Preparation and Photocatalytic Activity of Mesoporous TiO2 Photocatalyst Co‐doped with Fe and H3PW12O40

The mesoporous titanium dioxide (MTiO₂) photocatalysts co‐doped with Fe and H₃PW₁₂O₄₀ were synthesized by template method using tetrabutyl titanate (Ti(OC₄H₉)₄), Fe(NO₃)k₃9H₂Oand H₃PW₁₂O₄₀ as precursors and Pluronic P123 as template. The as‐prepared photocatalyst was characterized by N₂ adsorption‐desorption measurements, X‐ray diffraction (XRD), scanning electron microscopy (SEM) and UV‐vis adsorption spectroscopy, and the photocatalytic activities of the prepared samples under UV and visible light were estimated by measuring the degradation rate of methyl blue (MB) (50 mg/L) in an aqueous solution. The characterizations indicated that the photocatalysts possessed a homogeneous pore diameter of ca. 10 nm with high surface area of ca. 150 m²/g. The results of MB photodecomposition showed that co‐doped mesoporous TiO₂ exhibited higher photocatalytic activities than un‐doped, single‐doped mesoporous TiO₂ under UV and visible light irradiation. It was shown that the co‐doped MTiO₂ could be activated by visible light and could thus be used as an effective catalyst in photo‐oxidation reactions. The synergistic effect of Fe and H₃PW₁₂O₄₀ co‐doping played an important role in improving the photocatalytic activity.     

Photocatalytic activity of nitrogen and copper doped TiO2 nanoparticles prepared by microwave-assisted sol-gel process

Cu and N-doped TiO₂ photocatalysts were synthesized from titanium (IV) isopropoxide via a microwave-assisted sol-gel method. The synthesized materials were characterized by X-ray diffraction, UV-vis diffuse reflectance, photoluminescence (PL) spectroscopy, SEM, TEM, FT-IR, Raman spectroscopy, photocurrent measurement technique, and nitrogen adsorption–desorption isotherms. Raman spectra and XRD showed an anatase phase structure. The SEM and TEM images revealed the formation of an almost spheroid mono disperse TiO₂ with particle sizes in the range of 9-17 nm. Analysis of N₂ isotherm measurements showed that all investigated TiO₂ samples have mesoporous structures with high surface areas. The optical absorption edge for the doped TiO₂ was significantly shifted to the visible light region. The photocurrent and photocatalytic activity of pure and doped TiO₂ were evaluated with the degradation of methyl orange (MO) and methylene blue (MB) solution under both UV and visible light illumination. The doped TiO₂ nanoparticles exhibit higher catalytic activity under each of visible light and UV irradiation in contrast to pure TiO₂. The photocatalytic activity and photocurrent ability of TiO₂ have been enhanced by doping of the titania in the following order: (Cu, N) - codoped TiO₂ > N-doped TiO₂ > Cu-doped TiO₂ > TiO₂. COD result for (Cu, N)-codoped TiO₂ reveals ∼92% mineralization of the MO dye on six h of visible light irradiation.     

Synthesis of Fe<Superscript>3+</Superscript> doped ordered mesoporous TiO<Subscript>2</Subscript> with enhanced visible light photocatalytic activity and highly crystallized anatase wall

Fe³⁺ doped mesoporous TiO₂ with ordered mesoporous structure were successfully prepared by the solvent evaporation-induced self-assembly process using P123 as soft template. The properties and structure of Fe³⁺ doped mesoporous TiO₂ were characterized by means of XRD, EPR, BET, TEM, and UV–vis absorption spectra. The characteristic results clearly show that the amount of Fe³⁺ dopant affects the mesoporous structure as well as the visible light absorption of the catalysts. The photocatalytic activity of the prepared mesoporous TiO₂ was evaluated from an analysis of the photodegradation of methyl orange under visible light irradiation. The results indicate that the sample of 0.50%Fe–MTiO₂ exhibits the highest visible light photocatalytic activity compared with other catalysts.     

Preparation,Characterization and Photocatalytic Activity of Fe,La Co-doped Nanometer Titanium Dioxide Photocatalysts

A series of photocatalysts of un-doped, single-doped and co-doped nanometer titanium diox-ide (TiO₂) have been successfully prepared by template method using Fe(NO₃)₃·9H₂O, La(NO₃)₃·6H₂O, and tetrabutyl titanate as precursors and glucan as template. Scanning electron microscopy, X-ray diffraction, and N₂ adsorption-desorption measurement were em-ployed to characterize the morphology, crystal structure and surface structure of the samples. The photo-absorbance of the obtained catalysts was measured by UV-Vis absorption spec-troscopy, and the photocatalytic activities of the prepared samples under UV and visible light were estimated by measuring the degradation rate of methyl orange in an aqueous solu-tion. The characterizations indicated that the prepared photocatalysts consisted of anatase phase and possessed high surface area of ca. 163-176 m²/g. It was shown that the Fe and La co-doped nano-TiO₂ could be activated by visible light and could thus be used as an effective catalyst in photo-oxidation reactions. The synergistic effect of Fe and La co-doping played an important role in improving the photocatalytic activity. In addition, the possibil-ity of cyclic usage of co-doped nano-TiO₂ was also confirmed, the photocatalytic activity of codoped nano-TiO₂ remained above 89.6% of the fresh sample after being used four times.     

Doping level effect on visible-light irradiation W-doped TiO2–anatase photocatalysts for Congo red photodegradation

A series of W-modified TiO₂ (W–TiO₂) photocatalysts were synthesized by a simple sol–gel method. The new photocatalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis-diffuse reflectance spectroscopy (DRS), and Brunauer, Emmett and Teller (BET) surface area analyzer. The photoactivity of the W–TiO₂ photocatalysts was evaluated by the photocatalytic oxidation of Congo red (CR) dye. It was found that the average size of the prepared photocatalysts is 10 nm. Moreover, they have high surface areas (∼ 216 m² g⁻¹) and their light-absorption extends to the visible region compared to pure TiO₂. The effects of W-loading and of the calcination temperature of the prepared photocatalysts on their photocatalytic activity were also studied. The obtained results show that the W_0.5–TiO₂ photocatalyst calcined at 350 °C is much highly photoactive than non-doped or highly doped TiO₂. The enhanced photocatalytic activity of the weakly doped TiO₂ may be attributed to the increase in the charge separation efficiency and the presence of surface acidity on the W_0.5–TiO₂ photocatalyst.     

Synthesis and photocatalytic activity of co-doped mesoporous TiO2 on Brij98/CTAB composite surfactant template

Using composite surfactant templates, polyoxyethylene (20) oleyl ether (Brij98) and cetyl trimethyl ammonium bromide (CTAB), as structure-directing agents, N and La co-doped mesoporous TiO₂ complex photocatalysts were synthesized successfully. The micromorphology of co-doped mesoporous TiO₂ samples was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transformed infrared spectroscopy (FT-IR), energy-dispersive X-ray spectrometer (EDS) and N₂ adsorption-desorption measurements. The results indicated that the complex photocatalyst prepared with a molar ratio of Brij98:CTAB=1:1 showed a uniform pore size of ca. 7 nm and a high specific surface area (S_BET) of 279.0 m² g⁻¹, and exhibited the highest photocatalytic activity for degradation of papermaking wastewater under ultra-violet light irradiation. The chemical oxygen demand (CODc_r) percent degradation was about 73% in 12 h and chroma percent degradation was 100% in 8 h.     

Modification of the Optical and Electronic Properties of TiO<Subscript>2</Subscript> By N Anion-Doping for Augmentation of the Visible Light Assisted Photocatalytic Performance

In this work, a nitrogen-doped anatase TiO₂ nanocrystal is prepared by a modified sol-gel preparation method using the nonionic surfactant (polyoxyethylene sorbitan monooleate) as a structural controller and a soft template. The as-prepared samples are characterized by X-ray diffraction, Raman spectroscopy, UVVis diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy techniques. Then the photocatalytic activity of these samples is assessed by the photocatalytic oxidation of phenol under visible light irradiation. The phenol concentration is measured using a UV-Vis spectrometer. Experimental results show that N-doping leads to an excellent visible light photocatalytic activity of the TiO₂ nanocatalyst. Furthermore, the formation energy and electronic structure of pure and N-doped anatase TiO₂ are described by density functional theory (DFT) calculations. It is found that N-doping narrowed the band gap of bare TiO₂, which leads to an excellent visible light photocatalytic activity of N–TiO₂ nanocatalysts. Therefore, the prepared N–TiO₂ photocatalyst is expected to find the use in organic pollutant degradation under solar light illumination.     

Photocatalytic Activity of Fe and Ce Co‐doped Mesoporous TiO2 Catalyst under UV and Visible Light

The catalysts of un‐doped, single‐doped and co‐doped mesoporous titanium dioxide (MTiO₂) were prepared by a template method with tetrabutyltitanate (Ti(OC₄H₉)₄) as a Ti source material and Pluronic P123 as a template. The photo‐absorbance of the obtained catalysts was measured by UV‐vis absorption spectroscopy, and the photocatalytic activities of the prepared samples under UV and visible light were estimated by measuring the degradation rate of methyl orange (MO) (50 mg/L) in an aqueous solution. It was shown that the co‐doped MTiO₂ could be activated by visible light and could thus be used as an effective catalyst in photo‐oxidation reactions. The effect of Fe and Ce co‐dopants on the material properties was investigated by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and N₂ adsorption‐desorption isotherm measurement. The characterizations indicated that the photocatalysts possessed a homogeneous pore diameter of ca. 10 nm with high surface area of ca. 150 m²/g. The photocatalytic activity of MTiO₂ co‐doped with Fe and Ce was markedly improved due to the synergistic actions of the two dopants.     

N,B, Si-tridoped mesoporous TiO<Subscript>2</Subscript> with high surface area and excellent visible-light photocatalytic activity

N, B, Si-tridoped mesoporous TiO₂, together with N-doped, N, B-codoped and N, Si-codoped TiO₂, was prepared by a modified sol–gel method. The samples were characterized by wide-angle X-ray diffraction (WAXRD), N₂ adsorption–desorption, transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, UV–visible adsorbance spectra (UV–vis) and X-ray photoelectron spectra (XPS). The N, B, Si-tridoped mesoporous TiO₂ showed small crystallite size, large specific surface area (350 m²/g), uniform pore distribution (3.2 nm) and strong absorption in the visible light region. The photocatalytic activities of the samples were evaluated by the photodegradation of 2,4-dichlorophenol (2,4-DCP) aqueous solution. The N, B, Si-tridoping sample exhibited much higher photocatalytic activity compared with other synthesized photocatalysts. The high activity could be attributed to the strong absorption in the visible light region, large specific surface area, small crystallite size, large amount of surface hydroxyl groups, and mesoporosity.     

钯氮共掺杂TiO2的制备与表征及其可见光催化活性

在空气气氛和N₂中热处理表面均匀分散有尿素和氯化钯的纳米管钛酸,制备了两个系列Pd/N共掺杂的TiO₂光催化剂,并对所得样品进行了X射线衍射、透射电镜、X射线光电子能谱、紫外-可见漫反射光谱、荧光光谱和电子自旋共振等表征.结果表明,焙烧气氛对样品的形貌、晶体结构、光谱吸收、生成的氧空位浓度和可见光光催化性能的影响很大,其中在空气气氛中制备的样品光催化性能优于在N₂中制备的样品.在可见光(λ≥420nm)照射下,以丙烯为模型污染物考察了样品的光催化活性,发现在空气中400℃下焙烧的样品具有最佳的可见光催化活性.另外,讨论了Pd/N共掺杂TiO₂光催化剂具有可见光响应的机理,认为掺杂的Pd/N元素和制备过程中生成的氧空位是影响可见光催化性能的重要因素.     

Adsorption properties and photocatalytic activity of TiO2 and La-doped TiO2

Photocatalysts of TiO₂ and La-doped TiO₂ were prepared by calcining the pure TiO₂ sols and the sols mixed with La(NO₃)₃⋅6H₂O at 873 K, respectively. These photocatalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and N₂ adsorption-desorption isotherms measurement. As results, the BET surface area, pore diameter, mesopore volume and micropore volume slightly increased, while the crystallite size and the phase structure were little affected by lanthanum doping. The equilibrium adsorption of methylene blue (MB) on the photocatalysts were measured in a dark room. The adsorption isotherms were confirmed to fit to the Langmuir theory. Photocatalytic activities of the photocatalysts were studied by employing the photocatalytic degradation of MB in water and degradation of acetaldehyde in air under UV-irradiation using a black light. Kinetic analysis revealed that the rate controlling steps could be the surface reaction of the adsorbed MB on the catalyst surface for MB degradation and the reaction of adsorbed acetaldehyde with the gaseous acetaldehyde for degradation of acetaldehyde, respectively.     

Direct synthesis of Nd3+ doped mesoporous TiO2 and investigation of its photocatalytic performance

Nd³⁺ doped mesoporous TiO₂ samples with different molar ratio of Nd/Ti were synthesized by a sol?Cgel method. The textural and optical properties of the samples were systematical characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption?Cdesorption isotherms, Fourier transform infrared spectroscopy and UV?CVisible absorbance spectroscopy. It was revealed that Nd³⁺ doping inhibited the phase transformation from anatase to rutile after calcination, and the mesoporous structure of doped samples was still retained with the increase of Nd/Ti molar ratio. The surface area of the samples varied from 137 to 210 m²g^?1 and the average pore size of them ranged between 5.7 and 8.2?nm. The photocatalytic activities of all the samples were evaluated by degradation methyl orange (MO) in aqueous solution as a model reaction under UV light irradiation. The results showed that the doped samples demonstrated a higher photocatalytic activity than the mesoporous TiO₂, and the 3?mol% Nd³⁺ doped mesoporous TiO₂ exhibited the best photocatalytic performance. Meanwhile, a promotion effect of the H₂O₂ added was verified in the degradation of MO.     

球磨法制备Y3+/TiO2光催化剂及处理海水养殖废水

采用机械球磨法制备Y~(3+)修饰TiO_2光催化剂,利用紫外-可见漫反射光谱(UV-Vis DRS)、X射线光电子能谱(XPS)、X射线粉末衍射(XRD)、扫描电镜(SEM)等对其进行表征,在紫外光下,以亚甲基蓝(MB)为去除物来考察催化剂活性并优化球磨工艺。将最佳条件下制得的Y~(3+)/TiO_2光催化剂负载于不同半径的塑料浮球上,分别在紫外光和模拟太阳光照射下处理海水养虾废水,通过CODCr(chemical oxygen demand)及三维荧光观察有机物含量变化。结果表明,当Y~(3+)的物质的量分数为2%,球磨时间4 h,球料质量比4∶1,转速为500 r·min~(-1)时,MB光催化降解反应速率常数可达0.111 3 min~(-1),是纯TiO 2的4.2倍。由UV-Vis DRS、XPS、N_2吸附-脱附、XRD、SEM等表征结果显示,2%Y~(3+)/TiO_2样品的禁带宽度降低至3.05 eV,光吸收发生红移,并产生可见光响应,表面吸附氧含量明显增加,比表面积增大到104 m~2·g~(-1)。采用纯TiO_2及2%Y~(3+)/TiO_2为光催化剂处理养虾废水,在可见光和紫外光下CODCr的去除率分别为14.7%和18.8%、26.9%和37.5%。考察3种直径分别为1、2、3 cm负载Y~(3+)/TiO_2浮球的光催化效果,显示直径为2 cm浮球效果最佳,CODCr去除率可达38.5%。     

Synthesis and characterization of TiO<Subscript>2</Subscript> doping with rare earths by sol–gel method: photocatalytic activity for phenol degradation

The enhancement of TiO₂ photocatalyst activity will lead to more practical applications of this technology. In this work we studied the effect of rare earth doping of sol–gel synthesized TiO₂ for phenol degradation and we compared the performance with commercial catalyst. Photocatalysts were characterized by nitrogen adsorption to determine textural properties, ultraviolet visible light diffuse reflectance spectrometry (UV-Vis DRS), X-ray diffraction, STEM-EDS (scanning transmission electronic microscopy-energy dispersive X-ray spectroscopy) and XPS (X-ray photoelectron spectroscopy). Main phase for materials calcined at 500 °C was anatase. Residual nitrogen from NH₄OH used in the sol–gel synthesis was identified by XPS analysis. Ti³⁺/Ti⁴⁺ ratio increased when TiO₂ was doped with 0.5 wt% of Ce. Anatase phase was stabilized in photocatalysts doped with La even after calcination at 800 °C, for Pr and Nd a mixture of anatase-rutile phases was obtained, whereas for Ce doping only rutile phase was found. For the photocatalytic oxidation of phenol, the best results were obtained for Ce doped TiO₂, which could be related to the ability of Ce^IV/Ce^III oxidation/reduction cycle.     

超声波制备介孔结构的氮掺杂TiO2纳米晶及其可见光催化性能

采用超声波辐射法制备了具有介孔结构的高浓度氮掺杂TiO₂纳米晶(N/TiO₂).采用N₂物理吸附、X射线粉末衍射、X射线光电子能谱、透射电镜、光致发光谱和紫外-可见漫反射光谱等手段对N/TiO₂进行了表征.以波长为400~660nm的可见光为光源,以水体污染物邻苯二甲酸二甲酯为降解对象,考察了不同制备方法对N/TiO₂光催化性能的影响.结果表明,超声波辐射使氮掺杂浓度提高了2.2倍,该法制备的N/TiO₂同时具有较好的介孔结构,表现了更高的光催化降解邻苯二甲酸二甲酯的活性.其活性提高的主要原因是N/TiO₂含有更高浓度的氮和对可见光具有更强的吸收能力.     

Samarium-doped mesoporous TiO2 nanoparticles with improved photocatalytic performance for elimination of gaseous organic pollutants

Mesoporous TiO₂ doped with different amounts of Sm were prepared via a sol-gel route with Pluronic P123 as template. The materials were characterized by X-ray diffraction, transmission electron microscopy, and N₂ sorption experiments, etc. The photocatalytic activity of the mesoporous TiO₂ was tested in elimination of gaseous methanol and acetone. The Sm doped mesoporous TiO₂ have higher activity than those of the commercial photocatalyst (Degussa, P25) and Sm doped TiO₂ counterparts without mesopore structure under ultraviolet light irradiation. A possible mechanism was proposed to account for the high photocatalytic activity of the Sm doped mesoporous TiO₂. The superior activity of the Sm doped mesoporous TiO₂ may be attributed to the synergic effect of the high surface area, mesopore structure and doped Sm species.     

RE/TiO2光催化剂的谱学特性与气相光催化性能的研究

采用改进的sol-gel法和浸渍法制备了TiO₂掺杂稀土离子La³⁺、Y³⁺、Gd³⁺、Er³⁺、Nd³⁺、Pr³⁺的RE/TiO₂光催化剂,运用FTIR、XRD、TEM、低温氮吸附/脱附、TG/DTA、UV-Vis DRS、表面光电压谱(SPS)等进行表征,以气相光催化降解乙烯、溴代甲烷作为探针反应,阐明了RE/TiO₂光催化剂的谱学特性与气相光催化性能的关系。结果显示,稀土离子掺杂后,TiO₂的锐钛矿含量增加,比表面积增大,粒径变小,吸收边发生蓝移,表面光电压的响应阈值增大,此外,Pr³⁺除外的其它稀土离子掺杂的TiO₂的表面光电压信号增强;光催化降解实验表明,与纯TiO₂相比,La³⁺、Y³⁺、Gd³⁺、Er³⁺、Nd³⁺掺杂TiO₂样品上乙烯、溴代甲烷的光催化活性均有不同程度的增强,而且表现出较强的矿化能力。但是,掺杂Pr³⁺的TiO₂的光催化性能降低恰好对应较弱的表面光电压信号。所以,本文认为提高光生电子-空穴对的分离效率是改善光催化性能的关键因素。     

铋掺杂二氧化钛纳米颗粒的制备及其可见光催化性能

采用水热法,以纳米管钛酸为前驱物制备了Bi掺杂的TiO₂,并利用X射线衍射、透射电子显微镜、X射线光电子能谱、紫外-可见漫反射光谱等手段对样品进行了表征. 以甲基橙的光催化降解为模型反应评价了样品的可见光催化性能. 结果表明,Bi离子并没有进入TiO₂的晶格中,而是以BiOCl的形式存在. 所制得的BiOCl/TiO₂复合物对甲基橙降解表现出较优越的可见光催化活性;当Bi/Ti摩尔比为1%,水热温度为130℃时,所制催化剂的光催化性能最佳,并对光催化活性提高的机理进行了讨论. 同时,该催化剂对4-氯苯酚降解也表现出较高的光催化性能.     

Effect of Erbium on the Photocatalytic Activity of TiO2/Ag Nanocomposites under Visible Light Irradiation

Erbium co‐doped TiO₂/Ag catalysts are synthesized by using a simple, one‐step solvothermal method and characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy, Raman analysis, X‐ray photoelectron spectroscopy, and diffuse reflectance spectroscopy. The catalysts exhibit anatase crystal structures with increased visible light absorption compared with pure TiO₂. Enhanced photocatalytic activity is observed with Er co‐doped TiO₂/Ag nanocomposites for Rhodamine B degradation under visible light irradiation. The photocatalytic activity of 1 % Er co‐doped TiO₂/Ag is much higher than that of TiO₂/Ag, TiO₂/Er, pure TiO₂, and commercial Degussa P25. The kinetics of the degradation process are studied and the pseudo‐first‐order rate constant (k) and half‐life time (t_1/2) of the reaction are calculated. The enhanced activity might be accredited to the efficient separation of electron–hole pairs by silver and higher visible light absorption of TiO₂ induced by Er.     

F and Fe co-doped TiO2 with enhanced visible light photocatalytic activity

Four different sols, pure TiO₂, F doped TiO₂, Fe doped TiO₂, and F–Fe co-doped TiO₂ sols, were prepared by peroxidation at low temperature. The crystal structure, morphology, light adsorption, and photocatalytic properties of the pure and doped TiO₂ were examined by X-ray diffraction, transmission electron microscopy, and ultraviolet–visible spectrophotometry. The relationship between the average size, crystal type, range of visible light absorption, and photocatalytic activity and content and type of doped ions were investigated. The results showed that the average size of the F–Fe co-doped TiO₂ composed of both the anatase and rutile phases was the same as that of pure TiO₂. Furthermore, the visible light photocatalytic activity of the F–Fe co-doped TiO₂ was significantly improved over pure TiO₂, F-doped TiO₂, and Fe-doped TiO₂ due to the large red shift in the light adsorption edge.