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.

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.

Preparation and photoelectric effect of Zn^(2+)-TiO_2 nanotube arrays

Zn 2+-TiO2 nanotube arrays were prepared by anodic oxidation method.The current-time curves were used to investigate their growth mechanism.Scanning electron microscopy and X-ray diffractometry were applied to characterizing their structures and properties.The photoelectrochemical properties were studied by electrochemical impedance spectrum(EIS).The optimised working conditions for TiO2 nanotube arrays were found to be pH 1,0.5%HF(mass fraction),20 V oxidation voltage and for 2 h.The produced sample was in anatase form,with length of 70-100 nm,thickness of 10 nm,uniform diameter and structure that does not collapse under the preparation conditions.The EIS results show that TiO2 nanotube arrays prepared with 0.5%HF(mass fraction) present a low impedance and TiO2 nanotube arrays loaded by Zn 2+could have a decreased resistance.This decrease could likely accelerate the transfer of carriers and even increase photoelectric conversion.

Morphology dependence of TiO_2 nanotube arrays on anodization variables and buffer medium

Vertically oriented TiO_2 nanotube arrays were prepared by potentiostatic anodization of Ti foils in HF/acetic acid（HAC） aqueous solution.Anodization variables including anodization electrolyte concentration,anodization voltage, anodization time and buffer medium can be chosen and adjusted to manipulate the nanotube arrays to give the required length and morphology.

An Energy-Efficient Electrochemical Method for CuO-TiO_2 Nanotube Array Preparation with Visible-Light Responses

A rapid and energy-efficient method was presented for preparing CuO-TiO2 nanotube arrays. TiO2 nanotube arrays were first prepared by anodic oxidation using titanium anode and platinum cathode. Then, the formed TiO2 nanotube arrays and Pt were used as cathode and anode, respectively, for subsequent formation of CuO-TiO2 nanotube arrays, through an electro- chemical process in a solution of 0.1 mol/L CuSO4. The morphology and composition of the CuO-TiO2 nanotube arrays were characterized using field-emission scanning electron microscopy, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, and UV-Vis diffusion reflection spectroscopy （UV-Vis DRS）. XPS and XRD analyses suggested that the Cu element in the nanotubes existed in CuO form, and its content changed along with the voltage during the second electrochemical process. The photocatalytic activities of the CuO-TiO2 nanotube arrays were evaluated by the degradation of a model dye, rhodamine B. The results showed that Cu incorporation aroused wide visible-light adsorption and improved the photocatalytic efficiency of TiO2 nanotube arrays significantly under visible-light irradiation. The stability of the CuO-TiO2 nanotube arrays was also detected.

Fabrication and photodegradation properties of TiO_2 nanotubes on porous Ti by anodization

Both Ti foil and porous Ti were anodized in 0.5%HF and in ethylene glycol electrolyte containing 0.5%NH4F(mass fraction) separately. The results show that TiO2 nanotubes can be formed on Ti foil by both processes, whereas TiO2 nanotubes can be formed on porous Ti only in the second process. The overhigh current density led to the failure of the formation nanotubes on porous Ti in 0.5%HF electrolyte. TiO2 nanotubes were characterized by SEM and XRD. TiO2 nanotubes on porous Ti were thinner than those on Ti foil. Anatase was formed when TiO2 nanotubes were annealed at 400 °C and fully turned into rutile at 700 °C. To obtain good photodegradation, the optimal heat treatment temperature of TiO2 nanotubes was 450 °C. The porosity of the substrates influenced photodegradation properties. TiO2 nanotubes on porous Ti with 60% porosity had the best photodegradation.

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.

Transient competition between photocatalysis and carrier recombination in TiO_2 nanotube film loaded with Au nanoparticles

Highly ordered TiO2 nanotube array （TNA） films are fabricated by using an anodic oxidation method. Au nanoparticles （NPs） films are decorated onto the top of TNA films with the aid of ion-sputtering and thermal annealing. An enhanced photocatalytic activity under ultraviolet C （UVC, 266 nm） light irradiation is obtained compared with that of the pristine TNA, which is shown by the steady-state photoluminescence （PL） spectra. Furthermore, a distinct blue shift in the nanosecond time-resolved transient photoluminescence （NTRT-PL） spectra is observed. Such a phenomenon could be well explained by considering the competition between the surface photocatalytic process and the recombination of the photo-generated carriers. The enhanced UV photocatalytic activities of the Au-TNA composite are evaluated through photo-degradation of methyl orange （MO） in an aqueous solution with ultraviolet-visible absorption spectrometry. Our current work may provide a simple strategy to synthesize defect-related composite photocatalytic devices.

N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

Electrocatalytic production of glycolic acid via oxalic acid reduction on titania debris supported on a TiO_(2)nanotube array

Electrodes prepared by anodic oxidation of Ti foils are robust and not toxic materials for the electrocatalytic reduction of oxalic acid to glycolic acid, allowing the development of a renewable energy-driven process for producing an alcoholic compound from an organic acid at low potential and room temperature. Coupled with the electrochemical synthesis of the oxalic acid from CO_(2),this process represents a new green and low-carbon path to produce added value chemicals from CO_(2). Various electrodes prepared by anodic oxidation of Ti foils were investigated. They were characterized by the presence of a TiO_(2) nanotube array together with the presence of small patches, debris, or TiO_(2) nanoparticles. The concentration of oxygen vacancies, the amount of Ti^(3+) measured by X-ray photoelectron spectroscopy(XPS) and the intensity of the anodic peak measured by cyclic voltammetry, were positively correlated with the achieved oxalic acid conversion and glycolic acid yield. The analysis of the results indicates the presence of small amorphous TiO_(2) nanoparticles(or surface patches or debris) interacting with TiO_(2) nanotubes, the sites responsible for the conversion of oxalic acid and glycolic acid yield. By varying this structural characteristic of the electrodes, it is possible to tune the glycolic acid to glyoxylic acid relative ratio. A best cumulative Faradaic efficiency(FE) of about 84% with FE to glycolic acid around 60% and oxalic conversion about 30% was observed.

Phase control and stabilization of 1T-MoS_(2) via black TiO_(2-x)nanotube arrays supporting for electrocatalytic hydrogen evolution

1T phase MoS_(2)(1T-MoS_(2)) is a promising substitute of platinum electrocatalyst for hydrogen evolution reaction(HER)due to its high intrinsic activity but suffering from thermodynamical instability.Although great efforts have been made to synthesize 1T-MoS_(2) and enhance its stability,it remains a big challenge to realize the phase control and stabilization of 1T-MoS_(2).Herein,based on crystal field theory analysis,we propose a new solution by designing an electrocatalyst of 1T-MoS_(2) nanosheets anchoring on black TiO2-xnanotube arrays in-situ grown on Ti plate(1T-MoS_(2)/TiO_(2-x)@Ti).The black TiO_(2-x)substrate is expected to play as electron donors to increase the charge in Mo 4 d orbits of 1T-MoS_(2) and thus weaken the asymmetric occupation of electrons in the Mo 4 d orbits.Experimental results demonstrate that black TiO_(2-x)nanotubes shift electrons to MoS_(2) and induce MoS_(2) to generate more 1 T phase due to stabilizing the 1T-MoS_(2) nanosheets compared with a Ti substrate.Thus 1T-MoS_(2/)TiO_(2-x)@Ti shows much improved HER performance with a small Tafel slope of 42 m V dec^(-1) and excellent catalytic stability with negligible degradation for 24 h.Theoretical calculations confirm that the black TiO_(2-x)substrate can effectively stabilize metastable 1T-MoS_(2) due to electrons transferring from black TiO_(2-x)to Mo 4 d orbits.This work sheds light on the instability of 1T-MoS_(2) and provides an essential method to stabilize and efficiently utilize 1T-MoS_(2) for HER.

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.

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.

Morphology Control of TiO_(2)Nanotubes towards High-Efficient Electrodes for Supercapacitor

This article studies the role of electrochemical parameters in controlling the morphology of oxidized TiO_(2)nanotubes and the electrochemical performance of modified TiO_(2)nanotubes.Humidity is a key factor for fabricating TiO_(2)nanotubes.When the relative humidity belows 70%,the TiO_(2)nanotubes can be successfully prepared.What's more,by changing the anodization voltage and time,the diameter and the length of TiO_(2)nanotubes can be adjusted.In addition,the TiO_(2)nanotubes are modified through electrochemical self-doping and loading Pt metal particles on the surface of the nanotubes,which promotes the performance of the supercapacitor.The sample anodized at 100 V for 3 h has a specific capacity of up to 2.576 mF/cm~2 at a scan rate of 100 mV/s after self-doping,and its capacity retention rate still remains at 89.55%after 5000 cycles,demonstrating excellent cycling stability.The Pt-modified sample has a specific capacity of up to 3.486 mF/cm~2 at the same scan rate,exhibiting more outstanding electrochemical performance.

纳米TiO_2的电化学嵌锂研究

应用苛性钠水热法制备粒度均匀、分散性好、质子钛酸盐纳米管(直径约10～15nm).经加热烧结脱水后,该纳米管逐渐转变成具有锐钛矿相结构的纳米柱(直径约15～20nm).初步研究表明,这种具有锐钛矿相结构的纳米柱,其电化学可逆嵌/脱锂容量较高,但循环稳定性还有待改进提高.

Interwoven scaffolded porous titanium oxide nanocubes/carbon nanotubes framework for high-performance sodium-ion battery

Supercapacitor-like Na-ion batteries have attracted much attention due to the high energy density of batteries and power density of capacitors.Titanium dioxide(TiO_(2)),is a promising anode material.Its performance is however seriously hindered by its low electrical conductivity and the sluggish diffusion of sodium ions(Na^(+))in the TiO_(2)matrix.Herein,this work combines porous TiO_(2)nanocubes with carbon nanotubes(CNTs)to enhance the electrical conductivity and accelerate Na^(+)diffusivity for Na-ion batteries(NIBs).In this composite,an interwoven scaffolded TiO_(2)/CNTs framework is formed to provide abundant channels and shorter diffusion pathways for electrons and ions.The in-situ X-ray diffraction and cyclic voltammetry confirm the low strain and superior transport kinetics in Na^(+)intercalation/extraction processes.In addition,the chemically bonded TiO_(2)/CNTs hybrid provides a more feasible channel for Na^(+)insertion/extraction with a much lower energy barrier.Consequently,the TiO_(2)/CNTs composite exhibits excellent electrochemical performance with a capacity of 223.4 m Ah g^(-1)at 1 C and a capacity of 142.8 m Ah g^(-1)at 10 C(3.35 A g^(-1)).The work here reveals that the combination of active materials with CNTs can largely improve the utilization efficiency and enhance their sodium storage.

Elastic properties of anatase titanium dioxide nanotubes:A molecular dynamics study

The elastic properties of anatase nanotubes are investigated by molecular dynamics(MD) simulations. Young's modulus, Poisson ratio, and shear modulus are calculated by transversely isotropic structure model. The calculated elastic constants of bulk rutile, anatase, and Young's modulus of nanotube are in good agreement with experimental values, respectively, demonstrating that the Matsui and Akaogi(MA) potential function used in the simulation can accurately present the elastic properties of anatase titanium dioxide nanotubes. For single wall anatase titanium dioxide nanotube, the elastic moduli are shown to be sensitive to structural details such as the chirality and radius. For different chirality nanotubes with the same radius, the elastic constants are not proportional to the chiral angle. The elastic properties of the nanotubes with the chiral angle of 0° are worse than those of other chiral nanotubes. For nanotubes with the same chirality but different radii, the elastic constant, Young's modulus, and shear modulus decrease as the radius increases. But there exist maximal values in a radius range of 10 nm-15 nm. Such information can not only provide a deep understanding of the influence of geometrical structure on nanotubes mechanical properties, but also present important guidance to optimize the composite behavior by using nanotubes as the addition.

Pt/TiO_(2) Nanosheets Array Dominated by {001} Facets with Enhanced Photocatalytic Activity

{001}facets dominated single crystalline anatase TiO_(2) nanosheet array(TNSA)was synthe-sized through an optimized organic solvothermal route on uorine-doped tin oxide substrate.The field emission scanning electron microscopy images and X-ray diffraction patterns re-vealed that the{001}synthesized facets dominated TNSA exhibited much higher orientation than that synthesized by hydrothermal route.The TNSAs were loaded with Pt nanoparti-cles in uniformly size by using a photodecomposition method,which were further con rmed by high resolution transmission electron microscopy(HRTEM).The HRTEM images also revealed that Pt nanoparticles preferred to deposit on{001}facets.With loading of Pt nanoparticles,the optical absorbance was significantly enhanced,while the photolumines-cence(PL)was inhibited.The photocatalytic activity of TNSA was signi cantly improved by Pt loading and reached the maximum with optimal amount of Pt loading.The optimal amount of Pt on{001}facets is far less than that on TiO_(2) nanoparticles,which may be attributed to the specific atom structure of reactive{001}facets.

Lithiophilic seeds and rigid arrays synergistic induced dendrite-free and stable Li anode towards long-life lithium-oxygen batteries

High energy density lithium-oxygen battery(LOB) is currently regraded as a promising candidate for next-generation power system.However,the dendrite and instability issues of Li metal anode lead to its poor cyclic stability and low energy density.In this work,lithiophilic Al_(2) O_(3) seeds induced rigid carbon nanotube arrays(CNTA)/three-dimensional graphene(3 DG) is developed as a host material for Li anode,namely Al_(2) O_(3)-CNTA/3 DG.It is demonstrated that the lithiophilic feature of Al_(2) O_(3) seeds and the enhanced rigidity of arrays can synergistically induce the uniform Li flux,inhibit the collapse of arrays,and stabilize electrolyte/electrode interfaces.As a result,the Al_(2) O_(3)-CNTA/3 DG-Li anode delivers a high Coulombic efficiency above 97% after 140 cycles(8 mAh cm^(-2) at 4 mA cm^(-2)).With this anode and the breathable CNTA/3 DG cathode,the full LOB exhibits a significantly increased life-span up to 160 cycles(500 mAh g^(-1) at 100 mA g^(-1)),which is almost 3 times longer than that with pure Li foil as the anodes.This work demonstrates a new approach to highly reversibly long-cycling performance of LOBs towards practical application.

BPQDs@TNTs药物载体的构建及其缓释性能研究

目的在骨科钛板表面构建能负载阿仑膦酸钠及硫酸庆大霉素的双载药复合药物载体。方法通过阳极氧化法在TiO_(2)表面制备纳米管阵列(TNTs),动态吸附阿伦磷酸钠后再填充载有硫酸庆大霉素的载药黑磷量子点(BPQDs),管口采用肉豆蔻醇进行封装,并利用X射线衍射、透射电镜进行表征,最后通过液相色谱法测定其上负载的阿仑膦酸钠及硫酸庆大霉素的缓释速率。结果X射线衍射表明构建的BPQDs@TNTs药物载体具备BP和TNTs的特征衍射峰,透射电镜扫描表明,肉豆蔻醇成功地对TNTs进行了封口,TiO_(2)纳米管中的阿仑膦酸钠及BPQDs载体的硫酸庆大霉素在72 h内已基本释放完毕,BPQDs@TNTs药物载体上阿仑膦酸钠及硫酸庆大霉素则在96 h内才基本释放完毕。结论BPQDs@TNTs药物载体能成功搭载阿仑膦酸钠及硫酸庆大霉素,且在体液中具有更好的缓释效能。