Synthesis,characterization and electrochemical properties of a compact titanium dioxide layer

In this paper, we report on the synthesis, characterization, and electrochemical properties of a compact titanium dioxide layer as well as its application in dye-sensitized solar cells (DSCs). The compact TiO₂ layer, which was prepared via a facile approach by the hydrolysis of TiCl₄ aqueous solution, has been characterized by XRD, SEM, UV–vis absorption spectroscopy, voltammetry, and electrochemical impedance spectroscopy (EIS). Experimental results show that the compact TiO₂ layer with the thickness of about 100 nm is composed of anatase-phase nanoparticles with the particle size of 10–15 nm. Impedance measurements display that the compact layer of TiO₂ can prevent the back reaction of electrons with tri-iodide ions under low applied potentials, increase the open circuit voltage (V_oc) and fill factor (FF), and finally improve the conversion efficiency (η) for the DSCs from 7.5 to 8.1%.     

Highly efficient CdSe quantum-dot-sensitized TiO2 photoelectrodes for solar cell applications

With 4.2 nm quantum-dots (QDs) as seeds on TiO₂ film, a highly efficient TiO₂ photoelectrode was prepared by a seed-growing process using chemical bath deposition technique, followed by a covering process with ZnS layer, and a post-sintering process at 400 °C. The assembled solar cells presented IPCE peak values of 73% and power conversion efficiency of 3.21% under AM 1.5 G irradiation.     

Facile synthesis of thick ordered mesoporous TiO2 film for dye-sensitized solar cell use

Crack-free thick ordered mesoporous TiO₂ films with excellent optical quality have been synthesized by combination of “Doctor Blade” technique and a two-step evaporation induced self-assembly (EISA) method. By employing the as-synthesized mesoporous film with the thickness of 7 μm as the photoanode in dye-sensitized solar cell (DSC), a solar conversion efficiency of 6.53% has been obtained at 30 mW cm⁻² light intensity.     

TiO2/polyaniline composites： An efficient photocatalyst for the degradation of methylene blue under natural light

Polyaniline (PAn) sensitized nanocrystalline TiO_2 composites (TiO_2/PAn) were successfully prepared and used as an efficient photocatalyst for the degradation of dye methylene blue (MB).The results showed that PAn was able to sensitize TiO_2 efficiently and the composite photocatalyst could be activated by absorbing both the ultraviolet and visible light (λ:190～800nm),whereas pure TiO_2 absorbed ultraviolet light only (λ<380nm).Under the irradiation of natural light,MB could be degraded more efficiently on the TiO_2/PAn composites than on the TiO_2.Furthermore,it could be easily separated from the solution by simple sedimentation.     

AgSbS2 semiconductor-sensitized solar cells

We present a ternary semiconductor nanoparticle sensitizer – AgSbS₂ – for solar cells. AgSbS₂ nanoparticles were grown using a two-stage successive ionic layer adsorption and reaction process. First, Ag₂S nanoparticles were grown on the surface of a nanoporous TiO₂ electrode. Secondly, a Sb–S film was coated on top of the Ag₂S. The double-layered structure was transformed into AgSbS₂ nanoparticles ~ 40 nm in diameter, after post-deposition heating at 350 °C. The AgSbS₂-sensitized TiO₂ electrodes were fabricated into liquid-junction solar cells. The best cell yielded a power conversion efficiency of 0.34% at 1 sun and 0.42% at 0.1 sun. The external quantum efficiency (EQE) spectrum covered the range of 380–680 nm with a maximal EQE of 10.5% at λ = 470 nm. The method can be applied to grow other systems of ternary semiconductor nanoparticles for solar absorbers.     

Effects of electron beam irradiation on the photoelectrochemical properties of TiO2 film for DSSCs

TiO₂ has been widely utilized for various industrial applications such as photochemical cells, photocatalysts, and electrochromic devices. The crystallinity and morphology of TiO₂ films play a significant role in determining the overall efficiency of dye-sensitized solar cells (DSSCs). In this study, the preparation of nanostructured TiO₂ films by electron beam irradiation and their characterization were investigated for the application of DSSCs. TiO₂ films were exposed to 20–100 kGy of electron beam irradiation using 1.14 MeV energy acceleration with a 7.46 mA beam current and 10 kGy/pass dose rates. These samples were characterized using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and X-ray photoelectron spectroscopy (XPS) analysis. After irradiation, each TiO₂ film was tested as a DSSC. At low doses of electron beam irradiation (20 kGy), the energy conversion efficiency of the film was approximately 4.0% under illumination of simulated sunlight with AM 1.5 G (100 mW/cm²). We found that electron beam irradiation resulted in surface modification of the TiO₂ films, which could explain the observed increase in the conversion efficiency in irradiated versus non-irradiated films.     

Photocatalytic decomposition of 4-chlorophenol over an efficient N-doped TiO2 under sunlight irradiation

Using a new nitrogen precursor of a mixture of ammonia and hydrazine hydrate, N-doped TiO₂ photocatalyst with a high efficiency under visible light was synthesized by a precipitation method. The analysis of X-ray photoelectron spectroscopy (XPS) suggested that the doping concentration of nitrogen was 0.45 at%, while it was 0.21 at% or 0.24 at% using single ammonia or hydrazine hydrate as nitrogen precursor. The patterns of the electron paramagnetic resonance spectroscopy (EPR) indicated that the paramagnetic species of NO₂^2?, NO and Ti³⁺ existed as the proposed active species. The ultraviolet–visible (UV–vis) spectra revealed that the band-gap of the N-doped TiO₂ was 3.12 eV, which was slightly lower than 3.15 eV of pure TiO₂. The N-doped TiO₂ showed higher efficiency under both ultraviolet (UV) and visible light irradiations. Moreover, the degradation grade of 4-chlorophenol (4-CP) using the as-synthesized N-doped TiO₂ under sunlight irradiation for 6 h was 82.0%, which was higher than 66.2% of the pure TiO₂, 60.1% or 65.2% of the N-doped TiO₂ using single ammonia or hydrazine hydrate as precursor. Density functional theory (DFT) calculations were performed to investigate the visible light response of the N-doped TiO₂. Our study demonstrated that the visible activities vary well with the concentrations of NO₂^2? species incorporated by N–TiO₂ series photocatalysts and the higher activity of the as-prepared N-doped TiO₂ was attributed to the enhancement of the concentration of NO₂^2? species.     

Radiation-induced catalytic degradation of p-nitrophenol (PNP) in the presence of TiO2 nanoparticles

The gamma radiation induced catalytic degradation of p-nitrophenol (PNP) in the presence of titanium dioxide (TiO₂) nanoparticles in aqueous solution was investigated. The initial concentration of PNP solution was 50 mg/L, and the additional TiO₂ doses were 0, 0.5, 1.0, and 2.0 g/L. The experimental results indicated that the PNP decomposition kinetics conformed to the modified pseudo-first order reaction equation under all applied conditions. When the TiO₂ dose was in the range of 0–2.0 g/L, the effect of additional TiO₂ on PNP decomposition rate was not obvious because PNP could be removed quite well by irradiation even in the absence of TiO₂ nanoparticles; however, the removal of total organic carbon (TOC) and total nitrogen (TN) was significantly accelerated in the presence of TiO₂ nanoparticles, the TOC removal efficiency increased from about 16% to 42%, and therefore the mineralization of PNP could be enhanced by TiO₂ nanoparticles. The inorganic nitrogen products were quantitatively measured to estimate the decomposition degree of PNP. The major aromatic intermediates, as well as carboxylic acids were identified by LCMS and IC. Possible reactions involved in radiation induced catalytic decomposition of PNP in aqueous solutions were proposed.     

Synthesis and characterization of push–pull organic semiconductors with various acceptors for solution-processed small molecule organic solar cells

New efficient push–pull organic semiconductors comprising of the bis(9,9-dimethyl-9H-fluoren-2-yl)aniline (bisDMFA) donor and the various acceptors such as NO₂, DCBP, and TCF, which were linked with bithiophene or vinyl bithiophene π-conjugation bridges, were synthesized, and their photovoltaic characteristics were investigated in solution-processed small molecule organic solar cells (SMOSCs). The intramolecular charge transfers of these materials were effectively appeared in between bisDMFA donor and acceptors, depending on the electron-withdrawing strength of acceptors. The organic semiconductors having NO₂ and DCBP acceptors exhibited the most efficient photovoltaic performance, showing power conversion efficiency (PCE) of 1.98% (±0.17) and 2.01% (±0.21), respectively. When the TiO_x thin layer was treated on photoactive layer, the organic semiconductor having NO₂ showed the best PCE of 2.70% with short circuit current of 8.19 mA/cm², fill factor of 0.40, and open circuit voltage of 0.83 V in SMOSC devices.     

Formation of porous TiOx biomaterials in H3PO4 electrolytes

In this work, formation of porous TiO_x layers and theirs corrosion behavior were studied. Application of H₃PO₄ electrolytes results in porous TiO_x formation. The process is enhanced by small amount of HF content in the electrolyte. The HF results in higher current density, enhancing dissolution. Small 0.5% HF concentration results in nanopores formation, with pore diameter of about 45 nm. Increase of HF concentration up to 10% results in pores with average diameter of about 5.2 μm. An increase of etching time results in larger pore diameter, but between large 2–5 μm diameter pores smallest ones were observed with diameter below 200 nm. In the initial etching process a remnants of the flat surface are presents with initial cracks in the surface, indicating places for growth of the pores.The TiO_x layers can be used as a biomaterial. The corrosion behavior of the layer investigated in Ringer’s solution, revealed an excellent corrosion resistance, with respect to pure Ti.     

Spectral broadening in quantum dots-sensitized photoelectrochemical solar cells based on CdSe and Mg-doped CdSe nanocrystals

In order to absorb a broad spectrum in visible region, a co-sensitized TiO₂ electrode was prepared by CdSe and Mg-doped CdSe quantum dots (Q dots). The power conversion efficiency of the co-sensitized Q dots photoelectrochemical solar cells (PECs) showed 1.03% under air mass 1.5 condition (I = 100 mW/cm²), which is higher than that of individual Q dots-sensitized PECs. The incident-photon-to-current conversion efficiency of the co-sensitized PECs showed absorption peaks at 541 and 578 nm corresponding to the two Q dots and displayed a broad spectral response over the entire visible spectrum in the 500–600 nm wavelength domains.     

Bubble-like CdSe nanoclusters sensitized TiO2 nanotube arrays for improvement in solar cell

Solar cells were fabricated using novel bubble-like CdSe nanoclusters sensitized highly ordered titanium oxide nanotube (TiO₂ NT) array, prepared by anodization technique. The CdSe sensitization of TiO₂ NT arrays was carried out by a chemical bath deposition method with freshly prepared sodium selenosufite, ammonium hydroxide and cadmium acetate dehydrate at different deposition times: 20, 40 and 60 min. The adsorption of CdSe nanoclusters on the upper and inner surface of the TiO₂ NT arrays has been confirmed by field emission scanning electron and transmission electron microscopes. The results show the variation in cell a performance with different deposition times (20, 40, and 60 min) of CdSe on TiO₂ NT arrays. The solar cell with CdSe, deposited for 60 min, shows reasonably high photovoltaic property compared to the reported results of similar studies. This solar cell shows the maximum photoelectric conversion efficiency of 1.56% (photocurrent of 7.19 mA/cm²; photovoltage of 0.438 V; and fill factor of 49.5%) and average incident photon to current efficiency of 50.2%. The photocurrent, incident photon-current efficiency and electron lifetime have been improved due to the increase of covered area and size of bubble-like CdSe nanoclusters on TiO₂ NT arrays with the increase of deposition time.     

Organic dyes with a novel anchoring group for dye-sensitized solar cell applications

Two novel trialkylsilyl-containing organic sensitizers (JK-53 and JK-54) have been designed and synthesized. Nanocrystalline TiO₂–silica-based dye-sensitized solar cells (DSSCs) were fabricated using these dyes. Under standard global AM 1.5 solar conditions, the JK-53-sensitized cell gave a short-circuit photocurrent density (J_sc) of 6.37 mA cm^?2, an open-circuit voltage (V_oc) of 0.70 V, and a fill factor of 0.74. These values correspond to an overall conversion efficiency (η) of 3.31%. By comparison, the JK-54-sensitized cell resulted in a J_sc of 7.52 mA cm^?2, a V_oc of 0.71 V, and a fill factor of 0.75. These values give an overall conversion efficiency of 4.01%.     

Photoelectrochemical solar cell properties of heteropolytungstic acid-incorporated TiO2 nanodisc thin films

Thin film of heteropolytungstic acid (HPA)-incorporated TiO₂ nanodisc was fabricated, and its photovoltaic performances were observed as a function of irradiation wavelength from 400 nm to 750 nm. Its incident photon-to-current efficiency (IPCE) was determined to be 18.6% around 500 nm, with energy conversion efficiency of 6.9%, which were observed to be further enhanced to 23% and 9%, respectively, by adsorption of ruthenium or porphyrin dyes. Complementary electron transports from both HPA and dyes to TiO₂ nanodisc seems to avoid most of the backward electron or hole transfer reactions to enhance the photoelectrochemical efficiencies of dye-sensitized solar cells.     

TiO2@CdS core–shell nanorods films: Fabrication and dramatically enhanced photoelectrochemical properties

In this paper, we prepared TiO₂@CdS core–shell nanorods films electrodes using a simple and low-cost chemical bath deposition method. The core–shell nanorods films electrodes were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and UV–vis spectrometry techniques. After applying these TiO₂@CdS core–shell nanorods electrodes in photovoltaic cells, we found that the photocurrent was dramatically enhanced, comparing with those of bare TiO₂ nanorods and CdS films electrodes. Moreover, TiO₂@CdS core–shell nanorods film electrode showed better cell performance than CdS nanoparticles deposited TiO₂ nanoparticles (P25) film electrode. A photocurrent of 1.31 mA/cm², a fill factor of 0.43, an open circuit photovoltage of 0.44 V, and a conversion efficiency of 0.8% were obtained under an illumination of 32 mW/cm², when the CdS nanoparticles deposited on TiO₂ nanorods film for about 20 min. The maximum quantum efficiency of 5.0% was obtained at an incident wavelength of 500 nm. We believe that TiO₂@CdS core–shell heterostructured nanorods are excellent candidates for studying some fundamental aspects on charge separation and transfer in the fields of photovoltaic cells and photocatalysis.     

A novel all-solid-state thin-film-type lithium-ion battery with in situ prepared positive and negative electrode materials

A novel all-solid-state thin-film-type rechargeable lithium-ion battery employing in situ prepared both positive and negative electrode materials is proposed. A lithium-ion conducting solid electrolyte sheet of Li₂O–Al₂O₃–TiO₂–P₂O₅-based glass–ceramic manufactured by OHARA Inc. (OHARA sheet) was used as the solid electrolyte, which was sandwiched by Cu and Mn metal films. The Cu/OHARA sheet/Mn layer became an all-solid-state lithium-ion battery after applying d.c. 16 V to the layer, and the resultant battery operated at 0.3–0.8 V with reversible capacity of 0.45 μAh cm^?2. High voltage battery was successfully prepared by applying the d.c. high voltage to a five-series of Cu/OHARA sheet/Mn layer, resulting in all-solid-state battery operating at 1.5–4.0 V. The proposed fabrication process will become a new technology to develop advanced all-solid-state rechargeable lithium-ion batteries.     

Enhanced electrochemical performance of carbon-coated TiO2 nanobarbed fibers as anode material for lithium-ion batteries

We report the electrochemical performance of carbon-coated TiO₂ nanobarbed fibers (TiO₂@C NBFs) as anode material for lithium-ion batteries. The TiO₂@C NBFs are composed of TiO₂ nanorods grown on TiO₂ nanofibers as a core, coated with a carbon shell. These nanostructures form a conductive network showing high capacity and C-rate performance due to fast lithium-ion diffusion and effective electron transfer. The TiO₂@C NBFs show a specific reversible capacity of approximately 170 mAh g^− 1 after 200 cycles at a 0.5 A g^− 1 current density, and exhibit a discharge rate capability of 4 A g^− 1 while retaining a capacity of about 70 mAh g^− 1. The uniformly coated amorphous carbon layer plays an important role to improve the electrical conductivity during the lithiation–delithiation process.     

Phosphatization: A promising approach to enhance the performance of mesoporous TiO2 anode for lithium ion batteries

We report phosphatization is a promising method to enhance the performance of mesoporous TiO₂ anode for lithium ion batteries. The resulting phosphated mesoporous TiO₂ possessed higher reversible capacity and better cycling stability than the pure mesoporous TiO₂. When cycled at 30 mA/g between 3.0 and 1.0 V, the initial capacity of phosphate mesoporous TiO₂ was 249 mA h/g, significantly higher than that of pure mesoporous TiO₂ (204 mA h/g). After 40 cycles, the capacity retention ratio of phosphate mesoporous TiO₂ reached 83.7%, while pure mesoporous TiO₂ had merely a capacity retention ratio of 62.3%. We believe that this phosphatization process could be used to enhance the electrochemical performance of other metal oxides for lithium ion batteries.     

Molecular dynamics simulations of adsorption of hydrophobic 1,2,4-trichlorobenzene (TCB) on hydrophilic TiO2 in surfactant emulsions and experimental process efficiencies of photo-degradation and -dechlorination

Molecular dynamics simulations have been carried out to assess event details in the adsorption of the hydrophobic substrate 1,2,4-trichlorobenzene (TCB) on the hydrophilic TiO₂ particle surface in the presence of the biosurfactant 4-O-(4′,6′-di-O-acetyl-2′,3′-di-O-alkanoyl-β-d-mannopyranosyl)-d-erythritol (MEL) and the SDS (sodium dodecylsulfate) surfactant in aqueous media at ambient temperature with interaction forces between organic molecules and TiO₂ calculated from Lennard–Jones and Coulomb potential models. The surfactant and the TCB substrate were arranged in the vicinity of TiO₂ using 768 water molecules in the simulations. Results indicate that the MEL molecules adsorb on the TiO₂ surface in ca. 5 ps (k = 2 × 10¹¹ s^?1) through the oxygen atoms of the hydrophilic functions. Contact distance between the MEL and the TiO₂ surface shortened further after 10 ps with adsorption controlled mostly by van der Waals’ forces. The TCB molecules are trapped within the alkyl chains of the MEL system, which subsumes TCB to a greater extent by the repulsion of water, thereby facilitating the TCB molecules to approach the highly hydrophilic and positively charged TiO₂ particle surface. Along with the simulations, also examined was the photodegradation of this hydrophobic TCB substrate that takes place at the TiO₂/water interface in the presence of the MEL biosurfactant. For comparison, the advantages of the MEL in this task and of the commonly used SDS surfactant were determined under otherwise identical experimental conditions (200 mg L^?1 of surfactants) by examining the dynamics of the photo-induced degradation and dechlorination of TCB. The photodegradation of TCB was nearly quantitative in MEL/TiO₂ in contrast to only ca. 22% complete in SDS/TiO₂ dispersions. It is deduced that wastewater treatments with the highly hydrophilic TiO₂ are seriously limited in their photodegradation of hydrophobic pollutants, an issue easily resolvable by the presence of biodegradable surfactants.     

High-surface-area microporous carbon as the efficient photocathode of dye-sensitized solar cells

This paper reports on the application of cornstalks-derived high-surface-area microporous carbon (MC) as the efficient photocathode of dye-sensitized solar cells (DSCs). The photocathode, which contains MC active material, Vulcan XC–72 carbon black conductive agent, and TiO₂ binder, was obtained by a doctor blade method. Electronic impedance spectroscopy (EIS) of the MC film uniformly coated on fluorine doped SnO₂ (FTO) glass displayed a low charge-transfer resistance of 1.32 Ω cm². Cyclic voltammetry (CV) analysis of the as-prepared MC film exhibited excellent catalytic activity for I₃^?/I^? redox reactions. The DSCs assembled with the MC film photocathode presented a short-circuit photocurrent density (J_sc) of 14.8 mA cm^?2, an open-circuit photovoltage (V_oc) of 798 mV, and a fill factor (FF) of 62.3%, corresponding to an overall conversion efficiency of 7.36% under AM 1.5 irradiation (100 mW cm^?2), which is comparable to that of DSCs with Pt photocathode obtained by conventional thermal decomposition.