Highly visible light active Ag@ZnO nanocomposites synthesized by gel-combustion route

Highly visible light active 1% and 3% Ag@ZnO nanocomposites were synthesized via a gel combustion route using citric acid as a fuel. The formation of the nanocomposites with enhanced properties was confirmed using a range of characterization techniques, photocatalysis and photoelectrochemical studies. Compared to the pristine ZnO nanoparticles, the Ag@ZnO nanocomposites exhibited enhanced visible light photocatalytic activity for the degradation of methylene blue and photoelectrochemical response. A mechanism was proposed to account for the photocatalytic activities of the Ag@ZnO nanocomposite that showed the surface plasmon resonance (SPR) of Ag is an effective way of enhancing the visible light photocatalytic activities.     

AgBr/ZnO复合材料光催化剂及其光催化性能

通过一步水热法制备了AgBr/ZnO复合光催化剂,并采用扫描电子显微镜、透射电子显微镜、X射线衍射仪、X射线光电子能谱仪、紫外–可见光漫反射光谱仪和光致发光光谱仪对样品进行表征,分析了AgBr/ZnO体系的合成对材料光催化性能的影响。以罗丹明B溶液为目标污染物,研究复合催化剂的光催化活性。结果表明:在制备的复合样品中,Ag Br与ZnO摩尔比为1:5时(AgBr/ZnO-2)光催化活性最好,在可见光照射下,60 min对罗丹明B的降解率可达98.98%,相比于ZnO光催化活性明显提升,降解速率常数提升了11.08倍;与商用TiO2(P25)相比,降解速率常数提升了10.14倍,这主要归因于Ag Br/ZnO拥有比ZnO更低的电子空穴复合概率,且复合催化剂的光学吸收带边发生红移,从而增强了对可见光的吸收。     

Preparation of rare earth-doped ZnO hierarchical micro/nanospheres and their enhanced photocatalytic activity under visible light irradiation

Rare earth-doped ZnO hierarchical micro/nanospheres were prepared by a facile chemical precipitation method and characterized by X-ray diffraction, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, UV-visible diffuse reflectance spectroscopy and photoluminescence spectroscopy. The results showed that the as-synthesized products were well-crystalline and accumulated by large amount of interleaving nanosheets. It was also observed that the rare earth doping increased the visible light absorption ability of the catalysts and red shift for rare earth-doped ZnO products appeared when compared to pure ZnO. The photocatalytic studies revealed that all the rare earth-doped ZnO products exhibited excellent photocatalytic degradation of phenol compared with the pure ZnO and commercial TiO₂ under visible light irradiation. Nd-doped ZnO had the highest photocatalytic activity among all of the rare earth-doped ZnO products studied. The optimal Nd content was 2.0 at% under visible light irradiation. The enhanced photocatalytic performance of rare earth-doped ZnO products can be attributed to the increase in the rate of separation of photogenerated electron–hole pairs and hydroxyl radicals generation ability as evidenced by photoluminescence spectra.     

Photocatalytic activity and DFT calculations on electronic structure of N-doped ZnO/Ag nanocomposites

N-doped ZnO/Ag nanocomposites were successfully prepared by two-step liquid deposition approach and plasma nitriding technology. The photocatalytic studies suggested that N-doped ZnO/Ag nanocomposites showed enhanced photocatalytic efficiency of photodegradation of methyl orange aqueous solution compared with the un-doped sample under UV light irradiation. The theoretical results indicated that the Fermi level shifted into the valence band, a narrow-deep acceptor level formed in the energy gap, then the transition of an electron from valence band to conduction band needs less energy which demonstrated the mechanism for the enhanced photocatalytic activity of N-doped ZnO/Ag nanocomposites.     

ZnO纳米棒阵列的改进水热方法制备、银修饰及光催化活性研究

ZnO纳米棒阵列是近来研究较多的光催化剂,通过银等贵金属修饰可提高光催化活性。以硝酸锌和六亚甲基四胺为前驱物,通过优化水热合成参数（包括种子层和水热生长液浓度等）以及光化学还原沉积银制备高活性ZnO纳米棒阵列。利用扫描电子显微镜、X射线粉末衍射以及紫外-可见漫反射光谱对样品进行表征。结果表明,种子层和水热反应液浓度均对ZnO纳米棒阵列的活性产生影响。银修饰后,光吸收增强,吸收带边从紫外光区拓展到可见光区。光催化降解甲基橙溶液结果表明,银修饰的ZnO纳米棒阵列较纯ZnO纳米棒阵列降解甲基橙的活性提高30%。     

Preparation of Ag nanoparticles loaded TiO2 nanoplate arrays on activated carbon fibers with enhanced photocatalytic activity

Ag loaded TiO₂ nanoplate array which grew on activated carbon fiber (ACF) was prepared in the present work. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV–Vis diffuse reflectance spectra (DRS). The photocatalytic degradation of methylene blue (MB) was used to investigate the activity of the synthesized samples. Under both UV and visible light irradiation, the Ag loaded samples showed enhanced photocatalytic activity. Besides, the effect of the deposition dosage of Ag nanoparticles on the photocatalytic activity was also investigated. Under UV light irradiation, the Ag nanoparticles acted as electron traps, which enhanced electron–hole separation efficiency of TiO₂. Under visible light irradiation, the Ag nanoparticles showed surface plasmon resonance, which induced the visible light responsive photocatalytic activity for the obtained samples.     

Self-assembly synthesis of ZnO with adjustable morphologies and their photocatalytic performance

ZnO with hierarchical microspheres and hexagonal prisms structures were successfully synthesized by hydrothermal microemulsion route. Based on X-ray diffraction and scanning electron microscopy observation of the products at the different reaction time periods, the formation mechanism of three-dimensional hierarchical ZnO microspheres was proposed. Ultraviolet and visible diffuse reflectance spectra indicated that as-synthesized ZnO microspheres had enhanced absorption in both ultraviolet and visible light areas. The photocatalytic activities of as-synthesized products were evaluated by monitoring the degradation of methylene blue solution. Due to the synergistic effects of the high crystallization and special hierarchical structure, the hierarchical ZnO microsphere exhibited the highest photocatalytic activity.     

Temperature-dependent properties of silver-poly(methylmethacrylate) nanocomposites synthesized by in-situ technique

Ag/PMMA nanocomposites were successfully synthesized by in-situ technique. Transmission electron microscopy (TEM) images show that the particles are spherical in shape and their sizes are dependent on temperature. The smallest particle achieved high stability as indicated from Zeta sizer analysis. The red shift of surface plasmon resonance (SPR) indicated the increases of particle sizes. X-ray diffraction (XRD) patterns exhibit a two-phase (crystalline and amorphous) structure of Ag/PMMA nanocomposites. The complexation of Ag/PMMA nanocomposites was confirmed using Raman spectroscopy. Fourier transform infrared spectroscopy spectra confirmed that the bonding was dominantly influenced by the PMMA and DMF solution. Finally, thermogravimetric analysis (TGA) results indicate that the total weight loss increases as the temperature increases.     

Facile Preparation of LaFeO<Subscript>3</Subscript>/rGO Nanocomposites with Enhanced Visible Light Photocatalytic Activity

The present work demonstrates a facile route for preparing LaFeO₃/rGO nanocomposites comprising of metal oxide nanoparticles and graphene. Structural, morphology, optical and photocatalytic studies of the samples were characterized using powder X-ray diffraction (XRD), FT-IR, Raman, high resolution scanning electron microscopy (HRSEM), high resolution transmission electron microscope (HRTEM), atomic force microscopy (AFM), thermogravimetry (TGA), X-ray photoelectron spectroscopy, UV–visible and photocatalytic. LaFeO₃/rGO nanocomposites believed as an effective photocatalyst for the degradation of methyl orange (MO) dye under visible light irradiation. The inclusion of carbon enhances the light absorption of LaFeO₃, resulting in the enhanced photocatalytic activity of the nanocomposite. The degradation of MO dye under visible light source was completely achieved using LaFeO₃/rGO as a catalyst.     

Preparation and visible light photocatalytic activity of Ag/TiO₂/graphene nanocomposite

Great efforts have been made to develop efficient visible light-activated photocatalysts in recent years. In this work, a new nanocomposite consisting of anatase TiO(2), Ag, and graphene was prepared for use as a visible light-activated photocatalyst, which exhibited significantly increased visible light absorption and improved photocatalytic activity, compared with Ag/TiO(2) and TiO(2)/graphene nanocomposites. The increased absorption in visible light region is originated from the strong interaction between TiO(2) nanoparticles and graphene, as well as the surface plasmon resonance effect of Ag nanoparticles that are mainly adsorbed on the surface of TiO(2) nanoparticles. The highly efficient photocatalytic activity is associated with the strong adsorption ability of graphene for aromatic dye molecules, fast photogenerated charge separation due to the formation of Schottky junction between TiO(2) and Ag nanoparticles and the high electron mobility of graphene sheets, as well as the broad absorption in the visible light region. This work suggests that the combination of the excellent electrical properties of graphene and the surface plasmon resonance effect of noble metallic nanoparticles provides a versatile strategy for the synthesis of novel and efficient visible light-activated photocatalysts.     

Preparation of Ag-sensitized ZnO and its photocatalytic performance under simulated solar light

ZnO was prepared rapidly by microwave heating method. The results of scanning electron microscopy show that the leaflike ZnO is composed of self-assembled ZnO particles of 30–50 nm. Ag-sensitized ZnO composite was prepared by UV-photoreduction and glycol reduction, respectively. The composite was characterized by means of scanning electron microscopy, X-ray diffraction and photoluminescence. The ZnO and Ag/ZnO prepared were applied in photocatalytic degradation of phenol and methyl orange as model of organic pollutant in water under simulated solar light. The results show that Ag doping in both methods of UV-photoreduction and glycol reduction can remarkably improve the photocatalytic activity of ZnO under simulated solar light. The utilization ratio of Ag in glycol reduction is high and the optimum content of Ag in Ag/ZnO composite is only 1.33%. Therefore, the glycol reduction is a novel and excellent method for preparing Ag-sensitized ZnO composite with high photocatalytic activity.     

Facile preparation of Bi-doped ZnO/β-Bi2O3/Carbon xerogel composites towards visible-light photocatalytic applications: Effect of calcination temperature and bismuth content

This work aimed to study the development and properties of Bi-doped ZnO/β-Bi₂O₃/Carbon xerogel composites towards visible light photocatalysis applications. The materials were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, dispersive energy spectroscopy, infrared spectroscopy, nitrogen adsorption isotherms, Raman spectroscopy, diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic activity of the developed composites was evaluated through the photodegradation of the 4-chlorophenol molecule and by chronoamperometry tests. The results obtained show that the calcination temperature poses a major influence in the final structure of the materials developed. The calcination temperature of 600 °C resulted in the formation of the β-Bi₂O₃ and Bi⁰ phases, consequently enhancing the photocatalytic activity of the composites due to the increased charge mobility provided by the heterojunctions between zinc oxide, carbon xerogel, bismuth oxide and metallic bismuth. The composite with intermediate bismuth composition (XC/ZnO–Bi₂O₃ 5%) displayed the best photocatalytic response among the materials tested, which was confirmed by its increased photocurrent generation capability. The photocatalytic mechanism is highly dependent in the generation of hydroxyl radicals and the composite presents good reusability properties.     

复合纳米棒状Ag3PO4/ZnO材料的光催化性能

以一维棒状ZnO为载体,采用原位生长法制备纳米棒状Ag_3PO_4/ZnO复合材料。通过XRD、SEM、TEM、XPS和UV-Vis-DRS等测试对纳米棒状Ag_3PO_4/ZnO复合材料进行了表征,并评价了样品在可见光下的光催化性能。结果显示,ZnO几乎无可见光活性,通过水热法制备的ZnO形貌发生了改变,为比表面积的增加做出了贡献,为Ag_3PO_4提供了更多的负载可能。在可见光照射下,纯ZnO和Ag_3PO_4对苯酚的降解率分别为20%和38%,复合材料Ag_3PO_4/ZnO对苯酚的降解率为91.24%,光催化降解性能明显高于纯ZnO和Ag_3PO_4。最后,光催化稳定性的研究证明,Ag_3PO_4/ZnO复合材料形成了有效的异质结结构,抑制了电子-空穴的复合,提高了Ag_3PO_4/ZnO复合材料的稳定性。     

Surface plasmon resonance-induced visible light photocatalytic reduction of graphene oxide: using Ag nanoparticles as a plasmonic photocatalyst

The present communication reports on the first preparation of reduced graphene oxide (rGO) via surface plasmon resonance (SPR)-induced visible light photocatalytic reduction of GO with the use of Ag nanoparticles (AgNPs) as a plasmonic photocatalyst in the presence of an electron donor (ED).     

基于表面等离子体共振效应的Ag(Au)/半导体纳米复合光催化剂的研究进展

由具有表面等离子体共振(surface plasmon resonance,SPR)效应的贵金属(Ag、Au等)纳米粒子和半导体纳米结构组成的纳米复合光催化剂具有优异的可见光光催化活性,成为新型光催化材料的研究热点之一。本文综述了Ag(Au)/半导体纳米复合光催化剂的制备方法、基本性质以及光催化应用方面的一些重要研究进展;重点介绍了Ag(Au)等纳米粒子的表面等离子共振增强可见光催化活性的机理,以及Ag(Au)纳米粒子与不同类型半导体复合的光催化剂的光催化性能,其中所涉及的半导体包括金属氧化物、硫化物和其他一些半导体;本领域未来几年的研究热点将集中于新型高效的Ag(Au)/半导体纳米复合光催化剂的微结构调控及其用于可见光驱动有机反应的机理研究。本文为基于SPR效应构建Ag(Au)/半导体纳米复合光催化剂的研究提供了有力的参考依据,并且指出Ag(Au)/半导体纳米复合光催化剂的研究是发展可见光高效光催化剂的重要方向。     

Enhanced photocatalytic hydrogen evolution over TiO2/g-C3N4 2D heterojunction coupled with plasmon Ag nanoparticles

2D heterojunction based on g-C₃N₄ nanosheets with other semiconductor nanosheets is a promising way to improve photocatalytic hydrogen evolution (PHE) activity over g-C₃N₄. However, current 2D heterojunction based on g-C₃N₄ are unsatisfactory due to their insufficient absorption of visible light and inefficient charge separation. In this work, Ag/TiO₂/g-C₃N₄ nanocomposites based on 2D heterojunction coupling with Ag surface plasmon resonance (SPR) were synthesized by a method combining facile wetness impregnation calcination. The PHE activity of Ag/TiO₂/g-C₃N₄ nanocomposites is attributed to the TiO₂/g-C₃N₄ 2D heterojunction and bare g-C₃N₄ nanosheet under visible light irradiation, indicating a cooperative effect between Ag and TiO₂/g-C₃N₄ 2D heterojunction. As a result of SPR effect, the composites strongly absorb visible light. In addition, the oscillating hot electrons from Ag can easily transfer to 2D heterojunction. This synergistic effect lead to sufficient visible light absorption and efficient charge separation of 2D heterojunction, which improved the PHE activity of g-C₃N₄. This work indicates that loading metal nanoparticles on 2D heterojunction as metal SPR-2D heterojunction nanocomposites may be a potential method for harvesting visible light for PHE.     

Boron-Doped Graphene/ZnO Nanoflower Heterojunction Composite with Superior Photocatalytic Activity

The boron-doped graphene (BG) is synthesized successfully by one pot reduce-doping of graphene oxide (GO) with borane tetrahydrofuran (BH₃·THF) and the novel BG/ZnO p–n heterojunction composite between p-type BG and n-type ZnO is obtained via a simple hydrothermal method. The samples are characterized by scanning electron microscopy, the Raman spectroscopy and the UV–Vis diffuse spectroscopy. The results confirm the formation of p–n junction between BG and ZnO. The photodegradation of MB demonstrate that the BG/ZnO composite has superior photocatalytic activity under UV–Vis or visible irradiation. The photocatalytic activity k value of BG/ZnO p–n heterojunction composite is 3.1 and 4.5 times as that of r-GO/ZnO and pure ZnO under white light and is 1.8 and 3.9 times under visible light, respectively. The superior photocatalytic activity of the BG/ZnO composite is ascribed to the formation of p–n heterojunction. The p–n heterojunction can promote the separation of electron/hole pairs and inhibit the recombination of electrons in conduction band and holes in valence band by transferring holes from the valence band of n-type ZnO to the valence band of p-type BG.     

Ag/AgX（X=Cl,Br,I）等离子共振光催化剂的研究进展

银/卤化银[Ag/AgX（X=Cl,Br,I）]光催化剂作为一种新型光催化剂,由于在可见光区域具有明显的等离子共振效应从而显示了优异的可见光催化降解有机污染物的活性,引起了人们的极大重视。本文主要对Ag/AgX（X=Cl,Br,I）等离子体光催化剂的结构、光催化降解有机物机理、催化剂制备等进行了综述。Ag/AgX（X=Cl,Br,I）的活性普遍较高,通过半导体复合及形貌尺寸的控制,光催化性能得到进一步改善。进而论述了Ag/AgX体系等离子体共振光催化剂在工业染料废水处理上的应用现状,并对Ag/AgX（X=Cl,Br,I）等离子体光催化剂在高浓度、成分复杂污水体系处理中的应用进行了展望。     

Improved photocatalytic performance of Gd and Nd co-doped ZnO nanorods for the degradation of methylene blue

This paper reports the synthesis of pure ZnO, Gd and Nd co-doped ZnO nanorods based nanocomposites via simple hydrothermal method. Subsequently, the prepared photocatalysts were characterized using XRD, SEM/EDX, TEM, UV–visible and PL spectroscopy. The XRD results demonstrate that Gd and Nd ions were incorporated into ZnO lattice in the synthesized ZnO based nanocomposites and showed hexagonal wurtzite structure. The SEM and TEM results show that nanorods having nanoscale diameter and length were successfully synthesized by hydrothermal method. The UV–visible spectroscopy verified that the band gap of ZnO was reduced due to incorporation of Gd and Nd into ZnO photocatalyst. Similarly, Gd and Nd incorporation into ZnO was found effective to reduce the recombination of electrons and holes as confirmed by PL spectroscopy. Moreover, the prepared nanocomposites with various atomic ratios (0.5–2%) were tested for photocatalytic degradation of methylene blue (MB), under visible light irradiation. The highly efficient and optimized 1.5% Nd/ZnO nanocomposite demonstrated enhanced photocatalytic performance for the degradation of methylene blue compared to pure ZnO and other nanocomposites. Furthermore, the recycling results show that the 1.5% Nd/ZnO nanocomposites displayed good stability and long-term durability. These finding suggest that the ZnO based nanocomposite could be efficiently used in various energy and environmental applications.     

Facile synthesis and investigation of NiO–ZnO–Ag nanocomposites as efficient photocatalysts for degradation of methylene blue dye

In the present study, NiO–ZnO–Ag photocatalytic nanocomposites were synthesized using two-stage precipitation method. The synthesized composite powders were investigated and characterized using different techniques including XRD, FESEM, FT-IR, TGA and UV–Vis. XRD results showed that by increasing the Ag content, the crystallite size of ZnO decreased. FESEM micrographs showed that addition of Ag could lead to formation of more uniform particles in the size range of 30–500 nm. Diffuse reflectance spectroscopy results confirmed that addition of Ag nanoparticles led to the increase of light absorption, which was attributed to the plasmon surface resonance of Ag. Band gap energies of NiO–ZnO, NiO–ZnO–5%Ag, NiO–ZnO–3%Ag, NiO–ZnO–1%Ag and ZnO–1%Ag were estimated to be 3.13, 3.14, 3.147, 3.19 and 3.17 eV, respectively. Investigation of degradation process showed that by adding up to 1 wt% Ag to NiO–ZnO composite led to the increase of methylene blue degradation from 67% to 94%, but further addition resulted in decrease of degradation.