Influence of MnO_(x)deposition on TiO_(2)nanotube arrays for electrooxidation

TiO_(2)has demonstrated outstanding performance in electrochemical advanced oxidation processes(EAOPs)due to its structural stability and high oxygen overpotential.However,there is still much room for improving its electrochemical activity.Herein,narrow bandgap manganese oxide(MnO_(x))was composited with TiO_(2)nanotube arrays(TiO_(2)NTAs)that in-situ oxidized on porous Ti sponge,forming the MnO_(x)-TiO_(2)NTAs anode.XANES and XPS analysis further proved that the composition of MnO_(x)is Mn2O3.Electrochemical characterizations revealed that increasing the composited concentration of MnO_(x)can improve the conductivity and reduce oxygen evolution potential so as to improve the electrochemical activity of the composited MnO_(x)-TiO_(2)NTAs anode.Meanwhile,the optimal degradation rate of benzoic acid(BA)was achieved using MnO_(x)-TiO_(2)NTAs with a MnO_(x)concentration of 0.1 mmol L^(-1),and the role of MnO_(x)was proposed based on DFT calculation.Additionally,the required electrical energy(EE/O)to destroy BA was optimized by varying the composited concentration of MnO_(x)and the degradation voltage.These quantitative results are of great significance for the design and application of high-performance materials for EAOPs.

Octahedral Cu_2O-modified TiO_2 nanotube arrays for efficient photocatalytic reduction of CO_2

A photocatalyst composed of TiO 2 nanotube arrays（TNTs） and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was studied. The average nanotube diameter and length was 100 nm and 5 μm,respectively. The different amount of octahedral Cu2 O modified TNTs were obtained by varying electrochemical deposition time. TNTs modified with an optimized amount of Cu2 O nanoparticles exhibited high efficiency in the photocatalysis,and the predominant hydrocarbon product was methane. The methane yield increased with increasing Cu2 O content of the catalyst up to a certain deposition time,and decreased with further increase in Cu2 O deposition time. Insufficient deposition time（5 min） resulted in a small amount of Cu2 O nanoparticles on the TNTs,leading to the disadvantage of harvesting light. However,excess deposition time（45 min） gave rise to entire TNT surface being most covered with Cu2 O nanoparticles with large sizes,inconvenient for the transport of photo-generated carriers. The highest methane yield under simulated solar and visible light irradiation was observed for the catalysts prepared at a Cu2 O deposition time of 15 and 30 min respectively. The morphology,crystallization,photoresponse and electrochemical properties of the catalyst were characterized to understand the mechanism of its high photocatalytic activity. The TNT structure provided abundant active sites for the adsorption of reactants,and promoted the transport of photogenerated carriers that improved charge separation. Modifying the TNTs with octahedral Cu2 O nanoparticles promoted light absorption,and prevented the hydrocarbon product from oxidation. These factors provided the Cu2O-modified TNT photocatalyst with high efficiency in the reduction of CO2,without requiring co-catalysts or sacrificial agents.

Robust S-doped TiO_(2)@N,S-codoped carbon nanotube arrays as free-binder anodes for efficient sodium storage

Titanium dioxide(TiO_2) has been investigated broadly as a stable,safe,and cheap anode material for sodium-ion batteries in recent years.However,the poor electronic conductivity and inherent sluggish sodium ion diffusion hinder its practical applications.Herein,a self-template and in situ vulcanization strategy is developed to synthesize self-supported hybrid nanotube arrays composed of nitrogen/sulfur-codoped carbon coated sulfur-doped TiO_2 nanotubes(S-TiO_2@NS-C) starting from H_2 Ti_2 O_5-H_2 O nanoarrays.The S-TiO_2@NS-C composite with one-dimensional nano-sized subunits integrates several merits.Specifically,sulfur doping strongly improves the Na~+ storage ability of TiO_2@C-N nanotubes by narrowing the bandgap of original TiO_2.Originating from the nanoarrays structures built from hollow nanotubes,carbon layer and sulfur doping,the sluggish Na~+ insertion/extraction kinetics is effectively improved and the volume variation of the electrode material is significantly alleviated.As a result,the S-TiO_2@NS-C nanoarrays present efficient sodium storage properties.The greatly improved sodium storage performances of S-TiO_2@NS-C nanoarrays confirm the importance of rational engineering and synthesis of hollow array architectures with higher complexity.

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.

Heterostructured ZnFe_2O_4/Fe_2TiO_5/TiO_2 Composite Nanotube Arrays with an Improved Photocatalysis Degradation Efficiency Under Simulated Sunlight Irradiation

To improve the visible light absorption and photocatalytic activity of titanium dioxide nanotube arrays(TONTAs), ZnFe_2O_4(ZFO) nanocrystals were perfused into pristine TONTA pipelines using a novel bias voltageassisted perfusion method. ZFO nanocrystals were well anchored on the inner walls of the pristine TONTAs when the ZFO suspensions(0.025 mg m L^(-1)) were kept under a60 V bias voltage for 1 h. After annealing at 750 °C for2 h, the heterostructured ZFO/Fe_2 TiO_5(FTO)/TiO_2 composite nanotube arrays were successfully obtained. Furthermore, Fe^(3+)was reduced to Fe^(2+)when solid solution reactions occurred at the interface of ZFO and the pristine TONTAs. Introducing ZFO significantly enhanced thevisible light absorption of the ZFO/FTO/TONTAs relative to that of the annealed TONTAs. The coexistence of type I and staggered type II band alignment in the ZFO/FTO/TONTAs facilitated the separation of photogenerated electrons and holes, thereby improving the efficiency of the ZFO/FTO/TONTAs for photocatalytic degradation of methylene blue when irradiated with simulated sunlight.

Direct growth of ordered N-doped carbon nanotube arrays on carbon fiber cloth as a free-standing and binder-free air electrode for flexible quasi-solid-state rechargeable Zn-Air batteries

The development of an air electrode that is flexible in physical property and highly active and durable at different geometric status for both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of crucial importance for the rational design of flexible rechargeable Zn-air batteries(ZABs).Considering their good elasticity,high conductivity,and superior thermal and chemical stability,carbon nanotubes have been widely used as a catalyst support in various electrocatalysts,while oxide or metal nanoparticles have been frequently deposited on the carbon nanotube substrate to perform as the active materials.Considering the poor contact between active materials and carbon nanotubes may introduce a challenge for long-term operating stability,in particular in flexible devices,pure carbon electrocatalyst is highly appreciated.Herein,a free-standing air electrode with cobalt nanoparticles encapsulated N-codoped carbon nanotube arrays uniformly grown on the surface of carbon fiber cloth is developed by a two-step in situ growth method.Such a carbon-based electrode shows outstanding activity for both ORR and OER.The flexible ZAB with such air electrode shows superior flexibility and stability working under extreme bending conditions.Moreover,the polarization and round-trip efficiency for the flexible battery is 0.67 V and 64.4%at 2 mA/cm2,respectively,even after being operated for 30 hours.This study provides a feasible way to design all carbon-based free-standing and flexible electrode and enlightens the electrode design for flexible energy conversion/storage devices.

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.

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.

Effect of Anodization Parameters on Morphologies of TiO2 Nanotube Arrays and Their Surface Properties

This work presents the potentiostatic anodization study of titania nanotube array films fabricated in fluoride-based organic electrolytes including DEG （diethylene glycol） and EG （ethylene glycol）. The work focuses on the effect of important anodization parameters such as applied voltage, anodization time, and electrolyte type on nanotube morphologies and corresponding surface properties. Depending upon unique nanotube formation structures obtained from each anodizing electrolyte, wettability of the nanotube array layer has been determined by means of the contact angle measurement. The EG nanotube array films with close-packing cell orientation are found to show hydrophilic behavior. While the well separated DEG nanotube array films are found to exhibit hydrophobic behavior, with the characteristics of more discrete, wider cell separation obtained through manipulating the electrolyte conditions and the fabrication techniques offering considerable prospects for developing the superhydrophobic sample surface. Such formation structures observed for the DEG fabricated nanotube is believed to play a prominent role in determining the surface wettability of the anodized nanotube array film. The achieved result in this work is anticipated to pave the way to other relevant applications, where interfacial properties are critically concerned.

Effects of pretreatment of substrates on the preparation of large scale ZnO nanotube arrays

Well-aligned hexagonal ZnO nanotubes （NTs） arrays were synthesized on pretreated indium tin oxide （ITO） substrates by a simple hydro- thermal method. The morphology and structure of the products were characterized by scanning electron microscopy （SEM） and X-ray diffraction analysis （XRD）. A new method of substrate pretreatment was introduced to prepare ZnO coated films. The size of ZnO seeds and the formation rate of ZnO NTs were investigated. Further, the mechanism of the preparation of ZnO NTs was discussed. The photoluminescence （PL） spectrum measurement shows fairly internal defects existing in ZnO nanotubes.

Preparation and Optical Properties of V_2O_5 Nanotube Arrays

V2 O5 nanotube arrays in porous atomic alumina （ PAA ） template were obtained from V2O5 sols prepared by melt quenching method. X-ray powder diffraction and selected area electron diffraction investigations demonstrate that V2O5 nanotubes are orthorhombic. Results by scanning electron mieroscopy and transmission electron microscopy results shove that V2O5 nanotubes with a uniform diameter form highly ordered arrays. The diameter and length of the nanotubes depend on the pore diameter and the thickness of the PAA template used. It is proved that the sol-gel template process is a cost-saving , simple and readily-controlled method to prepare metal oxides nanomaterials .Owing to the quantum size effect. the optical absorption edge of V2O5 nanotubes in PAA ehibits a significant blue shift with respect to that of bulk V2O5.

Fast Growth of Highly Ordered TiO2 Nanotube Arrays on Si Substrate under High-Field Anodization

Highly ordered TiO_2 nanotube arrays(NTAs) on Si substrate possess broad applications due to its high surfaceto-volume ratio and novel functionalities, however, there are still some challenges on facile synthesis. Here, we report a simple and cost-effective high-field(90–180V) anodization method to grow highly ordered TiO_2 NTAs on Si substrate,and investigate the effect of anodization time, voltage, and fluoride content on the formation of TiO_2 NTAs. The current density–time curves, recorded during anodization processes, can be used to determine the optimum anodization time. It is found that the growth rate of TiO_2 NTAs is improved significantly under high field, which is nearly 8 times faster than that under low fields(40–60 V). The length and growth rate of the nanotubes are further increased with the increase of fluoride content in the electrolyte.

Adjustable transmission properties through ring-shaped nanotube arrays using finite-difference time-domain method

Metallic ring-shaped nanotube arrays are proposed and its optical transmission properties are studied by using finite-difference time-domain （FDTD） method. Compared with the transmission spectra of conventional circular nanotube arrays, two photonic band gaps are emerged in the transmission spectra offing-shaped nanotube arrays, the two band gaps and transmission spectra are adjusted by the length, inner radius, intertube spacing and the dielectric constants of the core and embedding medium, and magnitude modification, redshift and blueshift of the resonance modes are observed. A metallic ring-shaped nanotube arrays for subwavelength band-stop filter in the range of visible light can be achieved. To understand its physical origin, field-interference mechanism was suggested by the field distributions. The proposed nanostructures and results may have great potential applications in subwavelength near-field optics.

Synthesis and Magnetic Properties of CuFe_2O_4 Nanotube Arrays

CuFe2O4 nanotube arrays with different outer diameters were synthesized in anodic aluminum oxide templates through sol-gel techniques followed by heating treatment processes. The morphology of the nanotube arrays was investigated by field emission scanning electron microscope and transmission electron microscopy, suggesting that the nanotube arrays are ordered and uniform. The X-ray diffraction results indicate that the crystal structure of the nanotube arrays is polycrystalline with a spinel-type structure. The measurements of magnetic properties indicate that CuFe2O4 nanotube arrays with outer diameter of 200 nm exhibit magnetic anisotropy with easy magnetization direction along the axis of nanotubes.

Investigation on the Formation Mechanism of Double-Layer Vertically Aligned Carbon Nanotube Arrays via Single-Step Chemical Vapour Deposition

The mechanism for the formation of double-layer vertically aligned carbon nanotube arrays(VACNTs) through single-step CVD growth is investigated. The evolution of the structures and defect concentration of the VACNTs are tracked by scanning electron microscopy(SEM) and Raman spectroscopy. During the growth, the catalyst particles are stayed constantly on the substrate. The precipitation of the second CNT layer happens at around 30 min as proved by SEM.During the growth of the first layer, catalyst nanoparticles are deactivated with the accumulation of amorphous carbon coatings on their surfaces, which leads to the termination of the growth of the first layer CNTs. Then, the catalyst particles are reactivated by the hydrogen in the gas flow, leading to the precipitation of the second CNT layer. The growth of the second CNT layer lifts the amorphous carbon coatings on catalyst particles and substrates. The release of mechanical energy by CNTs provides big enough energy to lift up amorphous carbon flakes on catalyst particles and substrates which finally stay at the interfaces of the two layers simulated by finite element analysis. This study sheds light on the termination mechanism of CNTs during CVD process.

Synthesis and photoelectrical performance of nanoscale PbS and Bi2S3 co-sensitized on TiO2 nanotube arrays

TiO2 films have been widely applied in photo- voltaic conversion techniques. TiO2 nanotube arrays （TiO2 NAs） can be grown directly on the surface of metal Ti by the anodic oxidation method. Bi2S3 and PbS nanoparticles （NPs） were firstly co-sensitized on TiOa NAs （denoted as PbS/Bi2S3（n）/TiO2 NAs） by a two-step process containing hydrothermal and sonication-assisted SILAR method. When the concentration of Bi3＋ is 5 mmol/L, the best photoelectrical performance was obtained under simulated solar irradiation. The short-circuit photocurrent （Jsc） and photoconversion efficiency （η） of PbS/Bi2S3（5）/TiO2 NAs electrode were 4.70 mA/cm and 1.13 %, respectively.

Highly Ordered Carbon Nanotube Arrays with Open Ends Grown in Anodic Alumina Nanoholes

Highly ordered multiwalled carbon nanotube arrays were fabricated by pyrolysis of acetylene within anodic alumina templates.Nanotubes are very uniform in diameter and open at both ends. High resolution transmission electron microscopy and electron diffraction analysis show that the carbon nanotubes are well graphitized. These standing and open carbon nanotubes are possible to offer a potential elegant technique for electron emitting devices,chemical functionalization and nanotube composites.

Fabrication and Photocatalytic Activity of Ag3PO4-TiO2 Heterostructural Nanotube Arrays

To extend the absorption capability of TiO_2 into visible light region and inhibit the recombination of photogenerated electrons and holes,we put forward an effective strategy of the coupling of TiO_2 with a suitable semiconductor that possesses a narrow band gap.Meanwhile,Ag_3PO_4-TiO_2 heterostructuralnanotube arrays were prepared by the two-step anodic oxidation to obtain the TiO_2 nanotube arrays and then by a deposition-precipitation method to load Ag_3PO_4.The samples were characterized by field emission scanning electron microscopy（FESEM）,energy dispersive spectrometry（EDS）,X-ray diffraction（XRD）,and UV-vis diffuse reflectance spectroscopy（UV-vis DRS）.The experimentalresults showed that Ag_3PO_4 nanoparticles were uniformly dispersed on the highly ordered TiO_2 nanotube arrays,which increased the visible-light absorption of TiO_2 photocatalyst.The photocurrent density and photocatalytic degradation of methylorange indicated that the performance of Ag_3PO_4-TiO_2 heterostructuralnanotube arrays was better than that of the TiO_2 nanotube arrays,which could be attributed to the effective electron-hole separation and the improved utilization of visible light.

Degradation of Rhodamine B in the photocatalytic reactor containing TiO_(2)nanotube arrays coupled with nanobubbles

Although photocatalytic technology is applied in water treatment,the challenge still exists due to its low photocatalytic performance.Herein,a photocatalytic reactor coupled with nanobubbles(NBs)is developed to degrade organic pollutants in wastewater.The reactor contains Ti mesh coated with TiO_(2)nanotube arrays as a photocatalyst.The introduction of NBs in the reactor increases the dissolved oxygen content to enhance photocatalytic performance.The photocatalytic reactor exhibits outstanding photocatalytic performance,and the degradation ability of Rhodamine B is 95.39%after 2 h of irradiation treatment.The reactor also shows excellent photodegradation performance for other organic pollutants,such as methylene blue(74.23%),tetracycline(68.68%),and oxytetracycline hydrochloride(64.10%).Radical trapping experiments further prove that·O_(2)−,h^(+)and·OH are the active species for the degradation of RhB in the photocatalytic system.Therefore,this work provides a feasible strategy to design a photocatalytic reactor coupling with nanobubbles technology for the photodegradation of organic pollutants in wastewater.

Construction of nanoreactors on TiO_(2)nanotube arrays as a POCT device for sensitive colorimetric detection

With increasing attention to personalized healthcare,miniaturized and easily implementable devices are desired for point-of-care testing(POCT).Herein,hydrophilic patterns were designed on freestanding TiO_(2)nanotube arrays(Ti NTs)as nanoreactors for a naked-eye colorimetric assay.With a high aspect ratio,TiN Ts can provide a long observation length combined with a limited volume.Moreover,by combining the photocatalytic property of TiO_(2)and spatiotemporal controllability of light,hydrophilic nanoreactors were fabricated with minimal volume,and thus the indicator and analyte are limited in a confined void by the hydrophobic surroundings,thus allowing a higher sensitivity for sensing.We believe the proposed sensing platform could provide a promising strategy in developing POCT devices for routine health monitoring.