CN109540992A - 基于石墨烯化碳纤维基底的超灵敏葡萄糖传感器及其制备方法 - Google Patents
基于石墨烯化碳纤维基底的超灵敏葡萄糖传感器及其制备方法 Download PDFInfo
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Abstract
本发明属于材料制备技术领域，具体涉及一种基于石墨烯化碳纤维基底的超灵敏葡萄糖传感器及其制备方法。所述方法包括选取表面生长了直立石墨烯的碳布经过预处理使其亲水后，直接置于葡萄糖氧化酶的pH＝7.4的PBS溶液中浸泡，然后取出后室温干燥得到葡萄糖传感器。本发明将葡萄糖检测下限推到了0.1mM左右，其还具有多段相应的特性，能够在不同的葡萄糖浓度范围实现不同检测系数和能力，大大提高了其使用范围和精度。
Description
技术领域
本发明属于材料制备技术领域，具体涉及一种基于石墨烯化碳纤维基底的超灵敏葡萄糖传感器及其制备方法。
背景技术
目前，碳纤维布由于其柔性及良好的化学稳定性被大量用作柔性传感器基底材料。市面上以碳布作为基底的电化学传感器数不胜数。葡萄糖电化学传感器由于其巨大的市场需求和温和的检测条件等有利因素，已经实现了较大规模的商业化生产。然而市场上的葡萄糖电化学传感器质量良莠不齐，灵敏度很低，大大限制了其在超低浓度高端生化检测中的应用。
特别是随着柔性电子、可穿戴和大健康几大新兴产业的兴起，对超低浓度超高灵敏度传感器的需求越来越大要求越来越高，现有产品明显不能满足市场的性能要求和检测能力。所以本发明从超灵敏检测出发，通过制备表面垂直功能化石墨烯的碳布成功制备了具有超灵敏检测能力的葡萄糖电化学检测器。
例如，现有技术CN106970128A公开了一种柔性ZnO纳米晶复合碳纤维及氧化石墨烯葡萄糖探测器及其制备方法，该传感器自下而上依次有碳纤维、氧化石墨烯、ZnO纳米晶层。其制备方法如下：先制备碳纤维复合氧化石墨烯做基底，然后在其上在一定温度下生长ZnO纳米晶自组装成柔性ZnO纳米晶复合碳纤维及氧化石墨烯葡萄糖探测器。其检测下限大概是在5mM左右，检测灵敏度还待进一步提高。
发明内容
鉴于现有技术存在的问题，本发明制备的石墨烯化碳纤维基底的超灵敏葡萄糖电化学传感器具有超低的检测浓度和超高的灵敏度，能够满足新兴的可穿戴电子体表数据采集的严苛要求和检测能力。
本发明将葡萄糖检测下限推到了0.1mM左右，其还具有多段相应的特性，能够在不用的葡萄糖浓度范围实现不同检测系数和能力，大大提高了其的使用范围和精度。
具体地，本发明通过以下技术方案来实现：
基于石墨烯化碳纤维基底的超灵敏葡萄糖传感器的制备方法，包括以下步骤：
(1)、选取石墨烯碳布(GR/CC)和预处理：
选取石墨烯碳布，将其依次置于异丙醇、H2SO4溶液及去离子水中浸泡，使其具有亲水性能；
(2)、溶液浸泡：
将预处理后的石墨烯碳布置于葡萄糖氧化酶(GOD)溶液中浸泡，取出干燥以得到葡萄糖传感器(GOD/GR/CC)。
作为本发明的一种优选技术方案，所述石墨烯碳布为生长了直立石墨烯的碳布(GR/CC)，采用热CVD的方法制备，具体为在1100摄氏度，95％的CH4和5％H2气氛条件下，进行石墨烯的气相沉积10小时。
通过大量的实验研究发现，采用前述方案表面垂直生长的石墨烯的碳布附着力强，附着葡萄糖氧化酶后，电化学检测能力优异。
作为本发明的一种优选技术方案，所示步骤(1)优选为选取石墨烯碳布将其依次置于异丙醇，0.1M的H2SO4溶液及去离子水中分别浸泡30min，使其具有亲水性能。该方法效果好，后处理简单。其中，亲水性能正式的测定可以通过测试表面接触角，工艺摸索阶段可以简单比较水对处理前后碳布的润湿润展能力，选取工艺操作窗口。
作为本发明的一种优选技术方案，所示步骤(2)优选为将预处理后的石墨烯碳布置于葡萄糖氧化酶(GOD)溶液中于4℃环境下浸泡72h，并且间断的摇晃，最后取出室温干燥以得到葡萄糖传感器(GOD/GR/CC)。
通过大量的实验研究发现，采用温度4摄氏度环境下浸泡，可保证酶不失活。浸泡时间72为小时，保证吸附充分和牢固。
作为本发明的一种优选技术方案，摇床的摇晃频率为0.5Hz。采用此摇晃条件进行间断的摇晃，增加体系扩散能力，避免出现局部区域浓度不均匀。
本发明的另一目的在于提供一种基于石墨烯化碳纤维基底的超灵敏葡萄糖传感器，所述超灵敏葡萄糖传感器通过前述制备方法制备得到。
本发明相对于现有技术的有益效果包括：
(1)本发明使用了表面生长了直立石墨烯的碳布，通过简单的物理吸附制备了葡萄糖传感器，其制备方法简单，在检测较低的葡萄糖浓度时具有巨大的应用前景。
(2)在本发明的前期研究中发现，如果碳布未通过前述制备方法在表面生长了直立石墨烯，则较难有葡萄糖氧化酶吸附，无法应用于葡萄糖的检测。
(3)本发明葡萄糖传感器用于检测葡萄糖，发现这种期在超低浓度葡萄糖下显示出优异的检测性能，具有极低的检测灵敏度和多段相应的性能，有望在柔性电子生物医学检测领域得到广泛的应用。
附图说明
图1，本发明葡萄糖传感器制备材料组成流程示意图；
图2，本发明制备得到的石墨烯碳布的SEM图片，图2a)为碳布在低分辨下的SEM，图2b)为碳布在高分辨下的SEM，图2c)为表面垂直生长了石墨烯的碳布在高分辨下的SEM；
图3，本发明葡萄糖传感器制备工艺流程示意图；
图4，利用微分脉冲伏安法(DPV)测得的实验数据图，图4a)GOD/GR/CC在0.1M pH＝7.4PBS溶液中的DPV曲线，由下到上各曲线分别为0mM至20mM下测定结果；图4b)对应的峰值电流与葡萄糖浓度的散点图。DPV参数:增加电位5mV，振幅25mV，脉冲宽度0.2s，脉冲周期0.5s。
图5为利用循环脉冲伏安法(CV)测得的实验数据图，图5a)GOD/GR/CC在0.1M pH＝7.4PBS溶液中的CV曲线，由下到上各曲线分别为0mM至20mM下测定结果；图5b)对应的峰值电流与葡萄糖浓度的散点图。CV参数:扫速为200mV.S-1。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述，但发明的实施方式不限于此。
实施例1基于石墨烯化碳纤维基底的超灵敏葡萄糖传感器及其制备方法
参照如图1和图3所示的本发明葡萄糖传感器的制备示意图：
(1)、选取石墨烯碳布和预处理：
选取1×3cm的石墨烯碳布将其依次置于异丙醇，0.1M的H2SO4溶液及去离子水中浸泡30min，使其具有亲水性能；
其中，所述石墨烯碳布为生长了直立石墨烯的碳布(GR/CC)，其采用热CVD的方法制备，具体为在1100摄氏度，95％的CH4和5％H2气氛条件下，进行石墨烯的气相沉积10h。石墨烯碳布的SEM图片如图2所示，其中图2a)为碳布在低分辨下的SEM，图2b)为碳布在高分辨下的SEM，图2c)为表面垂直生长了石墨烯的碳布在高分辨下的SEM。
(2)、溶液浸泡：
将预处理后的石墨烯碳布置于葡萄糖氧化酶(GOD)溶液中(溶液为0.1M pH＝7.4的PBS溶液)于4℃环境下浸泡72h，并且间断的摇晃，摇床的摇晃频率为0.5Hz，最后取出室温干燥以得到葡萄糖传感器(GOD/GR/CC)。
实施例2性能检测
将实施例1制备得到的葡萄糖传感器置于电解质为0.1M pH＝7.4的PBS溶液，工作电极为GOD/GR/CC，对电极为Pt片，参比电极为饱和甘汞电极的三电极体系中进行测量葡萄糖浓度。
图4为利用微分脉冲伏安法(DPV)测得的实验数据图，可见在低浓度下葡萄糖传感器的灵敏度较高，GOD/GR/CC为1.7μA mM-1cm-2(0～1mM)。本发明的传感器检测下限可以到达0.1mM，大大提高了葡萄糖的检测下限。
图5为利用循环脉冲伏安法(CV)测得的实验数据图，可见在低浓度下葡萄糖传感器的灵敏度较高，GOD/GR/CC为14.3μA mM-1cm-2(0～1mM)。本发明的传感器检测下限可以到达0.1mM，大大提高了葡萄糖的检测下限。
前述结果充分说明，本发明的传感器还实现了多段性能相应，在超低浓度段具有超大的线性相应系数来实现精确的浓度检测，在中等葡萄糖浓度范围具有较为合适的线性相应系数来实现较大的检测范围。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (6)
1.基于石墨烯化碳纤维基底的超灵敏葡萄糖传感器的制备方法，其特征在于，包括以下步骤：
(1)、选取石墨烯碳布和预处理：
选取石墨烯碳布，将其依次置于异丙醇、H2SO4溶液及去离子水中浸泡，使其具有亲水性能；
(2)、溶液浸泡：
将预处理后的石墨烯碳布置于葡萄糖氧化酶(GOD)溶液中浸泡，取出干燥以得到葡萄糖传感器(GOD/GR/CC)。
2.根据权利要求1所述的制备方法，其特征在于，所述石墨烯碳布为生长了直立石墨烯的碳布(GR/CC)，其采用热CVD的方法制备，具体为在1100摄氏度，95％的CH4和5％H2气氛条件下，进行石墨烯的气相沉积10h。
3.根据权利要求1所述的制备方法，其特征在于，所示步骤(1)为选取石墨烯碳布将其依次置于异丙醇，0.1M的H2SO4溶液及去离子水中分别浸泡30min，使其具有亲水性能。
4.根据权利要求1所述的制备方法，其特征在于，所示步骤(2)为将预处理后的石墨烯碳布置于葡萄糖氧化酶(GOD)溶液中于4℃环境下浸泡72h，并且间断的摇晃，最后取出室温干燥以得到葡萄糖传感器(GOD/GR/CC)。
5.根据权利要求1所述的制备方法，其特征在于，摇床的摇晃频率为0.5Hz。
6.一种基于石墨烯化碳纤维基底的超灵敏葡萄糖传感器，所述超灵敏葡萄糖传感器通过前述权利要求1-5任一权利要求所述的制备方法制备得到。
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