Preparation and photocatalytic properties of RuO2/TiO2 composite nanotube arrays

RuO₂/TiO₂ composite nanotube arrays were prepared using an anodic oxidation method combined with dipping. The photocatalytic properties of RuO₂/TiO₂ nanotube arrays in methylene blue solution were investigated under visible light irradiation. The results showed that Ru existing in the form of RuO₂ was dispersed uniformly on the surface of TiO₂ nanotubes, and the RuO₂ did not change the crystal structure of TiO₂ nanotubes. The load of RuO₂ on TiO₂ had a little influence on the band-gap energy and the absorption band edge, but could increase the amount of Ti-OH functional groups on the surface of TiO₂ nanotubes. The RuO₂/TiO₂ nanotube arrays with the optimal photocatalytic activity were formed in the ruthenium chloride solution with a concentration of 0.0030 mol/L. The 2 h photocatalytic degradation rate of methylene blue increased from 38% for pure TiO₂ nanotubes to 69% for RuO₂/TiO₂ nanotube arrays. This work demonstrated that RuO₂/TiO₂ nanotube arrays showed an improved photocatalytic property over pure TiO₂ nanotubes due to the fact that RuO₂ could capture the photo-generated holes, which greatly decreased the recombination of the photo-generated electrons and holes, and hence lengthen the lifetime of photo-induced electrons and increased the amount of hydroxyl groups absorbed on the TiO₂ nanotubes surface.     

Construction of g-C3N4/TiO2/Ag composites with enhanced visible-light photocatalytic activity and antibacterial properties

In this study, the multifunctional carbon nitride based composite graphitic-C₃N₄ (g-C₃N₄)/TiO₂/Ag was prepared through a simple and efficient vacuum freeze-drying route. TiO₂ and Ag nanoparticles were demonstrated to decorate onto the surface of g-C₃N₄ sheet. In the ultraviolet–visible absorption test, a narrower band gap and red-shift of light absorption edge were observed for g-C₃N₄/TiO₂/Ag compared to pristine g-C₃N₄ and single-component modified g-C₃N₄/TiO₂. The photodegradation property of g-C₃N₄/TiO₂/Ag was investigated toward the degradation of methylene blue (abbreviated as MB) under the irradiation of visible light. These results indicated that the degradation performance of organic dyes for g-C₃N₄/TiO₂/Ag was obviously improved compared with g-C₃N₄/TiO₂ and g-C₃N₄. The reaction rate constant of MB degradation for g-C₃N₄/TiO₂/Ag was 4.24 times higher than that of pristine g-C₃N₄. In addition, such rationally constructed nanocomposite presented evidently enhanced antibacterial performance against the Gram-negative Escherichia coli. Concentration dependent antibacterial performance was systematically investigated. And 84% bacterial cell viability loss had been observed at 500 μg/mL g-C₃N₄/TiO₂/Ag within 2 h visible light irradiation.     

Silver-modified TiO2 nanorods with enhanced photocatalytic activity in visible light region

Silver-modified TiO₂ nanorods (SMTN) have been synthesized via controlled hydrolysis of tetrabutyltitanate (TBOT) in ethanol and immersion method by using AgNO₃ as an Ag source. The physical and chemical properties of SMTN were studied by XRD, SEM, TEM, and UV–vis diffuse reflectance spectra (DRS). The photocatalytic activity of the as-prepared products was evaluated by photocatalytic decolorization of Rhodamine B (Rh B) aqueous solution at ambient temperature under visible light irradiation. The experimental results reveal that the TiO₂ nanorods, which are well dispersed and uniform, attached large numbers of silver nanoparticles on the surface, and the major crystalline phase of TiO₂ is anatase. The photocatalytic activity research shows that the SMTN exhibit an enhanced photocatalytic activity in visible light region compared with that of pure TiO₂ nanorods and commercial TiO₂ (P25).     

Optimal engineering of CdS/PbS co-sensitized TiO2 nanotube arrays for enhanced photoelectrochemical performance

TiO₂ nanotube arrays (NTAs) are decorated with CdS/PbS nano-sensitizers by successive ionic layer adsorption and reaction (SILAR) method. The uniform growth of the CdS and PbS nanoparticles on the surface and inner side of TiO₂ Nanotube Arrays (NTAs) has been confirmed by Transmission Electron microscopy measurements. The impact of the CdS and PbS semiconductor quantum dots (SQDs) on the photoelectrochemical performance (PEC) of TiO₂ NTAs was systematically investigated, and the optimal decoration of the CdS and PbS SQDs on the TiO₂ NTAs was obtained. CdS/PbS co-sensitized TiO₂ NTA photoanode films show excellent response to visible light (with absorption extended to 825 nm) and enhanced PEC performance. The best performing device showed an enhanced photocurrent density under the 0.62V vs SCE up to 8.2 mA/cm², and high photoconversion efficiency up to 5.35%, which is 16.7 times higher than the pure TiO₂ NTAs. The enhanced PEC performance of TiO₂ NTAs is attributed to the co-sensitization, heterojunction formation and electron “pool” effect imparted on the NTAs by the coupling of CdS and PbS SQDs.     

Facile fabrication of ordered assembled TiO2/g-C3N4 nanosheets with enhanced photocatalytic activity

A series of assembled porous TiO₂/g-C₃N₄ (TC) powders composed of spherical nanoparticles were synthesized by controlling the molar ratio of urea to tetrabutyl titanate (TBOT) in a facile hydrothermal process. A nanosheets-constructed hierarchical structure was obtained at the molar ratio of urea to TBOT of 10:1, which possessed uniform mesopores with bimodal distribution (0.5–1.5 nm and 2–20 nm) and interconnected macropores between TC nanosheets. The specific surface area achieved 98.4 m² g^?1. X-ray diffraction (XRD) patterns and high resolution transmission electron microscope (HRTEM) analysis proved that the nanosheets are made of overlapping TC nanocomposite. Photoluminescence (PL) spectra results illustrated that a well-defined hierarchical porous structure is particularly desired for the low recombination rate of carriers. Further, the TC-decorated carbon fiber (CF) cloth was obtained based on the nanosheets assembled hierarchical structure, which showed more outstanding photocatalytic behavior with high degradation capability for Rhodamine B (RhB) (99.9%) and tetracycline hydrochloride (89.8%) at 60 min by 500 W Xe lamp irradiation. After five consecutive cycles, the degradation efficiencies of TC/CF cloth for both RhB and tetracycline hydrochloride all remained above 90% of the initial value.     

Preparation and photocatalytic activity of g-C3N4/TiO2 heterojunctions under solar light illumination

The solar light sensitive g-C₃N₄/TiO₂ heterojunction photocatalysts containing 20, 50, 80, and 90 wt% graphitic carbon nitride (g-C₃N₄) were prepared by growing Titania (TiO₂) nanoparticles on the surfaces of g-C₃N₄ particles via one step hydrothermal process. The hydrothermal reactions were allowed to take place at 110 °C at autogenous pressure for 1 h. Raman spectroscopy analyses confirmed that an interface developed between the surfaces of TiO₂ and g-C₃N₄ nanoparticles. The photocatalyst containing 80 wt% g-C₃N₄ was subsequently heat treated 1 h at temperatures between 350 and 500 °C to improve the photocatalytic efficiency. Structural and optical properties of the prepared g-C₃N₄/TiO₂ heterojunction nanocomposites were compared with those of the pristine TiO₂ and pristine g-C₃N₄ powders. Photocatalytic activity of all the nanocomposites and the pristine TiO₂ and g-C₃N₄ powders were assessed by the Methylene Blue (MB) degradation test under solar light illumination. g-C₃N₄/TiO₂ heterojunction photocatalysts exhibited better photocatalytic activity for the degradation of MB than both pristine TiO₂ and g-C₃N₄. The photocatalytic efficiency of the g-C₃N₄/TiO₂ heterojunction photocatalyst heat treated at 400 °C for 1 h is 1.45 times better than that of the pristine TiO₂ powder, 2.20 times better than that of the pristine g-C₃N₄ powder, and 1.24 times better than that of the commercially available TiO₂ powder (Degussa P25). The improvement in photocatalytic efficiency was related to i) the generation of reactive oxidation species induced by photogenerated electrons, ii) the reduced recombination rate for electron-hole pairs, and iii) large specific surface area.     

Controlled synthesis of TiO2 nanorod arrays immobilized on ceramic membranes with enhanced photocatalytic performance

In this work, TiO₂ nanorod arrays (NRAs) were synthesized directly on flat sheet Al₂O₃ ceramic membrane (CM) substrates by a two-step hydrothermal method. The effects of the addition of anions and cations and the preparation parameters in the second step on the morphology and size of TiO₂ were investigated in detail, and the photocatalytic activities of the as-synthesized TiO₂-loaded ceramic membranes were investigated by the degradation of methylene blue (MB) under UV light. The results highlighted that the growth of TiO₂ on the CM strongly depended on the synthesis conditions. The anions of Cl^- and Br^- were favorable for the further growth of TiO₂ nanorods, while the anions of SO₄^2- and PO₄^3- with larger ionic radius and higher charge number could retard the growth of TiO₂ nanorods. The SO₄^2- and PO₄^3- could accelerate the formation of nanospheres or nanosheets, respectively. The cation like Na⁺, K⁺, Mg²⁺ and Ca²⁺ had no obvious impact on the formation of TiO₂ NRAs. TiO₂ nanorods exhibited the highest photocatalytic activity, as about 2.2 and 1.9 times larger than those of TiO₂ nanosheets and TiO₂ nanospheres, respectively. More importantly, the as-synthesized TiO₂ NRAs-loaded ceramic membrane could be easily reused and exhibited better photocatalytic stability. These findings would aid the development of TiO₂ photocatalytic materials with high performance.     

Nanoflower-like CdS and SnS2 loaded TiO2 nanotube arrays for photocatalytic wastewater treatment and hydrogen production

In this work, nanoflower-like CdS/SnS₂/TiO₂ NTs ternary heterojunction photocatalysts were synthesized by a hydrothermal method, the relationship between the morphology, microscopic morphology, crystallinity, elemental presence state and hydrogen production performance of the ternary photocatalysts were investigated by SEM, TEM, XRD and XPS, respectively. The photocatalytic performance, electrochemical property and hydrogen production capacity of CdS/SnS₂/TiO₂ NTs were compared with pure TiO₂ NTs, CdS/TiO₂ NTs and SnS₂/TiO₂ NTs. After 2 h of photocatalytic reaction, the removal efficiency of MB wastewater reached 100%, and the photocatalytic efficiencies toward RhB and Cr(VI) removal reached 86.08% and 80.93% after 3 h, respectively. The electron spin resonance (ESR) technique certified the active radical groups that played a role in the catalytic process and further investigated the possible photocatalytic mechanism. Hydrogen production per unit time achieved 97.14 μmol h^?1 cm^?2, this work provides the new technique to achieve solar energy conversion for hydrogen generation.     

S-scheme g-C3N4/TiO2/CFs heterojunction composites with multi-dimensional through-holes and enhanced visible-light photocatalytic activity

A novel multi-dimensional through-holes structure of g-C₃N₄ with adjustable pore size was prepared by controlling the mass ratio of oxamide (OA, structure guiding agent) to urea during one-step calcination process, and a break-rearrangement mechanism was explored. Then, a series of porous g-C₃N₄/TiO₂ (CT) composites with uniformly deposited TiO₂ nanoparticles were prepared based on the multi-dimensional framework by a facile hydrothermal method. The results show that a new S-scheme heterojunction with multi-dimensional through-channel structure was obtained, which is particularly desired for enhancing the visible-light utilization, reducing the carrier recombination rate and enhancing redox capacity. The CT composite obtained at hydrothermal treatment time of 2 h has a specific surface area of 180.15 m² g^-1, which shows high degradation capability (99.99%) for tetracycline hydrochloride (TC·HCl) under 350 W Xe lamp irradiation for 90 min. In addition, CT nanostructures was in-situ growth on carbon fiber (CFs), the degradation rate constant is 0.1566 min^-1, and 90% of the degradation efficiency can be maintained even after 5 consecutive cycles. It is expected to provide an effective reference for solving the problems of recovery difficulty and low reuse rate of powder photocatalytic materials.     

Ag nanoparticles loaded TiO2/MWCNT ternary nanocomposite: A visible-light-driven photocatalyst with enhanced photocatalytic performance and stability

A visible light active photocatalyst, Ag/TiO₂/MWCNT was synthesized by loading of Ag nanoparticles onto TiO₂/MWCNT nanocomposite. The photocatalytic activity of Ag/TiO₂/MWCNT ternary nanocomposite was evaluated for the degradation of methylene blue dye under UV and visible light irradiation. Ag/TiO₂/MWCNT ternary nanocomposite exhibits (~9 times) higher photocatalytic activity than TiO₂/MWCNT and (~2 times) higher than Ag/TiO₂ binary nanocomposites under visible light irradiation. The enhancement in the photocatalytic activity is attributed to the synergistic effect between Ag nanoparticles and MWCNT, which enhance the charge separation efficiency by Schottky barrier formation at Ag/TiO₂ interface and role of MWCNT as an electron reservoir. Effect of different scavengers on the degradation of methylene blue dye in the presence of catalyst has been investigated to find the role of photogenerated electrons and holes. Simultaneously, the Ag/TiO₂/MWCNT shows excellent photocatalytic stability. This work highlights the importance of Ag/TiO₂/MWCNT ternary nanocomposite as highly efficient and stable visible-light-driven photocatalyst for the degradation of organic dyes.     

Efficient photocatalytic degradation of methylene blue over BiVO4/TiO2 nanocomposites

BiVO₄/TiO₂ nanocomposites were successfully synthesized by coupling the modified sol-gel method with hydrothermal method. The samples were physically characterized X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer, Emmett and Teller (BET)-specific surface area, UV–vis diffuse reflectance spectrophotometry, zeta potential, and photoluminescence techniques. The BiVO₄/TiO₂ nanocomposites exhibited good photocatalytic activity in degradation of methylene blue under simulated solar light irradiation. The photodegradation of methylene blue demonstrated that 0.5BiVO₄/0.5TiO₂ photocatalyst exhibited much enhanced photoactivity than pure BiVO₄ and TiO₂. Based on the obtained results, the as-prepare BiVO₄/ TiO₂ nanocomposite possessed great adsorptivity of methylene blue, extended light adsorption range, and efficient charge separation properties. Overall, this work could provide new insights into the fabrication of a BiVO₄/TiO₂ composite as high performance photocatalyst and promise as a solar light photocatalyst for dye wastewater treatment.     

Design of TiO2 nanocrystals with enhanced sunlight photocatalytic activity by exploring calcining conditions

As a promising inorganic semiconductor photocatalyst, TiO₂ has been widespread concerned since 1972. However, its practical application is limited due to its low efficiency for utilizing solar light and rapid recombination of photo-generated charges. Here, we report a way to solve these problems by calcining TiO₂ samples under different conditions. It was found that the catalytic performance of TiO₂ catalysts was closely related to calcination temperature and calcination atmosphere. The XRD, Raman spectra, BET, UV–vis spectra, SEM and TG-DTA investigations of the catalysts revealed that the crystal structure of TiO₂, the specific surface area, and abundant oxygen vacancies were the primary factors influencing the performance of TiO₂ catalysts. Consequently, the TiO₂ nanocrystal calcined in a nitrogen/hydrogen mixed atmosphere at 300 °C for 3 h exhibited higher catalytic activity than others. These results demonstrated that annealing conditions can play an important role in catalyst activity.     

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。     

Preparation,structural and photocatalytic activity of Sn/Fe co-doped TiO2 nanoparticles by sol-gel method

Pure and Sn/Fe co-doped (0.2 at.% Sn and 0.6 at.% Fe, 0.6 at.% Sn and 0.2 at.% Fe, 1.0 at.% Sn and 1.0 at.% Fe) TiO₂ nanoparticles were synthesized via a sol-gel method and subsequently calcined at different temperatures. Furthermore, the particles were analyzed by TG-DSC, XRD, TEM, HRTEM, EDS, SAED and UV–Vis for investigating the influences of dopant and calcination temperature on the thermal effect, composition, morphology, energy band gap (E_g) and the degradation efficiency of methyl orange (MO) under various light irradiations respectively. Results indicated that Sn/Fe co-doping inhibited the crystallization transformation from anatase to rutile phase of TiO₂ and decreased the E_g. The increased calcination temperature and Sn/Fe co-doped effect brought about the abnormal grain growth of TiO₂ nanoparticles. 0.6 at.% Sn/0.2 at.% Fe and 1.0 at.% Sn/1.0 at.% Fe co-doped TiO₂ nanoparticles presented better photocatalytic performance than pure and 0.2 at.% Sn/0.6 at.% Fe co-doped TiO₂ nanoparticles under visible light irradiation mainly due to the decreased E_g. On the contrary, 0.2 at.% Sn and 0.6 at.% Fe co-doped TiO₂ nanoparticles calcined at 650 °C showed the most excellent photocatalytic performance under UV light irradiation, which was about twice as large as that of pure TiO₂ possibly due to the formed hybrid structure of anatase and rutile phase as well as the h⁺-mediated decomposition pathway.     

Au/TiO2复合物的制备、表征及其增强光催化灭菌活性

为提升TiO₂光催化活性克服其可见光响应能力差的问题,采用沉积-沉淀法制备了Au/TiO₂复合物光催化剂,利用X射线衍射（XRD）、傅里叶红外光谱（FTIR）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-vis DRS）、荧光发射光谱等对样品进行了表征。XRD、FTIR和XPS结果表明,Au/TiO₂中TiO₂为锐钛矿相且Au成功沉积至TiO₂。UV-vis DRS和荧光发射光谱结果表明,适量Au修饰不仅能提高TiO₂对可见光的吸收,还可促进TiO₂光生电子-空穴对分离,有利于增强其光催化活性。自由基捕获实验证实,形成?OH的数量与光照时间成正比且?OH生成量越多,光催化活性越高。对比考察了Au/TiO₂和TiO₂在氙灯光源照射下对大肠杆菌的光催化杀灭作用,并探讨了Au负载量、光照时间、光照强度、光催化剂浓度等因素对灭菌性能的影响。结果表明：Au/TiO₂的光催化灭菌活性优于TiO₂,且与光照时间和光照强度均成正比;Au的适宜负载量为3%（质量分数）;3%Au/TiO₂在光照时间60min、光照强度7mW/cm²、光催化剂浓度100μg/mL的条件下,对大肠杆菌的杀灭效率高达91.3%。     

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。     

Hollow TiO2 containing multilayer nanofibers with enhanced photocatalytic activity

Hollow titania containing multilayer nanofibers was fabricated through the combination of electrospinning with layer-by-layer technique. Two different solvents, methylbenzene and THF were used to remove the template. The morphology of the obtained hollow multilayer nanofibers confirmed that THF is better than methylbenzene. The obtained hollow multilayer fiber has a diameter of about 700 nm and its shell thickness is about 140 nm. FTIR spectra show the fabrication of multilayer nanofibers. XPS measurement indicates that TiO₂ nanoparticles can be assembled successfully. The obtained multilayer hollow nanofibers have highest photocatalytic activity to degrade methylene blue solution comparing with the TiO₂ film due to their unique hollow structure.     

氮钒共掺杂二氧化钛的制备及光催化性能

针对氮、钒单掺杂对二氧化钛改性的优势,利用溶剂热法重点研究了氮、钒共掺杂对TiO2光催化性能的提高.采用X射线衍射、透射电镜和紫外-可见吸收光谱表征了掺杂TiO2催化剂的物相、尺寸及光吸收性质.实验结果表明,当Ti∶N∶V的摩尔比达到1∶1∶16％时试样在紫外区和可见光区的吸收强度最佳,亚甲基蓝在紫外灯照射30 min后的降解率可达91.7％.     

Hydrothermal growth of TiO2 nanowire membranes sensitized with CdS quantum dots for the enhancement of photocatalytic performance

In this paper, TiO₂ nanowires (NWs) on Ti foils were prepared using a simple hydrothermal approach and annealing treatment. CdS quantum dots (QDs) were assembled onto the crystallized TiO₂ NWs by sequential chemical bath deposition. Ultraviolet-visible absorption spectra showed that CdS adds bands in the visible to the TiO₂ absorption and exhibited a broad absorption band in the visible region, which extended the scope of absorption spectrum and helped improve the photocatalytic degradation efficiency. The results of photocatalytic experiment revealed that CdS-TiO₂ NWs possessed higher photocatalytic activities toward methyl orange than pure TiO₂ nanowires. The degradation efficiency of 96.32% after ten cycles indicated that the as-prepared CdS-TiO₂ composite exhibited excellent long-time recyclable ability and can be reused for the degradation of contaminants.