Photocatalytic and antifouling properties of TiO2-based photocatalytic membranes

Photocatalysis has been extensively studied due to its potential ability to avoid the excessive use of chemical reagents and reduce the energy consumption by employing solar energy. Moreover, to alleviate the reduction in the membrane permeation selectivity, separation efficiency, and membrane service life caused by the emerging micro-pollutants and membrane fouling, membrane technology is often coupled with microbial, electrochemical, and catalytic processes. However, although physical/chemical cleaning and membrane module replacement can overcome the inherent limitations caused by membrane fouling and other membrane separation processes, high operating costs limit their practical applications. In this review, common preparation methods for TiO₂ photocatalytic membranes are described in detail, and the main approaches to enhancing their photocatalytic performance are discussed. More importantly, the mechanism of the TiO₂ photocatalytic membrane antifouling process is elucidated, and some applications of photocatalytic membranes in other areas are described. This review systematically outlines future research directions in the field of photocatalytic membrane modification, including metal and non-metal doping, fabrication of heterojunction structures, control over reaction conditions, increase in hydrophilicity, and increase in membrane porosity.     

Reversible superhydrophobic to superhydrophilic conversion of Ag@TiO2 composite nanofiber surfaces

A new type of superhydrophobic material consisting of a surface with supported Ag@TiO(2) core-shell nanofibers has been prepared at low temperature by plasma-enhanced chemical vapor deposition (PECVD). The fibers are formed by an inner nanocrystalline silver thread which is covered by a TiO(2) overlayer. Water contact angles depend on the width of the fibers and on their surface concentration, reaching a maximum wetting angle close to 180 degrees for a surface concentration of approximately 15 fibers microm(-2) and a thickness of 200 nm. When irradiated with UV light, these surfaces become superhydrophilic (i.e., 0 degrees contact angle). The decrease rate of the contact angle depends on both the crystalline state of the titania and on the size of the individual TiO(2) domains covering the fibers. To the best of our knowledge, this is one of the few examples existing in the literature where a superhydrophobic surface transforms reversibly into a superhydrophilic one as an effect of light irradiation.     

Droplet motion on designed microtextured superhydrophobic surfaces with tunable wettability

Superhydrophobic surfaces have shown promising applications in microfluidic systems as a result of their water-repellent and low-friction properties over the past decade. Recently, designed microstructures have been experimentally applied to construct wettability gradients and direct the droplet motion. However, thermodynamic mechanisms responsible for the droplet motion on such regular rough surfaces have not been well understood such that at present specific guidelines for the design of tunable superhydrophobic surfaces are not available. In this study, we propose a simple but robust thermodynamic methodology to gain thorough insight into the physical nature for the controllable motion of droplets. On the basis of the thermodynamic calculations of free energy (FE) and the free-energy barrier (FEB), the effects of surface geometry of a pillar microtexture are systematically investigated. It is found that decreasing the pillar width and spacing simultaneously is required to lower the advancing and receding FEBs to effectively direct droplets on the roughness gradient surface. Furthermore, the external energy plays a role in the actuation of spontaneous droplet motion with the cooperation of the roughness gradient. In addition, it is suggested that the so-called "virtual wall" used to confine the liquid flow along the undesired directions could be achieved by constructing highly advancing FEB areas around the microchannels, which is promising for the design of microfluidic systems.     

Defective TiO2 for photocatalytic CO2 conversion to fuels and chemicals

Photocatalytic conversion of CO₂ into fuels and valuable chemicals using solar energy is a promising technology to combat climate change and meet the growing energy demand. Extensive effort is going on for the development of a photocatalyst with desirable optical, surface and electronic properties. This review article discusses recent development in the field of photocatalytic CO₂ conversion using defective TiO₂. It specifically focuses on the different synthesis methodologies adapted to generate the defects and their impact on the chemical, optical and surface properties of TiO₂ and, thus, photocatalytic CO₂ conversion. It also encompasses theoretical investigations performed to understand the role of defects in adsorption and activation of CO₂ and identify the mechanistic pathway which governs the formation and selectivity of different products. It is divided into three parts: (i) general mechanism and thermodynamic criteria for defective TiO₂ catalyzed CO₂ conversion, (ii) theoretical investigation on the role of defects in the CO₂ adsorption–activation and mechanism responsible for the formation and selectivity of different products, and (iii) the effect of variation of physicochemical properties of defective TiO₂ synthesized using different methods on the photocatalytic conversion of CO₂. The review also discusses the limitations and the challenges of defective TiO₂ photocatalysts that need to be overcome for the production of sustainable fuel utilizing solar energy.

This review discusses photocatalytic CO₂ conversion using defective TiO₂, with emphasis on the mechanism, the role of defects on CO₂ adsorption–activation and product selectivity, as well as challenges of defective TiO₂ to produce solar fuels.     

Preparation of superhydrophobic silicon oxide nanowire surfaces

The paper reports on the preparation of superhydrophobic amorphous silicon oxide nanowires (a-SiONWs) on silicon substrates with a contact angle greater than 150 degrees by means of surface roughness and self-assembly. Nanowires with an average mean diameter in the range 20-150 nm and 15-20 microm in length were obtained by the so-called solid-liquid-solid (SLS) technique. The porous nature and the high roughness of the resulting surfaces were confirmed by AFM imaging. The superhydrophobicity resulted from the combined effects of surface roughness and chemical modification with fluorodecyl trichlorosilane.     

高纯纳米氧化钛的制备及催化活性

以工业级硫酸钛为原料,在酸性环境下以EDTA作为络合剂,采用控制沉淀法制备高纯度纳米TiO2。考察了pH值、反应温度、煅烧温度等工艺条件对TiO2颗粒晶型、大小和分布影响。利用TEM、XRD、ICP等手段对产物进行表征,TiO2纯度超过99.9%,粒径为10-20nm,分布均匀。经过对其光催化降解苯酚反应活性实验,结果表明样品具有较好的光催化活性。     

Wettability conversion on the liquid flame spray generated superhydrophobic TiO2 nanoparticle coating on paper and board by photocatalytic decomposition of spontaneously accumulated carbonaceous overlayer

Titanium dioxide (TiO₂) is a photoactive material with various interesting and useful properties. One of those is the perfect wettability of TiO₂ surface after ultraviolet (UV) illumination. Wettability of a solid surface plays an important role in the field of printing, coating, and adhesion among others. Here we report on a superhydrophobic and photoactive liquid flame spray (LFS) generated TiO₂ nanoparticle coating that can be applied on web-like materials such as paper and board in one-step roll-to-roll process. The LFS TiO₂ nanoparticle coated paper and board were superhydrophobic instantly after the coating procedure because of spontaneously accumulated carbonaceous overlayer on TiO₂, and thus there was no need for any type of separate hydrophobization treatment. The highly photoactive LFS TiO₂ nanoparticle coating could be converted steplessly from superhydrophobic to superhydrophilic by UV-illumination, and the coating gave strong response to natural daylight illumination even in the shade. The superhydrophobic LFS TiO₂ coated surface can be used as an intelligent substrate, where photo-generated hydrophilic patterns guide the fluid setting and figure formation. Our study reveals that the wettability changes on the LFS TiO₂ surface were primarily caused by the photocatalytic removal of the carbonaceous material from TiO₂ during the UV-illumination and spontaneous accumulation of the carbonaceous material on the surface of the metal oxide during storage in the dark. The latter mechanism was found to be a temperature activated process which could be significantly speeded up by heat treatment. If other mechanisms such as surface oxidization, increment of hydroxyl groups, or charge separation played a role in the wetting phenomena on TiO₂, their effect was rather secondary as the removal and accumulation of the carbonaceous material dominated the wettability changes on the surface. Our study gives valuable information on the complex issue of photo-induced wettability changes on TiO₂.     

Preparation and photocatalytic antibacterial property of nitrogen doped TiO2 nanoparticles

Nitrogen doped TiO₂ (N-TiO₂) nanoparticles with about 30 nm in size were produced by a sol–gel method and characterized respectively by UV–vis, X-ray diffraction (XRD), Transmission electron microscopy, X-ray photoelectron spectroscopy (XPS). Their photocatalytic antibacterial properties were evaluated by the antibacterial ratio against Escherichia coli in dark and under simulated sunlight respectively. The XRD pattern showed that the doped nano-TiO₂ was mainly composed of anatase phase. The XPS spectra of the N-TiO₂ sample indicated that TiO₂ was doped by nitrogen atom. The nitrogen doping created a new N 2p state slightly above the valence band top consists of O 2p state, and this pushes up the valence band top and decreased the band gap. Which leaded to the absorption edge was red-shifted to the visible light region of UV–vis spectra of nitrogen doped nano-TiO₂ comparing with pure nano-TiO₂. The antibacterial percentage of N-TiO₂ against E. coli reached to 90 % under simulated sunlight for 2 h, which was much better than that in dark, also than that of pure nano-TiO₂. The photo-catalytic antibacterial activity was activated under visible light. The structure and integrity of cell wall and cell membrane were destructed, and even caused the bacteria death.     

Preparation, characterization and photocatalytic activity of metalloporphyrins-modified TiO2 composites

Three new Cu(II), Zn(II), Co(II) 5,15-di (4-hydroxyphenyl)-10, 20-diphenyl-porphyrin (CuDHPP, ZnDHPP, CoDHPP) and the corresponding metalloporphyrins–TiO₂ photocatalysts CuDHPP–TiO₂, ZnDHPP–TiO₂, CoDHPP–TiO₂ were synthesized and characterized by SEM, XRD, FT-IR, and DRS. The results revealed that the metalloporphyrins impregnated onto the surface of TiO₂ did not change the phase composition and particle sizes of TiO₂ samples, but increased the photocatalytic efficiency. In addition, photoluminescence study showed that the three photocatalysts could successfully increase the separation efficiency of the photoinduced electron and hole. The photodegrading 4-NP experiments indicated that the three photocatalysts greatly enhanced the photocatalytic activity of bare TiO₂, and the photocatalytic activity of CuDHPP–TiO₂ was the highest. Moreover, the possible mechanism for the photodegradation of 4-NP was also proposed.     

Preparation and photocatalytic behavior of MoS2 and WS2 nanocluster sensitized TiO2

A new approach has been developed for the fabrication of visible light photocatalysts. Nanoclusters of MoS2 and WS2 are coupled to TiO2 by an in situ photoreduction deposition method taking advantage of the reducing power of the photogenerated electrons from TiO2 particles. The photocatalytic degradation of methylene blue and 4-chlorophenol in aqueous suspension has been employed to evaluate the visible light photocatalytic activity of the powders. The blue shift in the absorption onset confirms the size quantization of MS2 nanoclusters, which act as effective and stable sensitizers, making it possible to utilize visible light in photocatalysis. Quantum size effects alter the energy levels of the conduction and valence band edges in the coupled semiconductor systems, which favors the interparticle electron transfer. In addition, the coupled systems are believed to act in a cooperative manner by increasing the degree of charge carrier separation, which effectively reduces recombination.     

Ordering of TiO2-based nanostructures on SrTiO3(001) surfaces

A class of nanostructured surface phases on SrTiO3(001) is reported and characterized through atomic-resolution scanning tunneling microscopy and Auger electron spectroscopy. These surface phases are created via argon ion sputtering and UHV annealing and form close-packed domains of highly ordered nanostructures. Depending on the type of nanostructures present, the domain ordering exhibit either (6 x 2), (9 x 2), (12 x 2), (6 x 8), or (7 x 4) surface patterning. The nanostructures are composed of TiO2-derived complexes surrounded by a TiO2 surface termination. Such surface ordering phenomena introduce another level of complexity in the chemistry of perovskite oxide surfaces and provide a basis from which potential photocatalytic and molecular-ordering applications may be developed.     

Preparation and solar-light photocatalytic activity of TiO2 composites: TiO2/kaolin,TiO2/diatomite,and TiO2/zeolite

Three TiO₂ loaded composites, TiO₂/kaolin, TiO₂/diatomite, and TiO₂/zeolite, were prepared in order to improve the solar-light photocatalytic activity of TiO₂. The results showed that the photocatalytic activity could obviously be enhanced by loading appropriate amount of inorganic mineral materials. Meanwhile, TiO₂ content, heat-treatment temperature and heat-treatment time on the photocatalytic activity were reviewed. Otherwise, the effect of solar light irradiation time and dye concentration on the photocatalytic degradation of Acid Red B was investigated. Furthermore, the degradation mechanism and adsorption process were also discussed.     

钒掺杂TiO2/AC负载催化剂的制备及光催化活性

以TiO2为主要成分的光催化剂的研究已日益受到人们的广泛关注[1-6]。但TiO2粉末的回收和流失问题难以解决,固定化TiO2负载催化剂的研制是解决这一问题的有效手段[2-6]。从实际应用的观点看,TiO2的光催化剂活性还有待进一步提高。研究发现,大多数过渡金属离子和少数非金属离子的     

负载型混晶纳米TiO_2/硅藻土复合材料的制备及其光催化性能

选用市售硅藻土作为载体,采用液相沉积法制备了负载型混晶纳米TiO2/硅藻土复合材料;采用扫描电镜、X射线衍射仪及红外光谱仪分析了复合材料的表面形貌和晶体结构;基于甲醛光催化降解实验考察了不同组成的负载型TiO2/硅藻土复合材料的光催化性能.结果表明,TiO2负载量为33.3%(TiO2与硅藻土的质量比为1∶2)的复合材料对甲醛光催化降解具有最佳催化活性.     

C/Nd/TiO2催化剂的制备及光催化性能研究

利用溶胶-凝胶法以钛酸四丁酯为钛源、硝酸钕为钕源、葡萄糖为碳源,制备了C和Nd单掺杂及共掺杂TiO_2催化剂。通过XRD、XPS、漫反射、SEM和物理吸附对所制备的催化剂进行表征与评价。结果表明,C和Nd共掺杂TiO_2的晶型仍为锐钛矿型,表面光滑,晶粒大小分散均匀,孔径分布在20~34 nm之间;与其他三种催化剂相比,共掺杂催化剂比表面积较大;通过掺杂C和Nd元素,形成新能带E_(C2p)和E_(Nd3+4f),降低了电子跃迁能,有利于光催化活性增强。C和Nd共掺杂TiO_2对可见光的吸收能力有明显提高,对甲基橙染料降解效果较佳,其脱色率为61.24%。     

Preparation and photocatalytic activity of Cu-deposited TiO2 film with high transparency

Cu-deposited TiO₂ films were prepared by photoreduction of Cu(II) in the presence of sodium formate. With the initial Cu(II) concentrations more than 100 mg L^?1, induction periods were observed before the transmittance decreased. Scanning electron microscopy indicated that Cu particles of 2.6 ± 0.5 μm were deposited isolatedly with much open space in the induction periods. The films prepared by changing the irradiation time within the induction periods showed a higher photocatalytic activity than a pure TiO₂ for the degradation of methylene blue under the reaction condition without purging air.     

Reversible photocontrol of surface wettability between hydrophilic and superhydrophobic surfaces on an asymmetric diarylethene solid surface

By alternate UV and visible light irradiation, reversible topographical changes were observed on a newly synthesized diarylethene microcrystalline surface between the rough crystalline surface of an open-ring isomer and flat eutectic surfaces. The contact angle changes of a water droplet between 80° and 150° and peak intensities changes of the open-ring isomer in XRD patterns within 2 h of repeating cycle were observed. The results indicated that reversibly photogenerated rod-shaped crystals on the surface were produced based on the lattice of the open-ring isomer crystals in the subphase.     

Preparation and characterisation of membranes with entrapped TiO2 and preliminary photocatalytic tests

The possibility of entrapping polycrystalline TiO2 in a polymeric support, in order to couple the two unit operations, i.e. ultrafiltration and photodegradation of organic pollutants in aqueous solutions, was investigated. To this aim, polymeric membranes for ultrafiltration with entrapped TiO2 were prepared, characterised and tested. The polymeric support chosen was commercial polysulfone (PSf). The membrane preparation was carried out with the technique referred to as phase inversion. A three-component system, with a polymer, a solvent and a non-solvent was used. The best operative conditions were determined in order to obtain the desired membrane morphology. Permeability measurements and photostability tests were also carried out by using a system under pressure. Finally, a preliminary investigation was performed in order to evaluate the photocatalytic activity of the membranes with entrapped TiO2 for the oxidation of 4-nitrophenol as a model molecule in aqueous solutions.     

Au/ZnO/TiO_2复合薄膜的制备及光电转换性质

以含有Au和ZnO纳米颗粒的氢氧化钛溶胶作为成膜液,通过浸渍-提拉及灼烧处理在导电玻璃表面制备Au/ZnO/TiO2复合薄膜.利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)等方法对所得产物进行表征.结果表明,Au和ZnO纳米颗粒均匀地分布在多孔TiO2薄膜上,通过TiO2、ZnO和Au三组分的协同效应促进了光吸收和电荷分离,使Au/ZnO/TiO2复合薄膜具有较好的光电转换性质,可用作太阳能电池材料.