圆盘状Bi2WO6-BiPO4异质结的水热合成及光催化性能

采用水热法制备Bi2WO6-BiPO4异质结光催化剂．利用模拟太阳光照射下的罗丹明B降解实验评价了Bi2WO6-BiPO4复合物的光催化性能．结果表明,Bi2WO6-BiPO4光催化活性比Bi2WO6和BiPO4高得多．当Bi2WO6与BiPO4的摩尔比为1：1时复合光催化剂对罗丹明B的降解率最高．Bi2WO6-BiPO4催化活性增强主要归结为两者之间形成了有效的异质结结构,其内建电场能够促进光生载流子的分离．同时,Bi2WO6的加入增强了其对可见光的吸收．研究表明O2^· -和h^＋在光催化降解过程中是主要的活性物种.     

柠檬酸辅助水热法制备可见光高效去除甲基橙的Bi2WO6纳米片

以Bi(NO3)3·5H2O和Na2WO3 ·2H2O为原料,以柠檬酸为络合剂,采用辅助水热法制备了Bi2WO6纳米片,运用X射线衍射、扫描电镜、场发射高分辨透射电镜、拉曼光谱、红外光谱和紫外-可见漫反射光谱等手段对样品进行了表征,并考察了该催化剂光催化去除甲基橙反应性能.结果表明,通过调节体系的pH值可制得结晶度良好...     

Z-机制磷酸银/钨酸铋复合物的构建及其可见光催化降解有机污染物(英文)

环境危害不仅对人类健康构成巨大威胁,而且也阻碍了经济社会的快速发展.光催化剂通过利用太阳能来降解污染物为环境问题提供一条理想的途径.光催化剂的制备应该考虑以下几点:(1)对可见光响应;(2)高量子效率和稳定性;(3)安全、廉价、无毒的原材料.早期的一些催化剂如二氧化钛、氧化锌、硫化锌、锗酸锌和磷酸铋等在紫外线照射下表现出优秀的光催化活性.但是紫外光是稀有的,而且对人体健康有害.近年来,对宽带隙半导体的改性如掺杂、贵金属沉积、构建异质结或固溶体催化剂取得了有效进展.遗憾的是,受限于材料的固有属性,有限的改进仍然不能满足实际应用的需求.因此,探索高效稳定的可见光驱动的光催化剂依然是十分有意义的.磷酸银在可见光下表现出超强的光催化降解有机污染物和产氧的能力,但是磷酸银容易受到光腐蚀,光催化活性和稳定性很难维持.另外,磷酸银导带上的电子电势较正,这将导致其很难在光催化过程中被利用.而磷酸银导带上电子的积累会抑制其内部电子空穴对的分离,从而对磷酸银的光催化活性和稳定性造成不利影响.本文选择钨酸铋纳米片与磷酸银复合去抑制电子空穴对的复合和进一步提高磷酸银的活性和稳定性.样品的粉末X射线衍射、能谱和X光电子能谱的分析证实了磷酸银/钨酸铋复合物已经被成功合成.稳态荧光光谱证实了磷酸银/钨酸铋复合物的构建可以作为一种有效抑制电子和空穴对复合的手段.通过对样品进行光催化降解次甲基蓝的实验,我们发现磷酸银/钨酸铋复合材料展现出比磷酸银和钨酸铋更强的光催化活性.其中,磷酸银/钨酸铋光催化降解次甲基蓝的速率为0.61385 min~(-1),这是磷酸银(0.47179 min~(-1))和钨酸铋(0.10270 min~(-1))活性的1.3和6.0倍.同时,磷酸银/钨酸铋表现出耐久的稳定性,在连续五次光降解过程中几乎没有明显的活性损失.进一步通过对磷酸银/钨酸铋复合材料进行光催化活性成分的捕获实验,我们发现空穴、超氧负离子自由基和羟基自由基都发挥了一定的作用.最后,我们讨论了光催化机制,Z-机制光催化机制被认为是合理的.     

异质结构AgCl/Bi2WO6微米球制备、表征及其光催化性能

首先利用水热法制备了由纳米片组装的粒径为1.5–2μm的Bi2WO6微球,然后在微球表面沉积了不同含量的AgCl (5 wt%,10wt%,20wt%,30wt%),制备了异质结构AgCl/Bi2WO6微球光催化剂.利用X射线粉末衍射、扫描电镜、透射电镜、红外光谱、紫外-可见漫反射吸收等手段对所制的光催化剂进行表征,并以紫外光和可见光分别为光源,罗丹明B为降解对象测试了其光催化活性,考察复合不同含量的AgCl对Bi2WO6光催化剂的性能影响.结果表明,沉积AgCl对Bi2WO6的晶体结构、表面性能和光吸收性能没有产生明显影响,但大幅度提高了Bi2WO6的紫外和可见光催化活性.当复合20wt%AgCl时, AgCl/Bi2WO6光催化活性最佳,紫外光下比纯Bi2WO6提高了2.2倍,可见光下提高了1倍.这主要是由于形成的AgCl/Bi2WO6异质结能有效抑制光生电子和空穴的复合,从而提了其光催化性能.     

Synthesis and enhanced photocatalytic performance of graphene-Bi2WO6 composite

Graphene possesses excellent conductivity, adsorptivity, and controllability. The combination of photocatalysts and graphene will introduce these properties of graphene into photocatalysis. In this paper, graphene oxide-Bi(2)WO(6) composite was firstly prepared via in situ hydrothermal reaction in the presence of graphene oxide, then the graphene oxide was reduced by ethylene glycol and the graphene-Bi(2)WO(6) (G-BWO) composite was formed. The as-prepared graphene-Bi(2)WO(6) photocatalyst shows enhanced photocatalytic activity for the degradation of rhodamine B (RhB) under visible light (λ > 420 nm). The electronic interaction and charge equilibration between graphene and Bi(2)WO(6) lead to the shift of the Fermi level and decrease the conduction band potential, which has an important influence on the photocatalytic process. The enhanced photocatalytic activity could be attributed to the negative shift in the Fermi level of G-BWO and the high migration efficiency of photoinduced electrons, which may suppress the charge recombination effectively.     

可见光响应光催化剂BiYWO6的制备、表征及其完全分解水的研究

制备了一种可见光响应的光催化剂BiYWO6, 该体系是Bi2WO6-Y2WO6的伪二元固溶体, 其禁带宽度为2.71 eV. 其负载了助催化剂后, 可在紫外光和可见光下完全分解水生成氢气和氧气, 其中负载RuO2助催化剂的BiYWO6具有最好的光催化活性. 通过对光催化反应前后的BiYWO6和助催化剂的表面各元素的化学状态的研究证实了RuO2/BiYWO6体系的稳定性. 比较分析了BiYWO6的能带结构, 认为可见光完全分解水的性能可归因于Y和Bi在固溶体BiYWO6中形成了合适的能带结构.     

离子交换法制备高光催化活性Bi2WO6@Bi2S3异质结纳米片

社会经济快速发展的同时, 也带来了日益严峻的环境污染问题. 半导体光催化氧化技术因节能环保而在环境领域有广阔的应用前景. 作为最具有代表性的半导体光催化材料, TiO2因为其禁带宽度(3.2 eV)比较大, 只能被紫外光激发, 因而对太阳能的利用率较低. 作为一种最简单的含铋层状氧化物, Bi2WO6的禁带宽度(2.7 eV)相对较小, 可以部分利用太阳光中的可见光, 因而受到广大研究者的青睐. 但是, Bi2WO6光催化材料的可见光响应范围较窄, 仅能被波长小于450 nm的光激发, 且激发后的光生载流子容易复合, 导致光催化效率不高. 因此, 迫切需要对Bi2WO6光催化材料进行结构修饰与改性,采用拓展其光响应范围和抑制载流子复合, 来提高其光催化活性.本文采用离子交换法原位合成了具有核-壳结构的Bi2S3@Bi2WO6纳米片, 充分利用Bi2S3优良的可见光响应性能和半导体异质结光催化剂的构建, 来提高Bi2WO6的光催化活性. 结果表明, 随着Na2S·9H2O用量从0增加到1.5 g, 所得催化剂的光活性不断提高, X3B的降解速率常数由0.40×10-3min-1增加到6.6×10-3min-1, 催化剂活性提高了16.5倍. 当进一步增加Na2S·9H2O的用量时(1.5-3.0 g), 复合催化剂的光活性下降. 这是由于过多Na2S·9H2O的引入导致在催化剂表面生成了没有光活性的NaBiS2层(Bi2S3+ Na2S = 2NaBiS2), 占据了催化剂的活性位点, 阻碍了染料分子与催化剂的直接接触. Bi2WO6@Bi2S3异质结纳米片光活性的提高, 可归因于Bi2S3的敏化作用极大拓展了复合催化剂的光响应范围; 另一方面, Bi2WO6和Bi2S3两者之间的半导体异质结效应有效促进了光生载流子在空间的有效分离, 抑制了光生电子-空穴的复合, 从而提高了复合催化剂的催化效率. 本研究为其他半导体复合材料的原位生长制备提供了新的思路.     

增强光催化活性的3D分级结构Bi2W06微球及表面酸性

以KNO3为矿化剂,用水热法制备了3D分级结构Bi2WO6微球,通过XRD、SEM、BET对产物进行了表征．探讨了3D分级结构Bi2WO6微球可能的形成机理．以罗丹明B为模型污染物,研究了合成产物的光催化性质．结果表明：在紫外光下,RhB的降解以共轭结构断裂的光催化反应为主;而在可见光照射下,RhB的降解可能是光催化和光敏化共同作用的结果．进一步以吡啶为探针分子,通过吸附吡啶红外光谱探讨了Bi2W06表面酸性与光催化降解RhB之间的关系．研究显示,Bi2W06具有较强的表面酸性,增强了Bi2WO6与RhB分子之间吸附作用,有利于染料分子上的电子跃迁至催化剂上,易于发生光敏化和光催化反应。     

碳修饰钨酸铋光催化降解水体中的邻苯二甲酸酯

以Bi(NO3)3.5H2O、Na2WO4.2H2O为反应物,采用水热法,经由葡萄糖炭化合成了碳修饰Bi2WO6(C-Bi2WO6)催化剂;考察了C-Bi2WO6光催化降解3种邻苯二甲酸酯(PAEs)的催化性能.结果表明:C-Bi2WO6对PAEs的降解效果优于Bi2WO6,特别是在葡萄糖与Na2WO4.2H2O质量比约10∶100条件下得到的催化剂的催化性能最优.与此同时,当PAEs的pH=6时,降解效果最好;而PAEs的浓度也对PAEs的光催化降解有一定的影响.     

Photophysical properties and photocatalytic activities of bismuth molybdates under visible light irradiation

Aurivillius structure Bi(2)MoO(6) (BG: 2.70 eV) that is a low-temperature phase showed an intense absorption band in the visible light region and photocatalytic activity for O(2) evolution from an aqueous silver nitrate solution under visible light irradiation, among various bismuth molybdates (Bi(2)MoO(6), Bi(2)Mo(2)O(9), and Bi(2)Mo(3)O(12)) synthesized by solid-state and reflux reactions. Bi(2)Mo(3)O(12) (BG: 2.88 eV) also showed photocatalytic activity for O(2) evolution under full-arc irradiation of a Xe lamp (lambda > 300 nm). The photocatalytic activity of the Aurivillius structure Bi(2)MoO(6) prepared by the reflux method was dependent on the annealing temperature after the preparation. The crystallinity was the important factor for the activity. Calculation by the density functional method indicated that the conduction band of Aurivillius structure Bi(2)MoO(6) was made up of Mo 4d orbitals. It turned out that the visible-light absorption of this photocatalyst was due to the transition from the valence band consisting of O 2p orbitals to the conduction band. The corner-sharing structure of the MoO(6) octahedra contributed to the visible light response and the photocatalytic performance because excitation energy and/or photogenerated electron and hole pairs began to migrate easily in the Aurivillius structure.     

Facile in situ synthesis of the bismuth oxychloride/bismuth niobate/TiO(2) composite as a high efficient and stable visible light driven photocatalyst

Fe-ions modified mesoporous Bi(2)WO(6) nanosheets (Fe-Bi(2)WO(6)) were successfully synthesized via a simple two-step method, which involved a template-free hydrothermal process and a following impregnation treatment. The resultant products were characterized by XRD, TEM, XPS, EDX, ESR, UV-Vis, PL, and visible light photocatalytic measurements. Experimental results indicated that the addition of a small amount Fe-ions (optimized content at 0.1 wt.%) could evidently improve the activity of Bi(2)WO(6). The apparent reaction rate of Fe-Bi(2)WO(6)-0.1% (k, 0.099 min(-1)) was 3.2 times higher than that of Fe-Bi(2)WO(6)-0% (k, 0.031 min(-1)). The Fe-ions mainly existed as Fe(3+) and Fe(2+) ions, which were uniformly distributed on the surface of Bi(2)WO(6) nanosheets and some Fe(3+)-ions substituted Bi(3+)-ions in Bi(2)O(2) layers. Both of the concentration and state of Fe-ions played vital factors for the improved visible light photocatalytic activities.     

Cl-诱导的含氧空位原子层厚Bi2WO6的可控合成及其深度氧化NO性能

开发具有高量子效率的半导体光催化材料是极具前景的解决能源短缺和环境污染问题的策略.在已报道的诸多光催化材料中,超薄二维(2D)材料表现突出,凭借其高效的载流子分离传输性能备受研究者的青睐.然而,苛刻的合成条件、缺乏表面活性位点等问题制约了其应用.因此,温和可控地合成具有大量活性位点的原子层厚2D材料具有重要的意义.作为典型的Aurivillius氧化物,Bi₂WO₆具有独特的层状晶体结构和合适的能带位置;另一方面,其表面Bi?O键的能量较低,氧原子在缺氧条件下经热处理容易逸出,进而产生氧空位.已知氧空位引入是调节半导体能带组成和电子结构的有效手段,不仅能改善其光电性能,而且能提供反应活性位点;因此,Bi₂WO₆是设计合成具有大量活性位点(氧空位)的原子层厚2D材料的理想平台.基于此,本文拟开发温和可控的合成策略,制备表面相对干净的含氧空位原子层厚Bi₂WO₆材料,并将其用于大气污染物NO的氧化去除.本文首先通过理论计算预测了卤素离子在调控Bi₂WO₆晶体生长和表面氧空位引入方面的作用,发现卤素离子尤其是Cl^-不仅能减小原子层厚Bi₂WO₆的表面能(γ),使其稳定存在;而且能降低Bi₂WO₆(001)晶面上氧空位生成能(ΔE).受此启发,我们设计了Cl^-辅助的溶剂热法,成功制备了含表面氧空位的原子层厚Bi₂WO₆材料;并利用高分辨透射电镜技术、X射线光电子能谱等考察了Cl^-的存在形式,及其调控Bi₂WO₆晶体生长和表面氧空位形成的机理:Cl^-因为静电作用吸附在[Bi2O₂]²⁺层上,一方面抑制Bi₂WO₆原子层堆积;另一方面,Cl^-与[Bi2O₂]2+层上Bi原子成键,削弱相邻的Bi?O键,利于O原子逸出形成表面氧空位.在此基础上,将设计合成的含氧空位的原子层厚Bi₂WO₆材料用于空气污染物NO的光催化去除.结果表明,Cl^-辅助合成的BWO-Cl可见光催化去除NO的效率高达64%;且其氧化NO至NO3?的选择性为98%.为了进一步分析BWO-Cl在NO氧化反应中的高活性和高选择性的原因,进行了理论计算与光电化学测试、活性物种分析、原位漫反射红外光谱(in-situ DRIFTs)等表征.结果表明,反应的高活性源于材料原子层厚2D结构及其表面丰富的氧空位对光电性质的改善;高选择性则归因于氧空位增强了Bi₂WO₆吸附活化O₂为?O₂^?的能力,促使NO沿着热力学有利的路径氧化至NO3?.该工作初步展示了卤素离子在调控Bi₂WO₆晶体生长及表面氧空位引入方面的重要作用,对设计合成高活性的原子层厚2D材料具有指导意义;与此同时,材料在NO氧化方面展现出的高活性与高选择性也为构建高效的NO去除体系提供了新思路.     

Synthesis, characterization and visible light photocatalytic properties of Bi2WO6/rectorite composites

Visible light-induced Bi(2)WO(6)/rectorite (BR) composites were prepared by a sol-gel method. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectrum, Fourier transform infrared (FTIR) spectrum, X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmet-Teller (BET). The UV absorption edges of the BR-450 catalyst showed a marked red shift as compared to that of the pure Bi(2)WO(6). The photocatalytic activities of the as-prepared samples were evaluated by the photocatalytic degradation of 4BS dye in aqueous solution under visible light irradiation (>420 nm). The results showed that the BR-450 catalyst exhibited a strong adsorption capability and a higher photocatalytic degradation activity than the pure Bi(2)WO(6) for 4BS dye, which could be attributed to the synergetic effects of the adsorbability of rectorite and the photocatalytic property of Bi(2)WO(6) in it.     

Elucidating the structure-dependent photocatalytic properties of Bi2WO6: a synthesis guided investigation

Polycrystalline microspheres and single-crystalline microplates of Bi(2)WO(6) have been synthesized by ultrasonic spray pyrolysis. Herein, these materials are evaluated as photocatalysts for the visible light mediated degradation of rhodamine B, a model pollutant, and the results compared to those obtained with Bi(2)WO(6) prepared by traditional methods. The microplates, which displayed the best crystallinity and highest surface area, were anticipated to facilitate the greatest rate of dye photodegradation. However, the polycrystalline microspheres outperformed both the Bi(2)WO(6) microplates and traditional samples. To understand the origin of this result, the local and macroscale structures of the Bi(2)WO(6) samples were comprehensively characterized by spectroscopy techniques (diffuse reflectance, fluorescence, Raman, and X-ray photoelectron spectroscopy) as well as electron microscopy and diffraction. This analysis found that the enhanced performance of the Bi(2)WO(6) microspheres results from the expression of a hydrophilic surface, a low concentration of point defects, and a moderate surface area. This finding highlights the significant role synthesis plays in imparting structure and functionality to solid materials.     

Controllable synthesis and visible-light-responsive photocatalytic activity of Bi2WO6 fluffy microsphere with hierarchical architecture

Bismuth tungstate (Bi(2)WO(6)) has attracted great research interest as an important visible-light-responsive photocatalyst. In this paper, we report a facile hydrothermal route for the shape-controlled synthesis of micro/nanostructured Bi(2)WO(6), without adding surfactants or templates. The results show that various morphologies of Bi(2)WO(6) including coralloid spherical particles, packed nanosheets, fluffy microspheres, and plates can be obtained by adjusting the pH values of the precursors. The as-prepared porous fluffy microspheres with a hierarchical architecture synthesized at pH 8 exhibit the highest photocatalytic activity for the degradation of Rhodamine (RhB) under visible light irradiation. The photodegradation efficiency reaches as high as 99% within 20 min irradiation. This enhanced photocatalytic activity can be attributed to the unique porous structure and high BET surface area of fluffy microspheres with hierarchical architecture.     

盐辅助-超生喷雾热分解法合成中空Bi2WO6纳米微球去除NO的应用

氮氧化物(简称NOx,包括NO和NO2等)是形成二次有机气溶胶的重要前体物,其存在会严重影响空气质量并危害人类健康.目前用于NOx的去除的方法主要有过滤、物理吸附、热催化等.然而,这些技术存在高能耗及产生二次污染等缺点,严重制约其实际应用.近年来,光催化技术作为一种有效处理NOx的环保技术,因其具备在常温下高效处理低浓度NOx(大气污染浓度水平)的优点而获得广泛关注.最近,Bi2WO6光催化剂因其独特的层状结构以及特有的催化性质,表现出良好的可见光催化性能.Bi2WO6光催化性能与催化剂的形貌及尺寸大小密切相关,目前报道的Bi2WO6的形貌有片状、颗粒状、花状、中空微球等.其中,由小纳米颗粒堆积成的中空Bi2WO6微球因其大的比表面积和高的荷质传输速率,表现出显著优于其它形貌的光催化性能.目前已有少量关于中空结构Bi2WO6微球的制备方法的报道,这些方法均需引入纳米球状的"核"作为模板,并在其上生长Bi2WO6胶体颗粒,然后去除"核",从而得到中空结构.譬如,Shang等采用碳纳米球作为"核"制备出Bi2WO6微球,再通过煅烧手段去除碳"核".Thillai与合作者用硅球作为"核",为了得到中空结构Bi2WO6微球,用NaOH将硅"核"刻蚀.然而这类方法均涉及到复杂的制备过程和高昂的运行成本.超生喷雾热分解法是一种常见的制备尺寸可控的纳米球的方法.在之前的工作中,本研究组成功使用超声喷雾热解法制备出具有优良光催化活性的Bi2WO6实心微球.我们首次加入NaCl盐为模板,使用简单的超声喷雾热分解方法制备出具有中空结构的Bi2WO6微球光催化剂,合成过程无需采用复杂的除"核"手段.一系列表征表明:该微球由直径为41?148 nm的纳米片自组装而成,并在表面形成了不均匀分布的孔结构;并对Bi2WO6中空微球的生长机制做了详细的研究,考察了所制备Bi2WO6催化剂去除NO的效率.生长机制研究结果表明,NaCl盐在中空Bi2WO6微球的形成过程中发挥着关键性作用:(1)NaCl盐溶液在超生喷雾热分解法的高温过程中形成NaCl单晶并作为"核"模板,参与中空Bi2WO6微球的形成;(2)Na+离子有助于Bi2WO6微球的微结构-纳米片的生长;(3)Cl?离子有利于Bi2WO6微球表面微孔的形成;(4)NaCl模板水洗后留下中空结构的Bi2WO6微球;(5)NaCl盐也充当着多孔诱发剂,其水洗溢出过程会造成Bi2WO6微球表面的孔结构.性能测试表明,以NaCl盐为模板所制备的中空Bi2WO6微球表现出优异的光催化性能,其在模拟太阳光下去除NO的效率是未添加模板的1.7倍、以KCl为模板的1.5倍、以Na2SO4为模板的1.2倍.BET和DRS分析表明,中空结构Bi2WO6微球具有大的比表面积和高的可见光吸收,对提高催化性能起到重要作用.ESR测试结果表明,?OH和?O2?是中空Bi2WO6微球的光催化反应过程的主要活性物种,?O2?的产生有助于提高光催化剂降解NO的耐受性.     

Ti(Ⅳ)掺杂Bi_2O_3电子结构和可见光催化活性的原理

密度泛函理论(DFT)计算对掺杂体系新型环境光催化剂设计开发具有指导意义.基于DFT框架下的第一性原理平面波超软赝势方法(USPP),对α、β、γ、δ-Bi2O3晶体几何结构分别进行了优化计算,从理论上得到了Bi2O3的总体态密度(TDOS)和Bi、O原子的分波态密度(PDOS).在此基础上对Bi2O3超晶胞进行Ti(IV)的掺杂计算,讨论了Ti(IV)掺杂对各种Bi2O3的电子结构和光吸收特性的影响.结果表明Ti(IV)掺杂Bi2O3晶体后,Ti(IV)的3d轨道进入禁带并与O2p、Bi6p轨道作用,使禁带宽度(Eg)变小,Bi2O3的吸收边红移,从而有助于Bi2O3光催化活性的改善.通过水热合成法制备的Ti(IV)掺杂Bi2O3样品的紫外-可见光漫反射光谱验证了计算的结果.在光催化降解有机染料结晶紫的实验中,光催化剂活性的改善进一步得到证实.     

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.     

A templated method to Bi2WO6 hollow microspheres and their conversion to double-shell Bi2O3/Bi2WO6 hollow microspheres with improved photocatalytic performance

Bi(2)WO(6) hollow microspheres with dimension of ca. 1.5 μm were synthesized via a hydrothermal method using polystyrene particles as the template. The as-prepared Bi(2)WO(6) hollow microspheres can be further transformed to double-shell Bi(2)O(3)/Bi(2)WO(6) hollow microspheres. The samples were fully characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM, N(2)-sorption Brunauer-Emmett-Teller surface area, UV-vis diffuse-reflectance spectroscopy, and X-ray photoelectron spectroscopy. The as-formed double-shell Bi(2)O(3)/Bi(2)WO(6) hollow microspheres exhibit enhanced photocatalytic activity due to the hollow nature and formation of the p-n junction between p-type Bi(2)O(3) and n-type Bi(2)WO(6). The study provides a general and effective method in the fabrication of composition and dimension-tunable composite hollow microspheres with sound heterojunctions that may show a variety of applications.     

Visible light-induced photocatalysis through surface plasmon excitation of platinum-metallized titania for photocatalytic bleaching of rhodamine B

Abstract  

Nanocomposites consisting of titania nanoparticles and metallic platinum were prepared via a soft chemical reduction method. The detailed structural, compositional, and optical characterization and physicochemical properties of the obtained products were analyzed by X-ray diffraction, nitrogen adsorption, Raman spectroscopy, UV–Vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, and FT-IR spectroscopy techniques. Employing photodegradation of rhodamine B as the model reaction, we found that the as-prepared Pt/TiO₂ nanocomposite showed an excellent photocatalytic oxidation activity under visible light irradiation. On the basis of these results, the intrinsic mechanism of visible light-induced photocatalytic oxidation of organic compounds on the platinized titania is proposed and discussed. The superior visible light-driven photocatalytic efficiency of the Pt/TiO₂ nanocomposite photocatalyst can be ascribed to the high efficiency of charge-pair separation due to the presence of deposited Pt serving as electron sinks to retard the rapid e⁻–h⁺ couple recombination; the good photoabsorption capacity in the visible light region; and the higher concentration of surface hydroxyl groups, which are able to effectively scavenge photogenerated valence band holes. Accumulation of the holes at the catalyst surface increases the probability of the formation of OH· as a reactive species that readily oxidizes the organic dye molecule.