电解法制备纳米溴化银溶胶及其SERS活性研究

将一定量的十六烷基三甲基溴化铵溶于500mL去离子水中作为电解液,用直径为1.0cm、长为10.0cm银棒分别作为阴及阳电极,加上7V直流电压,通电3h,用电解方法得到了乳白色的纳米溴化银溶胶。用吸收光谱、对该进行研究。其吸收峰为292.5nm,透射式电镜表明纳米溴化银粒径分布在一个较大的范围,既有大小不一的球形粒子,也有大小不一的椭球形粒子,部分粒子产生了凝聚。为测试该纳米溴化银溶胶是否具有表面增强拉曼散射(SERS)活性,选用了阳离子型分子甲基橙(Methylorange)、中性分子苏丹红(Sudanred)及吡啶(Pyridine)作为测试分子,用二次去离子水配成适当浓度后,与纳米溴化银溶胶按1∶1的比例混合后,置入毛细管样品池中用Renishaw2000测定,激发波长514.5nm。结果发现电解法制备的纳米溴化银对这三种分子都具有较强的SERS活性,甲基橙中明显增强的峰是1123,1146,1392,1448,1594cm-1;苏丹红中明显增强的峰是1141,1179,1433,1590cm-1;吡啶中明显增强的峰是1003,1034,1121cm-1。值得注意的是在该方法制备的纳米溴化银上,得到了在常规方法制备的黄银胶、灰银胶上得不到的甲基橙分子的SERS谱,对可能的原因进行了讨论。

AgBr Colloids Prepared by Electrolysis and Their SERS Activity Research

Ivory-white AgBr colloids were prepared by means of electrolysis. Two silver rods 1.0 cm in diameter and 10.0 cm long were respectively used as the negative and positive electrodes, the aqueous solution of hexadecyl trimethyl ammonium bromide was used as the electrolyte, and a 7 V direct current was applied on the silver rods for three hours. The obtained AgBr colloids were characterized by UV-Vis spectroscopy, transmission electron microscopy, and SERS using a 514.5 nm laser line on Renishaw 2000 Raman spectrometer. These particles are about nanometer size and their shapes are as spherical or elliptic, with a slight degree of particle aggregation. The UV-Vis spectra exhibit a large plasmon resonance band at about 292.5 nm, similar to that reported in the literature. The AgBr colloids were very stable at room temperature for months. In order to test if these AgBr colloids can be used for SERS research, methyl orange, Sudan red and pyridine were used. It was found that AgBr colloids have SERS activity to these three molicules. For methyl orange, the intense Raman peaks are at 1 123, 1 146, 1 392, 1 448 and 1 594 cm-1; for Sudan red, the intense Raman peaks are at 1 141, 1 179, 1 433 and 1 590 cm-1; and for pyridine, the intense Raman peaks are at 1 003, 1 034 and 1 121 cm-1. It is noticeable that SERS of methyl orange was observed on AgBr colloids, but not on the gray and yellow silver colloids prepared by traditional means. The possible reason was explained. One major advantage of this means is the absence of the spectral interference such as citrate, BH-4 arising from reaction products of the colloids formation process. On AgBr colloids, one can get some molecular SERS impossible to get on the gray and yellow silver colloids.