具有SPR效应的Ag/Ag2MoO4材料在可见光区的光催化性能研究

作为一类新兴的光催化材料,钼酸盐纳米材料具有高表面能、多活性位点和高选择性等优点,在可见光催化降解污染物方面有着重要应用,近年来受到广泛关注.作为钼酸盐家族重要的一员,钼酸银在杀菌、表面增强拉曼光谱、气敏材料等方面均有重要应用,但其光催化性能却鲜见报道.这是由于它的光谱响应范围窄和广生载流子分离效率低所致.虽然近来有少量基于钼酸银的复合材料的光催化研究,但催化效果不佳.众所周知,作为自由电子体系,诸多金属纳米粒子,如贵金属、碱金属等,存在表面等离子体共振效应(SPR),使得贵金属,特别是Ag,Au等纳米粒子在可见区域有较强的吸收.利用这一特性,Awazu等将Ag纳米颗粒沉积在TiO2表面,创造性地将SPR应用于光催化反应,开发出在可见光谱区具有宽光谱吸收特征的Ag/TiO2.随后陆续合成出基于SPR效应的Ag@AgCl,Ag/Ag3PO4材料均具有良好的光催化性能.基于此,本文在十二烷基硫酸钠(SDS)的存在下,采用水热法一步合成了具有SPR效应的Ag/Ag2MoO4可见光催化材料,并利用X射线粉末衍射(XRD)、紫外可见漫反射(DRS)、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)等技术对材料进行了表征.系统地探讨了体系pH值、反应时间、表面活性剂用量对产物的晶相和微观形貌等的影响.此外,还利用罗丹明B降解实验考察了上述合成条件对材料可见光催化活性的影响,并通过捕获剂实验深入地研究了起催化作用的活性物种.XRD结果表明,体系的pH值对材料的晶型有极大影响,随着pH由酸性变至中性、碱性,最终得到的钼酸银也由Ag2Mo2O7过渡到Ag2MoO4.SEM图显示在最优条件(pH为7,加入0.5 g SDS,160oC下水热14 h)下制得的钼酸银为八面体的Ag2MoO4,且其表面均匀地分布着Ag纳米颗粒,与XPS图谱结果一致.另外表面活性剂SDS的用量对所合成材料的形貌影响很大.本文可一步得到以八面体Ag2MoO4为主的Ag/Ag2MoO4复合材料,是因为SDS的疏水长链可以诱导Ag2MoO4的各向异性生长.DRS结果表明,Ag2MoO4八面体上Ag颗粒的引入使其在可见光区的吸收明显加强,因而它在可见光下催化降解罗丹明B降解反应活性增加.捕获剂实验结果表明,起决定性作用的活性物种是光生空穴,另外?OH也起了一定作用.     

One‐pot self‐assembly and photoreduction synthesis of silver nanoparticle‐decorated reduced graphene oxide/MIL‐125(Ti) photocatalyst with improved visible light photocatalytic activity

In recent years, tremendous research efforts have been made towards developing metal–organic framework (MOF)‐based composites for photocatalytic applications. In this work, bipyramid‐like MIL‐125(Ti) frustum enwrapped with reduced graphene oxide (rGO) and dispersed silver nanoparticles (Ag NPs) was fabricated using an efficient one‐pot self‐assembly and photoreduction strategy. The as‐obtained materials were characterized using field emission scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, nitrogen adsorption–desorption isotherms, and X‐ray photoelectron, ultraviolet–visible diffuse reflectance and photoluminescence spectroscopies. It is found that the as‐prepared Ag/rGO/MIL‐125(Ti) ternary hybrids have large surface area, microporous structure, enhanced visible light absorption and prolonged lifetime of charge carriers. Compared with pure MIL‐125(Ti) and its binary counterparts, the ternary composite exhibits more efficient photocatalytic performance for Rhodamine B (RhB) degradation from water under visible light irradiation. The photodegradation rate of RhB on Ag/rGO/MIL‐125(Ti) is 0.0644 min^?1, which is 1.62 times higher than that of the pure MIL‐125(Ti). The improved photocatalytic performance is ascribed to the indirect dye photosensitization, the Ag NP localized surface plasmon resonance, the Ti³⁺–Ti⁴⁺ intervalence electron transfer and the synergistic effect among MIL‐125(Ti), Ag NPs and rGO. Ag NPs serve as an efficient ‘electron reservoir’ and rGO as an electron transporter and collector. Therefore, this work provides a new pathway into the design of MOF‐based composites for application in environmental and energy fields. Copyright © 2016 John Wiley & Sons, Ltd.     

原位合成具有高可见光催化活性的C3N4/CdS纳米复合材料

以硫氰酸铵和氯化镉为原料,采用无模板混合高温煅烧法一步合成氮化碳/硫化镉纳米晶(C3N4/CdS)的复合半导体材料。采用X射线衍射、傅立叶变换红外光谱和透射电镜等技术对其结构和形貌进行了表征。以有机污染物罗丹明B (RhB)为模拟污染物对复合催化剂的可见光催化活性进行测试。结果表明, C3N4/CdS复合材料中CdS以六方相纳米晶的形式均匀分散; CdS的复合基本不改变C3N4主体结构及聚合度;与纯C3N4相比,复合材料在可见区的光吸收能力有所增强。合适的能带匹配有利于光生载流子的迁移,抑制了其复合速率。在可见光照射下,复合半导体能够更加快速的降解有机污染物,且保持很好的稳定性。     

Surface-Modified CdS/ZnO Material: Single-Reactor Synthesis and Mechanism of Formation in Aqueous Solution

Method of chemical precipitation from aqueous solutions was used to cover the surface of polycrystalline ZnO nanotubes with a nanostructured CdS layer. The thus synthesized CdS/ZnO composite material was studied by the methods of X-ray diffraction analysis, electron microscopy, and optical spectroscopy. The fundamental time-related aspects of the process of CdS formation on the ZnO surface were examined. It was found that the amount of deposited CdS nanoparticles is independent of the deposition duration. The morphological specific features of ZnO nanotubes are preserved upon a prolonged keeping of ZnO in solution. The photocatalytic activity of CdS/ZnO under visible and UV light was examined in the reaction of hydroquinone oxidation. A possible mechanism of how the CdS/ZnO composite is formed in an aqueous solution in the course of growth of a layer constituted by CdS nanoparticles on the surface of ZnO nanotubes is suggested on the basis of the experimental data. It is demonstrated that the chemical-precipitation method can be used to obtain surface-active composite materials that are photoactive in the visible spectral range.     

Hydrothermal synthesis and characterization of Nd-doped ZnSe nanoparticles with enhanced visible light photocatalytic activity

In the present study, Nd³⁺-doped ZnSe nanoparticles with variable Nd contents were successfully synthesized via a hydrothermal process using Neodymium (III) chloride hexahydrate as the doping source. X-ray diffraction, UV–Vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy and transmission electron microscopy were used for characterization of the synthesized nanoparticles. It was confirmed by the DRS analysis that both of the undoped and Nd-doped ZnSe samples had significant optical absorption in the visible light range. The photocatalytic performance of as-synthesized nanoparticles was investigated towards the decolorization of C. I. Acid Orange 7 solution under visible light irradiation. Results indicated that the loading of Nd dopant into ZnSe nanoparticles significantly enhanced the photocatalytic activity of pure ZnSe with increasing Nd loading up to 6 mol% (color removal efficiency of 24.31 % for ZnSe and 84.20 % for Nd_0.06Zn_0.94Se after 120 min of treatment) and then the photocatalytic activity began to decrease.     

Preparation of silver/graphene/polymer hybrid microspheres and the study of photocatalytic degradation

Three-dimensional silver/graphene/polymer hybrid microspheres were prepared to depress the aggregation of two-dimensional graphene. Graphene oxide (GO) sheets were successfully wrapped on the surface of amine-functionalized polystyrene-poly (glycidyl methacrylate) (PS-PGMA) microspheres (～3 μm in diameter) to form graphene oxide/amino-microsphere (GO/AMS) core–shell structure. Subsequently, the wrapped GO sheets were reduced by using hydrazine hydrate as the reducing agents, meanwhile decorated with silver nanoparticles on the wrinkled surface to form Ag-rGO/AMS hybrid microspheres with monodisperse distributions in shape and diameter. The resulting materials were characterized by power X-ray diffraction, scanning electron microscope, Raman spectra, and ultraviolet–visible (UV–vis) absorption spectra. Since Ag nanoparticles behave surface plasmon resonance effect and rGO structure can improve the separation of photogenerated electrons and holes, the Ag-rGO/AMS composites present good photocatalytic activities for the degradation of methylene blue (MB) as 93 % MB were degraded after 2.5 h under irradiation.     

Synthesis of highly stable silver nanoparticles using imidazolium-based ionic liquid

Highly stable, aqueous dispersions, and hydrophilic ionic liquid-capped silver nanoparticles with positive surface charge were synthesized by in situ reduction of AgNO₃ with NaBH₄ in the presence of an imidazolium-based ionic liquid, viz., 1-dodecyl-3-methylimidazolium chloride ([C₁₂mim][Cl]) at room temperature. Prepared silver nanoparticles were characterized by UV–vis spectra, transmission electron microscopy (TEM), and zeta potential. UV–visible spectrum of the aqueous medium peaked at 407 nm corresponding to the plasmon absorbance of silver nanoparticles. TEM analysis revealed the spherical shape of the particles with sizes about 9 nm and low polydispersed. The surface charge of the synthesized silver nanoparticles was determined as +5.0 mV. The ionic liquid ([C₁₂mim][Cl]) capped silver nanoparticles were stable for at least 8 months.     

Nanocomposites based on cationic polyelectrolytes and silver nanoparticles: Synthesis,characterization, molybdate retention and antimicrobial activity

The objective of this work was to synthesize nanocomposites based on cationic polyelectrolytes and silver nanoparticles using poly(N-vinylbenzyl-N-triethylammonium chloride) as polymer phase. For that, a nanostructured crosslinker was synthesized from silver nanoparticles (AgNPs) and acrylic acid. Molybdate retention properties of nanocomposites were studied in function of pH and ionic strength. In addition, their antimicrobial properties were evaluated against E. coli and S. aureus. It was evidenced that AgNPs can be stabilized using acrylic acid and that this material can be incorporated to the polymer phase during polymerization by free radical of cationic monomers. The effect of pH on retention of molybdate, by the nanostructured polymer, was significant only to low ionic strength (the order seen was pH 5.0 > pH 7.0 > pH 9.0 for 0.0% NaCl). Results suggest that the main interaction influencing the molybdate retention is electrostatic in nature. Finally, antimicrobial activity was enhanced by incorporation of polymerizable nanostructured crosslinker based on AgNPs.     

A Facile One‐Pot Synthesis of Layered Protonated Titanate Nanosheets Loaded with Silver Nanoparticles with Enhanced Visible‐Light Photocatalytic Performance

Layered protonated titanate nanosheets (LPTNs) loaded with silver nanoparticles are prepared by a simple one‐pot hydrothermal route in silver‐ammonia solution. The as‐synthesized Ag‐loaded LPTNs possess large specific surface area. The Ag nanoparticles are highly dispersed on the surface of the LPTNs. They have negligible effects on the crystal structure, crystallinity, and surface area of the LPTNs but result in considerable enhancement of visible‐light absorption and in a red‐shift of the band gap for the LPTNs. The Ag‐loaded LPTNs show enhanced photocatalytic activity for both liquid‐ and gas‐phase reactions under visible‐light irradiation. Moreover, the photocatalytic activity first increases gradually with increasing Ag loading content, and then decreases after maximizing at an optimal Ag content. At the Ag loading content of 2.87 mol % and 1.57 mol %, the Ag‐loaded LPTNs exhibit the highest visible‐light photocatalytic activity for degradation of rhodamine B in water and mineralization of benzene in air, respectively. An alternative possible mechanism for the enhancement of the visible‐light photocatalytic activity is also proposed.     

Microwave‐Hydrothermal Preparation and Visible‐Light Photoactivity of Plasmonic Photocatalyst Ag‐TiO2 Nanocomposite Hollow Spheres

Visible‐light‐driven plasmonic photocatalyst Ag‐TiO₂ nanocomposite hollow spheres are prepared by a template‐free chemically‐induced self‐transformation strategy under microwave‐hydrothermal conditions, followed by a photochemical reduction process under xenon lamp irradiation. The prepared samples are characterized by using scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, N₂ adsorption‐desorption isotherms, X‐ray photoelectron spectroscopy, UV/Vis and Raman spectroscopy. Production of ?OH radicals on the surface of visible‐light illuminated TiO₂ was detected by using a photoluminescence method with terephthalic acid as the probe molecule. The photocatalytic activity of as‐prepared samples was evaluated by photocatalytic decolorization of Rhodamine B (RhB) aqueous solution at ambient temperature under visible‐light irradiation. The results show that the surface plasmon absorption band of the silver nanoparticles supported on the TiO₂ hollow spheres was red shifted, and a strong surface enhanced Raman scattering effect for the Ag‐TiO₂ nanocomposite sample was observed. The prepared nanocomposite hollow spheres exhibits a highly visible‐light photocatalytic activity for photocatalytic degradation of RhB in water, and their photocatalytic activity is higher than that of pure TiO₂ and commercial Degussa P25 (P25) powders. Especially, the as‐prepared Ag‐TiO₂ nanocomposite hollow spheres at the nominal atomic ratio of silver to titanium ( R ) of 2 showed the highest photocatalytic activity, which exceeds that of P25 by a factor of more than 2.     

Protein-mediated synthesis of antibacterial silver nanoparticles deposited on titanium dioxide nanotube arrays

We report on an effective route to decorate titanium nanotube arrays (TiNT) with silver nanoparticles (AgNPs). In this method, surface-adsorbed antibody molecules serve as templates to bind silver ions by electrostatic interaction. The photocatalytic activity of the TiNT under UV irradiation causes the photoreduction of AgNPs to occur, and the biological template is decomposed simultaneously. This route also was successfuly applied to gold nanoparticles (starting from negatively charged metallic precursor ions). Compared to undecorated samples, the AgNPs/TiNT samples under visible light display a much higher antibacterial activity against Escherichia coli.

The relationship between photocatalytic activity and photochromic state of nanoparticulate silver surface loaded titanium dioxide thin-films

Anatase titania thin-films were prepared by a modified spray-pyrolysis method. Glass substrates were coated at room temperature with an aerosol-spray of a titania sol-gel solution and then annealed at 500 °C to form rough, transparent, crystalline thin-films of anatase TiO(2). Silver nanoparticles were deposited on the surface of these films by a photo-assisted deposition method; films were dip-coated in methanolic solutions of silver nitrate salt and then photo-irradiated for 5 h with UVC light. The AgNO(3) concentration was adjusted to create an array of films with varying silver loadings. The films displayed photochromism; changing colour to orange-brown in UV-light to colourless under white light. The rates of photochromic change, when subjected to four different lighting conditions (UVC, UVA, white light and dark), were analysed by UV-visible spectroscopy. By assessing the photocatalytic activity to these light sources it was found that the initial photochromic state of the material had a profound effect on the films photocatalytic ability. This effect was more pronounced in the more concentrated silver loaded films; where significant enhancements in photoactivity occurred when reactions were initiated from the photo-reduced state. The mode of improved photocatalysis was attributed to the photo-generated electron trapping by silver nanoparticles, which stabilised photo-generated holes and drove photo-oxidation processes. We believe this is the first study in which the relationship between the photochromic state of a thin-film and its subsequent photocatalytic activity is reported.     

Preparation,characterization, and antibacterial activity of composite material: Cotton fabric/hydrogel/silver nanoparticles

A new composite cotton fabric with hydrogel containing silver nanoparticles (AgNPs) has been synthesized by two steps, and simultaneous in situ synthesis of AgNPs under visible light irradiation has been performed. The influence of silver nitrate concentration upon the hydrogel and AgNP properties was studied by colorimetric analysis, scanning electron microscopy, and transmission electron microscopy. The antibacterial activities of the composite materials have been investigated against Acinetobacter johnsonii and Escherichia coli in agar medium and meat-peptone broth. The results showed high inhibition activity toward both test cultures which were better expressed against A. johnsonii.     

Synthesis and plasmonic properties of silver and gold nanoshells on polystyrene cores of different size and of gold–silver core–shell nanostructures

Simple methods of preparing silver and gold nanoshells on the surfaces of monodispersed polystyrene microspheres of different sizes as well as of silver nanoshells on free-standing gold nanoparticles are presented. The plasmon resonance absorption spectra of these materials are presented and compared to predictions of extended Mie scattering theory. Both silver and gold nanoshells were grown on polystyrene microspheres with diameters ranging from 188 to 543 nm. The commercially available, initially carboxylate-terminated polystyrene spheres were reacted with 2-aminoethanethiol hydrochloride (AET) to yield thiol-terminated microspheres to which gold nanoparticles were then attached. Reduction of silver nitrate or gold hydroxide onto these gold-decorated microspheres resulted in increasing coverage of silver or gold on the polystyrene core. The nanoshells were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and UV–vis spectroscopy. By varying the core size of the polystyrene particles and the amount of metal (silver or gold) reduced onto them, the surface plasmon resonance of the nanoshell could be tuned across the visible and the near-infrared regions of the electromagnetic spectrum. Necklace-like chain aggregate structures of gold core–silver shell nanoparticles were formed by reducing silver nitrate onto free citrate-gold nanoparticles. The plasmon resonance absorption of these nanoparticles could also be systematically tuned across the visible spectrum.     

Hydrothermal synthesis and characterization of In<Superscript>3+</Superscript> modified BiVO<Subscript>4</Subscript> nanoparticles with enhanced photocatalytic activity

In³⁺-doped BiVO₄ nanoparticles with enhanced visible light activity have been successfully synthesized by a hydrothermal method. The synthesized materials were characterized by X-ray diffraction, Raman, X-ray photoelectron spectroscopy, scanning electron microscopy, BET surface areas analysis, and ultraviolet–visible diffuse reflectance spectra. In comparison with pure BiVO₄, the In³⁺-doped BiVO₄ displayed greater photocatalytic activity in the degradation of methyl blue under visible light illumination. All samples possessed a single monoclinic structure. The introduction of In ions resulted in structural distortion and the decreased band gap energy, producing more electrons and holes for photocatalytic reaction. In the meantime, the doping In ions entails a red shift in the absorption edge and an increase in the intensity of light absorption. The best photocatalytic performance was obtained with the BiVO₄ sample containing 5.0 mol% In ions.     

溴化银/二氧化钛复合材料的可见光催化性能

将硝酸银的乙醇溶液与溶胶凝胶TiO2混合得到前驱体,随后经共沉淀-煅烧制备得到AgBr/TiO2复合材料;采用扫描电镜、X射线衍射仪、X射线光电子能谱仪分析了复合材料的形貌、晶体结构、Ag元素的价态,采用紫外-可见漫反射光谱仪测定了其光吸收性能;进而以甲基橙(MO)的可见光降解为探针反应测定了AgBr/TiO2复合材料的可见光催化性能.结果表明,当前驱体在不同温度下煅烧后,无定形TiO2颗粒逐渐增大,并逐渐转变为锐钛矿结构;担载的AgBr可明显拓展TiO2的可见光吸收范围;Ag物种主要以Ag+形式存在.当煅烧温度为300℃时,复合材料的光催化活性最高,MO的降解率在60min内达到90%以上;随着煅烧温度的增加,催化活性逐渐降低.     

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.     

Exploration of silver decoration concentration to enhance photocatalytic efficiency of titanium dioxide photocatalysts

Ag decoration on TiO₂ is favorable to absorption of visible light and wider absorption range. Ag nanoparticles playing the role of electron receivers on TiO₂ surface enhance photodegradation. However, excess Ag nanoparticles caused reduced specific surface area of photocatalysts and increased probability of charge recombination, resulting in lower photocatalytic efficiency. In this study, the influence of various Ag decoration concentrations on photocatalytic activity was investigated. Surface treatment by nitric acid after Ag decoration was performed to avoid excessive Ag deposition. The extent of Ag elimination and its impacts on photocatalytic activity were also explored. An optimum Ag content in the photocatalyst was achieved and photocatalytic efficiency was obviously improved. It was found that the number of calcination times affected the crystallinity and stability of photocatalysts. Better photocatalytic efficiency could be obtained after twice calcinations.     

ZnO/graphene-oxide nanocomposite with remarkably enhanced visible-light-driven photocatalytic performance

In this work, a high-performance photocatalyst of ZnO/graphene-oxide (ZnO/GO) nanocomposite was synthesized via a facile chemical deposition route and used for the photodegradation of organic dye from water under visible light. The nanocomposite was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller N(2) adsorption-desorption analysis, and UV-Vis diffusion reflectance spectroscopy. The ZnO/GO nanocomposite consisting of flower-like ZnO nanoparticles anchored on graphene-oxide sheets has a high surface area and hierarchical porosity, which is benefit to the adsorption and mass transfer of dye and oxygen species. For the photodegradation of organic dyes under visible light, ZnO/GO nanocomposite exhibited remarkably enhanced photocatalytic efficiency than graphene-oxide sheets and flower-like ZnO particles. Moreover, the photocatalytic efficiency of ZnO/GO nanocomposite could be further improved by annealing the product in N(2) atmosphere. The outstanding photocatalytic performance was ascribed to the efficient photosensitized electron injection and repressed charge carriers recombination in the composite with GO as electron collector and transporter, thus leading to continuous generation of reactive oxygen species for the degradation of methylene blue.     

LaCoO_3-TiO_2纳米管阵列的构筑及可见光光催化性能

TiO_2纳米管阵列具有较高的光催化活性,但可见光吸收弱,限制了其太阳能利用和环境应用。窄带隙的钙钛矿(ABO3)型氧化物能够吸收大范围波段的可见光,且稳定性高,但光催化活性低。本文首先采用溶胶-凝胶法合成了LaCoO_3纳米颗粒,然后利用电泳沉积技术将LaCoO_3纳米颗粒修饰于TiO_2纳米管阵列表面,构筑了LaCoO_3-TiO_2纳米管阵列。扫描电子显微镜(SEM)、透射电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)的表征结果显示溶胶-凝胶法合成的纳米颗粒为LaCoO_3,其尺寸均匀,结晶度高,平均粒径约为100nm。LaCoO_3纳米颗粒与TiO_2纳米管阵列之间的结合力好。紫外可见吸收光谱(DRS)显示,随着电泳沉积时间的延长,LaCoO_3-TiO_2纳米管阵列的吸收带边逐渐红移700nm。可见光下光催化降解甲基橙(MO)的结果表明,电泳沉积15 min制得的LaCoO_3-TiO_2纳米管阵列对MO的光催化效率最高,其降解速率是相同条件下TiO_2纳米管阵列的4倍。光致发光光谱和电化学阻抗谱证实LaCoO_3纳米颗粒的负载有效地促进了光生电荷的分离和传输,可见光光催化活性明显增强。