Comparative study on the process behavior and reaction kinetics in sonocatalytic degradation of organic dyes by powder and nanotubes TiO2

Sonocatalytic degradation of various organic dyes (Congo Red, Reactive Blue 4, Methyl Orange, Rhodamine B and Methylene Blue) catalyzed by powder and nanotubes TiO₂ was studied. Both catalysts were characterized using transmission electron microscope (TEM), surface analyzer, Raman spectroscope and thermal gravimetric analyzer (TGA). Sonocatalytic activity of powder and nanotubes TiO₂ was elucidated based on the degradation of various organic dyes. The former catalyst was favorable for treatment of anionic dyes, while the latter was more beneficial for cationic dyes. Sonocatalytic activity of TiO₂ nanotubes could be up to four times as compared to TiO₂ powder under an ultrasonic power of 100 W and a frequency of 42 kHz. This was associated with the higher surface area and the electrostatic attraction between dye molecules and TiO₂ nanotubes. Fourier transform-infrared spectrometer (FT-IR) was used to identify changes that occurred on the functional group in Rhodamine B molecules and TiO₂ nanotubes after the reaction. Sonocatalytic degradation of Rhodamine B by TiO₂ nanotubes apparently followed the Langmuir-Hinshelwood adsorption kinetic model with surface reaction rate of 1.75 mg/L min. TiO₂ nanotubes were proven for their high potential to be applied in sonocatalytic degradation of organic dyes.     

The enhanced photocatalytic activity of CdS/TiO2 nanocomposites by controlling CdS dispersion on TiO2 nanotubes

CdS/TiO₂ nanocomposites were prepared via a simple wet chemical method, and characterized through X-ray diffraction (XRD) and transmission electron microscopy (TEM). Their ability to degrade Acid Rhodamine B was investigated under visible light irradiation. The results indicate that CdS/TiO₂ nanocomposite with a mass ratio of 4:1(TiO₂:CdS) showed high photocatalytic activity and the CdS loaded on TiO₂ nanotube surface exhibited a hexagonal phase. The dispersion of CdS on TiO₂ nanotube surface had an important effect on the degradation efficiency of pollutant, which provides a strategy for practical industry application.     

Enhancement of the photocatalytic activity of TiO2 nanoparticles by surface-capping DBS groups

TiO₂ nanoparticles capped with sodium dodecylbenzenesulfonate (DBS) are synthesized by a sol-hydrothermal process using tetrabutyl titanate and DBS as raw materials. The effects of surface-capping DBS on the surface photovoltage spectroscopy (SPS), photoluminescence (PL) and photocatalytic performance of TiO₂ nanoparticles are principally investigated together with their relationships. The results show that the surface of TiO₂ nanoparticles can be well capped by DBS groups while the pH value and added DBS amount are controlled at 5.0 and 2% of TiO₂ mass weight, respectively, and the linkage between DBS groups and TiO₂ surfaces is mainly by means of quasi-sulphonate bond. The intensities of SPS and PL spectra of TiO₂ obviously decrease after DBS-capping, while the activity can greatly increase during the photocatalytic degradation of Rhodamine B (RhB) solution, which are mainly attributed to the electron-withdrawing character of the DBS groups. Moreover, the enhancement of photocatalytic activity of DBS-capped TiO₂ is also related to the increase in the capability for adsorbing RhB.     

Surface modification of nanocrystalline anatase with CTAB in the acidic condition and its effects on photocatalytic activity and preferential growth of TiO2

The nanocrystalline anatase TiO₂, which was synthesized by a sol-hydrothermal process in advance, has successfully modified with cetyltrimethylammonium bromide (CTAB) in the acidic condition as well as in the basic condition. On the basis of the measurements of infrared spectrum and X-ray photoelectron spectroscopy of the resulting TiO₂, together with the phase-transfer experiments, it is suggested that the modification mechanism in the acidic condition is closely related to Br⁻. Interestingly, compared with un-modified TiO₂, the modified TiO₂ exhibits high photocatalytic activity for degrading Rhodamine B (RhB) solution, especially for that modified in the acid. The enhanced photocatalytic activity of modified TiO₂ in the acid is attributed to the role that the Br⁻ can easily capture photo-induced holes and then form active Br, consequently effectively inducing photocatalytic oxidation reactions, based on the surface photovoltage responses of the resulting TiO₂. After that, a one-pot sol-hydrothermal route at the temperature as low as 80 °C is developed to directly synthesize CTAB-modified nanocrystalline TiO₂ with a little preferred growth along 〈0 0 1〉 direction, which can be easily dispersed in the organic system and possess good photocatalytic performance. This work provides a feasible strategy to further improve the photocatalytic performance of nanocrystalline anatase and to synthesize TiO₂ nanocrystals with preferential growth.     

Gold nanoparticle shape effects on human serum albumin corona interface: a molecular dynamic study

Three-dimensional (3D) hierarchical rutile TiO₂ microspheres composed of nanorods with diameter of several-tens of nanometers, with different morphologies and with average size ranging from 1.3 to 1.8 μm, were successfully synthesized through a surfactant-free solvothermal route. The effects of the solvents n-hexane, chloroform, and cyclohexane on the microstructures of 3D hierarchical TiO₂ nanostructures were investigated. Results of scanning electron microscopy showed that 3D sea-urchin like hierarchical TiO₂ composed of nanorods with a diameter of ~10 nm can only be prepared in the cyclohexane-water system. The growth mechanism of 3D sea-urchin like hierarchical TiO₂ composed of numerous nanorods was further examined and found to differ from the well-known “growth → assembly” mode. The effects of surface tension and polarity of solvents on the morphology and crystal strength of 3D hierarchical TiO₂ nanostructure were also investigated. In addition, the prepared 3D sea-urchin like hierarchical TiO₂ showed highest photocatalytic activity compared with other 3D hierarchical TiO₂ nanostructures in this study and Degussa P25 for the degradation of Rhodamine B solution under UV light irradiation, which could be attributed to its special hierarchical superstructure, the increase of surface catalytic sites and its special composition units.     

Crystalline TiO2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

Crystalline TiO₂ films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO₂ films by self-assembling, and the HUPA on TiO₂ films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO₂ films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.     

氮掺杂TiO2的冲击合成及可见光催化活性研究

 冲击相变及冲击诱导化学反应可导致材料的物理、化学性能发生显著改变。采用炸药爆轰驱动飞片高速碰撞产生冲击波的方法,对富氮掺杂物双氰胺（C₂N₄H₄）与P25 TiO₂或偏钛酸（H₂TiO₃）的粉末混合物进行冲击加载,对回收产物进行X射线粉末衍射、透射电子显微镜、X光电子能谱、比表面积及紫外-可见漫反射光谱表征,通过亚甲基蓝和罗丹明B评价了回收产物的可见光催化降解活性。结果表明：以P25 TiO₂为原料的冲击氮掺杂浓度可达8.88%,掺杂样品具有明显的可见光吸收,能带宽度减小到1.75 eV,样品中形成了少量Srilankite高压相;而以偏钛酸为原料的冲击氮掺杂浓度为3%～4%,能带宽度变化较小,但是由于其独特的冲击脱水膨胀机理,比表面积剧增。冲击氮掺杂样品对亚甲基蓝和罗丹明B染料有较好的吸附和可见光催化降解作用,其中高飞片速度处理的样品有更高的光催化降解活性。     

Preparation of titania hollow spheres by catalyst-free hydrothermal method and their high thermal stabilities

TiO₂ hollow spheres have been prepared by hydrothermal method using carbon spheres as hard templates based on template-directed deposition and calcination in order to remove templates. The morphology and structure of samples were systematically characterized by using various techniques, including XRD, zeta analyzer, SEM, TEM, DRS and FTIR. In this approach, the anatase phase was retained for temperatures up to 900 °C. Moreover, negative charged titania is deposited onto the negative charged surface of carbon spheres, which is proved by nanoparticle size analyzer. Therefore, a possible formation mechanism of TiO₂ hollow spheres was proposed. TiO₂ hollow spheres calcined at 550 °C exhibited the superior photocatalytic activity for the degradation of Rhodamine B, 2.9 times greater than that of Degussa P25. Furthermore, thermal stability of TiO₂ hollow spheres was examined. Fortunately, we found that hollow structures could still be visible distinctly after calcining at 900 °C.     

Synthesis of efficient TiO2-based photocatalysts by phosphate surface modification and the activity-enhanced mechanisms

A simple strategy to greatly increase the thermal stability of nanocrystalline anatase has been put forward to fabricate efficient TiO₂-based photocatalysts under ultraviolet irradiation, via the surface modification with phosphate anions. The results show that the increased anatase thermal stability is attributed to the roles of the phosphate modification effectively inhibiting the contacts among anatase nanocrystals. Compared to un-modified TiO₂, the modified TiO₂ calcined at high temperature (over 700 °C) exhibits much high photocatalytic activity for degrading Rhodamine B (or phenol) solution, even superior to the commercial P25 TiO₂. The activity enhancement is mainly attributed to the increased separation rate of photogenerated charge carriers on the basis of the measurements of steady state- and transient state-surface photovoltage spectroscopy. This work would provide a practical route to reasonably design and synthesize high-performance TiO₂-based nanostructured photocatalysts with high anatase thermal stability.     

Preparation and characterization of amine-functionalized SiO2/TiO2 films for formaldehyde degradation

This paper investigated the gaseous formaldehyde degradation by the amine-functionalized SiO₂/TiO₂ photocatalytic films for improving indoor air quality. The films were synthesized via the co-condensation reaction of methyltrimethoxysilane (MTMOS) and 3-aminopropyltrimethoxysilane (APTMS). The physicochemical properties of prepared photocatalysts were characterized with N₂ adsorption/desorption isotherms measurement, X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FT/IR). The effect of amine-functional groups and the ratio of MTMOS/APTMS precursors on the formaldehyde adsorption and photocatalytic degradation were investigated. The results showed that the formaldehyde adsorption and photocatalytic degradation of the APTMS-functionalized SiO₂/TiO₂ film was higher than that of SiO₂/TiO₂ film due to the surface adsorption on amine sites and the relatively high of the specific surface area of the APTMS-functionalized SiO₂/TiO₂ film (15 times higher than SiO₂/TiO₂). The enhancement of the formaldehyde degradation of the film can be attributed to the synergetic effect of adsorption and subsequent photocatalytic decomposition. The repeatability of photocatalytic film was also tested and the degradation efficiency was 91.0% of initial efficiency after seven cycles.     

Fabrication of nitrogen-doped TiO2 layer on titanium substrate

In this paper, macropores TiO₂ layer was fabricated on titanium substrates based on plasma based ion implantation (PBII). In order to increase the photodegradation efficiency of fabricated TiO₂ layer, two approaches are used: (1) preparation of macropores on TiO₂ layer to increase the total photodegradation area and (2) nitrogen doping (N-doping) to increase light absorption efficiency. The fabrication process of the N-doped macropores TiO₂ layer comprises four steps: firstly, helium plasma based ion implantation (He-PBII) is employed to generate He bubbles in substrate; secondly, oxygen plasma based ion implantation (O-PBII) and a followed annealing in air are executed to obtain rutile and anatase mixture TiO₂ phases; thirdly, He bubbles are exposed to the surface via an Ar ion sputter process; lastly, the samples are doped by nitrogen PBII (N-PBII). The photodegradation of Rhodamine B solution under Xe lamp indicates that the TiO₂ layer with surface macropores and N-doping has higher light photocatalysis efficiency.     

硼(氮、氟)掺杂对TiO2纳米颗粒光学性能的影响

利用X射线衍射谱、拉曼光谱和紫外-可见光吸收光谱研究了硼(氮、氟)掺杂对TiO₂纳米颗粒光学性能的影响.X射线衍射谱和拉曼光谱结果表明,掺硼(氮、氟)对TiO₂纳米颗粒的锐钛矿相晶体结构无明显影响,而其锐钛矿晶格出现畸变(c/a值增大),这被归因于掺杂原子对TiO₂纳米颗粒表面氧原子缺位沿晶格c轴方向的占据.另外,掺硼(氮、氟)TiO₂纳米颗粒吸收带红移与TiO相似文献   

The effect of surface modification with silane coupling agent on suppressing the photo-catalytic activity of fine TiO2 particles as inorganic UV filter

The effect of surface modification with 3-aminopropyltriethoxysilane (APTES) and n-propyltriethoxysilane (PTES) on photo-catalytic activity and UV-shielding ability of fine TiO₂ particles were investigated. The number of surface groups (N_R) [nm⁻²] which shows the density of modifier on TiO₂ surface was calculated from the results of elemental analysis and BET measurement. The modified samples of which N_R are different were obtained by changing the concentration of modifier. When the photo-catalytic activity and UV-shielding ability of modified samples were evaluated, it was found that APTES was more effective modifier than PTES to obtained samples with low photo-catalytic activity and high UV-shielding ability. This is probably because the adsorption mechanisms on TiO₂ surface between modifiers were different and N_R is a key factor to control the performances of fine TiO₂ particles. The result of zeta potential showed that surface character of modified samples was varied by changing N_R. It suggested from these results that N_R affected the photo-catalytic activity and UV-shielding ability because N_R changed surface character of modified samples.     

Visible light sensitization effect of polyaminobenzoate adsorbed on TiO2 nanocrystal surface

Poly-o-aminobenzoate (POA) was prepared by oxidizing o-aminobenzoic acid with (NH₄)₂S₂O₈ in an acidic solution. POA was adsorbed on TiO₂ nanocrystal surface to obtain a POA-TiO₂ nanocomposite. The polymerization reaction, structure, adsorption reaction on TiO₂ surface, and visible light sensitization effect of the polymer adsorbed on TiO₂ surface were studied by FT-IR and UV-visible spectra, cyclic voltammetry, and measurements of visible light photoelectrochemical and photocatalytic activities. Three kinds of POA with different long conjugate structures can be formed. These polymers have large absorbance in wide visible light region. POA molecules can be adsorbed on TiO₂ surface by anchoring their carboxylate groups to the TiO₂ surface with a multi-bridging chelating mode, which causes formation of the POA-TiO₂ nanocomposite with a high stability. POA adsorbed on the TiO₂ nanocrystal showed high visible light sensitization effect in the photocatalytic reaction.     

A New Insight of the Photothermal Effect on the Highly Efficient Visible‐Light‐Driven Photocatalytic Performance of Novel‐Designed TiO2 Rambutan‐Like Microspheres Decorated by Au Nanorods

Photocatalyst‐assisted degradation of organic pollutants, which exhibits a novel strategy for solar‐energy utilization, possesses enormous potential in various applications. Extending the light‐absorption range in the spectrum of sunlight and improving light‐conversion efficiency are always primary issues to enhance the catalytic performance of these photocatalysts. Herein, a new structure of gold‐nanorod‐decorated TiO₂ rambutan‐like microspheres is designed, which exhibits superior photocatalytic ability toward Rhodamine B in the range of visible light due to the 3D distribution of the TiO₂ branches on the surface of the microspheres, which prompts the multireflection of photons. The absorption rate of photons is thereby tremendously enhanced. This is beneficial for the generation of hot electrons originating from the localized surface plasmonic resonance of Au nanorods, which can be used to both initiate the reaction and produce the photothermal effect. Hot electrons generated by a single Au nanorod in microspheres to initiate the degradation reaction can be as high as 2.5 times of those in the nanowires' counterpart. Moreover, the heating power of a single Au nanorod in microspheres reaches up to 4.4 times higher than that in nanowires, which further accelerates the degradation rate. The reaction pathway of visible‐light‐assisted RhB degradation catalyzed by Au/TiO₂ microspheres goes through an initial N‐deethylation process instead of the complete cycloreversion catalyzed by pure TiO₂ microspheres under UV irradiation. This strategy of structure design for improved photon absorption, which achieves high degradation rate and photothermal effect, is promising for the development of novel photocatalysts.     

Fabrication of amine-functionalized magnetite nanoparticles for water treatment processes

The anatase phase of titania (TiO₂) nano-photocatalysts was prepared using a modified sol gel process and thereafter embedded on carbon-covered alumina supports. The carbon-covered alumina (CCA) supports were prepared via the adsorption of toluene 2,4-diisocyanate (TDI) on the surface of the alumina. TDI was used as the carbon source for the first time for the carbon-covered alumina support system. The adsorption of TDI on alumina is irreversible; hence, the resulting organic moiety can undergo pyrolysis at high temperatures resulting in the formation of a carbon coating on the surface of the alumina. The TiO₂ catalysts were impregnated on the CCA supports. X-ray diffraction analysis indicated that the carbon deposited on the alumina was not crystalline and also showed the successful impregnation of TiO₂ on the CCA supports. In the Raman spectra, it could be deduced that the carbon was rather a conjugated olefinic or polycyclic hydrocarbons which can be considered as molecular units of a graphitic plane. The Raman analysis of the catalysed CCAs showed the presence of both the anatase titania and D and G band associated with the carbon of the CCAs. The scanning electron microscope micrographs indicated that the alumina was coated by a carbon layer and the energy dispersive X-ray spectra showed the presence of Al, O and C in the CCA samples, with the addition of Ti for the catalyst impregnated supports. The Brunauer Emmet and Teller surface area analysis showed that the incorporating of carbon on the alumina surface resulted in an increase in surface area, while the impregnation with TiO₂ resulted in a further increase in surface area. However, a decrease in the pore volume and diameter was observed. The photocatalytic activity of the nanocatalysts was studied for the degradation of Rhodamine B dye. The CCA-TiO₂ nanocatalysts were found to be more photocatalytically active under both visible and UV light irradiation compared to the free TIO₂ nanocatalysts.     

Improving the visible light photocatalytic activity of mesoporous TiO2 via the synergetic effects of B doping and Ag loading

B-doped together with Ag-loaded mesoporous TiO₂ (Ag/B–TiO₂) was prepared by a two-step hydrothermal method in the presence of boric acid, triblock copolymer surfactant, and silver nitrate, followed by heat treatment. The obtained samples were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), UV–vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption. It was revealed that all samples consist of highly crystalline anatase with mesoporous structure. For Ag/B–TiO₂, B was doped into TiO₂ matrix in the form of both interstitial B and substitutional B while Ag was deposited on the surface of B–TiO₂ in the form of metallic silver. Compared with the single B-doped or Ag-loaded TiO₂ one, mesoporous Ag/B–TiO₂ exhibits much higher visible light photocatalytic activity for the degradation of Rhodamine 6G, which can be ascribed to the synergistic effects of B doping and Ag loading by narrowing the band gap of the photocatalyst and preventing the fast recombination of the photogenerated charge carriers, respectively.     

Surface modification of PMMA/O-MMT composite microfibers by TiO2 coating

In the present work, poly(methyl methacrylate) (PMMA)/organically modified montmorillonite (O-MMT) composite microfibers were firstly prepared by emulsion polymerization combined with electrospinning, and then coated by nanosize titanium dioxide (TiO₂) using RF magnetron sputter technique. The modified surfaces of PMMA/O-MMT composite microfibers were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), UV-vis spectroscopy and drop shape analyzer. Finally, the photocatalytic properties of TiO₂ coated PMMA/O-MMT composite microfiber membranes were evaluated by degradation of methylene blue(MB) under UV illumination. The experimental results revealed that anatase-TiO₂ and rutile-TiO₂ nanoparticles were well spread and physically deposited on the surface of PMMA/O-MMT microfibers, and the wettability of the PMMA/O-MMT composite microfibers was improved after surface modification by sputter coating. Furthermore, the PMMA/O-MMT microfibers membrane coated with TiO₂ performed well in photocatalytic degradation of MB.     

Preparation of nanocrystalline Sn-TiO2−X via a rapid and simple stannous chemical reducing route

The Sn-TiO_2−X nanoparticles have been prepared via a rapid and simple stannous chemical reducing method. The as-prepared Sn-TiO_2−X nanoparticles were investigated by means of surface photovoltage spectroscopy (SPS), XPS, and DRS technology as well as photocatalytic degradation of RhB were studied under illumination. The experiment results revealed that the reduction of the TiO₂ particles raised their Fermi level, which can enhance the driven force of photoinduced electrons transferring from TiO₂ to adsorbed O₂ and SnO₂ on the surface of TiO₂. On the other hand, the amount of oxygen vacancies of the Sn-TiO_2−X increased after the stannous chemical reduction. The oxygen vacancies can also effectively inhibit the recombination of photoinduced electrons and holes pairs. These factors are favorable to the photocatalytic reaction.     

Effect of surface fluorination on the photocatalytic and photo-induced hydrophilic properties of porous TiO2 films

Porous surface-fluorinated TiO₂ (F-TiO₂) films were prepared through PEG modified sol-gel method and surface fluorination. The as-prepared films were characterized with XRD, FTIR, AFM, XPS and UV-vis DRS. The effects of surface fluorination on the photocatalytic activity and hydrophilicity of porous TiO₂ film were studied by photocatalytic degradation of rhodamine B (RhB) as well as water contact angle (CA) on porous TiO₂ film. The results showed that the surface fluorination increased the adsorption of RhB on the porous TiO₂ film and enhanced the photocatalytic degradation of RhB. The concentration and pH of NaF solutions affected much the photocatalytic activity of porous TiO₂ film. Porous F-TiO₂ film prepared in 40 mM NaF solution at pH 4.0 showed the highest photocatalytic activity. Because of its porous structure, the porous F-TiO₂ film had original water CA of 22.7°, which is much smaller than that of normal F-TiO₂ film. Under UV light irradiation, the water CA of porous F-TiO₂ film decreased to 5.1° in 90 min.