Biophotofuel cell anode containing self-organized titanium dioxide nanotube array

We made a biophotofuel cell consisting of a titanium dioxide nanotube array photosensitive anode for biomass decomposition, and a low-hydrogen overpotential metal, Pt, as the cathode for hydrogen production. The titanium dioxide nanotubes (TiO₂ NTs) were prepared via electrochemical oxidation of pure Ti in NaF solutions. Scanning electron microscopy was used to analyze the morphology of the nanotubes. The average diameter, wall thickness and length of the as-prepared TiO₂ NTs were 88 ± 16 nm, 10 ± 2 nm and 491 ± 56 nm, respectively. Such dimensions are affected by the NaF concentration and the applied voltage during processing. Higher NaF concentrations result in the formation of longer and thicker nanotubes. The higher the voltage is, the thicker the nanotubes. The photosensitive anode made from the highly ordered TiO₂ NTs has good photo-catalytic property, as can be seen from the test results of ethanol, apple vinegar, sugar and tissue paper decomposition under ultraviolet (UV) radiation. It is concluded that the biophotofuel cell with the TiO₂ nanotube photoanode and a Pt cathode can generate electricity, hydrogen and clean water depending on the pH value and the oxygen presence in the solutions.     

Photoelectrochemical responses of doped and coated titanium dioxide composite nanotube anodes

Nanostructured photoelectrochemical anodes were made from titanium dioxide nanotubes doped with various metals including Fe, Cu, Ni, Ag, and added with polyaniline to enhance the photosensitivity. The TiO₂ nanotubes were obtained through electrochemical oxidation of Ti foil in a glycerol aqueous solution. Electroplating followed by high temperature treatment induced element substitution approach was used to achieve doping effect. Transmission electron microscopy and energy dispersive X-ray diffraction analysis were performed to reveal the structure and obtain the composition information. To examine the photoelectrochemical response, the anode was polarized at the constant bias voltages of 0.5, 1.0, 1.5, 2.0 V and under the exposure of both ultraviolet and visible light. Linear scan was also performed in the potential range of 0–2 V. It is found that Fe, Ni, and Cu doped and polyaniline covered nanotubes show obvious photoelectrochemical activities. Polyaniline covered nanotube anode has better performance than others. Cu-doped anode shows the highest current density in the linear scan voltage range.     

Synthesis of TiO2 nanotubes coupled with CdS nanoparticles and production of hydrogen by photocatalytic water decomposition

The CdS/TiO₂NTs composite was prepared by a simple two-step chemical solution routes to directly transfer trititanate nanotubes to TiO₂NTs and simultaneously coupled with CdS nanoparticles. The results of XRD, TEM, Diffuse reflectance UV-Visible absorption spectra revealed that the CdS nanoparticles were homogeneously embedded on the surface of TiO₂NTs and the absorption spectrum of TiO₂NTs was extended to visible region. The activity of hydrogen production by photocatalytic water decomposition for the CdS/TiO₂NTs composite was examined under visible light irradiation (λ > 400 nm) and the quantity of H₂ evolution was ca. 1708 μL/g for 6 h.     

Novel UV–Visible Photodetector in Photovoltaic Mode with Fast Response and Ultrahigh Photosensitivity Employing Se/TiO2 Nanotubes Heterojunction

A feasible strategy for hybrid photodetector by integrating an array of self‐ordered TiO₂ nanotubes (NTs) and selenium is demonstrated to break the compromise between the responsivity and response speed. Novel heterojunction between the TiO₂ NTs and Se in combination with the surface trap states at TiO₂ help regulate the electron transport and facilitate the separation of photogenerated electron–hole pairs under photovoltaic mode (at zero bias), leading to a high responsivity of ≈100 mA W^?1 at 620 nm light illumination and the ultrashort rise/decay time (1.4/7.8 ms). The implanting of intrinsic p‐type Se into TiO₂ NTs broadens the detection range to UV–visible (280–700 nm) with a large detectivity of over 10¹² Jones and a high linear dynamic range of over 80 dB. In addition, a maximum photocurrent of ≈10⁷ A is achieved at 450 nm light illumination and an ultrahigh photosensitivity (on/off ratio up to 10⁴) under zero bias upon UV and visible light illumination is readily achieved. The concept of employing novel heterojunction geometry holds great potential to pave a new way to realize high performance and energy‐efficient optoelectronic devices for practical applications.     

Co/Mn co-doped TiO<Subscript>2</Subscript> nanotube arrays for enhanced photoelectrochemical properties: experimental and DFT investigations

In this study, we used first principle calculations to investigate the electronic properties of TiO₂ modified with eight different elements. Co/Mn co-doped TiO₂ nanotube arrays, which had the smallest band gap, were subsequently prepared using electrochemical anodization followed by atomic force microscopy (AFM) and field emission scanning electron microscopy (FE-SEM) measurements. The results showed that the TiO₂ nanotube arrays were highly ordered and well aligned. Finally, the photoconversion efficiency was measured using photoelectrochemical experiments and, under the same conditions, the photoconversion efficiency under visible light increased approximately three times from 9.35% for the undoped TiO₂ nanotubes to 21.25% for the Co/Mn co-doped TiO₂ nanotubes. These results indicate that Co/Mn co-doped TiO₂ nanotube arrays can improve the efficiency of visible-light utilization and could be a promising material in such fields as photocatalysis and solar cells.     

Au Nanoclusters Sensitized Black TiO2−x Nanotubes for Enhanced Photodynamic Therapy Driven by Near‐Infrared Light

The low reactive oxygen species production capability and the shallow tissue penetration of excited light (UV) are still two barriers in photodynamic therapy (PDT). Here, Au cluster anchored black anatase TiO_2?x nanotubes (abbreviated as Au₂₅/B‐TiO_2?x NTs) are synthesized by gaseous reduction of anatase TiO₂ NTs and subsequent deposition of noble metal. The Au₂₅/B‐TiO_2?x NTs with thickness of about 2 nm exhibit excellent PDT performance. The reduction process increased the density of Ti³⁺ on the surface of TiO₂, which effectively depresses the recombination of electron and hole. Furthermore, after modification of Au₂₅ nanoclusters, the PDT efficiency is further enhanced owing to the changed electrical distribution in the composite, which forms a shallow potential well on the metal–TiO₂ interface to further hamper the recombination of electron and hole. Especially, the reduction of anatase TiO₂ can expend the light response range (UV) of TiO₂ to the visible and even near infrared (NIR) light region with high tissue penetration depth. When excited by NIR light, the nanoplatform shows markedly improved therapeutic efficacy attributed to the photocatalytic synergistic effect, and promotes separation or restrained recombination of electron and hole, which is verified by experimental results in vitro and in vivo.     

Influence of the size-controlled TiO<Subscript>2</Subscript> nanotubes fabricated by low-temperature chemical synthesis on the dye-sensitized solar cell properties

Titanium dioxide nanotubes (TiO₂ NTs) with various sizes have been prepared by low-temperature chemical synthesis using commercial anatase TiO₂ particles with different crystallite size in NaOH solution and used as a photoelectrode in a dye-sensitized solar cell (DSSC). The relationship between the physicochemical properties of electrode materials and photovoltaic performance was investigated. The electrodes made from modified TiO₂ NTs showed a strong dependency on their specific surface area and resultant amount of dye adsorption; the surface area decreased with increase in the diameter of the NT from 9.8 to 23.6 nm. The conversion efficiency of the cell made from TiO₂ NT, 12.9 nm in diameter, was enhanced by 12% compared to that of the smallest NT. These results suggested that the photovoltaic performance improved by the suppression of photogenerated charge recombination in spite of a 25.3% reduction in the specific surface area. In addition, larger TiO₂ NTs could be utilized as a scattering layer on the top of the TiO₂ nanoparticulate working electrode. It was observed that this controlled TiO₂ photoelectrode architecture exhibited enhanced conversion efficiency without TiCl₄ treatment.     

Synthesis and characterization of anodized titanium-oxide nanotube arrays

Anodized titanium-oxide containing highly ordered, vertically oriented TiO₂ nanotube arrays is a nanomaterial architecture that shows promise for diverse applications. In this paper, an anodization synthesis using HF-free aqueous solution is described. The anodized TiO₂ film samples (amorphous, anatase, and rutile) on titanium foils were characterized with scanning electron microscopy, X-ray diffraction, and Raman spectroscopy. Additional characterization in terms of photocurrent generated by an anode consisting of a titanium foil coated by TiO₂ nanotubes was performed using an electrochemical cell. A platinum cathode was used in the electrochemical cell. Results were analyzed in terms of the efficiency of the current generated, defined as the ratio of the difference between the electrical energy output and the electrical energy input divided by the input radiation energy, with the goal of determining which phase of TiO₂ nanotubes leads to more efficient hydrogen production. It was determined that the anatase crystalline structure converts light into current more efficiently and is therefore a better photocatalytic material for hydrogen production via photoelectrochemical splitting of water.     

Efficient visible-light driven photocatalysts: coupling TiO<Subscript>2</Subscript>(AB) nanotubes with g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> nanoflakes

The wide application of the titanium dioxide (TiO₂) as the photocatalysts is greatly hindered by its intrinsic large band gap and usually fast electron–hole recombination. Here, we reported the exploration of coupling g-C₃N₄ nanoflakes to TiO₂ nanotubes with the anatase and TiO₂(B) mixed phases (TiO₂(AB)) toward the efficient visible-light-driven hybrid photocatalyst. It is found that coupling TiO₂(AB) nanotubes with g-C₃N₄ nanoflakes could bring a profoundly extension the visible light adsorption capacity and enhanced photogenerated carrier separation. Accordingly, they exhibit much higher efficient photocatalytic activities toward the degradation of sulforhodamine B under the visible light irradiation, which is enhanced for nearly 15 times to those of the TiO₂(AB) and g-C₃N₄, suggesting their promising practical applications as novel and efficient semiconductor photocatalysts for the water purification.     

Novel construction of CdS-encapsulated TiO2 nano test tubes corked with ZnO nanorods

A novel TiO₂ nanotube array/CdS nanoparticle/ZnO nanorod (TiO₂ NT/CdS/ZnO NR) photocatalyst was constructed by chemical assembling CdS into the TiO₂ NTs, and then laying ZnO NRs on the surface. The SEM results showed that the TiO₂ NTs looked like many “nano test tubes” and the ZnO NRs served as the corks to seal the nozzle. This photocatalyst exhibited a wide absorption range (200-535 nm) in both ultraviolet and visible regions (UV-vis region), and maintained very high photoelectrocatalytic (PEC) activities. The maximum photoelectric conversion efficiencies (η) of TiO₂ NT/CdS/ZnO NRs are 31.8 and 5.98% under UV light (365 nm) and visible light (420-800 nm), respectively.     

Facile preparation and photoelectrochemical properties of CdSe/TiO2 NTAs

In the present work we report the design and synthesis of CdSe/TiO₂ nanotube arrays (NTAs) and their implementation as a photoanode for photoelectrochemical (PEC) application. CdSe nanoparticles with well dispersion were decorated on the inner and outer surfaces of 2.5 μm-long TiO₂ nanotubes via electrodeposition. These CdSe/TiO₂ NTAs exhibit a significant photocurrent responds under visible light illumination (λ ≥ 420 nm). The results presented in this study display a promising method that the photoelectrochemical performance could be improved via composition, size and crystalline control of CdSe/TiO₂ NTAs. And the tubular morphology is also able to facilitate charge transport in nanostructure-based PEC cells. This research demonstrates a new approach, which have great potential applications in fabricating novel heterostructure-photoelectrochemical devices.     

Removal of fluoride from aqueous solution by polypyrrole/Fe3O4 magnetic nanocomposite

Highly efficient visible light TiO₂ photocatalyst was prepared by the sol-gel method at lower temperature (≤300 °C), and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and differential scanning calorimetry-thermogravimetric analysis (DSC-TGA). The effects of the heat treatment temperature and time of the as-prepared TiO₂ on its visible light photocatalytic activity were investigated by monitoring the degradation of methyl orange solution under visible light irradiation (wavelength ≥ 400 nm). Results show that the as-prepared TiO₂ nanoparticles possess an anatase phase and mesoporous structure with carbon self-doping and visible photosensitive organic groups. The visible light photocatalytic activity of the as-prepared TiO₂ is greatly higher than those of the commercial TiO₂ (P-25) and other visible photocatalysts reported in literature (such as PPy/TiO₂, P3HT/TiO₂, PANI/TiO₂, N-TiO₂ and Fe³⁺-TiO₂) and its photocatalytic stability is excellent. The reasons for improving the visible light photocatalytic activity of the as-prepared TiO₂ can be explained by carbon self-doping and a large amount of visible photosensitive groups existing in the as-prepared TiO₂. The apparent optical thickness (τ_app), local volumetric rate of photo absorption (LVRPA) and kinetic constant (k_T) of the photodegradation system were calculated.     

Photochemical deposition of platinum on titanium dioxide–tungsten trioxide nanocomposites: an efficient photocatalyst under visible light irradiation

Highly ordered titanium dioxide–tungsten trioxide nanotubular composites (TiO₂–WO₃) were fabricated on titanium sheets by electrochemical anodizing. Platinum nanoparticles have been successfully deposited onto TiO₂–WO₃ nanotubes by UV light photoreduction method. In this work, X-ray diffraction, field emission scanning electron microscope, ultraviolet–visible spectroscopy and energy dispersive X-ray spectrometer methods were adopted to characterize the samples. The degradation of methylene blue (MB) was used as a model reaction to evaluate the photocatalytic activity of the obtained samples. After irradiated under visible light for 60 min, the degradation rate of MB solution on unmodified TiO₂–WO₃ and Pt/TiO₂–WO₃ reached 77 and 93 %, respectively. Under the same condition, no obvious photodegradation of MB was found for bare TiO₂ (T). Kinetic research showed that photodegradation process followed the first-order reaction; the apparent reaction rate constant of Pt/TiO₂–WO₃-1 was 4.56 × 10^?2 min^?1 which is approximately 1.75 times higher than that on the unmodified TiO₂–WO₃. This work provides an insight into designing and synthesizing new TiO₂–WO₃ nanotubes based hybrid materials for effective visible light-activated photocatalysis.     

Enhancement of visible light-induced hydrophilicity on nitrogen and sulfur-codoped TiO2 thin films

We fabricated N, S-codoped, N-doped, S-doped TiO₂ anatase thin films by a radio-frequency (RF) sputtering method and evaluated the photoelectrochemical and photoinduced hydrophilic activities. The N, S-codoped TiO₂ thin film showed obviously higher activities than either the N-doped or S-doped TiO₂ under visible light irradiation. The photoinduced hydrophilic activity of the N, S-codoped TiO₂ was also greater than that of the undoped TiO₂ even under fluorescent light bulb, which contained both visible and UV lights. The high activities of the N, S-codoped TiO₂ could be attributed to the hybridization of the introduced N 2p and S 3p, which was supported by the results of ab initio calculations.     

Performance evaluation of a novel visible-driven CNT/TiO2/WO3/CdS heterojunction in photocatalytic fuel cell: Photodegradation of Reactive Blue 19 and electricity production

A photoelectrochemical degradation of reactive blue 19 (RB19) and electricity generation was modeled and optimized in a photocatalytic fuel cell with CNT/TiO₂/WO₃/CdS/FTO photoanode and Cu₂S/FTO photocathode using response surface methodology-central composite design. The coated photocatalyst on fluorine-doped tin oxide (FTO) was characterized by surface and cross-section FESEM, EDX spectrum, EDS mapping, XRD, and DRS analysis. The CNT/TiO₂/WO₃/CdS and Cu₂S were coated on FTO glass by applying the dip coating and combined dip coating-SILAR method, respectively. The efficiency of RB19 and Chemical oxygen demand removal under the optimum circumstances of 15 mg/L dye concentration, pH = 4, and the light intensity of 890 lm were obtained at 99.9 % and 70 % after 4.5 h, respectively. Moreover, the generated current density during the photocatalytic process was calculated at about 41.3 µA/cm² after 90 min. The effect of air injection, open and closed electrical circuits, light radiation, and adsorption rate of photocatalysts on RB19 removal was examined. The five times reusability confirmed the good stability and photoactivity of coated catalyst on the FTO electrodes at the optimum conditions. The result indicated that the photocatalytic fuel cell is an excellent technology not only for wastewater treatment but also for energy production.     

Photocatalytic degradation of 2,4-dichlorophenol wastewater using porphyrin/TiO2 complexes activated by visible light

The use of TiO₂ as photocatalyst to degrade the organic compounds is an effective method of oxidation process and has been widely studied in environmental engineering. However, TiO₂ absorbed the UV light which is only small part of sunlight reaching earth surface to activate photocatalytic procedure effectively is a major disadvantage. Therefore, studies on the development of new TiO₂ wherein its photocatalytic activity can be activated by visible light which is the major part of sunlight will be valuable for field application. In this study, we evaluate the photocatalytic degrading efficiency of porphyrins/TiO₂ complexes on the organic pollutants under irradiation with visible light (λ = 419 nm). The results showed that the photodecomposition efficiency of 2,4-dichlorophenol (2,4-DCP) wastewater by using porphyrin/TiO₂ irradiated under visible light for 4 h was up to 42-81% at pH 10. These evidences reveal that the system of porphyrin/TiO₂ complexes has also significantly efficiency of photocatalytic degradation for some hazardous or recalcitrant pollutants under visible light irradiation.     

Spectroscopic Characterization of Nanohybrids Consisting of Single-walled Carbon Nanotubes and Fullerodendron

Hydrogen gas, which can be used in fuel cells to generate electricity, is considered the ultimate clean energy source. Recently, it was reported that a photo-induced electron transfer system consisting of single-walled carbon nanotubes (SWCNTs) and fullerodendrons shows photo-catalytic activity with a very high quantum yield for splitting water under visible light irradiation. However, the mechanism of high efficiency hydrogen generation is not yet clearly understood. We report here the spectroscopic characterizations of the SWCNT-fullerodendron composites. The results indicate two important fundamental properties of the composite system. First, fullerodendrons preferentially interact with the semiconducting SWCNTs instead of with their metallic counterparts. Second, the photo-induced electron transfer process from the C₆₀ moiety of fullerodendrons to SWCNTs occurs more efficiently with an increasing tube diameter.     

A review of growth mechanism,structure and crystallinity of anodized TiO2 nanotubes

This paper reviews the state of the art of anodized titanium dioxide nanotubes (TiO₂ NTs), with an emphasis on the growth mechanism leading to their formation and the effect of heat treatment on their structure and properties. The discussion is primarily focused on TiO₂ NTs grown in fluoride containing electrolytes, although the mechanism of formation of NTs in fluoride free solutions via Rapid Breakdown Anodization (RBA) is briefly covered. After an initial overview of progress made on the synthesis of anodized TiO₂ NTs the review provides an analysis of the factors affecting the anodizing process (fluoride concentration, electrolyte type, applied potential and anodizing time). Details of the current-time transient, the chemistry of the process and the chemical composition of the anodic films are described which provide key information to unveil the nanotube growth mechanism. The main debate is whether NTs growth in fluoride containing solutions occurs via field-assisted plastic flow (i.e. a constant upward displacement of the oxide to form the NTs) combined with field-assisted ejection of the Ti⁴⁺ ions (i.e. ions are ejected into the electrolyte without oxide formation) or via field-assisted dissolution (i.e. preferential dissolution at the pore base where the field is stronger) or whether both processes play a role. Whenever anodization takes place in organic solutions the experimental evidence supports the plastic flow model, whereas in aqueous media field-assisted (and chemical) dissolution occur. The mechanism of rib formation on the walls of the NTs is also reviewed, and it clearly emerges that the applied potential and water content in the electrolyte are key factors in determining whether the NTs are ribbed or smooth. There also appears to be a relationship between the presence of ribs and the evolution of oxygen bubbles at the anode. The impact of thermal treatment on the properties of the NTs is also described. A variety of crystalline structures are present in the NTs (i.e. anatase or rutile), depending on the heat treatment temperature and atmosphere and the resulting electrical properties can be varied from dielectric to semi-metallic. A heat treatment temperature limit ranging from 500 to 800 °C exists, depending on preparation history, above which sintering of nanoscale titania particles occurs leading to collapse of the NTs structure. Future work should aim at using annealing not just to influence the resulting crystalline phase, but also for generating defects to be exploited in specific applications (i.e. photocatalysis, water splitting and photovoltaics).     

Visible-light-active silver- , vanadium-codoped TiO<Subscript>2</Subscript> with improved photocatalytic activity

Optimized doped TiO₂ is necessary for efficient visible light harvesting and widening the applications spectrum of TiO₂-based materials. Titanium dioxide doped with silver and/or vanadium has been synthesized by one-pot hydrothermal method without post-calcination. Codoping induced visible light absorption while maintaining the photoactive anatase phase along with good crystallinity. Synthesized products are in nanometer range and possess high specific surface area. Having nearly spherical morphology, the particles are distributed and the particle size estimated from TEM observation is in accordance with the XRD results. Spectroscopic investigations reveal that the doped atoms successfully entered the TiO₂ lattice modifying the band structure. The narrowed band gap allows visible light photons for absorption, and the codoped samples displayed enhanced visible light absorption among the synthesized samples. Photodegradation performance evaluated under visible light irradiations showed that silver- , vanadium-codoped TiO₂ have the best visible light photocatalytic activity attributed to stable configuration, high visible light absorption, coupling between silver and vanadium and their optimal doping concentration.     

Reduced graphene oxide-based photocatalysts containing Ag nanoparticles on a TiO2 nanotube array

A simple one-step electrochemical deposition method was demonstrated to fabricate reduced graphene oxide/Ag nanoparticle co-decorated TiO₂ nanotube arrays (RGO/Ag–TiO₂NTs) photocatalyst in this study. The structures and properties of these photocatalysts were characterized using scanning electron microscope, X-ray diffraction, UV–Vis diffuse reflection spectra, and photoluminescence. By taking the advantages of TiO₂, graphene, and Ag nanoparticles (AgNPs), RGO/Ag–TiO₂NTs showed a greatly improved photocatalytic activity compared with the bare TiO₂NTs, Ag–TiO₂NTs or RGO–TiO₂NTs. The deposited RGO and AgNPs not only reduce the recombination of photogenerated electrons and holes, but also increase the surface area of the catalyst. Both photocatalytic performance and adsorptivity of the catalyst have been improved. The ternary photocatalyst exhibited over 93 % removal efficiency of typical herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) under simulated solar light irradiation with good stability and easy recovery, which justifies the photocatalytic system, a promising application for herbicide or other organic pollutant removal from water.