多尺度结构Ag/PA6纳米纤维膜的制备及其催化性能（英文）

随着工业的进步,废水处理特别是印染废水的处理成为亟待解决的问题.银纳米粒子因其特殊的物理化学性能而表现出催化活性,但银纳米粒子的团聚限制了其使用,所以出现了一系列新的载体材料,如微球、薄膜和纤维等.其中电纺纳米纤维由于具有高比表面积,作为载体材料具有非常大的优势,而将常规电纺纳米纤维作为载体也已有报道.但是,将具有更高比表面积的电纺纳米纤维作为载体,特别是一种类似于树枝状结构的多尺度纳米纤维作为载体还鲜有报道.本文制备了一种多尺度结构的PA6纳米纤维膜,该纳米纤维膜由直径为50-120 nm的主纤维和10-50 nm的分支纤维构成;由于分支纤维的出现,多尺度结构纳米纤维膜的比表面积得到了提高,可以为银纳米粒子的负载提供更多附着位点.制备的多尺度结构纳米纤维膜通过银胶溶液浸渍成功地负载银纳米粒子,对制备的纳米纤维膜的形态、化学结构以及对亚甲基蓝的催化性能进行了探讨.SEM,EDS和TEM结果表明,银纳米粒子成功地负载在多尺度结构纳米纤维的表面,并且银纳米粒子的粒径以及负载量可以通过变换银胶溶液的浓度合理调控.此外,与常规PA6纳米纤维膜相比,多尺度结构纳米纤维膜更有利于银纳米粒子的分散,同样通过银胶溶液A浸渍,负载在多尺度结构纳米纤维上银纳米粒子粒径为8.6 nm,而负载在普通PA6纳米纤维上银纳米粒子粒径为11.2 nm.XPS分析表明,银纳米粒子成功地负载到多尺度结构纳米纤维上,并且经不同银胶溶液处理,纳米纤维膜的载银量不同.通过O的高能XPS分析发现,银纳米粒子与PA6分子间形成了配位键,这在一定程度上有利于Ag纳米粒子的固定,阻止了Ag纳米粒子的团聚.Ag/PA6纳米纤维膜以及多尺度结构Ag/PA6纳米纤维膜催化降解实验表明,多尺度结构Ag/PA6纳米纤维膜具有较高的催化活性,反应2 h后对10 mg/L亚甲基蓝的降解率达到98.13%,并且降解过程符合伪一级动力学.不同浸渍液浓度处理纳米纤维膜催化实验表明,Ag纳米粒子的大小以及含量都会影响纳米纤维的催化活性,纳米粒子粒径越小,其催化活性越高;不同NaBH_4加入量催化体系催化实验表明,随着NaBH_4加入量的增大,催化体系的降解率增高,其对催化体系的催化性能起着至关重要的作用;其他条件一定,随着染料初始浓度的增大,催化体系的催化性能下降;循环实验表明,经5次循环之后,其降解率仍高达83.5%,该纳米纤维膜具有一定的循环使用性能.     

以新的沉积方法在微乳液中制备Ag/SiO2催化剂

 将硅溶胶引入到微乳液中,成功地制备出负载型Ag/SiO2过氧化氢分解催化剂. 此方法操作简单,分离容易,负载完全. 制备的银纳米粒子粒径在10 nm左右,银粒子在载体上分布均匀, 聚集度低. 采用紫外-可见吸收光谱考察了催化剂的制备过程,发现硅溶胶与银纳米粒子之间存在一定的相互作用,这种相互作用可以促进微乳液中的银粒子在硅溶胶表面的吸附和沉积. 过氧化氢催化分解实验显示,此方法制备的Ag/SiO2催化剂具有很高的催化活性,反应速率常数比同等条件下用浸渍法制备的催化剂高两个数量级.     

聚丙烯腈纳米纤维载银复合膜绿色制备及其催化性能

采用静电纺丝技术和化学镀方法相结合的方法,用聚丙烯腈(PAN)纳米纤维作为载体,以绿色环保的胺化改性替代化学镀传统的敏化、活化前处理,再化学镀银制备胺化聚丙烯腈纳米纤维载银复合膜(Ag/APAN).SEM、XPS、XRD、FTIR等结果表明,银离子能够吸附在经胺化处理后的PAN纳米纤维表面,且能够在纤维表面生成少量单质银;单质银作为催化活性中心,有效地促进化学镀银的进行,在PAN纳米纤维表面生成均匀致密的银纳米粒子层,制备出了以PAN纳米纤维为核,银层为壳的核壳结构复合膜.银纳米粒子附着在纳米纤维表面,可以使银纳米粒子的催化性能得到充分发挥.通过对催化邻-硝基苯胺与硼氢化钠之间氧化还原反应的研究表明,所制备的Ag/APAN纳米纤维复合膜具有很好的催化效果,且不会造成反应体系的二次污染.     

Ag/AgCl复合纳米粒子/聚丙烯腈纳米纤维膜的制备及可见光催化降解甲基橙

通过电纺丝法结合原位还原及原位氧化反应, 成功制备了均匀负载Ag/AgCl复合纳米粒子/聚丙烯腈(PAN)复合纳米纤维膜. 首先利用电纺丝技术制备了PAN/AgNO₃复合纳米纤维, 然后用乙二醇将硝酸银还原成银纳米粒子, 最后采用三氯化铁溶液对材料进行原位氧化. 所得纤维膜材料可以作为高效的可见光催化剂, 具有高可见光利用率, 优异的柔性和高光催化动力学等特性.     

银纳米颗粒负载TiO2复合薄膜的光催化活性及其光电流性质

制备了3种不同粒径的Ag纳米颗粒,将它们分别掺入二氧化钛溶胶, 制备成复合二氧化钛薄膜。利用TEM测定了Ag粒子的大小,测量TiO₂复合膜的光电流,以亚甲基蓝降解反应评价了Ag/TiO₂薄膜的光催化活性.结果表明,负载不同粒径Ag纳米粒子后,TiO₂薄膜的光电流和光催化活性均得到一定程度的提高.当负载平均粒径6.9 nm的Ag粒子后,薄膜具有最高的光电流和最强的光催化活性.     

一种新的高活性CO氧化催化剂Ag/SBA-1

 以SBA-15为载体,采用后修饰法制备了Ag/SBA-15催化剂. XRD和TEM结果表明,金属Ag粒子均匀分散于SBA-15的纳米孔道中,粒子平均大小为4～5 nm. 同时,负载金属Ag纳米粒子后,载体的介孔结构仍然能很好地保持. CO催化氧化测试结果表明,Ag/SBA-15具有很高的催化活性,120 ℃时就能使CO完全氧化. 而在富H2气氛下,80 ℃时CO的转化率达到最大值(48%),此时O2的选择性为28%. 高温H2还原是活化Ag/SBA-15的必要步骤.     

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.     

聚苯乙烯/银纳米粒子复合微球的合成及催化性能

首先通过乳液聚合和浓硫酸酸化制备表面富含磺酸根的磺化聚苯乙烯(PS)微球(直径532 nm),再用其静电吸附[Ag(NH_3)_2]~+离子,最后采用聚乙烯吡咯烷酮还原表面吸附的[Ag(NH_3)_2]~+离子,得到了负载银纳米粒子的PS/AgNPs复合微球.采用扫描电子显微镜、透射电子显微镜、紫外-可见光谱、红外光谱和X射线衍射表征了PS/AgNPs复合微球,并考察了其对甲基蓝(MB)的催化性能.结果表明,Ag纳米粒子高度分散在磺化PS微球表面;该PS/AgNPs复合微球对催化转化MB有较高的催化活性,并可多次重复利用.本研究在催化降解有机污染物方面有一定的实用价值.     

静电纺丝法制备抑菌性聚酰亚胺纳米纤维

采用静电纺丝技术,以联苯四甲酸二酐(BPDA)和4,4'-二氨基二苯醚(ODA)为单体,硝酸银为银源,通过两步法制备含银聚酰亚胺(PI/Ag)纳米纤维.通过X射线衍射(XRD)、透射电子显微镜(TEM)及扫描电子显微镜(SEM)表征了PI/Ag纳米纤维的结构和微观形貌;通过浸渍培养法研究了聚酰亚胺(PI)及PI/Ag纳米纤维的抑菌性能.结果表明,聚酰亚胺基体中存在单质银的立方晶体结构,银粒子在聚酰亚胺基体表面均匀分散,平均粒径为10 nm;PI/Ag纳米纤维对大肠杆菌(E.coli)、金黄色葡萄球菌(S.aureus)和枯草芽孢杆菌(B.subtilis)表现出良好的抑菌效果,最大抑菌率可达99.1%,为聚酰亚胺在耐高温抑菌生物医用材料等领域的应用提供了新的方向.     

维生素E绿色还原法制备银纳米粒子的研究

采用一种绿色还原法制备银纳米粒子,以维生素E为还原剂,淀粉为稳定剂,在液相中还原硫酸银,通过改变溶液的pH值和反应时间,得到不同粒径的黄色银纳米粒子,并分别采用透射电镜、红外光谱、紫外-可见吸收光谱、扫描电镜和电化学方法对银纳米粒子进行表征。结果表明:维生素E在溶液中被氧化生成苯醌,反应得到的银纳米粒子为球形,粒径为8~25 nm;在较强碱性条件下,得到的银纳米粒子尺寸较小,分布较均匀,其平均粒径约为10 nm;不同条件下生成的银溶胶分别在417、411、409、408 nm处出现紫外吸收峰,这些吸收峰均为银纳米粒子的表面共振吸收;生成的银纳米粒子具有很好的电化学性质,并对L-半胱氨酸的电化学反应显示了良好的催化活性。     

Metallogel Template Fabrication of pH‐Responsive Copolymer Nanowires Loaded with Silver Nanoparticles and Their Photocatalytic Degradation of Methylene Blue

Poly(N,N′‐methylenebisacrylamide–4‐vinylpyridine) (P(MBA‐4VP)) nanowires loaded with silver nanoparticles (Ag NPs) have been fabricated by silver metallogel template copolymerization, and subsequently, silver ions are reduced instead of the template being removed. Ag NPs with a diameter of 5–15 nm were dispersed throughout the core of P(MBA‐4VP) nanowires. The size and distribution of the formed Ag NPs could be finely controlled by reduction time. The pH sensitivity of P(MBA‐4VP) nanowires offers the possibility of Ag NP release from the nanowires under acidic conditions. The photocatalytic performance of the P(MBA‐4VP) nanowires loaded with Ag NPs was evaluated for the degradation of methylene blue (MB) under UV light irradiation. Their rate of degradation is dependent on the content and size of the Ag NPs, as well as the pH values of the MB solution. Moreover, the P(MBA‐4VP) nanowires loaded with Ag NPs exhibited high photostability, and the photocatalytic efficiency reduced by only 1.81 % after being used three times.     

Synthesis,Characterization, and Photocatalytic Properties of Ag/TiO2 Composite Nanofibers Prepared by Electrospinning

Ag nanoparticles (Ag NPs) embedded titanium dioxide (TiO₂) nanofibers were fabricated by colloidal sol process, electrospinning, and calcination technique. Calcination of the electrospun nanofibers were heat treated at 600°C for 180 minutes in air atmosphere. X-ray diffraction patterns exhibited that the anatase phase and silver coexisted in the resulted Ag NPs/TiO₂ nanofibers; transmission electron microscopy demonstrated Ag NPs well spread in the porous microstructure of composite fibers. The prepared nanofibers were utilized as photocatalyst for degradation of methyl orange. The degradation rate of methyl orange dye solution containing Ag/TiO₂ composite nanofibers is 99% only after irradiation for 3 hours. It is proposed that these new Ag NPs/TiO₂ composite nanofibers will have potential application in water pollution treatment.      

Deposition of silver nanoparticles on cellulosic fibers via stabilization of carboxymethyl groups

The stabilizing role of carboxymethyl groups on the conformal deposition of Ag NPs over cellulosic fibers was elucidated while developing a method for the deposition of silver nanoparticles (NPs) on cellulose acetate (CA), cellulose and partially carboxymethylated cellulose (CMC) electrospun fibers. CMC fibers were prepared through judicious anionization of deacetylated cellulose acetate fibers. Ag NPs were chemically reduced from silver nitrate using sodium borohydride and further stabilized using citrate. Ag NPs were directly deposited onto CA, cellulose and CMC electrospun fibers at pH conditions ranging from 2.5 to 9.0. The resulting composites of Ag/fiber were characterized by field emission scanning electron microscopy (FESEM) and energy-dispersive X-ray spectroscopy (EDX). The results revealed that the amount of Ag agglomerates and NPs deposited on CMC fibers was higher than that deposited on cellulose fibers at similar pH conditions, and that barely any Ag agglomerates or NPs were deposited on the CA fibers. These results implied that functional groups on the cellulose backbone played two important roles in the deposition of NPs as follows: (1) Hydrogen bonding was the main driving force for agglomeration of NPs when the medium pH was below 4.4, which corresponds to the pKa of carboxylic acid groups; (2) Carboxymethyl groups could replace citrate groups as stabilizers allowing the fabrication of a uniform and evenly distributed Ag NPs layer over CMC fibers at higher pH values. This report also highlights the importance of the substrate’s surface charge and that of the pH of the medium used, on the deposition of NPs. The composite of Ag NPs on CMC electrospun fibers appears to be a promising candidate for wound dressing applications due to its superior antibacterial properties originated by the uniform and even distribution of Ag NPs on the surface of the fibers and the wound healing aptness of the CMC fibers.     

ZnO-based ternary nanocomposite for decolorization of methylene blue by photocatalytic dynamic membrane

In this article, novel Ag–ZnO/g-C₃N₄/GO ternary nanocomposites were prepared via co-precipitation method by 1%w Ag, 50% w g-C₃N₄, 10% w GO concentration and applied in dynamic membranes. The characteristics of Ag–ZnO/g-C₃N₄/GO nanocomposite were evaluated by various techniques such as X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray map, transmission electron microscopy, X-ray photoelectron spectroscopy, photocatalyst. The photocatalytic degradation of methylene blue was investigated under visible light. The photocatalytic efficiency of 93.43% for methylene blue degradation was obtained for Ag–ZnO/g-C₃N₄/GO nanocomposite after 50 min of irradiation, which was remarkably higher than that of pure ZnO, bare g-C₃N₄, Ag–ZnO, and Ag–ZnO/g-C₃N₄ at the same irradiation time. Likewise, in self-forming and pre-coated membranes, ternary nanocomposites can play a vital role in the membrane surface properties, as well as their decolorization performance. The rejection of methylene blue was 30% in pure polyethersulfone membrane, while the photocatalytic degradation of methylene blue in Ag–ZnO/g-C₃N₄/GO nanocomposites was 88.46% and 98.86% after 10 and 15 min of irradiation in both self-forming and pre-coated dynamic membranes, respectively. Experimental results show that the dynamic membrane possesses a higher ability for degradation of MB in a shorter period of time than the static system.     

同轴静电纺丝法在纳米中空Ti02纤维中填充Ag的应用

以聚乙烯吡咯烷酮(PVP)溶胶,钛酸四正丁酯和PVP溶胶,银颗粒为前驱体,以共轴静电纺丝法制备了银填充的TiO2中空纳米纤维.将双组分纤维在200℃下热处理去除乙醇与表面吸附水后,继而在空气气氛中焙烧至600℃.可以得到在内表面上沉积银颗粒的TiO2纳米管,银颗粒的直径为5-40 nm,TiO2纳米管的外径150-300 nm.管臂厚10-20 nm.用红外吸收光谱(IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等测试手段对超细纤维进行了表征.中空纤维的直径和管壁可以通过改变电纺参数来调节.与Ag-TiO2纳米纤维、TiO2纳米中空纤维、TiO2纳米纤维及TiO2纳米粉体相比较,Ag颗粒填充的TiO2纳米中空纤维在光分解亚甲基蓝上表现出了更好的光催化性能.     

Antibacterial thermoplastic polyurethane electrospun fiber mats prepared by 3-aminopropyltriethoxysilane-assisted adsorption of Ag nanoparticles

Antibacterial thermoplastic polyurethane(TPU) electrospun fiber mats were prepared by adsorption of Ag nanoparticles(Ag NPs) onto TPU/3-aminopropyltriethoxysilane(APS) co-electrospun fiber mats from silver sol. The use of APS can functionalize TPU fibers with amino groups, facilitating the adsorption of Ag NPs. The effects of p H of silver sol and APS content on Ag NP adsorption and antibacterial activity were investigated. Ag NP adsorption was evidenced by TEM, XPS and TGA. Significant Ag NP adsorption occurred at p H = 3-5. The main driving force for Ag NP adsorption is electrostatic interaction between ―NH3~+ of the fibers and ―COO-derived from the ―COOH group capped on the surfaces of Ag NPs. The antibacterial activity of the Ag NP-decorated TPU/APS fiber mats was investigated using both gram-negative Escherichia coli and gram-positive Bacillus subtilis. The antibacterial rate increases with increasing APS content up to 5% where the antibacterial rates against both types of bacteria are over 99.9%.     

新型杂多酸盐光催化降解亚甲基蓝染料废水

以水热自组装法合成的新型杂多酸盐[PMo₈V₆O₄₂][Co(Phen)₂][Him]₂·2H₃O·3H₂O(1),通过红外光谱、拉曼光谱、紫外-可见光谱、光电子能谱和X粉末衍射等技术手段进行表征。 以此物质为催化剂光催化降解亚甲基蓝染料废水。 分别讨论催化剂投加量、亚甲基蓝废水初始浓度、废水溶液酸度(pH)对亚甲基蓝降解率的影响。 实验结果表明:催化剂投加量为50 mg/L、亚甲基蓝初始浓度为4 mg/L、模拟废水溶液的初始pH=1、降解时间220 min时,废水降解率可达到99.2%。 光催化动力学分析显示,以合成杂多酸盐为催化剂光催化降解亚甲基蓝废水降解过程满足一级动力学方程,该一级方程反应速率常数为0.0144 min^-1,拟合常数为0.9918。 另外,此催化剂还表现出较好的重复使用性能,连续使用5 次后降解率仍为92.4%。     

Hierarchical‐Structured Anatase‐Titania/Cellulose Composite Sheet with High Photocatalytic Performance and Antibacterial Activity

Bulk hierarchical anatase‐titania/cellulose composite sheets were fabricated by subjecting an ultrathin titania gel film pre‐deposited filter paper to a solvo‐co‐hydrothermal treatment by using titanium butoxide as the precursor to grow anatase‐titania nanocrystallites on the cellulose nanofiber surfaces. The titanium butoxide specie is firstly absorbed onto the nanofibers of the cellulose substance through a solvothermal process, which was thereafter hydrolyzed and crystallized upon the subsequent hydrothermal treatment, leading to the formation of fine anatase‐titania nanoparticles with sizes of 2–5 nm uniformly anchored on the cellulose nanofibers. The resulting anatase‐titania/cellulose composite sheet shows a significant photocatalytic performance towards degradation of a methylene blue dye, and introduction of silver nanoparticles into the composite sheet yields an Ag‐NP/anatase‐titania/cellulose composite material possessing excellent antibacterial activity against both Gram‐positive and Gram‐negative bacteria.     

Design synthesis and photocatalytic activity of a novel lilac-like silver-vanadate hybrid solid based on dicyclic rings of [V4O12]4- with {Ag7}7+ cluster

An unusual two-dimensional bicyclic [V(4)O(12)](4-)-based coordination polymer with a novel maximum {Ag(7)}(7+) cluster and containing five crystallographically-independent silver atoms was obtained and showed good photocatalytic activity for the degradation of methylene blue.     

Fabrication and characterization of silver nanostructures conformal coating layer onto electrospun N6 nanofibers with improved physical properties

In this communication, colloidal silver (Ag) nanostructures were synthesized and deposited directly onto electrospun nylon 6 (N6) fibers without using surface modifier in the form of an ultrathin conformal coating layer via a hydrothermal treatment. The morphological, structural, and thermal properties of the Ag/N6 nanocomposite membranes were analyzed by field-emission scanning electron microscopy (FESEM), X-ray diffraction, X-ray photoelectron spectroscopy, and differential scanning calorimetry (DSC). FESEM imaging showed that the Ag coating on individual N6 nanofibers was continuous, uniform, and compact. A DSC study of the nanocomposites illustrated a strong interfacial adhesion of the Ag layer with N6 nanofiber surfaces via strong hydrogen bonds. A possible mechanism for hydrogen bond formation during the hydrothermal process was proposed. Further, it was found that the transition of the meta-stable γ-form into the thermodynamically more stable α-form of N6 structure was achieved; therefore, the hydrothermal process did not cause chain degradation.