Photocatalytic decolorization of soluble dyes by a bis-ions coexistence system of NH4(+) and NO3(-) with high photoreduction ability

In this paper, we found that the acidic and basic dyes were easily decolorized by a bis-ions coexistence system of NH(4)(+) and NO(3)(-) under UV light irradiation. The coexistence of NH(4)(+) and NO(3)(-) is a necessary condition for the photocatalytic decolorization of soluble dyes. The photocatalytic decolorization of methyl orange (MO) and methylene blue (MB) follows the first order rate kinetics. The location of an absorption peak in the visible region is blue-shifted with the increase in the illumination time. It is proposed that the photocatalytic decolorization of soluble dyes in the bis-ions coexistence system of NH(4)(+) and NO(3)(-) is a photoreduction reaction, in which the ammonium nitrate acts as a photocatalyst. The chromophore of acidic and basic dyes reacts with hydrogen and then results in their rapid decolorization.     

Semiconductor-mediated photocatalysed degradation of two selected azo dye derivatives, amaranth and bismarck brown in aqueous suspension

Semiconductor-mediated photocatalysed degradation of two selected azo dye derivatives such as amaranth (1) and bismarck brown (2) has been investigated in aqueous suspension by monitoring the change in substrate concentration employing UV spectroscopic analysis technique as a function of irradiation time. The degradation was studied under different conditions such as types of TiO(2), pH, substrate concentration, catalyst concentration, and in the presence of electron acceptors such as hydrogen peroxide (H(2)O(2)), potassium bromate (KBrO(3)) and ammonium persulphate (NH(4))(2)S(2)O(8) besides air. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 showed comparatively highest photocatalytic activity. The dye derivative, bismarck brown (2) was found to degrade faster than amaranth dye (1).     

RGO-MIL-68(Fe)复合材料的静电自组装合成及光催化还原Cr(Ⅵ)的性能

采用静电自组装方法制备氧化石墨烯（GO）-MIL-68（Fe）复合物,并通过简单溶剂热处理,将GO还原为还原氧化石墨烯（RGO）,首次制得RGO-MIL-68（Fe）复合物。通过XRD、FESEM、紫外-可见漫反射光谱（UV-Vis DRS）等方法对RGO-MIL-68（Fe）复合催化剂的晶体结构、形貌、光吸收性能等物理化学性质进行表征。在可见光照射下,以草酸铵（（NH₄）₂C₂O₄）为牺牲剂,对RGO-MIL-68（Fe）复合材料进行光催化还原Cr（Ⅵ）性能评价,结果表明,只需复合少量的RGO,MIL-68（Fe）的光催化活性就能显著地提高。当RGO含量为1wt%时,RGO-MIL-68（Fe）复合材料表现出最优的光催化活性,反应60 min,体系中的Cr（Ⅵ）的还原率高达81%。结合电化学分析可知,这主要是由于RGO的引入在增强MIL-68（Fe）光吸收性能的同时也促进了光生载流子的分离。      

Synthesis and photo-degradation application of WO3/TiO2 hollow spheres

A WO(3)/TiO(2) composite, hollow-sphere photocatalyst with average diameter of 320 nm and shell thickness of 50 nm was successfully prepared using a template method. UV-vis diffuse reflectance spectra illustrated that the main absorption edges of the WO(3)/TiO(2) hollow spheres were red-shifted compared to the TiO(2) hollow spheres, indicating an extension of light absorption into the visible region of the composite photocatalyst. The WO(3) and TiO(2) phases were confirmed by X-ray diffraction analysis. BET isotherms revealed that the specific surface area and average pore diameter of the hollow spheres were 40.95 m(2)/g and 19 nm, respectively. Photocatalytic experiments indicate that 78% MB was degraded by WO(3)/TiO(2) hollow spheres under visible light within 80 min. Under the same conditions, only 24% MB can be photodegraded by TiO(2). The photocatalytic mineralization of MB, catalyzed by TiO(2) and WO(3)/TiO(2), proceeded at a significantly higher rate under UV irradiation than that under visible light, and more significant was the increase in the apparent rate constant with the WO(3)/TiO(2) composite semiconductor material which was 3.2- and 3.5-fold higher than with the TiO(2) material under both UV and visible light irradiation. The increased photocatalytic activity of the coupled nanocomposites was attributed to photoelectron/hole separation efficiency and the extension of the wavelength range of photoexcitation.     

Heterogeneous photo-Fenton decolorization of methylene blue over LiFe(WO4)2 catalyst

Heterogeneous photo-Fenton process using LiFe(WO(4))(2) as catalyst was studied to degrade Methylene blue (MB) dye in aqueous solution. The results indicated that LiFe(WO(4))(2) could effectively catalyze the decolorization of MB in the presence of UV light and H(2)O(2). The effects of different parameters such as amounts of catalyst, H(2)O(2) concentration, initial pH of the dye solution, initial dye concentration and UV light intensity on the decolorization efficiency of the process were investigated. It was found that LiFe(WO(4))(2) possessed a wide applicable pH range. X-ray photoelectron spectroscopy (XPS) was applied to investigate the transformation between Fe(III) and Fe(II). It was also observed that catalytic behavior could be reproduced in consecutive experiments without a considerable drop in the process efficiency.     

水热法制备Cu掺杂可见光催化剂BiVO4及其光催化性能研究

以Bi(NO3)3.5H2O、NH4VO3、Cu(NO3)2.3H2O为原料,采用水热法合成了Cu-BiVO4光催化剂,并利用X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)、紫外漫反射(UV-Vis)等测试手段对催化剂进行了表征.结果表明,提高前驱液pH值,可得到单斜晶系白钨矿型Cu-BiVO4光催化剂,BiVO4的晶型结构并未随着Cu掺入量的增加而改变.光催化剂中的Cu元素以CuO和Cu2O的形式存在.Cu的引入使可见光吸收带发生红移,吸收强度明显提高.可见光催化降解亚甲基蓝溶液的结果表明,Cu掺杂有利于提高BiVO4的活性.其中pH值为5.0、Cu掺入量为1.0wt%的BiVO4具有最好的光催化效果,可见光照射60 min后,对初始浓度为10 mg/L的亚甲基蓝溶液的最高降解率由纯BiVO4的57.4%提高到97.8%.并对Cu掺入后光催化活性提高的机理进行了分析.     

Nanocrystalline zinc indium vanadate: a novel photocatalyst for hydrogen generation

Hydrogen is a future fuel and hence production of cheap hydrogen is an important area of research. Recently, the photocatalysts were used to generate hydrogen from water and hydrogen sulfide splitting under solar light. Hence, we designed Zinc Indium Vanadate, a novel visible light active photocatalyst and used for the generation of hydrogen by using solar light. We have demonstrated the synthesis of ZnIn2V2O9 (ZIV) catalyst by sonochemical route using NH4VO3, In (NO3)3 and Zn(CH3COO)2 as a precursors and PVP as a capping agent. The obtained product was further characterized by XRD, UV-DRS and FESEM. The XRD pattern reveals the existence of monoclinic crystal structure and broader peaks indicating the nanocrystalline nature of the material. The particle size was observed in the range of 50-70 nm. The optical study showed the absorption edge cut off at 520 nm with estimated band gap about 2.3 eV. Considering the band gap in visible range, ZnIn2V2O9 was used as a photocatalyst for photodecomposition of H2S under visible light irradiation to produce hydrogen. We observed excellent photocatalytic activity for the hydrogen generation by using this photocatalyst.     

Structural, photophysical and photocatalytic properties of novel Bi2AlVO7

Bi(2)AlVO(7) was prepared by solid-state reaction technique for the first time and the structural and photocatalytic properties of Bi(2)AlVO(7) and Bi(2)InTaO(7) were investigated. The results showed that Bi(2)AlVO(7) crystallized in the tetragonal crystal system with space group I4/mmm. In addition, the band gaps of Bi(2)AlVO(7) and Bi(2)InTaO(7) were estimated to be about 2.06 and 2.81 eV. The photocatalytic degradation of aqueous methylene blue (MB) dye with Bi(2)AlVO(7) or Bi(2)InTaO(7) as catalyst was investigated under visible light irradiation. Bi(2)AlVO(7) showed higher photocatalytic activity compared with Bi(2)InTaO(7) for photocatalytic degradation of MB under visible light irradiation. Complete removal of aqueous MB dye was realized after visible light irradiation for 160 min with Bi(2)AlVO(7) as the photocatalyst. The reduction of the total organic carbon (TOC) and the formation of inorganic products, SO(4)(2-) and NO(3)(-) revealed the continuous mineralization of aqueous MB dye during the photocatalytic process. The possible photocatalytic degradation pathway of aqueous MB dye was revealed under visible light irradiation.     

TiO2-UV photocatalytic oxidation of Reactive Yellow 14: effect of operational parameters

The photocatalytic decolourisation and degradation of an azo dye Reactive Yellow (RY14) in aqueous solution with TiO(2) as photocatalyst in slurry form has been carried out using UV-A radiation (365 nm). The effect of various parameters such as catalyst loading, radiation intensity and initial dye concentration on the dye removal was investigated to find optimum conditions. The decolourisation and degradation kinetics have been analysed. Both follow modified Langmuir-Hinshelwood kinetic (L-H) model. A study on the effect of electron acceptors on photooxidation reveals that both decolourisation and degradation increase in the presence of H(2)O(2), (NH(4))(2)S(2)O(8), KBrO(3), to certain dosage beyond which the enhancement effect is negligible. But negative effects are observed in the presence of NaCl or Na(2)CO(3).     

TiO2负载锶铁氧体磁性材料光催化性能及表征

采用溶胶-凝胶法合成了TiO₂负载锶铁氧体光催化剂, 通过XRD、TEM、UV-Vis、VSM等方法对催化剂结构进行了表征, 并以高压汞灯为光源, 亚甲基兰为目标降解物, 对其光催化活性进行了研究. 结果表明, TiO₂负载锶铁氧体为复合型光催化剂, 负载后的复合光催化剂保持了良好的磁性能; 锶铁氧体的负载拓宽了催化剂的光响应区域, 光吸收带进入可见光区; 在负载量为20％, 催化剂用量1.5g/L条件下, 催化降解亚甲基兰的效率可达99.1％.     

Structural, photophysical and photocatalytic properties of Bi2MTaO7 (M = La and Y)

Bi₂MTaO₇ (M = Y and La) were synthesized by solid-state reaction method and their structural and photocatalytic properties were investigated. The results indicated that these compounds crystallize in the pyrochlore-type structure, cubic system with space group Fd-3 m. In addition, the band gaps of Bi₂LaTaO₇ and Bi₂YTaO₇ were estimated to be about 2.17(3) and 2.22(7) eV, respectively. For the photocatalytic water splitting reaction, H₂ or O₂ evolution was observed from pure water respectively with Bi₂MTaO₇ (M = Y and La) as the photocatalysts under ultraviolet light irradiation. Photocatalytic degradation of aqueous methylene blue (MB) dye over these compounds was further investigated under visible light irradiation. Bi₂MTaO₇ (M = Y and La) showed markedly higher catalytic activity compared to P-25 for MB photocatalytic degradation under visible light irradiation. Complete removal of aqueous MB was observed after visible light irradiation for 190 min with Bi₂LaTaO₇ as the photocatalyst and for 200 min with Bi₂YTaO₇ as the photocatalyst. The decrease of the total organic carbon (TOC) and the formation of inorganic products, SO₄²⁻ and NO₃⁻, demonstrated the continuous mineralization of aqueous MB during the photocatalytic process.     

Preparation and characterization of visible-light-driven TiO2 photocatalyst Co-doped with nitrogen and erbium

A series of nitrogen and erbium co-doped TiO2 photocatalyst was prepared by sol-hydrothermal method. The structure and properties of the photocatalyst were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, X-ray photoelectron spectroscopy (XPS), and UV-vis diffuse reflectance spectra (DRS). The XRD and BET results showed that co-doping inhibited the increase of crystallite size and enlarged specific surface areas. XPS spectroscopy indicated nitrogen atoms were incorporated into TiO2 lattice, and erbium atoms mostly existed in the forms of Er2O3. A shift of the absorption edge to the lower energy and four absorption bands located at 654, 544, 524 and 489 nm attributed to the 4f transitions of 4I15/2 --> 4F2/9, 4I15/2 --> 4S3/2, 4I15/2 --> 2H11/2, 4I15/2 --> 4F7/2 of Er3+ were observed using DRS spectroscopy. The catalytic efficency was evaluated by the photocatalytic degradation of methyl orange (MO) under visible light irradiation. The results showed that the photocatalytic performance of the co-doped TiO2 was related with the hydrothermal temperature and the molar ratio of N/Ti, and they showed higher acitivites than pure TiO2. Results determined by fluorescence technique revealed that irradiation (lambda > 400 nm) of TiO2 photocatalyst dispersed in MO solution induces the generation of the highly active hydroxyl radicals (OH). It indicated the photocatalytic activities of TiO2 photocatalyst were correlation with the formation rate of hydroxyl radicals (OH) and other active oxygen species.     

S、RE共掺杂TiO2的制备及其可见光分解水制氢性能

采用溶胶-凝胶法制备了系列稀土(La、Eu、Nd、Tb、Er)和硫共掺杂TiO2光催化剂RE/S/TiO2。通过紫外-可见(UV-Vis)漫反射、X射线衍射(XRD)对催化剂进行了表征。以EDTA为电子给体,考察了光催化剂在可见光照射下的制氢活性。研究结果表明,S/TiO2具有可见光活性,稀土掺杂进一步提高了S/TiO2可见光活性,其活性顺序依次为Eu/S/TiO2>La/S/TiO2>Nd/S/TiO2>Tb/S/TiO2>Er/S/TiO2。与纯TiO2和S/TiO2光催化剂相比,稀土掺杂使催化剂的粒径减小,晶格畸变应力增大,从而提高了催化剂可见光制氢活性。     

Degradation of nitrobenzene using titania photocatalyst co-doped with nitrogen and cerium under visible light illumination

A type of nitrogen and cerium co-doped titania photocatalyst, which could degrade nitrobenzene under visible light irradiation, was prepared by the sol-gel route. Titanium isopropoxide, ammonium nitrate, and cerium nitrate were used as the sources of titanium, nitrogen, and cerium, respectively. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffusive reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and N(2) adsorption-desorption isotherm were employed to characterize the as-prepared photocatalyst. The degradation of nitrobenzene under visible light illumination was taken as probe reaction to evaluate the photoactivity of the co-doped photocatalyst. The commercial TiO(2) photocatalyst (Degussa P25), which was thought as a high active photocatalyst, was chosen as standard photocatalyst to contrast the photoactivity of the nitrogen and cerium co-doped titania photocatalyst. The results showed that the photocatalytic performance of the nitrogen and cerium co-doped titania was related with the calcination temperature and the component. The nitrogen atoms were incorporated into the crystal of titania and could narrow the band gap energy. The doping cerium atoms existed in the forms of Ce(2)O(3) and dispersed on the surface of TiO(2). The improvement of the photocatalytic activity was ascribed to the synergistic effects of the nitrogen and cerium co-doping.     

Preparation of Fe3+-doped TiO2 catalysts by controlled hydrolysis of titanium alkoxide and study on their photocatalytic activity for methyl orange degradation

Fe3+-doped TiO2 (Fe-TiO2) porous microspheres were prepared by controlled hydrolysis of Ti(OC4H9)4 with water generated "in situ" via an esterification reaction between acetic acid and ethanol, followed by hydrothermal treatment. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption flame emission spectroscopy (AAS), electron paramagnetic resonance (EPR) spectrum, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), and nitrogen adsorption-desorption methods. All of the undoped TiO2 and Fe-TiO2 samples exclusively consist of primary anatase crystallites, which further form porous microspheres with diameters ranging from 150 to 500 nm. The photocatalytic activity of Fe-TiO2 catalysts was evaluated from the photodegradation of methyl orange (MO) aqueous solution both under UV and visible light irradiation. Fe3+ doping effectively improves the photocatalytic activity under both UV light irradiation and visible light irradiation with an optimal doping concentration of 0.1 and 0.2%, respectively. The photocatalytic mechanisms of Fe-TiO2 catalysts were tentatively discussed.     

Fabrication characterization and activity of a solar light driven photocatalyst: cerium doped TiO2 magnetic nanofibers

A novel magnetic separable composite photocatalytic nanofiber consisting of TiO2 as the major phase, CeO(2-y) and CoFe2O4 as the dopant phase was prepared by sol-gel method and electrospinning technique, and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectrum (UV-vis DRS) and vibrating sample magnetometer (VSM). The photocatalytic activity of the resultant CoFe2O4-TiO2 and CeO(2-y)/CoFe2O4-TiO2 nanofibers was evaluated by photodegradation of methylene blue (MB) in an aqueous solution under xenon lamp (the irradiation spectrum energy distribution is similar to sunlight) irradiation in a photochemical reactor. The results showed that the dopant of Ce could affect the absorbance ability and photo-response range. The sample containing 1.0 wt% CeO(2-y) exhibited the highest degradation with 35% for MB under simulate solar light irradiation. Furthermore, the as-synthesized composite photocatalytic nanofibers could be separated easily by an external magnetic field, thus it might hold potential for application in wastewater treatment.     

TiO_2-Fe_3O_4/MIL-101(Cr)磁性复合光催化材料的制备及其光催化性能

采用原位水热法合成了TiO_2-Fe_3O_4/MIL-101(Cr)磁性复合光催化材料,利用XRD、SEM、UV-Vis DRS、BET和磁学测量系统对复合光催化材料的结构和性能进行了表征,并以亚甲基蓝(MB)为模拟污染物,研究了该复合光催化材料的可见光催化活性,并考察了光催化材料的稳定性。结果表明:巯基官能化的Fe_3O_4和TiO_2与MIL-101(Cr)结合成功,复合后的TiO_2-Fe_3O_4/MIL-101(Cr)光催化材料的可见光响应范围得到明显拓宽;当TiO_2的添加量为400mg时所制得的磁性复合光催化材料具有相对较好的光催化降解效果,经过120min光照后,对MB的去除率高达80%;该磁性复合光催化材料具有良好的稳定性和磁分离性能。     

SiO2同步合成与固载酞菁的制备及可见光催化性能

首先通过对羟基苯甲酸和8-羟基喹啉分别与4-硝基邻苯二腈反应制备了羧基苯氧基邻苯二腈(CPPN)和喹啉氧基邻苯二腈(QPN),然后利用开环反应将CPPN键合到聚甲基丙烯酸缩水甘油酯改性的硅胶(PGMA/SiO2)表面,得到键合有邻苯二腈的硅胶CPPN-PGMA/SiO2,再通过“同步合成与固载”的方法在PGMA/SiO2表面固载喹啉氧酞菁(QPc)或金属喹啉氧酞菁(MQPc),制备了固载化的酞菁QPc-PGMA/SiO2或CoQPc-PGMA/SiO2。通过红外光谱、扫描电镜、热重分析、紫外-可见漫反射光谱等对其结构、形貌和酞菁键合量进行表征和测定。考察了催化剂DBU用量对“同步合成与固载”酞菁过程的影响。最后以亚甲基蓝(MB)和苯酚为目标降解物,研究所制得的固载化酞菁催化剂QPc-PGMA/SiO2或CoQPc-PGMA/SiO2的可见光催化活性。结果表明,借助“同步合成与固载”的方法能够成功在PGMA/SiO2表面固载喹啉氧酞菁(QPc)或金属喹啉氧酞菁(CoQPc),得到固载化酞菁QPc-PGMA/SiO2或CoQPc-PGMA/SiO2。在可见光照射下,QPc-PGMA/SiO2和CoQPc-PGMA/SiO2均具有较好的光催化活性。较低浓度时,CoQPc-PGMA/SiO2催化降解亚甲基蓝的效果优于QPc-PGMA/SiO2;碱性条件有利于CoQPc-PGMA/SiO2光催化降解MB性能的发挥,在pH值为10.0时,0.2g/L的CoQPc-PGMA/SiO2能使MB的降解率高达97%以上。固载化金属酞菁周边取代基的性质对其光催化降解苯酚有一定的影响,有供电子共轭效应的CoQPc-PGMA/SiO2对苯酚的光降解效果最优,5min内苯酚的降解率达58%,2h内苯酚的降解率高达100%。此外,固载化金属酞菁还具有良好的重复使用性。     

Visible light-activated cadmium-doped ZnO nanostructured photocatalyst for the treatment of methylene blue dye

An attempt was made to prepare Cd-doped ZnO photocatalyst for visible light assisted degradation of a textile dye (methylene blue, MB) in aqueous solutions by a traditional sol–gel process. The as-prepared nanoparticles were characterized by X-ray diffraction, UV–vis diffuse reflectance spectroscopy, and photoluminescence spectra techniques. The results showed that the Cd-doped ZnO possess the single-phase hexagonal wurtzite structure. The photocatalytic activity of the nanoparticles under visible light was investigated by measuring the photodegradation of MB in aqueous dispersion. The effects of key operation parameters such as initial dye concentration, catalyst loading as well as initial pH value on the decolorization extents were investigated. The results indicate that the decolorization of the organic molecule followed a pseudo-first-order kinetics according to the Langmuir–Hinshelwood model. Under the optimum operation conditions, approximately 85.0% dye removal was achieved within 3.5 h.     

纳米α-Fe2O3/TiO2光催化剂的制备及其光催化性能研究

以硝酸铁为铁源,NaOH为沉淀剂合成单分散性良好的纳米α-Fe2O3粒子,然后与纳米TiO2胶体复合制备了纳米α-Fe2O3/TiO2光催化剂。利用动态光散射粒径分析仪、扫描电子显微镜、紫外-可见分光光度计、X射线衍射仪对光催化剂的物相、形貌进行了表征。在室温条件下,以甲醛作为有机污染物,在可见光照射下探讨了纳米α-Fe2O3粒径、α-Fe2O3摩尔分数等对甲醛光催化降解的影响。结果表明,在一定范围内,随着粒径的减小,纳米α-Fe2O3光催化活性增强,在120min内粒径40nm的纳米α-Fe2O3对甲醛的降解效果最好,降解率约为93.05%。与纯TiO2相比,纳米α-Fe2O3/TiO2光催化剂的可见光催化活性明显增强,纳米α-Fe2O3最佳含量为0.20%(摩尔分数)。纳米α-Fe2O3含量过大,纳米α-Fe2O3/TiO2光催化剂的催化活性将降低。