Au Nanoparticles Supported Nanoporous ZnO Sphere for Enhanced Photocatalytic Activity Under UV-Light Irradiation

Monodispersed 200 nm-sized ZnO spheres (SPs) with porous structure emanating from 8 nm zinc oxide nanoparticles (NPs) composing the SPs were synthesized by dissolving zinc acetate dihydrate in diethylene glycol at 160 °C. The prepared SPs were employed in fabricating the gold (Au) loaded ZnO (Au/ZnO SP) composite materials, exhibiting high photocatalytic activity in decomposing salicylic acid under UV-light irradiation. It is deduced that its high catalytic activity originates from the charge separation by transferring photoinduced electrons from the conduction band (CB) of ZnO to Au, since the CB level of ZnO (?0.5 V vs. NHE) is located more negative side than that of Au (+0.5 V vs. NHE). The evidence for the charge separation was provided by monitoring^.OH radical with bare ZnO SPs and Au/ZnO SP produced in the solution which readily react with 1,4-terephthalic acid (TA) inducing 2-hydroxy terephthalic acid (TAOH) that shows unique fluorescence peak at 426 nm.     

Au纳米粒子负载的ZnO空心球复合材料的光生电荷转移行为及光催化活性

通过简单的两步法合成了不同负载量的Au/ZnO空心球。采用扫描电子显微镜(SEM),X射线衍射(XRD),X射线光电子能谱(XPS)及紫外-可见漫反射光谱(UV-Vis DRS)对样品的形貌、结构、组成和晶相等进行一系列的表征。以罗丹明B (RhB)为目标降解物,探究了Au/ZnO空心球的光催化活性。结果表明,适量Au修饰的ZnO光催化剂在混合光下20 min内对RhB的降解率达到73%。利用表面光电压谱(SPS)和瞬态光电压(TPV)技术,探讨了Au修饰后对ZnO光诱导电荷转移行为与光催化性能之间的关系。结果表明,混合光照下Au/ZnO空心球光降解性能的提高主要归因于作为电子受体的Au纳米粒子与ZnO之间形成的强的电子相互作用。适量Au纳米粒子的负载能够提高ZnO空心球中光生载流子的分离效率,相应地延长载流子的传输时间,增加光生电荷的寿命,从而促进其光催化活性的提高。     

Ta2O5空心球的制备及光催化性能

采用无皂乳液聚合法合成了粒径为500 nm的聚苯乙烯(PS)球。运用层层自组装技术在PS球表面交替沉积单分子层的TaO3纳米页与聚二烯丙基二甲基氯化铵(PDDA)多层膜,650℃煅烧除去PS模板和PDDA高分子层后,得到Ta2O5空心球。空心球的直径为500 nm左右,壁厚约10 nm。XRD结果显示该空心球为正交晶系Ta2O5。空心结构显著提高了Ta2O5的光催化活性,在紫外光照射60 min后,Ta2O5空心球降解亚甲基蓝达90%以上,而商品Ta2O5只能降解28%。     

ZnO/BiOI微球的合成及其光催化性能

通过一步溶剂热法合成ZnO/BiOI纳米复合材料,在Bi（NO₃）₃·6H₂O、KI、ZnO和乙二醇（EG）溶剂中,制备出的样品尺寸和形貌采用X射线粉末衍射（XRD）、场发射扫描电镜（FESEM）、高分辨透射电镜（HRTEM）、紫外-可见漫反射光谱（DRS）、X射线光电子能谱（XPS）、N₂吸附-脱附等,对实验所得产物的组成、结构及光学性质等进行表征。以染料罗丹明B（RhB）水溶液和气态乙醛作为降解对象,采用BiOI、ZnO/BiOI和ZnO微纳材料作为光催化剂,通过对BiOI、ZnO/BiOI和ZnO微纳材料在可见光下光催化降解染料罗丹明B（RhB）水溶液和气态乙醛,结果表明多孔微纳材料的ZnO/BiOI具有更高的降解效率,实验表明多孔微纳材料的ZnO/BiOI具有更高的氧空位浓度,因此使其催化活性增强,讨论了其可能的催化活性机理。     

ZnO/CdS复合材料的合成与可见光催化性能

采用喷雾辅助气相沉积法在水热法合成的ZnO纳米线上沉积CdS纳米颗粒。采用X射线衍射仪（XRD）、激光拉曼仪（Raman）、扫描电镜（SEM）、透射电镜（TEM）、X射线光电子能谱分析谱（XPS）和紫外可见漫反射光谱等测试手段对复合光催化剂进行表征。结果表明,3~10 nm的CdS纳米粒子修饰在直径约为100 nm ZnO纳米线的表面。XPS和Raman表明复合材料中ZnO和CdS之间存在化学相互作用。可见光催化降解罗丹明B实验结果表明ZnO/CdS复合材料的催化性能优于单相CdS或ZnO,沉积时间为30 s合成的ZnO/CdS速率常数分别是CdS和ZnO的2.91和4.03倍,且具有较高的稳定性。ZnO/CdS复合材料光催化性能增强的可能原因为光吸收范围的拓展和光生载流子分离效率的提高。     

水热合成掺Fe氧化锌复合材料及其光催化活性

以Zn(Ac)2•2H2O、Fe(NO3)3•9H2O和NaOH为原料,采用水热法合成了Fe掺杂ZnO复合材料。并用x射线衍射和扫描电子显微镜技术对合成样品的结构和形貌进行了表征,Fe掺杂ZnO合成产物为直棒状,直径为500 nm,长度为3 µm左右。样品的紫外可见漫反射分析,在300~500 nm紫外可见光区域均有强的吸收。利用Fe掺杂ZnO作为光催化剂降解有机染料,发现对于光催化降解有机染料有较好的降解功能,且光降解性能优于纯ZnO材料。     

ZnO/BiOI微球的合成及其光催化性能

通过一步溶剂热法合成ZnO/BiOI纳米复合材料,在Bi（NO₃）₃·6H₂O、KI、ZnO和乙二醇（EG）溶剂中,制备出的样品尺寸和形貌采用X射线粉末衍射（XRD）、场发射扫描电镜（FESEM）、高分辨透射电镜（HRTEM）、紫外-可见漫反射光谱（DRS）、X射线光电子能谱（XPS）、N₂吸附-脱附等,对实验所得产物的组成、结构及光学性质等进行表征。以染料罗丹明B（RhB）水溶液和气态乙醛作为降解对象,采用BiOI、ZnO/BiOI和ZnO微纳材料作为光催化剂,通过对BiOI、ZnO/BiOI和ZnO微纳材料在可见光下光催化降解染料罗丹明B（RhB）水溶液和气态乙醛,结果表明多孔微纳材料的ZnO/BiOI具有更高的降解效率,实验表明多孔微纳材料的ZnO/BiOI具有更高的氧空位浓度,因此使其催化活性增强,讨论了其可能的催化活性机理。     

不同表面形貌Cu2O空心球的制备及光催化性能

采用一步溶剂热法,以Cu(NO_3)_2·3H_2O为铜源,乙二醇(EG)为还原剂,聚乙烯吡咯烷酮(PVP)为表面活性剂,高温条件下制备形貌可控的Cu_2O空心球纳米材料。研究Cu(NO_3)_2·3H_2O与PVP的质量比值(w_(Cu(NO_3)_2·3H_2O)/w_(PVP))对Cu2O结构、形貌、比表面积以及光吸收特性的影响,并结合光催化机理讨论其对Cu_2O光催化性能的影响。此外,通过改变反应时间来研究Cu_2O的生长过程。结果表明,w_(Cu(NO_3)_2·3H_2O)/w_(PVP)=45时,得到的形貌为空心球表面覆盖纳米刺的Cu_2O纳米材料光催化性能最佳,在可见光辐照10 min的条件下,对甲基橙的降解率达94.3%。     

Fe掺杂ZnO空心微球的制备与光催化性能

ZnO是一种重要的Ⅱ-Ⅵ族半导体材料,其能带宽度约为3.37eV,在光电子学、传感、光催化、发电等诸多领域都具有巨大的应用潜力。本文采用简单的离子交换和热蒸发法成功制备了Fe掺杂ZnO空心微球,并利用扫描电镜、透射电镜、X射线粉末衍射仪对其形貌、结构以及成分等进行了详细的表征。光吸收测试证明Fe元素掺杂能够扩展ZnO的光吸收波段,实现波长375~600nm的光波吸收。另外,光催化实验证明Fe掺杂ZnO空心微球能够有效地促进罗丹明B的降解,表明合成的Fe掺杂ZnO空心微球是一种优异的光催化剂。     

Template-free polyoxometalate-assisted synthesis for ZnO hollow spheres

ZnO hollow spheres with diameters ranging from 400 to 600 nm and the thickness of shell approximate 80 nm were synthesized by a simple polyoxometalate-assisted solvothermal route without using any templates. The effect of polyoxometalate concentration, reaction time and temperature on the formation of the hollow spheres was investigated. The results indicated that the hollow spheres were composed of porous shells with nanoparticles and polyoxometalate play a key role in controlling morphology of ZnO. A possible growth mechanism based on polyoxometalate-assisted assembly and slow Ostwald ripening dissolution in ethanol solution is tentatively proposed. In addition, the room temperature photoluminescence spectrum showed that the ZnO hollow spheres exhibit exciting emission features with wide band covering nearly all the visible region.     

可移动金核的二氧化钛空心球合成及光催化性质

Uniform hollow Au@TiO₂ core shell spheres with moveable Au nanoparticles were synthesized based on templating against Au@carbon spheres. The diameter of the shell of the Au@TiO₂ spheres could be controlled by adjusting the Ti(OC₄H₉)₄ hydrolyzing reaction time or the ratio of Ti(OC₄H₉)₄ to Au@carbon spheres, and the shell thickness of the core-shell spheres can be varied from 25 nm to 40 nm. As prepared hollow Au@TiO₂ core-shell spheres display enhanced photocatalytic activity in the initial stage of photocatalytic degradation of methylene blue compared with pure hollow TiO₂ spheres and the commercial photocatalyst TiO₂(P-25).     

不同形貌氧化锌的微波水热法制备及其光催化性能

采用微波水热法在乙二醇的辅助下,制备出一系列不同形貌的氧化锌(Zn O)纳米/微米颗粒。扫描电子显微镜测试结果表明,乙二醇的加入量对样品的形貌有着非常显著的影响,通过控制乙二醇的加入量,可以得到不规则片状、六方棱柱孪晶、梭子形和球形等形貌的Zn O纳米/微米颗粒。从微波反应器检测压力结果可以看出,乙二醇的加入量对反应体系的压力影响非常显著,这起到了调控纳米晶生长速度的效果进而得到不同形貌的样品。在此基础上,系统测试了样品在氙灯照射下光催化降解罗丹明B的能力,结果表明,乙二醇加入量大于12 m L时的球状样品光催化效率要远高于其他样品,在50 min内能完成对罗丹明B的降解。     

砚状ZnO/石墨烯复合物的制备及其光催化性能

采用一步溶液法制备了具有砚状形貌的ZnO/石墨烯复合材料。利用扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)等研究不同制备条件下ZnO形貌、石墨烯的复合状态和砚状ZnO的生长机理;通过测试300W氙灯对甲基蓝溶液(MB)的光催化效率,研究制备条件、形貌结构对复合物的光催化性能的影响;通过对复合物光致发光(PL)光谱以及紫外-可见光谱测试,研究石墨烯复合物对光生电子-空穴对的复合以及光吸收效率的影响。研究结果表明,砚状ZnO的生长机理为掏蚀机理;复合石墨烯增强了这种ZnO的光吸收效率、降低了ZnO的带隙,并且降低了光生电子-空穴对复合几率,有利于提高光催化性能;砚状ZnO的砚底上表面粗糙,有利于反应面积的增加,砚底的厚度较薄,有利于光生电子-空穴对在较强的内建电场下迅速向相反方向分离,降低其复合几率,从而使其具有优异的光催化性能。     

Heterointerface Engineering of ZnO/CdS Heterostructures through ZnS Layers for Photocatalytic Water Splitting

Solar-driven water splitting to produce clean and renewable hydrogen offers a green strategy to address the energy crisis and environmental pollution. Heterostructure catalysts are receiving increasing attention for photocatalytic hydrogen generation. ZnO/ZnS/CdS and ZnO/CdS heterostructures have been successfully designed and prepared according to two different strategies. By introducing a heterointerface layer of ZnS between ZnO and CdS, a Z scheme charge-transfer channel was promoted and achieved superior photocatalytic performance. A highest hydrogen generation rate of 156.7 μmol g⁻¹ h⁻¹ was achieved by precise control of the thickness of the heterointerface layer and of the CdS shell. These findings demonstrated that heterostructures are promising catalysts for solar-driven water splitting, and that heterointerface engineering is an effective way to improve the photocatalytic properties of heterostructures.     

Au Modified F-TiO2 for Efficient Photocatalytic Synthesis of Hydrogen Peroxide

In this work, Au-modified F-TiO₂ is developed as a simple and efficient photocatalyst for H₂O₂ production under ultraviolet light. The Au/F-TiO₂ photocatalyst avoids the necessity of adding fluoride into the reaction medium for enhancing H₂O₂ synthesis, as in a pure TiO₂ reaction system. The F⁻ modification inhibits the H₂O₂ decomposition through the formation of the ≡Ti–F complex. Au is an active cocatalyst for photocatalytic H₂O₂ production. We compared the activity of TiO₂ with F⁻ modification and without F⁻ modification in the presence of Au, and found that the H₂O₂ production rate over Au/F-TiO₂ reaches four times that of Au/TiO₂. In situ electron spin resonance studies have shown that H₂O₂ is produced by stepwise single-electron oxygen reduction on the Au/F-TiO₂ photocatalyst.     

Binary Au/MWCNT and Ternary Au/ZnO/MWCNT Nanocomposites: Synthesis,Characterisation and Catalytic Performance

Gold nanoparticles of 10–24 and 5–8 nm in size were obtained by chemical citrate reduction and UV photoreduction, respectively, on acid‐treated multiwalled carbon nanotubes (MWCNTs) and on ZnO/MWCNT composites. The shape and size of the deposited Au nanoparticles were found to be dependent upon the synthetic method used. Single‐crystalline, hexagonal gold particles were produced in the case of UV photoreduction on ZnO/MWCNT, whereas spherical Au particles were deposited on MWCNT when the chemical citrate reduction method was used. In the UV photoreduction route, n‐doped ZnO serves as the e^? donor, whereas the solvent is the hole trap. All materials were fully characterised by UV/Vis spectroscopy, scanning electron microscopy, transmission electron microscopy, X‐ray photoelectron spectroscopy, Raman spectroscopy and BET surface analysis. The catalytic activity of the composites was studied for the selective hydrogenation of α,β‐unsaturated carbonyl compound 3,7‐dimethyl‐2,6‐octadienal (citral). The Au/ZnO/MWCNT composite favours the formation of unsaturated alcohols (selectivity=50 % at a citral conversion of 20 %) due to the presence of single‐crystalline, hexagonal gold particles, whereas saturated aldehyde formation is favoured in the case of the Au/MWCNT nanocomposite that contains spherical gold particles.     

中空碳球合成方法及其电化学应用进展

中空碳球由于具有大的比表面积、良好的导电性以及高的化学稳定性等优异性能,现已被广泛地用于电化学储能、电化学催化和电化学传感领域。基于此,本文主要概述了中空碳球的各种合成方法及在电化学领域的研究进展,并对该领域面临的挑战及未来的发展方向进行了讨论。     

原位碳、氮共掺杂二氧化钛空心球的制备与可见光光催化性能

在H₂O₂-HF 的乙醇-水混合溶液中, 通过水热处理碳氮化钛(TiCN)制备了碳、氮共掺杂TiO₂ 空心球(CNTH). 用X 射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X 射线光电子能谱(XPS)和紫外-可见(UV-Vis)吸收光谱表征了所制备的样品. 在可见光(λ≥400 nm)照射下, 通过降解甲基蓝检测了碳、氮共掺杂TiO₂空心球的光催化活性. 结果表明, 源于TiCN中的部分碳和氮原子原位掺入了TiO₂的晶格中, 部分碳掺入TiO₂点阵的间隙中. 该材料在整个可见光区展示了增强的可见光吸收, 其带边明显红移. 光催化研究表明在强可见光吸收和独特的空心球结构的协同作用下, 碳、氮共掺杂TiO₂空心球展示了比P25更高的可见光光催化活性.     

Water Detoxification: Photocatalytic Decomposition of Phenol on Au/TiO2

 Photodeposition of gold on TiO₂ was conducted in situ in the photoreactor used for the reaction of phenol photodestruction. The Au/TiO₂ system shows better photocatalytic properties in the destruction of phenol contaminants in water than pure TiO₂. The gold cocatalyst prevents also the decrease of the rate of the photocatalytic reaction at higher phenol concentration observed for pure TiO₂. Hydroquinone, p-benzoquinone, and catechol are main intermediates of the photoreaction, which finally leads to total phenol mineralization.