The fabrication of TiO<Subscript>2</Subscript> nanoparticle/ZnO nanowire arrays bi-filmed photoanode and their effect on dye-sensitized solar cells

Porous TiO₂ nanoparticles coated on ZnO nanowire arrays (TiO₂ NP/ZnO NW) as photoanode for dye-sensitized solar cell (DSSC) has been fabricated and investigated to improve the power conversion efficiency. The TiO₂ NP/ZnO NW photoanode consists of single crystalline ZnO NWs synthesized via hydrothermal method and porous TiO₂ NP film covered on the surface of ZnO NW arrays by screen printing technique. The effect of TiO₂ NPs thickness of the bi-filmed photoanode on the cell performance has been investigated, and TiO₂ NP/ZnO NW DSSC with NP thickness of ~5 μm exhibits the best efficiency of 4.68%, higher than 1.16% of ZnO NW DSSC and 3.18% of TiO₂ NPs DSSC, prepared and tested under identical conditions. The efficiency increase is attributed to the enlarged photocurrent, due to the greatly enhanced surface area for dye absorption and light harvesting efficiency resulted from TiO₂ NPs, and improved open-circuit voltage, due to reduced electron recombination by providing direct conduction pathway along ZnO NWs.     

Synthesis and characterization of Co(OH)<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> nanotube composites as supercapacitor materials

A novel composite of Co(OH)₂ and TiO₂ nanotubes was synthesized by a chemical precipitation method. Co(OH)₂/TiO₂ nanotube composites and its microstructure were characterized by transmission electron microscopy (TEM), X-ray diffraction pattern (XRD). The electrochemical capacitance performance of this composite was investigated by cyclic voltammetry and charge–discharge tests with a three-electrode system in 6 M KOH solution. We synthesized different weight ratios of Co(OH)₂/TiO₂ nanotubes, a maximum specific capacitance of 229 F/g was obtained for the composite. Based on these tests, we propose that TiO₂ nanotubes provide the three-dimensional nanotube network structure for the composite and make the Co(OH)₂ dispersed. For these reasons, the TiO₂ nanotubes used as a framework for Co(OH)₂ improve the utilization of Co(OH)₂ greatly.     

Dye-Sensitized Solar Cell Utilizing TiO<Subscript>2</Subscript> Nanostructure Films: Effect of Synthesis Temperature

This paper is concerned with a study of the influence of synthesis temperature on the properties of TiO₂ films and the performance of dye-sensitized solar cell (DSSC). The TiO₂ film samples synthesized via liquid phase deposition for 5 h at various temperatures, namely, 40, 50, 60, 70 and 80°C. It was found that the morphological shape of the film changes with growth temperature. The optical absorption increases with growth temperature. However, the photoluminescence decreases with growth temperature. These TiO₂ samples were applied in a DSSC of ITO/TiO₂/electrolyte/platinum. The DSSC utilizing the sample grown at 40°C demonstrated the highest photovoltaic parameters with the J_sc, and η of 1.40 mA cm^–2 and 0.44% respectively. This is due to the smallest grain size of TiO₂ films and the smallest bulk resistance of the device.     

Preparation and photocatalytic activity of TiO<Subscript>2</Subscript> films with Ni nanoparticles

Titania thin films were synthesized by sol–gel dip-coating method with metallic Ni nanoparticles synthesized separately from an organometallic precursor Ni(COD)₂ (COD = cycloocta-1,5-diene) in presence of 1,3-diaminopropane as a stabilizer. Titania was obtained from a titanium isopropoxide precursor solution in presence of acetic acid. A Ni/TiO₂ sol system was used to coat glass substrate spheres (6, 4 and 3 mm diameter sizes), and further heat treatment at 400 °C was carried out to promote the crystallization of titania. XRD analysis of the TiO₂ films revealed the crystallization of the anatase phase. Transmission Electron Microscopy (TEM) and High Resolution TEM studies of Ni nanoparticles before mixing with the TiO₂ solution revealed the formation of Ni nanostructures with an average size of 5–10 nm. High-angle annular dark-field images of the Ni/TiO₂ system revealed well-dispersed Ni nanoparticles supported on TiO₂ and confirmed by AFM analysis. The photocatalytic activity of the Ni/TiO₂ films was evaluated in hydrogen evolution from the decomposition of ethanol using a mercury lamp for UV light irradiation. Titania films in presence of Ni nanoparticles show higher efficiency in their photocatalytic properties in comparison with TiO₂.     

Synthesis,characterization of B-doped TiO<Subscript>2</Subscript> nanotubes with high photocatalytic activity

B-doped TiO₂ nanotubes (B/TiO₂ NTs) were prepared by the combination of sol–gel process with hydrothermal treatment. The prepared catalysts were characterized by XRD, TEM and XPS. The photocatalytic activity of B/TiO₂ NTs was evaluated through the photodegradation of aqueous methyl orange. The results demonstrated that the 1.5% B/TiO₂ NTs calcined at 300 °C possessed the best photocatalytic activity. Compared with pure TiO₂ nanotubes, the doping with B significantly enhanced the photocatalytic efficiency.     

A double-layered photoanode made of ZnO/TiO<Subscript>2</Subscript> composite nanoflowers and TiO<Subscript>2</Subscript> nanorods for high efficiency dye-sensitized solar cells

We present a simple sol-gel hydrothermal process for the fabrication of a double-layered structure composed of a TiO₂ nanorod overlayer and TiO₂ nanoparticle-embedded ZnO nanoflower (ZNFs@TNPs-TNRs) underlayer. The ZNFs@TNPs-TNRs was used as a photoanode in dye-sensitized solar cells (DSSCs) and their photovoltaic performance was analyzed. The ZNFs@TNPs-TNRs can enhance the adsorption of N719 dyes, charge transport, and light scattering. The cell performances can be maximized by optimizing thickness ratio and total thickness of the double-layered photoanode, and the preliminary results demonstrate that a promising power conversion efficiency (PCE) of 8.01% is determined on the DSSC with ZNFs@TNPs-TNRs anode, yielding a 28.9% enhancement in the PCE in comparison to pristine TiO₂–P25 nanoparticle-based DSSC.     

Sonication-polished anodic TiO<Subscript>2</Subscript> nanotube array-based photoanode for efficient solar energy conversion

In this work, the capping layer atop anodic TiO₂ nanotube arrays (NTAs), which hinders filling of other guest materials and transport of charge carriers, is discerned to be TiO₂ nanotapes. Then, it is completely removed by a novel sonication-polishing (SP) treatment, after which Sb₂S₃ is subsequently introduced to fill the nanotubes by chemical bath deposition. The morphological, structural, and optical properties of the SP-treated TiO₂ NTAs and TiO₂ NTAs/Sb₂S₃ heterogeneous structures are characterized systematically. The results indicate that SP treatment opens the tops of nanotubes with diameters of ～120 nm, which endure a phase conversion from amorphous to anatase after calcination at 450 °C; besides, stibnite Sb₂S₃ with a band gap of ～1.75 eV inside the TiO₂ networks is formed upon heat treatment at 330 °C in Ar, which enhances the absorption in visible light range. The photoelectrochemical (PEC) and photovoltaic properties for the SP-treated TiO₂ NTAs are investigated. Results shows that the photoresponse of TiO₂ NTAs is improved by the SP treatment, and the photocurrent for the TiO₂ NTAs/Sb₂S₃ electrode is substantially enhanced as compared to the bare TiO₂ one. A high efficiency of 6.28 % is achieved in a TiO₂ NTAs/Sb₂S₃ PEC cell. In addition, charge recombination in the photoanode of dye-sensitized solar cells (DSSCs) is observed to be greatly retarded by using the SP-treated TiO₂ NTAs as compared to TiO₂ nanoparticles (NPs). Thus, the SP anodic TiO₂ NTAs are promising in applications in various PEC areas such as photocatalysis and sensitized solar cells.     

Extensive enhancement in power conversion efficiency of dye-sensitized solar cell by using Al-doped TiO<Subscript>2</Subscript> photoanode

In this work, we have prepared Al-doped TiO₂ nanoparticles via a hydrothermal method and used it for making photoanode in dye-sensitized solar cell (DSSC). Material characterizations were done using XRD, AFM, SEM, TEM and EDAX. XPS results reveal that Al is introduced successfully into the structure of TiO₂ creating new impurity energy levels in the forbidden gap. This resulted in tuning of the conduction band of TiO₂ and reduced charge recombination which led to better current conversion efficiency of DSSC. Greater dye loading and enhanced surface area was obtained for Al-doped TiO₂ compared to un-doped TiO₂. I-V analysis, EIS and Bode plots are employed to evaluate photovoltaic performance. The short-circuit current density (J _sc) and efficiency (η) of cell employing Al-doped TiO₂ photoanode were extensively enhanced compared to the cell using un-doped TiO₂. The optical band gap (E _g) for Al-doped and un-doped TiO₂ was obtained as 2.8 and 3.2 eV, respectively. J _sc and η were 13.39 mAcm^?2 and 4.27%, respectively, under illumination of 100 mWcm^?2 light intensity when thin films of 1% Al-doped TiO₂ was employed as photoanode in DSSC using N719 as the sensitizer dye. With the use of un-doped TiO₂ as photoanode under similar conditions, J _sc 5.12 mAcm^?2 and η 1.06% only could be obtained. The maximum IPCE% obtained with Al-doped TiO₂ and un-doped TiO₂ was 67 and 38% respectively at the characteristic wavelength of dye (λ _max = 540 nm). The EIS analyses revealed resistive and capacitive elements that provided an insight into various interfacial processes in terms of the charge transport. It was observed that Al-doping reduced the interfacial resistance leading to better charge transport which has improved both photocurrent density and conversion efficiency. Higher electron mobility and fast diffusion resulting in greater charge collection efficiency was obtained for Al-doped TiO₂ compared to the un-doped TiO₂. Using the Mott–Schottky plot, the donor density was calculated for un-doped and Al-doped TiO₂. The work demonstrated that the Al-doped TiO₂ is potential photoanode material for low-cost and high-efficiency DSSC.     

Array of electrodeposited Ru-decorated TiO<Subscript>2</Subscript> nanotubes with enhanced photoresponse

Although TiO₂ anatase phase has been widely chosen as the main photocatalyst, it presents high electron/hole recombination rate. However, today, what is sought is a semiconductor material with enhanced photocatalytic activity with higher photon to electron conversion efficiency by introduction of electrons trap dopants. In this paper, TiO₂ nanotubes arrays obtained by anodization of Ti substrates were decorated with Ru via electrodeposition, and their photo-response was investigated. First, voltammetric experiments were performed to elucidate the route of Ru reduction on the TiO₂ surface and to select the range of potentials for Ru deposition. The reduction potentials were used for controlling the amount of Ru distributed all over the surface. Although Ru was electrodeposited at potentials over the range from ??0.025 to ??0.188 V vs. Ag/AgCl, the deposition of 3.7 mC cm^?2 at ??0.100 V for 30 min resulted in a tenfold greater photocurrent when compared to the recorded photocurrent for the undecorated TiO₂ nanotubes array. Next, Ru-decorated TiO₂ nanotubes with a length of 323?±?18 nm and inner and outer diameters of 91 and 104 nm, respectively, were characterized using SEM-WDS, SEM-FEG, XRD, and XPS. UV-Vis-NIR diffuse reflectance spectroscopy and photoluminescence (PL) measurements, which revealed a maximum PL emission at 445 nm, showed that for the array of Ru-decorated TiO₂ nanotubes, the electron-hole recombination may be effectively inhibited by the presence of ruthenium electrodeposited, which can make this photocatalyst even more attractive for environmental applications. The performances of the TiO₂ and Ru-decorated TiO₂ catalysts were compared in heterogeneous photocatalysis experiments for color removal of an azo-dye, which presented a pseudo-first-order rate constant more than twofold greater for the Ru-decorated TiO₂ catalysts.     

Interlaced polyaniline/carbon nanotube nanocomposite co-electrodeposited on TiO<Subscript>2</Subscript> nanotubes/Ti for high-performance supercapacitors

A series of PANI-CNTs/TiO₂ nanotubes/Ti electrodes were fabricated via pulse current co-electrodeposition of polyaniline and functionalized carbon nanotubes onto TiO₂ nanotubes/Ti electrodes. FT-IR spectrometry, X-ray photoelectron spectroscopy, and scanning electron microscopy were applied in order to characterize the modified TiO₂ nanotubes/Ti electrodes. The morphology studies showed that the PANI-CNTs/TiO₂ nanotubes/Ti nanocomposite electrode has many interlaced PANI-CNTs nanorods on the surface of TiO₂ nanotubes. The electrochemical measurements of the modified electrodes confirmed that the CNTs in the composite can significantly improve the capacitive behavior as well which have been compared with that of PANI/TiO₂ nanotubes/Ti electrodes. The modified electrode exhibited much higher specific capacitance (190 mF cm^?2 with 90% retention after 1000 cycles) compared to the PANI/TiO₂ nanotubes/Ti (70 mF cm^?2 with 77% retention after 1000 cycles) at a current density of 0.85 mA cm^?2, indicating its great potential for supercapacitor applications.

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Graphical abstract Interlaced polyaniline/carbon nanotube nanocomposite electrodeposited on TiO₂ nanotubes/Ti

     

Entrapment of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles in TiO<Subscript>2</Subscript> nanotubes for visible light-driven photocatalysis

In this study, we prepared nanoparticles of the visible light-responsive photocatalyst, Bi₂O₃ entrapped in anatase TiO₂ nanotubes (Bi₂O₃-in-TNTs) via a vacuum-assisted precursor-filling process followed by annealing. Owing to the unique tubular electronic structure of TiO₂ nanotubes, the interior of the nanotube is in an electron-deficient state, which was confirmed by XPS spectra and H₂-TPR. Electrochemical impedance studies showed that the Bi₂O₃-in-TNTs demonstrated a more efficient separation of photogenerated carriers than when Bi₂O₃ nanoparticles were deposited on the outer wall of TiO₂ nanotubes (Bi₂O₃-out-TNTs). Due to the confinement effect of TiO₂ nanotubes, which inhibits photogenerated carriers’ recombination, the Bi₂O₃-in-TNTs exhibited a better photocatalytic performance for the photo-degradation of methyl orange under visible light compared to Bi₂O₃-out-TNTs.     

Single-Step Synthesis of SiO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript> Hydrophobic Core–Shell Nanocomposite by Hydrothermal Method

The objective of this work is the synthesis and characterization of an appropriate hydrophobic nanoparticle as a collector for flotation of hematit in Gol-E-Gohar Iron Mine Iran. In this investigation, SiO₂–TiO₂ nanocomposites have been successfully synthesized by hydrothermal process. The morphology, structure, and composition of the as-synthesized nanostructures have been investigated by scanning electron microscopy and transmission electron microscopy. The ability of SiO₂–TiO₂ nanocomposite to facilitate the froth flotation of pyrite was correlated to the hydrophobicity of the nanoparticles. Furthermore, the efficiency of the mineral flotation process was evaluated in terms of final recovery and grade of S in Gol-e Gohar Iron Ore Complex, Sirjan, Iran.     

Synthesis and Characterization of Spindle-Like TiO<Subscript>2</Subscript> Nanostructures and Photocatalytic Activity on Methyl Orange and Methyl Blue Dyes Under Sunlight Radiation

Spindle-like TiO₂ nanostructures was prepared by a simple one pot solvothermal method followed by calcination at 400 °C for 3 h. The sample was characterized using various techniques such as X-ray diffractometer, transmission electron microscopy, Fourier transform infrared spectroscopy and UV–Vis absorption spectroscopy. The crystal structure of TiO₂ nanostructure was measured by X-ray diffractometer. According to the XRD result, the peaks in the sample can be indexed to anatase phase of TiO₂. The morphological characterization of TiO₂ sample was examined by transmission electron microscopy. The synthesized sample consisted of spindle-like shape with size in the range of 50–70 nm. The band gap value of Spindle-like TiO₂ nanostructures is 2.92 eV, which is lower than that of bulk TiO₂ of 3.2 eV. The FTIR bands observed at 493, 443 and 428 cm^?1 confirms the presence of TiO₂. The Spindle-like TiO₂ nanostructures showed photodegradation ability for methyl orange and methyl blue dye. The reuse evaluation of the Spindle-like TiO₂ nanostructures showed that their photocatalytic activity had good durability.     

Morphological,electrochemical and photoelectrochemical characterization of nanotubular TiO2 synthetized electrochemically from different electrolytes

The electrochemical synthesis of auto-organized TiO₂ arrays generated by Ti anodization in different non-aqueous electrolytes was analyzed. Propylene carbonate-based electrolytes seem to be good electrolytic media for the controlled growth of titania nanotube structures. Scanning electron microscopy (SEM) analysis indicated that, depending on the media employed in the synthesis of the TiO₂ nanotubes, different aspect ratios (length/diameter) could be obtained. Impedance analysis using the passive pit model gave the electrical properties of the layers during the different stages of nanotubes formation. Mott–Schottky analysis and the impedance results showed that the TiO₂ nanotubes layers were n-type semiconductors with highly defective walls on top of a resistive barrier layer. Photoelectrochemical measurements showed that tetra(4-carboxyphenyl)porphyrin (TCPP) adsorbed onto the TiO₂ nanotube arrays, which could be employed as an efficient photosensitizer for solar-energy conversion by TCPP-sensitized nanotubular TiO₂ electrodes.     

Visible-light-sensitive N-doped TiO<Subscript>2</Subscript> photocatalysts prepared by a mechanochemical method: effect of a nitrogen source

Nitrogen-doped titanium dioxide (N-doped TiO₂) photocatalysts were prepared by a mechanochemical method by using a high-speed ball milling of P25 TiO₂ with nitrogen sources such as ammonia solution, hexamine, and urea. Visible-light absorption was determined from the onset of diffused reflectance spectrum. The photocatalytic activity of the N-doped TiO₂ was evaluated through the removal of methylene blue (MB) under visible-light irradiation. The effects of nitrogen precursors used during the mechanochemical synthesis on the catalysts’ properties, such as the effective particle size, surface area, and photocatalytic activity, were extensively investigated.     

Nanosized TiO<Subscript>2</Subscript> particles decorated on SiO<Subscript>2</Subscript> spheres (TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript>): synthesis and photocatalytic activities

Nanosized TiO₂ and nano-anatase TiO₂ decorated on SiO₂ spherical core shells were synthesized by using a sol–gel method. The synthesized pure TiO₂ nano particle and TiO₂ grafted on SiO₂ sphere with various ratios have been characterized for their structure and morphologies by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectrophotometry (FTIR) and transmission electron microscopy (TEM). Their surface areas were measured using the BET method. The photocatalytic activity of all nanocomposites was investigated using methylene blue as a model pollutant. The synthesized TiO₂/SiO₂ particles appeared to be more efficient in the degradation of methylene blue pollutant, as compared to pure TiO₂ particles.     

Synthesis,Adsorptive, and Photocatalytic Properties of Carbon Nanotubes/TiO<Subscript>2</Subscript> Nanocomposite Photocatalysts

The carbon nanotubes/TiO₂ (CNTs/TiO₂) composite photocatalysts composed of TiO₂ nanoparticles and multiwalled carbon nanotubes (CNTs) were prepared by a facile hydrothermal method. The photocatalysts were characterized by a range of analytical techniques including X-ray powder diffraction, field emission scanning electron microscope, thermal gravimetric analysis and UV–Vis optical absorption spectra, etc. The amount of TiO₂ nanoparticles growing on CNTs could be tuned by adjusting the dosage of precursor in the reaction solution. Both the adsorptivity and photocatalytic activities of pure CNTs, pure TiO₂, and the CNTs/TiO₂ nanocomposites were tested by the removal of methylene blue from water in dark and under a simulated sunlight, respectively. By comparison, the improved photocatalytic activity of the CNTs/TiO₂ nanocomposite is mainly due to that the CNTs can disperse the active component of TiO₂ nanoparticles, provide a larger the specific surface area, as well as act as an electron sink to accelerate the separation of the photogenerated charges.     

Atomic layer deposition of TiO2 nanotubes and its improved electrostatic capacitance

Titanium dioxide (TiO₂) nanotubes are fabricated into anodic aluminum oxide (AAO) membrane via atomic layer deposition (ALD). For the ALD of TiO₂, gaseous precursors, titanium (IV) isopropoxide and water are sequentially applied and chemically reacted with each other. A thickness of nanotubes is precisely controlled by the applied cycle numbers of ALD and the morphology of nanostructures is investigated by SEM and TEM. The amorphous property of TiO₂ nanostructures is revealed by XRD and the composition of nanotubes is measured by TEM–EDX. The impurity contents and binding structure of the nanostructures are analyzed by XPS. The electrostatic capacitance of TiO₂ nanotubes into AAO is 480 μF/cm² and it is about 3 times higher compared with AAO membrane (172 μF/cm²).     

Three-dimensional hierarchical CeO<Subscript>2</Subscript> nanowalls/TiO<Subscript>2</Subscript> nanofibers heterostructure and its high photocatalytic performance

Combining the versatility of electrospinning technique and hydrothermal growth of nanostructures enabled the fabrication of hierarchical CeO₂/TiO₂ nanofibrous mat. The as-prepared hierarchical heterostructure consisted of CeO₂ nanowalls growing on the primary TiO₂ nanofibers. Interestingly, not only were secondary CeO₂ nanowalls successfully grown on TiO₂ nanofibers substrates, but also the CeO₂ nanowalls were uniformly distributed without aggregation on TiO₂ nanofibers. The photocatalytic studies suggested that the CeO₂/TiO₂ heterostructures showed enhanced photocatalytic efficiency compared with bare TiO₂ nanofibers under UV light irradiation.     

Photocatalytic activity of Au/TiO<Subscript>2</Subscript> nanocomposite for azo-dyes degradation

The structural properties of Au/TiO₂ catalyst were studied by X-ray diffraction, UV-visible diffuse reflectance, photoluminescene, scanning transmission and electron microscope, and temperature programmed reduction. The photocatalytic activity of the catalysts was evaluated for the degradation of various azo-dyes such as methylene blue, methyl orange, reactive blue-4, and eosin-B under solar irradiation. It was found that TiO₂ catalyst modified with gold exhibits higher percentage of degradation compared to starting TiO₂. For example, TiO₂ showed 35% of methyl orange degradation whereas gold modified TiO₂ possessed 82%. Effect of different parameters such as pH and dye concentration has been evaluated and the photocatalytic activity was correlated with physico-chemical properties. The dye degradation rate followed first order kinetics.