Effects of doping La and Cu on photoinduced charge properties of TiO_2 and its relationships with photocatalytic activity

In recent years, nanosized TiO2 materials have been widely studied in photocatalytic and photoelectric conversion fields because of their intrinsic characteris- tics, such as stable chemical property, strong oxidizing capability and nontoxicity[1,2]. And the preparation, characterization and modification of nanosized TiO2 are always crucial contents in semiconductor photo- electric chemistry and photocatalytic researches[3,4]. To further improve TiO2 performance, doping metal ion is consider…     

The preparation and characterization of La doped TiO2 nanoparticles and their photocatalytic activity

In this paper, pure and La doped TiO₂ nanoparticles with different La content were prepared by a sol-gel process using Ti (OC₄H₉)₄ as raw material, and also were characterized by XRD, TG-DTA, TEM, XPS, DRS and Photoluminescence (PL) spectra. We mainly investigated the effects of calcining temperature and La content on the properties and the photocatalytic activity for degrading phenol of as-prepared TiO₂ samples, and also discussed the relationships between PL spectra and photocatalytic activity as well as the mechanisms of La doping on TiO₂ phase transformation. The results showed that La³⁺ did not enter into the crystal lattices of TiO₂ and was uniformly dispersed onto TiO₂ as the form of La₂O₃ particles with small size, which possibly made La dopant have a great inhibition on TiO₂ phase transformation; La dopant did not give rise to a new PL signal, but it could improve the intensity of PL spectra with a appropriate La content, which was possibly attributed to the increase in the content of surface oxygen vacancies and defects after doping La; La doped TiO₂ nanoparticles calcined at 600°C exhibited higher photocatalytic activity, indicating that 600°C was an appropriate calcination temperature. The order of photocatalytic activity of La doped TiO₂ samples with different La content was as following: 1>1.5>3>0.5>5>0 mol%, which was the same as the order of their PL intensity, namely, the stronger the PL intensity, the higher the photocatalytic activity, demonstrating that there were certain relationships between PL spectra and photocatalytic activity. This could be explained by the points that PL spectra mainly resulted from surface oxygen vacancies and defects during the process of PL, while surface oxygen vacancies and defects could be favorable in capturing the photoinduced electrons during the process of photocatalytic reactions.     

Structural characterization and photocatalytic activity of hollow binary ZrO2/TiO2 oxide fibers

The formation of hollow binary ZrO₂/TiO₂ oxide fibers using mixed precursor solutions was achieved by activated carbon fibers templating technique combined with solvothermal process. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption, X-ray photoelectron spectroscopy (XPS), UV-vis, and infrared (IR) spectroscopy. The binary oxide system shows the anatase-type TiO₂ and tetragonal phase of ZrO₂, and the introduction of ZrO₂ notably inhibits the growth of TiO₂ nanocrystallites. Although calcined at 575 °C, all hollow ZrO₂/TiO₂ fibers exhibit higher surface areas (>113 m²/g) than pure TiO₂ hollow fibers. The Pyridine adsorption on ZrO₂/TiO₂ sample indicates the presence of stronger surface acid sites. Such properties bring about that the binary oxide system possesses higher efficiency and durable activity stability for photodegradation of gaseous ethylene and trichloromethane than P25 TiO₂. In addition, the macroscopic felt form for the resulting materials is more beneficial for practical applications than traditional catalysts forms.     

Catalytic oxidation of no to NO2 over Cr/TiO2 and Cu/TiO2 under oxidizing atmosphere

The catalytic activity of Cr/TiO₂ and Cu/TiO₂ for the oxidation of NO under an oxidizing atmosphere has been examined. Both catalysts had excellent ability for the oxidation of NO to NO₂ in the temperature range of 350–400°C.     

Synthesis of nanosized TiO2/SiO2 catalysts by the ultrasonic microemulsion method and their photocatalytic activity

Nanosized TiO₂/SiO₂ catalysts prepared by hydrolysis of titanium n-butoxide in microemulsion showed enhanced photocatalytic activity. In the presence of catalyst ME-2 and after 90 min irradiation by UV light, methylene blue was completely converted evidenced by the absence of its absorption band in the UV-Vis spectra. This catalyst demonstrated much better degradation ability than P-25 and naked TiO₂.     

TiO2/CuS异质结的制备及光催化降解染料废水的研究

以原位沉淀法和水热法混合的合成手段,制备了TiO_2/CuS异质结光催化剂。这种异质结改善了单一TiO_2半导体光催化剂的缺陷,明显提高了太阳光下光催化降解甲基橙的效率。TiO_2与CuS之间形成的异质结结构和合适的能带结构能够扩展材料对太阳光谱的响应范围并且很好地收集和传输光诱导载流子,从而提高了载流子的分离效率,最终使半导体的光催化活性明显增强。结果表明,太阳光照射25min后,相比于TiO_2/MnS、TiO_2/CdS和TiO_2/ZnS异质结,TiO_2/CuS异质结(TiO_2和CuS的摩尔比为3∶1)对甲基橙的降解效果最佳,降解效率能达到97.3%。为提高半导体的光催化活性提供了一条可行的路径。     

TiO2 nanoparticles incorporated with CuInS2 clusters: preparation and photocatalytic activity for degradation of 4-nitrophenol

TiO₂ nanoparticles incorporated with CuInS₂ clusters were prepared in a solvothermal process and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy-dispersion X-ray analysis (EDX). Compared with pure TiO₂ nanoparticles, the TiO₂ nanoparticles incorporated with CuInS₂ clusters display higher photocatalytic activity with 99.9% of degradation ratio of 4-nitrophenol after 2 h irradiation. In order to investigate the effect of the CuInS₂ clusters on the photocatalytic activity of TiO₂ nanoparticles, diffuse reflectance UV–Vis spectra (DRS), photoluminescence (PL) spectra, and photocurrent action spectra were measured. The results indicate that the enhanced photocatalytic activity is probably due to the interface between TiO₂ and CuInS₂ as a trap of the photogenerated electrons to decrease the recombination of electrons and holes.     

冷等离子体强化制备TiO2光催化材料及其机理

等离子体技术在材料制备和改性方面的优势得到众多研究者的认可。Ti O2具有化学稳定性高、氧化活性强、生产成本低等优势,被广泛应用于太阳能电池和光催化领域。本文综述了近年来介质阻挡放电等离子体在强化制备Ti O2光催化材料方面的研究成果,包括等离子体辅助制备Ti O2光催化薄膜和Ti O2的等离子体法掺杂两个方面,并分析了其作用机理。从目前的研究成果来看,等离子体技术制得的Ti O2光催化材料具有更好的均匀性和催化活性,这主要得益于等离子体中的高能电子,一方面,Ti O2粒子吸附电子,彼此之间产生静电场的斥力作用,可以抑制颗粒的团聚,另一方面,电子的强还原能力,能够打断Ti-O键,形成氧空位,从而提高其催化性能。     

ZnFe2O4/Ag/TiO2复合材料的制备及其光催化性能

以硝酸银、钛酸四丁酯、无水氯化锌、六水氯化铁为原料,采用溶胶-凝胶法与溶剂热相结合的方法制备了ZnFe₂O₄/Ag/TiO₂复合材料,通过扫描电子显微镜、能谱分析仪、X射线粉末衍射仪、X射线光电子能谱仪、振动样品磁强计、紫外可见分光光度计对样品进行表征及测试。结果表明： ZnFe₂O₄/Ag/TiO₂-10具有最佳的光催化效果,在紫外和可见光下对染料的降解率都能达到90%以上,具有优异的紫外可见光光催化活性。ZnFe₂O₄/Ag/TiO₂具有独特的磁性,能在外部磁场作用下进行回收利用,这使其在实际应用中成为可能。通过磁分离技术重复回收利用5次后仍然保持优良的光催化性能,说明ZnFe₂O₄/Ag/TiO₂-10具有优异的磁性及较高的光催化循环稳定性。     

ZnFe2O4/Ag/TiO2复合材料的制备及其光催化性能

以硝酸银、钛酸四丁酯、无水氯化锌、六水氯化铁为原料,采用溶胶-凝胶法与溶剂热相结合的方法制备了ZnFe₂O₄/Ag/TiO₂复合材料,通过扫描电子显微镜、能谱分析仪、X射线粉末衍射仪、X射线光电子能谱仪、振动样品磁强计、紫外可见分光光度计对样品进行表征及测试。结果表明：ZnFe₂O₄/Ag/TiO₂-10具有最佳的光催化效果,在紫外和可见光下对染料的降解率都能达到90%以上,具有优异的紫外可见光光催化活性。ZnFe₂O₄/Ag/TiO₂具有独特的磁性,能在外部磁场作用下进行回收利用,这使其在实际应用中成为可能。通过磁分离技术重复回收利用5次后仍然保持优良的光催化性能,说明ZnFe₂O₄/Ag/TiO₂-10具有优异的磁性及较高的光催化循环稳定性。     

双锥状纳米晶TiO2微管的制备及其光催化性能

本文采用模板法与溶胶-凝胶法结合,以脱脂棉为模板制备出了TiO2中空微管光催化材料.利用红外光谱(FTIR)、扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)对其在不同煅烧温度下产物的表面形貌及晶型进行了表征.以甲基橙的脱色降解为模式反应,考察了宏观形貌及煅烧温度对TiO2光催化性能的影响.结果表明:以脱脂棉为模板制得的TiO2中空微管直径3～8μm、壁厚0.5～1μm,TiO2晶体直径为30～80 nm,长径比约为5:1,呈双锥状结构,微管样品在酸性条件下30min内对甲基橙催化降解效率提高了约16%～40%.     

Synthesis of bimodal porous structured TiO2 microsphere with high photocatalytic activity for water treatment

In this work bimodal structured titanium dioxide (TiO₂) microsphere has been prepared from commercial TiO₂ powder and nano-sized titania gel via sol–gel spray-coating technique. Crystallization and transformation behavior of titania gel were investigated. The results revealed that the crystallization and transformation of anatase particles were substantially affected by the concentration of solvent and calcination temperature. Anatase crystallite size of 10 nm was obtained at mole ratio of solvent/precursor 50/1 and calcination temperature of 450 °C. The prepared nano-sized titania gel was embedded within the core (commercial TiO₂, P25) during the spraying process. The prepared TiO₂ microsphere was characterized using X-ray diffractometer (XRD), scanning electron microscope (SEM), field emission electron microscope (FESEM) and micropore analysis. The photocatalytic activity was monitored by following the degradation of phenol with activity benchmarked against commercial P25 (Degussa). The increase of photocatalytic activity of TiO₂ microsphere was attributed to the nano-sized anatase crystallite which has been incorporated into the TiO₂ microsphere.     

N 掺杂TiO2光催化剂的制备及其可见光活性研究

A visible-light-active photocatalyst was prepared by calcination of the hydrolysis product of tetrabutyl titanate with ammonia as precipitant. The photocatalyst was characterized by X-ray diffraction (XRD), UV-Vis diffuse reflection spectra (DRS), thermal gravimetric-differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM). The color of the photocatalyst was yellow and could absorb light wavelength under 550 nm as measured by DRS. The catalyst calcined at higher temperature will give lower absorbance for visible light. Structures of the sample were characterized mainly to be anatase by XRD except for the sample calcined at 700 ℃ which gave mixtures of anatase and rutile. TG-DTA results showed that temperature for anatase formation was 415 ℃. XPS results showed that doped-nitrogen was presented in the sample, they are important to show visible-light absorbency. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants, the results showed that over 90% of phenol could be degraded under visible light using N/TiO₂ as the catalyst after 4 hours reaction. Almost the same activity was found for the TiO₂ photocatalyst calcined at different temperature under sunlight but activities were different when the treatment was under UV light.     

TiO2胶粒在铝合金表面的电泳沉积及所制薄膜的光催化性能研究

TiO₂ membranes were prepared on aluminum-alloy thin plates by electrophoretic deposition and dip coating in a colloid solution of TiO₂, respectively. The photocatalytic activity of TiO₂ membrane was compared using ethylene as reactant, and the crystal and morphological structure of the membrane were characterized by XRD and SEM. The results showed that a more compact membrane with high loading of TiO₂ but lower photocatalytic activity of unit TiO₂ mass was obtained by electrophoresis compared with dip coating method. The addition of polyethylene glycol (PEG) to the sol of TiO₂ could improve the specific photocatalytic activity (ethylene conversion per unit mass TiO₂ and unit area of membrane piece) of the electrophoresis-membrane prepared from the sol, but could not change the specific photocatalytic activity of the dip-coating membrane from the sol. The ethylene conversion on the electrophoresis membrane prepared from the sol containing PEG (50 g·L^-1) was 9 times of that on the dip coating membrane. The effect of PEG on the properties of electrophoresis-membrane of TiO₂ was attributed to the change of electrokinetic properties of sol. Addition of PEG decreased ζ potential value of the sol and the mobility of the sol particle, increased viscidity of the colloid, thus decreasing both the electrophoresis deposition velocity of colloid particles and the electroosmosis velocity of diffuse layer of colloid particles. These favored the formation of a low compact and porous membrane on the electrode in electric field, and thus increasing the availability of TiO₂ in photocatalytic process.     

H2 production with low CO selectivity from photocatalytic reforming of glucose on metal/TiO2 catalysts

H₂ with low CO concentration is produced via photocatalytic reforming of glucose (as a representative of biomass component) on metal/TiO₂ catalyst (metals: Pt, Rh, Ru, Ir, Au, Ni, Cu). It is shown that the loaded metals generally enhance the rate of H₂ production, while they depress the CO selectivity. Both H₂ production and CO selectivity are strongly dependent on the kind of deposited metals on TiO₂. For example, Rh/TiO₂ catalyst is found to be most active for H₂ production while with the most extremely low CO concentration from the photocatalytic reforming of glucose. Supported by the National Natural Science Foundation of China (Grant No. 20403018, 20503034), National Basic Research Program of China (Grant No. 2003CB214504), and Knowledge Innovation Program of the Chinese Academy of Sciences (DICP K2006E2)     

TiO2纳米纤维无纺布的制备及光催化性能研究

以聚乙烯吡咯烷酮(PVP)作为配位剂与钛酸正丁酯(Ti(C₄H₉O)₄)反应制得前驱体，再以乙醇为溶剂，CH3COOH作为催化剂，采用静电纺丝法制得PVP/TiO₂复合纳米纤维，经550 ℃、700 ℃和900 ℃焙烧后分别得到以锐钛矿型的TiO₂为主、以金红石型TiO₂为主和完全金红石晶型的TiO₂纳米纤维。对所制得的纳米纤维的结晶度、纯度和形貌，分别采用差热-热重分析(TG-DTA)、红外光谱(IR)、X射线粉末衍射(XRD)、扫描电镜(SEM)等进行了表征。光降解苯酚水溶液的实验结果表明，550 ℃下煅烧得到的以锐钛矿占主体的TiO₂纳米纤维，2 h使浓度为50 mg·L^-1苯酚水溶液的降解率超过85%，这充分说明这种TiO₂电纺纳米纤维具有良好的光催化性能。     

载有C60的TiO2纳米粒子光催化活性

以水溶性C₆₀和TiO₂粒子为前驱体,采用水热法制备了载有C₆₀的锐钛矿型TiO₂纳米粒子。应用X射线衍射、透射电子显微镜、红外光谱、紫外-可见漫反射光谱、荧光光谱对产物进行了表征。以对-硝基苯酚为模型污染物研究了产物的光催化活性,结果表明适量负载C₆₀可以提高TiO₂纳米粒子的光催化活性,C₆₀起着传输电子、促进TiO₂光生载流子分离的作用,且经7次循环使用后对-硝基苯酚的降解效率仍能达到74%。讨论了载有C₆₀的TiO₂纳米粒子光催化降解对-硝基苯酚的机理。     

TiO2/Cu2O/Pt复合空心微球的制备及其光催化性能

以锐钛矿相TiO₂溶胶为基底,采用沉淀法和液相沉积法制备了TiO₂/Cu₂O/Pt复合空心微球,通过改变n_Ti⁴⁺∶ n_Cu²⁺和H₂PtCl₆·6 H₂O溶液的加入量对TiO₂的形貌和结构进行调控,采用不同的方法对不同样品的物相及结构、微观形貌和光学性能进行了对比分析。分析结果表明,复合材料中Pt与Cu₂O的引入产生协同效应,不仅在一定程度上阻止了电子-空穴的复合,还降低了禁带宽度,在可见光区域光吸收明显增强。与TiO₂、Cu₂O和TiO₂/Cu₂O光催化剂相比较,TiO₂/Cu₂O/Pt降解有机污染物的能力显著增强,首次光照120 min可降解93%的甲基橙(MO)溶液,4次循环后降解率为71%,具有良好的光催化稳定性能。     

TiO2/Cu2O/Pt复合空心微球的制备及其光催化性能

以锐钛矿相TiO₂溶胶为基底,采用沉淀法和液相沉积法制备了TiO₂/Cu₂O/Pt复合空心微球,通过改变n₍Ti⁴⁺)∶n_Cu2+和H₂Pt Cl₆·6H₂O溶液的加入量对TiO₂的形貌和结构进行调控,采用不同的方法对不同样品的物相及结构、微观形貌和光学性能进行了对比分析。分析结果表明,复合材料中Pt与Cu₂O的引入产生协同效应,不仅在一定程度上阻止了电子-空穴的复合,还降低了禁带宽度,在可见光区域光吸收明显增强。与TiO₂、Cu₂O和TiO₂/Cu₂O光催化剂相比较,TiO₂/Cu₂O/Pt降解有机污染物的能力显著增强,首次光照120 min可降解93%的甲基橙(MO)溶液,4次循环后降解率为71%,具有良好的光催化...     

碱土金属掺杂纳米TiO2催化剂的制备与光催化活性的评价

The nanometer TiO₂ were prepared by the hydrolyze-gel method and fellowed by doping alkaline-earth metals (Mg, Ca, Sr, Ba). XRD, SEM, diffuse reflection spectra were used to investigate their characteristices. The result indicates that the average particles size of the TiO₂ is about 80 nm and keep uniformity in distributing. The product was mainly anatase in 300～400 ℃ calcinations, the einstein shift of absorption spectrum was observed after doping the alkaline-earth metals. The best mole percentages of Mg, Ca, Sr and Ba are 0.5%, 1.0%, 1.5%, 1.5% respectively. Under the same reaction conditions, it is more effective to the UV-catalyed degradation reaction that the catalysts containing Mg and Ca were calcined at 300 ℃ for 1h or containing Sr and Ba were calcined at 400 ℃ for 1 h. The photocatalystic activity is considerably depondent on pH and the concentration of the oxidant. Using the sunlight to do the degradation experimental, the result also show that the doping catalysts has higher degradation efficiency than that of pure TiO₂.