CN106970065B - 一种Ag修饰的ZnO纳米棒基底的自清洁传感器及制备方法和用途 - Google Patents
一种Ag修饰的ZnO纳米棒基底的自清洁传感器及制备方法和用途 Download PDFInfo
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Abstract
本发明提供了一种Ag修饰的ZnO纳米棒基底的自清洁传感器及制备方法和用途,制备步骤如下:步骤1、ZnO纳米棒的制备;步骤2、ZnO/Ag的制备;步骤3、Ag修饰的ZnO纳米棒基底的自清洁传感器的制备。本发明将拉曼检测技术与分子印迹技术相结合,使其产物具有灵敏的检测性与高度的选择性;在本发明中,将用生物低毒性的银纳米粒子修饰的氧化锌基底与分子印迹技术相结合,使其聚合产物具有良好的生物兼容性,能够应用于对罗丹明的检测。
Description
技术领域
本发明涉及一种Ag修饰的ZnO纳米棒基底的自清洁传感器及制备方法和用途,属功能材料制备技术领域。
背景技术
目前,贵金属纳米粒子(M NPs)材料,具有独特的光学和电学性能,在传感、催化和生物医学等领域有广泛的应用。
表面增强拉曼散射技术(SERS),作为一种分析检测技术,具有高灵敏度、快速响应和指纹谱图等特性,已成为无损化学和生化分析最有价值的工具之一,近年来已经广泛应用于化学/生物传感器、单分子检测、生物医学检测等领域。
在金属纳米粒子表面或接近表面的探针分子的拉曼信号能明显放大108倍以上,使表面增强拉曼光谱技术可用于单分子的检测与分析。更重要的是,银纳米粒子比金纳米粒子具有更强和更灵敏的拉曼信号,因此成为更具有竞争力的等离子体传感器并且拓宽了增强表面增强拉曼散射(SERS)的应用范围。然而,使用金属纳米粒子的主要缺点是:重复性和稳定性相对较低,特别是为提高灵敏度添加聚合剂的时候,重复性和稳定性会更低。重要的是,传统的SERS基底不能轻易清洗以及再生后重复用于表面增强拉曼光谱分析。
最近,一些报道都集中于金属纳米粒子在固体基质上活性的研究,如越来越多的玻璃组件、硅晶片和金属半导体甚至是用滤纸调整的基底。一方面,它能解决传统金属纳米基底含有的缺陷,进一步促进和拓宽SERS应用。另一方面,一些调查报道,发现金属纳米颗粒与金属半导体接触时拉曼信号显著增强。例如,有人制备三维Al2O3膜负载金纳米粒子探索SERS增强机理。还有人制备表面用Ag NPs修饰的活性相TiO2纳米纤维用于4-MBA的检测。认为消逝场的增加可以增强的SERS效应,增强金属纳米粒子或金属/半导体之间的关联效应,可使特定的金属半导体界面的相互作用增强。此外,最近的研究证明,金属半导体也能产生弱SERS信号。
最近,分子印迹技术(MIT)与SERS检测技术联用,提高了传统的SERS基底材料的选择性。关于分子印迹聚合物(MIPs)基于表面增强拉曼光谱的研究已经提出,例如:胡亚锡等人制备的新型生物传感器结合分子印迹聚合物和表面增强拉曼光谱测定牛奶中的三聚氰胺。Kamra等人建立了基于表面增强拉曼光谱分子印迹聚合物,用于检测尼古丁。虽然这些方法对SERS的检测具有诸多优点,但是关于贵金属与半导体相结合,作为异质结基底材料并结合MIPs用于SERS检测的研究仍鲜有报道。
在本发明中,选取异质结构的SERS基底结合MIPs用于检测水中罗丹明6G,从而提高了选择性。一般来说,罗丹明6G(R6G)作为模板分子,首先尝试制备基于氧化锌/银异质结构作为SERS基底的MIPs。在最佳条件下,R6G为模板分子,氧化锌/银作为SERS基底,丙烯酰胺(AM)为功能单体、乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,通过沉淀聚合制备具有高灵敏度的氧化锌/银/R6G的分子印迹聚合物。制备的此基底可以选择性吸附R6G,显著提高了R6G的拉曼信号。此外研究表明,ZOA-MIPs在紫外光照射下具有自洁的性能。传感装置可以实现对R6G快速检测,这种技术提供一个有吸引力的和具有成本效益的方法,拓宽了SERS检测的应用范围。
发明内容
本发明的目的是通过三步反应合成Ag修饰的ZnO纳米棒基底的自清洁传感器,并探索其应用。首先,将氯化锌(ZnCl2)分散到去离子水中,在室温下超声,在搅拌条件下滴加NH3·H2O。将混合液转移到高压釜中反应数小时。反应后,反复洗涤,离心分离,烘干备用;其次,将氧化锌纳米棒(ZnO NRs)分散在乙醇和水的混合溶液中,加入0.1mol L-1的AgNO3溶液和0.2mol L-1的PVP,避光条件下磁力搅拌数小时后,加入乙醇胺(EA),反应数小时,真空干燥待用;最后,将ZnO/Ag分散到甲苯和甲基丙烯酰氧基丙基三甲氧基硅烷(MPS)的混合溶液中,然后通N2。数小时后,将合成产物离心分离;将ZnO/Ag分散到乙腈中,充分超声,然后将R6G、AM和EGDMA加入溶液中,通N2数分钟。最后,将AIBN加入到混合溶液中,放入恒温水浴中振荡,采用两步聚合方法制备。
本发明采用的技术方案如下:
一种Ag修饰的ZnO纳米棒基底的自清洁传感器,所述传感器是由ZnO纳米棒、Ag、印迹层复合而成的,Ag负载在ZnO纳米棒表面,形成ZnO/Ag;印迹层是由丙烯酰胺(AM)、乙二醇二甲基丙烯酸酯(EGDMA)和偶氮二异丁腈(AIBN)聚合而成的,所述印迹层负载在ZnO/Ag表面,形成Ag修饰的ZnO纳米棒基底的自清洁传感器;所述Ag修饰的ZnO纳米棒基底的自清洁传感器对罗丹明6G具有选择性吸附的特性。
一种Ag修饰的ZnO纳米棒基底的自清洁传感器的制备方法,步骤如下:
步骤1、ZnO纳米棒的制备
将ZnCl2分散到去离子水中,在室温下超声,在搅拌条件下滴加NH3·H2O,将得到的混合液转移到高压釜中,在140~160℃进行水热反应;反应完毕后,将合成的产物离心分离,洗涤,真空干燥,得到ZnO纳米棒,记为ZnO NRs;待用;
步骤2、ZnO/Ag的制备
将ZnO纳米棒分散在乙醇/水混合溶液中,加入0.1mol L-1的AgNO3溶液和0.2molL-1的PVP溶液,避光条件下磁力搅拌,加入乙醇胺(EA),温度升高到40~60℃反应11-13h;反应完毕后,将合成的产物离心分离,洗涤,真空干燥,得到ZnO/Ag;待用;
步骤3、Ag修饰的ZnO纳米棒基底的自清洁传感器的制备
将ZnO/Ag分散到甲苯/MPS混合液中80~100℃下通足量惰性气体以排除溶液中氧气;11-13h后,将固体离心分离,洗涤,真空干燥,得到固体A,待用;
将固体A分散到乙腈中,充分超声,然后将R6G、AM和EGDMA加入到溶液中,通惰性气体以排除溶液中氧气;最后,将AIBN加入到混合溶液中,放入恒温水浴中振荡,得到Ag修饰的ZnO纳米棒基底的自清洁传感器,产物记为ZOA-MIPs。
步骤1中,所述ZnCl2与去离子水的用量比为1g:60~80mL;NH3·H2O与去离子水的体积比为5.0mL:60-80mL;所述水热反应的时间为2.0-4.0h。
步骤2中,ZnO纳米棒、乙醇/水混合溶液、AgNO3溶液和PVP溶液的用量比为100mg:40~60mL:1~3mL:4~6mL,所述AgNO3溶液的浓度为0.1mol L-1,所述PVP溶液的浓度为0.2mol L-1;所述ZnO纳米棒与所述EA的用量比为100mg:200~400μL;所述磁力搅拌的时间为3.0-5.0h;所述温度升高到40~60℃反应的时间为11-13h。
步骤3中,制备固体A时,ZnO/Ag与甲苯/MPS混合液中的MPS用量比为1.0g:1.0~3.0mL,甲苯/MPS混合液中,甲苯与MPS的体积比为40~60:1~3;制备Ag修饰的ZnO纳米棒基底的自清洁传感器时,固体A、乙腈、R6G、AM、EGDMA、AIBN的用量比为1.0g:50~70mL:0.1~0.3mmol:0.3~0.5mmol:1.0~3.0mmol:9.0~11mg。
步骤1~3中,所述的洗涤,均为乙醇和水分别洗涤3次。
所述的Ag修饰的ZnO纳米棒基底的自清洁传感器用于选择性吸附罗丹明6G。
本发明对应的非印迹聚合物的制备方法类似合成方法如上,但不加R6G,产物记为ZOA-NIPs。
本发明的技术优点:
本发明将拉曼检测技术与分子印迹技术相结合,使其产物具有灵敏的检测性与高度的选择性;在本发明中,将用生物低毒性的银纳米粒子修饰的氧化锌基底与分子印迹技术相结合,使其聚合产物具有良好的生物兼容性,能够应用于对罗丹明的检测。银纳米粒子比金纳米粒子具有更强和更灵敏的表面增强拉曼信号,使它们成为更具有竞争力的等离子体传感器拓宽了表面增强拉曼散射(SERS)的应用。
附图说明
图1:ZnO纳米粒子(a),ZnO-Ag(b)和ZOA-MIPs(c)(比例尺尺寸为1μm)的扫描电镜图;
图2:ZOA-MIPs(a)和ZOA-NIPs(b)的红外光谱图;
图3:ZOA-MIPs和ZOA-NIPs的吸附性能显示图;
图4:ZOA-MIPS对于不同浓度R6G检测的拉曼光谱(a)和拉曼强度与R6G浓度变化的检测线性关系图(b);
图5:ZOA-MIPs的选择性检测性能力图(a:R6G检测曲线;b:RB检测曲线;c:CV检测曲线);
图6:ZOA-MIPs的重复检测性能。
具体实施方式
下面结合具体实施实例对本发明做进一步说明。
实施例1:
(1)ZnO纳米棒的合成
在150mL单口烧瓶中,将1.0g氯化锌分散到60mL的去离子水中,在室温下超声,在搅拌条件下滴加5.0mL NH3·H2O。将混合液转移到高压釜中140℃反应2.0h。随后,将合成的产物离心分离,反复洗涤数次,真空干燥待用。
(2)ZnO/Ag的合成
在150mL单口烧瓶中,将100mg ZnO NRs分散在40mL乙醇和水(体积比4/1)的混合溶液中,加入1.0mL浓度为0.1mol L-1的AgNO 3溶液和4.0mL浓度为0.2mol L-1的PVP,避光条件下磁力搅拌3.0h后,加入200μL EA,温度升高到40℃反应11h。随后,将合成的产物离心分离,用乙醇和水反复洗涤三次,真空干燥待用。
(3)ZnO/Ag分子印迹聚合物的制备
在150mL单口烧瓶中,将1.0g ZnO/Ag分散到40mL甲苯和1.0mL MPS的混合溶液80℃下通足量N2以排除溶液中氧气。11h后,将合成产物离心分离,乙醇洗涤三次,真空干燥待用。
在150mL单口烧瓶中,将1.0g ZnO/Ag分散到50mL乙腈中,充分超声,然后将0.1mmol R6G、0.3mmol AM和1.0mmol EGDMA加入溶液中,通足量N2以排除溶液中氧气。最后,将9mg AIBN加入到混合溶液中,放入恒温水浴振荡器,采用两步聚合方法制备。
其中,步骤(1)所述的反应体系中,NH3·H2O与去离子水的体积比为5.0mL:60mL。步骤中所述的洗涤,均为乙醇和水分别洗涤3次。
步骤(2)所述的反应体系中,ZnO与AgNO3质量体积比为100mg:1.0mL,ZnO与混合溶液的质量体积比为100mg:40mL,ZnO与PVP的质量体积比为100mg:4.0mL,ZnO与EA的质量体积比为100mg:200μL。
步骤(3)所述的反应体系中,ZnO/Ag与MPS的质量体积比为1.0g:1.0mL,ZnO/Ag与甲苯的质量体积比为1.0g:40mL,ZnO/Ag与乙腈的质量体积比为1.0g:50mL。步骤中所述的洗涤,均为乙醇和水分别洗涤3次。
本发明对应的非印迹聚合物的制备方法类似合成方法如上,但不加R6G。
实施例2:
(1)ZnO纳米棒的合成
在150mL单口烧瓶中,将1.0g氯化锌分散到70mL的去离子水中,在室温下超声,在搅拌条件下滴加5.0mL NH3·H2O。将混合液转移到高压釜中150℃反应3小时。随后,将合成的产物离心分离,反复洗涤数次,真空干燥待用。
(2)ZnO/Ag的合成
在150mL单口烧瓶中,将100mg ZnO NRs分散在50mL乙醇和水(体积比4/1)的混合溶液中,加入2.0mL浓度为0.1mol L-1的AgNO 3溶液和5.0mL浓度为0.2mol L-1的PVP,避光条件下磁力搅拌4h后,加入300μL EA,温度升高到50℃反应12h。随后,将合成的产物离心分离,用乙醇和水反复洗涤三次,真空干燥待用。
(3)ZnO/Ag分子印迹聚合物的制备
在150mL单口烧瓶中,将1.0g ZnO/Ag分散到50mL甲苯和2.0mL MPS的混合溶液90℃下通足量N2以排除溶液中氧气。12h后,将合成产物离心分离,乙醇洗涤三次,真空干燥待用。
在150mL单口烧瓶中,将1.0g ZnO/Ag分散到60mL乙腈中,充分超声,然后将0.2mmol R6G、0.4mmol AM和2.0mmol EGDMA加入到溶液中,通足量N2以排除溶液中氧气。最后,将10mg AIBN加入到混合溶液中,放入恒温水浴中振荡,采用两步聚合方法制备。
其中,步骤(1)所述的反应体系中,NH3·H2O与去离子水的体积比为5.0mL:70mL。步骤中所述的洗涤,均为乙醇和水分别洗涤3次。
步骤(2)所述的反应体系中,ZnO与AgNO3质量体积比为100mg:2.0mL,ZnO与混合溶液的质量体积比为100mg:50mL,ZnO与PVP的质量体积比为100mg:5.0mL,ZnO与EA的质量体积比为100mg:300μL。
步骤(3)所述的反应体系中,ZnO/Ag与MPS的质量体积比为1.0g:2.0mL,ZnO/Ag与甲苯的质量体积比为1.0g:50mL,ZnO/Ag与乙腈的质量体积比为1.0g:60mL。步骤中所述的洗涤,均为乙醇和水分别洗涤3次。
本发明对应的非印迹聚合物的制备方法类似合成方法如上,但不加R6G。
实施例3:
(1)ZnO纳米棒的合成
在150mL单口烧瓶中,将1.0g氯化锌分散到80mL的去离子水中,在室温下超声,在搅拌条件下滴加5.0mL NH3·H2O。将混合液转移到高压釜中160℃反应4.0h。随后,将合成的产物离心分离,反复洗涤数次,真空干燥待用。
(2)ZnO/Ag的合成
在150mL单口烧瓶中,将100mg ZnO NRs分散在60mL乙醇和水(体积比4/1)的混合溶液中,加入3.0mL浓度为0.1mol/l的AgNO3溶液和5.0mL浓度为0.2mol L-1的PVP,避光条件下磁力搅拌5.0h后,加入400μL EA,温度升高到60℃反应13h。随后,将合成的产物离心分离,用乙醇和水反复洗涤三次,真空干燥待用。
(3)ZnO/Ag分子印迹聚合物的制备
在150mL单口烧瓶中,将1.0g ZnO/Ag分散到60mL甲苯和3.0mL MPS的混合溶液100℃下通足量N2以排除溶液中氧气。13h后,将合成产物离心分离,乙醇洗涤三次,真空干燥待用。
在150mL单口烧瓶中,将1.0g ZnO/Ag分散到60mL乙腈中,充分超声,然后将0.3mmol R6G、0.4mmol AM和3.0mmol EGDMA加入溶液中,通足量N2以排除溶液中氧气。最后,将11mg AIBN加入到混合溶液中,放入恒温水浴中振荡,采用两步聚合方法制备。
其中,步骤(1)中所述的反应体系中,NH3·H2O与去离子水的体积比为5.0mL:80mL。步骤中所述的洗涤,均为乙醇和水分别洗涤3次。
步骤(2)所述的反应体系中,ZnO与AgNO3质量体积比为100mg:3.0mL,ZnO与混合溶液的质量体积比为100mg:60mL,ZnO与PVP的质量体积比为100mg:6.0mL,ZnO与EA的质量体积比为100mg:400μL。
步骤(3)所述的反应体系中,ZnO/Ag与MPS的质量体积比为1.0g:3.0mL,ZnO/Ag与甲苯的质量体积比为1.0g:60mL,ZnO/Ag与乙腈的质量体积比为1.0g:70mL。步骤中所述的洗涤,均为乙醇和水分别洗涤3次。
本发明对应的非印迹聚合物的制备方法类似合成方法如上,但不加R6G。
图1:ZnO纳米粒子(a),ZnO-Ag(b)和ZOA-MIPs(c)的扫描电镜图。所述传感器是由ZnO纳米棒、Ag、印迹层复合而成的,Ag负载在ZnO纳米棒表面,形成ZnO/Ag;印迹层是由丙烯酰胺(AM)、乙二醇二甲基丙烯酸酯(EGDMA)和偶氮二异丁腈(AIBN)聚合而成的,所述印迹层负载在ZnO/Ag表面,形成Ag修饰的ZnO纳米棒基底的自清洁传感器,该印迹聚合物已经成功合成;
图2:ZOA-MIPs(a)和ZOA-NIPs(b)的红外光谱图。由图中可以看出,这两种材料都呈现出明显的峰值,从红外谱图中,可以看出,该聚合物已经成功合成;
图3:ZOA-MIPs和ZOA-NIPs的吸附性能显示图。在紫外光谱图中,ZOA-MIPs和ZOA-NIPs吸附效率分别为71.23%和30.26%;
图4:ZOA-MIPS对于不同浓度R6G检测的拉曼光谱(a)和拉曼强度与R6G浓度变化的检测线性关系图(b)。
图5:ZOA-MIPs的选择性检测性能力图。R6G有明显的拉曼增强信号,但对于RB和CV的拉曼强度比R6G小;
图6:ZOA-MIPs的重复检测性能,从图中可以看出,ZOA-MIPs具备良好的可重复性能。
本发明具体的拉曼检测按照下述方法进行:在拉曼光谱中反应出SERS对ZOA-MIPs的检测能力。在本实验中,所有的拉曼检测条件均一致:激发光波长为633nm。每个样品的光谱收集与曝光时间均为10秒,入射激光的功率为0.25mW。SERS谱图用50×尼康镜头收集。所有的SERS基底放在载玻片上,自然干燥后用于表面增强拉曼光谱的检测。
试验例1:如图4(a)所示,检测了ZOA-MIPS的SERS活性,罗丹明6G为探针分子,确定检测限。该图表明,在1654cm-1处的表面增强拉曼光谱强度最强。此外,根据文献可知,由于有对称形式的C-C伸缩振动存在,所以将1654cm-1作为特征峰。从数据中可以看出,随着R6G浓度从10-7mol L-1到10-13mol L-1的变化,SERS的强度也随之变化。当R6G浓度为10-14mol L-1,拉曼信号几乎消失。此外,如图4(b)所示,特征峰强度的变化与R6G浓度的改变呈线性关系。R6G浓度在10-7mol L-1到10-13mol L-1之间时(R2)的检测系数为0.95。
试验例2:为了研究ZOA-MIPs对R6G的特异选择性,用浓度为10-7mol L-1结构类似于罗丹明6G的RB和CV做平行实验来进一步研究。如图5所示,由于RB和CV分子结构与R6G不同,不能被ZOA-MIPs选择性吸附,所以只能观察到微弱的表面增强拉曼光谱强度。
试验例3:传统的SERS传感器无法实现循环利用,所以SERS传感器的检测效果受到限制。因此需要一个方法来制造一个用于检测R6G的可再生使用的SERS传感器。在该试验中制备的材料不仅拥有检测功能,而且拥有自清洁功能。在图6中所示,通过适当的漂洗和光降解过程,ZOA-MIPs中检测不到有模板分子残留。这证明了模板分子从MIPS的表面完全除去了。
Claims (7)
1.一种Ag修饰的ZnO纳米棒基底的自清洁传感器,其特征在于,所述传感器是由ZnO纳米棒、Ag、印迹层复合而成的,Ag负载在ZnO纳米棒表面,形成ZnO/Ag;印迹层是由丙烯酰胺、乙二醇二甲基丙烯酸酯和偶氮二异丁腈聚合而成的,所述印迹层负载在ZnO/Ag表面,形成Ag修饰的ZnO纳米棒基底的自清洁传感器;所述Ag修饰的ZnO纳米棒基底的自清洁传感器对罗丹明6G具有选择性吸附的特性。
2.如权利要求1所述的一种Ag修饰的ZnO纳米棒基底的自清洁传感器的制备方法,其特征在于,步骤如下:
步骤1、ZnO纳米棒的制备
将ZnCl2分散到去离子水中,在室温下超声,在搅拌条件下滴加NH3·H2O,将得到的混合液转移到高压釜中,在140~160℃进行水热反应;反应完毕后,将合成的产物离心分离,洗涤,真空干燥,得到ZnO纳米棒,记为ZnO NRs;待用;
步骤2、ZnO/Ag的制备
将ZnO纳米棒分散在乙醇/水混合溶液中,加入0.1mol L-1的AgNO3溶液和0.2mol L-1的聚乙烯吡咯烷酮溶液,避光条件下磁力搅拌,加入乙醇胺,温度升高到40~60℃反应11-13h;反应完毕后,将合成的产物离心分离,洗涤,真空干燥,得到ZnO/Ag;待用;
步骤3、Ag修饰的ZnO纳米棒基底的自清洁传感器的制备
将ZnO/Ag分散到甲苯/甲基丙烯酰氧基丙基三甲氧基硅烷混合液中80~100℃下通足量惰性气体以排除溶液中氧气;11-13h后,将固体离心分离,洗涤,真空干燥,得到固体A,待用;
将固体A分散到乙腈中,充分超声,然后将罗丹明6G、丙烯酰胺和乙二醇二甲基丙烯酸酯加入到溶液中,通惰性气体以排除溶液中氧气;最后,将偶氮二异丁腈加入到混合溶液中,放入恒温水浴中振荡,得到Ag修饰的ZnO纳米棒基底的自清洁传感器。
3.如权利要求2所述的一种Ag修饰的ZnO纳米棒基底的自清洁传感器的制备方法,其特征在于,步骤1中,所述ZnCl2与去离子水的用量比为1g:60~80mL;NH3·H2O与去离子水的体积比为5.0mL:60-80mL;所述水热反应的时间为2.0-4.0h。
4.如权利要求2所述的一种Ag修饰的ZnO纳米棒基底的自清洁传感器的制备方法,其特征在于,步骤2中,ZnO纳米棒、乙醇/水混合溶液、AgNO3溶液和聚乙烯吡咯烷酮溶液的用量比为100mg:40~60mL:1~3mL:4~6mL,所述AgNO3溶液的浓度为0.1mol L-1,所述聚乙烯吡咯烷酮溶液的浓度为0.2mol L-1;所述ZnO纳米棒与所述乙醇胺的用量比为100mg:200~400μL;所述磁力搅拌的时间为3.0-5.0h;所述温度升高到40~60℃反应的时间为11-13h。
5.如权利要求2所述的一种Ag修饰的ZnO纳米棒基底的自清洁传感器的制备方法,其特征在于,步骤3中,制备固体A时,ZnO/Ag与甲苯/甲基丙烯酰氧基丙基三甲氧基硅烷混合液中的甲基丙烯酰氧基丙基三甲氧基硅烷用量比为1.0g:1.0~3.0mL,甲苯/甲基丙烯酰氧基丙基三甲氧基硅烷混合液中,甲苯与甲基丙烯酰氧基丙基三甲氧基硅烷的体积比为40~60:1~3;制备Ag修饰的ZnO纳米棒基底的自清洁传感器时,固体A、乙腈、罗丹明6G、丙烯酰胺、乙二醇二甲基丙烯酸酯、偶氮二异丁腈的用量比为1.0g:50~70mL:0.1~0.3mmol:0.3~0.5mmol:1.0~3.0mmol:9.0~11mg。
6.如权利要求2所述的一种Ag修饰的ZnO纳米棒基底的自清洁传感器的制备方法,其特征在于,步骤1~3中,所述的洗涤,均为乙醇和水分别洗涤3次。
7.权利要求1所述的Ag修饰的ZnO纳米棒基底的自清洁传感器用于选择性吸附罗丹明6G的用途。
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