微波辅助制备掺铁纳米TiO2溶胶及其性能研究

为了进一步提高纳米二氧化钛溶胶的光催化活性,采用微波辅助胶溶的方法制备了不同铁掺杂量的纳米二氧化钛(Fe-TiO2)溶胶,并以偶氮染料活性艳红X-3B为目标物,分别考察不同铁掺杂量对纳米Fe-TiO2溶胶光催化活性的影响,研究表明原子数分数为0.05%的Fe3+掺杂量最佳;对Fe-TiO2溶胶、TiO2溶胶及P25(Degussa纳米TiO2)悬浮液的光催化活性进行对比,结果表明:TiO2溶胶与P25悬浮液光催化活性相当,而Fe-TiO2溶胶较前两者具有更高的光催化活性.采用XRD、DLS、AFM和DRS的分析方法对溶胶进行表征,结果表明:微量铁掺杂对纳米TiO2的晶型及粒径分布无显著影响;但铁掺杂可以使纳米TiO2对紫外光的吸收有较大程度的增强,同时吸收边带发生了较明显的红移.铁掺杂对于提高纳米TiO2溶胶的光催化活性和拓展其光吸收范围均具有显著的积极的作用.     

Visible light induced electron transfer process over nitrogen doped TiO(2) nanocrystals prepared by oxidation of titanium nitride

Nitrogen doped TiO(2) nanocrystals with anatase and rutile mixed phases were prepared by incomplete oxidation of titanium nitride at different temperatures. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), core level X-ray photoelectron spectroscopy (CL XPS), valence band X-ray photoelectron spectroscopy (VB XPS), UV-vis diffuse reflectance spectra (UV-vis DRS), and visible light excited photoluminescence (PL). The photocatalytic activity was evaluated for photocatalytic degradation of toluene in gas phase under visible light irradiation. The visible light absorption and photoactivities of these nitrogen doped TiO(2) nanocrystals can be clearly attributed to the change of the additional electronic (N(-)) states above the valence band of TiO(2) modified by N dopant as revealed by the VB XPS and visible light induced PL. A band gap structure model was established to explain the electron transfer process over nitrogen doped TiO(2) nanocrystals under visible light irradiation, which was consistent with the previous theoretical and experimental results. This model can also be applied to understand visible light induced photocatalysis over other nonmetal doped TiO(2).     

Synthesis of 3D micro- and nano-hierarchical structure InVO4 porous microspheres with improved visible-light photocatalytic activities

Three-dimensional (3D) hierarchical structure InVO₄ porous microspheres were fabricated by a hydrothermal method with the assistance of cetyltrimethyl-ammonium bromide (CTAB). X-ray diffractometer, scanning electron microscopy, transmission electron microscopy, adsorption analyzer, diffuse refection spectroscopy, UV–Vis spectroscopy, and photoluminescence spectroscopy were adopted to analyze the structure–property relationship of samples, and the formation mechanism was also discussed. The results show that the concentration of CTAB solution has important influence on the grain size, crystal structure, and morphology of as-synthesized InVO₄ samples, thus affecting the optical property and photocatalytic activity. When the concentration of CTAB solution is 1 wt%, we can obtain perfect 3D hierarchical porous microspheres. Such microspheres with diameter size about 2–5 μm are assembled by numerous nanocrystals, and exhibit an enhanced photocatalytic activity in the degradation of Rhodamine B under visible light irradiation. Moreover, Oswald ripening and self-assembly aggregation are presumed to play an important role in the formation of these 3D hierarchical structure InVO₄ porous microspheres.     

Effects of N precursor on the agglomeration and visible light photocatalytic activity of N-doped TiO2 nanocrystalline powder

N-doped TiO2 nanocrystalline powders were prepared by the sol-gel method using various N precursors, including triethylamine, hydrazine hydrate, ethylenediamine, ammonium hydroxide, and urea. The samples were characterized by X-ray diffraction, N2 adsorption isotherms, transmission electron microscopy, ultraviolet-visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The photocatalytic activities of as-prepared samples under irradiation of visible light (lambda > 405 nm) were evaluated by photodecomposition of methyl orange. The alkalinity of N precursor was found to play a key role in the gel process. The N precursor with moderate alkalinity causes TiO2 nanoparticles to be sol-transformed into a loosely agglomerated gel. This transformation facilitates the preparation of an N-doped TiO2 powder with small nanocrystal size, large specific surface area, and high N doping level and results in high visible light photocatalytic activity. The N in TiO2 with N is binding energy at 399-400 eV may be assigned to the N-H species located in interstitial sites of TiO2 lattice which is the active N species responsible for the visible light photocatalytic activity. The N species of N 1s peak at 402 and 405 eV are ineffective to the visible light photocatalytic activity and may inhibit the photocatalytic activity. Moreover, a TiO2 nanoparticle powder with large specific area can be achieved by using urea as a template and then by using ammonium hydroxide to transform the sol into gel.     

Photocatalytic activity of La, Y Co-doped TiO2 nanoparticles synthesized by ultrasonic assisted sol-gel method

Bare TiO2 (T), La-doped TiO2 (LT), Y-doped TiO2 (YT), La, Y co-doped TiO2 (LYT) were successfully prepared by facile ultrasonic assisted sol-gel synthesis using Ti(OC4H9)4 as the precursor. The products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-visible diffuse reflectance spectra (DRS), and X-ray photoelectron spectroscopy (XPS), respectively. The photocatalytic activities of anatase samples, with the average particle diameters ranging from 14 nm to 21 nm, were evaluated for photodegradation of methyl orange (MO). The XPS results indicated that Y atoms were incorporated into titania lattice, while La atoms existed on the crystal surface. Due to doping, the optical absorption edges of LT, YT, and LYT shifted to the visible light region by 21 nm, 29 nm and 35 nm, respectively. The photocatalytic performances of the doped samples, such as LT, YT and LYT, were much higher than that of bare TiO2 under UV-visible light irradiation. And the photoreactivity efficiency of the LYT was the highest. It indicated that a strong La-Y synergistic interaction appeared to play a decisive role in driving the excellent photocatalytic performance of titania.     

Rapid microwave-assisted solvothermal synthesis and visible-light-induced photocatalytic activity of Er3+-doped BiOI nanosheets

BiOI nanosheet photocatalysts with different Er³⁺ doping contents were rapidly synthesized by microwave-assisted solvothermal method using water and ethylene glycol as a mixed solvent. All synthesized photocatalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), N₂ adsorption, photoluminescence (PL) spectra, and UV–vis diffuse reflectance spectroscopy (DRS). The photocatalytic activities of the as-prepared Er³⁺-doped BiOI nanosheets were investigated by the photodegradation of Rhodamine B (RhB) dye in aqueous solution under visible light irradiation. The photodegradation results indicate the optimal doping of 1?mol.% Er³⁺ in BiOI nanosheets (doping content is from 0?mol.% to 4?mol.%) to be the most beneficial for photodegradation of RhB. 1Er-BiOI nanosheets also possesses good photocatalytic activity for representative anionic methyl orange (MO). From the scavenger testing results, the reactive species of holes (h⁺) and superoxide radical anions (O^2?) show major impacts on the photodegradation progress of RhB and MO dyes over 1Er-BiOI photocatalyst under visible light irradiation.     

Fabrication and enhanced visible light photocatalytic activity of fluorine doped TiO2 by loaded with Ag

F-doped TiO2 loaded with Ag (Ag/F-TiO2) was prepared by sol-gel process combined with photoreduction method. The physical and chemical properties of the prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), high-resolution transmission electron microscope (HRTEM), UV-Vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). XPS analysis indicated Ag species existed as Ag0 in the structure of Ag/F-TiO2 samples. UV-Vis diffuse reflectance spectra showed that the light absorption of Ag/F-TiO2 in the visible region had a significant enhancement compared with the F-doped TiO2 (F-TiO2). PL analysis indicated that the electron-hole recombination rate had been effectively inhibited when Ag loaded on the surface of F-TiO2. The photocatalytic activities of the samples were evaluated for the degradation of X-3B (Reactive Brilliant Red dye, C.I. reactive red 2) under visible light (lambda > 420 nm) irradiation. Compared with F-TiO2, the sample of 0.50 Ag/F-TiO2 showed the highest photocatalytic activity. The interaction between F species and metallic Ag was responsible for improving the visible light photocatalytic activity.     

锶元素改性TiO2／杭锦2#土复合物的光催化性能

以Ti（OBu）4和内蒙古杭锦2^#土为主要原料，Sr（NO3）2为掺杂剂，采用溶胶-凝胶法制备了一系列Sr元素掺杂改性的TiO2／杭锦2^#土复合光催化剂，并用X射线衍射、傅立叶红外光谱和扫描电子显微镜等对样品进行了表征。紫外光照射下，以亚甲基蓝水溶液为光降解体系，考察了Sr的掺杂量和热处理温度对光降解率的影响，结果表明，Sr的掺杂量为0．5％，焙烧温度为500℃条件下制得复合物的催化活性明显优于相同条件下的TiO2／杭锦2^#土。该复合物催化剂的优点是易于从分散体系中分离和可循环使用。     

微波加热法制备Ag/TiO_2及光催化降解气相甲苯

以钛酸四丁酯为钛源,分别使用微波加热法和水热法制备Ag改性的TiO2,采用X射线衍射(XRD)、X射线荧光探针(XRF)、紫外-可见漫反射(UV-Vis)和扫描电镜(SEM)对其进行表征.以气相甲苯为降解对象,分别在紫外和可见光辐照下,对样品进行光催化活性试验.结果表明:与水热法比较,微波加热法更有利于Ag对TiO2微观结构的改性,所制备的Ag改性TiO2包含了锐钛矿、金红石和板钛矿三种晶相,其粒径更小(16.4nm)、孔道结构更丰富、团聚体更小(80~200nm)、带隙能更低(2.87eV),表现出对气相甲苯更有效的紫外光和可见光降解能力.     

Development of titanium-dioxide-based aerogel catalyst with tunable nanoporosity and photocatalytic activity

Nanostructured highly porous TiO(2)/WO(3)/Fe(3+) aerogel composite photocatalysts are prepared, characterized and tested for model photocatalytic reactions. The catalyst structure is tailored to capture environmental pollutants and enable their decomposition in situ under both ultraviolet (UV) and visible light through oxidation to smaller benign molecules. A novel and green method is utilized to prepare the unique surfactant-templated aerogel composite photocatalyst that has a highly accessible porous nanostructure with high surface area and tailored pore size distribution. The sol-gel process is combined with supercritical extraction and drying. Supercritical drying with heat treatment results in titanium dioxide with anatase crystal form. Templates used further enable retention and tuning of the nanopore structure and surface properties. The synthesized catalysts were characterized using SEM, FIB, XRD and porosimetry prior to post-evaluation in model reactions. The bandgap of the catalyst particles was also determined using diffuse reflectance. The resulting aerogel TiO(2)/WO(3)/Fe(3+) has similar photocatalytic capability compared to highly optimized commercial Degussa P25 under UV exposure and offers much superior photocatalytic capability under visible light exposure. The model reaction utilized employed methylene blue (MB) photooxidation under visible and UV light.     

Synthesis of porous Fe3O4/g-C3N4 nanospheres as highly efficient and recyclable photocatalysts

A facile approach for the preparation of Fe₃O₄/g-C₃N₄ nanospheres with good porous structure has been demonstrated by a hydrothermal method. The as-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet–visible light (UV–vis) absorbance spectra and X-ray photoelectron spectroscopy (XPS). The photocatalytic decomposition of methyl orange (MO) by the as-prepared samples was carried out under visible light irradiation. The reusability and magnetic properties were also investigated. The results revealed that the porous Fe₃O₄/g-C₃N₄ nanospheres showed considerable photocatalytic activity, and exhibited excellent reusability and magnetic properties with almost no change after five runs.     

Novel method for doping nano TiO2 photocatalysts by chemical vapour deposition

Highly active photocatalytic Fe-doped nano TiO₂ was successfully synthesised by chemical vapour deposition (CVD) method using FeCl₃ as Fe source. CVD was carried out by evaporating FeCl₃ at 350°C in nitrogen flow during 30–90?min. The amount of Fe incorporated into TiO₂ framework is adjusted by the amount of FeCl₃ used and the evaporation time. The obtained sample was characterised by X-ray diffraction (XRD), atomic absorption spectroscopy (AAS), energy dispersive X-ray spectroscopy (EDS), UV-Vis, Fourier transform-infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). Photocatalytic activities of the samples were tested in photocatalytic decomposition of 2-propanol in liquid phase using visible light instead of UV light irradiation. Non-doped TiO₂ and high Fe loading TiO₂ samples showed very low photocatalytic activity, whereas the low Fe loading TiO₂ sample exhibited high photocatalytic activity under visible light. The high photocatalytic activity of this sample was rationalised by the existence of defects (Ti–OH groups) as the active sites.     

Construction of hierarchical nanostructured TiO2/Bi2MoO6 heterojunction for improved visible light photocatalysis

In this study, Bi2MoO6 hollow microspheres were modified by depositing TiO2 nanoparticles through a simple hydrothermal method. The prepared TiO2/Bi2MoO6 photocatalysts were characterized by scanning and transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The photocatalytic performance of the heterostructured catalysts was evaluated by degradation of methylene blue (MB) under visible-light irradiation (lambda>420 nm). The photocatalysts based on nanostructured Bi2MoO6 and TiO2 exhibit much higher photocatalytic activity than the single-phase Bi2MoO6 or TiO2 and the mechanical mixture of Bi2MoO6 and TiO2 for degradation of MB under the same conditions. The results reported in this study provide insight into constructing other heterostructured photocatalysts.     

Photoinduced hydroxyl radical and photocatalytic activity of samarium-doped TiO(2) nanocrystalline

Sm(3+)-doped TiO(2) nanocrystalline has been prepared by sol-gel auto-combustion technique and characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, and also UV-vis diffuse reflectance spectroscopy (DRS). These Sm(3+)-doped TiO(2) samples were tested for methylene blue (MB) decomposition and *OH radical formation. The analysis of *OH radical formation on the sample surface under UV irradiation was performed by fluorescence technique with using terephthalic acid, which readily reacted with *OH radical to produce highly fluorescent product, 2-hydroxyterephthalic acid. It was observed that the presence of Sm(3+) ion as a dopant significantly enhanced the photocatalytic activity for MB degradation under UV light irradiation because both the larger specific surface area and the greater the formation rate of *OH radical were simultaneously obtained for Sm(3+)-doped TiO(2) nanocrystalline. The adsorption experimental demonstrated that Sm(3+)-TiO(2) had a higher MB adsorption capacity than undoped TiO(2) and the adsorption capacity of MB increased with the increase of samarium ion content. The results also indicated that the greater the formation rate of *OH radical was, the higher photocatalytic activity was achieved. In this study, the optimum amount of Sm(3+) doping was 0.5 mol%, at which the recombination of photo-induced electrons and holes could be effectively inhibited, the highest formation rate of *OH radicals was, and thereby the highest photocatalytic activity was achieved.     

Visible light irradiated photocatalytic and magnetic properties of Fe-doped SnS<Subscript>2</Subscript> nanopowders

Fe-doped SnS₂ (SnS₂:Fe) nanopowders were synthesized by cost effective chemical method and characterized by thermo gravimetric-differential thermal analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and vibrating sample magnetometer techniques. The photocatalytic activity was evaluated for the degradation of congo red dye under visible light irradiation. XRD studies indicate that both the undoped and doped SnS₂ nanopowders exhibit hexagonal crystal structure with a strong (1 0 1) preferential growth. Nanosized grains are evinced from the TEM images. XPS spectra confirmed the presence of Fe in the doped samples. Photodegradation efficiency increased with increase in Fe doping concentration and the SnS₂:Fe nanopowder with 10 wt% Fe doping concentration exhibits a maximum efficiency of 93.94% after 180 min light irradiation. Ferromagnetic ordering of pure SnS₂ improved with Fe doping. The outcome of the results indicated that Fe-doped SnS₂ nanopowders are well suited as diluted magnetic semiconductor and also can be used as an efficient photocatalyst.     

γ-Bi2O3/TiO2复合纤维的制备及光催化性能

采用静电纺丝技术与溶剂热法相结合制备了γ-Bi2O3/TiO2复合纤维光催化材料.利用X射线衍射(XRD)、扫描电镜(SEM)、电子能谱(EDS)、透射电镜(TEM)、高分辨透射电镜(HRTEM)和紫外–可见吸收光谱(UV-Vis)等分析测试手段对材料进行了表征,并以罗丹明B(RB)的脱色降解为模式反应,考察了材料的可见光催化性能.结果表明:γ-Bi2O3纳米片均匀地生长在TiO2纤维上,形成了具有异质结构的γ-Bi2O3/TiO2复合纤维光催化材料,其光谱响应范围拓宽至可见光区,有利于TiO2光生电子和空穴的分离,增强了体系的量子效率.与纯TiO2纤维相比可见光催化活性明显提高,对RB的脱色率达87.8%.     

Study on activities of vanadium (IV/V) doped TiO2(R) nanorods induced by UV and visible light

Vanadium (IV/V) doped rutile TiO₂ naonorods had been successfully synthesized through a single step hydrothermal method. The photocatalyst was characterized by transmission electron microscopy (TEM), selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), UV–vis diffusive reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS). The results showed that the doping of V ions had significant influence on the band gap energy and the surface state of TiO₂. The photo-activities of the new catalysts were investigated under ultraviolet (UV) and visible light. The UV-photocatalytic activity of the as-prepared catalysts was hardly influenced by doping V ions; while under visible light, the samples with 1 wt% and 0.1 wt% V exhibited enhanced activity to the oxidation of methylene blue (MB) and the reduction of Cr (VI), respectively.     

Direct formation of reusable TiO2/CoFe2O4 heterogeneous photocatalytic fibers via two-spinneret electrospinning

A reusable photocatalytic TiO2/CoFe2O4 composite nanofiber was directly formed by using a vertical two-spinneret electrospinning process and sol-gel method, followed by heat treatment at 550 degrees C for 2 h. The high photocatalytic activity of the composite nanofibers depends on the good morphology of the fibers and the appropriate calcination temperature. The crystal structure and magnetic properties of the fibers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersion spectroscopy (EDS), transmission electron microscope (TEM) and vibrating sample magnetometer (VSM). The photocatalytic activity of the TiO2/CoFe2O4 fibers was investigated through ultraviolet-visible absorbance following the photo-oxidative decomposition of phenol. Meanwhile, the presence of CoFe2O4 not only broadens the response region of visible light, but also enhances the absorbance of UV light. Furthermore, these fibers displayed photocatalytic activity associated with magnetic activity of CoFe2O4 ferrites, allowing easy separated of the photocatalysts after the photo-oxidative process and effectively avoided the secondary pollution of the treated water.     

The synthesis and photocatalytic activity of ZnSe microspheres

This paper reports the synthesis of semiconductor ZnSe microspheres composed of nanoparticles via a solvothermal route between the organic molecule selenophene (C(4)H(4) Se) and ZnCl(2) without adding any surfactant. The ZnSe microspheres were characterized by x-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), specific surface area measurement, and photoluminescence (PL) spectra. A strong and broad blue PL emission at 443 nm in wavelength (～2.79 eV in photon energy) is attributed to the near-band-edge (NBE) emission of ZnSe, while the 530 nm peak is a defect-related (DL) emission. The photocatalytic activity of the as-prepared ZnSe microspheres was evaluated by photodegradation of methyl orange (MO) dye under ultraviolet (UV) light and visible light irradiation. The degradations of MO reach 94% or 95.1%, close to 100%, in the presence of the as-synthesized ZnSe microspheres or commercial ZnSe powder after 7 or 10 h under UV irradiation, respectively. Meanwhile the degradations of MO reach 94.3% or 60.6% in the presence of the as-synthesized ZnSe microspheres or commercial ZnSe powder after 12 h, respectively. The degradation rate of ZnSe microspheres is twice that of ZnSe commercial powder under UV light irradiation, and three times under visible light irradiation. The degradation process of MO dye on ZnSe microspheres under UV or visible light is also discussed.     

H(2)O(2)-sensitized TiO(2)/SiO(2) composites with high photocatalytic activity under visible irradiation

TiO(2)/SiO(2) composite photocatalysts were prepared by depositing of TiO(2) onto nano-SiO(2) particles. X-ray diffraction (XRD), transmission electron micrograph (TEM), Raman spectrometer, UV-Vis diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy (FT-IR) were employed to characterize the properties of the synthesized TiO(2)/SiO(2) composites. These results indicated that the products without calcination were amorphous, and calcination could enhance the crystallinity of TiO(2). Increases in the amount of TiO(2) would decrease the dispersion in the composites. H(2)O(2)-sensitized TiO(2)/SiO(2) composite photocatalysts could absorb visible light at wavelength below 550 nm. The photocatalytic activity of as-prepared catalysts was characterized by methyl-orange degradation. The results showed the uncalcined composite photocatalysts with amorphous TiO(2) exhibited higher photocatalytic activity under visible light, and the activity of catalysts with TiO(2) content over 30% decreased with increasing of TiO(2) content. Increases in the calcination temperature and TiO(2) content promote the formation of bulk TiO(2) and result in a decrease in activity.