CN110629203B - 一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法及其检测葡萄糖的应用 - Google Patents
一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法及其检测葡萄糖的应用 Download PDFInfo
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Abstract
一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法及其检测葡萄糖的应用,它涉及一种多孔掺硼金刚石复合电极的制备方法及应用。本发明要解决现有不存在制备多孔掺硼金刚石复合电极的方法,现有利用掺硼金刚石电极非酶葡萄糖传感器检测葡萄糖灵敏度较低的问题。制备方法:一、掺硼金刚石薄膜的制备;二、溅射镀膜及退火处理。应用:用于检测葡萄糖。本发明用于具有双金属协同效应的多孔掺硼金刚石复合电极的制备及其检测葡萄糖的应用。
Description
技术领域
本发明涉及一种多孔掺硼金刚石复合电极的制备方法及应用。
背景技术
葡萄糖在生物学领域具有重要地位,是活细胞的能量来源和新陈代谢中间产物,即生物的主要供能物质。人体的多种疾病与体内的葡萄糖含量有关,比如糖尿病。除此之外,葡萄糖在糖果制造等领域也有着广泛的应用。因此对葡萄糖含量的测定在生物医药、食品加工等领域都具有重要的意义。目前葡萄糖探测器主要是基于葡萄糖氧化酶的葡萄糖生物传感器来检测葡萄糖。然而,这种传感器价格昂贵,对环境温度、湿度敏感,缺乏长期稳定性。
相比而言,掺硼金刚石材料作为非酶葡萄糖传感器具有价格低廉、稳定性好等优点。除此之外,掺硼金刚石材料具有良好的耐磨性、化学稳定性、生物相容性和一些优异的电化学性能,如较低的背景电流、较宽的电势窗口、表面耐酸碱特性等。因此利用掺硼金刚石电极非酶葡萄糖传感器检测葡萄糖具有巨大的应用潜力。然而掺硼金刚石电极材料的电化学检测灵敏度较低,一般要求葡萄糖浓度不低于0.25mmol/L,为了提供更精确的葡萄糖浓度检测,需要提高掺硼金刚石表面灵敏度。
发明内容
本发明要解决现有不存在制备多孔掺硼金刚石复合电极的方法,现有利用掺硼金刚石电极非酶葡萄糖传感器检测葡萄糖灵敏度较低的问题,而提供一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法及其检测葡萄糖的应用。
一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,它是按以下步骤进行的:
一、掺硼金刚石薄膜的制备:
将硅片置于旋涂仪中,在转速为500转/秒~2000转/秒的条件下,滴入质量百分数为2%~15%的纳米金刚石悬浊液,旋涂3次~6次,晾干,得到旋涂有纳米金刚石的硅片,将旋涂有纳米金刚石的硅片和石墨片并列放置于微波等离子化学气相沉积装置的样品台上,通入氢气及乙硼烷气体,在氢气流速为100sccm~500sccm、乙硼烷气体流速为1sccm~20sccm、旋涂有纳米金刚石的硅片温度为550℃~1000℃、石墨片温度为650℃~1100℃、压强为100mbar~300mbar及微波功率为1800W~4500W的条件下,沉积60min~30h,得到表面沉积有掺硼金刚石薄膜的衬底;
二、溅射镀膜及退火处理:
将表面沉积有掺硼金刚石薄膜的衬底置于多靶磁控溅射设备中,在镍靶的溅射功率为100W~200W及金靶的溅射功率为40W~80W的条件下,溅射2min~20min,在掺硼金刚石薄膜上共沉积厚度为0.02μm~0.1μm的金/镍双金属混合薄膜,然后置于到管式炉中,加热至温度为800℃~1000℃,在氩气气氛及温度为800℃~1000℃的条件下,保温1h~3h,然后冷却至室温,即完成具有双金属协同效应的多孔掺硼金刚石复合电极的制备。
具有双金属协同效应的多孔掺硼金刚石复合电极用于检测葡萄糖,检测葡萄糖浓度检测限为0.0026mmol/L。
本发明的有益效果是:
本发明通过表面修饰双金属金和镍,并通过退火得到具有双金属协同效应的多孔掺硼金刚石复合电极。经过退火后,两种金属由薄膜形态变为了纳米团聚体的形态,这主要是因为高温导致金属融化,之后随着温度的降低融化的金属逐渐凝固形成颗粒状团聚。同时由于镍对掺硼金刚石具有刻蚀作用,在高温环境下复合电极表面由金属团聚和刻蚀的作用呈现出多孔结构。
利用双金属协同作用,其原理在于金对葡萄糖良好的氧化性能和生物相容性以及镍对葡萄糖的良好的催化性能,来提高掺硼金刚石对葡萄糖检测的灵敏度。其次得到的多孔掺硼金刚石与平整的掺硼金刚石比较,具有更大的表面积,也就是说多孔掺硼金刚石可以与葡萄糖溶液更充分的接触,同样有助于对葡萄糖的检测。
本发明由金、镍双金属修饰的掺硼金刚石薄膜组成的多孔复合电极传感器,用于检测葡萄糖浓度。该探测器在葡萄糖浓度为0.02mmol/L~9mmol/L范围内与响应电流展现出良好的线性关系,检测限可达到0.0026mmol/L。具有双金属协同效应的多孔掺硼金刚石复合电极对葡萄糖有更强的氧化还原性,并且电极利用循环伏安法循环30圈后,电流下降小于10μA,具有较高的稳定性。
本发明用于一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法及其检测葡萄糖的应用。
附图说明
图1为实施例一步骤一得到的衬底表面沉积的掺硼金刚石薄膜的表面形貌图;
图2为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极放大20000倍的表面形貌图;
图3为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极放大160000倍的表面形貌图,1为裸露的掺硼金刚石,2为金/镍双金属层;
图4为拉曼光谱对比图,a为实施例一步骤一得到的衬底表面沉积的掺硼金刚石薄膜,b为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极;
图5为XRD对比图;a为实施例一步骤一得到的衬底表面沉积的掺硼金刚石薄膜,b为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极;
图6为循环伏安曲线对比图;a为实施例一步骤一得到的纯掺硼金刚石薄膜电极,b为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极;
图7为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极30圈循环伏安曲线图;
图8为图7中A区的放大图;
图9为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极安培响应曲线;
图10为图9中B区的放大图;
图11为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极对葡萄糖浓度检测曲线。
具体实施方式
具体实施方式一:本实施方式一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,它是按以下步骤进行的:
一、掺硼金刚石薄膜的制备:
将硅片置于旋涂仪中,在转速为500转/秒~2000转/秒的条件下,滴入质量百分数为2%~15%的纳米金刚石悬浊液,旋涂3次~6次,晾干,得到旋涂有纳米金刚石的硅片,将旋涂有纳米金刚石的硅片和石墨片并列放置于微波等离子化学气相沉积装置的样品台上,通入氢气及乙硼烷气体,在氢气流速为100sccm~500sccm、乙硼烷气体流速为1sccm~20sccm、旋涂有纳米金刚石的硅片温度为550℃~1000℃、石墨片温度为650℃~1100℃、压强为100mbar~300mbar及微波功率为1800W~4500W的条件下,沉积60min~30h,得到表面沉积有掺硼金刚石薄膜的衬底;
二、溅射镀膜及退火处理:
将表面沉积有掺硼金刚石薄膜的衬底置于多靶磁控溅射设备中,在镍靶的溅射功率为100W~200W及金靶的溅射功率为40W~80W的条件下,溅射2min~20min,在掺硼金刚石薄膜上共沉积厚度为0.02μm~0.1μm的金/镍双金属混合薄膜,然后置于到管式炉中,加热至温度为800℃~1000℃,在氩气气氛及温度为800℃~1000℃的条件下,保温1h~3h,然后冷却至室温,即完成具有双金属协同效应的多孔掺硼金刚石复合电极的制备。
本具体实施方式鉴于金和镍的沉积速度不同,在设备中金的沉积速度比镍的沉积速度快一些,所以可以通过控制镍靶和金靶的溅射功率来调节镍与金的沉积量。
本实施方式所述的表面沉积有掺硼金刚石薄膜的衬底也可以是以甲烷为碳源,以乙硼烷或硼酸三甲酯为硼源,利用化学气相沉积法制备而成。
本实施方式的有益效果是:
本实施方式通过表面修饰双金属金和镍,并通过退火得到具有双金属协同效应的多孔掺硼金刚石复合电极。经过退火后,两种金属由薄膜形态变为了纳米团聚体的形态,这主要是因为高温导致金属融化,之后随着温度的降低融化的金属逐渐凝固形成颗粒状团聚。同时由于镍对掺硼金刚石具有刻蚀作用,在高温环境下复合电极表面由金属团聚和刻蚀的作用呈现出多孔结构。
利用双金属协同作用,其原理在于金对葡萄糖良好的氧化性能和生物相容性以及镍对葡萄糖的良好的催化性能,来提高掺硼金刚石对葡萄糖检测的灵敏度。其次得到的多孔掺硼金刚石与平整的掺硼金刚石比较,具有更大的表面积,也就是说多孔掺硼金刚石可以与葡萄糖溶液更充分的接触,同样有助于对葡萄糖的检测。
本实施方式由金、镍双金属修饰的掺硼金刚石薄膜组成的多孔复合电极传感器,用于检测葡萄糖浓度。该探测器在葡萄糖浓度为0.02mmol/L~9mmol/L范围内与响应电流展现出良好的线性关系,检测限可达到0.0026mmol/L。具有双金属协同效应的多孔掺硼金刚石复合电极对葡萄糖有更强的氧化还原性,并且电极利用循环伏安法循环30圈后,电流下降小于10μA,具有较高的稳定性。
具体实施方式二:本实施方式与具体实施方式一不同的是:步骤一中所述的石墨片纯度为99.9%。其它与具体实施方式一相同。
具体实施方式三:本实施方式与具体实施方式一或二不同的是:步骤一中所述的石墨片为边长为20mm~60mm及厚度为2mm~5mm的方片。其它与具体实施方式一或二相同。
具体实施方式四:本实施方式与具体实施方式一至三之一不同的是:步骤一中将硅片置于旋涂仪中,在转速为1000转/秒~2000转/秒的条件下,滴入质量百分数为2%~10%的纳米金刚石悬浊液,旋涂3次~6次,晾干,得到旋涂有纳米金刚石的硅片。其它与具体实施方式一至三相同。
具体实施方式五:本实施方式与具体实施方式一至四之一不同的是:步骤一中通入氢气及乙硼烷气体,在氢气流速为200sccm~500sccm、乙硼烷气体流速为2sccm~20sccm、旋涂有纳米金刚石的硅片温度为600℃~1000℃、石墨片温度为700℃~1100℃、压强为200mbar~300mbar及微波功率为2000W~4500W的条件下,沉积60min~30h。其它与具体实施方式一至四相同。
具体实施方式六:本实施方式与具体实施方式一至五之一不同的是:步骤二中将表面沉积有掺硼金刚石薄膜的衬底置于多靶磁控溅射设备中,在镍靶的溅射功率为150W~200W及金靶的溅射功率为50W~80W的条件下,溅射10min~20min,在掺硼金刚石薄膜上共沉积厚度为0.02μm~0.1μm的金/镍双金属混合薄膜。其它与具体实施方式一至五相同。
具体实施方式七:本实施方式与具体实施方式一至六之一不同的是:步骤二中将表面沉积有掺硼金刚石薄膜的衬底置于多靶磁控溅射设备中,在镍靶的溅射功率为100W~150W及金靶的溅射功率为40W~50W的条件下,溅射2min~10min,在掺硼金刚石薄膜上共沉积厚度为0.02μm~0.1μm的金/镍双金属混合薄膜。其它与具体实施方式一至六相同。
具体实施方式八:本实施方式与具体实施方式一至七之一不同的是:步骤二中然后置于到管式炉中,加热至温度为800℃~900℃,在氩气气氛及温度为800℃~900℃的条件下,保温1h~2h。其它与具体实施方式一至七相同。
具体实施方式九:本实施方式与具体实施方式一至八之一不同的是:步骤二中然后置于到管式炉中,加热至温度为900℃~1000℃,在氩气气氛及温度为900℃~1000℃的条件下,保温2h~3h。其它与具体实施方式一至八相同。
具体实施方式八:本实施方式制备的具有双金属协同效应的多孔掺硼金刚石复合电极用于检测葡萄糖,检测葡萄糖浓度检测限为0.0026mmol/L。
采用以下实施例验证本发明的有益效果:
实施例一:
一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,它是按以下步骤进行的:
一、掺硼金刚石薄膜的制备:
将硅片置于旋涂仪中,在转速为1500转/秒的条件下,滴入质量百分数为2%的纳米金刚石悬浊液,旋涂3次,晾干,得到旋涂有纳米金刚石的硅片,将旋涂有纳米金刚石的硅片和石墨片并列放置于微波等离子化学气相沉积装置的样品台上,通入氢气及乙硼烷气体,在氢气流速为200sccm、乙硼烷气体流速为2sccm、旋涂有纳米金刚石的硅片温度为950℃、石墨片温度为1100℃、压强为165mbar及微波功率为3000W的条件下,沉积8h,得到表面沉积有掺硼金刚石薄膜的衬底;
二、溅射镀膜及退火处理:
将表面沉积有掺硼金刚石薄膜的衬底置于多靶磁控溅射设备中,在镍靶的溅射功率为100W及金靶的溅射功率为40W的条件下,溅射2min,在掺硼金刚石薄膜上共沉积厚度为0.04μm的金/镍双金属混合薄膜,然后置于到管式炉中,加热至温度为900℃,在氩气气氛及温度为900℃的条件下,保温2h,然后冷却至室温,得到具有双金属协同效应的多孔掺硼金刚石复合电极,即完成具有双金属协同效应的多孔掺硼金刚石复合电极的制备;
步骤一中所述的石墨片纯度为99.9%。
步骤一中所述的石墨片为边长为40mm及厚度为2mm的方片。
步骤二制备的具有双金属协同效应的多孔掺硼金刚石复合电极即为具有多孔结构的金/镍/掺硼金刚石复合电极。
步骤一制备的表面沉积有掺硼金刚石薄膜的衬底即为纯掺硼金刚石薄膜电极。
图1为实施例一步骤一得到的衬底表面沉积的掺硼金刚石薄膜的表面形貌图;图2为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极放大20000倍的表面形貌图;图3为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极放大160000倍的表面形貌图,1为裸露的掺硼金刚石,2为金/镍双金属层;由图2可知,镀镍和金并退火之后,在掺硼金刚石表面形成了多孔的金/镍双金属纳米团聚层。由图3可知,双金属层是由多个纳米颗粒团聚组合而成,下方裸露出掺硼金刚石薄膜。
图4为拉曼光谱对比图,a为实施例一步骤一得到的衬底表面沉积的掺硼金刚石薄膜,b为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极;由图可知,对比纯掺硼金刚石薄膜和金/镍/掺硼金刚石复合电极的拉曼图,二者都具有金刚石的拉曼峰(1331.6cm-1)以及由硼掺入引起的振动峰(473.5,690.1,1201.6cm-1)。金/镍/掺硼金刚石还有明显的石墨峰(1582.2cm-1),这也是导致金/镍/掺硼金刚石电化学性能提升的原因之一。
图5为XRD对比图;a为实施例一步骤一得到的衬底表面沉积的掺硼金刚石薄膜,b为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极;图中Graphite为石墨,BDD为掺硼金刚石;由图可知,金、镍金属成功的镀在掺硼金刚石的表面,且没有阻碍掺硼金刚石的XRD信号。
图6为循环伏安曲线对比图;a为实施例一步骤一得到的纯掺硼金刚石薄膜电极,b为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极;由图可知,在1mol/L磷酸缓冲盐溶液及0.1V/s扫描速度下,与纯掺硼金刚石相比,金/镍/掺硼金刚石电极具有更明显的氧化还原电流强度,氧化电流和还原电流均为100μA左右。
图7为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极30圈循环伏安曲线图;图8为图7中A区的放大图;由图可知,金/镍/掺硼金刚石电极较稳定,利用循环伏安法循环30圈后,电流下降小于10μA,具有较高的稳定性。
采用安培电流响应测试,利用实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极对浓度分别为20μmol/L、40μmol/L、60μmol/L、80μmol/L、100μmol/L、400μmol/L、1mmol/L、2mmol/L、5mmol/L及9mmol/L的葡萄糖溶液进行检测,得出不同的电流响应强度,如图9所示,随着葡萄糖浓度的增加,电流强度也逐渐增加,且响应速度较快,响应时间约为2s~5s,葡萄糖浓度与响应电流之间呈正相关线性关系,如图11。图9为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极安培响应曲线;图10为图9中B区的放大图;图11为实施例一制备的具有双金属协同效应的多孔掺硼金刚石复合电极对葡萄糖浓度检测曲线;由图可知,采用安培响应测试发现,金/镍/掺硼金刚石探测器在葡萄糖浓度0.02mmol/L~9mmol/L范围内与响应电流展现出良好的线性关系,检测限可达到0.0026mmol/L。
Claims (10)
1.一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,其特征在于它是按以下步骤进行的:
一、掺硼金刚石薄膜的制备:
将硅片置于旋涂仪中,在转速为500转/秒~2000转/秒的条件下,滴入质量百分数为2%~15%的纳米金刚石悬浊液,旋涂3次~6次,晾干,得到旋涂有纳米金刚石的硅片,将旋涂有纳米金刚石的硅片和石墨片并列放置于微波等离子化学气相沉积装置的样品台上,通入氢气及乙硼烷气体,在氢气流速为100sccm~500sccm、乙硼烷气体流速为1sccm~20sccm、旋涂有纳米金刚石的硅片温度为550℃~1000℃、石墨片温度为650℃~1100℃、压强为100mbar~300mbar及微波功率为1800W~4500W的条件下,沉积60min~30h,得到表面沉积有掺硼金刚石薄膜的衬底;
二、溅射镀膜及退火处理:
将表面沉积有掺硼金刚石薄膜的衬底置于多靶磁控溅射设备中,在镍靶的溅射功率为100W~200W及金靶的溅射功率为40W~80W的条件下,溅射2min~20min,在掺硼金刚石薄膜上共沉积厚度为0.02μm~0.1μm的金/镍双金属混合薄膜,然后置于到管式炉中,加热至温度为800℃~1000℃,在氩气气氛及温度为800℃~1000℃的条件下,保温1h~3h,然后冷却至室温,即完成具有双金属协同效应的多孔掺硼金刚石复合电极的制备。
2.根据权利要求1所述的一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,其特征在于步骤一中所述的石墨片纯度为99.9%。
3.根据权利要求1所述的一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,其特征在于步骤一中所述的石墨片为边长为20mm~60mm及厚度为2mm~5mm的方片。
4.根据权利要求1所述的一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,其特征在于步骤一中将硅片置于旋涂仪中,在转速为1000转/秒~2000转/秒的条件下,滴入质量百分数为2%~10%的纳米金刚石悬浊液,旋涂3次~6次,晾干,得到旋涂有纳米金刚石的硅片。
5.根据权利要求1所述的一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,其特征在于步骤一中通入氢气及乙硼烷气体,在氢气流速为200sccm~500sccm、乙硼烷气体流速为2sccm~20sccm、旋涂有纳米金刚石的硅片温度为600℃~1000℃、石墨片温度为700℃~1100℃、压强为200mbar~300mbar及微波功率为2000W~4500W的条件下,沉积60min~30h。
6.根据权利要求1所述的一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,其特征在于步骤二中将表面沉积有掺硼金刚石薄膜的衬底置于多靶磁控溅射设备中,在镍靶的溅射功率为150W~200W及金靶的溅射功率为50W~80W的条件下,溅射10min~20min,在掺硼金刚石薄膜上共沉积厚度为0.02μm~0.1μm的金/镍双金属混合薄膜。
7.根据权利要求1所述的一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,其特征在于步骤二中将表面沉积有掺硼金刚石薄膜的衬底置于多靶磁控溅射设备中,在镍靶的溅射功率为100W~150W及金靶的溅射功率为40W~50W的条件下,溅射2min~10min,在掺硼金刚石薄膜上共沉积厚度为0.02μm~0.1μm的金/镍双金属混合薄膜。
8.根据权利要求1所述的一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,其特征在于步骤二中然后置于到管式炉中,加热至温度为800℃~900℃,在氩气气氛及温度为800℃~900℃的条件下,保温1h~2h。
9.根据权利要求1所述的一种具有双金属协同效应的多孔掺硼金刚石复合电极的制备方法,其特征在于步骤二中然后置于到管式炉中,加热至温度为900℃~1000℃,在氩气气氛及温度为900℃~1000℃的条件下,保温2h~3h。
10.如权利要求1制备的具有双金属协同效应的多孔掺硼金刚石复合电极检测葡萄糖的应用,其特征在于具有双金属协同效应的多孔掺硼金刚石复合电极检测葡萄糖浓度检测限为0.0026mmol/L。
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