Single-step fabrication of phase-controllable nanocrystalline TiO2 films for enhanced photoelectrochemical water splitting and dye-sensitized solar cells

We introduce a single-step procedure for growing a phase-controllable bilayer-structured TiO₂ film directly onto transparent conductive oxide glass by precipitation from hydrolysis of TiCl₄ in acid solution containing sulfate ions. The obtained bilayer-structured film with anatase nanoparticles in the inner layer which provide high surface area, and an outer layer of larger rutile particles for incident light scattering. In both the water splitting and the dye-sensitized solar cells under AM 1.5 simulated solar light, the bilayer-structured film outperformed the single layer-structured films with either anatase or rutile TiO₂ alone by at least 50%.     

Direct Z-scheme anatase/rutile bi-phase nanocomposite TiO2 nanofiber photocatalyst with enhanced photocatalytic H2-production activity

Design and preparation of direct Z-scheme anatase/rutile TiO₂ nanofiber photocatalyst to enhance photocatalytic H₂-production activity via water splitting is of great importance from both theoretical and practical viewpoints. Herein, we develop a facile method for preparing anatase and rutile bi-phase TiO₂ nanofibers with changing rutile content via a slow and rapid cooling of calcined electrospun TiO₂ nanofibers. The phase structure and composition, surface morphology, specific surface area, surface chemical composition and element chemical states of TiO₂ nanofibers were analyzed by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). By a rapid cooling of 500 °C-calcined electrospun TiO₂ precursor, anatase/rutile bi-phase TiO₂ nanofibers with a roughly equal weight ratio of 55 wt.% anatase and 45 wt.% rutile were prepared. The enhanced H₂ production performance was observed in the above obtained anatase/rutile composite TiO₂ nanofibers. A Z-scheme photocatalytic mechanism is first proposed to explain the enhanced photocatalytic H₂-production activity of anatase/rutile bi-phase TiO₂ nanofibers, which is different from the traditional heterojunction electron–hole separation mechanism. This report highlights the importance of phase structure and composition on optimizing photocatalytic activity of TiO₂-based material.     

Construction of three-dimensional hierarchical Pt/TiO2@C nanowires with enhanced methanol oxidation properties

Three-dimensional (3D) hierarchical Pt/TiO₂@C core-shell nanowire networks with high surface area have been constructed via wet chemical approaches. The 3D TiO₂ nanowire framework was in situ synthesized within a porous titanium foam by hydrothermal method followed by carbon coating and self-assembled growth of ultrathin Pt nanowires. Structural characterization indicates that single crystalline ultrathin Pt nanowires of 3–5 nm in diameter were vertically distributed on the anatase TiO₂ nanowires covered with a 2–4 nm thin carbon layer. The 3D hierarchical Pt/TiO₂@C nanostructure demonstrates evidently higher catalytic activities towards methanol oxidation than the commercial Pt/C catalyst. The catalytic current density of the hierarchical catalyst is 1.6 times as high as that of the commercial Pt/C, and the oxidation onset potential (0.35 V vs. Ag/AgCl) is more negative than the commercial one (0.46 V vs. Ag/AgCl). Synergistic effect between the ultrathin Pt nanowires and the TiO₂@C core-shell nanostructure accounts for the enhanced catalytic properties, which can be determined by X-ray photoelectron spectroscopy (XPS) investigation. The obtained hierarchical Pt/TiO₂@C nanowire networks promise great potential in producing anode catalysts for direct methanol fuel cells applications.     

Oxide/polymer interfaces for hybrid and organic solar cells: Anatase vs. Rutile TiO2

In this work, we study the effect of the transparent conducting oxide (TCO) and the polymer applied (MEH-PPV or P3HT) on the photovoltaic properties of TCO/TiO₂/polymer/Ag bi-layer solar cells. The solar cells were analyzed under inert atmosphere conditions resembling an encapsulated or sealed device. We demonstrate that the substrate applied, ITO or FTO, modifies the crystalline structure of the TiO₂: on an ITO substrate, TiO₂ is present in its anatase phase, on an FTO, the rutile phase predominates. Devices fabricated on an FTO, where the rutile phase is present, show better stability under inert atmospheres than devices fabricated on an ITO, anatase phase. With respect to the polymer, devices based on MEH-PPV show higher Voc (as high as 1 V), while the application of P3HT results in lower Voc, but higher J_sc and longer device stability. These observations have been associated to (a), the crystalline structure of TiO₂ and (b) to the form the polymer is bonded to the TiO₂ surface. In-situ IPCE analyses of P3HT-based solar cells show a red shift on the peak corresponding to TiO₂, which is not present on the MEH-PPV-based solar cells. The latter suggest that P3HT can be linked to the TiO₂ though the S-end atom, which results in devices with lower Voc. All these observations are also valid for devices, where the bare TiO₂ is replaced by an Nb-TiO₂. The application of an Nb-TiO₂ with rutile structure in these polymer/oxide solar cells is the reason for their higher stability under inert atmospheres. We conclude that the application of TiO₂ in its rutile phase is beneficial for long-term stability devices. Moreover there is an interplay between low Voc and J_sc in devices applying P3HT, since power conversion efficiency can be partially canceled by their lower Voc in comparison with MEH-PPV. These findings are important for polymer/oxide solar cells, but also for organic solar cells, where a layer of semiconductor oxides are in direct contact with a polymer, like in an inverted or tandem organic solar cells.     

Electrospun TiO2/SnO2 nanofibers with innovative structure and chemical properties for highly efficient photocatalytic H2 generation

Innovative TiO₂/SnO₂ nanofibers were fabricated via electrospinning an innovated precursor solution and used for photocatalytic H₂ generation. The nanofibers exhibited greatly enhanced H₂ evolution rate compared to bare TiO₂ nanofiber and P25. The enhanced efficiency of the TiO₂/SnO₂ nanofibers was attributed to its excellent synergistic properties: (1) its good mesoporosity; (2) the red-shift of absorbance spectra to enhance light absorbance capability; (3) its long nanofibrous structure and (4) anatase TiO₂ – rutile TiO₂ – rutile SnO₂ ternary junctions favorable for the separation of electrons and holes. Based on our experimental results, the optimum ratio of TiO₂/SnO₂ nanofibers with 3% Sn demonstrated the highest efficiency in H₂ generation.     

Investigation on the electron transfer between anatase and rutile in nano-sized TiO2 by means of surface photovoltage technique and its effects on the photocatalytic activity

Photoinduced electron transfer between anatase and rutile in nanosized TiO₂, prepared by a sol–gel method, was revealed by means of the surface photovoltage technique, and its effects on the photocatalytic performance in the degradation of a phenol solution were investigated. Also, the role of the surface states during the processes of photo-physics and photochemical reactions was discussed. In the as-prepared TiO₂ sample consisting of anatase and rutile, the photoinduced electrons can easily transfer from anatase surface states to rutile, as well as from anatase conduction band to rutile. These factors are responsible for the strong surface photovoltage response and high photocatalytic activity. Moreover, the surface states related to oxygen vacancies can induce photocatalytic reactions under visible irradiation, especially in the resulting biphase TiO₂, due to the electron transfer from anatase surface states to rutile.     

Formation of single-crystalline rutile TiO2 splitting microspheres for dye-sensitized solar cells

The morphological evolution of specimen taken out after the different duration in TiCl₃ solution was investigated by field emission scanning electron microscopy (FE-SEM). The rutile TiO₂ splitting microspheres may be formed by the splitting crystal growth mechanism through the multistep process. The microsphere composed of the 20 nm width nanorods was in the range of 1.5–2.5 μm in the diameter. The dye-sensitized solar cell (DSC) based on the microspheres received 3.57% conversion efficiency under simulated AM 1.5 (100 mW/cm²) solar illumination, which exhibited remarkably higher charge collection efficiency and light scattering compared to that of P25. Electrochemical impedance spectroscopy (EIS) measurement revealed that impedance resistance at the surface of single-crystalline rutile TiO₂ splitting microspheres was 6 times larger than that of P25 nanoparticles, indicating electron recombination was significantly retarded.     

Single crystalline TiO2 nanorods with enhanced visible light activity for solar hydrogen generation

Single crystalline TiO₂ nanorods and polycrystalline nanotubes were fabricated with same length to investigate the effects of their nanostructures on photocatalytic properties for splitting water. In order to enhance the visible light absorbance, TiO₂ nanorods and nanotubes were sensitized with semiconductor nanoparticles such as CdS, CdSe, and CdS/CdSe, and compared in viewpoint of solar hydrogen generation. It was observed that single-crystalline nanorods showed superior photocatalytic properties to polycrystalline nanotubes, and also the potential level of the nanorods with rutile phase was measured as lower than that of the nanotubes with mixture of anatase and rutile. Further improvement of photo-conversion efficiency was obtained by subsequent heat treatments of the sensitized photoelectrodes. It turns out that the improvement is attributed to the improved crystallinity and the increased size of the nanoparticles during the post-annealing treatments. It was demonstrated that TiO₂ nanorods with lower potential level and a single crystalline phase on FTO glass were advantageous for effective charge injection from the sensitized nanoparticles and transport without recombination lost at grain boundaries.     

TiO2-rutile/anatase homojunction with enhanced charge separation for photoelectrochemical water splitting

The mismatched interfaces of heterojunction usually have lots of defects, deriving in recombination of generated electron-hole pairs. On the other hand, homojunction interfaces are considered to be beneficial to the separation of charge carriers due to the similar characteristics in two sides of homojunction. TiO₂ have rutile and anatase two typical photoactive phases in nature. In this work, TiO₂-rutile/anatase (TiO₂-R/A) homojunction photoanode is fabricated by in situ growth of anatase TiO₂ on TiO₂-R surface. By contrast with TiO₂-rutile/rutile (TiO₂-R/R) photoanode, TiO₂-R/A displays higher photocurrent density (1.70 mA cm^?2 at 0.6 V vs. SCE). Deep insight into the mechanism suggests that TiO₂-R/A homojunction has intense band bending and enhanced surface area, which facilitate the charge separation and transmission. This study offers some novel insights to design and fabricate semiconductors photoanodes for highly efficient photocatalytic reactions.     

Surface treated TiO2 nanorod arrays for the improvement of water splitting

Water splitting is widely employed for the hydrogen production for its abundant sources of water and sunlight. The TiO₂ nanostructures are the most promising materials because of their properties of the non-toxicity and relatively low cost. Surface treatments with TiCl₄ solution and titanium butoxide solution are applied on the TiO₂ nanorod arrays respectively. On the surface of the TiO₂ nanorods, TiO₂ nanoparticles are prepared through hydrolysis of TiCl₄ and homogeneous phase of TiO₂ synthesized with assist of second hydrothermal synthesis in titanium butoxide, resulting in the increase of the surface area of the TiO₂. Comparing with that of the original TiO₂ nanorod arrays, the incident photon-to-electron conversion efficiency (IPCE) of the TiO₂–TiCl₄ and TiO₂–H₂O samples is greatly enhanced by 25% and 250% in the ultraviolet region, respectively. The obviously enhanced activity is due to the larger surface structure after treatments, which could contribute to the improved performance in the water splitting. These surface treatments provide an efficient way to regulate the properties of the TiO₂ nanorod arrays for their extensive applications in the solar device for the hydrogen production.     

TiO2 nanowire arrays with mixed phases directly grown on Ti foil and their electrochemical properties as anode material for Li ion batteries

Abstract

TiO₂ nanowire arrays with mixed phases are directly grown on Ti foil using a facile hydrothermal method. X-ray diffraction and Raman spectroscopy analyses indicate that the hybrid samples consist of mixed crystallographic phases of anatase and TiO₂(B). Morphological characterisation shows that the samples have a unique nanostructure with ultra long, fine and uniform nanowires. Compared with the standard Degussa P25 TiO₂ nanoparticles, the hybrid TiO₂ nanowire arrays exhibit larger reversible capacity, improved cycling stability and rate capability, which can be attributed to their hybrid nanowire array structure.     

Fabrication and electrochemical properties of three-dimensional net architectures of anatase TiO2 and spinel Li4Ti5O12 nanofibers

As a new type of electrodes engineering method with three-dimensional (3D) architecture for 3D rechargeable lithium ion batteries, an electrospinning has been successfully employed to prepare 3D net architectures of anatase TiO₂ and spinel Li₄Ti₅O₁₂ nanofibers. Scanning electron microscopy, X-ray diffraction, cyclic voltammetry and the discharge/charge measurements were used to characterize their structures and electrochemical properties. Our results demonstrated that 3D architectures stacked from a cross-bar array of electrospun anatase TiO₂ nanofibers could be accomplished but were destroyed after the insertion of Li ion. Significantly, spinel Li₄Ti₅O₁₂ could be selected as one of promise candidates for the realization of 3D batteries considering its structure stability of 3D spinel Li₄Ti₅O₁₂ nanofibers associated with well cyclability.     

Oxidative photoelectrochemical technology with Ti/TiO2 anodes

Rutile and anatase TiO₂ films have been grown on Ti plates by thermal (500–800°C) and anodic oxidation followed by thermal annealing (400–500°C), respectively. The photoelectrochemical efficiency of these photoanodes, evaluated by current density measurements in the photooxidation of 4-methoxybenzyl alcohol in deaerated CH₃CN, has been determined. The photocurrent efficiency increases with the thickness of the TiO₂ rutile film up to 1 μm (the most efficient thickness). At the wavelengths furnished by the irradiation apparatus similar thicknesses of anatase and rutile films show nearly the same efficiencies. Anodic bias produces similar relative increases of current intensity in both crystalline forms.     

Branched multiphase TiO2 with enhanced photoelectrochemical water splitting activity

An efficient hierarchical structure, nano-branch containing anatase TiO₂ nanofibers and rutile nanorods, was prepared via the combination of the electrospinning and hydrothermal processes. This novel configuration of TiO₂ multiphase possessed higher surface area, roughness, and fill factors compared with each single phase component prepared in the same condition, which significantly enhanced its light absorption. Our experimental results showed that within the interface of multiphase TiO₂, the heterojunction promoted the charge separation and improved the charge transfer rate, leading to higher efficiency for photoelectrochemical water splitting. The photocurrent density of the nano-branched TiO₂ electrode could reach 0.95 mA/cm², which was almost twice as large as that of the pristine TiO₂ nanorod. Our work provides a simple and feasible routine to synthesize complex TiO₂ nanoarchitectures, which lays a foundation for improving energy storage and conversion efficiency of TiO₂-based photoelectrodes.     

In2O3:Sn/TiO2/CdS heterojunction nanowire array photoanode in photoelectrochemical cells

The design of photoanode with highly efficient light harvesting and charge collection properties is important in photoelectrochemical (PEC) cell performance for hydrogen production. Here, we report the hierarchical In₂O₃:Sn/TiO₂/CdS heterojunction nanowire array photoanode (ITO/TiO₂/CdS-nanowire array photoanode) as it provides a short travel distance for charge carrier and long light absorption pathway by scattering effect. In addition, optical properties and device performance of the ITO/TiO₂/CdS-nanowire array photoanode were compared with the TiO₂ nanoparticle/CdS photoanode. The photocatalytic properties for water splitting were measured in the presence of sacrificial agent such as SO₃²⁻ and S²⁻ ions. Under illumination (AM 1.5G, 100 mW/cm²), ITO/TiO₂/CdS-nanowire array photoanode exhibits a photocurrent density of 8.36 mA/cm² at 0 V versus Ag/AgCl, which is four times higher than the TiO₂ nanoparticle/CdS photoanode. The maximum applied bias photon-to-current efficiency for the ITO/TiO₂/CdS-nanowire array and the TiO₂ nanoparticle/CdS photoanode were 3.33% and 2.09%, respectively. The improved light harvesting and the charge collection properties due to the increased light absorption pathway and reduced electron travel distance by ITO nanowire lead to enhancement of PEC performance.     

Anatase/rutile-TiO2 hollow hierarchical architecture modified by SnO2 toward efficient lithium storage

Hierarchical architecture of anatase/rutile-mixed phases TiO₂ with hollow interior was successfully fabricated via a Topotactic synthetic method, including the synthesis of CaTiO₃ precursors and transforming them into TiO₂ through ion-exchange process. The as-synthesized TiO₂ hierarchical architectures as the anode materials were used as lithium-ion batteries (LIBs). Compared with TiO₂ samples, the TiO₂@SnO₂-5% shows the improved lithium storage capacity, cycling performance and rate properties. The impedance of the TiO₂ electrode decreases evidently after adding few amount of SnO₂. The hollow hierarchical structure with different compositions provide much more active sites, and well connect interface among anatase, rutile, and SnO₂, facilitating the electron and ion transport quickly and efficiently. Addition appropriate number of SnO₂ not only well kept the hierarchical architecture but also enhanced the capacity and conductivity of the TiO₂ sample. As a result, TiO₂@SnO₂-5% exhibited excellent lithium storage performance.     

Electron microscopy studies of TiO2 micelles

The microstructural properties of nanosized TiO₂ micelles, generated in situ in a water-in-oil (w/o) microemulsion composed of water, dioctyl sulfosuccinate sodiun salt (AOT) and cyclohexane, by controlled hydrolysis of TiCl₄, were investigated. The samples were characterized by analytical electron microscopy combining electron diffraction. TiO₂ film consisted of isotropic grains of anatase. The grain sizes were 5 nm, which is in agreement with the average grain size R, previously obtained by grazing-incidence wide-angle X-ray diffraction (GIWAXD), of 5.0±1.3 nm. Grains were gathered in a number of clusters, differently oriented with respect to the electron beam.     

Photocatalytic properties of redox-treated Pt/TiO2 photocatalysts for H2 production from an aqueous methanol solution

The influence of redox-treated Pt/TiO₂ photocatalysts on H₂ production is investigated. Catalyst characterizations are performed by TEM, XPS, XRD, BET, and UV–vis/DR spectroscopy techniques. In terms of production rate, the oxidation treatment shows higher reactivity than the reduction treatment. The reduction treatment allows the formation of metallic Pt(0), which more easily catalyzes the transition of TiO₂ from the anatase to the rutile phases. Reduction-treated Pt/TiO₂ photocatalysts have lower S_BET values than oxidation-treated Pt/TiO₂ photocatalysts due to the higher percentage of TiO₂ in the rutile phase. Combining the results of XPS and optical analyses, PtO/TiO₂ shows a higher energy band gap than metallic Pt(0)/TiO₂, indicating that oxidation-treated Pt/TiO₂ is more capable of achieving water splitting for H₂ production. According to the results of this study, the oxidation treatment of Pt/TiO₂ photocatalysts can significantly enhance the reactivity of photocatalytic H₂ production because of their homogenous distribution, lower phase transition, higher S_BET, and higher energy band gap.     

TiO2 and TiO2–SiO2 thin films and powders by one-step soft-solution method: Synthesis and characterizations

Simple soft-solution method has been developed to synthesize films and powders of TiO₂ and mixed TiO₂–SiO₂ at relatively low temperatures. This method is simple and inexpensive. Furthermore, reactor can be designed for large-scale applications as well as to produce large quantities of composite powders in a single step. For the preparation of TiO₂, we used aqueous acidic medium containing TiOSO₄ and H₂O₂, which results in a peroxo-titanium precursor while colloidal SiO₂ has been added to the precursor for the formation of TiO₂–SiO₂. Post annealing at 500 °C is necessary to have anatase structure. Resulting films and powders were characterized by different techniques. TiO₂ (anatase) phase with (1 0 1) preferred orientation has been obtained. Also in TiO₂–SiO₂ mixed films and powders, TiO₂ (anatase) phase was found. Fourier transform infrared spectroscopy (FTIR) results for TiO₂ and mixed TiO₂–SiO₂ films have been presented and discussed. The method developed in this paper allowed obtaining compact and homogeneous TiO₂ films. These compact films are highly photoactive when TiO₂ is used as photo anode in an photoelectrochemical cell. Nanoporous morphology is obtained when SiO₂ colloids are added into the solution.     

Chemical bath deposition synthesis of TiO2/Cu2O core/shell nanowire arrays with enhanced photoelectrochemical water splitting for H2 evolution and photostability

In this study, we have developed a facile chemical bath deposition (CBD) method to grow p-type Cu₂O nanoparticles on n-type TiO₂ nanowire arrays (TiO₂ NWAs) to fabricate TiO₂/Cu₂O core/shell heterojunction nanowire arrays (TiO₂/Cu₂O core/shell NWAs). When used as photoelectrode, the fabricated TiO₂/Cu₂O core/shell NWAs show improved photoelectrochemical (PEC) water splitting activity to pure TiO₂ NWAs. The effects of the CBD cycle times on the PEC activities have been studied. The TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode prepared by cycling 5 times in the CBD process achieves the highest photocurrent of 2.5 mA cm^?2, which is 2.5 times higher than that of pure TiO₂ NWAs. In addition, the H₂ generation rate of this photoelectrode reaches to 32 μmol h^?1 cm^?2, 1.7 times higher than that of pure TiO₂ NWAs. Furthermore, the TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode shows excellent photostability and achieves a stable photocurrent of over 2.3 mA cm^?2 during long light illumination time of 5 h. The enhanced photocatalytic activity of TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode is attributed to the synergistic actions of TiO₂ and Cu₂O for improving visible light harvesting, and efficient transfer and separation of photogenerated electrons and holes.