Novel one-step preparation of tungsten loaded TiO2 nanotube arrays with enhanced photoelectrocatalytic activity for pollutant degradation and hydrogen production

Highly ordered tungsten doped TiO₂ nanotube arrays (W-TiO₂NTs) were prepared in glycerol/fluoride electrolyte solution containing sodium tungstate via the electrochemical oxidation of a Ti substrate. The resulting arrays were characterized by XRD, SEM, and XPS. The 15 mM W-TiO₂NTs exhibited better photoelectrochemical activity than the TiO₂NTs and W-TiO₂NTs fabricated using other W concentrations under Xe illumination. The W ion was successfully introduced into the TiO₂ crystal lattice in the W^6 + form according to the XPS analysis, which enhanced the photoelectrocatalytic activity of the W-TiO₂NTs, as indicated by the efficient removal of Rhodamine B and the production of hydrogen.     

Preparation of CdS/TiO2 nanotube arrays and the enhanced photocatalytic property

In this paper, a series of CdS/TiO₂ NTs have been synthesized by SILAR method. The as-prepared CdS/TiO₂ NTs have been analyzed by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive spectrometer (EDS), and ultraviolet–visible (UV–vis). And their photocatalytic activities have been investigated on the degradation of methylene blue under simulated solar light irradiation. XRD results indicate that TiO₂ NTs were anatase phase, CdS nanoparticles were hexagonal phase. FESEM results indicate that low deposition concentration can keep the nanotubular structures. UV–vis results indicate that CdS can be used to improve the absorbing capability of TiO₂ NTs for visible light, and the content of CdS affects the band gap. Photocatalytic results indicate that CdS nanoparticles are conducive to improve the photocatalytic efficiency of TiO₂ NTs, and the highest degradation rate can reach 93.8%. And the photocatalytic mechanism of CdS/TiO₂ NTs to methylene blue is also described.     

Au对TiO2光电催化材料的改性策略研究进展

近年来,环境污染、能源枯竭问题日益严重,成为制约人类生存与发展的主要因素。光电催化技术能够同时实现污染物的降解与清洁能源的制备,有助于缓解环境污染与能源枯竭问题。作为典型的光（电）催化材料,TiO₂具有光活性强、性质稳定、廉价易得、环境友好等诸多优点,数十年来已成为光催化及相关领域的研究热点。然而,TiO₂存在的本征缺陷依然制约着其进一步推广应用,为此研究人员已提出多种方式对TiO₂进行改性。其中贵金属/TiO₂复合材料可显著提升TiO₂的光学活性并拓宽其吸收波长范围,尤其是Au/TiO₂材料体系已受到广泛关注和认可,表现出良好的应用前景。本文通过对目前Au/TiO₂复合材料的发展现状进行了总结,首先简单介绍了Au和TiO₂的化学性质及Au对TiO₂光学性能的增强原理;随后对Au/TiO₂复合材料的改性策略及相关作用机制展开讨论,包括Au对TiO₂光学性能的影响及调控、修饰方法的选择与影响等;最后总结出目前Au/TiO₂复合材料依然以克服TiO₂的两大本征缺陷为主,探讨各类新型Au/TiO₂复合材料有望使其得到逐步推广与实际应用。最后对目前Au/TiO₂复合材料的研究现状进行系统总结并探讨该材料未来的研究和发展方向。     

CdSe纳米颗粒敏化TiO_2纳米管阵列的光催化降解及光电催化制氢

采用胶体化学法制备不同尺寸的硒化镉纳米颗粒(CdSe-NP)胶体,并利用原位吸附法将CdSe-NP与由阳极氧化法得到的TiO2纳米管阵列(TN)复合,在可见光下降解甲基橙溶液和外加偏压制氢,分别考察CdSe-NP敏化的TiO2纳米管阵列(CdSe-NP/TN)的光催化性能和光电催化性能。对比TN,CdSe-NP/TN表现出明显增强的光催化活性及更优异的光电催化性能,而过大的CdSe-NP尺寸则不利于复合材料的催化活性。表征结果表明,CdSe-NP/TN优异的性能是由于敏化CdSe-NP后吸收边红移以及光生电子和空穴复合率降低。     

Improved photoelectrocatalytic degradation of methylene blue by Ti3C2Tx/Bi12TiO20 composite anodes

In order to effectively reduce the high recombination rate of photogenerated carriers when Bi₁₂TiO₂₀ (BTO) was excited by visible light, Ti₃C₂T_x/BTO/fluorine-doped tin oxide photoanodes were conveniently prepared with the aid of mechanical coating by gentle ultrasonic mixing. Systematic characterization and the degradation of methylene blue in a photoelectrochemical cell were performed. The results showed that the Ti₃C₂T_x/BTO composite exhibited a strong light absorption ability and the effective separation of photogenerated carriers. The optimal anode (6 wt% Ti₃C₂T_x/BTO) degraded 85.4% of methylene blue within 120 min at an applied electric field of 1 V, with a reaction rate that was 3.5 times that of BTO. It was proved that Ti₃C₂T_x, as a useful co-catalyst, creates an internal electric field at the contact interface with BTO and an external electric field, which are responsible for the enhanced photoelectrocatalytic degradation capacity of the composite anode materials.     

Low temperature CO oxidation over Au/TiO2 and Au/SiO2 catalysts

After a high-temperature reduction (HTR) at 773 K, TiO₂-supported Au became very active for CO oxidation at 313 K and was an order of magnitude more active than SiO₂-supported Au, whereas a low-temperature reduction (LTR) at 473 K produced a Au/TiO₂ catalyst with very low activity. A HTR step followed by calcination at 673 K and a LTR step gave the most active Au/TiO₂ catalyst of all, which was 100-fold more active at 313 K than a typical 2% Pd/Al₂O₃ catalyst and was stable above 400 K whereas a sharp decrease in activity occurred with the other Au/TiO₂ (HTR) sample. With a feed of 5% CO, 5% O₂ in He, almost 40% of the CO was converted at 313 K and essentially all the CO was oxidized at 413 K over the best Au/TiO₂ catalyst at a space velocity of 333 h^–1 based on CO + O₂. Half the chloride in the Au precursor was retained in the Au/TiO₂ (LTR) sample whereas only 16% was retained in the other three catalysts; this may be one reason for the low activity of the Au/TiO₂ (LTR) sample. The reaction order on O₂ was approximately 0.4 between 310 and 360 K, while that on CO varied from 0.2 to 0.6. The chemistry associated with this high activity is not yet known but is presently attributed to a synergistic interaction between gold and titania.     

Size Effect in Hybrid TiO2:Au Nanostars for Photocatalytic Water Remediation Applications

TiO₂:Au-based photocatalysis represents a promising alternative to remove contaminants of emerging concern (CECs) from wastewater under sunlight irradiation. However, spherical Au nanoparticles, generally used to sensitize TiO₂, still limit the photocatalytic spectral band to the 520 nm region, neglecting a high part of sun radiation. Here, a ligand-free synthesis of TiO₂:Au nanostars is reported, substantially expanding the light absorption spectral region. TiO₂:Au nanostars with different Au component sizes and branching were generated and tested in the degradation of the antibiotic ciprofloxacin. Interestingly, nanoparticles with the smallest branching showed the highest photocatalytic degradation, 83% and 89% under UV and visible radiation, together with a threshold in photocatalytic activity in the red region. The applicability of these multicomponent nanoparticles was further explored with their incorporation into a porous matrix based on PVDF-HFP to open the way for a reusable energy cost-effective system in the photodegradation of polluted waters containing CECs.     

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.     

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。     

Methanol oxidation on Au/TiO2 catalysts

We have investigated the adsorption and reaction of methanol with Au/TiO₂ catalysts using a pulsed flow reactor, DRIFTS and TPD. The TiO₂ (P25) surface adsorbed a full monolayer of methanol, much of it in a dissociative manner, forming methoxy groups associated with the cationic sites, and hydroxyl groups at the anions. The methoxy is relatively stable until 250 °C, at which point decomposition occurs, producing mainly dimethyl ether by a bimolecular surface reaction. As the concentration of methoxy on the surface diminishes, so the mechanism reverts to a de-oxygenation pathway, producing mainly methane and water (at ~330 °C in TPD), but also with some coincident CO and hydrogen. Au catalysts were prepared by the deposition-precipitation method to give Au loadings between 0.5–3 wt %. The effect of low levels of Au on the reactivity is marked. The pathway which gives methane, which is characteristic of titania, remains, but a new feature of the reaction is the evolution of CO₂ and H₂ at lower temperature (a peak is seen in TPD at 220 °C), and the elimination of the DME-producing state. Clearly this is associated with the presence of Au and appears to be due to the production of a formate species on the surface of the Au component. This formate species is mainly involved in the reaction of methanol with the Au/TiO₂ catalysts which results in a combustion pathway being followed, with complete conversion occurring by ~130 °C.     

鞭毛辅助CdS/TiO_2纳米复合薄膜的制备以及显著增强的光电催化活性

采用鞭毛作为生物模板剂制备Cd S/TiO_2复合纳米结构薄膜,采用SEM、XRD、IR、紫外-可见漫反射和电化学工作站等对其结构和光电化学性质进行表征。结果表明,鞭毛的引入不但减小了CdS颗粒尺寸和增大了比表面积,而且改善了复合材料的带隙结构。该薄膜可见光光电催化活性比未加入鞭毛的空白样品高1.4倍。提供了一个利用生物模板剂控制半导体纳米结构单元生长与组装及改善光电性能的简单方法。     

Resistive switching of Au/ZnO/Au resistive memory: an in situ observation of conductive bridge formation

A special chip for direct and real-time observation of resistive changes, including set and reset processes based on Au/ZnO/Au system inside a transmission electron microscope (TEM), was designed. A clear conducting bridge associated with the migration of Au nanoparticles (NPs) inside a defective ZnO film from anode to cathode could be clearly observed by taking a series of TEM images, enabling a dynamic observation of switching behaviors. A discontinuous region (broken region) nearby the cathode after reset process was observed, which limits the flow of current, thus a high resistance state, while it will be reconnected to switch the device from high to low resistance states through the migration of Au NPs after set process. Interestingly, the formed morphology of the conducting bridge, which is different from the typical formation of a conducting bridge, was observed. The difference can be attributed to the different diffusivities of cations transported inside the dielectric layer, thereby significantly influencing the morphology of the conducting path. The current TEM technique is quite unique and informative, which can be used to elucidate the dynamic processes in other devices in the future.     

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。     

Construction of Au/TiO2 Heterojunction with high photocatalytic performances under UVA illumination

Anatase TiO₂ nanoparticles (NPs) were successfully prepared through a hydrothermal approach, and Au NPs at various Au (0.1–2 wt%) contents were photodeposited onto the TiO₂ NPs surface. The photocatalytic efficiency for the Au/TiO₂ NPs for resorcinol photodegradation throughout UVA illumination was assessed. The TEM images and XPS findings indicated that the Au NPs are highly distributed onto TiO₂ surface in the metallic state. The 0.1%Au/TiO₂ NPs exhibited the highest photocatalytic efficiency of about 95.34%; however, 72.36% is given by pure TiO₂ NPs. It was found that the photodegradation rate of 0.1% Au/TiO₂ NPs exhibited 1.5 times of magnitude higher than pure TiO₂ NPs. 0.1%Au/TiO₂ NPs was considered to be the outstanding photoactive due to the ultimate efficient charge-carriers separation through charge transfer between Au and TiO₂ NPs. The Au NPs sizes, its dispersity on TiO₂ surface and surface plasmon resonance (SPR) were believed the critical factors for the higher photocatalytic performance of 0.1% Au/TiO₂ NPs. The prepared photocatalysts are found to be the promising materials for toxic organic compounds remediation and solar conversion.     

双相等离子体Au/TiO2纳米复合材料抗菌研究

具有独特的表面等离子体共振（SPR）的金属纳米晶体是一种良好的宽带隙半导体可见光敏化材料。本研究通过溶剂热和煅烧合成了0.3％摩尔比的金修饰氧化钛（Au/TiO2）纳米复合材料。利用X射线晶体衍射（XRD）,X射线光电子能谱（XPS）,透射电子显微镜（TEM）和紫外-可见（UV-vis）等方法对合成的Au/TiO2纳米复合材料进行表征。结果表明,由于强的表面等离子体共振效应,Au纳米颗粒可以显著提高TiO2的可见光吸收性能。随着煅烧温度的升高,可见光吸收峰从?550 nm红移到670 nm,这便于更好地利用太阳光谱。Au/TiO2纳米复合材料对大肠杆菌（E. coli）的抗菌活性显示,在450 ℃下煅烧后形成的金修饰的锐钛矿相和金红石相的混晶相,具有最好的光催化抗菌活性。     

氧化石墨烯负载金纳米颗粒及其催化活性研究

在不外加任何还原剂的情况下,利用氯金酸和氧化石墨烯之间的氧化还原反应将金纳米颗粒成功负载到氧化石墨烯上,合成了金纳米颗粒/氧化石墨烯复合材料。利用透射电镜(TEM)和X-射线衍射(XRD)对复合材料进行了结构表征与形态分析,并研究了金纳米颗粒/氧化石墨烯复合材料对Suzuki-Miyaura偶联反应的催化效果。结果表明,通过调节氯金酸与氧化石墨烯的质量比,可以得到不同形状的金纳米颗粒;金纳米颗粒/氧化石墨烯复合材料对Suzuki-Miyaura偶联反应具有很高的催化活性,并且很容易从反应体系中回收。     

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。     

Au／TiO2的制备及其光催化氧化丙烯的研究

采用浸渍法制备了Au/TiO2光催化剂，使用X射线能谱(XPS)和透射电子显微镜(TEM)对样品进行了表征．结果表明，Au颗粒的尺度约为4—6nm；Au4f7／2的结合能为83．3eV，与Au^0的标准峰位(84．0ev)相比，向低结合能方向移动了0．7eV，使其表现出俘获电子的特性．以丙烯的光催化氧化为指标反应，对制备的Au/TiO2的活性进行了评价，结果显示，Au/TiO2的光催化活性明显高于单一TiO2的，且当Au的担载量在0．1-5．0％范围内变化时，催化活性随着担载量的增加而显著增加．     

Rational design of gold catalysts with enhanced thermal stability: post modification of Au/TiO2 by amorphous SiO2 decoration

Au/TiO₂ is highly active for CO oxidation, but it often suffers from sintering in high-temperature environments. In this work, we report on a novel design of gold catalysts, in which pre-formed Au/TiO₂ catalysts were post decorated by amorphous SiO₂ to suppress the agglomeration of gold particles. Even after being aged in O₂–He at 700 °C, the SiO₂-decorated Au/TiO₂ was still active for CO oxidation at ambient temperature.