CN105819434A - 一种表面增强拉曼基底材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种表面增强拉曼基底材料及其制备方法。本发明材料以氧化石墨烯为模板和载体,在其表面修饰半胱氨酸和自组装纳米银颗粒;其制备的具体步骤如下:1)取氧化石墨烯和半胱氨酸溶解在二次蒸馏水中后,使其于PBS缓冲液体系中室温条件下反应,反应结束后,离心分离,将得到的沉淀洗涤,洗涤后沉淀再溶解于PBS缓冲液中,得到第一溶液;2)将纳米银胶体溶液加入到第一溶液中,室温反应、离心分离,得到的沉淀再次溶解在水中,即得到表面增强拉曼基底材料;本发明的表面增强拉曼基底材料,具有环境污染小,操作简单,成本低廉等特点,该材料对有机分子的拉曼检测具有良好的表面增强作用。
Description
技术领域
本发明涉及功能材料技术领域,具体的说,涉及一种表面增强拉曼基底材料及其制备方法。
背景技术
表面增强拉曼散射(SERS)是指当目标分子被吸附到某些金属(如金、银、铜等)颗粒的表面时,其目标分子的拉曼信号能得到极大的增强现象。SERS技术在对待检测的分子具有极高的检测灵敏度和选择性,可在分子水平上实时观测界面各种物质的化学结构和组成,促进拉曼技术获得突破性的发展。
从SERS现象被发现开始,人们就一直在研究SERS的增强机理,但是由于SERS的体系过于复杂,几十年过去了,人们还未完全能够清晰的解释SERS的机理,研究者们提出了许多可能的模型解释SERS的增强机理,其中包括物理增强和化学增强模型。物理增强也叫做电磁增强。该机理认为在有一定程度粗糙度的金属表面有一束入射光照射,如果金属表面能产生放大的一个局域电磁场,而分子又凑巧在这个放大的电磁场中被吸附时,那么也就会相对应的放大拉曼散射信号。化学增强机理研究者普遍已经承认了SERS的物理增强机理,但是很多后来的实验数据分析发现,电磁场增强机理无法完全解释清楚,所以一定还有其他的机理在起作用。例如基底表面的吡啶分子达到一定量的覆盖度时吡啶分子的N原子上面的孤对电子会通过化学吸附到基底上,这样就会出现拉曼增强的现象。实验表明并不是一切被吸附的分子都可以产生拉曼增强效应,仅有那些被吸附在基底表面称作活性点的分子才会有较强的增强效应,还有实验数据证明,一般基底上能有SERS效应的活性点是极少的。另外,若干个单分子层连续被吸附到SERS基底上之后,它们与金属基底表面直接连接的被吸附的官能团的SERS效应增强最大。除此之外物理增强机理应是没有选择性,对于每个吸附在基底表面上的分子都是一样的贡献,例如CO和N2具有几乎相同的拉曼散射截面在同样的实验条件时,但它们的化学增强因子却相差了200多倍。
过去几十年来,许多工作者都致力于构建各种各样的表面增强拉曼基底材料的制备,然而大多数的表面增强拉曼基底材料的制备方法都比较复杂,环境污染大。发展具有制备简单且环保的表面增强拉曼基底为解决该问题提供了一种新的思路,能促进SERS技术在更广泛的领域内实现实时和原位检测。在现有技术中,有关氧化石墨烯负载贵金属纳米溶胶的制备方法也有相关报道,中国专利(公开号105445254A)提出将硼氢化钠作为还原剂加入碳基量子点和银离子的溶液中,得到碳基量子点/纳米银复合材料。这个技术的缺点在于硼氢化钠还原性能较强,难以获得形貌可控且重现性好的碳基量子点/纳米银复合材料,从而限制其应用。中国专利(公开号104999088A)提出以聚乙烯亚胺和聚丙烯酸为聚电解质,利用电解质的电荷和还原特性,制备金纳米粒子-还原氧化石墨烯多层膜复合材料,这个技术的缺点在于电解质原位还原得到的金纳米粒子容易团聚,较难得到形貌均匀可控的复合石墨烯基纳米材料。
发明内容
为了克服现有技术的不足,本发明的目的在于提供一种表面增强拉曼基底材料及其制备方法。本发明制备方法简单、快速、环保,制备得到的表面增强拉曼基底材料具有表面形貌可控,稳定性好和拉曼增强活性高等特点。
本发明技术方案具体介绍如下。
本发明提供一种表面增强拉曼基底材料,其以氧化石墨烯为模板,通过在氧化石墨烯表面修饰半胱氨酸和自组装纳米银颗粒获得;其中:氧化石墨烯和半胱氨酸的质量比为1:100~1:500。优选的,氧化石墨烯与纳米银颗粒的质量比1:1~1:10。
本发明还提供一种上述表面增强拉曼基底材料的制备方法,具体步骤如下:
1)取氧化石墨烯和半胱氨酸溶解在二次蒸馏水中后,使其于磷酸盐(PBS)缓冲液体系中,室温条件下反应20-30小时,反应结束后,离心分离,并将得到的沉淀洗涤,洗涤后沉淀再次溶解在磷酸盐(PBS)缓冲液中,得到第一溶液;其中:氧化石墨烯和半胱氨酸的质量比为1:100~1:500;
2)将纳米银胶体溶液加入到步骤1)所得的第一溶液中,在室温条件下,搅拌反应,反应结束后,离心分离,得到的沉淀再次溶解在水中,即得到表面增强拉曼基底材料。
本发明中,氧化石墨烯和纳米银颗粒的质量比1:1~1:10。
本发明中,步骤1)中,氧化石墨烯的质量和二次蒸馏水的体积比值为1:1~1:20mg/mL。
本发明中,步骤2)中的纳米银胶体溶液通过将硝酸银和柠檬酸钠在水和甘油混合溶液中95℃温度下反应得到。
和现有技术相比,本发明的有益效果在于:
1)该表面增强拉曼基底材料的构建方法简单、快速、无污染。
2)通过改变半胱氨酸与氧化石墨烯的配比,可获得不同表面形貌的负载纳米银颗粒的石墨烯(银纳米粒子/石墨烯)复合材料,该材料具有较高的拉曼增强活性,可用于10-9mol/L对巯基苯胺溶液的分析检测。该材料连续放置5周过程中检测对巯基苯胺的拉曼光谱,其拉曼信号强度的变化小于10%,因此,该材料具有良好的稳定性。
3)半胱氨酸不仅可原位还原氧化石墨烯获得还原石墨烯,还可通过巯基共价连接纳米银,从而构建形貌可控的负载纳米银石墨烯复合材料。
4)该复合材料使用氧化石墨烯作为模板,通过还原得到的还原石墨烯对芳香化合物具有良好的吸附作用,因此,该复合材料具有超灵敏增强效应。
附图说明
图1为实施例1条件下,所用纳米银产物的透射电子显微镜图。
图2为实施例1条件下,所制得银纳米粒子/石墨烯复合材料的透射电子显微镜图。
图3为实施例1条件下,所制备银纳米粒子/石墨烯复合材料的紫外光谱图。横坐标为波长(nm),纵坐标为吸光度。
图4为实施例2条件下,银纳米粒子/石墨烯复合材料对对巯基苯胺不同浓度(从上到下依次10-3,10-4,10-5,10-6,10-7,10-8,10-9mol/L)的表面增强拉曼图。横坐标为拉曼位移(cm-1),纵坐标为拉曼信号强度(CPS)。
图5为实施例2条件下,对巯基苯胺的拉曼特征峰在1074cm-1,银纳米粒子/石墨烯复合材料对对巯基苯胺梯度浓度的表面增强拉曼在1074cm-1位置的信号强度与对巯基苯胺梯度浓度取对数的线性关系图,横坐标为对巯基苯胺浓度的对数Log(Cmol/L),纵坐标为拉曼强度(CPS)。
图6为实施例2条件下,同样的条件下,银纳米粒子/石墨烯复合材料对对巯基苯胺(10-7mol/L)在0到5周每隔1周检测一次(从上到下分别为0、1、2、3、4、5周)的表面增强拉曼图,横坐标为拉曼位移(nm),纵坐标为1074cm-1处的拉曼信号强度(CPS)。
具体实施方式
下面结合实例对本发明的技术方案作进一步的说明。
实施例1
1)低温冰浴的条件下在200mL烧杯中加入1g鳞片石墨,然后加入60mL的98%浓硫酸,在磁力搅拌下,缓慢加入6g高锰酸钾(约30min加完),进行30min的反应。将上述烧杯放在水浴的35℃下,进行反应2小时,随着进一步延长中温时间会导致整个溶液体系变粘稠。反应结束后取出烧杯放入高温85℃油浴中,用滴定管缓慢加入20mL水(40分钟加完,滴加速度过快的话,反应温度不容易控制),进行20分钟的反应(延长高温时间,溶液会逐渐变成黄色或者亮黄色,可以不需要加双氧水),加入10mL的双氧水。在室温的条件下进行4次离心分离,沉淀用二次蒸馏水洗涤,然后进行冷冻干燥处理,就得到固体氧化石墨烯。
2)在250mL的三口烧瓶中加入大号转子,并一起加入30mL水和20mL甘油(防止合成的纳米银团聚),在油浴锅中加热95℃,加入30mg柠檬酸钠,两分钟后开始滴加1mg/mL的硝酸银溶液9mL,1小时后,停止反应(如图1),取出溶液用封口膜封口4℃冷藏。图1为实施例1条件下,所用纳米银产物的透射电子显微镜图,纳米银颗粒的粒径在30±3nm。
3)取上述1mg的氧化石墨烯和150mg的半胱氨酸溶解在10mL二次蒸馏水中,使其在磷酸盐(PBS)缓冲液体系中进行反应,室温条件下搅拌24小时,进行3次高速离心分离去除多余的半胱氨酸,沉淀用二次蒸馏水洗涤,将沉淀再次溶解在5mL的磷酸盐(PBS)缓冲液中。
4)将步骤2)合成的纳米银从冰箱中取出20mL,在10000rpm转速下离心分离2次,沉淀溶解在2mL二次蒸馏水的中,所得纳米银溶液的浓度约为1mg/mL。
5)将步骤4)分离的2mL纳米银胶体溶液(浓度约为1mg/mL)加入到步骤3)所得的溶液中,在室温条件下,搅拌反应12小时。即将得到的反应液进行2次高速离心分离,去除多余的纳米银颗粒,得到沉淀再次溶解在水中。即可得到所想要的表面增强拉曼基底材料。
图2为实施例1条件下,所制得银纳米粒子/石墨烯复合材料的透射电子显微镜图,从图2中可以看出,纳米银颗粒已经负载到石墨烯片层上,形成表面均匀有序的复合纳米材料。
图3为实施例1条件下,所制备银纳米粒子/石墨烯复合材料的紫外吸收图。横坐标为波长(nm),纵坐标为吸收系数(a.u.),从图中可以看出在410nm出现了纳米银的紫外吸收峰,可以证明纳米银负载到石墨烯片层上了,而紫外在410nm的吸收峰也能间接地证明纳米银的粒径在30±3nm。
实施例2
1)取上述1mg的氧化石墨烯和400mg的半胱氨酸溶解在10mL二次蒸馏水中,使其在磷酸盐(PBS)缓冲液体系中进行反应,室温条件下搅拌24小时,进行3次高速离心分离去除多余的半胱氨酸,沉淀用二次蒸馏水洗涤,将沉淀再次溶解于5mL的磷酸盐(PBS)缓冲液。
2)将合成的纳米银溶胶离心分离8mL(浓度约为1mg/mL)加入步骤1中,在室温条件下,搅拌反应12小时。即将得到的反应液进行2次高速离心分离,去除多余的纳米银颗粒,得到沉淀再次溶解在水中。即可得到所想要的表面增强拉曼基底材料。
3)取实施例2中1mL复合材料,加入0.5mL的对巯基苯胺的梯度浓度溶液(10-3,10-4,10-5,10-6,10-7,10-8,10-9mol/L图4中从上到下),混合均匀,反应2小时。
4)将上述反应液3)滴加到硅片上干燥,重复6~7次操作,待液体干燥后用拉曼光谱仪器对硅片上的混有对巯基苯胺复合材料进行拉曼检测。拉曼光谱检测条件是激发功率25mW,采集时间5s。
图4为实施例2条件下,取银纳米粒子/石墨烯复合基底材料对对巯基苯胺的不同浓度(从g到a依次为10-9,10-8,10-7,10-6,10-5,10-4,10-3mol/L)进行拉曼检测,在图4中,1706cm-1处的拉曼光谱峰是对巯基苯胺的特征峰,此外,1706cm-1的拉曼信号随着浓度递增而增强(从g到a的浓度依次是10-9,10-8,10-7,10-6,10-5,10-4,10-3mol/L)。从图4中可以看出在10-9mol/L的对巯基苯胺依然可见1706cm-1处有明显的拉曼信号,表明该复合材料具有较强拉曼活性和灵敏性。
5)将上述步骤4)中混有10-7mol/L对巯基苯胺的复合材料干燥保存,每隔一周进行拉曼检测一次,连续观察5周过程中拉曼特征峰1074cm-1处信号强度变化,考察该复合材料的稳定性,经过5周的放置,拉曼特征峰1074cm-1处信号强度变化小于10%。
图5为实施例2条件下,银纳米粒子/石墨烯复合材料对对巯基苯胺梯度浓度的表面增强拉曼在1074cm-1位置的信号强度与对巯基苯胺浓度对数的线性关系图,横坐标为对巯基苯胺浓度的对数Log(C,mol/L),纵坐标为拉曼强度(CPS)。可以看出,随着对巯基苯胺的浓度的增加,拉曼信号强度随之增加。
图6为实施例2条件下,在步骤5)中,银纳米粒子/石墨烯复合材料对对巯基苯胺(10-7mol/L)在0到5周(从上到下依次为0,1,2,3,4,5周)的表面增强拉曼图。说明复合材料具有良好的稳定性。
Claims (6)
1.一种表面增强拉曼基底材料,其特征在于,其以氧化石墨烯为模板和载体,通过在氧化石墨烯表面修饰半胱氨酸和自组装纳米银颗粒获得;其中:氧化石墨烯和半胱氨酸的质量比为1:100~1:500。
2.如权利要求1所述的表面增强拉曼基底材料,其特征在于,氧化石墨烯与纳米银颗粒的质量比1:1~1:10。
3.一种如权利要求1所述的表面增强拉曼基底材料的制备方法,其特征在于,具体步骤如下:
1)取氧化石墨烯和半胱氨酸溶解在二次蒸馏水中后,使其于磷酸盐缓冲液体系中,室温条件下反应20-30小时,反应结束后,离心分离,并将得到的沉淀洗涤,洗涤后沉淀再次溶解在磷酸盐缓冲液中,得到第一溶液;其中:氧化石墨烯和半胱氨酸的质量比为1:100~1:500;
2)将纳米银胶体溶液加入到步骤1)所得的第一溶液中,在室温条件下,搅拌反应,反应结束后,离心分离,得到的沉淀再次溶解在水中,即得到表面增强拉曼基底材料。
4.如权利要求3所述的制备方法,其特征在于,氧化石墨烯和纳米银颗粒的质量比1:1~1:10。
5.如权利要求3所述的制备方法,其特征在于,步骤1)中,氧化石墨烯的质量和二次蒸馏水的体积的质量体积比为1:1~1:20mg/mL。
6.如权利要求3所述的制备方法,其特征在于,步骤2)中的纳米银胶体溶液通过将硝酸银和柠檬酸钠在水和甘油混合溶液中95℃温度下反应得到。
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CN109294234A (zh) * | 2018-09-26 | 2019-02-01 | 北京市政建设集团有限责任公司 | 一种可重复利用基于石墨烯-贵金属纳米粒子复合物杂化薄膜及其制备方法 |
CN112176721A (zh) * | 2019-09-27 | 2021-01-05 | 华北电力大学(保定) | 一种提高银纳米粒子负载稳定性的复合纤维膜制备方法 |
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CN106346016A (zh) * | 2016-08-30 | 2017-01-25 | 电子科技大学 | 银/石墨烯复合薄膜的制备方法及在紫外探测器中的应用 |
CN106346016B (zh) * | 2016-08-30 | 2018-04-06 | 电子科技大学 | 银/石墨烯复合薄膜的制备方法及在紫外探测器中的应用 |
CN109294234A (zh) * | 2018-09-26 | 2019-02-01 | 北京市政建设集团有限责任公司 | 一种可重复利用基于石墨烯-贵金属纳米粒子复合物杂化薄膜及其制备方法 |
CN112176721A (zh) * | 2019-09-27 | 2021-01-05 | 华北电力大学(保定) | 一种提高银纳米粒子负载稳定性的复合纤维膜制备方法 |
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