CN106086880A - 一种自清洁可复用sers衬底的制备及其应用 - Google Patents

一种自清洁可复用sers衬底的制备及其应用 Download PDF

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CN106086880A
CN106086880A CN201610478428.6A CN201610478428A CN106086880A CN 106086880 A CN106086880 A CN 106086880A CN 201610478428 A CN201610478428 A CN 201610478428A CN 106086880 A CN106086880 A CN 106086880A
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automatically cleaning
sers substrate
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梁培
吴燕雄
曹艳亭
白阳
刘越
董前民
舒海波
黄杰
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China Jiliang University
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Abstract

本发明涉及一种自清洁可复用SERS衬底的制备及其应用。本发明利用TiO2在紫外光下能够光催化降解有机物的原理，提出自清洁可复用SERS衬底的制备方法，并给出了对应的应用，实现了可重复测量不同待测物质的SERS衬底的制备和应用，有效降低了基于SERS衬底的拉曼检测技术的检测成本，大大提高了基于SERS衬底的拉曼检测技术的检测效率。

Description

一种自清洁可复用SERS衬底的制备及其应用
技术领域
本发明涉及一种自清洁可复用SERS衬底的制备及其应用，属于SERS衬底制备及应用领域。
背景技术
表面增强拉曼散射(Surface Enhanced Raman Spectroscopy，SERS)效应是指分子等物种吸附或者非常靠近具有某种纳米结构基底表面时，其拉曼信号显著增强的现象。SERS光谱技术有效地克服了常规拉曼光谱灵敏度低的缺点，因而被广泛地应用于表面科学、分析科学和生物科学等各个领域。自SERS技术问世以来，相关领域的研究主要都聚焦在SERS衬底的制备方面，其实际应用取决于提供具有高灵敏度、高均一性、低检测极限、热点均匀、稳定的SERS衬底。
然而现阶段的基于SERS衬底的拉曼检测技术都是将待检测物质吸附在SERS衬底表面进行拉曼检测的，由于待检测物质一旦吸附在SERS衬底表面，就很难对SERS衬底进行清洁，因此无法重复使用SERS衬底，而一般SERS衬底采用的都是银或金的纳米结构作为原料，无法做到SERS衬底的可重复利使用，这就增加了基于SERS衬底的拉曼检测技术的检测成本，且每进行一次检测还需重新制作SERS活性基底，这大大影响了基于SERS衬底的拉曼检测技术的检测效率。
近些年来，使用半导体作为光催化剂(如TiO2)在紫外光下照射的光催化过程被广泛地应用于降解有机化合物。二氧化钛(TiO2)是一种化学性质稳定、无毒、无污染的半导体材料。已有很多研究成果证实了TiO2半导体作为优秀的光催化剂能够在紫外光下降解大范围的有机污染物。如中国专利申请号201310382115.7《一种光诱导自清洁玻璃的制备方法》具体提出了一种涂覆ZnO/TiO2复合薄膜的自清洁玻璃的制备方法，能够有效降解有机物或无机物。因此，本发明采用在SERS衬底中加入一层纳米TiO2薄膜，利用TiO2在紫外光的照射下，价带电子会跃迁到导带，价带上的空穴把周围的水分子和氧气激发成高活性的·OH自由基和·O2-自由基，这些高活性的自由基能够分解大部分有机物和无机物，并通过罗丹明6G(R6G)分子考察了自清洁可复用SERS衬底的自清洁性能。
发明内容
基于现有技术中存在的SERS活性基底无法可重复利用，检测成本高的问题，本发明专利提供一种自清洁可复用SERS衬底的制备及其应用，能实现SERS衬底的自清洁和可复用功能，克服了原有SERS衬底一次性使用的缺点，有效降低了基于SERS衬底的拉曼检测技术的检测成本，大大提高了基于SERS衬底的拉曼检测技术的检测效率。
为了解决上述技术问题，本申请采用如下技术方案予以实现：
一种自清洁可复用SERS衬底的制备及其应用，包括，首先，采用提拉方法在洁净的导电物质上涂覆纳米TiO2薄膜，然后，对涂覆了纳米TiO2薄膜的导电物质进行煅烧处理，接着，采用液相还原法制备纳米贵金属溶胶，最后将纳米贵金属溶胶沉积在涂覆了纳米TiO2薄膜的导电物质上，得自清洁可复用SERS衬底。
所述的导电物质为金属片，合金片，硅片或导电玻璃片。
所述的纳米贵金属溶胶为纳米银溶胶或纳米金溶胶。
所述的纳米银溶胶是以硝酸银为前驱物，抗坏血酸或柠檬酸钠或硼氢化钠为还原剂，聚乙烯吡咯烷酮(PVP)为表面活性剂来配置的；
所述的纳米金溶胶是以氯金酸为前驱物，柠檬酸钠或硼氢化钠或抗坏血酸为还原剂来配置的。
所述的煅烧处理包括如下：将涂覆了纳米TiO2薄膜的导电物质放入马沸炉中，升温至400～600℃，并且保温1～2h，而后自然冷却，完成煅烧处理。
所述的自清洁可复用SERS衬底的应用步骤如下：
第一步，将待测物质(固体或溶液)附着在自清洁可复用SERS衬底上，通过常规拉曼激光照射后，由拉曼探头接收到待测物质和自清洁可复用SERS衬底的拉曼信号；
第二步，将附着了待测物质的自清洁可复用SERS衬底放到紫外光下进行照射，并通入O2供自清洁可复用SERS衬底中的TiO2在紫外光下降解待测物质所需，紫外光下照射1～2h后，将待测物质经TiO2在紫外光下转化成的H2O和CO2用水或空气清洗掉，再次得到自清洁可复用SERS衬底；
第三步，将第二步清洗得到的自清洁可复用SERS衬底，通过常规拉曼激光照射，由拉曼探头接收到自清洁可复用SERS衬底的拉曼信号，比较与第一步中得到的拉曼信号，判断待测物质的拉曼特征峰是否已消失，若待测物质的拉曼特征峰已消失，则说明第二步的自清洁已完成，若待测物质的拉曼特征峰仍存在，则说明第二步的自清洁还未完成，需重复第二步，直到待测物质的拉曼特征峰消失为止。
上述技术方案具有如下有益效果：
(1)所述的一种自清洁可复用SERS衬底的制备及其应用，其自清洁可复用SERS衬底最上层采用纳米贵金属，其SERS性能能够得到很好的保证，并且能够得到很强的拉曼检测峰。
(2)所述的一种自清洁可复用SERS衬底的制备及其应用，采用TiO2在紫外光下光催化的原理，能够降解绝大部分有机物和无机物，使其转化为H2O和CO2，降解产物对仪器和环境都无毒无害，且产物很容易处理。
(3)所述的一种自清洁可复用SERS衬底的制备及其应用，其自清洁可复用SERS衬底采用导电物质作为最下层，可以通过加入微电压，加速自清洁过程，且有利于该衬底的其他性能的检测，如扫描电镜检测、透射电镜检测。
附图说明
图1是一种自清洁可复用SERS衬底的结构示意图；
图中1.纳米贵金属，2.纳米TiO2薄膜，3.导电物质.
具体实施方式
以下结合实施例和附图对本发明作进一步描述，但本发明不限于以下所述范围。
如图1是一种自清洁可复用SERS衬底的结构示意图：
最底下一层为导电物质(金属片，合金片，硅片或导电玻璃片)；
中间一层为采用提拉方法和煅烧处理在洁净的导电物质上涂覆的纳米TiO2薄膜；
最上面一层为纳米贵金属(纳米银或纳米金)，采用液相还原法制备纳米贵金属(纳米银或纳米金)溶胶，并将纳米贵金属溶胶沉积在涂覆了纳米TiO2薄膜的导电物质上，得自清洁可复用SERS衬底。
所述的纳米银溶胶是以硝酸银为前驱物，抗坏血酸或柠檬酸钠或硼氢化钠为还原剂，聚乙烯吡咯烷酮为表面活性剂来配置的。
所述的纳米金溶胶是以氯金酸为前驱物，柠檬酸钠或硼氢化钠或抗坏血酸为还原剂来配置的。
所述的煅烧处理包括如下：将涂覆了纳米TiO2薄膜的导电物质放入马沸炉中，升温至400～600℃，并且保温1～2h，而后自然冷却，完成煅烧处理。
实施例一：
为本发明专利一种自清洁可复用SERS衬底的制备及其应用，实施例一具体为Ag-TiO2衬底，并且采用罗丹明6G(R6G)分子作为标记分子，Ag-TiO2衬底的制备过程包括：
第一步：导电物质清洗和干燥
(1)将导电物质依次放入丙酮溶液、酒精溶液、去离子水中，各超声振荡清洗10分钟；
(2)将清洗好的导电物质放入真空干燥箱中，60℃干燥30分钟，取出自然冷却到室温。
第二步：导电物质涂覆上纳米TiO2薄膜并煅烧
将洁净的导电物质用提拉法涂覆上纳米TiO2薄膜，提拉镀膜机的提拉速度为10cm/min，提拉结束后，静置30s后将涂覆了纳米TiO2薄膜的导电物质放入煅烧专用的陶瓷杯中，并连同陶瓷杯一起放入马沸炉中，靠近温度探针，确保受热均匀，升温至600℃，并且保温2h，而后自然冷却，完成煅烧处理。
第三步：纳米银溶胶的制备
(1)取0.5ml硝酸银溶液(2mol/L)、3ml聚乙烯吡咯烷酮溶液(1.5％)和15ml去离子水于烧杯中；
(2)将混合溶液在磁力搅拌器下搅拌，搅拌均匀后迅速加入0.5ml抗坏血酸溶液(0.3mol/L)，搅拌10min；
(3)将溶液倒入离心管中进行离心，离心速率8000r/min，离心时间为15min；
(4)将离心后的上清液倒掉，重新加入去离子水，将离心产物溶解后即得纳米银溶胶。
第四步：纳米银溶胶沉积
将制备的纳米银溶胶滴在涂覆了纳米TiO2薄膜的导电物质上，放入真空干燥箱里干燥，干燥结束，即得到Ag-TiO2衬底。
制得的Ag-TiO2衬底的具体应用如下：
a)将R6G溶液附着在Ag-TiO2衬底上，通过常规拉曼激光照射后，由拉曼探头接收到R6G和Ag-TiO2衬底的拉曼信号；
b)将附着了R6G的Ag-TiO2衬底放到紫外光下进行照射，并通入O2供Ag-TiO2的TiO2在紫外光下降解R6G所需，紫外光下照射1h后，将R6G经TiO2在紫外光下转化成的H2O和CO2用水清洗掉，再次得到Ag-TiO2衬底；
c)将b)中清洗得到的Ag-TiO2衬底，通过常规拉曼激光照射，由拉曼探头接收到Ag-TiO2衬底的拉曼信号，比较与a)中得到的拉曼信号，判断R6G的拉曼特征峰是否已消失，若R6G的拉曼特征峰已消失，则说明b)中的自清洁已完成，若R6G的拉曼特征峰仍存在，则说明b)的自清洁还未完成，需重复第二步，直到R6G的拉曼特征峰消失为止。
本实施例一中所述的导电物质为金属片，合金片，硅片或导电玻璃片。
实施例二：
为本发明专利一种自清洁可复用SERS衬底的制备及其应用，实施例二具体为Au-TiO2衬底，并且采用罗丹明6G(R6G)分子作为标记分子，Au-TiO2衬底的制备过程包括：
第一步：导电物质清洗和干燥
(1)将导电物质依次放入丙酮溶液、酒精溶液、去离子水中，各超声振荡清洗10分钟；
(2)将清洗好的导电物质放入真空干燥箱中，60℃干燥30分钟，取出自然冷却到室温。
第二步：导电物质涂覆上纳米TiO2薄膜并煅烧
将洁净的导电物质用提拉法涂覆上纳米TiO2薄膜，提拉镀膜机的提拉速度为10cm/min，提拉结束后，静置30s后将涂覆了纳米TiO2薄膜的导电物质放入煅烧专用的陶瓷杯中，并连同陶瓷杯一起放入马沸炉中，靠近温度探针，确保受热均匀，升温至500℃，并且保温2h，而后自然冷却，完成煅烧处理。
第三步：纳米金溶胶的制备
50ml的氯金酸溶液(0.24mmol/L)加热到沸腾保存15min后，迅速加入1ml柠檬酸钠(1％)，保持沸腾20min，溶液变成酒红色。最后使溶液在搅拌下冷却到室温，即得到纳米金溶胶。
第四步：纳米金溶胶沉积
将制备的纳米金溶胶滴在涂覆了纳米TiO2薄膜的导电物质上，放入真空干燥箱里干燥，干燥结束，即得到Au-TiO2衬底。
制得的Au-TiO2衬底的具体应用如下：
a)将待测物质附着在Au-TiO2衬底上，通过常规拉曼激光照射后，由拉曼探头接收到待测物质和Au-TiO2衬底的拉曼信号；
b)将附着了待测物质的Au-TiO2衬底放到紫外光下进行照射，并通入O2供Au-TiO2的TiO2在紫外光下降解待测物质所需，紫外光下照射2h后，将待测物质经TiO2在紫外光下转化成的H2O和CO2用空气清洗掉，再次得到Au-TiO2衬底；
c)将b)中清洗得到的Au-TiO2衬底，通过常规拉曼激光照射，由拉曼探头接收到Au-TiO2衬底的拉曼信号，比较与a)中得到的拉曼信号，判断待测物质的拉曼特征峰是否已消失，若待测物质的拉曼特征峰已消失，则说明b)中的自清洁已完成，若待测物质的拉曼特征峰仍存在，则说明b)的自清洁还未完成，需重复第二步，直到待测物质的拉曼特征峰消失为止。
本实施例二中所述的导电物质为金属片，合金片，硅片或导电玻璃片。

Claims (5)

1.一种自清洁可复用SERS衬底的制备及其应用，其特征在于，首先，采用提拉方法在洁净的导电物质上涂覆纳米TiO2薄膜，然后，对涂覆了纳米TiO2薄膜的导电物质进行煅烧处理，接着，采用液相还原法制备纳米贵金属溶胶，最后将纳米贵金属溶胶沉积在涂覆了纳米TiO2薄膜的导电物质上，得自清洁可复用SERS衬底；
所述的导电物质为金属片，合金片，硅片或导电玻璃片；
所述的纳米贵金属溶胶为纳米银或纳米金溶胶。
2.根据权利要求1所述一种自清洁可复用SERS衬底的制备及其应用，其特征在于所述的纳米银溶胶是以硝酸银为前驱物，抗坏血酸或柠檬酸钠或硼氢化钠为还原剂，聚乙烯吡咯烷酮为表面活性剂来配置的。
3.根据权利要求1所述一种自清洁可复用SERS衬底的制备及其应用，其特征在于所述的纳米金溶胶是以氯金酸为前驱物，柠檬酸钠或硼氢化钠或抗坏血酸为还原剂来配置的。
4.根据权利要求1所述一种自清洁可复用SERS衬底的制备及其应用，其特征在于所述的煅烧处理包括如下：将涂覆了纳米TiO2薄膜的导电物质放入马沸炉中，升温至400～600℃，并且保温1～2h，而后自然冷却，完成煅烧处理。
5.根据权利要求1所述一种自清洁可复用SERS衬底的制备及其应用，其特征在于所述的自清洁可复用SERS衬底的应用步骤如下：
第一步，将待测物质(固体或溶液)附着在自清洁可复用SERS衬底上，通过常规拉曼激光照射后，由拉曼探头接收到待测物质和自清洁可复用SERS衬底的拉曼信号；
第二步，将附着了待测物质的自清洁可复用SERS衬底放到紫外光下进行照射，并通入O2供自清洁可复用SERS衬底中的TiO2在紫外光下降解待测物质所需，紫外光下照射1～2h后，将待测物质经TiO2在紫外光下转化成的H2O和CO2用水或空气清洗掉，再次得到自清洁可复用SERS衬底；
第三步，将第二步清洗得到的自清洁可复用SERS衬底，通过常规拉曼激光照射，由拉曼探头接收到自清洁可复用SERS衬底的拉曼信号，比较与第一步中得到的拉曼信号，判断待测物质的拉曼特征峰是否已消失，若待测物质的拉曼特征峰已消失，则说明第二步的自清洁已完成，若待测物质的拉曼特征峰仍存在，则说明第二步的自清洁还未完成，需重复第二步，直到待测物质的拉曼特征峰消失为止。
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