Nanostructured TiO2 and Its Application in Lithium‐Ion Storage

Titania nanorods and nanowires are synthesized via a hydrothermal reaction of amorphous TiO₂ in alkaline NaOH, followed by ion exchange in HCl aqueous solution, and dehydration at 400 °C. Although the hydrothermal treatment produces three different particle morphologies depending on the reaction time (nanosheets, nanorods, and nanowires), the products exhibit the same crystal structure. Ion exchange of Na₂Ti₃O₇ in HCl aqueous solution brings about a phase change to H₂Ti₃O₇, but there is no change in the particle morphology. Dehydration of the nanostructured H₂Ti₃O₇ leads to two types of crystal structure—anatase TiO₂ for the nanorods, and TiO₂–B for the nanowires—although no significant difference is found in the morphology of the products even after dehydration. The nanorods are 40–50 nm in length and 10 nm in diameter, whereas the nanowires are several micrometers in length and tens to hundreds of nanometers in thickness. In‐situ X‐ray diffraction revealed the formation of anatase TiO₂ from the TiO₂–B above 450 °C. This finding implies that the phase transformation occurs rather slowly for the TiO₂–B nanowires due to the larger particle size and higher crystallinity of H₂Ti₃O₇. Tests with Li‐metal half cells indicated that the anatase TiO₂ nanorods are more favorable for the storage and release of Li ions because of their greater surface area than the TiO₂–B nanowires.     

Layered H2Ti6O13‐Nanowires: A New Promising Pseudocapacitive Material in Non‐Aqueous Electrolyte

Layered H₂Ti₆O₁₃‐nanowires are prepared using a facile hydrothermal method and their Li‐storage behavior is investigated in non‐aqueous electrolyte. The achieved results demonstrate the pseudocapacitive characteristic of Li‐storage in the layered H₂Ti₆O₁₃‐nanowires, which is because of the typical nanosize and expanded interlayer space. The as‐prepared H₂Ti₆O₁₃‐nanowires have a high capacitance of 828 F g^?1 within the potential window from 2.0 to 1.0 V (vs. Li/Li⁺). An asymmetric supercapacitor with high energy density is developed successfully using H₂Ti₆O₁₃‐nanowires as a negative electrode and ordered mesoporous carbon (CMK‐3) as a positive electrode in organic electrolyte. The asymmetric supercapacitor can be cycled reversibly in the voltage range of 1 to 3.5 V and exhibits maximum energy density of 90 Wh kg^?1, which is calculated based on the mass of electrode active materials. This achieved energy density is much higher than previous reports. Additionally, H₂Ti₆O₁₃//CMK‐3 asymmetric supercapacitor displays the highest average power density of 11 000 W kg^?1. These results indicate that the H₂Ti₆O₁₃//CMK‐3 asymmetric supercapacitor should be a promising device for fast energy storage.     

Nanostructured Sheets of Ti?O Nanobelts for Gas Sensing and Antibacterial Applications

Three types of Ti? O‐compound‐based nanobelts (Na₂Ti₃O₇, H₂Ti₃O₇, TiO₂) are prepared from commercial TiO₂ powders via an alkaline hydrothermal process. Nanostructured sheets based on the as‐synthesized nanobelts are prepared using a paper‐making process. The nanobelts are connected with hydrogen bonds or/and bridge oxygen atoms and packed together, forming a paperlike porous network structure, with an average pore size of ～500 nm. The electrical properties and gas sensing of the nanostructured sheets are demonstrated to display sensitivity down to sub‐ppb levels. H₂Ti₃O₇ nanobelts decorated with Ag nanoparticles have also been applied as an antibacterial agent.     

Hydrothermal Reaction Mechanism and Pathway for the Formation of K2Ti6O13 Nanowires

Calculations and detailed first principle and thermodynamic analyses have been performed to understand the formation mechanism of K₂Ti₆O₁₃ nanowires (NWs) by a hydrothermal reaction between bulk Na₂Ti₃O₇ crystals and a KOH solution. It is found that direct ion exchange between K⁺ and Na⁺ plus H⁺ interactions with [TiO₆] octahedra in Na₂Ti₃O₇ promote the formation of an intermediate H₂K₂Ti₆O₁₄ phase. The large lattice mismatch between this intermediate phase and the bulk Na₂Ti₃O₇ structure, and the large energy reduction associated with the formation of this intermediate phase, drive the splitting of the bulk crystal into H₂K₂Ti₆O₁₄ NWs. However, these NWs are not stable because of large [TiO₆] octahedra distortion and are subject to a dehydration process, which results in uniform K₂Ti₆O₁₃ NWs with narrowly distributed diameters of around 10 nm.     

An efficient titanium‐based photoanode for dye‐sensitized solar cell under back‐side illumination

Pretreatment of H₂O₂ is performed on titanium (Ti) foil as an efficient photoanode substrate for dye‐sensitized solar cell (DSSC). The H₂O₂‐treated Ti shows high surface area because of the formation of networked TiO₂ nanosheets, which enhances electrical contact between screen‐printed TiO₂ nanoparticles and Ti foil. Electron transfer on the photoanode is improved, as identified by reduced charge transfer resistance and improved electron transport properties. Compared with DSSC based on non‐treated Ti photoanode, DSSC with this H₂O₂‐treated Ti photoanode exhibits remarkable increases in short‐circuit current density (from 8.55 to 14.38 mA/cm²) and energy conversion efficiency (from 4.68 to 7.10%) under AM1.5 back‐side illumination. Copyright © 2011 John Wiley & Sons, Ltd.     

Fabrication of oxygen-deficient TiO2 coatings with nano-fiber morphology for visible-light photocatalysis

In this study, heat treatment in carbon powder is developed as a safe, simple, and effective strategy to fundamentally enhance the visible-light photocatalytic activity of titanium dioxide (TiO₂) coatings. The target TiO₂ coatings were fabricated using the prepared Ti coatings by a heat treatment process involving pretreatment in carbon powder, followed by oxidation in air, and reduction in carbon powder. The results show that Ti₂CO coatings are formed and micro-cracks appear in the surface of the coatings during pretreatment. The Ti₂CO coatings and micro-cracks are beneficial for forming rutile TiO₂ coatings with nano-fiber morphology during subsequent oxidation. During reduction, oxygen vacancies, which promote the narrowing of band gap, are generated in the lattice of rutile TiO₂. The visible-light photocatalytic activity of the target TiO₂ coatings is effectively enhanced more than 8 times, compared with the TiO₂ coatings prepared solely by oxidation of Ti coatings. The ability to fabricate highly visible-light photoactive TiO₂ materials by simple and safe heat treatment in carbon powder opens up new opportunities in various areas, such as the preparation of powders, nanowires, films.     

A New Triclinic Phase Na2Ti3O7 Anode for Sodium‐Ion Battery

A new phase Na₂Ti₃O₇ compound is synthesized by solid‐state method for the first time, which is verified to belong to the triclinic structure in P‐1 space group. Compared to the conventional monoclinic Na₂Ti₃O₇ (m‐NTO), in P2₁/m1 space group, the triclinic Na₂Ti₃O₇ (t‐NTO) possesses a shorter O‐O band in the distorted TiO₆ octahedron, which accounts for more smooth Na⁺ transport channels and a more stable layered structure with smaller fluctuation. The experimental results show that the t‐NTO keeps a low charge potential plateau at 0.3 V compared to the m‐NTO, but with much promoted structure resilience. It delivers a capacity retention of 94.7%, far exceeding the 25.7% of the m‐NTO upon decades of cycles. In situ X‐ray diffraction reveals that the conventional m‐NTO experiences an irreversible phase transition during insertion/de‐insertion of Na⁺, while the new t‐NTO can recover its structure reversibly after discharge and charge, which is consistent with its improved cycling performance. The results demonstrate a new t‐NTO anode and provide a new understanding for the phase diversity of sodium‐ion battery materials.     

Ti3+ Self‐Doped Dark Rutile TiO2 Ultrafine Nanorods with Durable High‐Rate Capability for Lithium‐Ion Batteries

Dark‐colored rutile TiO₂ nanorods doped by electroconducting Ti³⁺ have been obtained uniformly with an average diameter of ≈7 nm, and have been first utilized as anodes in lithium‐ion batteries. They deliver a high reversible specific capacity of 185.7 mAh g^?1 at 0.2 C (33.6 mA g^?1) and maintain 92.1 mAh g^?1 after 1000 cycles at an extremely high rate 50 C with an outstanding retention of 98.4%. Notably, the coulombic efficiency of Ti³⁺–TiO₂ has been improved by approximately 10% compared with that of pristine rutile TiO₂, which can be mainly attributed to its prompt electron transfer because of the introduction of Ti³⁺. Again the synergetic merits are noticed when the promoted electronic conductivity is combined with a shortened Li⁺ diffusion length resulting from the ultrafine nanorod structure, giving rise to the remarkable rate capabilities and extraordinary cycling stabilities for applications in fast and durable charge/discharge batteries. It is of great significance to incorporate Ti³⁺ into rutile TiO₂ to exhibit particular electrochemical characteristics triggering an effective way to improve the energy storage properties.     

Oxygen Rich Titania: A Dopant Free,High Temperature Stable,and Visible‐Light Active Anatase Photocatalyst

The simultaneous existence of visible light photocatalytic activity and high temperature anatase phase stability up to 900 °C in undoped TiO₂ is reported for the first time. These properties are achieved by the in‐situ generation of oxygen through the thermal decomposition of peroxo‐titania complex (formed by the precursor modification with H₂O₂). Titania containing the highest amount of oxygen (16 H₂O₂‐TiO₂) retains 100% anatase phase even at 900 °C, where as the control sample exists as 100% rutile at this temperature. The same composition exhibits a six‐fold and two‐fold increase in visible light photocatalytic activities in comparison to the control sample and the standard photocatalyst Degussa P‐25 respectively. Among the various para­meters affecting the photocatalytic action, such as band gap narrowing, textural properties, crystallite size, and anatase phase stability, band gap narrowing was identified as the major factor responsible for the visible light photocatalytic activity. Increased Ti–O–Ti bond strength and upward shifting of the valence band (VB) maximum, which is responsible for the high temperature stability and visible light activity respectively, are identified from FT–IR, XPS, and photoluminescence (PL) spectroscopic studies. It is therefore proposed that the oxygen excess defects present in these titania samples are responsible for the high temperature stability and enhanced visible light photocatalytic activities.     

V2O5 Nanowires with an Intrinsic Peroxidase‐Like Activity

V₂O₅ nanowires exhibit an intrinsic catalytic activity towards classical peroxidase substrates such as 2,2‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid) (ABTS) and 3,3,5,5,‐tetramethylbenzdine (TMB) in the presence of H₂O₂. These V₂O₅ nanowires show an optimum reactivity at a pH of 4.0 and the catalytic activity is dependent on the concentration. The Michaelis‐Menten kinetics of the ABTS oxidation over these nanowires reveals a behavior similar to that of their natural vanadium‐dependent haloperoxidase (V‐HPO) counterparts. The V₂O₅ nanowires mediate the oxidation of ABTS in the presence of H₂O₂ with a turnover frequency (k_cat) of 2.5 × 10³ s^?1. The K_M values of the V₂O₅ nanowires for ABTS oxidation (0.4 μM ) and for H₂O₂ (2.9 μM ) at a pH of 4.0 are significantly smaller than those reported for horseradish peroxidases (HRP) and V‐HPO indicating a higher affinity of the substrates for the V₂O₅ nanowire surface. Based on the kinetic parameters and similarity with vanadium‐based complexes a mechanism is proposed where an intermediate metastable peroxo complex is formed as the first catalytic step. The nanostructured vanadium‐based material can be re‐used up to 10 times and retains its catalytic activity in a wide range of organic solvents (up to 90%) making it a promising mimic of peroxidase catalysts.     

Br‐Doped Li4Ti5O12 and Composite TiO2 Anodes for Li‐ion Batteries: Synchrotron X‐Ray and in situ Neutron Diffraction Studies

Synchrotron X‐ray diffraction data were used to determine the phase purity and re‐evaluate the crystal‐structure of Li₄Ti₅O_12‐xBr_x electrode materials (where the synthetic chemical inputs are x = 0.05, 0.10 0.20, 0.30). A maximum of x′ = 0.12 Br, where x′ is the Rietveld‐refined value, can be substituted into the crystal structure with at least 2% rutile TiO₂ forming as a second phase. Higher Br concentrations induced the formation of a third, presumably Br‐rich, phase. These materials function as composite anodes that contain mixtures of TiO₂, Li₄Ti₅O_12‐xBr_x, and a Br‐rich third, unknown, phase. The minor quantities of the secondary phases in combination with Li₄Ti₅O_12‐xBr_x where x′ ～ 0.1 were found to correspond to the optimum in electrochemical properties, while larger quantities of the secondary phases contributed to the degradation of the performance. In situ neutron diffraction of a composite anatase TiO₂/Li₄Ti₅O₁₂ anode within a custom‐built battery was used to determine the electrochemical function of the TiO₂ component. The Li₄Ti₅O₁₂ component was found to be electrochemically active at lower voltages (1.5 V) relative to TiO₂ (1.7 V). This enabled Li insertion/extraction to be tuned through the choice of voltage range in both components of this composite or in the anatase TiO₂ phase only. The use of composite materials may facilitate the development of multi‐component electrodes where different active materials can be cycled in order to tune power output.     

An In Situ Simultaneous Reduction‐Hydrolysis Technique for Fabrication of TiO2‐Graphene 2D Sandwich‐Like Hybrid Nanosheets: Graphene‐Promoted Selectivity of Photocatalytic‐Driven Hydrogenation and Coupling of CO2 into Methane and Ethane

A novel, in situ simultaneous reduction‐hydrolysis technique (SRH) is developed for fabrication of TiO₂‐‐graphene hybrid nanosheets in a binary ethylenediamine (En)/H₂O solvent. The SRH technique is based on the mechanism of the simultaneous reduction of graphene oxide (GO) into graphene by En and the formation of TiO₂ nanoparticles through hydrolysis of titanium (IV) (ammonium lactato) dihydroxybis, subsequently in situ loading onto graphene through chemical bonds (Ti–O–C bond) to form 2D sandwich‐like nanostructure. The dispersion of TiO₂ hinders the collapse and restacking of exfoliated sheets of graphene during reduction process. In contrast with prevenient G‐TiO₂ nanocomposites, abundant Ti³⁺ is detected on the surface of TiO₂ of the present hybrid, caused by reducing agent En. The Ti³⁺ sites on the surface can serve as sites for trapping photogenerated electrons to prevent recombination of electron–hole pairs. The high photocatalytic activity of G‐TiO₂ hybrid is confirmed by photocatalytic conversion of CO₂ to valuable hydrocarbons (CH₄ and C₂H₆) in the presence of water vapor. The synergistic effect of the surface‐Ti³⁺ sites and graphene favors the generation of C₂H₆, and the yield of the C₂H₆ increases with the content of incorporated graphene. The work may open a new doorway for new significant application of graphene for selectively catalytic C–C coupling reaction     

Porous Ti4O7 Particles with Interconnected‐Pore Structure as a High‐Efficiency Polysulfide Mediator for Lithium–Sulfur Batteries

Multifunctional Ti₄O₇ particles with interconnected‐pore structure are designed and synthesized using porous poly(styrene‐b ‐2‐vinylpyridine) particles as a template. The particles can work efficiently as a sulfur‐host material for lithium–sulfur batteries. Specifically, the well‐defined porous Ti₄O₇ particles exhibit interconnected pores in the interior and have a high‐surface area of 592 m² g^?1; this shows the advantage of mesopores for encapsulating of sulfur and provides a polar surface for chemical binding with polysulfides to suppress their dissolution. Moreover, in order to improve the conductivity of the electrode, a thin layer of carbon is coated on the Ti₄O₇ surface without destroying its porous structure. The porous Ti₄O₇ and carbon‐coated Ti₄O₇ particles show significantly improved electrochemical performances as cathode materials for Li–S batteries as compared with those of TiO₂ particles.     

1D Tellurium Nanostructures: Photothermally Assisted Morphology‐Controlled Synthesis and Applications in Preparing Functional Nanoscale Materials

A facile visible‐light‐assisted solution‐phase approach has been successfully developed to synthesize trigonal Te 1D nanostructures. By varying the relative amount of H₂TeO₃ and water‐soluble polymers, wirelike, beltlike, tubular Te, and Te nanoparticle‐joined 1D aggregates, as well as a novel thorny 1D assembly of Te nanothreads can be synthesized on a large scale. The diameter of the Te nanowires can be modulated by controlling the nucleation and growth process through modulation of the pH value of the reaction mixture. It is believed that the light irradiation and thermal effect play a significant role in this photothermally assisted technique. We have shown that the Te nanowires can be used as a template to prepare Pt–Te nanochains, where the composition of Pt in the Pt–Te 1D products can be modulated by adjusting the ratio of the Te nanowires and Pt salts. Preliminary optical investigations reveal that blue–violet emission of Te nanowires can be enhanced by the formation of defects or dislocations in the Te region through the galvanic replacement reaction between Te nanowires and H₂PtCl₆. In addition, we demonstrate that Te 1D nanostructures can be utilized to prepare Te at carbon‐rich nanocables and carbonaceous nanotubes. Te–Pt at carbon‐rich nanocables can also be fabricated using Te–Pt nanochains as the template. These Pt–Te nanochains and carbonaceous nanostructures are expected to find wide applications in electrochemistry, catalysis, fuel cells, sensors, and other fields. Furthermore, the successful preparation of Te 1D nanostructures with abundant shapes, Pt–Te nanochains, and their carbonaceous composite nanomaterials will offer great opportunities to explore the dependence of novel properties of nanomaterials on their morphology and composition, regulate the photoconductivity of semiconductors, and also be essential for the manufacture of potential optoelectronic devices.     

Syntheses,Li Insertion,and Photoactivity of Mesoporous Crystalline TiO2

Ordered mesoporous rutile and anatase TiO₂ samples are prepared using mesoporous silica SBA‐15 as template and freshly synthesized titanium nitrate and titanium chloride solutions as precursors. The rutile material formed from the nitrate solution is monocrystalline and contains minimal amounts of Si with a Si:Ti ratio of 0.031(4), whereas the anatase material formed from the chloride solution comprises nanocrystals and contains a higher content of Si with a Si:Ti ratio of 0.18(3). It is found that control of temperature and selection of Ti‐containing precursor play important roles in determining the crystal phase and crystallinity. A possible formation mechanism of porous crystalline TiO₂ is suggested. Characterization of these porous materials is performed by XRD, HRTEM, and nitrogen adsorption/desorption. SBA‐15‐templated mesoporous rutile TiO₂ exhibits a higher Li ion insertion capability than KIT‐6‐templated TiO₂ due to its larger surface area. Likewise mesoporous anatase TiO₂:SiO₂ composite has a better photoactivity than bulk TiO₂ or TiO₂‐loaded SBA‐15 for bleaching methylene blue.     

A New Strategy to Build a High‐Performance P′2‐Type Cathode Material through Titanium Doping for Sodium‐Ion Batteries

Herein, Ti⁴⁺ in P′2‐Na_0.67[(Mn_0.78Fe_0.22)_0.9Ti_0.1]O₂ is proposed as a new strategy for optimization of Mn‐based cathode materials for sodium‐ion batteries, which enables a single phase reaction during de‐/sodiation. The approach is to utilize the stronger Ti–O bond in the transition metal layers that can suppress the movements of Mn–O and Fe–O by sharing the oxygen with Ti by the sequence of Mn–O–Ti–O–Fe. It delivers a discharge capacity of ≈180 mAh g^?1 over 200 cycles (86% retention), with S‐shaped smooth charge–discharge curves associated with a small volume change during cycling. The single phase reaction with a small volume change is further confirmed by operando synchrotron X‐ray diffraction. The low activation barrier energy of ≈541 meV for Na⁺ diffusion is predicted using first‐principles calculations. As a result, Na_0.67[(Mn_0.78Fe_0.22)_0.9Ti_0.1]O₂ can deliver a high reversible capacity of ≈153 mAh g^?1 even at 5C (1.3 A g^?1), which corresponds to ≈85% of the capacity at 0.1C (26 mA g^?1). The nature of the sodium storage mechanism governing the ultrahigh electrode performance in a full cell with a hard carbon anode is elucidated, revealing the excellent cyclability and good retention (≈80%) for 500 cycles (111 mAh g^?1) at 5C (1.3 A g^?1).     

A Water Stable,Near‐Zero‐Strain O3‐Layered Titanium‐Based Anode for Long Cycle Sodium‐Ion Battery

Layered transition metal (TM) oxides of the stoichiometry Na_xMO₂ (M = TM) have shown great promise in sodium‐ion batteries (SIBs); however, they are extremely sensitive to moisture. To date, most reported titanium‐based layered anodes exhibit a P2‐type structure. In contrast, O3‐type compounds are rarely investigated and their synthesis is challenging due to their higher percentage of unstable Ti³⁺ than the P2 type. Here, a pure phase and highly crystalline O3‐type Na_0.73Li_0.36Ti_0.73O₂ with high performance is successfully proposed in SIBs. This material delivers a reversible capacity of 108 mAh g^?1 with a stable and safe potential of 0.75 V versus Na/Na⁺. In situ X‐ray diffraction reveals that this material does not undergo any phase transitions and exhibits a near‐zero volume change upon Na⁺ insertion/de‐insertion, which ensures exceptional long cycle life over 6000 cycles. Importantly, it is found that this O3‐Na_0.73Li_0.36Ti_0.73O₂ shows superior moisture stability, even when immersed into water, which are both elusive for conventional layered TM oxides in SIBs. It is believed that the small interlayer distance and high occupation of interlayer vacancy promise such unprecedented water stability.     

Self‐Assembled In‐Plane Growth of Mg2SiO4 Nanowires on Si Substrates Catalyzed by Au Nanoparticles

In‐plane growth of Mg₂SiO₄ nanowires on Si substrates is achieved by using a vapor transport method with Au nanoparticles as catalyst. The self‐assembly of the as‐grown nanowires shows dependence on the substrate orientation, i.e., they are along one, two, and three particular directions on Si (110), (100), and (111) substrates, respectively. Detailed electron microscopy studies suggest that the Si substrates participate in the formation of Mg₂SiO₄, and the epitaxial growth of the nanowires is confined along the Si <110> directions. This synthesis route is quite reliable, and the dimensions of the Mg₂SiO₄ nanowires can be well controlled by the experiment parameters. Furthermore, using these nanowires, a lithography‐free method is demonstrated to fabricate nanowalls on Si substrates by controlled chemical etching. The Au nanoparticle catalyzed in‐plane epitaxial growth of the Mg₂SiO₄ nanowires hinges on the intimate interactions between substrates, nanoparticles, and nanowires, and our study may help to advance the developments of novel nanomaterials and functional nanodevices.     

Gram‐Scale Synthesis of Ultrathin Tungsten Oxide Nanowires and their Aspect Ratio‐Dependent Photocatalytic Activity

Preparation of size‐tunable ultrathin W₁₈O₄₉ nanowires by an alcohol‐assisted solvothermal decomposition of tungstic acid is reported. The synthesis of ultrathin W₁₈O₄₉ nanowires can be achieved at large scale and low cost, while changing the molecular size of the used alcohols can control the nanowire morphology. With increasing the molecular size of the alcohol, the synthesized W₁₈O₄₉ nanowires have smaller diameters and longer lengths. The as‐prepared blue W₁₈O₄₉ nanomaterials show a very strong visible light absorption caused by oxygen defects and an aspect ratio‐dependent photocatalytic activity on the degradation of pollutant rhodamine B (RhB) under simulated solar light irradiation. It is found that the W₁₈O₄₉ nanowires with highest aspect ratio show the highest activity in the photodegradation of RhB, which could be related to their higher density of oxygen surface defects in combination with a higher adsorption capability of RhB. This new synthetic route of size tunable ultrathin W₁₈O₄₉ nanomaterials will enlarge their potential applications and can be possibly used in the pyrolyzing synthesis of other metal oxide nanomaterials.     

Synthesis of thin p-type rutile films

The structure and electrical and optical properties of heterostructures formed on the surface of single-crystal silicon wafers as a result of the heat treatment and pulsed photon treatment of Ti films in oxygen, air, and nitrogen are investigated. It is shown that a TiO₂/Ti₅Si₃/p-Si heterostructure is formed upon heat treatment in air, whereas a TiO₂/TiSi₂/p-Si heterostructure is formed upon photon treatment. It is established that rutile films with pronounced n-type conductivity are formed as a result of the heat treatment of Ni-doped Ti films in oxygen. Rutile films with p-type conductivity are formed upon the thermal annealing of Ti films in air with subsequent photon treatment in nitrogen.