Construction of self‐organized free‐standing TiO2 nanotube arrays for effective disinfection of drinking water

BACKGROUND: In this study, the efficacy of disinfection surface water using anodic TiO₂ films was investigated. The as‐prepared photocatalyst demonstrated excellent photocatalytic disinfection of E. coli cells. Free‐standing and self‐organized TiO₂ nanotube arrays were synthesized via a facile electrochemical anodization method, prior to calcination. RESULTS: Over 95% of the initial 10⁶ cpu mL^?1 E. coli cells were inactivated within 50 min of UV‐A photocatalytic disinfection, despite the influence of various ionic species and organic compounds commonly present in groundwater. This was justified by the unique double‐walled nanotubular structure of the TiO₂ photocatalyst, which provided efficient delocalization of electron carriers and promoted anti‐recombination of photogenerated pairs of electrons and holes. Based on the experimental results obtained, cations enhanced the overall disinfection process while anions had an inhibitory effect on disinfection rates. CONCLUSION: The photocatalyst exhibited high efficiency in terms of photocatalytic disinfection of E. coli cells present in groundwater. It is deemed promising for applications in drinking water treatment owing to its superior disinfection performance, as well as high settleability, which promotes recovery and reuse of the catalyst. Copyright © 2010 Society of Chemical Industry     

氧化钛纳米管阵列制备及应用

氧化钛纳米管阵列因其独特的高度有序的阵列结构而具有良好的力学、化学稳定性以及抗腐蚀性能,在光解水制氢、太阳能电池、光催化、环境净化、气敏传感器等领域具有潜在的应用价值,引起了人们的广泛关注。对近年来TiO2纳米管在制备技术、形成机理、离子掺杂及其应用研究方面取得的成果做了综合评述,在此基础上探讨了TiO2纳米管制备及改性方面存在的问题,并对今后的发展方向予以展望。     

TiO2纳米管阵列的制备改性及应用研究进展

TiO₂纳米管阵列作为一种新型的三维立体纳米材料,因其大的比表面积及特殊的几何结构而受到了广泛的关注与研究。本文回顾了近年来阳极氧化法在Ti基底上原位生成TiO₂纳米管阵列所用电解液的发展趋势,介绍了TiO₂纳米管阵列的特性,如晶型结构、光学和电学特性以及催化活性,阐述了TiO₂纳米管阵列的金属离子掺杂、非金属离子掺杂、金属沉积、导电聚合物复合、半导体复合以及其他等多种改性手段,探讨了TiO₂纳米管阵列在光电催化降解污染物、光解水制氢、染料敏化太阳能电池和传感器以及其他多个领域的应用研究进展。最后,展望了TiO₂纳米管阵列的主要研究方向是对其形貌调控与表面改性等方面作进一步研究,以期为后续研究提供参考依据。     

有序TiO_2纳米管阵列光催化性能研究进展

高度有序TiO₂纳米管阵列由于具有结构的有序性及尺寸的可控性,已成为近年来光催化材料领域的研究热点之一。本文针对有序TiO₂纳米管阵列特殊的结构形貌特点,阐述了管壁粗糙度、管长、管壁厚度、管径及表面积对其光催化性能的影响。在不同的催化剂载体（透明玻璃基底、无基底、钛丝网基底、非平面钛片基底）生长TiO₂纳米管阵列是有效地提高其光催化性能的途径之一,介绍了这些新型结构的TiO₂纳米管阵列的研究进展。最后总结了现阶段主要掺杂改性TiO₂纳米管阵列的方法及掺杂效果。在此基础上,指出了当前研究中存在的主要问题,并展望今后的研究方向。     

Au@TiO2纳米管阵列的制备及光催化性能

利用一种简单易行、可控的方法制备了均匀的Au@TiO₂纳米管阵列。首先在室温下通过阳极氧化的方法形成TiO₂纳米管,再在氧化后的TiO₂纳米管上用磁控溅射沉积不同厚度的Au膜,最后将沉积Au膜后的TiO₂纳米管在空气中450℃退火2h。热处理过程导致了Au向TiO₂纳米管的扩散,在纳米管表面形成了Au“岛”包裹的Au@TiO₂纳米管。对制备的Au@TiO₂纳米管的微观结构利用了扫描电子显微镜、能谱、X射线衍射和透射电子显微镜进行表征。并且用光电流、紫外可见光光漫反射光谱、荧光光谱和降解亚甲基蓝溶液的方法分析测量了Au@TiO₂纳米管的光电性能及光催化性能。结果表明：当可见光照射含Au@TiO₂纳米管催化剂的亚甲基蓝水溶液时,其光催化性能远远高于纯TiO₂纳米管,这是由于Au颗粒表面等离子体共振效应（LSPR）增加了电子-空穴对的分离并且延缓了其重组所致。     

Fabrication,modification and environmental applications of TiO2 nanotube arrays (TNTAs) and nanoparticles

Among the semiconductors, titanium dioxide has been identified as an effective photocatalyst due to its abundance, low cost, stability, and superior electronic energy band structure. Highly ordered nanotube arrays of titania were produced by anodization and mild sonication. The band gap energy of the titania nanotube arrays was reduced to 2.6 eV by co-doping with Fe, C, N atoms using an electrolyte solution containing K₃Fe(CN)₆. The photoconversion of phenol in a batch photoreactor increased to more than 18% based on the initial concentration of phenol by using a composite nanomaterial consisting of titania nanotube arrays and Pt/ZIF-8 nanoparticles. A layer-by-layer assembly technique for the deposition of titania nanoparticles was developed to fabricate air filters for the degradation of trace amounts of toluene in the air and preparation of superhyrophobic surfaces for oil-water separation and anti-corrosion surfaces.     

TiO2纳米管阵列粗糙度调控及其与蛋白相互作用

采用电化学阳极氧化法,通过改变电解液氟离子浓度(0.4%、0.3%、0.2%(质量))和电压(15、25、35、45 V),制备一系列不同管径和粗糙度的TiO₂纳米管阵列(TiO₂ nanotube arrays, TNAs)。通过扫描电子显微镜以及原子力显微镜(atomic force microscopy, AFM)表征,结果表明随着电解液中氟离子浓度的降低,制备得到的TNAs表面平整度更好,壁厚增大,粗糙度降低。采用AFM力学表征研究了表面粗糙度以及管径对TNAs表面力学性质以及与细胞色素C(Cytochrome C, Cyt C)相互作用的影响,结果表明,黏附力与接触面积呈正比,随着TNAs管径增加,壁厚减小,TNAs与Cyt C的有效接触面积先增大后减小,两者之间作用力也先增加后减小;同时,同管径条件下粗糙度降低,TNAs有效面积增加,相互作用力也增加;由此可见,通过改变电解液氟离子浓度可以有效调控TNAs表面粗糙度及有效接触面积,进一步利于促进与蛋白分子之间相互作用。     

TiO_2纳米管在不同条件光催化降解的活性研究

本文利用阳极氧化法在纯钛片表面制备了TiO2纳米管阵列膜,解决TiO2光催化剂的涂敷固定问题。采用场发射扫描电镜(FESEM)和XRD对制备TiO2纳米管阵列膜的形貌和晶体结构进行表征。结果发现,所制得的纳米管管径70～80nm,壁厚5～10nm,XRD显示经420℃热处理的TiO2纳米管为锐钛矿晶型,经500℃热处理的TiO2纳米管出现金红石晶型。以10mg·L-1的甲基橙溶液为降解物进行光催化试验,分别研究了溶液的初始pH值、TiO2纳米管阵列膜的晶型、TiO2膜的使用次数对降解率的影响。试验结果表明,当溶液初始pH值为1时,TiO2纳米管阵列的光催化性能最好,同时随着TiO2膜使用次数的增加,其光催化效果有所下降。     

TiO2纳米管阵列孔径调控葡萄糖氧化酶生物传感器性能

采用电化学阳极氧化法制备出不同孔径（21、62、83、102 nm）的TiO₂纳米管阵列（TNA）,研究了孔径对固定化葡萄糖氧化酶（GOx）的传感器性能的影响。循环伏安测试结果表明固定在不同孔径大小的TNA上的GOx在葡萄糖溶液中均具有良好的酶活性。计时电流法和交流阻抗法测试发现,当孔径是83 nm时,灵敏度达到最大值27.2 μA·（mmol·L^-1）^-1·cm^-2。调控TNA的孔径可改变固定化GOx的活性及溶液扩散阻抗,从而显著提高生物传感器性能。     

Investigating photocatalytic property of TiO2 nanorods fabricated hydrothermally at equal molar ratio of KOH and NaOH

TiO₂ photocatalysts were prepared by hydrothermal method at temperatures of 110, 155, and 200°C for 24 hours, using KOH (5 mol/L):NaOH (5 mol/L) solution and anatase TiO₂ powder with an average particle size of 0.13 μm as precursor and by calcining at two different temperatures of 450 and 700°C. An overall photocatalytic removal efficiency of 93% was achieved for Rhodamine B dye under UV light irradiation by the photocatalyst obtained at synthesis and calcination temperatures of 155 and 700°C, respectively, which indicated a nanorod morphology with a mean diameter of about 34 nm.     

Synthesis and investigation of TiO2 nanotube arrays prepared by anodization and their photocatalytic activity

TiO₂ nanotube arrays were successfully prepared by anodic oxidation method in the electrolyte of ethylene glycol and deionized water mixed in 9:1 volumetric ration including 0.5 wt.% NH₄F. The microstructure and phase compositions of samples annealing from 0 °C to 800 °C were characterized by field-emission scanning electron microscope (FESEM) and X-ray diffraction (XRD). FESEM showed that the obtained nanotubes with diameter 80–100 nm and length 4.89 μm were highly ordered and perpendicular to Ti substrate. The tubular structure collapsed at 680 °C. The photocatalytic activity of samples annealing at different temperature were calculated by the degradation of a model dye, methyl orange (MO), under UV light illumination. The results indicated the phase composition and the morphology of TiO₂ nanotubes both played an important role in the degradation of MO. In addition, the effects of initial solution pH and dye concentration on degradation of MO had also been investigated. As a result, the optimum values of calcination temperature, initial solution pH and dye concentration were found to be 550 °C, 3, 10 mg/l, respectively. The best photodegradation of MO was 76% under illumination for 3 h.     

La3+掺杂TiO2光催化性能研究

采用溶胶-凝胶法制备了La^3＋／TiO2光催化剂,研究了该催化剂对亚甲基蓝的光催化降解效果。结果表明,La^3＋掺杂量（摩尔分数）2．8％、催化剂用量1．2g／L、体系pH值为11时,12mg／L亚甲基蓝溶液经2h光催化降解,其降解率可达99．1％。与纯TiO2相比,La^3＋/TiO2光催化剂显示出良好的光催化活性。     

Conformal electrodeposition of poly(phenylene oxide) on TiO2 nanotube arrays with high performance for lithium ion battery

In order to improve electrochemical performances of lithium ion battery (LIB), electrochemical integration of the membrane with the electrode was accomplished by conformal electrodeposition of poly(phenylene oxide) (PPO) on three‐dimensional (3D) oriented TiO₂ nanotube arrays (TiO₂NT). The as‐synthesized PPO/TiO₂NT membrane/electrode was investigated in terms of AC impedance, XPS, SEM, EDX, galvanostatic charge/discharge, rate performance, and cycle stability. As expected, PPO was indeed combined with TiO₂NT via conformal electrodeposition; furthermore, the integrated PPO/TiO₂NT membrane/electrode delivered much better rate performance than the traditional membrane/electrode, mainly attributed to large area of membrane/electrode/electrolyte, short ionic diffusion paths and fast ionic transport. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43685.     

TiO_2电极制备、表征及光电催化研究

文章采用阳极氧化法制备了TiO2纳米管电极、TiO2膜电极,对其进行了SEM、XRD表征的比较。研究了电化学过程、光解、TiO2纳米管的光催化、TiO2纳米管电极的光电催化对五氯苯酚的降解,研究表明光电催化降解速度最快。此外,TiO2纳米管电极和TiO2膜电极对五氯苯酚的光电催化降解也进行了研究。结果表明,TiO2纳米管电极对五氯苯酚光电催化效果明显好于TiO2膜电极,2h二者的降解率分别为81.5%,69%。     

Gd~(3+)掺杂TiO_2纳米纤维的制备、表征及其光催化性能

采用静电纺丝技术并结合溶胶-凝胶方法制备TiO2和TiO2/Gd2O3纳米纤维,采用差热-热重分析(TG-DTA)?场发射扫描电镜(FE-SEM)、红外光谱(FTIR)、X射线粉末衍射(XRD)对材料进行表征,通过亚甲基蓝光降解反应研究其催化性能。结果表明,掺杂Gd3+可以强烈抑制TiO2由锐钛矿相向金红石相的转变,抑制晶粒生长,减少晶粒尺寸;Gd3+掺杂TiO的纳米纤维对亚甲基蓝的光催化活性明显提高。     

碳纳米管/纳米TiO2-聚苯胺复合膜电极的制备及电化学性能

在含有0.2 mol·L^-1苯胺的0.5 mol·L^-1 H2SO4溶液中;采用循环伏安法（CV）;以扫描速度50 mV·s^-1;扫描电位为-0.1～0.9 V;在碳纳米管/纳米TiO₂（CNT/nanoTiO₂）膜电极上实现了苯胺的电化学聚合;通过CV法和电化学阻抗谱（EIS）并结合电子扫描显微镜和红外谱图对制备的碳纳米管/纳米TiO₂-聚苯胺（CNT/nanoTiO₂-PAn）复合膜电极的电化学性质和结构进行了表征;同时研究了复合膜电极对抗坏血酸（AH₂）的电催化性能;发现该复合膜电极对抗坏血酸的氧化具有较高的电催化活性。     

二氧化钛纳米管阵列制备和光催化降解亚甲基蓝

采用电化学阳极氧化的方法,以氟化铵水溶液为电解液,在纯钛表面制备了TiO2纳米管阵列。以亚甲基蓝为模拟污染物,考察了TiO2纳米管阵列光催化降解效果。结果表明,TiO2纳米管阵列催化降解效果要好于TiO2薄膜电极,当降解时间为1h、2h、3h和4h时,降解率分别为57.84%、86.44%、93.66%和95.72%;而TiO2薄膜电极的降解率分别为50.18%、76.27%、87.31%和91.53%。在此基础上,考察了阳极氧化电压、氧化时间和焙烧温度对阳极氧化过程的影响规律。结果表明,阳极氧化电压在25V,氧化时间在1h,焙烧温度在500℃时所制备的TiO2纳米管阵列的光催化降解性能最好。     

强化TiO2膜光催化性能的研究进展

概述了TiO2膜光催化机理,在光催化技术理论的基础上,根据TiO2膜的最新研究发展,重点介绍了目前TiO2膜光催化效率提高和光催化剂改良的新技术,对影响TiO2膜光催化性的因素进行了总结归纳。     

强化TiO_2膜光催化性能的研究进展

概述了TiO2膜光催化机理,在光催化技术理论的基础上,根据TiO2膜的最新研究发展,重点介绍了目前TiO2膜光催化效率提高和光催化剂改良的新技术,对影响TiO2膜光催化性的因素进行了总结归纳。     

Photocatalytic degradation of gaseous trichloroethene using immobilized ZnO/SnO2 coupled oxide in a flow‐through photocatalytic reactor

The photocatalytic degradation of gaseous trichloroethene (TCE) was investigated on immobilized ZnO/SnO₂ coupled oxide in a flow‐through photocatalytic reactor. It was found that gaseous photocatalysis is an efficient method for volatile organic compounds' abatement and air purification. Degradation of ～100% was found for TCE at the concentrations examined, up to 400 ppmv, in a flow‐through dry synthetic gas stream. In our tested conditions, the flow rate had little influence on the photocatalytic degradation efficiencies of TCE, while the relative humidity had a significant influence on the photocatalytic degradation of TCE. The photocatalytic degradation efficiencies of TCE increased slowly below 20% relative humidity and then decreased as the relative humidity increased further. The deactivation of used immobilized photocatalyst was not observed within the 200 h testing period in the present experiment, although the surface of the photocatalyst changed greatly during the use of the photocatalyst. Copyright © 2004 Society of Chemical Industry