光催化合成金属Ag纳米颗粒的生长机制——晶核密度控制的生长模式转换

利用AgNO₃水溶液,通过严格控制TiO₂薄膜的化学活性,系统研究了在TiO₂表面光催化合成金属Ag纳米颗粒的生长行为。研究发现,光催化合成金属Ag纳米颗粒存在着两个完全不同的生长机制,分别对应着金属Ag纳米颗粒的各向同性和各向异性生长。当溶液浓度较低时,Ostwald熟化（OR）机制主导着金属Ag纳米颗粒的长大过程;当溶液浓度较高时,取向附生（OA）机制决定着金属Ag纳米颗粒长大成纳米片。原位消光光谱分析表明,OR机制和OA机制生长的前期具有相近消光特征,决定金属Ag纳米颗粒生长模式的关键是AgNO₃溶液的浓度,更准确地说是金属Ag初级晶核的局域密度。在此基础上提出了有关光催化合成金属Ag纳米颗粒的生长模型。     

聚氧乙烯类表面活性剂体系中银纳米颗粒的合成

将AgNO3水溶液与非离子表面活性剂AEO 7按一定比例混合,即可形成六方液晶.体系中的Ag＋被表面活性剂分子AEO 7还原成Ag,形成Ag的纳米颗粒.在这一过程中,非离子表面活性剂液晶既是还原剂,又是反应介质和稳定剂.在合成过程中,聚氧乙烯类表面活性剂的乙氧基形成了氢过氧化物,从而具有了将Ag＋还原成单质Ag的能力. Ag纳米颗粒生长到一定时间不再继续变大,这表明颗粒的长大是靠自身的生长,并不发生颗粒聚集.控制液晶体系中反应物的浓度、含量以及反应时间可得到不同大小的Ag纳米颗粒.所形成的Ag纳米颗粒的平均粒径一般小于10 nm.     

TiO_2分级结构/Ag_3PO_4复合材料的可见光催化性能

制备了具有分级结构的海胆状TiO2纳米材料,并通过原位沉积法将可见光响应的Ag3PO4纳米颗粒沉积到TiO2的纳米分级结构上,合成了具有高效稳定可见光催化性能的系列TiO2分级结构/Ag3PO4复合材料,对比测试了系列材料对罗丹明B(RhB)的光催化降解性能.结果表明,TiO2分级结构/Ag3PO4复合材料光催化性能明显高于纯相的Ag3PO4光催化剂,同时也明显优于TiO2(P25)/Ag3PO4复合光催化剂,其中分级结构TiO2与Ag3PO4摩尔比为1∶1的复合材料具有最强的光催化性能,在可见光照射6min内可实现RhB的完全脱色.分析结果表明,与纳米颗粒TiO2相比,具有海胆状纳米结构的TiO2可为Ag3PO4的负载提供更多的担载位点,增加TiO2和Ag3PO4的接触面积,进而提升Ag3PO4光激发产生的光生电子-空穴的分离效率.同时在光降解过程中,Ag3PO4表面存在的少量Ag+会逐渐还原成单质Ag0,通过Ag0的等离子体共振效应,可增加对光子的吸收转换能力,从而进一步提高该复合材料光催化降解染料的性能.     

Ag／TiO2复合纳米催化剂的制备和表征及其光催化活性

 采用光还原沉积贵金属法，制备了Ag／TiO2复合纳米催化剂．通过调节溶液的pH值控制TiO2表面负载银的形貌，利用AAS，XRD，TEM和XPS等手段对样品进行了表征．以苯胺氧化为模型反应，考察了Ag／TiO2复合纳米催化剂样品的光催化活性以及银沉积量和沉积形貌对催化剂活性的影响．结果表明，通过调控光还原沉积条件，可在平均粒径为24nm左右的TiO2颗粒上获得3nm左右均匀分散的银粒子；在TiO2上沉积适量的具有较高分散度的金属Ag，能有效提高TiO2对苯胺氧化反应的光催化活性．     

高活性Ag修饰TiO2空心八面体光催化剂的简易模板诱导合成

贵金属修饰的TiO2空心纳米光催化材料由于具有大的比表面积、低的质量密度、良好的表面渗透性、强的光吸收能力以及界面电荷的快速转移,因而表现出优异的光催化性能.为了制备结构可控且精良的贵金属修饰TiO2空心纳米光催化材料,人们先后采用湿化学法、高温固相法、声化学法及光化学沉积法等.由于在制备过程中涉及多种异相材料的合成和结构控制,因此上述合成方法通常需要复杂且多步过程(有些过程甚至很容易导致结构破坏),从而限制了其在光催化领域的实际应用.本文开发了一种简单的模板诱导法,成功制备了Ag纳米粒子修饰的TiO2空心八面体光催化剂.合成过程包括模板指导沉积和原位模板溶解.以Ag2O八面体为模板, TiF4水溶液为前驱体,首先通过TiF4水解形成TiO2纳米粒子沉积在Ag2O模板表面,而TiF4水解产生的酸性HF水溶液可原位溶解碱性的Ag2O模板,从而一步制得TiO2空心八面体.同时,利用Ag2O以及Ag+离子的光敏特性,在光照条件下使Ag2O和Ag+离子生成Ag纳米颗粒,直接沉积在TiO2空心八面体的内外表面,得到Ag/TiO2光催化剂.由此可见,该合成方法具有明显的步骤少的优点.扫描电镜、透射电镜、能量散射和紫外-可见光谱等表征结果表明成功制得内外Ag纳米粒子修饰的TiO2空心八面体光催化剂,其中TiO2空心八面体的壁厚约为25 nm,边长约为1μm,而修饰在其表面的Ag纳米粒子尺寸仅为5–10 nm.此外,通过控制TiF4前驱体浓度,还可制备核壳结构的Ag2O@TiO2八面体以及不同壁厚Ag修饰的TiO2空心八面体,表明该方法在Ag/TiO2形貌合成上的多样性和可控性.为了获得良好的光催化活性,对制备的Ag纳米粒子修饰的TiO2空心八面体光催化剂进行了不同温度的热处理. X射线衍射结果表明,即使在600 oC高温下,制备的Ag/TiO2空心八面体光催化剂依然能够保持原有的特殊形貌和锐钛矿TiO2晶型.该温度明显高于TiO2从锐钛矿向金红石转变的温度.这说明合成的Ag/TiO2能在保持高活性锐钛矿相的同时获得更好的结晶性.这可能是由于分散在TiO2原始晶粒周围的Ag纳米粒子能阻止其进一步长大,从而抑制了其晶型转变.不同样品光催化降解甲基橙的结果表明,经600oC高温热处理的样品表现出最高的光催化活性,相应的反应速率常数为0.11 min？1.这应得益于该光催化剂具有以下三个特点：(1) TiO2空心八面体的薄壁结构能够缩短光照条件下光生电子和空穴从内部扩散到表面的距离;(2)由于贵金属Ag纳米粒子沉积在TiO2薄壁的内外两个表面以及TiO2和Ag形成肖脱基势垒,因此在它们接触的界面上能够发生更快的界面电荷转移;(3)高温处理导致TiO2良好的晶化以及高活性锐钛矿TiO2晶型的保持.     

纳米TiO2对Ag(Ⅰ)配合物的吸附

利用纳米TiO2的表面吸附活性,以[S2O3] 2-为络合剂,应用火焰原子吸收光谱检测方法,高效吸附分离了水中痕量Ag(Ⅰ).系统研究了纳米TiO2的晶体结构、溶液的pH值、吸附时间、 Ag(Ⅰ)的起始浓度及常见共存离子对吸附率的影响,确定了最佳吸附条件.FTIR光谱分析结果表明,Ag(Ⅰ)配合物以物理作用吸附在纳米TiO2颗粒表面.纳米TiO2对Ag(Ⅰ)的吸附等温线为S型,表现出多分子层吸附特征.硝酸和硫脲混合溶液可将吸附在TiO2纳米颗粒表面的Ag(Ⅰ)全部洗脱.     

纳米TiO2对Ag(I)配合物的吸附

利用纳米TiO2的表面吸附活性, 以[S2O3]2-为络合剂, 应用火焰原子吸收光谱检测方法, 高效吸附分离了水中痕量Ag(Ⅰ). 系统研究了纳米TiO2的晶体结构、溶液的pH值、吸附时间、Ag(Ⅰ)的起始浓度及常见共存离子对吸附率的影响, 确定了最佳吸附条件. FTIR光谱分析结果表明, Ag(Ⅰ)配合物以物理作用吸附在纳米TiO2颗粒表面. 纳米TiO2对Ag(Ⅰ)的吸附等温线为S型, 表现出多分子层吸附特征. 硝酸和硫脲混合溶液可将吸附在TiO2纳米颗粒表面的Ag(Ⅰ)全部洗脱.     

TiO_2/Ag_2NCN复合光催化剂的制备与可见光催化性能

利用银盐与单氰胺水溶液的沉淀反应,通过共混不同质量分数的纳米TiO2粒子制备了TiO2/Ag2NCN复合光催化剂.使用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、傅里叶变换红外(FTIR)光谱仪和紫外-可见(UV-Vis)吸收光谱仪对复合光催化剂的结构进行了表征.结果表明,锐钛矿相TiO2纳米颗粒沉积在Ag2NCN表面形成异质结构,二者间以弱的物理作用力相结合.TiO2的掺杂使得复合颗粒的UV-Vis吸收光谱发生红移,带隙变窄.以亚甲基蓝(MB)为光催化降解对象,研究了TiO2/Ag2NCN复合颗粒的可见光催化活性.结果表明,与单一Ag2NCN相比,复合颗粒表现出增强的光催化性能.对TiO2/Ag2NCN复合颗粒的光催化反应动力学过程及光催化机理进行了探讨.     

Ag/TiO2聚丙烯负载膜的制备及其光催化与抗菌特性研究

以聚丙烯负载二氧化钛膜为载体,在一定浓度的AgNO3水溶液中,利用光还原在氧化钛膜表面还原Ag,制备载银二氧化钛负载膜,在室光和太阳光下,分别选择Ag/TiO2聚丙烯膜、TiO2聚丙烯膜和活性炭聚丙烯膜,研究膜的抗菌特性和光催化特性.结果表明:Ag/TiO2负载膜由于同时具有Ag和TiO2的双重效用,显示了良好的杀菌特性,无论是在室内还是太阳光下,都没有检测到活的微生物;在水溶液中检测Ag/TiO2负载膜和TiO2负载膜的光催化特性,发现由于银离子的催化活性中心的作用,光催化降解甲基橙的能力与TiO2负载膜相比,能够提高10%左右,显示了良好的光化学特性.     

局部表面等离子体共振可调的MoO3-x-TiO2纳米复合物用于提高可见光下光催化还原CO2的性能

利用太阳能光催化还原CO2和H2O到燃料和化学品是一条极具吸引力但又充满挑战性的转化途径.迄今为止,只有非常有限的光催化剂已经被报道可以在可见光照射下光催化还原CO2.局部表面等离子体共振(LSPR)现象可以被用作一种有效的开发可见光催化剂的策略.贵金属Au,Ag,Pt等的LSPR现象已经被较为广泛的研究,并应用于光催化、光热、气敏等多种领域.而低价态金属自掺杂的金属氧化物,如MoO3-x和WO3-x,也被证明具有LSPR现象,可用于开发更加廉价的可见光催化剂.本文通过简单的溶剂热法成功合成了低价态Mo自掺杂的MoO3-x纳米片催化剂,并在合成过程中原位加入TiO2纳米颗粒(TiO2-NP)和TiO2纳米棒(TiO2-NT),构建了MoO3-x-TiO2纳米复合物.电镜表征显示,MoO3-x-TiO2-NT纳米复合物中,MoO3-x纳米片和TiO2纳米管的结合更为紧密.UV-vis光谱显示,TiO2的复合不仅可以增强MoO3-x可见区的吸收强度,同时吸收峰的位置也发生了蓝移.XPS表征显示,TiO2复合后,MoO3-x中Mo5+的比例明显增加,从而提高了MoO3-x中自由电子的浓度,进而增强了LSPR现象和LSPR吸光能力,且TiO2纳米管相对TiO2纳米颗粒具有更好的促进效果.MoO3-x纳米片具有在可见光照射下光催化还原CO2的性能,CO的生成速率为2.8μmol g-1 h-1.复合TiO2纳米颗粒后,MoO3-x-TiO2-NP纳米复合物上,CO的生成速率提高到6.8μmol g-1 h-1.当复合TiO2纳米管时,光催化性能显著提高,在MoO3-x-TiO2-NT纳米复合物上,CO的生成速率可达12μmol g-1 h-1,约为MoO3-x纳米片的四倍,此外还可观测到CH4的生成.当我们将反应气氛由CO2替换成N2后,CO和CH4的生成量几乎为零,证明CO和CH4的生成主要来自CO2的光催化还原.此外,我们还考察了MoO3-x-TiO2-NT纳米复合物光催化还原CO2的催化性能稳定性,以12 h反应时间为一个循环,经3个循环反应后,催化剂的活性基本保持不变,证明该催化剂具有较好的稳定性.综上,我们通过MoO3-x纳米片和TiO2复合的策略,增强了MoO3-x纳米片的LSPR效应,提升了催化剂对可见光的吸收能力,进而提高了MoO3-x-TiO2-NT纳米复合物光催化还原CO2的性能.MoO3-x-TiO2-NT纳米复合物是一种具有发展潜力的光催化还原CO2的可见光催化剂,且该纳米复合物调变LSPR效应的策略还有望用于增强其他LSPR光催化材料的光催化性能.     

Synthesis of Cu2O/Ag Composite with Visible Light Photocatalytic Degradation Activity for in situ SERS Analysis

A multifunctional Cu₂O/Ag micro-nanocomposite, which has the characteristics of high catalytic activities under the visible light and high surface-enhanced Raman scattering (SERS) activity, was fabricated via a facile method and employed for the in situ SERS monitoring of the photocatalytic degradation reaction of crystal violet. Through the variation of the AgNO₃ concentration, Ag content on the Cu₂O template can be controllably tuned, which has great influence on the SERS effect. The results indicate that Ag nanoparticles form on the Cu₂O nanoframes to obtain the Cu₂O/Ag nanocomposite, which can act as an excellent bifunctional platform for in situ monitoring of photocatalytic degradation of organic pollutions by SERS.     

Fabrication and Formation Mechanism of Ag Nanoplate‐Decorated Nanofiber Mats and Their Application in SERS

We report a new simple method to fabricate a highly active SERS substrate consisting of poly‐m‐phenylenediamine/polyacrylonitrile (PmPD/PAN) decorated with Ag nanoplates. The formation mechanism of Ag nanoplates is investigated. The synthetic process of the Ag nanoplate‐decorated PmPD/PAN (Ag nanoplates@PmPD/PAN) nanofiber mats consists of the assembly of Ag nanoparticles on the surface of PmPD/PAN nanofibers as crystal nuclei followed by in situ growth of Ag nanoparticles exclusively into nanoplates. Both the reducibility of the polymer and the concentration of AgNO₃ are found to play important roles in the formation and the density of Ag nanoplates. The optimized Ag nanoplates@PmPD/PAN nanofiber mats exhibit excellent activity and reproducibility in surface‐enhanced Raman scattering (SERS) detection of 4‐mercaptobenzoic acid (4‐MBA) with a detection limit of 10^?10 m , making the Ag nanoplates@PmPD/PAN nanofiber mats a promising substrate for SERS detection of chemical molecules. In addition, this work also provides a design and fabrication process for a 3D SERS substrate made of a reducible polymer with noble metals.     

Antibacterial ultrafiltration membrane with silver nanoparticle impregnation by interfacial polymerization for ballast water

Interfacial polymerization technology was employed to immobilize silver (Ag) nanoparticles on the surface of commercial polyethersulfone (PES) membrane to develop antibacterial and antifouling ultrafiltration membrane. Ag nanoparticles were prepared from the reduction of silver nitrate (AgNO₃) by sodium borohydride in the presence of polyethyleneimine (PEI) as the stabilizer. The encapsulated Ag nanoparticles in the PEI solution were embedded into the PEI membrane when trimesoyl chloride solution was used to crosslink the PEI solution with the PES membrane, forming Ag-polyamide (PA) networks through the interfacial polymerization reaction. Experimental results showed that the membrane prepared with 50 mmol/L of AgNO₃ and 20 mmol/L of PEI had the optimized antibacterial effect against Escherichia coli. Bacterial concentration and species were also investigated. Exiguobacterium aestuarii and Staphylococcus aureus which are gram-positive bacteria, needed significantly more time for the Ag-PA/PES membrane to kill the bacteria completely when compared to E.coli and Vibrio coralliilyticus which are gram-negative bacteria. This study showed that Ag nanoparticles impregnated in membrane surfaces were 100% effective in killing various types of marine bacteria and bacteria in the seawater collected off Sentosa Island in Singapore. These membranes exhibit excellent antibacterial and antifouling properties which can be used to kill bacteria in ballast water and seawater.     

Synthesis, Structure and Growth Mechanism of Size and Shape Tunable Au/Ag Bimetallic Nanoparticles

By simply adding ascorbic acid in advance of AgNO₃, the size and shape controllable Au/Ag bimetallic nanoparticles (NP) were prepared in the traditional Au growth solution free of seed at room temperature. The size distribution of NP is well uniform with ca. 10%–15% standard deviation in diameter. By changing CTAB concentration, the size and shape of NPs are tunable. After researching the surface‐enhanced Raman spectroscopy (SERS) behavior of the prepared NPs, an enhancement factor varied from 4.3×10⁴ to 1.1×10⁵ was obtained for the NP centered at ca. (64±8) nm. Electrochemical cyclic voltammetric results revealed that the so formed nanoparticles were Au riched Au/Ag bimetallic NP, and this formation might be due to the disproportionation reaction of Au⁺ prompted by Ag⁺ and the under potential deposition process of Ag⁺ on Au.     

Preparation and characterization of Ag‐deposited aminosilane‐modified silicate by chemical reduction method

Nanocomposites based on silver (Ag) and organically modified silicate (Ormosil) were prepared by an in situ reduction method, in which silver nitrate, tetraethoxysilane and N‐[3‐(trimethoxysilyl)propyl]diethylenetriamine (ATS) acted as precursor, linker, and colloidal suspension stabilizer, respectively. The objective of the study was to produce silver nanoparticles through AgNO₃ chemical reduction in a continuous media, in which aminosilanes act as superficial modifiers of Ag nanoparticles, inhibiting their growth and preventing aggregation. The physical properties of the Ormosil/Ag composites were examined using NMR, electron spin resonance, scanning electron microscope, transmission electron microscope, and thermal gravimetric analysis spectroscopy, the results of which indicated that Ag was incorporated in the Ormosil matrix after impregnation. The Ag content and surface morphology of the Ormosil/Ag composites depended on the initial concentration of AgNO₃. The antibacterial effects of the Ormosil/Ag composites were assessed by the zone of inhibition and plate‐counting methods, and an excellent antibacterial performance was discovered. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Photoinduced charge property of Ag‐TiO2 films and its relationships with photocatalytic activity under visible illumination

In this article, TiO₂ films were synthesized by traditional spin coating method. To improve their photocatalytic activities, we deposited silver on these films by photodeposition. These films also were characterized by several testing techniques, such as X‐ray diffraction, ultraviolet–visible diffuse reflection spectrum, XPS, Raman spectroscopy (Raman), surface photovoltage spectroscopy, and SEM. The activity of different films was evaluated for degrading rhodamine B solution under visible illumination. The effects of AgNO₃ solution concentration on photoinduced charge property and photocatalytic activity were investigated. The results show that the Ag‐TiO₂ film immersed in 10^?3 mol·L^?1 AgNO₃ solution exhibits higher activity, which is in good agreement with the characterization results. The weaker the surface photovoltage spectroscopy signal, the higher the photocatalytic activity. Moreover, the activity of some films is higher than that of international Degussa P‐25 TiO₂ under visible illumination. Copyright © 2012 John Wiley & Sons, Ltd.     

Silver nanoparticles dispersed in electrospun polyacrylonitrile nanofibers via chemical reduction

Silver (Ag) nanoparticles were prepared in PAN nanofibrous film by a sol–gel derived electrospinning and subsequent chemical reduction for 30 min in hydrazine hydroxide (N₂H₅OH) aqueous solution. Antimicrobial properties of the AgNO₃/PAN precursor solution against gram positive Staphylococcus aureus ATCC 6538 and gram negative Escherichia coli ATCC 25922 were investigated. The formation of clear zone suggested that the PAN solution containing Ag⁺ ions were effective on the inhibition of bacterial growth. The Ag/PAN nanocomposite film, characterized by XRD, TEM and UV absorption spectrophotometer, revealed that highly crystallized cubic Ag particles with diameters of less than 5.8 nm were dispersed homogeneously in PAN nanofibers.     

Ag/AgBr/Co–Ni–NO3 Layered Double Hydroxide Nanocomposites with Highly Adsorptive and Photocatalytic Properties

A facile anion‐exchange precipitation method was used to synthesize bifunctional Ag/AgBr/Co–Ni–NO₃ layered double hydroxide (LDH) nanocomposites by adding AgNO₃ solution to a suspension of Co–Ni–Br LDH. The Ag/AgBr nanoparticles were highly dispersed on the sheets of Co–Ni–NO₃ LDH. The prepared nanocomposites were used to adsorb and photocatalytically degrade organic pollutants from water. Without light illumination, the nanocomposites quickly adsorbed methyl orange, and the adsorptive capacity, which can reach 230 mg g^?1, is much higher than those of Co–Ni–Br LDH, Ag/AgBr, and activated carbon. The photocatalytic activities of the nanocomposites for the removal of dyes and phenol are higher than those of Co–Ni–Br LDH and Ag/AgBr. The proposed method can be applied to prepare other LDH/silver salt composites. The high absorptive capacity and good photocatalytic activity of such nanostructures could have wide applications in wastewater treatment.     

Preparation and characterization of stable monodisperse silver nanoparticles via photoreduction

Silver nanoparticles were synthesized by UV irradiation of [Ag(NH₃)₂]⁺ aqueous solution using poly(N-vinyl-2-pyrrolidone) (PVP) as both reducing and stabilizing agents. The formation of silver nanoparticles was confirmed from the appearance of surface plasmon absorption maxima around 420 nm. It was found that the formation rate of silver nanoparticles from Ag₂O was much quicker than that from AgNO₃, and the absorption intensity increased with PVP concentration as well as irradiation time. The maximum absorption wavelength (λ_max) was blue shift with increasing PVP content until 8 times concentration of [Ag(NH₃)₂]⁺ (wt%). The transmission electron microscopy (TEM) showed the resultant particles were 4–6 nm in size, monodisperse and uniform particle size distribution. X-ray diffraction (XRD) demonstrated that the colloidal nanoparticles were the pure silver. In addition, the silver nanoparticles prepared by the method were stable in aqueous solution over a period of 6 months at room temperature (25 °C).