Ag/ZnO heterostructure nanocrystals: synthesis, characterization, and photocatalysis

A high yield of the dimer-type heterostructure of Ag/ZnO nanocrystals with different Ag contents is successfully prepared through a simple solvothermal method in the absence of surfactants. The samples are characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, UV-vis spectroscopy, and IR spectroscopy. The results show that all samples are composed of metallic Ag and ZnO; Ag nanoparticles locate on the surface of ZnO nanorods; the binding energy of Ag 3d(5/2) for the Ag/ZnO sample with a Ag content of 5.0 atom % shifts remarkably to the lower binding energy compared with the corresponding value of pure metallic Ag because of the interaction between Ag and ZnO nanocrystals; the concentration of oxygen vacancy for the as-synthesized samples varies with the increasing Ag content, and the Ag/ZnO sample with a Ag content of 5.0 atom % has the largest density of oxygen vacancy. In addition, the relationship between their structure and photocatalytic property is investigated in detail. It is found that the photocatalytic property is closely related to its structure, such as heterostructure, oxygen defect, and crystallinity. The presence of metallic Ag nanoparticles and oxygen vacancy on the surface of ZnO nanorods promotes the separation of photogenerated electron-hole pairs and thus enhances the photocatalytic activity.     

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.     

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.     

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.     

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.     

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．     

ZnO纳米粒子的表面光电压谱和光催化性能

采用焙烧前驱物碱式碳酸锌的方法制备了不同粒径的ZnO纳米粒子，而用粒径 最小的作为光催化剂，通过光还原过程分别得了贵金属质量分数为0.5%和0.75%的 Pd/ZnO或Ag/ZnO复合纳米粒子。利用XRD，TEM，XPS，SPS和EFISPS等测试技术对样 品进行了表征，并通过光催化氧化气相正庚烷评估了样品的光催化活性，考察了微 晶尺寸和贵金属Pd或Ag的沉积对ZnO纳米粒子表面光电压信号以及光催化活性的影 响，探讨了样品表面光电压谱与其光催化活性的关系，说明了可以通过表面光电压 谱的测试来初步地评估纳米粒子的光催化活性。结果表明：随着ZnO纳米微晶尺寸 的减小，其SPS信号强度逐渐变弱，而光催化活性逐渐升高；沉积适量的贵金属Pd 或Ag后，ZnO纳米粒子的SPS信号强度明显下降，而其光催化活性却有所升高。此外 ，对ZnO纳米粒子光催化剂的失活机理进行了分析。     

复合Ag/ZnO分级结构微球的制备及其光催化性能研究

采用化学沉淀法制备ZnO微球,利用柠檬酸三钠（TCD）避光还原硝酸银在ZnO表面沉积银粒子制备Ag/ZnO复合材料.利用XRD、SEM、TEM、EDS、FTIR、UV-vis DRS、PL、BET等对Ag/ZnO的结构、组分、形貌及光谱性质进行了表征,通过紫外及可见光照降解甲基橙溶液评价样品的光催化性能.结果表明：ZnO纳米微球是由ZnO纳米片相互交错构筑而成的具有丰富孔道的分级结构,Ag纳米粒子均匀沉积在ZnO纳米片上.Ag的沉积显著增加了ZnO的可见光吸收,猝灭了ZnO荧光,提高了ZnO催化活性.     

Pd/ZnO和Ag/ZnO复合纳米粒子的SPS和XPS研究

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分别得到了质量分数为0.5％的Pd/ZnO和Ag/ZnO复合纳米粒子，并利用XRD、TEM、XPS和SPS等测试技术对样品进行表征.初步探讨了贵金属在ZnO纳米粒子表面形成原子簇的原因及沉积贵金属对ZnO纳米粒子表面光电压信号的影响.以光催化氧化气相正庚烷为模型反应，考察了沉积贵金属对ZnO纳米粒子光催化活性的影响，并探讨了光催化活性有所提高的内在原因.结果表明， ZnO纳米粒子沉积贵金属后，其表面光电压信号明显下降，而光催化活性却大大地提高，这说明可以通过表面光电压谱的测试来初步的评估纳米粒子的光催化活性，即粒子的表面光电压信号越弱，其光催化活性越高.     

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。     

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.     

Controlled orientation in a bio-inspired assembly of Ag/AgCl/ZnO nanostructures enables enhancement in visible-light-induced photocatalytic performance

In a bio-inspired approach, polyamine-mediated mineralization of ZnO was explored to develop an environmentally benign methodology for synthesizing Ag/AgCl/ZnO nanostructures. The assembling properties displayed by the polyamines to create composite structures was utilized to have the nanocomponents effectively interact with each other in a way that is desirable for the application envisaged. The polyamines, which act as a mineralizing agent for ZnO nanoparticles, also facilitate the formation of Ag/AgCl within ZnO under ambient conditions. Thus synthesized Ag/AgCl/ZnO nanostructures represent a multi-heterojunction system in which the nanocomponents lead in a synergistic way to enhancement in the photocatalytic activity under visible-light irradiation.     

Controlled Orientation in a Bio‐Inspired Assembly of Ag/AgCl/ZnO Nanostructures Enables Enhancement in Visible‐Light‐Induced Photocatalytic Performance

In a bio‐inspired approach, polyamine‐mediated mineralization of ZnO was explored to develop an environmentally benign methodology for synthesizing Ag/AgCl/ZnO nanostructures. The assembling properties displayed by the polyamines to create composite structures was utilized to have the nanocomponents effectively interact with each other in a way that is desirable for the application envisaged. The polyamines, which act as a mineralizing agent for ZnO nanoparticles, also facilitate the formation of Ag/AgCl within ZnO under ambient conditions. Thus synthesized Ag/AgCl/ZnO nanostructures represent a multi‐heterojunction system in which the nanocomponents lead in a synergistic way to enhancement in the photocatalytic activity under visible‐light irradiation.     

Photochemical Synthesis and Spectral-Optical Characteristics of ZnO/Cu and ZnO/Ag/Cu Nanoheterostructures

The photoreduction of Cu²⁺ at the surface of ZnO nanoparticles and ZnO/Ag nanostructures was investigated. The spectral characteristics of the obtained ZnO/Cu and ZnO/Ag/Cu composites were studied in relation to the reaction conditions. It was shown that the ZnO/Ag nanoparticles have higher photocatalytic activity in the reduction of Cu²⁺ ions than the individual ZnO particles.     

Structural,optical, electrical,and photocatalytic properties of manganese doped zinc oxide nanocrystals

Manganese-doped and undoped ZnO nanocrystals were synthesized via wet-chemical methods. The structure, physico-chemical, electrical and optical properties of the as-prepared products were characterized by using the X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PLS) and electrochemical impedance spectroscopy (EIS) techniques. The photocatalytic activity of Mn-doped ZnO nanocrystal (mixed phases) has been examined under the visible-irradiation by using photocatalytic oxidation of rhodamine B (RhB) dye as a model reaction, and compared with that of known system such as pure ZnO nanocrystal (single-phase). The results showed that Mn doped ZnO nanocrystals bleaches RhB much faster than undoped ZnO upon its exposure to the visible light. The enhancement of the photocatalytic activity was discussed as an effect due to the Mn doping in the Mn-doped ZnO semiconductors, which shifts the optical absorption edge to the visible region and alters the electron-hole pair separation conditions. These factors are responsible for the higher photocatalytic performance of Mn/ZnO composites.     

ZnO和TiO2纳米粒子的光致发光性能及其与光催化活性的关系

采用沉淀法和溶胶-凝胶法制备了ZnO和TiO2及掺Zn2+的TiO2纳米粒子,用XRD和荧光光谱(FS)等手段对样品进行了表征,重点探讨了样品光致发光机制及与光催化活性的关系.结果表明,ZnO和TiO2样品在大于带隙能的光激发下均表现出明显的FS信号,热处理温度升高,FS信号强度下降,并且二者的FS信号类似,这可能与二者具有类似的电子能带结构有关,同时也说明FS信号主要源于表面氧空位以及吸附氧物种等引起的激子或表面态能级.掺杂Zn2+使TiO2纳米粒子FS信号增强,这主要与表面氧空位和缺陷等量增加有关;此外,在光催化氧化苯酚实验中,样品光催化活性与其FS信号强度顺序一致,即FS信号越强,活性越高.这是由于在光致发光过程中,FS信号主要源于表面氧空位,而在光催化反应中,表面氧空位有利于氧化反应进行.     

可循环SERS基底ZnO/Ag纳米材料合成和表征

利用简易、绿色、一锅煮的水热法合成了花状氧化锌/银复合纳米材料。然后利用各种光谱和显微技术对复合物进行了表征,并讨论了其表面增强拉曼(SERS)性能和光催化性能。结果表明氢氧化钠的量对于这种复合纳米材料的形貌和性能具有重要的调节作用。和其他形貌的氧化锌/银复合纳米材料相比较,花状氧化锌/银复合纳米材料具有最佳的光催化性能。同时进一步以花状氧化锌/银复合纳米材料作为SERS基底研究其表面增强拉曼性能,结果表明这种复合材料同时具有很好的表面增强拉曼性能。光催化和表面增强拉曼结果表明这种花状氧化锌/银复合纳米材料有望在有机物检测中作为一种具有很好的可循环性的新表面增强拉曼基底材料。     

One pot synthesis of Ag nanoparticle modified ZnO microspheres in ethylene glycol medium and their enhanced photocatalytic performance

Ag nanoparticles (NPs) modified ZnO microspheres (Ag/ZnO microspheres) were prepared by a facile one pot strategy in ethylene glycol (EG) medium. The EG played two important roles in the synthesis: it could act as a reaction media for the formation of ZnO and reduce Ag⁺ to Ag⁰. A series of the characterizations indicated the successful combination of Ag NPs with ZnO microspheres. It was shown that Ag modification could greatly enhance the photocatalytic efficiency of ZnO microspheres by taking the photodegradation of Rhodamine B as a model reaction. With appropriate ratio of Ag and ZnO, Ag/ZnO microspheres showed the better photocatalytic performance than commercial Degussa P-25 TiO₂. Photoluminescence and surface photovoltage spectra demonstrated that Ag modification could effectively inhibit the recombination of the photoinduced electron and holes of ZnO. This is responsible for the higher photocatalytic activity of Ag/ZnO composites.     

可循环SERS基底ZnO/Ag纳米材料合成和表征

利用简易、绿色、一锅煮的水热法合成了花状氧化锌/银复合纳米材料。然后利用各种光谱和显微技术对复合物进行了表征,并讨论了其表面增强拉曼（SERS）性能和光催化性能。结果表明氢氧化钠的量对于这种复合纳米材料的形貌和性能具有重要的调节作用。和其他形貌的氧化锌/银复合纳米材料相比较,花状氧化锌/银复合纳米材料具有最佳的光催化性能。同时进一步以花状氧化锌/银复合纳米材料作为SERS基底研究其表面增强拉曼性能,结果表明这种复合材料同时具有很好的表面增强拉曼性能。光催化和表面增强拉曼结果表明这种花状氧化锌/银复合纳米材料有望在有机物检测中作为一种具有很好的可循环性的新表面增强拉曼基底材料。     

Synthesis and photocatalytic performance of Ag/AgCl/ZnO tetrapod composites

Ag/AgCl is a visible-light plasmonic photocatalyst that has attracted considerable attention because of its high visible-light absorption and activity owing to the surface plasmon resonance of noble-metal nanoparticles. In this study, Ag/AgCl/ZnO tetrapod composite was prepared by introducing ZnO tetrapods into Ag/AgCl prepared by a polydopamine reduction route. Ag/AgCl was densely deposited on the three-dimensional support framework provided by the ZnO tetrapods. The framework possessed a certain degree of porosity, thereby improving the specific surface area of the Ag/AgCl/ZnO composite. The interaction of ZnO with Ag/AgCl further increased the separation and transfer of electron–hole pairs. The Ag/AgCl/ZnO composite showed excellent photocatalytic activity and good stability. Under xenon lamp irradiation for 20 min, degradation of rhodamine B reached 90%. After four recycling tests, degradation remained stable without any sign of reduction. Ag/AgCl/ZnO tetrapod composite is shown to be a kind of green photocatalyst offering high activity, good stability, and recyclability.