particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO₂/SiO₂ particles decreases as compared to pure TiO₂ at high calcination temperatures. The TiO₂/SiO₂ particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO₂ particles.     

Conducting polyaniline-rutile TiO2 nanocomposites for the development of high-k dielectric materials

Inorganic dielectrics encapsulated in an organic matrix are showing excellent promise as novel dielectric materials. In this work, firstly highly organized crystalline nanoparticles of rutile TiO₂ were synthesized by acid hydrolysis of titanium isopropoxide at room temperature. Then we developed a novel dielectric material consisting of highly organized rutile TiO₂/polyaniline (PAni) nanocomposites by in-situ chemical oxidative polymerization. The structural, morphological, conducting, and dielectric properties of the rutile TiO₂/PAni nanoparticles have been evaluated by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution-transmission emission microscopy (HR-TEM), four-point probe technique, CV (Capacitance versus Voltage), and Impedance analyzer. The nanocomposites show 70 times higher permittivity compared to rutile nanoparticles and much higher compared to anatase/PAni (ES) nanocomposites at 10 MHz. Large interfacial polarizations, nanostructure, and dopant levels are the key factors for the large dielectric constant of the nanocomposites. The rutile/PAni (ES) nanocomposites might see potential uses in super-capacitors, gate dielectric in transistors, and capacitive-type gas sensors.     

Remarkable Charge Separation and Photocatalytic Efficiency Enhancement through Interconnection of TiO2 Nanoparticles by Hydrothermal Treatment

Although tremendous effort has been directed to synthesizing advanced TiO₂, it remains difficult to obtain TiO₂ exhibiting a photocatalytic efficiency higher than that of P25, a benchmark photocatalyst. P25 is composed of anatase, rutile, and amorphous TiO₂ particles, and photoexcited electron transfer and subsequent charge separation at the anatase–rutile particle interfaces explain its high photocatalytic efficiency. Herein, we report on a facile and rational hydrothermal treatment of P25 to selectively convert the amorphous component into crystalline TiO₂, which is deposited between the original anatase and rutile particles to increase the particle interfaces and thus enhance charge separation. This process produces a new TiO₂ exhibiting a considerably enhanced photocatalytic efficiency. This method of synthesizing this TiO₂, inspired by a recently burgeoning zeolite design, promises to make TiO₂ applications more feasible and effective.     

High lithium electroactivity of hierarchical porous rutile TiO2 nanorod microspheres

Here we report on the hierarchical porous rutile TiO₂ nanorod micospheres as an anode material for lithium-ion batteries. The resulting hierarchical porous rutile TiO₂ nanorod microspheres possessed much higher reversible capacity, cycling stability and rate capability than nanosized rutile TiO₂ previously reported in the literatures. These good electrochemical performances may be attributed to the facile diffusion of Li⁺ ions from outside through the porous channels into the TiO₂ nanorods in the microspheres and the high electrode–electrolyte contact area offered by hierarchical porous microspheres with a large specific surface area.     

Emerging polymorphism in nanostructured TiO2: Quantum chemical comparison of anatase,rutile, and brookite clusters

Density functional theory (DFT) and time‐dependent DFT calculations have been performed on a set of 34 titanium dioxide clusters ((TiO2)_n with n ≤ 125) to investigate structural and electronic properties of nanostructured TiO₂ (nano‐TiO₂) materials. The investigated clusters include models of the three low‐energy polymorphic forms of TiO₂ anatase, rutile, and brookite. A systematic comparison of clusters of increasing size show clear trends for emerging bulk properties in the investigated systems as the surface‐to‐bulk ratio changes from small clusters dominated by undercoordinated surface atoms to more realistic model nanocrystals with significant bulk components. Differences and similarities in terms of atomic coordination, structural stability, and electronic properties for the three different polymorphic forms of nano‐TiO₂ are discussed. The calculations provide evidence for emerging polymorphism with increasing cluster sizes so that the different TiO₂ forms can be clearly distinguished based on structural characteristics associated with the local bonding environment of the constituent atoms. © 2013 Wiley Periodicals, Inc.     

Active Sites for Adsorption and Reaction of Molecules on Rutile TiO2(110) and Anatase TiO2(001) Surfaces (cited: 1)

The reactivity of specific sites on rutile TiO₂(110)-(1×1) surface and anatase TiO₂(001)-(1×4) surface has been comparably studied by means of high resolution scanning tunneling microscopy. At the rutile TiO₂(110)-(1×1) surface, we find the defects of oxygen vacancy provide distinct reactivity for O₂ and CO₂ adsorption, while the terminal fivefold-coordinated Ti sites dominate the photocatalytic reactivity for H₂O and CH₃OH dissociation. At the anatase TiO₂(001)-(1×4) surface, the sixfold-coordinated terminal Ti sites at the oxidized surface seem to be inert in both O₂ and H₂O reactions, but the Ti-rich defects which introduce the Ti³⁺ state into the reduced surface are found to provide high reactivity for the reactions of O₂ and H₂O. By comparing the reactions on both rutile and anatase surfaces under similar experimental conditions, we find the reactivity of anatase TiO₂(001) is actually lower than rutile TiO₂(110), which challenges the conventional knowledge that the anatase (001) is the most reactive TiO₂ surface. Our findings could provide atomic level insights into the mechanisms of TiO₂ based catalytic and photocatalytic chemical reactions.     

AC conductivity,structural, and dielectric properties of zinc supported on titanium dioxide: Facile synthesis and DFT calculation

We present a simple and systematic synthesis method of Zn doped TiO₂ (Zn/TiO₂) that is usually prepared with sophisticated preparation procedures. Zn/TiO₂ have been synthesized following a facile and efficient incipient wet impregnation method. The resulting Zn/TiO₂ has been characterized by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy, which revealed the successful formation of the anatase phase and traces of the rutile phase. The existence of the rutile phase in smaller proportion was a clear sign of the Zn doping induced anatase-to-rutile phase transition. Sensible enhancement in the dielectric constant due to Zn addition has also been observed from experiment and approximate first-principle calculation. Thus, our results have significant impact on TiO₂ based semiconductor technology.     

An ONIOM and DFT study of water adsorption on rutile TiO2 (110) cluster

Density functional theory (DFT) calculations performed at ONIOM DFT B3LYP/6‐31G**‐MD/UFF level are employed to study molecular and dissociative water adsorption on rutile TiO₂ (110) surface represented by partially relaxed Ti₂₅O₃₇ ONIOM cluster. DFT calculations indicate that dissociative water adsorption is not favorable because of high activation barrier (23.2 kcal/mol). The adsorption energy and vibration frequency of both molecularly and dissociatively adsorbed water molecule on rutile TiO₂ (110) surface compare well with the values reported in the literature. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011