纳米银胶体的制备和表征
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摘要
作为一种纳米材料,纳米银具有体积效应、表面效应、量子尺寸效应和宏观量子隧道效应,在超导、光电、抗菌、催化等领域具有极大的开发潜力和应用价值。要使纳米银走出实验室,实现产业化,必须掌握纳米银晶体的生长规律和影响因素,探索出一套快速、稳定而又绿色的制备方法。
国内外纳米银的制备方法繁多,其中液相化学还原法是目前实验室和工业上广泛采用的一种方法。该方法工艺条件易控制,设备要求相对不高,生产速度快、产率高,便于工业化大规模生产。本实验以硝酸银为原料,鞣酸为还原剂和保护剂,控制反应条件,制备出了球形、分散性和稳定性好、粒度可控的纳米银溶胶,同时原料对环境无害,生产过程中杂质少,符合环境友好的要求。
实验结果表明,AgNO3和鞣酸溶液的浓度、反应温度、pH等条件都会对纳米银胶体的粒度产生影响,其中AgNO3溶液浓度的影响最大,调节其浓度,可以控制粒度在20-80 nm之间。pH在7.0左右时,纳米银的产率最高。超声分散有利于提高纳米银胶体的分散性和稳定性,通过对比发现,间歇超声的分散效果更好。
通过紫外可见吸收光谱、X射线衍射、红外光谱、透射电镜等手段对纳米银胶体颗粒进行了表征。结果表明,纳米银颗粒的形态为球形或类球形,晶体为面心立方,分散比较均匀。纳米银颗粒的粒度变大,最大吸收波长红移,胶体的外观颜色变深。纳米银颗粒与羟基发生电荷吸附作用,固定在鞣酸的空间网状结构中,稳定存在。
Due to their volume effect, surface effect, quantum dimension effect and macroscopic quantum tunneling effect, Ag nanoparticles are the prominent candidates for applications in superconduction, electronics, antibacterial actions and catalysis. It is of great importance to know the growth rules of Ag nanocrystal and the factors which influence the growth process in order to get a fast, stable and green way of Ag nanoparticles preparation.
There are many methods to prepare Ag nanoparticles domestic and abroad, in which the chemical reduction in liquid phase is the method we often use in present laboratory and industry because of its multiple advantages such as low cost and high efficiency. In this paper, sphere-shaped Ag nanoparticles were prepared using silver nitrate, tannic acid as both reducing agent and protecting agent. The monodispersity and stability of Ag nanoparticles can be well controlled and meets the environment-benign demand.
The experiment results show that the average size of Ag nanoparticles is in relation to the temperature and the concentration of silver nitrate and tannic acid. Among them, the concentration of silver nitrate makes the biggest contribution. By means of adjusting the amount of silver nitrate, the size of Ag nanoparticles can be controlled between 20 and 80 nm. The yield of Ag nanoparticles gets higher when the pH is about 7.0. Ultrasonic treatment is helpful to improve the monodispersity and stability of Ag nanoparticles. We found intermittent ultrasonic treatment is more effective compared with continuous treatment.
The prepared Ag nanoparticles were characterized by UV-Vis, XRD, FTIR and TEM. It demonstrated that the resulting nanoparticles are spherical, of face-centered structure and well-dispersed. When the average size of Ag nanoparticles gets bigger, the color of Ag colloids gets darker and the UV-Vis spectra gets red-shifted. There could be a coordination bond between the silver atom and the hydroxyl group of tannic acid, which stabilize the Ag nanoparticles in the spatial reticulate structure of tannic acid.
国内外纳米银的制备方法繁多,其中液相化学还原法是目前实验室和工业上广泛采用的一种方法。该方法工艺条件易控制,设备要求相对不高,生产速度快、产率高,便于工业化大规模生产。本实验以硝酸银为原料,鞣酸为还原剂和保护剂,控制反应条件,制备出了球形、分散性和稳定性好、粒度可控的纳米银溶胶,同时原料对环境无害,生产过程中杂质少,符合环境友好的要求。
实验结果表明,AgNO3和鞣酸溶液的浓度、反应温度、pH等条件都会对纳米银胶体的粒度产生影响,其中AgNO3溶液浓度的影响最大,调节其浓度,可以控制粒度在20-80 nm之间。pH在7.0左右时,纳米银的产率最高。超声分散有利于提高纳米银胶体的分散性和稳定性,通过对比发现,间歇超声的分散效果更好。
通过紫外可见吸收光谱、X射线衍射、红外光谱、透射电镜等手段对纳米银胶体颗粒进行了表征。结果表明,纳米银颗粒的形态为球形或类球形,晶体为面心立方,分散比较均匀。纳米银颗粒的粒度变大,最大吸收波长红移,胶体的外观颜色变深。纳米银颗粒与羟基发生电荷吸附作用,固定在鞣酸的空间网状结构中,稳定存在。
Due to their volume effect, surface effect, quantum dimension effect and macroscopic quantum tunneling effect, Ag nanoparticles are the prominent candidates for applications in superconduction, electronics, antibacterial actions and catalysis. It is of great importance to know the growth rules of Ag nanocrystal and the factors which influence the growth process in order to get a fast, stable and green way of Ag nanoparticles preparation.
There are many methods to prepare Ag nanoparticles domestic and abroad, in which the chemical reduction in liquid phase is the method we often use in present laboratory and industry because of its multiple advantages such as low cost and high efficiency. In this paper, sphere-shaped Ag nanoparticles were prepared using silver nitrate, tannic acid as both reducing agent and protecting agent. The monodispersity and stability of Ag nanoparticles can be well controlled and meets the environment-benign demand.
The experiment results show that the average size of Ag nanoparticles is in relation to the temperature and the concentration of silver nitrate and tannic acid. Among them, the concentration of silver nitrate makes the biggest contribution. By means of adjusting the amount of silver nitrate, the size of Ag nanoparticles can be controlled between 20 and 80 nm. The yield of Ag nanoparticles gets higher when the pH is about 7.0. Ultrasonic treatment is helpful to improve the monodispersity and stability of Ag nanoparticles. We found intermittent ultrasonic treatment is more effective compared with continuous treatment.
The prepared Ag nanoparticles were characterized by UV-Vis, XRD, FTIR and TEM. It demonstrated that the resulting nanoparticles are spherical, of face-centered structure and well-dispersed. When the average size of Ag nanoparticles gets bigger, the color of Ag colloids gets darker and the UV-Vis spectra gets red-shifted. There could be a coordination bond between the silver atom and the hydroxyl group of tannic acid, which stabilize the Ag nanoparticles in the spatial reticulate structure of tannic acid.
引文
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[2]黄礼煌.金银提取技术,北京:冶金工业出版社,2001, 7-12
[3] Brust M, Kiely C J. Some recent advances in nanostructure preparation from gold and silver: a short topical review, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2002, 202: 175-186
[4]张立德,牟季美.纳米材料和纳米结构,北京:科学出版社,2001,1-3
[5]王永康,王立.纳米材料科学与技术,杭州:浙江大学出版社,2002,7-8
[6] Kumpmann A, Gunther B, Kunze H D. Thermal stability of ultrafine-grained metals and alloys, Material Science Engineering, 1993, A168(2): 165-169
[7]顾宁,付得刚,张海黔.纳米技术与应用,北京:人民邮电出版社,2002: 16-18
[8] Alvarez M M, Khoury J T, Schaaff T G, et al. Optical absorption spectra of nanocrystal gold molecules, Journal Physical Chemistry B, 1997, 101:3706-3710
[9]张文征,张羽天.载银抗菌材料的研究与开发,化工新型材料,1997(7):20-22
[10]孙成林,张宝荣.纳米银水悬浮液抗菌材料的研制,硫磷设计与粉体工程,2006(4):26-29
[11]石川,程漠杰等.纳米银催化的甲烷选择还原NO反应研究,复旦学报(自然科学版),2002,41 (3):269-273
[12]李新平,刘建军,于迎春等.纳米银/蒙脱土催化剂的制备及对亚甲基蓝的催化降解,北京化工大学学报,2006,33(5):86-89
[13]曾戎,石智敏.纳米银粒子/有机溶剂的界面作用、分散性及光学性能,材料研究学报,2001,15 (6):654-658
[14]熊金钮,徐国财.纳米银粉的制各及表征,金属功能材料,2004, 11 (2):38-42
[15] Terabe K, Hasegawa T, Nakayama T, et al. Quantized conductance atomic switch, Nature, 2005, 433(7021): 47-50
[16]任湘菱,唐芳琼.超细银—金复合颗粒增强酶生物传感器的研究,化学学报,2002,60(3):393-397
[17] Wadayama T, Oishi M, Hatta A. Surface enhanced Raman scattering of organic sample powders spread over vacuum-evaporated silver thin film, Applied Surface Science, 2006, 253: 2713-2717
[18]郑军伟,陆天虹.细胞色素c突变体的共振拉曼光谱研究,高等学校化学学报,2002,23(1):42-45
[19] Franck F, Kelly S M, Ben W, et al. Silver nanoparticles and polymeric medical devices: a new approach to prevention of infection, Journal of AntimicrobialChemotherapy, 2004, 54: 1019-1024
[20] Chun N L, Chi M H, Rong C, et al. Proteomic analysis of the mode of antibacterial action of silver nanoparticles, Journal of Proteome Research, 2006, 5(4): 916-924
[21]吴之传,陶庭先,叶生梅等.键合型纳米银-腈纶纤维的制备及其抗菌性质,功能材料,2004,35(3):371-372
[22]刘维良,陈汁现.纳米抗菌粉体材料的制备与应用研究,江苏陶瓷,2002, 35(1):9-12
[23]陈水挟,刘进荣,增汉民.几类载银活性炭纤维抗菌活性比较,新型炭材料,2002,17(1):26-29
[24]张文征,王广文.纳米银抗菌材料研发现状,化工新型材料,2003,31(2): 42-44
[25]张云竹,代凯,施利毅等.纳米银粒子的制备及其表征,化工新型材料,2006,34(7):31-32
[26] Yan L, Yu M, Roland W, et al.‘Nano-tree’-type spherical polymer brush particles as templates for metallic nanoparticles, Polymer, 2006, 47: 4985-4995
[27]孙红刚,刘恒,尹光福.粒径可控纳米银的制备研究,材料导报,2005,19(11):154-156
[28] Wang W Z, Xiong X L, Chen L Y, et al. Formation of flexible Ag/C coaxial nanocables through a novel solution process, Crystal Growth & Design, 2006, 6(11): 2422-2426
[29]刘绍璞,周贤杰,孔玲.银纳米微粒的光谱研究,西南师范大学学报:自然科学版,2005,30(4):690-694
[30]魏智强,夏天东,冯旺军等.纳米银粉的制备及表征,贵金属,2006,27(2):1-4
[31]张庆敏,李彦,黄福志等.聚氧乙烯类表面活性剂体系中银纳米颗粒的合成,物理化学学报,2001,17(6):537-541
[32] Takeshi T, Toshihiko K, Masaharu T. Preparation of nano-size particles of silver with femtosecond laser ablation in water, Applied Surface Science, 2003, 206: 314-320
[33] Tilaki R M, Irajizad A, Mahdavi S M. Stability, size and optical properties of silver nanoparticles prepared by laser ablation in different carrier media, Applied Physics, 2006, 84: 215-219
[34] Lim P Y, Liu R S, She P L, et al. Synthesis of Ag nanospheres particles in ethylene glycol by electrochemical-assisted polyol process, Chemical Physics Letters, 2006, 420: 304-308
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