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.

纳米Cu^2＋／TiO2抗菌膜对禽流感病毒(H9N2)的灭活效应

利用病毒滴度测定和MDCK细胞电镜观察法,初步探讨了在365nm的黑光灯(UV)照射下,纳米Cu2+/TiO2抗菌膜对禽流感病毒(H9N2)的光催化灭活效应,并分别考察了UV强度、UV照射时间以及H9N2病毒量对H9N2病毒光催化灭活效应的影响。实验结果表明,在365nm黑光灯的照射下,纳米Cu2+/TiO2抗菌膜对H9N2病毒具有显著的灭活效应,在UV强度为0.5mW/cm2、UV照射时间为2.5h、病毒量为0.1ml时,H9N2病毒的灭活率达到了100%。研究结果表明,纳米Cu2+/TiO2抗菌膜在抑制禽流感(H9N2)病毒在环境媒介中的扩散与传播方面有潜在的应用价值。

N2O和CO2在N＋Fe／TiO2(101)面吸附的第一性原理研究

基于周期性密度泛函理论,研究了N2O和CO2气体在N/Fe共掺杂锐钛矿TiO2(101)面最稳定结构的吸附,并与其在洁净TiO2(101)面的结果进行了对比.详细比较了三原子气体不同吸附位、不同吸附端在Fe位及N位吸附的吸附能、键长和键角的变化.结果表明:N2O在Fe位吸附较清洁表面强,为化学吸附;CO2在改性表面的吸附较清洁表面弱.

Two-dimensional ultrathin MoS2-modified black Ti^3+-TiO2 nanotubes for enhanced photocatalytic water splitting hydrogen production

Two-dimensional (2D) ultrathin MoS2-modified black Ti^3+-TiO2 nanotubes were fabricated using an electrospinning-hydrothermal treatment-reduction method.Bare TiO2 nanotubes were fabricated via electrospinning.Then,2D MoS2 lamellae were grown on the surface of the nanotubes and Ti^3+/Ov ions were introduced by reduction.The photocatalytic performance of the 2D MoS2/Ti^3+-TiO2 nanotubes was^15 times better than that of TiO2.The HER enhancement of the MoS2/Ti^3+-TiO2 nanotubes can be attributed to the Pt-like behavior of 2D MoS2 and the presence of Ti^3+-ions,which facilitated the quick diffusion of the photogenerated electrons to water,reducing the H2 activation barrier.The presence of Ov ions in the nanotubes and their hollow structure increased their solar utilization.

Supporting IrO2 and IrRuOx nanoparticles on TiO2 and Nb-doped TiO2 nanotubes as electrocatalysts for the oxygen evolution reaction

IrO2 and IrRuOx(Ir:Ru 60:40 at%),supported by 50 wt%onto titania nanotubes(TNTs)and(3 at%Nb)Nb-doped titania nanotubes(Nb-TNTs),as electrocatalysts for the oxygen evolution reaction(OER),were synthesized and characterized by means of structural,surface analytical and electrochemical techniques.Nb doping of titania significantly increased the surface area of the support from 145(TNTs)to 260 m2g-1(Nb-TNTs),which was significantly higher than those of the Nb-doped titania supports previously reported in the literature.The surface analytical techniques showed good dispersion of the catalysts onto the supports.The X-ray photoelectron spectroscopy analyses showed that Nb was mainly in the form of Nb(IV)species,the suitable form to behave as a donor introducing free electrons to the conduction band of titania.The redox transitions of the cyclic voltammograms,in agreement with the XPS results,were found to be reversible.Despite the supported materials presented bigger crystallite sizes than the unsupported ones,the total number of active sites of the former was also higher due to their better catalyst dispersion.Considering the outer and the total charges of the cyclic voltammograms in the range 0.1–1.4 V,stability and electrode potentials at given current densities,the preferred catalyst was Ir O2 supported on the Nb-TNTs.The electrode potentials corresponding to given current densities were between the smallest ones given in the literature despite the small oxide loading used in this work and its Nb doping,thus making the Nb-TNTs-supported IrO2 catalyst a promising candidate for the OER.The good dispersion of IrO2,high specific surface area of the Nb-doped supports,accessibility of the electroactive centers,increased stability due to Nb doping and electron donor properties of the Nb(IV)oxide species were considered the main reasons for its good performance.

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.

Electrochemical Fabrication of rGO-embedded Ag-TiO2 Nanoring/Nanotube Arrays for Plasmonic Solar Water Splitting

Effective utilization of hot electrons generated from the decay of surface plasmon resonance in metal nanoparticles is conductive to improve solar water splitting efficiency.Herein,Ag nanoparticles and reduced graphene oxide(rGO)co-decorated hierarchical TiO2 nanoring/nanotube arrays(TiO2 R/T)were facilely fabricated by using two-step electrochemical anodization,electrodeposition,and photoreduction methods.Comparative studies were conducted to elucidate the effects of rGO and Ag on the morphology,photoresponse,charge transfer,and photoelectric properties of TiO2.Firstly,scanning electron microscope images confirm that the Ag nanoparticles adhered on TiO2 R/T and TiO2 R/T-rGO have similar diameter of 20 nm except for TiO2 R-rGO/T.Then,the UV-Vis DRS and scatter spectra reveal that the optical property of the Ag-TiO2 R/T-rGO ternary composite is enhanced,ascribing to the visible light absorption of plasmonic Ag nanoparticles and the weakening effect of rGO on light scattering.Meanwhile,intensity-modulated photocurrent spectroscopy and photoluminescence spectra demonstrate that rGO can promote the hot electrons transfer from Ag nanoparticles to Ti substrate,reducing the photogenerated electron-hole recombination.Finally,Ag-TiO2 R/T-rGO photoanode exhibits high photocurrent density(0.98 mA cm?2)and photovoltage(0.90 V),and the stable H2 evolution rate of 413μL h?1 cm?2 within 1.5 h under AM 1.5 which exceeds by 1.30 times than that of pristine TiO2 R/T.In line with the above results,this work provides a reliable route synergizing rGO with plasmonic metal nanoparticles for photocatalysis,in which,rGO presents a broad absorption spectrum and effective photogenerated electrons transfer.

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.

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.

Photothermal Therapy Using TiO2 Nanotubes in Combination with Near-Infrared Laser

We report the in vitro cell test and in vivo animal test results of titanium oxide nanotubes (TiO2 NTs) as a potential therapeutic agent used for cancer thermotherapy in combination with near-infrared (NIR) laser. The in vitro cell test results show that both the cells exposed to NIR laser without TiO2 NTs treatment and the cells treated with TiO2 NTs but not with NIR irradiation had cell viabilities higher than 96%. Combination of these two techniques, however, shows cell viability less than 1%. The cell death rate strongly depended on the concentration of TiO2 NTs. Also, the cell deaths were mostly due to necrosis but partly due to late apoptosis. The in vivo animal test results show that tumor cells can be completely destroyed without nearly giving damage to surrounding healthy cells by an injection of an adequate amount of TiO2 NTs/NaCl suspension and a subsequent single continuous laser treatment at a moderately low laser illumina-tion intensity for the exposure time optimized for the tumor size. These results suggest that TiO2 NTs can be effectively utilized as a therapeutic agent for cancer thermotherapy due to their excellent photothermal property and high bio-compatibility.

Photocatalytic Oxidation of Low Molecular Weight Hydrocarbon Gases over Pt-TiO2 Nanotubes

Pt-TiO2 nanotubes with tube diameter of -120 nm and uniformly dispersed Pt particles（size of -2 nm） were successfully synthesized via a carbon nanotube（CNT） templating method followed by a photo-deposition processing of Pt nanoparticles. The as-obtained Pt-TiO2 NTs possess both enhanced visible light absorption and reduced recombination of photogenerated electrons and holes. These merits boost the Pt-TiO2 NTs an excellent photocatalytic material toward photooxidation of a variety of low molecular hydrocarbons under atmospheric environment.

Experimental and computational study of visible light-induced photocatalytic ability of nitrogen ions-implanted TiO2 nanotubes

Nitrogen-doped TiO2 nanotubes(TNTs)were prepared by ion implantation and anodic oxidation.The prepared samples were applied in photocatalytic(PC)oxidation of methyl blue,rhodamine B,and bisphenol A under light irradiation.To explore the influence of doped ions on the band and electronic structure of TiO2,computer simulations were performed using the VASP code implementing spin-polarized density functional theory(DFT).Both substitutional and interstitial nitrogen atoms were considered.The experimental and computational results propose that the electronic structure of TiO2 was modified because of the emergence of impurity states in the band gap by introducing nitrogen into the lattice,leading to the absorption of visible light.The synergy effects of tubular structures and doped nitrogen ions were responsible for highly efficient and stable PC activities induced by visible and ultraviolet(UV)light.

Preparation and Characterization of TiO2 Nanotubes Decorated by CuO and CeO2 Particles

A novel catalyst,TiO2 nanotubes(TiO2 NTs)composite decorated by CuO and CeO2 particles,was prepared by a simple and cost-effective method.The TiO2 NTs were fabricated by the hydrothermal method,and CuO and CeO2 particles loaded onto TiO2 NTs(CuO/CeO2@TiO2 NTs)were prepared by the water bath heating method.The CuO/CeO2@TiO2 NTs were investigated and characterized by transmission electron microscope(TEM),energy dispersive spectrometer(EDS),photoluminescence(PL),X-ray diffractometer(XRD)and ultraviolet-visible light diffuse reflectance spectrum(UV-Vis DRS).Both the p-n heterojunction formed at the p-CuO and n-TiO2 interfaces and the highly induced electron transfer of CeO2 can greatly promote the separation of electrons-holes.Therefore,CuO/CeO2@TiO2 NTs show enhanced absorption and have potential applications in photocatalysis.

Analysis of the factors controlling performances of Au-modified TiO2 nanotube array based photoanode in photo-electrocatalytic(PECa)cells

The efficiency of photo-electrocatalytic（PECa） devices for the production of solar fuels depends on several limiting factors such as light harvesting, charge recombination and mass transport diffusion. We analyse here how they influence the performances in PECa cells having a photo-anode based on Au-modified TiOnanotube（TNT） arrays, with the aim of developing design criteria to optimize the photo-anode and the PECa cell configuration for water photo-electrolysis（splitting） and ethanol photo-reforming processes.The TNT samples were prepared by controlled anodic oxidation of Ti foils and then decorated with gold nanoparticles using different techniques to enhance the visible light response through heterojunction and plasmonic effects. The activity tests were made in a gas-phase reactor, as well as in a PECa cell without applied bias. Results were analysed in terms of photo-generated current, Hproduction rate and photoconversion efficiency. Particularly, a solar-to-hydrogen efficiency of 0.83% and a Faradaic efficiency of 91%were obtained without adding sacrificial reagents.

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.

Fabrication and Characterization of Lanthanide-TiO2 Nanotube Composites

Titanium dioxide (TiO2) doped with neodymium (Nd) and/or Gadolinium (Gd) rare-earth elements were fabricated into nanotubes via the hydrothermal method in a KOH solution and in-situ doping. Titanium dioxide nanotubes (TNTs) and in-situ Nd-doped and/or Gd-doped TNTs were characterized with transmission and scanning electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction, Raman spectroscopy, and Fourier-transform infrared spectroscopy. Morphologies indicated a network of aggregated nanotubes. The phase and composition analyses revealed that the lanthanide TNTs had anatase phases with Nd and/or Gd nanoparticles in the TNT lattice. The nanoparticles were uniformly deposited on the surface because of hydroxyl groups on the TNT surfaces, resulting in a very high loading density. The outer diameter and the length of the TNTs increased with doping. The mechanisms for the formation of multiwall TNTs are discussed.

溶剂热法制备TiO2／g-C3N4及其光催化性能

采用溶剂热法合成了可见光响应的TiO_2/g-C_3N_4复合光催化剂,并对TiO_2/g-C_3N_4进行质子化处理。通过X射线衍射(XRD)、氮气吸附-脱附BET法、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、紫外-可见漫反射(UV-vis DRS)和荧光光谱(PL)等方法对样品进行了表征,并以甲基橙(MO)光催化降解为模型反应,考察了可见光下制备的样品的光催化性能。结果表明,多孔TiO_2纳米晶与g-C_3N_4形成具有"芝麻饼"形貌的复合结构;TiO_2/g-C_3N_4复合光催化剂的光吸收带边扩展到465 nm,较TiO_2出现明显红移;TiO_2与g-C_3N_4能带匹配耦合,有效地抑制了电子与空穴的复合;质子化处理过程能够提高可见光区吸收强度和电子的传导能力,增强了TiO_2的光催化活性。

g-C3N4/TiO2复合光催化剂的制备及其性能研究

以四异丙醇钛和三乙胺为原料,通过水解法合成TiO2。三聚氰胺于580℃煅烧得到g-C3N4,g-C3N4与TiO2按一定比例混合,在超声波条件下加入适量的甲醇得到复合材料g-C3N4/TiO2。以甲基橙为光催化反应模型考察了复合材料的紫外光催化活性。结果表明,g-C3N4/TiO2具有良好的光催化活性,用量3%时,甲基橙脱色率达96.6%。

N、S共掺杂TiO2催化剂的制备及其光催化性能

以硫脲作为N、S源,尿素作为水解调节剂,水热合成了N/S-TiO_2催化剂。采用XRD、SEM、XPS等手段对产品进行了表征。产品分散后,以质量浓度为0.02g·L^(-1)的甲基橙水溶液为模拟污染物,采用UV-vis光谱,多点BET分析及光催化实验研究了所得产品的光催化活性效果。实验结果表明:S以+6价形式进入TiO_2晶格取代Ti形成Ti-O-S键,N通过取代晶格中的O形成O-Ti-N键而改变了TiO_2能带结构。当煅烧温度为500℃时,水热合成出的产品结晶度较高,粒径较小,约17nm左右。光催化活性实验结果表明:当紫外灯照射时间达到1.5h时,N/S-TiO_2催化剂降解甲基橙溶液基本完成,脱色率达到96%以上。

表面In掺杂TiO2的N719/TiO2-Inx%/FTO薄膜电极的光电转换效率

采用溶胶-凝胶法制备出In表面修饰的TiO2(TiO2-Inx%)纳米粒子,x%代表在In掺杂的TiO2样品中In3+与In3+和Ti4+离子摩尔百分含量.利用二(四丁基铵)顺式-双(异硫氰基)双(2,2-联吡啶-4,4-二羧酸)钌(II)(N719)作为敏化剂,制备出N719/TiO2/FTO(氟掺杂锡氧化物)和N719/TiO2-Inx%/FTO染料敏化薄膜电极.光电转换效率实验表明,在薄膜电极+0.5mol.L-1LiI+0.05mol.L-1I2的三甲氧基丙腈(MPN)溶液+Pt光电池体系中,N719/TiO2-Inx%/FTO薄膜电极的光电转换效率均高于N719/TiO2/FTO,其中N719/TiO2-In0.1%/FTO的光电转换效率比N719/TiO2/FTO提高了20%.利用X射线衍射(XRD)、X射线光电子能谱(XPS)、漫反射吸收光谱(DRS)、荧光(PL)光谱和表面光电流作用谱确定了TiO2-Inx%样品中In3+离子的存在方式和能带结构;利用表面光电流作用谱研究了N719/TiO2-Inx%/FTO薄膜电极的光致界面电荷转移过程.结果表明,In3+离子在TiO2表面形成O-In-Cln(n=1,2)物种,该物种的表面态能级位于导带下0.3eV处;在光电流产生过程中,O-In-Cln(n=1,2)表面态能级有效地抑制了光生载流子在TiO2-Inx%层的复合,促进了阳极光电流的增加,从而导致N719/TiO2-Inx%/FTO薄膜电极的光电转化效率高于N719/TiO2/FTO,并进一步讨论了光致界面电荷转移的机理.