CN108867026A - 一种可循环使用的柔性表面增强拉曼散射基底及其制备和应用 - Google Patents
一种可循环使用的柔性表面增强拉曼散射基底及其制备和应用 Download PDFInfo
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Abstract
本发明涉及一种可循环使用的柔性表面增强拉曼散射基底及其制备和应用,采用超声浸渍法将二氧化钛粒子沉积在棉织物表面,制备Cotton‑TiO2织物,并采用原位还原法在Cotton‑TiO2织物表面生长Ag NPs,得到可循环使用表面增强拉曼‑棉织物基底。将TiO2与Ag NPs结合,制备了可循环使用SERS‑棉织物,实现基底的循环使用。
Description
技术领域
本发明属于拉曼散射基底材料及其制备和应用领域,特别涉及一种可循环使用的柔性表面增强拉曼散射基底及其制备和应用。
背景技术
随着纳米技术的发展以及仪器设备性能的提高,SERS技术的应用也越来越受到研究者的关注。SERS基底的表面结构决定了其SERS性能,如灵敏性、重复性以及稳定性,因此研究SERS基底的制备是SERS领域的一大热点。
目前,金属纳米粒子是研究较多的一种SERS活性基底,由于Ag NPs具有特殊的局域等离子体共振特性,因此Ag NPs是最常用的SERS活性基底材料之一。Ag NPs作为SERS活性基底主要以两种形式存在:Ag NPs溶胶和将Ag NPs组装在固体基材表面。由于Ag NPs溶胶稳定性差,拉曼信号重现性差,因此将Ag NPs组装在固体基材表面作为SERS基底受到了研究者的关注。相比于传统的玻璃、硅片等硬基材,柔性基底如纸张、薄膜以及石墨烯等具有更广阔的应用领域。与便携式拉曼检测仪相配合,柔性SERS活性基底可以实现对爆炸物、食品以及水果等的现场检测。
棉织物是一种具有三维立体框架结构的轻薄、可弯曲折叠的基材。由于其与纤维基SERS基底相似,具有良好的吸附性以及较好的机械柔韧性,因此可用于制备柔性SERS基底。而且,棉织物是由经纱和纬纱有序交织而成,这种规律性结构有利于Ag NPs在其表面的均匀分散,可以提高SERS基底的均一性。其次在经纱与纬纱的交织点处,有利于Ag NPs的聚集,增加粒子间耦合程度,提高SERS的灵敏性。
基于传统纤维织物制备SERS检测传感器的研究报道,据了解,仅有如下相关报道。其中,王训该课题组(Liu J,Zhou J,Tang B,et al.Surface enhanced Raman scattering(SERS)fabrics for trace analysis[J].Applied Surface Science,2016,386:296-302.)采用金纳米粒子修饰丝织物对PATP、4-Mpy、CV的检测限均达到10-9M;吴济宏课题组(Cheng D,He M,Ran J,et al.Depositing a flexible substrate of triangularsilver nanoplates onto cotton fabrics for sensitive SERS detection[J].Sensors&Actuators B Chemical,2018,270:508-517.)将银三角片组装到阳离子化棉织物上对PATP检测限达到10-8M;课题组采用自组装银纳米粒子制备的SERS-棉织物(Chen Y,Ge F,Guang S,et al.Self-assembly of Ag nanoparticles on the woven cottonfabrics as mechanical flexible substrates for surface enhanced Ramanscattering[J].Journal of Alloys&Compounds,2017,726.)对PATP检测限为10-7M;课题组以棉织物为生长界面采用原位合成银纳米粒子制备的SERS-棉织物(Chen Y,Ge F,GuangS,et al.Low-cost and large-scale flexible SERS-cotton fabric as a wipesubstrate for surface trace analysis[J].Applied Surface Science,2018,436:111-116.),对PATP检测限可达10-12M。
此外,上述传统的柔性SERS基底在使用过程中,由于吸附的探针分子不能从柔性基底表面解吸下来,导致SERS基底在拉曼测试时只能使用一次,不可以循环使用。由于SERS基底多数由金、Ag NPs构成,其价格昂贵,因此,制备可循环使用的SERS基底具有很重要的研究价值。
发明内容
本发明所要解决的技术问题是提供一种可循环使用的柔性表面增强拉曼散射基底及其制备和应用,克服了现有技术导致SERS基底在拉曼测试时只能使用一次,不可以循环使用的缺陷,该发明采用TiO2作为光催化剂,将其整理在棉织物上,制备一种Cotton-TiO2棉织物,然后通过原位还原的方法在Cotton-TiO2棉织物表面沉积Ag NPs,制备高灵敏性的可循环使用的柔性SERS-棉织物。
本发明的一种可循环使用的柔性表面增强拉曼散射基底,所述基底为负载有二氧化钛粒子、银纳米粒子Ag NPs的棉织物,其中二氧化钛以粒子方式沉积在棉织物表面,然后银纳米粒子再分散在外层。
所述二氧化钛粒子在棉织物上的负载量分别为2.00~3.50mg/g,银纳米粒子在棉织物上的负载量范围为12.42mg/g-37.26mg/g。
本发明的一种可循环使用的柔性表面增强拉曼散射基底的制备方法,包括:
(1)采用溶胶凝胶法制备纳米二氧化钛溶胶;
(2)将棉织物浸渍纳米二氧化钛溶胶,超声振荡,二浸二轧,轧余率为(80%),烘干,得到沉积二氧化钛粒子的棉织物Cotton-TiO2棉织物;
(3)采用原位还原法在沉积二氧化钛粒子的棉织物表面生长AgNPs,即得可循环使用的柔性表面增强拉曼散射基底。
所述步骤(1)中采用溶胶凝胶法制备具体为:配置钛酸四丁酯、冰醋酸和乙醇的混合液,其摩尔比为1:5:2;配置pH为2的冰醋酸溶液;将钛酸四丁酯、冰醋酸和乙醇的混合液以1drop/Sec的速度逐滴加入冰醋酸溶液中,在滴加的过程中控制反应温度为30℃,转速为1200r/min;滴加结束后继续反应2h,将实验所得溶胶陈化,最后将其放置在高压灭菌锅中,进行热晶化处理,得到锐钛矿型二氧化钛水溶胶。
所述步骤(2)中棉织物为氢氧化钠清洗后的棉织物。
所述步骤(2)超声振荡时间为5-15min,优选10min。
所述步骤(3)中原位还原法具体为:将沉积二氧化钛粒子的棉织物浸渍在硝酸银溶液中,在水浴温度为30℃下振荡处理15-40min(优选30min),水洗,随后,浸渍在抗坏血酸溶液中,在水浴温度为30℃下振荡处理15-40min(优选30min),洗涤,烘干。
所述硝酸银溶液的浓度为0.1-0.3mol/L,优选0.2mol/L。
所述抗坏血酸溶液的浓度为0.05-0.2mol/L,优选0.1mol/L。
所述洗涤具体为:用0.5%的醋酸室温下水洗10-15min,再用乙醇清洗。
所述烘干为65℃下烘干。
本发明的一种可循环使用的柔性表面增强拉曼散射基底的应用,所述可循环使用的柔性表面增强拉曼散射基底在检测罗丹明、西维因中的应用。
有益效果
(1)本发明通过擦拭检测的方法获取样品分子即采用拉曼增强基底通过擦拭物质表面获取样品分子,这种方式快速、简便、无污染而且可以最大限度的采集样品分子。
(2)本发明以棉织物作为柔性基材,采用超声浸渍法将二氧化钛粒子沉积在棉织物表面,制备Cotton-TiO2织物,并采用原位还原法在Cotton-TiO2织物表面生长Ag NPs,得到可循环使用表面增强拉曼-棉织物基底;可循环使用表面增强拉曼-棉织物对罗丹明6G(R6G)的检测限可以达到10-9M。
(3)目前未见可循环SERS织物用于表面拉曼增强检测的相关报道。
(4)本发明中由于贵金属银纳米颗粒具有表面等离子共振效应可有效地扩展TiO2的光响应范围,TiO2具有较宽的带隙,能够直接吸收太阳光中的紫外光,进行光催化降解反应,可以将其表面吸附的有机污染物降解为CO2和H2O。因此,实现了SERS基底的无损纯化的效果。
(5)将TiO2的光催化特性与Ag NPs的等离子体共振特性相结合,以棉织物为基底,制备一种可以循环使用的的SERS柔性基底,从环保、节能及功能化织物的开发方面考虑均具有重大应用意义和研究价值。
(6)以棉织物作为SERS柔性基底,并应用于擦拭检测。
(7)将TiO2与Ag NPs结合,制备了可循环使用SERS-棉织物,实现基底的循环使用。
附图说明
图1可循环使用表面增强拉曼散射-棉织物的制备流程图。
图2二氧化钛和不同棉织物的X-射线衍射分析(XRD)(a)TiO2,(b)原棉织物,(c)Cotton-TiO2,(d)可循环使用SERS-棉织物;
图3不同棉织物的场发射扫描电镜图(FE-SEM):(a)原棉织物;(b)Cotton-TiO2;(c)和(d)可循环使用SERS-棉织物;
图4可循环使用SERS-棉织物对R6G的检测灵敏度;
图5(a)R6G在不同时间的紫外光的照射下的表面增强拉曼光谱图;(b)经不同时间紫外光照射后可循环使用织物在1508cm-1处的R6G拉曼信号强度;
图6(a)可循环使用SERS-棉织物多次循环检测R6G的流程示意图;(b)可循环使用SERS-棉织物多次循环检测R6G的SERS谱图;
图7不同基底对香梨表面西维因的擦拭检测(a)原棉织物;(b)可循环使用SERS-棉织物;(c)吸附在可循环使用SERS-棉织物的西维因经紫外光的照射后的表面增强拉曼光谱图;插图为擦拭检测的光学照片。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
配置钛酸四丁酯、冰醋酸和乙醇的混合液,总体积为36.6mL,其摩尔比为1:5:2。配置pH为2的冰醋酸溶液180mL,将钛酸四丁酯、冰醋酸和乙醇的混合液以1drop/Sec的速度逐滴加入冰醋酸溶液中,在滴加的过程中控制反应温度为30℃,转速为1200r/min。滴加结束后继续反应2h,将实验所得溶胶陈化7天,最后将其放置在120℃的高压灭菌锅中2h,进行热晶化处理,得到锐钛矿型二氧化钛水溶胶。
将棉织物浸渍在NaOH溶液中(1M,浴比为1:30),在水浴温度为90℃条件下振荡处理30min。取出处理后的棉织物,充分水洗后烘干。按照图1的制备示意图,将处理后的棉织物浸渍在自制的TiO2水溶胶中,超声振荡10min,二浸二轧,轧余率为(80%),80℃下烘干,得到Cotton-TiO2棉织物。
将Cotton-TiO2棉织物浸渍在0.2mol/L的硝酸银溶液中,在水浴温度为30℃下振荡处理30min,水洗。随后,将织物浸渍在0.1mol/L的抗坏血酸溶液中,在水浴温度为30℃下振荡处理30min。将上述棉织物用0.5%的醋酸室温下水洗15min,再用乙醇清洗,并在65℃下烘干,即得到可循环使用SERS-棉织物,其中二氧化钛粒子、银纳米粒子在棉织物上的负载量分别为3.00mg/g和24.84mg/g。
图1显示可循环使用SERS-棉织物的制备流程。
图2显示二氧化钛和不同棉织物的X-射线衍射分析(XRD)(a)TiO2,(b)原棉织物,(c)Cotton-TiO2,(d)可循环使用SERS-棉织物。
图3显示不同棉织物的场发射扫描电镜图(FE-SEM):(a)原棉织物;(b)Cotton-TiO2;(c)和(d)可循环使用SERS-棉织物。
实施例2
本实施例选取实施例1中所制备的可循环使用SERS-棉织物,将其分别置于浓度为10-5M、10-6M、10-7M、10-8M以及10-9M的R6G溶液中,溶液体积为20ml,静置20min,60℃烘干。利用英国Renishaw公司的激光显微拉曼光谱仪(Invia-reflex),分别对承载有不同浓度的R6G分子的可循环使用SERS-棉织物进行测试。采用633nm的He-Ne气体激光器作为激发光源,光栅为1200line/mm,在室温条件下测定其在500-2000nm波段范围内的拉曼光谱。
图4显示可循环使用SERS-棉织物对R6G的检测灵敏度。由图可知,可循环使用SERS-棉织物具有良好的灵敏性,其对R6G的检测极限可以达到10-9M。
实施例3
本实施例选取实施例1中所制备的可循环使用SERS-棉织物,将其置于浓度为10-5M的R6G溶液中,溶液体积为20ml,静置20min,60℃烘干。将其在紫外光下照射不同的时间,分别为30min、60min、90min、120min以及180min。利用英国Renishaw公司的激光显微拉曼光谱仪(Invia-reflex),对经不同时间的紫外光照射的可循环使用SERS-棉织物进行测试。采用633nm的He-Ne气体激光器作为激发光源,光栅为1200line/mm,在室温条件下测定其在500-2000nm波段范围内的拉曼光谱。
图5(a)为R6G在不同时间的紫外光的照射下的表面增强拉曼光谱图。(b)为经不同时间紫外光照射后可循环使用织物在1595cm-1处的R6G拉曼信号强度。
实施例4
本实施例选取实施例1中所制备的可循环使用SERS-棉织物,将其置于浓度为10-5M的R6G溶液中,溶液体积为20ml,静置20min,60℃烘干。利用英国Renishaw公司的激光显微拉曼光谱仪(Invia-reflex),对承载有R6G分子的SERS-棉织物进行测试。采用633nm的He-Ne气体激光器作为激发光源,光栅为1200line/mm,在室温条件下测定其在500-2000nm波段范围内的拉曼光谱。将承载有R6G分子的可循环使用SERS-棉织物在紫外光下照射180min,再利用英国Renishaw公司的激光显微拉曼光谱仪(Invia-reflex),对其进行SERS测试。采用633nm的He-Ne气体激光器作为激发光源,光栅为1200line/mm,在室温条件下测定其在500-2000nm波段范围内的拉曼光谱。如此反复进行4次。
图6为可循环使用SERS-棉织物多次循环检测R6G的SERS谱图。由图可知,可循环使用SERS-棉织物可以实现自清洁,可以循环使用。
实施例5
本实施例选取实施例1中所制备的可循环使用SERS-棉织物,将0.5ml的10-4M西维因溶液滴在香梨表面,在室温下烘干,其中西维因溶液所涂覆的面积为4cm2。将用乙醇润湿的原棉织物以及可循环使用SERS-棉织物(5mm×5mm)擦拭香梨表面西维因所涂覆的区域。利用英国Renishaw公司的激光显微拉曼光谱仪(Invia-reflex),对承载有西维因分子的SERS-棉织物进行测试。采用633nm的He-Ne气体激光器作为激发光源,光栅为1200line/mm,光谱分辨率为2cm-1,在室温条件下测定其在500-2000nm波段范围内的拉曼光谱。将将承载有R6G分子的可循环使用SERS-棉织物在紫外光下照射180min,再利用英国Renishaw公司的激光显微拉曼光谱仪(Invia-reflex),对其进行SERS测试。采用633nm的He-Ne气体激光器作为激发光源,光栅为1200line/mm,光谱分辨率为2cm-1,在室温条件下测定其在500-2000nm波段范围内的拉曼光谱。
图7为不同基底对苹果表面西维因的擦拭检测(a)原棉织物;(b)可循环使用SERS-棉织物。(c)吸附在可循环使用SERS-棉织物的西维因经紫外光的照射后的表面增强拉曼光谱图。由图可知,可循环使用SERS-棉织物达到预期的实际应用性能,可以实现擦拭检测。
Claims (10)
1.一种可循环使用的柔性表面增强拉曼散射基底,其特征在于:所述基底为负载有二氧化钛粒子、银纳米粒子Ag NPs的棉织物;其中二氧化钛以粒子方式沉积在棉织物表面,然后银纳米粒子再分散在外层。
2.根据权利要求1所述的基底,其特征在于,所述二氧化钛粒子在棉织物上的负载量为2.00~3.50mg/g,银纳米粒子在棉织物上的负载量范围为12.42mg/g~37.26mg/g。
3.一种如权利要求1所述的可循环使用的柔性表面增强拉曼散射基底的制备方法,包括:
(1)采用溶胶凝胶法制备纳米二氧化钛溶胶;
(2)将棉织物浸渍纳米二氧化钛溶胶,超声振荡,二浸二轧,烘干,得到沉积二氧化钛粒子的棉织物;
(3)采用原位还原法在沉积二氧化钛粒子的棉织物表面生长AgNPs,即得可循环使用的柔性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:所述步骤(2)中棉织物为氢氧化钠清洗后的棉织物。
5.根据权利要求3所述的制备方法,其特征在于:所述步骤(2)超声振荡时间为5-15min。
6.根据权利要求3所述的制备方法,其特征在于:所述步骤(3)中原位还原法具体为:将沉积二氧化钛粒子的棉织物浸渍在硝酸银溶液中,在水浴温度为30℃下振荡处理15-40min,水洗,随后,浸渍在抗坏血酸溶液中,在水浴温度为30℃下振荡处理15-40min,洗涤,烘干。
7.根据权利要求6所述的制备方法,其特征在于:所述硝酸银溶液的浓度为0.1-0.3mol/L;抗坏血酸溶液的浓度为0.05-0.2mol/L。
8.根据权利要求6所述的制备方法,其特征在于:所述洗涤具体为:用0.5%的醋酸室温下水洗10-15min,再用乙醇清洗。
9.根据权利要求6所述的制备方法,其特征在于:所述烘干为65℃下烘干。
10.一种可循环使用的柔性表面增强拉曼散射基底的应用。
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