Enhanced Raman scattering and photocatalytic activity of Ag/ZnO heterojunction nanocrystals

In this work, we study the enhancement of Raman signals and photocatalytic activity of Ag/ZnO heterojunctions with an Ag content of 1 at.%, which were synthesized by photochemical deposition of Ag nanoparticles onto pre-synthesized ZnO nanorods. A strong interaction between Ag and ZnO nanocrystals were evidenced by XPS and UV-vis spectroscopy. The binding energy of Ag nanoparticles shifts toward lower energy compared to that of pure Ag nanoparticles, revealing that electrons transfer from Ag to the ZnO nanocrystals. The red shift of the plasmon absorption peak of Ag nanoparticles in Ag/ZnO heterojunctions further confirms the strong interaction between the two components. This strong interaction, arising from the coupling between Ag and ZnO nanocrystals, is responsible for the enhancement of Raman signals and photocatalytic activity of the Ag/ZnO heterojunctions.     

Microwave-assisted solution synthesis and photocatalytic activity of Ag nanoparticles supported on ZnO nanostructure flowers

Ag nanoparticles supported on the surface of three-dimensional (3D) flower-like ZnO nanostructure were synthesized by a microwave-assisted solution method. The obtained products were characterized by X-ray diffraction analysis, field-emission scanning electron microscopy, Fourier-transform infrared spectroscopy, Raman spectrophotometry, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy. The analytical results confirmed homogeneously distributed Ag nanoparticles supported on the surface of flower-like ZnO nanostructure. The photocatalytic effect of the heterostructure Ag/ZnO nanocomposites was investigated using photodegradation under ultraviolet (UV) light of methylene blue as model dye. The heterostructure Ag/ZnO nanocomposites exhibited much higher photocatalytic activity than pure ZnO flowers. The improved photocatalytic properties are attributed to formation of a Schottky barrier at the metal–semiconductor interface of the Ag/ZnO nanocomposites.     

Ag/ZnO/ZnSe三元异质结的合成及其可见光光催化性能

以Ag纳米线为模板,通过两步水浴法合成了Ag/ZnO/ZnSe三元异质结光催化材料。利用场发射扫描电子显微镜(FESEM)、X射线能谱仪(EDS)、X射线衍射仪(XRD)以及透射电子显微镜(FETEM)对样品的形貌和结构进行了表征。结果显示,Ag/ZnO/ZnSe三元异质结为蠕虫状的Ag/ZnO二元异质结外镶嵌着ZnSe小颗粒。在可见光下,对比纯Ag纳米线、纯ZnO纳米球、Ag/ZnO异质结对罗丹明B的可见光降解效率,结果发现Ag/ZnO/ZnSe异质结表现出了更高的光催化效率。其光催化性能的提高主要是由于Ag/ZnO/ZnSe异质结的作用促使电子空穴对的分离,降低了电子空穴对的复合机率,从而提高了材料的光催化效率。     

Ag/ZnO纳米纤维的制备及光催化性能

采用静电纺丝技术及煅烧法制备了氧化锌纳米纤维, 然后采用水热法将银纳米颗粒负载到了氧化锌纳米纤维表面. 利用X射线衍射(XRD)、 X射线光电子能谱(XPS)、 能量色散X射线光谱(EDX)、 扫描电子显微镜(SEM)及透射电子显微镜(TEM)等技术对合成的Ag/ZnO纳米纤维的结构和组成进行了表征. SEM结果表明, 直径在5~100 nm之间的银纳米颗粒附着在直径在80~330 nm之间的氧化锌纤维表面形成了异质结构. 以常见的有机污染物甲基橙、 亚甲基蓝和罗丹明B等为降解底物, 对Ag/ZnO纳米纤维的光催化性能进行了表征. 结果表明, 负载银纳米颗粒后, 复合催化剂的光催化性能明显提高.     

Ag/ZnO/ZnSe三元异质结的合成及其可见光光催化性能

以Ag纳米线为模板,通过两步水浴法合成了Ag/Zn O/Zn Se三元异质结光催化材料。利用场发射扫描电子显微镜(FESEM)、X射线能谱仪(EDS)、X射线衍射仪(XRD)以及透射电子显微镜(FETEM)对样品的形貌和结构进行了表征。结果显示,Ag/Zn O/Zn Se三元异质结为蠕虫状的Ag/Zn O二元异质结外镶嵌着Zn Se小颗粒。在可见光下,对比纯Ag纳米线、纯Zn O纳米球、Ag/Zn O异质结对罗丹明B的可见光降解效率,结果发现Ag/Zn O/Zn Se异质结表现出了更高的光催化效率。其光催化性能的提高主要是由于Ag/Zn O/Zn Se异质结的作用促使电子空穴对的分离,降低了电子空穴对的复合机率,从而提高了材料的光催化效率。     

ZnO纳米柱状阵列表面AgX等离子基元修饰及其可见光光催化活性

采用浸渍法制备了表面AgX（X=I,Br）等离子基元修饰的ZnO纳米柱状阵列,研究了浸渍浓度和时间以及紫外光光照预处理对ZnO纳米柱状阵列可见光光催化活性的影响.采用场发射扫描电子显微镜、X射线衍射仪、紫外可见漫反射吸收光谱以及X射线光电子能谱仪等手段对ZnO纳米柱状阵列的形貌、相组成、禁带宽度及其表面特性进行了表征.结果显示,AgBr颗粒分布于ZnO纳米柱状阵列的顶端及顶端侧面,同时AgBr颗粒之间相互接触而形成网状结构.通过紫外光光照预处理,AgBr表面出现细小颗粒,形成Ag/AgBr/ZnO纳米复合结构.可见光光催化降解甲基橙结果表明,在相同工艺条件下所制AgBr/ZnO的可见光光催化活性明显优于AgI/ZnO,且与浸渍浓度及时间有关.由于ZnO纳米柱状阵列的比表面积大,AgBr的可见光响应特性以及Ag/AgBr纳米结构的表面等离子效应,经过紫外光光照预处理形成的Ag/AgBr/ZnO纳米复合结构表现出最好的可见光光催化活性.     

纳米Ag/ZnO光催化剂及其催化降解壬基酚聚氧乙烯醚性能

采用氨浸法制备了不同Ag负载量的纳米Ag/ZnO光催化剂,并用X射线衍射、比表面积测定、X射线光电子能谱和漫反射紫外-可见光谱测定了Ag/ZnO的晶型结构、比表面积、表面组成和光谱特征.以壬基酚聚氧乙烯醚(NPE-10)为模型污染物,分别在紫外光和可见光照射下考察了纳米Ag/ZnO的光催化活性.结果表明,Ag能成功地负载到ZnO表面,且随着Ag负载量的增加,ZnO的粒径逐渐增大,比表面积逐渐减小.与纳米ZnO样品相比,Ag/ZnO中Ag 3d5/2结合能减小,而Zn 2p和O 1s结合能增大,ZnO表面的羟基氧和吸附氧含量增加.当Ag负载量大于0.5%时,Ag/ZnO样品的吸收光谱发生红移,在可见光区出现吸收.光催化降解结果表明,0.5%Ag/ZnO样品的光催化活性最高,在紫外光和可见光照射3 h后NPE-10降解率分别约为77%和56%,而ZnO样品的光催化活性仅约为61%和40%.     

花状ZnO/ZnS异质结构的简易合成、结构表征及光催化活性

采用简便的两步溶液相化学方法,在较低温度下(80℃),制备出了花状的ZnO/ZnS异质结构。分别利用X射线衍射、X射线光电子能谱仪、扫描电子显微镜、透射电子显微镜、紫外-可见光谱仪等测试手段对所制备的样品进行表征,结果表明ZnO/ZnS异质结构是由花状ZnO纳米结构和ZnS纳米粒子组成。在光降解罗丹明B(RhB)的测试中,ZnO/ZnS异质结构样品体现出了比ZnO前驱物和商业P25光催化剂更高的光催化效率,这主要可归因于异质结构更有利于电子-空穴的有效分离。ZnO/ZnS光催化剂体现出良好的循环稳定性。     

Fabrication of urchin‐like Ag/ZnO hierarchical nano/microstructures based on galvanic replacement mechanism and their enhanced photocatalytic properties

Urchin‐like Ag/ZnO hierarchical nano/microstructures have been synthesized through a facile low‐temperature hydrothermal growth method based on galvanic replacement mechanism. The experimental results show that the urchin‐like Ag/ZnO heterostructures are formed through the epitaxial growth of ZnO nanorods on the {111} facets of Ag nanoparticles along their own c‐axis. The photocatalytic properties of the products were evaluated by the degradation of RhB dye solution under ultraviolet irradiation, and the results show that the products exhibit significantly enhanced photocatalytic properties comparing with pure ZnO nanorods. The products with a Ag content of 35.64 atom % prepared with a Ag⁺ concentration in solution of 5 mM exhibit surprisingly high degradation rate (99.5%) for RhB dye solution (4 mg/L) after photocatalytic reaction for only 14 min under ultraviolet irradiation. The Schottky barrier formed at the metal‐semiconductor interfaces improves the segregation of charges and prevents the charge recombination, and thus significantly enhances the photocatalytic activities of the products. On the other hand, the high stability of the urchin‐like Ag/ZnO hierarchical nano/microstructures can effectively prevent the aggregation of nanostructures with simultaneously preserving high photocatalytic properties due to the existence of nanosized unites. Copyright © 2016 John Wiley & Sons, Ltd.     

Pd/ZnO和Ag/ZnO复合纳米粒子的制备、表征及光催化活性

 用焙烧前驱物碱式碳酸锌的方法制备了ZnO纳米粒子，采用光还原沉积贵金属的方法制备了Pd／ZnO和Ag／ZnO复合纳米粒子，并利用ICP，XRD，TEM和XPS等测试技术对样品进行了表征，初步探讨了贵金属在ZnO纳米粒子表面形成原子簇的原因．以光催化氧化气相正庚烷为模型反应，考察了样品的光催化活性以及贵金属沉积量对催化剂活性的影响．结果表明：沉积适量的贵金属，ZnO纳米粒子光催化剂的活性大幅度提高．同时，深入探讨了表面沉积贵金属的ZnO纳米粒子光催化剂活性有所提高的内在原因．     

梨形核壳结构氧化锌/银亚微米球的制备、表征及光学性能

利用亚锡离子还原银离子生成的金属银沉积在合成的梨形氧化锌表面作为晶种,进一步生长银纳米粒子,制备了梨形的、核壳结构的、单分散的氧化锌/银亚微米球。利用X射线衍射、透射电镜、能量色散X射线谱、紫外可见吸收谱及光致发光谱对所制备样品的形貌、微观结构、组成和光学性能进行了表征。结果表明:(1)样品是由梨形亚微米氧化锌核和银纳米颗粒壳组成;(2)在氧化锌表面的银纳米粒子作为光激发产生的电子捕获剂提高了光产生的载流子的分离效率,在能量没有改变的情况下减少了紫外发射光的强度,淬灭了可见发射光。     

ZnO/Ag微米球的合成与光催化性能

用微波辅助多元醇法对预先制备的ZnO微米球进行修饰,合成了载银氧化锌微米球（ZnO/Ag）. 利用X射线衍射仪、场发射扫描电子显微镜、透射电子显微镜、X射线光电子能谱仪、紫外-可见双光束分光光度计和光致发光光谱仪等对样品的结构、形貌和光学性能进行了表征. 在紫外光照射下,通过亚甲基蓝的降解反应研究了样品的光催化活性. 结果表明,所制备的ZnO/Ag微米球是由面心立方的Ag纳米颗粒附着在纤锌矿结构的ZnO球表面形成;与ZnO相比,ZnO/Ag的紫外-可见光吸收光谱发生明显红移,在紫外和可见光范围均有较强的吸收;随着Ag含量的增加,ZnO/Ag荧光光谱强度先减弱后增强;与ZnO相比,ZnO/Ag的光催化活性明显提高,AgNO₃ 浓度为0.05 mol/L时制得的ZnO/Ag光催化活性最高.     

Efficient photodegradation of resorcinol with Ag2O/ZnO nanorods heterostructure under a compact fluorescent lamp irradiation

Ag₂O/ZnO heterostructure has been recently synthesized using a facile chemical-precipitation method. X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectroscopy results confirmed the Ag₂O nanoparticles loading on ZnO nanorods. The Ag₂O addition increased the visible light absorption ability and a red shift for Ag₂O/ZnO heterostructure appeared when compared to pure ZnO. Photoluminescence spectra showed lower emission yield on the Ag₂O/ZnO heterostructure than on pure ZnO. Such a decrease in the emission yield represents the fraction of the excited state Ag₂O sensitizer involved in the charge injection process. Under compact fluorescent lamp irradiation, the Ag₂O/ZnO heterostructure demonstrated higher photocatalytic activity than pure ZnO in the degradation of resorcinol, which can be attributed to the high separation efficiency of the photogenerated electron-hole pairs based on the cooperative roles of Ag₂O loading on ZnO nanarods. All these characteristics represent a significant contribution of the Ag₂O/ZnO heterostructure to the practical applications in indoor environmental remediation.     

Defect-enhanced Photocatalytic Activity of ZnO Micro/nanostructures

ZnO micro/nanocrystals with controlled oxygen defects are successfully prepared through annealing precursors obtained via a simple solvothermal method. The size and surface defects of the as-synthesized ZnO mi- cro/nanocrystals increase with the solvent volume ratio of water/ethanol increasing; the BET surface areas of the corresponding samples decrease during these processes; photoluminescence reveals that the type and concentration of surface defects （oxygen vacancy and interstitial oxygen） are quite different for the samples prepared via different solvent volume ratio of water/ethanol. In addition, it is found that the photocatalytic activity of the synthesized ZnO nanocrystals is mainly dependent on the concentration of surface defects. The sample with more surface defects ex- hibits higher photocatalytic activity toward the degradation of methylene blue （MB）. The possible photocatalytic mechanism is discussed in detail.     

富表面氧空位Fe2O3/ZnO催化剂在光催化合成氨中的应用

光催化合成氨是一种绿色节能的合成氨技术,设计制造丰富的表面氧空位和异质结构是促进氮分子活化和抑制电子-空穴复合的重要方法。我们以乙二醇作为还原剂,采用溶剂热法制备合成了Fe2O3/ZnO光催化剂,利用X射线衍射(XRD)、透射电镜(TEM)、电子顺磁共振(EPR)、紫外-可见漫反射(UV-Vis DRS)、荧光光谱(PL)及光电流(PC)对Fe2O3/ZnO催化剂进行表征,并考察了Fe2O3/ZnO催化剂在常温、常压下的光催化合成氨的性能。4%Fe2O3/ZnO催化剂在无牺牲剂下用于光催化合成氨,有较好的光催化效率和稳定性,其合成氨效率达到2059μmol·L-1·g-1·h-1。其高催化效率归因于:可见光区域吸收的提高、氮分子在表面氧空位与Fe3+活性中心上的协同活化及光生电子与空穴的高分离效率。     

Photocatalytic oxidation of organic dyes with nanostructured zinc dioxide modified with silver metals

Silver-doped nano-ZnO samples with different Ag loadings were prepared by a one-spot solvothermal method. The structure, physico-chemical and optical properties of the products are characterized by using X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive X-ray analysis (EDS), diffuse reflectance spectroscopy (DRS) and photoluminescence spectra (PL). The photocatalytic activity of the as-prepared samples was examined by using photocatalytic oxidation of methyl orange (MO) as a model reaction, and the effects of the noble metal content on the photocatalytic activity were investigated. The results indicated that the photocatalytic activity of ZnO nanoparticles can be greatly improved by depositing appropriate amount of noble metal on their surface as electron scavengers. In addition, a key mechanism was proposed in order to account for the enhanced activity. The enhancement for the photocatalytic activities can be attributed to the interaction between Ag particles and ZnO, which made Ag particles act as electron traps to effectively separate the excited electron-hole pairs.     

Effects of Ag Doping Content and Dispersion on the Photocatalytic and Antibacterial Properties in ZnO Nanoparticles

ZnO nanoparticles(NPs)with different contents of Ag dopants were obtained by one-step solvothermal method.The crystalline structures of the prepared composites were characterized by means of X-ray diffraction(XRD).The morphology and composition of the samples were studied by means of scanning transmission electron microscopy(TEM)5 X-ray photoelectron spectroscopy(XPS)and electron microscopy(SEM).Photoluminescence(PL)spectra have been used to investigate pure ZnO,Ag-ZnO and Ag-ZnO-PVP NPs to determine the effect of composition on PL properties.It was found that the Ag-ZnO samples showed stronger emissions than pure ZnO.The catalytic activity of samples was measured by the degradation rate of R6G,which exhibited that Ag-ZnO nanocomposite demonstrated enhanced photocatalytic activity compared to the pure ZnO NPs.The possible influence factors to the photocatalytic and antibacterial activities of the sample were explored,including Ag contents and dispersion.It was presented that the photocatalytic activity of Ag-ZnO-PVP was better than that of Ag-ZnO and it showed the highest photocatalytic activity with 7%of Ag content.The Ag-ZnO-PVP can kill the Escherichia coli(E.coli)cells.     

Controlled reduction of the deleterious effects of photocatalytic activity of ZnO nanoparticles by PVA capping

Nanoparticles of uncapped and PVA (poly vinyl alcohol) capped zinc oxide were synthesized by precipitation method. The synthesized ZnO nanoparticles were characterized by fourier transform infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and thermogravimetric-differential thermal analysis. The photocatalytic activity of bare and modified ZnO nanoparticles was studied by monitoring the degradation of Rhodamine B. The results show that PVA capped ZnO nanoparticles has reduced photocatalytic activity than the bare ZnO nanoparticles. The reduction in the chemical oxygen demand and total organic carbon results also revealed the reduced photocatalytic activity of PVA capped ZnO. The UV-shielding property was evaluated by measuring the transmittance which shows that both bare and PVA capped ZnO nanoparticles possess good UV-shielding ability.     

Ag+/Ag/ZnO多孔纳米结构纤维材料的制备及可见光催化性能

借助棉花纤维模板, 采用两步法制备了Ag⁺/Ag/ZnO多孔纳米结构纤维材料, 并利用X射线衍射(XRD)、 X射线光电子能谱(XPS)、 扫描电子显微镜(SEM)和紫外-可见光谱(UV-Vis)等对其进行了表征. 以亚甲基蓝(MB)的脱色降解为模型反应, 考察了银修饰量(摩尔分数, 0~1.50%)对ZnO纳米结构纤维材料光催化性能的影响. 结果表明, 利用模板辅助的两步法制备了Ag⁺-Ag共修饰的ZnO多孔纳米结构纤维材料Ag⁺/Ag/ZnO, Ag⁺和Ag通过改变ZnO的晶胞结构、 光吸收特性及形貌等影响其光催化性能; 在可见光条件下, Ag⁺/Ag/ZnO的催化性能优于纯ZnO, 且与修饰量有关.     

Luminescence and photocatalytic activity of ZnO nanocrystals: correlation between structure and property

Low-dimensional ZnO nanocrystals with controlled size, aspect ratio, and oxygen defects (e.g., type and concentration) are successfully prepared through simple solvothermal and thermal treatment methods. The structure of the as-synthesized samples is characterized by XRD, N2 physical adsorption, TEM, and IR and XPS spectra. The results show that the aspect ratio and size of the as-synthesized ZnO nanocrystals increase with increasing [OH-]/[Zn2+]; the morphology evolves from nanorod to nanoparticle with an increase in the annealing temperature; the BET surface areas of the corresponding samples decrease during these processes, respectively; and different oxygen defects, which are likely to be oxygen vacancy (Vo**) and interstitial oxygen (Oi'), are formed in our experiments accordingly. With evolution of the structure, IR absorption bands and visible photoluminescence emission peaks of the synthesized ZnO nanocrystals shift and split, which is ascribed to the change of oxygen defects. In addition, it is found that the photocatalytic activity of the synthesized ZnO nanocrystals is mainly dependent on the type and concentration of oxygen defects. The relationship of structure-property and the possible photocatalytic mechanism are discussed in detail.