CN111661841B - 石墨烯-磁性纳米线探针及其制备方法 - Google Patents
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Abstract
本发明涉及一种石墨烯‑Fe3O4固相微萃取探针,该探针的基体为金属丝,其特征在于:在金属丝表面依次沉积有Fe3O4纳米线阵列和石墨烯纳晶。Fe3O4纳米线阵列通过模板‑水热法制得;石墨烯纳晶通过电子回旋等离子体溅射沉积得到。充分利用石墨烯二维纳米材料,其具有大的比表面积,使得探针具有良好的萃取、富集效果,探针的灵敏度高、稳定性好。通过模板‑水热法,预先在金属丝表面获得多孔结构的阳极氧化铝,实现Fe3O4纳米线阵列的可控生长,保障了后续的石墨烯纳晶的沉积。直接将磁性Fe3O4纳米线阵列沉积在金属丝和石墨烯纳晶之间,探针在对样品进行处理的过程中,可以通过施加外加磁场来优化萃取效果,方法简便。
Description
技术领域
本发明涉及一种探针,用于固相微萃取领域,具体涉及一种石墨烯-磁性纳米线阵列固相微萃取探针及其制备方法。
背景技术
固相微萃取(Solid Phase Microextraction,SPME)技术是一种样品分析测定技术,可以于气相色谱、液相色谱、质谱、电泳等仪器配合使用,广泛应用于食品分析、环境分析、生物样品分析、药物分析等领域。
固相微萃取探针是固相微萃取技术中的核心部件。但是目前的固相微萃取探针主要是基于熔融石英纤维,价格高、稳定性差、寿命短。需要开发新的灵敏度高、稳定性好、成本低、绿色环保的固相微萃取探针。
石墨烯(graphene)作为一种新型材料,由于其独特的二维蜂窝状晶体结构,具有超高的比表面积,良好的导电、导热性,硬度强,吸附能力强等性质,具有应用在各类传感器、分析检测等领域中的前景。
此外,磁分离技术是一种绿色分离技术,且在化工、冶金等领域已经有一定的应用基础,其是以磁性粒子为核心,利用磁力分离和收集目标物质,具有效率高、灵敏度高、应用范围广等优点。
本发明的研究者发现,将石墨烯材料和磁分离技术结合,可以获得成本低、灵敏度高、稳定性好的固相微萃取探针。即,本发明旨在提供一种磁性纳米线辅助强化的石墨烯固相微萃取探针。
发明内容
针对现有的固相微萃取探针中存在的不足,本发明提供了一种磁性纳米线阵列辅助强化的石墨烯固相微萃取探针,具体为石墨烯-Fe3O4固相微萃取探针,通过将石墨烯和磁性Fe3O4纳米线阵列相结合,改善固相微萃取探针的灵敏度、稳定性。
即,本发明提供一种石墨烯-Fe3O4固相微萃取探针,该探针的基体为金属丝,其特征在于:在金属丝表面依次沉积有Fe3O4纳米线阵列和石墨烯纳晶。
其中,金属丝选自钛丝或不锈钢丝,金属丝的直径为0.2-1mm。
其中,Fe3O4纳米线阵列通过模板-水热法制得。
其中,石墨烯纳晶通过电子回旋等离子体溅射沉积得到。
具体而言,本发明提供的一种石墨烯-Fe3O4固相微萃取探针的制备方法如下:
(1)将金属丝清洗、干燥后,在金属丝表面热浸镀铝,镀铝层厚度为5-50um,然后对镀铝层进行阳极氧化,在镀铝层上形成纳米级孔道后,清洗、干燥备用;
(2)将FeCl3、柠檬酸钠、乙酸钠、乙二醇混合,搅拌溶解,超声分散均匀,得到溶胶;所述FeCl3、柠檬酸钠、乙酸钠的质量比为2:1:4;所述乙二醇的体积用量以FeCl3的质量计为30~50mL/g;
(3)将步骤(2)的溶胶施加在步骤(1)制得的金属丝表面,并施加超声振动10-30min,促使溶胶渗透到纳米级孔道中,然后将其浸没于步骤(2)的溶胶中,加热至200°C反应5-10h后,冷却取出,置于1mol/L的NaOH溶液,所述浸泡的时间为30-60min,将表面的阳极氧化铝以及未氧化的铝层完全溶解,得到表面生长有Fe3O4纳米线阵列的金属丝;
(4)将表面生长有Fe3O4纳米线阵列的金属丝置于电子回旋等离子体溅射沉积腔室中,抽真空至1×10-4Pa时通入氩气,使气压保持在1×10-2Pa;施加线圈磁场并导入微波,在磁场和微波的耦合作用下产生氩等离子体,施加200V的靶材偏压,轰击碳靶,基底施加-100V的偏压,溅射沉积5-20min,在Fe3O4纳米线阵列表面沉积石墨烯纳晶。
相较于现有的固相微萃取探针,本发明具有以下有益效果:
1、充分利用石墨烯二维纳米材料,其具有大的比表面积,使得探针具有良好的萃取、富集效果,探针的灵敏度高、稳定性好。具体采用电子回旋等离子体溅射沉积方法来制备石墨烯纳晶,通过磁场和微波的耦合作用下产生的氩等离子体轰击碳靶,使得所得到的石墨烯纳晶膜层与基底的结合性良好,且呈现输送多孔结构,进一步增加其比表面积,进而增强探针的萃取、富集效果。
2、直接将磁性Fe3O4纳米线阵列沉积在金属丝和石墨烯纳晶之间,探针在对样品进行处理的过程中,可以通过施加外加磁场来优化萃取效果,方法简便,不需要在样品中增加额外的磁性颗粒。
3、由于直接进行水热反应制备磁性Fe3O4容易团聚,无法获得Fe3O4纳米线阵列,本发明通过模板-水热法,预先在金属丝表面获得多孔结构的阳极氧化铝,实现Fe3O4纳米线阵列的可控生长,保障了后续的石墨烯纳晶的沉积。
附图说明
图1 实施例1和对比例的探针的电化学发光信号比较图。
具体实施方式
下面,将结合具体的实例对本发明进行详细说明。当然,所描述的实施例仅仅是本发明的一部内创造内容,而不是全部。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的情况下所获得的其他实例均落入本发明的保护范围內。
实施例1
一种石墨烯-Fe3O4固相微萃取探针,其制备方法如下:
(1)将金属丝清洗、干燥后,在金属丝表面热浸镀铝,镀铝层厚度为20um,然后对镀铝层进行阳极氧化,在镀铝层上形成纳米级孔道后,清洗、干燥备用;
(2)将FeCl3、柠檬酸钠、乙酸钠、乙二醇混合,搅拌溶解,超声分散均匀,得到溶胶;所述FeCl3、柠檬酸钠、乙酸钠的质量比为2:1:4;所述乙二醇的体积用量以FeCl3的质量计为30mL/g;
(3)将步骤(2)的溶胶施加在步骤(1)制得的金属丝表面,并施加超声振动20min,促使溶胶渗透到纳米级孔道中,然后将其浸没于步骤(2)的溶胶中,加热至200°C反应6h后,冷却取出,置于1mol/L的NaOH溶液,所述浸泡的时间为40min,将表面的阳极氧化铝以及未氧化的铝层完全溶解,得到表面生长有Fe3O4纳米线阵列的金属丝;
(4)将表面生长有Fe3O4纳米线阵列的金属丝置于电子回旋等离子体溅射沉积腔室中,抽真空至1×10-4Pa时通入氩气,使气压保持在1×10-2Pa;施加线圈磁场并导入微波,在磁场和微波的耦合作用下产生氩等离子体,施加200V的靶材偏压,轰击碳靶,基底施加-100V的偏压,溅射沉积10min,在Fe3O4纳米线阵列表面沉积石墨烯纳晶。
其中,所述金属丝为金属钛丝。
实施例2
一种石墨烯-Fe3O4固相微萃取探针,其制备方法如下:
(1)将金属丝清洗、干燥后,在金属丝表面热浸镀铝,镀铝层厚度为50um,然后对镀铝层进行阳极氧化,在镀铝层上形成纳米级孔道后,清洗、干燥备用;
(2)将FeCl3、柠檬酸钠、乙酸钠、乙二醇混合,搅拌溶解,超声分散均匀,得到溶胶;所述FeCl3、柠檬酸钠、乙酸钠的质量比为2:1:4;所述乙二醇的体积用量以FeCl3的质量计为50mL/g;
(3)将步骤(2)的溶胶施加在步骤(1)制得的金属丝表面,并施加超声振动30min,促使溶胶渗透到纳米级孔道中,然后将其浸没于步骤(2)的溶胶中,加热至200°C反应10h后,冷却取出,置于1mol/L的NaOH溶液,所述浸泡的时间为60min,将表面的阳极氧化铝以及未氧化的铝层完全溶解,得到表面生长有Fe3O4纳米线阵列的金属丝;
(4)将表面生长有Fe3O4纳米线阵列的金属丝置于电子回旋等离子体溅射沉积腔室中,抽真空至1×10-4Pa时通入氩气,使气压保持在1×10-2Pa;施加线圈磁场并导入微波,在磁场和微波的耦合作用下产生氩等离子体,施加200V的靶材偏压,轰击碳靶,基底施加-100V的偏压,溅射沉积15min,在Fe3O4纳米线阵列表面沉积石墨烯纳晶。
其中,所述金属丝为不锈钢丝。
实施例3
一种石墨烯-Fe3O4固相微萃取探针,其制备方法如下:
(1)将金属丝清洗、干燥后,在金属丝表面热浸镀铝,镀铝层厚度为5um,然后对镀铝层进行阳极氧化,在镀铝层上形成纳米级孔道后,清洗、干燥备用;
(2)将FeCl3、柠檬酸钠、乙酸钠、乙二醇混合,搅拌溶解,超声分散均匀,得到溶胶;所述FeCl3、柠檬酸钠、乙酸钠的质量比为2:1:4;所述乙二醇的体积用量以FeCl3的质量计为30mL/g;
(3)将步骤(2)的溶胶施加在步骤(1)制得的金属丝表面,并施加超声振动10min,促使溶胶渗透到纳米级孔道中,然后将其浸没于步骤(2)的溶胶中,加热至200°C反应5h后,冷却取出,置于1mol/L的NaOH溶液,所述浸泡的时间为30min,将表面的阳极氧化铝以及未氧化的铝层完全溶解,得到表面生长有Fe3O4纳米线阵列的金属丝;
(4)将表面生长有Fe3O4纳米线阵列的金属丝置于电子回旋等离子体溅射沉积腔室中,抽真空至1×10-4Pa时通入氩气,使气压保持在1×10-2Pa;施加线圈磁场并导入微波,在磁场和微波的耦合作用下产生氩等离子体,施加200V的靶材偏压,轰击碳靶,基底施加-100V的偏压,溅射沉积20min,在Fe3O4纳米线阵列表面沉积石墨烯纳晶。
其中,所述金属丝为金属钛丝。
实施例4
一种石墨烯-Fe3O4固相微萃取探针,其制备方法如下:
(1)将金属丝清洗、干燥后,在金属丝表面热浸镀铝,镀铝层厚度为40um,然后对镀铝层进行阳极氧化,在镀铝层上形成纳米级孔道后,清洗、干燥备用;
(2)将FeCl3、柠檬酸钠、乙酸钠、乙二醇混合,搅拌溶解,超声分散均匀,得到溶胶;所述FeCl3、柠檬酸钠、乙酸钠的质量比为2:1:4;所述乙二醇的体积用量以FeCl3的质量计为45mL/g;
(3)将步骤(2)的溶胶施加在步骤(1)制得的金属丝表面,并施加超声振动25min,促使溶胶渗透到纳米级孔道中,然后将其浸没于步骤(2)的溶胶中,加热至200°C反应9h后,冷却取出,置于1mol/L的NaOH溶液,所述浸泡的时间为50min,将表面的阳极氧化铝以及未氧化的铝层完全溶解,得到表面生长有Fe3O4纳米线阵列的金属丝;
(4)将表面生长有Fe3O4纳米线阵列的金属丝置于电子回旋等离子体溅射沉积腔室中,抽真空至1×10-4Pa时通入氩气,使气压保持在1×10-2Pa;施加线圈磁场并导入微波,在磁场和微波的耦合作用下产生氩等离子体,施加200V的靶材偏压,轰击碳靶,基底施加-100V的偏压,溅射沉积20min,在Fe3O4纳米线阵列表面沉积石墨烯纳晶。
其中,所述金属丝为不锈钢丝。
实施例5
一种石墨烯-Fe3O4固相微萃取探针,其制备方法如下:
(1)将金属丝清洗、干燥后,在金属丝表面热浸镀铝,镀铝层厚度为15um,然后对镀铝层进行阳极氧化,在镀铝层上形成纳米级孔道后,清洗、干燥备用;
(2)将FeCl3、柠檬酸钠、乙酸钠、乙二醇混合,搅拌溶解,超声分散均匀,得到溶胶;所述FeCl3、柠檬酸钠、乙酸钠的质量比为2:1:4;所述乙二醇的体积用量以FeCl3的质量计为35mL/g;
(3)将步骤(2)的溶胶施加在步骤(1)制得的金属丝表面,并施加超声振动15min,促使溶胶渗透到纳米级孔道中,然后将其浸没于步骤(2)的溶胶中,加热至200°C反应8h后,冷却取出,置于1mol/L的NaOH溶液,所述浸泡的时间为45min,将表面的阳极氧化铝以及未氧化的铝层完全溶解,得到表面生长有Fe3O4纳米线阵列的金属丝;
(4)将表面生长有Fe3O4纳米线阵列的金属丝置于电子回旋等离子体溅射沉积腔室中,抽真空至1×10-4Pa时通入氩气,使气压保持在1×10-2Pa;施加线圈磁场并导入微波,在磁场和微波的耦合作用下产生氩等离子体,施加200V的靶材偏压,轰击碳靶,基底施加-100V的偏压,溅射沉积5min,在Fe3O4纳米线阵列表面沉积石墨烯纳晶。
其中所述金属丝为金属钛丝。
对比例
相较于实施例1,省略其中的Fe3O4纳米线阵列,直接在金属钛丝表面沉积石墨烯纳晶。
为了测试本发明的固相微萃取探针的萃取效率,分别将实施例1和对比例的探针萃取相同浓度的BPA,然后采用相同的实验条件测定电化学发光强度,结果如图1所示。结果表明,在探针中沉积磁性Fe3O4纳米线阵列中间层,电化学发光信号更强,表明其萃取的BPA更多,萃取效率更高。
Claims (2)
1.一种石墨烯-Fe3O4固相微萃取探针的制备方法,该探针的基体为金属丝,在金属丝表面依次沉积有Fe3O4纳米线阵列和石墨烯纳晶,其特征在于:包括如下步骤:
(1)将金属丝清洗、干燥后,在金属丝表面热浸镀铝,镀铝层厚度为5-50um,然后对镀铝层进行阳极氧化,在镀铝层上形成纳米级孔道后,清洗、干燥备用;
(2)将FeCl3、柠檬酸钠、乙酸钠、乙二醇混合,搅拌溶解,超声分散均匀,得到溶胶;所述FeCl3、柠檬酸钠、乙酸钠的质量比为2:1:4;所述乙二醇的体积用量以FeCl3的质量计为30~50mL/g;
(3)将步骤(2)的溶胶施加在步骤(1)制得的金属丝表面,并施加超声振动10-30min,促使溶胶渗透到纳米级孔道中,然后将其浸没于步骤(2)的溶胶中,加热至200°C反应5-10h后,冷却取出,置于1mol/L的NaOH溶液,浸泡的时间为30-60min,将表面的阳极氧化铝以及未氧化的铝层完全溶解,得到表面生长有Fe3O4纳米线阵列的金属丝;
(4)将表面生长有Fe3O4纳米线阵列的金属丝置于电子回旋等离子体溅射沉积腔室中,抽真空至1×10-4Pa时通入氩气,使气压保持在1×10-2Pa;施加线圈磁场并导入微波,在磁场和微波的耦合作用下产生氩等离子体,施加200V的靶材偏压,轰击碳靶,基底施加-100V的偏压,溅射沉积5-20min,在Fe3O4纳米线阵列表面沉积石墨烯纳晶;
金属丝选自钛丝或不锈钢丝,金属丝的直径为0.2-1mm。
2.如权利要求1所述的一种石墨烯-Fe3O4固相微萃取探针的制备方法制备得到的石墨烯-Fe3O4固相微萃取探针。
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