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1.
采用溶胶-凝胶法在钛酸丁酯水解过程引入硼酸、硝酸铈,制备具有光催化活性的硼铈共掺杂纳米二氧化钛(TiO2),经XRD、TEM、FT-IR、UV-Vis-DRS表征晶体结构,在日光灯照射下,光催化降解三氯杀螨醇、高氟氯氰菊酯、氟戊菊酯农药。结果表明:硼铈共掺杂的TiO2只有锐钛矿型,而纯的或掺铈的TiO2有含有锐钛矿型、金红石相和少量板钛矿型,UV-Vis-DRS测定结果表明硼铈共掺杂的TiO2禁带宽度变小,硼铈共掺杂的TiO2在可见光区吸光度高于掺杂铈和不掺杂的TiO2,在420nm~850nm有强的吸收;在同样光照下对三氯杀螨醇、高氟氯氰菊酯、氟戊菊酯的降解试验证明硼铈共掺杂纳米TiO2的光催化活性高于不掺杂或只掺杂铈的TiO2。  相似文献   

2.
《中国化学会会志》2017,64(1):103-116
This review covers the various synthetic methods of doped and undoped TiO2 nanomaterials, ranging from single‐doped and co‐doped to multidoped with transition‐metal ions, rare earth metal ions, and other metals and nonmetals ions. The effects of doping on the physiochemical propertiesas well as the photocatalytic and antimicrobial activities of TiO2 nanomaterial are discussed. The results from the literature show that doping of TiO2 shifts the absorption edge to the visible region as a result of the decrease in the bandgap due to the formation of new energy levels in the bandgap. The dopent also acts as a trapping center for electrons and holes, thereby reducing the recombination rate of charge carriers and increasing the photocatalytic and antimicrobial activity of TiO2 nanomaterials. All multidoped TiO2 nanomaterials show higher activity than their undoped, single‐doped, and co‐doped counterparts.  相似文献   

3.
吴晓宏  ab  王松a  郭云b  谢朝阳b  韩璐a  姜兆华a 《中国化学》2008,26(10):1939-1943
在染料敏化太阳能电池中,TiO2膜和敏化剂决定着电池的总体效率和机械性能。本文以4-甲基吡啶为原料,经过偶联、氧化、配位和配体交换反应合成了cis-RuL2(SCN)2, (L=2,2’-联吡啶-4,4’-二羧酸),通过溶胶-凝胶法制备了TiO2膜。为了提高TiO2膜的光电性能,将不同浓度的La(NO3)3 (0.1%、0.3%、0.5%和0.7%) 加入到溶胶中,采用cis-RuL2(SCN)2将掺杂前后的TiO2膜进行敏化。利用X射线衍射仪、原子力显微镜和X射线光电子能谱对所得薄膜进行结构表征。结果表明,当La离子的浓度为0.5%时,太阳能电池的效率最高,短路电流和开路电压比未掺杂的分别提高了0.54 mA/cm2和30.41 mV。  相似文献   

4.
In this study, a silicic acid and tetra isopropyl ortho titanate ceramic precursor and a metallocene polyethylene‐octene elastomer (POE) or acrylic acid grafted metallocene polyethylene‐octene elastomer (POE‐g‐AA) were used in the preparation of hybrids (POE/SiO2? TiO2 and POE‐g‐AA/SiO2? TiO2) using an in situ sol‐gel process, with a view to identifying a hybrid with improved thermal and mechanical properties. Hybrids were characterized using Fourier transform infrared spectroscopy, 29Si solid‐state nuclear magnetic resonance (NMR), X‐ray diffraction, differential scanning calorimetry, thermogravimetry analysis, dynamic mechanical thermal analysis, and Instron mechanical testing. Properties of the POE‐g‐AA/SiO2? TiO2 hybrid were superior to those of the POE/SiO2? TiO2 hybrid. This was because the carboxylic acid groups of acrylic acid acted as coordination sites for the silica‐titania phase to allow the formation of stronger chemical bonds. 29Si solid‐state NMR showed that Si atoms coordinated around SiO4 units were predominantly Q3 and Q4. The 10 wt % SiO2? TiO2 hybrids gave the maximum values of tensile strength and glass transition temperature in both POE/SiO2? TiO2 and POE‐g‐AA/SiO2? TiO2. It is proposed that above this wt %, excess SiO2? TiO2 particles caused separation between the organic and inorganic phases. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1690–1701, 2005  相似文献   

5.
王阳  邵翔  王兵 《物理化学学报》2013,29(7):1363-1369
采用脉冲激光沉积术(PLD)同质外延生长了表面原子级平整的6%(原子比)Cr 掺杂的金红石相TiO2(110)单晶薄膜, 采用扫描隧道显微镜(STM)、扫描隧道谱(STS)、X 射线光电子能谱(XPS)和紫外光电子能谱(UPS)对其进行了表征. 结果表明: Cr 掺杂对TiO2(110)-(1×1)表面的形貌没有明显影响, 但是提高了掺杂薄膜在负偏压的导电性; Cr与晶格O键合而呈现+3价态, 由此在TiO2的价带顶上方~0.4 eV处引入杂质能级. 紫外-可见光吸收谱显示薄膜的光吸收能力被扩展到~650 nm, 处于可见光范围. 借助STM以单个甲醇分子的光解反应检测了薄膜的光催化活性. 仅观察到紫外光照射下甲醇分子的脱氢反应, 在可见光照射下(λ>430 nm)甲醇分子没有发生反应, 表明单独的Cr掺杂可能不足以提高TiO2在可见光下的催化活性.  相似文献   

6.
Photocatalytic multilayer nanocomposite films composed of anatase TiO2 nanoparticles and lignosulfonates (LS) were fabricated on quartz slides by the layer‐by‐layer (LBL) self‐assembly technique. X‐ray photoelectron spectroscopy (XPS), UV‐vis spectroscopy and atomic force microscopy (AFM) were used to characterize the TiO2/LS multilayer nanocomposite films. Moreover, the photocatalytic properties (decomposition of methyl orange and bacteria) of multilayer nanocomposite films were investigated. XPS results indicated that the intensities of titanium and sulfur peaks increased with the LBL deposition process. A linear increase in absorbance at 280 nm was found by UV‐Vis spectroscopy, suggesting that stepwise multilayer growth occurs on the substrate and this deposition process is highly reproducible. AFM images showed that quartz slide was completely covered by TiO2 nanoparticles when a 10‐bilayer multilayer film was formed. The decomposition efficiency of methyl orange by TiO2/LS multilayer films under the same UV irradiation time increased linearly with the number of TiO2 layers, and the results of decomposition of bacteria under UV irradiation showed that TiO2/LS multilayer nanocomposite films exhibited excellent decomposition activity of bacteria (Escherichia coil).  相似文献   

7.
The photocatalytic activity of TiO2 nanoparticles (nano‐TiO2) and its hybrid with SiO2 (nano‐TiO2–SiO2) for degradation of some organic dyes on cementitious materials was studied in this work. Nanohybrid photocatalysts were prepared using an inorganic sol–gel precursor and then characterized using XRD, SEM and UV–Vis. The grain sizes were estimated by Scherrer's equation to be around 10 nm. Then, a thin layer was applied to Portland cement concrete (PCC) blocks by dipping them into nano‐TiO2 and nano‐TiO2–SiO2 solution. The efficiency of coated PCC blocks for the photocatalytic decomposition of two dyes, Malachite Green oxalate (MG) and Methylene Blue (MB), was examined under UV and visible irradiation and then monitored by the chemical oxygen demand tests. The results showed that more than 80% and 92% of MG and MB were decomposed under UV–Vis irradiation using blocks coated with nano‐TiO2–SiO2. TiO2/PCC and TiO2–SiO2/PCC blocks showed a significant ability to oxidize dyes under visible and UV lights and TiO2–SiO2/PCC blocks require less time for dye degradation. Based on these results, coated blocks have increased photocatalytic activity which can make them commercially accessible photocatalysts.  相似文献   

8.
Nitrogen‐doped TiO2 nanofibres of anatase and TiO2(B) phases were synthesised by a reaction between titanate nanofibres of a layered structure and gaseous NH3 at 400–700 °C, following a different mechanism than that for the direct nitrogen doping from TiO2. The surface of the N‐doped TiO2 nanofibres can be tuned by facial calcination in air to remove the surface‐bonded N species, whereas the core remains N doped. N‐Doped TiO2 nanofibres, only after calcination in air, became effective photocatalysts for the decomposition of sulforhodamine B under visible‐light irradiation. The surface‐oxidised surface layer was proven to be very effective for organic molecule adsorption, and the activation of oxygen molecules, whereas the remaining N‐doped interior of the fibres strongly absorbed visible light, resulting in the generation of electrons and holes. The N‐doped nanofibres were also used as supports of gold nanoparticle (Au NP) photocatalysts for visible‐light‐driven hydroamination of phenylacetylene with aniline. Phenylacetylene was activated on the N‐doped surface of the nanofibres and aniline on the Au NPs. The Au NPs adsorbed on N‐doped TiO2(B) nanofibres exhibited much better conversion (80 % of phenylacetylene) than when adsorbed on undoped fibres (46 %) at 40 °C and 95 % of the product is the desired imine. The surface N species can prevent the adsorption of O2 that is unfavourable for the hydroamination reaction, and thus, improve the photocatalytic activity. Removal of the surface N species resulted in a sharp decrease of the photocatalytic activity. These photocatalysts are feasible for practical applications, because they can be easily dispersed into solution and separated from a liquid by filtration, sedimentation or centrifugation due to their fibril morphology.  相似文献   

9.
Although TiO2 is an efficient photocatalyst, its large band gap limits its photocatalytic activity only to the ultraviolet region. An experimentally synthesized ternary Fe/C/S‐doped TiO2 anatase showed improved visible light photocatalytic activity. However, a theoretical study of the underlying mechanism of the enhanced photocatalytic activity and the interaction of ternary Fe/C/S‐doped TiO2 has not yet been investigated. In this study, the defect formation energy, electronic structure and optical property of TiO2 doped with Fe, C, and S are investigated in detail using the density functional theory + U method. The calculated band gap (3.21 eV) of TiO2 anatase agree well with the experimental band gap (3.20 eV). The defect formation energy shows that the co‐ and ternary‐doped systems are thermodynamically favorable under oxygen‐rich condition. Compared to the undoped TiO2, the absorption edge of the mono‐, co‐, and ternary‐doped TiO2 is significantly enhanced in the visible light region. We have shown that ternary doping with C, S, and Fe induces a clean band structure without any impurity states. Moreover, the ternary Fe/C/S‐doped TiO2 exhibit an enhanced photocatalytic activity, a smaller band gap and negative formation energy compared to the mono‐ and co‐doped systems. Moreover, the band edges of Fe/C/S‐doped TiO2 align well with the redox potentials of water, which shows that the ternary Fe/C/S‐doped TiO2 is promising photocatalysts to split water into hydrogen and oxygen. These findings rationalize the available experimental results and can assist the design of TiO2‐based photocatalyst materials.  相似文献   

10.
Cerium‐doped titanium dioxide (TiO2) with a hollow fiber structure was successfully prepared using ammonium ceric nitrate and tetrabutyltitanate as precursors and cotton fiber as the template. The effects of cerium (Ce)‐doping on the crystallite sizes, crystal pattern, and optical property of the prepared catalysts were investigated by means of techniques such as scanning electron microscopy (SEM), X‐ray diffraction (XRD), BET surface area, and UV‐vis diffuse absorption spectroscopy. SEM observation showed that the prepared TiO2 fibers possessed fibrous shape inherited from the cotton fiber and had a hollow structure. As confirmed by XRD and UV‐vis diffuse absorption spectroscopy examinations, Ce‐doping restrained the growth of grain size and extended the photoabsorption edge of TiO2 hollow fiber into the visible light region. The present photocatalyst showed higher photocatalytic reactivity in photodegradation of highly concentrated methylene blue (MB) solutions than pure TiO2 under UV and visible light, and the amount of Ce‐doped significantly affected the catalytic property. In the experiment condition, the photocatalytic activity of 0.5 mol% Ce‐doped TiO2 fiber was optimal of all the prepared samples. In addition, the possibility of cyclic usage of the photocatalyst was also confirmed. The material was easily removed by centrifugal separation. Therefore, using the template method and by doping with cerium, TiO2 may hopefully become a low‐energy consuming, high activity and green environmentally friendly catalytic material.  相似文献   

11.
Double‐shelled zirconia/titania (ZrO2/TiO2) hollow microspheres were prepared by the selective removal of the polymer components via the calcination of the corresponding tetra‐layer poly(N,N′‐methylenebisacryl amide‐co‐methacrylic acid) (P(MBA‐co‐MAA))/Zr(OH)4/poly(ethyleneglycol dimethacrylate‐co‐methacrylic acid) (P(EGDMA‐co‐MAA))/TiO2 hybrid microspheres. These tetra‐layer microspheres were synthesized by the combination of the distillation copolymerization of N,N(‐methylenebisacryl amide‐co‐methacrylic acid (MBA) or ethyleneglycol dimethacrylate (EGDMA) crosslinker and methacrylic acid (MAA) for the preparation of polymer core and third‐layer as well as the controlled sol‐gel hydrolysis of inorganic precursors for the construction of zirconium hydroxide (Zr(OH)4) and titania (TiO2) layers. The thicknesses of zirconia and titania shell‐layers were conveniently controlled via varying the feed of zirconium n‐butoxide (Zr(OBu)4) and titanium tetrabutoxide (TBOT) during the sol‐gel hydrolysis, while the sizes of polymer layers were tuned through a multi‐stage distillation precipitation copolymerization. The structure and morphology of the resultant microspheres were characterized by transmission electron microscopy (TEM), X‐ray diffractometer (XRD), X‐ray photoelectronic spectroscopy (XPS), and thermogrametric analysis (TGA).  相似文献   

12.
In this study, titanium tetra‐isopropoxide was used as a precursor of TiO2 for in situ coating on cotton fabric by sol–gel method. Subsequently, silver nitrate was used as doping agent to prepare silver‐doped TiO2‐coated cotton fabric during hydrothermal treatment. The treated samples were characterized through field‐emission scanning electron microscopy, energy‐dispersive X‐ray analysis, inductively coupled plasma‐mass spectroscopy and UV–visible absorption spectroscopy to study morphology, composition of deposited elements and light absorption behavior of treated samples. X‐ray photoelectron spectroscopy was carried out to analyze the electronic state of silver in TiO2‐coated fabric after hydrothermal treatment. Doping of silver on TiO2‐coated fabric and subsequent hydrothermal treatment was found to enhance dye decolorization rate of rhodamine B dye solution in both UV and visible light radiations with respect to undoped TiO2. The study shows that an optimal level of silver‐doped TiO2‐coated fabric can be used repeatedly for dye decolorization without significant loss in its photocatalytic activity. The self‐cleaning properties of samples were also studied using methylene blue as a staining agent. It was observed that the presence of 1.8% silver on the weight of titanium in doped samples provides almost 82% of stain degradation.  相似文献   

13.
Thermally stable mesoporous TiO2/SiO2 hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle‐assembly method. A triblock copolymer, poly(styrene‐b‐2‐vinyl pyridine‐b‐ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO2/SiO2 hybrid films with different compositions can be synthesized. The presence of amorphous SiO2 phase effectively retards the growth of anatase TiO2 crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO2/SiO2 hybrid films are of very high quality, without any cracks or voids. The addition of SiO2 phase to mesoporous TiO2 films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO2 film without SiO2 phase.  相似文献   

14.
Perovskite type oxides, sodium bismuth titanate (Na0.5Bi0.5TiO3), and Ag+, Cu2+, and Sn2+ doped Na0.5Bi0.5TiO3 were prepared by pechini and ion exchange methods, respectively. Photocatalytic activities of these catalysts were tested by decomposition of methylene blue (MB) under visible light irradiation. Results showed that the photocatalytic activity of metal ion doped Na0.5Bi0.5TiO3 was higher than undoped Na0.5Bi0.5TiO3. Relatively high photocatalytic performance of Ag+‐doped Na0.5Bi0.5TiO3 is mainly ascribed to the efficient separation of electron‐hole (e, h+) pairs, lower bandgap energy and the creation of active hydroxyl radicals ( ? OH). Further, the Ag+‐doped Na0.5Bi0.5TiO3 catalyst showed good reusability up to four cycles. A possible mechanism for the enhanced photocatalytic performance was proposed. The synthesized photocatalysts were characterized by XRD, SEM, EDS, XPS, FT‐IR, and UV/Vis DRS techniques.  相似文献   

15.
Mg3(BN2)N was prepared by solid state metathesis reactions and several europium (Eu2+) doped samples were prepared to discover novel red‐emitting photoluminescent (PL) materials. It turned out that the undoped and doped samples showed very broad deep‐red photoluminescence ranging from about 500 nm into the near infrared. Due to the similar spectra of the undoped and doped samples and unusually high FWHM values of about 5780 cm–1 we conclude that the luminescence process originates from defect sites. This was confirmed by decay measurements which show that the decay constants for all samples were in the range of several milliseconds.  相似文献   

16.
Nitrogen-doped TiO2 nanoparticle photocatalysts were obtained by an annealing method with gaseous ammonia and nitrogen. The influence of dopant N on the crystal structure was characterized by XRD, XPS, BET, TEM and UV-Vis spectra. The results of XRD indicate that, the crystal phase transforms from anatase to rutile structure gradually with increase of annealing temperature from 300 to 700 ℃. XPS studies indicate that the nitrogen atom enters the TiO2 lattice and occupies the position of oxygen atom. Agglomeration of particles is found in TEM images after annealing. BET results show that the specific surface areas of N-doped samples from 44.61 to 38.27 m2/g are smaller than that of Degussa TiO2. UV-Vis spectra indicate that the absorption threshold shifts gradually with increase of annealing temperature, which shows absorption in the visible region. The influence of annealing condition on the photocatalytic property has been researched over water decomposition to hydrogen, indicating that nitrogen raises the photocatalytic activity for hydrogen evolution, and the modified TiO2 annealed for 2 h at 400 ℃ under gas of NH3/N2 (V/V=1/2) mixture shows better efficiency of hydrogen evolution. Furthermore, the N-doped TiO2 nanoparticle catalysts have obvious visible light activity, evidenced by hydrogen evolution under visible light (λ>400 nm) irradiation. However, the catalytic activity under visible light irradiation is absent for Degussa as reference and the N-doped TiO2 annealed at 700 ℃.  相似文献   

17.
A new method for deposition nitrogen‐doped TiO2 nanofibers films was proposed. By using atmospheric pressure plasma jet generated by dual‐frequency power sources, the morphologies of these TiO2 films were investigated by scanning electron microscopy. The structures of these films were characterized by X‐ray diffraction and Raman Shift Spectroscopy. The elemental composition of these films [Colour figure can be viewed at wileyonlinelibrary.com ] were characterized by means of X‐ray photoelectron spectroscopy. The optical absorption of these films were studied by UV‐vis absorbance spectra. These results indicated that the nitrogen‐doped nanofibers TiO2 films have mixed phases of anatase and rutile. They also display narrow band gap. The I‐V characteristics curves exhibited good conductivity ability. Optical emission spectroscopy (OES) was measured to analyze the active group.  相似文献   

18.
This study was focused on the photocatalytic activity of polyaniline (Pani)/iron doped titanium dioxide (Fe–TiO2) composites for the degradation of methylene blue as a model dye. TiO2 nanoparticles were doped with iron ions (Fe) using the wet impregnation method and the doped nanoparticles were further combined with Pani via an in situ polymerization method. For comparison purposes, Pani composites were also synthesized in the presence undoped TiO2. The photocatalyst and the composites were characterized by standard analytical techniques such as FTIR, XRD, SEM, EDX and UV–Vis spectroscopies. Fe–TiO2 and its composites exhibited enhanced photocatalytic activity under ultraviolet light irradiation. Improved photocatalytic activity of Fe–TiO2 was attributed to the dopant Fe ions hindering the recombination of the photoinduced charge carriers. Pani/Fe–TiO2 composite with 30?wt.% of TiO2 nanoparticles achieved 28% dye removal and the discoloration rate of methylene blue for the sample was 0.0025?min?1. FTIR, XRD, SEM, EDX and UV–Vis spectroscopies supported the idea that Fe ions integrated into TiO2 crystal structure and Pani composites were successfully synthesized in the presence of the photocatalyst nanoparticles. The novelty of this study was to investigate the photocatalytic activity of Pani composites, containing iron doped TiO2 and to compare their results with that of Pani/TiO2.  相似文献   

19.
In recent decades, solar‐driven hydrogen production over semiconductors has attracted tremendous interest owing to the global energy and environmental crisis. Among various semiconductor materials, TiO2 exhibits outstanding photocatalytic properties and has been extensively applied in diverse photocatalytic and photoelectric systems. However, two major drawbacks limit practical applications, namely, high charge‐recombination rate and poor visible‐light utilization. In this work, heterostructured TiO2 nanotube arrays grafted with Cr‐doped SrTiO3 nanocubes were fabricated by simply controlling the kinetics of hydrothermal reactions. It was found that coupling TiO2 nanotube arrays with regular SrTiO3 nanocubes can significantly improve the charge separation. Meanwhile, doping Cr cations into SrTiO3 nanocubes proved to be an effective and feasible approach to enhance remarkably the visible‐light response, which was also confirmed by theoretical calculations. As a result, the rate of photoelectrochemical hydrogen evolution of these novel heteronanostructures is an order of magnitude larger than those of TiO2 nanotube arrays and other previously reported SrTiO3/TiO2 nanocomposites under visible‐light irradiation. Furthermore, the as‐prepared Cr‐doped SrTiO3/TiO2 heterostructures exhibit excellent durability and stability, which are favorable for practical hydrogen production and photoelectric nanodevices.  相似文献   

20.
Atomic‐layer deposition (ALD) is a thin‐film growth technology that allows for conformal growth of thin films with atomic‐level control over their thickness. Although ALD is successful in the semiconductor manufacturing industry, its feasibility for nanoparticle coating has been less explored. Herein, the ALD coating of TiO2 layers on ZnO nanoparticles by employing a specialized rotary reactor is demonstrated. The photocatalytic activity and photostability of ZnO nanoparticles coated with TiO2 layers by ALD and chemical methods were examined by the photodegradation of Rhodamine B dye under UV irradiation. Even though the photocatalytic activity of the presynthesized ZnO nanoparticles is higher than that of commercial P25 TiO2 nanoparticles, their activity tends to decline due to severe photocorrosion. The chemically synthesized TiO2 coating layer on ZnO resulted in severely declined photoactivity despite the improved photostability. However, ultrathin and conformal ALD TiO2 coatings (≈0.75–1.5 nm) on ZnO improved its photostability without degradation of photocatalytic activity. Surprisingly, the photostability is comparable to that of pure TiO2, and the photocatalytic activity to that of pure ZnO.  相似文献   

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