Enhanced Photoelectrochemical Property of Zn Loaded TiO2 Nanotube Arrays Electrode

TiO2 nanotube arrays （TNTs） electrode loaded with Zn nanoparticles was prepared by anodization and the size of Zn nanoparticle loaded on TNTs electrode was controlled by chronoamperometry deposition time. Results of SEM and XRD analysis show that Zn nanoparticles had a diameter of about 15-25 nm when the deposition time was 3-5 s. The UV-Vis diffuse reflectance spectra show the Zn loaded harvest light with 480-780 nm more effectively than the unloaded sample. The photocurrent response of Zn loaded TNTs electrodes were studied, the results showed that TNTs electrodes loaded with Zn nanoparti-cles has 50% increased photocurrent response under high-pressure mercury lamp irradiation compared with unloaded TNTs electrode.

Crack initiation,propagation and saturation of TiO_2 nanotube film

Vertically orientated TiO2 nanotube array with diameters ranging from 60 up to 80 nm and length of 4 μm was grown on titanium by anodization.Crack initiation,propagation and saturation were studied using the substrate straining test.The results show that annealing obviously modifies the interfaces.With the increase of tensile strain,cracks in TiO2 nanotube films propagate rapidly and reach the saturation within a narrow strain gap.Interfacial shear strengths of TiO2 nanotube films without annealing,with 250 ℃ annealing and with 400 ℃ annealing can be estimated as 163.3,370.2 and 684.5 MPa,respectively.The critical energy release rates of TiO2 nanotube films are calculated as 49.6,102.6 and 392.7 J/m2,respectively.The fracture toughnesses of TiO2 nanotube films are estimated as 0.996,1.433 and 2.803 MPa-m1/2,respectively.The interfacial bonding mechanism of TiO2 nanotube film is chemical bonding.

Buckling pattern of TiO_2 nanotube film

Substrate straining test was carried out to study the buckling pattern of TiO2 nanotube film. The results show that the tensile strains of buckling occurrence of TiO2 nanotube films without annealing, with 250 ℃ annealing and with 400 ℃ annealing are 2.5%, 8.9% and 7.8%, respectively, which indicates the modifying effects of temperature annealing. Through the SEM observation, the critical buckling stresses of TiO2 nanotube films without annealing, with 250 ℃ annealing and with 400 ℃ annealing can be estimated as 180.4, 410.2 and 619.5 MPa, respectively. The critical buckling stress of TiO2 nanotube films with 250 ℃ annealing from AFM observation is estimated as 470.2 MPa, which indicates good agreement with the critical buckling stress from SEM observation. The true stress and the critical energy release rate of TiO2 nanotube film with 250 ℃ annealing are given as 840.3 MPa and 77.2 J/m2, respectively. Excellent agreement of the critical energy release rate of TiO2 nanotube film with 250 ℃ annealing in terms of buckling perspective and crack perspective is obtained.

Debonding phenomenon of TiO_2 nanotube film

Curvature method was used to measure the residual stress and substrate straining tensile test was carried out to study the debonding behavior of TiO2 nanotube film. The results indicate that the internal residual stress is -54 MPa. The strains of debonding initiation of TiO2 nanotube films without annealing, with 250 °C annealing and with 400 °C annealing are 2.6%, 5.1% and 8.6%, respectively, and the average radii of the debonding patches with debonding initiation are 27.5, 17.1 and 19.4 μm, respectively. The true critical debonding stresses of TiO2 nanotube films without annealing, with 250 °C annealing and with 400 °C annealing can be estimated as 220.4, 394.5 and 627.9 MPa, respectively. Interfacial shear lag model is modified and polynomial fitting equation of the interfacial shear strength of TiO2 nanotube film is demonstrated under debonding conditions. The modification and polynomial fitting are reliable since good agreement of the interfacial shear strengths after fitting is obtained compared with those results from the crack density analysis.

Electrochemical oxidation of rhodamine B by PbO_2/Sb-SnO_2/TiO_2 nanotube arrays electrode

A PbO2/Sb-SnO2/TiO2 nanotube array composite electrode was successfully synthesized and its electrochemical oxidation properties were investigated.Field-emission scanning electron microscopy(FE-SEM)and X-ray diffraction(XRD)results showed that the PbO2 coating was composed of anα-PbO2 inner layer and aβ-PbO2 outer layer.Accelerated life measurement indicated that the composite electrode had a lifetime of 815 h.Rhodamine B(RhB)was employed as a model pollutant to analyze the electrocatalytic activity of the electrode.The effects of initial RhB concentration,current density,initial pH,temperature,and chloride ion concentration on the electrochemical oxidation were investigated in detail.Inductively coupled plasma atomic emission spectroscopy(ICP-AES)results suggested that the concentration of leached Pb^2+in the electrolyte during the electrocatalytic oxidation process can be neglected.Finally,the degradation mechanism during the electrocatalytic oxidation process was proposed based on the results of solid-phase micro-extraction-gas chromatography-mass spectrometry(SPME-GC-MS).The high electrocatalytic performance of the composite electrode makes it a promising anode for the treatment of organic pollutants in aqueous solution.

Photo-degradation of Acid-red 3B dye catalyzed by TiO_2 nanotubes

TiO2 nanotube precursor was synthesized by the hydrothermal reaction of TiO2 powders with NaOH solution and the properties of the nanotube materials were tuned using different post-treatments. Transmission electron microscopic （TEM） observation revealed that the nanotube could be obtained by either a direct rinse with acid solution or rinse with distilled water followed by acid solution. The results of X-ray diffraction （XRD） and inductively coupled plasma （ICP） analysis indicated that the nanotube material was composed of H2Ti2O5·H2O. In addition, the photocatalytic activities of the resulting catalysts were found to be strongly dependent on the post-treatment. The results of the photocatalytic reaction showed that the degradation of Acid-red 3B dye fitted pseudo-zero-order kinetics and TiO2 nanotube prepared under direct rinse with acid solution exhibited a higher catalytic efficiency compared to other catalysts.

Efficient Photoelectrochemical Water Splitting by g-C_3N_4/TiO_2 Nanotube Array Heterostructures

Well-ordered TiO_2 nanotube arrays(TNTAs)decorated with graphitic carbon nitride(g-C_3N_4) were fabricated by anodic oxidization and calcination process.First, TNTAs were prepared via the anodic oxidation of Ti foil in glycerol solution containing fluorinion and 20%deionized water. Subsequently, g-C_3N_4 film was hydrothermally grown on TNTAs via the hydrogen-bonded cyanuric acid melamine supramolecular complex. The results showed that g-C_3N_4 was successfully decorated on the TNTAs and the g-C_3N_4/TNTAs served as an efficient and stable photoanode for photoelectrochemical water splitting. The facile deposition method enables the fabrication of efficient and low-cost photoanodes for renewable energy applications.

TEM Study on the Formation Process of TiO_2 Nanotubes

The process, that the polycrystalline TiO2 powders were converted into TiO2 nanotubes, was observed with transmission electron microscope. The results obtained indicated that in concentrated NaOH aqueous solution, anisotropic swelling appears on the polycrystalline TiO2 granula at first, and then the nanotubes are formed.

Enhanced Photoelectrochemical Properties of Cu_2O-loaded Short TiO_2 Nanotube Array Electrode Prepared by Sonoelectrochemical Deposition

Copper and titanium remain relatively plentiful in earth crust.Therefore,using them in solar energy conversion technologies are of significant interest.In this work,cuprous oxide（Cu2O）-modified short TiO2 nanotube array electrode was prepared based on the following two design ideas:first,the short titania nanotubes obtained from sonoelectrochemical anodization possess excellent charge separation and transportation properties as well as desirable mechanical stability;second,the sonoelectrochemical deposition technique favours the improvement in the combination between Cu2O and TiO2 nanotubes,and favours the dispersion of Cu2O particles.UV-Vis absorption and photo-electronchemical measurements proved that the Cu2O coating extended the visible spectrum absorption and the solar spectrum-induced photocurrent response.Under AM1.5 irradiation,the photocurrent density of the composite electrode（i.e.sonoelectrochemical deposition for 5 min） was more than 4.75 times as high as the pure nanotube electrode.Comparing the photoactivity of the Cu2O/TiO2 electrode obtained using sonoelectrochemical deposition with others that synthesized using plain electrochemical deposition,the photocurrent density of the former electrode was 2.2 times higher than that of the latter when biased at 1.0 V（vs.Ag/AgCl）.The reproducible photocurrent response under intermittent illumination demonstrated the excellent stability of the composite electrode.Such kind of composite electrode material will have many potential applications in solar cell and other fields.

TiO_2 composite nanotubes embedded with CdS and upconversion nanoparticles for near infrared light driven photocatalysis

We report a colloidal process to coat a layer of TiO2onto SiO2composite nanofibers containing embedded CdS and upconversion nanoparticles(UCNPs).The SiO2composite nanofibers were fabricated by electrospinning.To improve the energy transfer efficiency,UCNPs and CdS nanoparticles were bound in close proximity to each other within the SiO2matrix.β‐NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%)core–shell nanoparticles were used as nanotransducers for near infrared light.These nanoparticles exhibited enhanced upconversion fluorescence compared withβ‐NaYF4:Yb(30%),Tm(0.5%)orβ–NaYF4:Yb(30%),Tm(0.5%)@NaYF4nanoparticles.The morphologies,size and chemical compositions have been extensively investigated using field emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM),X‐ray diffraction(XRD)and X‐ray photoelectron spectra(XPS),respectively.The TEM images showed that the TiO2composite nanotubes were embedded with a large amount of UCNPs and CdS nanoparticles.The composite TiO2nanotubes degraded more than90%of rhodamine B(RhB)dye during20min of irradiation by simulated solar light.In particular,more than50%of RhB was decomposed in70min,under irradiation of near infrared light(NIR).This high degradation was attributed to the full spectrum absorption of solar light,and the enhanced transfer efficiency for near infrared light.The as‐prepared nanostructures can harness solar energy,and provide an alternative to overcome energy shortages and environmental protection.

Electrochemical Preparation and Photoelectric Properties of Cu_2O-loaded TiO_2 Nanotube Arrays

TiO2 nanotube （TNT） arrays were fabricated by anodic oxidation of titanium foil in a fluoride- based solution, on which Cu20 particles were loaded via galvanostatic pulse electrodeposition in cupric acetate solutions in the absence of any other additives. The structure and optical properties of Cu2O-loaded TiO2 nanotube arrays （Cu2O-TNTs） were analyzed by scanning electron microscopy （SEM）, X-ray diffraction （XRD） and UV-Vis absorption, and the photoelectrochemical performance was measured using an electrochemical work station with a three-electrode configuration. The results show that the Cu2O particles distribute uniformly on the highly ordered anatase TiO2 nanotube arrays. The morphologies of Cu2O crystals change from branched, truncated octahedrons to dispersive single octahedrons with increasing deposition current densities. The Cu2O- TNTs exhibited remarkable visible light responses with obvious visible light absorption and greatly enhanced visible light photoelectrochemical performance. The I-V characteristics under visible light irradiation show a distinct plateau in the region between approximately -0.3 and 0 V, resulting in higher open-circuit voltages and larger short-circuit currents with increased Cu2O deposition.

Nitrogen-doped carbon encapsulated in mesoporous TiO2 nanotubes for fast capacitive sodium storage

Controllable synthesis of insertion-type anode materials with beneficial micro-and nanostructures is a promising approach for the synthesis of sodium-ion storage devices with high-reactivity and excellent electrochemical performance.In this study,we developed a sacrificial-templating route to synthesize TiO_(2)@N-doped carbon nanotubes(TiO_(2)@NC-NTs)with excellent electrochemical performance.The asprepared mesoporous TiO_(2)@NC-NTs with tiny nanocrystals of anatase TiO_(2) wrapped in N-doped carbon layers showed a well-defined tube structure with a large specific surface area of 198 m^(2) g^(-1) and a large pore size of~5 nm.The TiO_(2)@NC-NTs delivered high reversible capacities of 158 m A h g^(-1) at 2 C(1 C=335 m A g^(-1))for 2200 cycles and 146 m A h g^(-1) at 5 C for 4000 cycles,as well as an ultrahigh rate capability of up to 40 C with a capacity of 98 m A h g^(-1).Even at a high current density of 10 C,a capacity of 138 m A h g^(-1) could be delivered over 10,000 cycles.Thus,the synthesis of mesoporous TiO_(2)@NC-NTs was demonstrated to be an efficient approach for developing electrode materials with high sodium storage and long cycle life.

Fabrication, annealing, and electrocatalytic properties of platinum nanoparticles supported on self-organized TiO_2 nanotubes

The platinum nanoparticles supported on self-organized TiO2 nanotubes （Pt-TiO2/Ti） were prepared using electrochemical anodic oxidation followed by cathodic reduction. The structure and chemical nature of the Pt-TiO2/Ti electrocatalyst were investigated by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. Both XRD and SEM results indicate the presence of platinum on nanotubular TiO2. The stability of the Pt deposits was also investigated in 0.5 mol/L H2SO4 solution by cyclic voltammetry. The electrocatalytic activity of the Pt-TiO2/Ti catalyst exhibits enhancement effect during electro-oxidation of methanol when annealed to anatase. Successive cyclic voltam- mograms of methanol oxidation on the Pt-TiO2/Ti electrocatalyst shows unique electrocatalytic characteristics when compared to methanol oxidation on the bulk Pt catalyst. This is because of further quick oxidation of adsorbed CO by Pt （111） facets of Pt particles on self-organized TiO2 nanotubes when the formation of an electroactive film onto the working catalyst surface occurs.

Photocatalytic decompositions of gaseous HCHO and methylene blue with highly ordered TiO_2 nanotube arrays

The highly ordered TiO2 nanotubes (NTs) were fabricated by the anodic oxidation method. Their morphology, structure and crystalline phase were characterized by scanning electron microscopy (SEM) and X-ray diffractometer (XRD). The effects of morphology, specific surface area, pore structures and photo catalytic activity of the TiO2 NTs were investigated. UV-vis spectra analysis showed that its light absorption had been extended to the visible light range. The photocatalytic activity of the as-prepared samples was evaluated by photocatalytic oxidation of gaseous HCHO and MB aqueous solution. The samples had better adhesion strength in the dark and showed a higher photocatalytic activity than nanoparticles. Especially, with ultraviolet light pretreatment, the nanotubes exhibited more stable active for photocatalytic decomposition and the photodecomposition rate remained at high level after 3 cycles of the photocatalysis experiment. Thus, how the number of surface active group center dot OH increased and the mechanism for the great improvement for the photocatalytic activity are discussed. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Electrochemical Synthesis of Novel Zn-Doped TiO_2 Nanotube/ZnO Nanoflake Heterostructure with Enhanced DSSC Efficiency

The paper reports the fabrication of Zn-doped TiO_2 nanotubes(Zn-TONT)/ZnO nanoflakes heterostructure for the first time,which shows improved performance as a photoanode in dye-sensitized solar cell(DSSC).The layered structure of this novel nanoporous structure has been analyzed unambiguously by Rutherford backscattering spectroscopy,scanning electron microscopy,and X-ray diffractometer.The cell using the heterostructure as photoanode manifests an enhancement of about an order in the magnitude of the short circuit current and a seven-fold increase in efficiency,over pure TiO_2 photoanodes.Characterizations further reveal that the Zn-TONT is preferentially oriented in [001] direction and there is a Ti metal-depleted interface layer which leads to better band alignment in DSSC.

Theoretic and Experimental Studies on Titania Nanotube Doped with Ag Metal Ions

The electronic state density and energy bands of Ag-doped anatase TiO2 are studied by WIEN2k software package based on DFT. The calculation results show that the band-gap of anatase titania became bigger after doping with Ag metal ions. The band-gap transfers from 2.04 to 2.5 eV, but a new energy band appears among the forbidden band after the Ag atom substitution. The interband width of Ag-TiO2 is 0.17 eV, which is located at –0.07 eV; more excitation and jump routes are opened for the electrons. The lowest excitation energy can achieve 1.2 eV, which may allow the photons with lower energy （at longer wavelength, such as visible light） to be absorbed. Ag ions are implanted into the titania nanotube sample by MEVVA （Metal Vapor Vacuum Arc） implanter. The photo-electrochemical response and photo-degradation experiment of titania nanotube samples implanted with Ag ions are tested under UV and visible light; the results indicated that the performance of implanted titania naotubes is enhanced both under UV and visible light; it is worth mentioning that the photocurrent density can reach 0.145 mA/cm2 under visible light, which is 181 times higher than those of pure TiNT, and the k value of degradation methyl orange can obtain 0.30 h-1, which is 71 times higher than that of pure TiNT. All the experimental results are consistent well with the theoretic ones.

BiVO4/TiO2(N2) Nanotubes Heterojunction Photoanode for Highly Efficient Photoelectrocatalytic Applications

We report the development of a novel visible response BiVO_4/TiO_2(N_2) nanotubes photoanode for photoelectrocatalytic applications. The nitrogen-treated TiO_2 nanotube shows a high carrier concentration rate, thus resulting in a high efficient charge transportation and low electron–hole recombination in the TiO_2–BiVO_4. Therefore, the BiVO_4/TiO_2(N_2) NTs photoanode enabled with a significantly enhanced photocurrent of 2.73 mA cm^(-2)(at 1 V vs. Ag/Ag Cl) and a degradation efficiency in the oxidation of dyes under visible light. Field emission scanning electron microscopy, X-ray diffractometry, energy-dispersive X-ray spectrometer, and UV–Vis absorption spectrum were conducted to characterize the photoanode and demonstrated the presence of both metal oxides as a junction composite.

Application of TiO_2 with different structures in solar cells

The application of TiO2-based devices is mainly dependent on their crystalline structure, morphology, size, and exposed facets. Two kinds of TiO2 with different structures, namely TiO2 pompons and TiO2 nanotubes, have been prepared by the hydrothermal method. TiO2 with different structures is characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, and Brunauer Emmett-Teller （BET） surface area analysis. Solar cells based on poly（3-hexylthiophene） （P3HT） and TiO2 with different structures are fabricated. In the device ITO/TiO2/P3HT/Au, the P3HT is designed to act as the electron donor, and TiO2 pompons and TiO2 nanotubes act as the electron acceptor. The effects of the TiO2 structure on the performance of hybrid heterojunction solar cells are investigated. The device with TiO2 pompons has an open circuit voltage （Voc） of 0.51 V, a short circuit current （Jsc） of 0.21 mA/cm2, and a fill factor （FF） of 28.3%. Another device with TiO2 nanotubes has a Voc of 0.5 V, Jsc of 0.27 mA/cm2, and FF of 28.4%. The results indicate that the TiO2 nanotubes with a unidimensional structure have better carrier transport and light absorption properties than TiO2 pompons. Consequently, the solar cell based on TiO2 nanotubes has a better performance.

Simple Method to Fabricate Au Nanoparticle-Decorated TiO2 Nanotube Arrays for Enhanced Visible Light Photocurrent

Au nanoparticle-decorated TiO2 nanotube arrays are prepared by a simple method, which is a thermal annealing thin gold film deposited on anodie oxidized TiO2 nanotube arrays. These electron microscope images present that Au nanoparticles are well dispersed within the wall and on the surface of the XiO2 nanotubes. Meanwhile, the morphologies of Au nanoparticles can be controlled by changing the thickness of the deposited gold film. Associ- ated with the excitation of localized surface plasmon resonances, the prepared Au nanoparticle-decorated TiO2 nanotube arrays could work as visible light responsive photocatalysts to produce a greatly enhanced photocurrent density. By varying the initial gold film thickness, such Au nanoparticle-decorated TiO2 nanotube arrays could be optimized to obtain the highest photocurrent generation efficiency in the visible and UV light regions.

Inverted polymer solar cells with employing of electrochemical-anodizing synthesized TiO_2 nanotubes

An inverted structure of polymer solar cells based on Poly（3-hexylthiophene）（P3HT）：[6-6] Phenyl-（6） butyric acid methyl ester （PCBM） with using thin films of TiO2 nanotubes and nanoparticles as an efficient cathode buffer layer is developed. A total of three cells employing TiO2 thin films with different thickness values are fabricated. Two cells use layers of TiO2 nanotubes prepared via self-organized electrochemical-anodizing leading to thickness values of 203 and 423.7 nm, while the other cell uses only a simple sol-gel synthesized TiO2 thin film of nanoparticles with a thickness of 100 nm as electron transport layer. Experimental results demonstrate that TiO2 nanotubes with these thickness values are inefficient as the power conversion efficiency of the cell using 100-nm TiO2 thin film is 1.55%, which is more than the best power conversion efficiency of other cells. This can be a result of the weakness of the electrochemical anodizing method to grow nanotubes with lower thickness values. In fact as the TiO2 nanotubes grow in length the series resistance （Rs） between the active polymer layer and electron transport layer increases, meanwhile the fill factor of cells falls dramatically which finally downgrades the power conversion efficiency of the cells as the fill factor falls.