The improvement of solar photocatalytic activity of ZnO by doping with Er3+:Y3Al5O12 during dye degradation

The Er³⁺:Y₃Al₅O₁₂, an upconversion luminescence agent, which is able to transform the visible light to ultraviolet light, was synthesized by nitrate-citric acid method. And then, a novel photocatalyst, Er³⁺:Y₃Al₅O₁₂/ZnO composites, was prepared by ultrasonic dispersing and liquid boil method. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the structural morphology and surface properties of the Er³⁺:Y₃Al₅O₁₂/ZnO. Azo Fuchsine dye was selected as target organic pollutant to inspect the photocatalytic activity of Er³⁺:Y₃Al₅O₁₂/ZnO. The key parameters affecting the photocatalytic activity of Er³⁺:Y₃Al₅O₁₂/ZnO, such as Er³⁺:Y₃Al₅O₁₂ content, heat-treatment temperature and heat-treatment time, were studied. In addition, the effects of dye initial concentration, Er³⁺:Y₃Al₅O₁₂/ZnO amount and solar light irradiation time were also reviewed, as well as the photocatalytic activity in degradation of other organic dyes were compared. It was found that the photocatalytic activity of Er³⁺:Y₃Al₅O₁₂/ZnO was much superior to pure ZnO under the same conditions. Thus, the Er³⁺:Y₃Al₅O₁₂/ZnO is a useful photocatalyst for the wastewater treatment because it can efficiently utilize solar light by converting visible light into ultraviolet light.     

The influence of Yb, B, and Ga-doped Er3+:Y3Al5O12 on solar light photocatalytic activity of TiO2 in degradation of organic dyes

Five up-conversion luminescence agents (Er³⁺:Y₃Al₅O₁₂, Er³⁺:Yb _n Y_{3 ? n} Al₅O₁₂, Er³⁺:Y₃B _a Al_{5 ? a} O₁₂, Er³⁺:Y₃Ga _b Al_{5 ? b} O₁₂, and Er³⁺:Yb _n Y_{3 ? n} B _a Ga _b Al_{5 ? a ? b} O₁₂) were synthesized using sol-gel method and then the corresponding coated composites (Er³⁺:Y₃Al₅O₁₂/TiO₂, Er³⁺:Yb _n Y_3?n Al₅O₁₂/TiO₂, Er³⁺:Y₃B _a Al_{5 ? a} O₁₂/TiO₂, Er³⁺:Y₃Ga _b Al_{5 ? b} O₁₂/TiO₂, and Er³⁺:Yb _n Y_{3 ? n} B _a Ga _b Al_{5 ? a ? b} O₁₂/TiO₂) as photocatalysts were prepared by sol-gel coating process. The XRD and SEM were used to confirm the crystalline phase and surface morphology. The UV-vis absorption and fluorescence-emission spectra were used to research the effect of doping category and amount on the up-conversion emission ability. The photocatalytic activities were detected through the degradation of Acid Red B dye in aqueous solution. Some key parameters of catalyst amount and initial concentration of organic dye on solar light photocatalytic degradation were also examined. The extensive feasibility of prepared photocatalysts in solar light degradation was detected by other organic dyes. The results suggest that the photocatalysts can be widely used in sewage treatment.     

Preparation of Er3+:Y3Al5O12/TiO2 composite film and influence of layer number and layer sequence on the visible-light photocatalytic activity

In this work, the Er³⁺:Y₃Al₅O₁₂ as up-conversion luminescence agent was mixed with TiO₂ and the corresponding Er³⁺:Y₃Al₅O₁₂/TiO₂ composite films were prepared on the one-sided surface of treated sheet glass through sol-gel dip-coating method. The prepared Er³⁺:Y₃Al₅O₁₂/TiO₂ composite films were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Their photocatalytic activities were examined through the degradation of some organic dyes under visible-light irradiation. The degradation process of organic dyes was monitored by UV-Vis spectrophotometer. Furthermore, some main influence factors on the visible-light photocatalytic activity of Er³⁺:Y₃Al₅O₁₂/TiO₂ composite film such as heat-treatment temperature and heat-treatment time were studied. The results indicate that three layer Er³⁺:Y₃Al₅O₁₂/TiO₂ composite films with one Er³⁺:Y₃Al₅O₁₂/TiO₂ composite film (as first layer close to sheet glass) and two pure TiO₂ film (as second and third layers) display a higher visible-light photocatalytic activity during photocatalytic degradation of Azo Fuchsine. In addition, the results showed that the visible-light photocatalytic activity of Er³⁺:Y₃Al₅O₁₂/TiO₂ composite film related to the layer number and layer sequence on the sheet glass. Perhaps, the research results may offer some meaningful references for developing solar energy continuous flow wastewater treatment reactor.     

Y3Al5O12:Ce phosphors as a scattering layer for high-efficiency dye sensitized solar cells

Y(3)Al(5)O(12):Ce phosphors have been prepared and used as an effective scattering layer on top of a transparent layer of nanocrystalline TiO(2) for dye sensitized solar cells (DSSCs). The Y(3)Al(5)O(12):Ce scattering layer increases the photocurrent of DSSCs due to the enhanced light harvesting mainly via the improved light absorption and scattering. Under one sun illumination (AM 1.5G, 100 mW cm(-2)), a high efficiency of 7.91% was achieved for the cell with a Y(3)Al(5)O(12):Ce scattering layer, which is an increase of 13.5% compared to the cell without a scattering layer (6.97%).     

Absorption spectra and energy levels of Sm3+:Y3Al5O12

Absorption spectra between 0.2 and 6.7 μm are reported for trivalent samarium in single-crystal yttrium aluminum garnet, Y₃Al₅O₁₂, at liquid-helium, liquid-nitrogen, and room temperatures. Energy levels (4f⁵[SL]Jμ) associated with sextet, quartet, and doublet states of Sm³⁺ are established from data between 1500 and 46000 cm⁻¹. Most samarium ions occupy yttrium ion sites, which have D₂ point-group symmetry in the lattice. A free-ion wavefunction calculation predicts the assignment of 35 isolated [SL]J manifolds with an rms deviation of 32 cm⁻¹ between calculated and observed centers of gravity. A hamiltonian consisting of coulombic, spin—orbit, and crystalline electric field (D₂ symmetry) terms is diagonalized for the two lowest sextet states [6H]J and [6F]J. The calculated Stark levels based on a single set of B_km crystal field parameters are compared to the observed levels (54) yielding an rms deviation of 4.9 cm⁻¹.     

Y2O3:Er3+粒子的微波制备

采用微波法和溶胶-凝胶法制备了(Y2O3:Er3+)粒子. 微波法制备过程中烧结温度降低到600 ℃. 980 nm激光激发下得到550 和660 nm两个上转换发射带. 微波法制备的上转换材料得到了强的红光发射和弱的绿光发射, 溶胶-凝胶法制备的材料得到了强的绿色发射和弱的红光发射. 结果表明, 微波促进了S6对称性的形成, S6对称性促进了红光的发射.     

First-principles calculations for the cooperative transitions of Yb3+ dimer clusters in Y3Al5O12 and Y2O3 crystals

A first-principles multielectron method is applied to the calculations for the cooperative transitions of trivalent ytterbium ions (Yb3+) in yttrium aluminum garnet (Y3Al5O12; YAG) and yttrium sesquioxide (Y2O3) crystals. The method is based on a molecular-orbital method, in which the overlap between the Yb 4f and the oxygen 2p orbitals is directly considered through a self-consistent procedure. A Yb2(3+) two-ion model and a (Yb2O14)22- dimer cluster embedded in the point charges of the YAG lattice are compared. The 4f-2p overlaps in the cluster model is needed to explain the cooperative transition probability originating from electric dipole transitions. A (Yb2O10)14- dimer molecule in Y2O3 lattice produces larger electric dipole transition probabilities than the case of YAG. The smaller coordination number in Y2O3 produces the larger 4f-2p overlaps, which result in the larger transition probabilities.     

C/Cr2O3/TiO2复合材料的制备及其光催化性能研究

本文以制革含铬革屑为原材料,基于矿物鞣剂复鞣的原理,将Ti(IV)均匀、稳定地负载到含铬革屑上,在氮气氛围下,经高温热解制备得到C/Cr₂O₃/TiO₂光催化剂,并研究了其对四环素(TC)的光催化降解效果及机理。结果表明,C/Cr₂O₃/TiO₂光催化剂具有明显的介孔结构,比表面积较大,为277.47 m²·g^-1,Cr₂O₃和TiO₂已实现复合并负载在生物炭(C)上。通过光催化降解发现,在模拟自然光照下,当催化剂用量为0.04 g,TC初始浓度为50 mg·L^-1,溶液pH为2时,TC的去除率可高达99.99%。结合自由基捕获实验发现,C/Cr₂O₃/TiO₂光催化剂对TC的降解作用主要依靠反应体系中产生的大量·O₂^-,·OH和h⁺。     

Facile decoration of TiO2 nanoparticles on graphene for solar degradation of organic dye

The reduced graphene oxide is interesting material for the synthesis of TiO₂-based photocatalyst. In the present investigation, blackberry fruit, which contains high levels of anthocyanins and other phenolic compounds, was employed as a reducing agent mainly due to its high antioxidant capacity. The nano-crystalline TiO₂ was decorated on different amounts of graphene oxide with sol–gel method and then the photocatalytic activity for degradation of cationic dye was evaluated by UV spectroscopy to achieve the optimum content of graphene oxide. The decoration of anatase nanoparticles on prepared reduced graphene oxide was investigated by X-ray diffraction, scanning and transmission electron microscopy techniques. The new composite gives significantly higher activity when is compared to the compositions fabricated by graphene oxide. The compact layer provides a large TiO₂-graphene contact area and reduces the electron recombination. The decoration of TiO₂ nanoparticles, 5–10 nm, on the graphene oxide reduced by blackberry juice further improves the dye removal. The results imply that the nanoparticle decoration is the key strategy to increase the degradation capacity.     

凝胶-燃烧法合成YAG∶Eu3+纳米荧光材料的结构和发光性能

Y₃Al₅O₁₂∶Eu nanophosphors were synthesized by a gel combustion method. The structure of phosphors was characterized by XRD and FTIR. YAG phase came to occur when YAG∶Eu precursors were sintered at 800 ℃, although the phase was mainly amorphous. The organic groups pyrolyzed completely and pure YAG phase was obtained in the samples sintered at 900 ℃. In the formation of YAG phase, no intermediate phases such as YAP and YAM were detected. Both ⁵D₀ → ⁷F₁ orange and ⁵D₀ → ⁷F₂ red emission could be observed for all the sintered samples. However, the emission of amorphous samples was greatly different from that of crystalline ones. The former was mainly ⁵D₀→ ⁷F₂ red emission, but the latter was ⁵D₀ → ⁷F₁ orange emission. As sintering temperature rises, the ratio of orange to red for phosphors increases. Eu could be doped up to 8% in YAG host lattice, and fluorescence quenching was absent. It indicated that the gel combustion synthesis method can increase emission intensity and quenching concentration due to a good distribution of Eu³⁺ activators in Y₃Al₅O₁₂ matrix.     

Fabrication of nanoporous polymeric crystalline TiO2 composite for photocatalytic degradation of aqueous organic pollutants under visible light irradiation

A nanoporous polymeric crystalline TiO₂ composite (TiO₂/PDVB‐MA) has been successfully synthesized through an in situ synthesis method using divinylbenzene (DVB), methacrylic acid (MA) and tetrabutyl titanate. The experimental results showed that TiO₂ nanoparticles composed of the mixture phases of anatase and rutile were homogeneously dispersed into the PDVB‐MA support. The TiO₂/PDVB‐MA composite was used as photocatalyst for Rhodamine B (RhB), bisphenol A and 2,4,6‐trichlorophenol degradation under visible light irradiation. More interestingly, the excellent photocatalytic performance of the composite was observed with regard to RhB and bisphenol A, which might be ascribed to the synergistic effect between TiO₂ nanoparticles and PDVB‐MA. Moreover, TiO₂/PDVB‐MA composite could be recycled at least four times in the removal of RhB, suggesting that it is a promising photocatalyst to catalyze the degradation of organic pollutants under visible light irradiation.     

ZnO nanopowders and their excellent solar light/UV photocatalytic activity on degradation of dye in wastewater

Low-cost and scalable preparation,high photocatalytic activity,and convenient recycle of Zn O nanopowders(NPs)would determine their practical application in purifying wastewater.In this contribution,ZnO NPs were scalably synthesized via the simple reaction of Zn powder with H_2O vapor in autoclave.The structural,morphological and optical properties of the samples were systematically characterized by X-ray diffraction,scanning electron microscopy,Fourier transform infrared spectra,transmission electron microscopy,Micro-Raman,photoluminescence,and ultraviolet-visible spectroscopy.The as-prepared Zn O NPs are composed of nanoparticles with 100–150 nm in diameter,and have a small Brunauer-Emmett-Teller surface area of 6.85 m~2/g.The formation of Zn O nanoparticles is relative to the peeling of H_2 release.Furthermore,the product has big strain-stress leading to the red-shift in the band gap of product,and shows a strong green emission centered at 515 nm revealing enough atomic defects in Zn O NPs.As a comparison with P25,the obtained dust gray Zn O NPs have a strong absorbance in the region of 200–700 nm,suggesting the wide wave-band utilization in sunlight.Based on the traits above,the Zn O NPs show excellent photocatalytic activity on the degradation of rhodamine B(Rh-B)under solar light irradiation,close to that under UV irradiation.Importantly,the Zn O NPs could be well recycled in water due to the quick sedimentation in themselves in solution.The low-cost and scalable preparation,high photocatalytic activity,and convenient recycle of Zn O NPs endow themselves with promising application in purifying wastewater.     

Ti~(3+)自掺杂的纳米TiO_2的制备及其可见光催化性能

以TiH2为Ti源,H2O2为氧化剂,首先通过表面氧化得到不同状态的前驱体凝胶,然后采用后续水热处理制备Ti3+自掺杂的纳米Ti O2.考察了前驱体凝胶状态及水热处理时间对材料结构和性能的影响.利用X射线衍射、透射电子显微镜、X射线光电子能谱、电子顺磁共振波谱和紫外-可见漫反射光谱手段对样品进行表征.以次甲基蓝溶液为模拟废水评价样品的可见光催化降解性能.结果表明,与纯Ti O2相比,Ti3+的自掺杂使材料在可见光区有明显的吸收,并具有良好的可见光催化降解性能和循环使用性能.当采用黄色凝胶为前驱体时,在160°C下水热处理24 h所得样品在可见光下光催化降解次甲基蓝的反应速率常数(0.0439 min-1)是纯Ti O2的18.3倍.     

Enhancement of photocatalytic activity of P25 TiO2 by vanadium-ion implantation under visible light irradiation

An ion-implantation method was used to prepare V-ion-implanted P25 TiO2 photocatalysts. Their photocatalytic activity for the degradation of formic acid under visible light irradiation (lambda>450 nm) was investigated. Upon implantation of V ions into the lattice of P25 TiO2, the photoactivity was remarkably enhanced. HRTEM images showed that the implanted V ions existed in the form of VO2(T) in the lattice of P25 TiO2. The intensity of photoluminescence (PL) spectra of V-ion-implanted P25 TiO2 decreased with the increase of the amount of implanted V ions, indicating the decrease of electron-hole pair recombination. It was also observed that the lower the PL intensity of V-ion-implanted P25 TiO2, the higher the photoactivity.     

亚微米级Y3Al5O12:Ce3+荧光粉的共沉淀法合成、表征及光致发光

以金属硝酸盐为原料,使用NH3·H2O-NH4HCO3混合沉淀剂,开展了以反滴化学共沉淀方式和两步煅烧法合成掺铈的钇铝石榴石(Y3Al5O12Ce3+)黄色荧光粉研究.采用DTA-TGA和XRD研究共沉淀法制备的前驱体粉末热分解与钇铝石榴石晶相形成过程,通过荧光光谱和SEM研究荧光粉光致发光及添加剂对其发光和形貌影响规律.结果表明,采用化学共沉淀法合成温度比传统高温固相法降低300 ℃以上;荧光粉粒径0.3～1 μm,颗粒规则呈类球状;468 nm激发下荧光粉发射峰为532 nm;煅烧阶段添加氟化物,可使荧光粉的发射强度等发光特性明显提高,对控制Y3Al5O12Ce3+荧光粉的形貌有显著作用;与蓝光LED芯片封装后形成的白光LED色温Tc为5571 K,光效率为45 lm·W-1,显色指数Ra为79.9,色坐标为(0.3308,0.3476).     

Preparation of Er3+:YAlO3/Fe-doped ZnO composite and investigation on solar light photocatalytic degradation of organic dyes

The Er³⁺:YAlO₃/Fe-doped ZnO composite, a new photocatalyst which could effectively utilize visible light, was prepared. In succession, the Er³⁺:YAlO₃/Fe-doped ZnO was characterized by XRD and SEM, respectively. Acid Red B dyes, was degraded under solar light irradiation to evaluate the photocatalytic activity of the Er³⁺:YAlO₃/Fe-doped ZnO. In addition, the effects of Er³⁺:YAlO₃ content, heat-treatment temperature and time on the photocatalytic activity of Er³⁺:YAlO₃/Fe-doped ZnO were reviewed. Otherwise, the effect of initial dye concentration, Er³⁺:YAlO₃/Fe-doped ZnO amount and solar light irradiation time on the photocatalytic degradation of Acid Red B were also investigated. It was found that the photocatalytic activity of Er³⁺:YAlO₃/Fe-doped ZnO is much higher than that of Fe-doped ZnO and pure ZnO for the similar system. Perhaps, the use of the Er³⁺:YAlO₃/Fe-doped ZnO may provide a new way to take advantage of ZnO in sewage treatment aspects using solar energy.     

Improved photocatalytic activity of WO3 through clustered Fe2O3 for organic degradation in the presence of H2O2

Photocatalytic degradation of organic substrates over WO(3) in an aerated aqueous suspension is very slow due to the difficulty of O(2) reduction by the conduction band electron on WO(3). In this work, we report on H(2)O(2) as an electron scavenger significantly accelerating the photodegradation of phenol and azo-dye X3B in water under UV or visible light. More importantly, an iron-containing WO(3) (FeW) synthesized through thermal decomposition of a ferrotungstenic acid displayed a much higher activity than pure WO(3) (HW) prepared in parallel. As the sintering temperature increased, both FeW and HW showed an exponential increase in activity. The maximum rate constant of phenol degradation obtained with FeW at 400 °C was about 2 times larger than that with HW at 600 °C. Sample characterization with electron paramagnetic resonance (EPR) spectroscopy and other techniques revealed that ferric species (0.3 wt % Fe(2)O(3)) were mainly present as clusters on the oxide surface at 120 °C and then they diffused toward the lattice sites of WO(3) at high temperature, which was detrimental to the photocatalytic reaction. 5,5-Dimethyl-1-pyrroline N-oxide spin-trapping EPR showed that the production of hydroxyl radicals was greatly enhanced upon the addition of H(2)O(2), the trend of which among different catalysts was the same as that of the rate of phenol degradation. The catalysts after excitation at 350 nm displayed a blue emission centered at 469 nm, the intensity of which varied with the catalyst activity nearly as expected. A possible mechanism for the improved photoactivity of WO(3) is proposed involving the electron transfer from WO(3) to Fe(2)O(3) and the reaction of the reduced oxide with H(2)O(2) to generate hydroxyl radicals.     

Effect of polyvinylpyrrolidone on the morphology and spectral luminescence of Y3Al5O12:Ce+3

Results from investigating the effect of different molecular masses and amounts of polyvinylpirrolidone (PVP) on the structural-phase, morphological, and spectral luminescence properties of YAG:Ce powders produced using a colloid chemical approach to synthesis (co-precipitation from solutions of the respective salts followed by thermal treatment of xerogels in air) are presented. The optimum thermal treatment regimes for precursors synthesized in the presence of PVP and its concentration in precipitation solutions that facilitate the formation of weakly aggregated nanosized powders of well-crystallized garnet characterized by enhanced (by a factor of 1.5–2) luminescence relative to a standard sample (without PVP) are determined.     

Study on the formation of H2O2 on TiO2 photocatalysts and their activity for the photocatalytic degradation of X-GL dye

Titanium dioxide (TiO₂) nanoparticles of both anatase and rutile phases were synthesized by hydrothermal treatment of microemulsions, and their photocatalytic activity for the degradation of X-GL dye was investigated. The only difference between the two methods used was that different acids were added to the microemulsions to make a direct comparison of the photocatalytic activity of the polymorphs possible. UV — Vis reflectance and XRD spectroscopic investigations of these titanium dioxides indicated that a rutile structure could be formed (PR) when hydrochloric acid was used, and anatase formed (PA) when nitric acid was used. The activity of the two polymorphs and P-25 for the photocatalytic degradation of dye in water was also examined. It was found that P-25 consisting of anatase and rutile has the highest activity, and PR consisting of rutile has the lowest. Photodegradation of X-GL in the presence of these different TiO₂ particles under air-equilibrated controlled conditions led to the formation of hydrogen peroxide. The formation rate of H₂O₂ depended on the difference in crystalloid phase. These results indicate that the observed differences in the photocatalytic activity for the three TiO₂ photocatalysts are directly related to the formation rate of H₂O₂.     

有序复合光催化剂H6P2W18O62/TiO2的低温制备及其可见光光催化降解一氯苯

近年来,随着人们环保意识的增加,越来越多的人开始关注河流污染问题,各种处理有机污染物的方法逐渐被人们所研究.常见的方法主要有物化法、化学法、生物法和光催化氧化法等.其中,利用光催化氧化技术来处理各种有机污染物,如一氯苯的研究成为人们关注的热点[1-4].在大量的研究中,人们发现常见的光催化材料如TiO2,ZrO2和杂多酸的带隙较宽,光谱反应范围较窄,吸收主要集中在紫外区,光生载流子的复合效率较高,量子效率较低,因而,他们的实际应用受到了限制.为此将两种光催化剂通过掺杂改性来提高催化活性成为一种趋势.本文采用非离子表面活性剂C18H37(OCH2CH2)10OH(Brij-76)作为模板剂,利用Dawson结构的杂多酸H6P2W18O62对TiO2进行掺杂改性来提高复合催化剂的性能,并选择具有生物蓄积性的一氯苯[5,6]为探针分子,考察了该复合催化剂在可见光条件下的光催化活性,实验结果显示,H6P2W18O62/TiO2对有机污染物一氯苯的光催化降解效果良好.