CN107099787B - 一种表面增强拉曼散射基底及其制备方法 - Google Patents
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Abstract
本发明提供了一种表面增强拉曼散射基底及其制备方法，该表面增强拉曼散射基底使用十六烷基三甲基溴化铵(CTAB)作为形貌控制剂；以三维大孔泡沫镍为基质；利用氯金酸与镍的置换反应制备得到；具有丰富的高增强活性的金微纳米锥刺状结构并且其分布均匀。其制备方法为在十六烷基三甲基溴化铵(CTAB)作用下，氯金酸与镍在20‑30℃条件下反应一段时间。该表面增强拉曼散射基底具有独特的、均匀分布的金微纳米锥状阵列式结构及三维大孔结构，其对探针分子拉曼信号的增强性能高、增强信号重现性好；可用于对环境中结晶紫、孔雀石绿、亚甲基蓝等染料分子的高灵敏表面增强拉曼光谱检测。该制备方法简单易行，成本低，无需特殊仪器，可重复性高。
Description
技术领域
本发明涉及化学分析检测领域，具体涉及一种表面增强拉曼散射基底及其制备方法。
背景技术
表面增强拉曼散射(Surface Enhanced Raman Scattering,SERS)是一种高灵敏的分析方法，它是指当分子吸附在金银等固体尤其是粗糙的固体(即基底)表面时，分子的拉曼散射强度会极大地增强(103-106倍甚至更高)的现象。要实现这一增强，一个好的增强基底是必不可少的。一个好的增强基底需要满足几个条件：增强能力高，增强信号重现性好，基底稳定性高。此外，成本低，易于制备，且能够大规模制备对于基底的实际应用也至关重要。从成分方面讲，增强效果最好的材料为金和银。迄今为止，增强基底的制备主要通过三种途径实现：一是将平滑的金银电极表面粗造化处理；二是制备不同形貌的金或者银纳米粒子然后诱导其聚集或者可控地自组装；三是利用化学气相沉积、微纳米刻蚀技术等制备纳米阵列式结构。第一种增强基底增强效果相对较低，增强信号重现性差，该方法也不适宜大批量制备增强基底。第三种基底的制备信号重现性很高，增强效果也较高，但是制备过程用到化学气相沉积技术，光刻蚀技术，电子(离子)束刻蚀技术等，这使得整个的基底制备过程复杂，而且造价昂贵，这些限制了其实际应用。
相比较而言，第二种基底制备较为简单，其种类也最为多样，各种不同形貌的金银纳米粒子及其聚集体或者组装体也是目前应用最多的一类增强基底。尽管如此，这类基底也还有一些不足之处：(1)球状金银纳米粒子增强基底最容易制备，应用也最广，但是其对分子的拉曼散射信号的增强效果较低；(2)具有尖刺状结构的增强基底(如金纳米海胆，金纳米星等)增强效果好，但是制备过程复杂，对反应条件要求高，制备方法的可重复性较低；(3)金银纳米粒子聚集体的增强效果好，但是增强信号重现性差；(4)金银纳米粒子组装体的增强效果较好，成本较低，但自组装过程涉及微弱作用力的精确控制，需要较高的技术水平，也难以大规模制备。此外多数组装结构是球状粒子的组装结构。(5)与在溶液中制备金银纳米粒子不同，直接在固体基质上制备不同形貌、结构(特别是具有尖刺结构)的金银纳米材料的报道相对较少，对产物形貌的控制较为困难。
表面增强拉曼散射已经被广泛的应用于生化分析，环境检测及疾病诊断等领域。而要实现其高灵敏度的分析性能，制备一个具有高效增强能力，高信号重现性的，稳定的基底是必不可少的。因而设计一种简单，低成本，可重复的方法制备具有高增强效果和高信号重现性的SERS基底对于SERS技术的推广应用具有重要意义。
发明内容
本发明的目的在于提供一种表面增强拉曼散射基底，以降低表面增强拉曼散射基底的成本，提高增强效果和信号重现性。
本发明的另一目的在于提供一种表面增强拉曼散射基底的制备方法，以简单地、可高度重复地制备表面增强拉曼散射基底。
本发明通过氯金酸与泡沫镍的置换反应，在表面活性剂十六烷基三甲基溴化铵的作用下，通过简单的化学反应就可以制得高活性、高重现性的表面增强拉曼散射基底。
一种表面增强拉曼散射基底(简称AuNCA@Ni基底)，其特征在于：使用十六烷基三甲基溴化铵(CTAB)作为形貌控制剂，以三维大孔泡沫镍为基质，利用氯金酸与镍的置换反应制备得到；具有丰富的高增强活性的金微纳米锥刺状结构并且其分布均匀。
上述表面增强拉曼散射基底的制备方法，其特征在于：在十六烷基三甲基溴化铵(CTAB)作用下，氯金酸与镍在20-30℃条件下反应一段时间，即制备出该表面增强拉曼散射基底(AuNCA@Ni基底)。
上述制备方法的具体步骤为：
(1)将泡沫镍片放置在小烧杯中，依次用丙酮、3mol/L的稀盐酸、超纯水各超声清洗10min得到干净的泡沫镍片，氮气吹干备用；
(2)在塑料离心管中注入2-200mg/mL的CTAB溶液1mL，然后注入24mM的HAuCl4溶液0.5mL，盖上盖子，上下翻动混匀；再打开盖子，迅速放入干净的泡沫镍片，盖上盖子上下翻动10次(约5s)后，20-30℃静置反应2-12小时；
(3)上一步结束后，取出泡沫镍片，用乙醇、超纯水依次清洗，得到表面金黄色的产物AuNCA@Ni基底。
优选的，第(2)步中CTAB溶液的浓度为20mg/mL。
优选的，第(2)步中反应温度为20℃。
优选的，第(2)步中反应时间为6小时。
本发明的有益效果是：(1)AuNCA@Ni基底含有丰富的锥刺状金微纳米结构，可以产生很高的拉曼散射信号增强效果，其增强效果比没有加入CTAB时所得到的基底增强效果提高8倍，比常用的金球状纳米颗粒的增强效果提高3倍；对拉曼探针分子(结晶紫，一种芳香烃类有机染料)的检测限可降低到10-10mol/L(比未加入CTAB时所得到的基底降低两个数量级)。(2)AuNCA@Ni基底对分子的拉曼散射增强信号具有较高的重现性：所述基底表面结构均匀，具有较大面积的均匀阵列式结构，所述基底对探针分子结晶紫的拉曼散射增强信号的相对标准偏差小于13％，而不加入CTAB时所得到基底的响应信号的相对标准偏差为24％。(3)AuNCA@Ni基底具有独特的、均匀分布的金微纳米锥状阵列式结构及三维大孔结构，可用于对环境中结晶紫、孔雀石绿、亚甲基蓝等染料分子的高灵敏表面增强拉曼光谱检测。(4)AuNCA@Ni基底的制备方法简单，成本低，易于实现；制备过程避免了专门的、昂贵的仪器(如各种刻蚀仪器系统)或者特殊的、稀有的化学试剂的使用，易于实现，可重复性高，造价低廉，产率高。
附图说明
图1是本发明所述的AuNCA@Ni基底的制备流程示意图。
图2是实施例1制备的AuNCA@Ni基底材料的表面形貌的扫描电镜图片(a-c)，及其元素分析结果EDS图(d)。
图3是对比例1所制备的增强基底的表面形貌的扫描电镜图片。
图4是对比例2所制备的增强基底的表面形貌的扫描电镜图片。
图5是对比例3所制备的增强基底的表面形貌的扫描电镜图片。
图6是实施例2(a,b)和实施例3(c,d)所制备的增强基底的表面形貌的扫描电镜图片。
图7是实施例4(a,b)，实施例5(c,d)，实施例6(e,f)所制备的增强基底的表面形貌的扫描电镜图片。
图8(a)是染料分子结晶紫(1×10-5M)在实施例1及对比例1-3所制备的基底上的SERS响应信号强度对比图；(b)是结晶紫(1×10-5M)在实施例1基底上任意7个位置的SERS响应信号强度对比图。
图9是染料分子结晶紫(1×10-5M)在实施例1-3和对比例1所制备的基底上的SERS响应信号强度对比图。
图10是染料分子结晶紫(1×10-5M)实施例1及实施例4-6所制备的基底上的SERS响应信号强度对比图。
图11是不同浓度的结晶紫溶液在(a)实施例1所得基底(AuNCA@Ni基底)及(b)对比例1所得基底上的SERS响应信号强度对比图。
具体实施方式
以下具体实施方式中用于表征的装置为Hitachi S3400型场发射扫描电子显微镜，掘场(Horiba)JY HR800型显微激光拉曼光谱仪。所用试剂为：泡沫镍、丙酮、盐酸、氯金酸、二水合柠檬酸钠、十六烷基三甲基溴化胺(CTAB)、聚乙烯吡咯烷酮(PVP K30)，所用试剂均购自上海国药化学试剂有限公司。所有溶液均用超纯水(18.2MΩ·cm)配制。
实施例1
表面增强拉曼散射基底(AuNCA@Ni基底)的制备过程如图1所示，具体制备步骤包括以下三步：
(1)泡沫镍剪成长宽都是1cm的四方片，将其放置在小烧杯中依次用10mL丙酮、10mL稀盐酸(3mol/L)、10mL超纯水各超声清洗10min得到干净的泡沫镍片，氮气吹干备用。
(2)取一个1.5mL的塑料离心管，注入1mL 20mg/mL的CTAB溶液，然后用微量移液器注入0.5mL24mM的HAuCl4溶液，盖上盖子，上下翻动10次混匀(约5秒)，得到反应液。打开盖子，迅速放入1片干净的泡沫镍片，盖上盖子上下翻动10次混匀(约5秒)后，20℃静置反应6小时。
(3)上一步结束后，取出泡沫镍片，用乙醇、超纯水依次冲洗，得到表面橙黄色的产物即表面负载有金微纳米锥状结构阵列的泡沫镍片，也就是本发明所指的AuNCA@Ni基底。
实施例2
重复实施例1的操作，仅将第(2)步的CTAB溶液的浓度由20mg/mL改为2mg/mL。
实施例3
重复实施例1的操作，仅将第(2)步的CTAB溶液的浓度由20mg/mL改为200mg/mL。
实施例4
重复实施例1的操作，仅将第(2)步的反应时间由6小时改为2小时。
实施例5
重复实施例1的操作，仅将第(2)步的反应时间由6小时改为4小时。
实施例6
重复实施例1的操作，仅将第(2)步的反应时间由6小时改为12小时。
对比例1
重复实施例1的操作，仅将第(2)步的1mL20mg/mL的CTAB溶液换为1mL超纯水。
对比例2
重复实施例1的操作，仅将第(2)步的1mL 20mg/mL的CTAB溶液换为1mL 20mg/mL的PVP溶液。
对比例3
重复实施例1的操作，仅将第(2)步的1mL 20mg/mL的CTAB溶液换为1mL 20mg/mL的柠檬酸钠溶液。
AuNCA@Ni基底的形貌表征：
图2是实施例1所得到的AuNCA@Ni基底的表面形貌的扫描电镜照片。从低倍率的扫描电镜照片可以看到该AuNCA@Ni基底保留了泡沫镍的三维大孔结构(图2a)；高倍率的照片表面，三维泡沫镍骨架表面均匀生长了一层刺状凸起(图2b)；更高倍率的图片可以看出，这些刺状凸起呈现锥状结构，其末端较为尖锐(图2c)。锥状结构的高度在100-300nm，末端尖锐处直径在5-20nm。元素分析结果(图2d)表明这些锥状产物主要成分为Au，其他元素如Ni元素来自作为支撑骨架及反应物的Ni泡沫，C来自作为表面活性剂的CTAB。
所用表面活性剂CTAB对控制产物的形貌起到至关重要的作用。图2、3、4、5依次是实施例1、对比例1、对比例2、对比例3所得到的基底的表面形貌的扫描电镜SEM图片。通过对比这些图片可以说明，没有CTAB的情况下(对比例1，图3)，或者用PVP代替CTAB(对比例2，图4)，或者用柠檬酸钠代替CTAB(对比例3，图5)，都不能得到金的纳米锥状阵列式结构。从而证明，表面活性剂CTAB在AuNCA@Ni基底制备中的作用至关重要。
此外，表面活性剂CTAB的用量也对最终所得到的基底的形貌具有显著的影响。图6是实施例2(图6a,b)，实施例3(图6c,d)所得到的基底的表面形貌SEM图片。将其与实施例1所得的基底的SEM照片(图2)比较，可以看出CTAB浓度太低(2mg/mL，图6a,b)或者太高(200mg/mL，图6c,d)都不利于生成锥状产物，此外，产物结构也不如实施例1所得基底那样分布均匀。所以优化的CTAB浓度为20mg/mL。
最后，氯金酸与泡沫镍反应的时间也会影响产物的形貌。图7是实施例4-6所得到的基底的表面形貌SEM图片。将其与实施例1所得基底SEM图片(图2a-c)比较，可知反应时间过短或者过长都不能得到锥状结构产物。所以优化的反应时间为6小时。
AuNCA@Ni作为SERS基底的应用举例：
图8(a)是同样量的探针分子结晶紫(1mL 10-5mol/L)滴加到实施例1、对比例1、对比例2、对比例3基底上的SERS响应信号强度。通过对比可以看出，在实施例1所得基底(AuNCA@Ni基底)上的SERS信号强度是对比例1基底(没有加入CTAB时所得到的基底)上信号强度的8倍多，且响应信号明显强于对比例2基底及对比例3基底。表明表面活性剂CTAB对形貌的控制有利于提升基底的SERS增强能力。此外，结晶紫的SERS响应信号的标准偏差从对比例1基底的23.6％下降到实施例1基底的12.4％(图8b)。从而证明实施例1基底(AuNCA@Ni基底)不仅具有高的SERS信号增强能力，同时也具有很好的信号重现性。这些结果进一步表明CTAB作用至关重要以及所得的金纳米锥状结构增强基底的优越性能。
图9是同样量的探针分子结晶紫(1mL 10-5mol/L)在不同浓度的CTAB作用下得到的基底(即实施例1-3基底及对比例1基底)上的SERS响应信号。从图中可以看出，结晶紫在实施例1所得基底上的SERS响应信号最强。进一步证实优化的CTAB用量20mg/mL所得的锥状结构产物具有最好的SERS增强效果。
图10是同样量的探针分子结晶紫(1mL 10-5mol/L)在不同反应时间下得到的基底(即实施例1基底及实施例4-6基底)上的SERS响应信号。从图中可以看出，结晶紫在实施例1所得基底上的SERS响应信号最强。进一步证实优化的反应时间6小时所得的锥状结构产物具有最好的SERS增强效果。
图11是将实施例1所得到基底(a)及对比例1所得基底(b)用于水溶液中不同浓度的芳香烃类染料结晶紫的检测。在实施例1基底(AuNCA@Ni基底)上，当结晶紫的浓度低至10-10M时仍可以得到结晶紫的特征拉曼散射峰(图11a)；而在没有加入CTAB时得到的对比例1基底上对结晶紫的最低检测浓度为10-8M(图11b)。即AuNCA@Ni基底对结晶紫的最低检测浓度比后者降低了两个数量级，灵敏度大幅提升。从而进一步证实CTAB对形貌控制的重要性及所得到的AuNCA@Ni基底的高效SERS增强能力。
Claims (6)
1.一种表面增强拉曼散射基底，其特征在于：使用十六烷基三甲基溴化铵（CTAB）作为形貌控制剂，以三维大孔泡沫镍为基质，利用氯金酸与镍的置换反应制备得到；具有丰富的金微纳米锥刺状结构并且锥刺状结构分布均匀。
2.权利要求1所述的表面增强拉曼散射基底的制备方法，其特征在于：在十六烷基三甲基溴化铵（CTAB）作用下，氯金酸与泡沫镍在20-30℃条件下反应一段时间，即制备出该表面增强拉曼散射基底。
3.根据权利要求2所述的制备方法，其特征在于：包括以下步骤：
（1）将泡沫镍片放置在小烧杯中，依次用丙酮、3 mol/L的稀盐酸、超纯水各超声清洗10min得到干净的泡沫镍片，氮气吹干备用；
（2）在塑料离心管中注入2-200 mg/mL的CTAB溶液，然后注入24 mM的HAuCl4溶液，盖上盖子，上下翻动混匀；再打开盖子，迅速放入干净的泡沫镍片，盖上盖子上下翻动10次后，20-30℃静置反应2-12小时；
（3）上一步结束后，取出泡沫镍片，用乙醇、超纯水依次清洗，得到表面金黄色的产物，即所述的表面增强拉曼散射基底。
4.根据权利要求3所述的制备方法，其特征在于：第（2）步中CTAB溶液的浓度为20 mg/mL。
5.根据权利要求3所述的制备方法，其特征在于：第（2）步中反应温度为20℃。
6.根据权利要求3所述的制备方法，其特征在于：第（2）步中反应时间为6小时。
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