巯基苯并咪唑在银电极表面的自组装吸附特性及表面增强拉曼光谱

刘文涵; 马苏珍; 滕渊洁; 刘江美; 何昌璟

doi:10.3788/fgxb20153601.0106

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巯基苯并咪唑在银电极表面的自组装吸附特性及表面增强拉曼光谱

发光学应用及交叉前沿 | 更新时间：2020-08-12

- 巯基苯并咪唑在银电极表面的自组装吸附特性及表面增强拉曼光谱
- Self-assembly Behavior of 2-Mercaptobenzimidazole on Silver Electrode Investigated by Surface Enhancement Raman Scattering
- 发光学报 2015年36卷第1期页码：106-112
- 作者机构：
  
  浙江工业大学化学工程学院, 绿色化学合成技术国家重点实验室培育基地,浙江杭州,310032
- 作者简介：
- 基金信息：
  
  浙江省教育厅应用技术研究计划(Y201432432)();浙江省公益性技术应用研究(分析测试)计划(2014C37044)();上海市功能性材料化学重点实验室开放课题(
- DOI：10.3788/fgxb20153601.0106
  中图分类号： O657
- 纸质出版日期：2015-1-3，
  
  网络出版日期：2014-11-7，
  
  收稿日期：2014-10-19，
  
  修回日期：2014-11-3，
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刘文涵, 马苏珍, 滕渊洁等. 巯基苯并咪唑在银电极表面的自组装吸附特性及表面增强拉曼光谱[J]. 发光学报, 2015,36(1): 106-112

LIU Wen-han, MA Su-zhen, TENG Yuan-jie etc. Self-assembly Behavior of 2-Mercaptobenzimidazole on Silver Electrode Investigated by Surface Enhancement Raman Scattering[J]. Chinese Journal of Luminescence, 2015,36(1): 106-112
刘文涵, 马苏珍, 滕渊洁等. 巯基苯并咪唑在银电极表面的自组装吸附特性及表面增强拉曼光谱[J]. 发光学报, 2015,36(1): 106-112 DOI： 10.3788/fgxb20153601.0106.

LIU Wen-han, MA Su-zhen, TENG Yuan-jie etc. Self-assembly Behavior of 2-Mercaptobenzimidazole on Silver Electrode Investigated by Surface Enhancement Raman Scattering[J]. Chinese Journal of Luminescence, 2015,36(1): 106-112 DOI： 10.3788/fgxb20153601.0106.

摘要

采用循环伏安法处理Ag电极

得到活化的具有表面增强拉曼光谱(SERS)效应的粗糙Ag表面

进一步采用激光拉曼光谱探讨了2-巯基苯并咪唑(MBI)在其表面的自组装分子层的吸附特性。实验表明

在活性Ag表面的MBI自组装分子层能够产生理想的SERS效应

其强度随探针分子MBI浓度的增加先提高后减弱

达到一定浓度时因受其空间位阻等因素的影响

增强效应减弱。MBI在110

-6

molL

-1

浓度时增强效果最大。拉曼增强效应随着体系酸度的变化有着明显不同

在强酸性条件下的增强效应明显优于中性和碱性条件。MBI分子存在两种不同的异构体和在不同酸度下存在3种不同的存在形态

并形成动态平衡。pH

2时

MBI分子主要以硫酮式MBI

存在

并以巯基上的S:与活性Ag以配位方式吸附成键

其整个大键平面垂直地吸附于Ag表面

产生相对较大的SERS信号。pH

2时

由于硫酮式和硫醇式与活性Ag的键合方式和能力不同

硫醇式上的S与Ag以SAg共价方式同时双键侧上的N以配位方式协同参与吸附成键

比硫酮式MBI

的单纯配位吸附要强

因而形成了竞争吸附

表现为SERS在pH=2~3.7之间的急剧下降。MBI硫醇式由于以SAg、NAg键的协同吸附

形成了倾斜侧卧式垂直吸附

而使拉曼增强效应相对减弱。

Abstract

The activated Ag electrode which was treated by electrochemical cyclic voltammetry to obtain surface enhancement Raman scattering (SERS) effect was used to investigate the self-assembled monolayers (SAMs) behavior of 2-mercaptobenzimidazole (MBI). The results show that SAMs of MBI are of ideal SERS effect on roughened Ag electrode and its SERS effect is related to concentration and pH. With the increasing of concentration

the SERS effect is strengthened firstly but weakened latterly because of its steric hindrance when it happens to the high concentration. As a result

the most effective enhancement is at 110

-6

molL

-1

. On the other hand

the SERS effect of MBI in acid solution is better than in alkaline or neutral solution. It is further illustrated that MBI molecule has two different isomers and three kinds of existing forms

and all of them keep dynamic balance in solution. When the pH is lower than 2

MBI

the main form of MBI molecule

is absorbed on roughened Ag electrode with coordinate bond between S: and Ag. MBI molecules stand vertically on Ag surface through bond and produce relatively higher SERS effect. When the pH is higher than 2

thiol absorbed on Ag surface with SAg covalent bond and NAg coordinate bond is stronger than thione. This results in competitive absorption between thiol and thione of MBI

so SERS effect rapidly decreases from pH=2 to pH=3.7. As a result

thiol form of MBI lays aslant to Ag surface with SAg covalent bond and NAg coordinate bond

making the weaker SERS effect than thione.

关键词

巯基苯并咪唑表面增强拉曼光谱硫酮式电化学自组装吸附

Keywords

2-mercaptobenzimidazolesurface enhancement Raman spectroscopythioneelectrochemistryself-assembly behavior

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