CN107117599A - 一种氯杂石墨烯的制备方法 - Google Patents
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Abstract
本发明涉及一种氯杂石墨烯的制备方法，包括：将氧化石墨烯超声均匀分散于盐酸中，氮气保护下于80‑180℃回流反应2‑12h；冷却至室温后进行离心分离，洗涤、干燥，即得氯杂石墨烯。本发明合成过程绿色环保、操作简单快速、可宏量制备氯杂石墨烯，基于制备的氯杂石墨烯所构筑的氯霉素电化学传感器具有灵敏度高、稳定性好、可重复使用的特点，在电化学传感器中具有潜在的应用前景。
Description
技术领域
本发明属于催化剂材料领域，特别涉及一种氯杂石墨烯的制备方法。
背景技术
石墨烯良好的导电性使其成为重要的电催化剂材料，在电化学传感器中得到了广泛应用。目前普遍的制备方法是将石墨粉先氧化再还原进行剥离制备石墨烯，在还原时通过选择合适的还原剂则可制备杂化石墨烯，如选用水合肼还原则可制备氮杂石墨烯等。以碘化氢或溴化氢作还原剂来制备石墨烯是一种有效的方法(Pei S.and Cheng H.-M.,Carbon,2012,50,3210),但这些还原剂毒性太强，大大限制了其应用。因此开发绿色环保的石墨烯制备过程仍然具有挑战性和具有重要应用价值。
氯霉素是一类广谱抗生素药物，滥用会导致再生障碍性贫血、白血病和灰婴综合症等疾病，因此近年来开发氯霉素的检测方法备受人们关注。
发明内容
本发明所要解决的技术问题是提供一种氯杂石墨烯的制备方法，该方法合成过程绿色环保、操作简单快速、可宏量制备氯杂石墨烯，基于制备的氯杂石墨烯所构筑的氯霉素电化学传感器具有灵敏度高、稳定性好、可重复使用的特点，在电化学传感器中具有潜在的应用前景。
本发明提供了一种氯杂石墨烯的制备方法，包括：
将氧化石墨烯按质量体积比10-30mg:20-40mL超声均匀分散于盐酸中，氮气保护下于80-180℃回流反应2-12h；冷却至室温后进行离心分离，洗涤、干燥，即得氯杂石墨烯；其中，氯杂石墨烯中氯含量为1-3％。
所述氧化石墨烯的制备方法包括：将石墨粉与浓硝酸和浓硫酸在冰水浴中混合，搅拌下加入高锰酸钾，逐步升温至45℃和90℃各反应1小时，冷却，静置过夜；将所得沉淀洗涤、干燥即得氧化石墨烯。
所述石墨粉、高锰酸钾、浓硫酸和浓硝酸的比例为0.5-1g:2-5g:15-30mL:1.5-3mL。
所述盐酸的浓度为2-12M。
所述得到的氯杂石墨烯用于制备电化学传感器检测氯霉素。
所述电化学传感器的制备方法包括：将氯杂石墨烯超声分散在乙醇中得到浓度为1-2mg/mL的催化剂分散液，移取10-20μL转移至玻碳电极活性表面，经红外灯干燥即得电化学传感器。
所述电化学传感器检测氯霉素的方法包括：电化学传感器为工作电极，饱和甘汞电极为参比电极，铂丝为辅助电极，测试底液为磷酸盐缓冲液；采用示差脉冲伏安分析法，通过对氯霉素标准溶液进行测试，以氯霉素浓度为横坐标，电流强度为纵坐标，建立标准工作曲线，通过电流强度的数值计算样品中氯霉素的浓度。
所述磷酸盐缓冲液pH＝7.4，浓度为5-10mM。
测试电压范围为-0.4V至-0.7V。
所述电化学传感器的工作浓度范围为1-46μM，检测下限为0.5μM，可直接保存于室温空气中一个月后电化学传感性能并无明显衰退。
本发明开发了一种通过浓盐酸回流快速制备氯杂石墨烯的绿色环保方法，并将所得氯杂石墨烯材料应用于构筑氯霉素电化学传感器。该方法中采用的还原剂和制备过程绿色环保、时间短、效率高、能宏量生产、不需要使用任何有机还原剂而减少了二次污染；开发的氯霉素电化学传感器具有灵敏度高、检测线性范围宽、稳定性好并可长期重复使用等特点，在电化学传感器开发中具有潜在应用前景。
有益效果
(1)本发明采用操作简便可控的盐酸作为氧化石墨烯的绿色环保还原剂，快速还原的同时掺杂了氯元素，合成过程绿色环保、操作简单快速、可宏量制备；
(2)本发明采用氯杂石墨烯修饰电极，提高了电极的活性面积和检测灵敏度；
(3)本发明基于氯杂石墨烯构筑的电化学传感器测定氯霉素，具有灵敏度高、线性范围宽、稳定性好和可重复使用的特点，在电化学传感器中具有潜在的应用前景。
附图说明
图1为氯杂石墨烯的光电子能谱(XPS)图；
图2为氯杂石墨烯的透射电镜(TEM)图；
图3为不同电极对氯霉素响应的示差脉冲伏安曲线；
图4为基于氯杂石墨烯材料制备的电化学传感器对不同浓度氯霉素响应的示差脉冲伏安曲线(a)以及相应电流强度与氯霉素浓度之间的线性关系(b)。
图5为基于氯杂石墨烯材料制备的电化学传感器暴露于空气中保存一个月的稳定性。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
氧化石墨烯的制备。
将1g石墨粉与市售浓硝酸(3mL)和浓硫酸(30mL)在冰水浴中混合，搅拌下加入5g高锰酸钾，升温至45℃反应1小时，再升温至90℃反应1小时，冷却至室温，静置过夜；将所得沉淀使用蒸馏水洗涤3次、乙醇洗涤1次后于40℃干燥24小时，即得氧化石墨烯固体。
实施例2
氯杂石墨烯(Cl-RGO)的制备。
称取实施例1中所制备的氧化石墨烯10mg并超声30分钟均匀分散于20mL浓度为6M的盐酸中，将其转移至50-100mL圆底烧瓶中，氮气保护下在100℃回流6h还原氧化石墨烯；冷却至室温后转移至离心管进行离心分离，所得固体用蒸馏水洗涤3次、乙醇洗涤1次后置于40℃烘箱中干燥24小时。在所得固体的XPS谱图(图2)中200eV处明显检测到Cl2p峰表明氯元素成功掺杂，含量为1-3％；结合TEM测试(图1)表明氯杂石墨烯Cl-RGO已被成功制备。
实施例3
电化学传感器制备及对氯霉素的定量测定。
称取实施例2中所制备的氯杂石墨烯Cl-RGO 2mg并超声5分钟均匀分散于1mL无水乙醇中，配制浓度为2.0mg/mL的催化剂分散液，用移液枪转移10μL分散液至干净的玻碳电极的活性面并利用红外灯烘干，即得电化学传感器。分别以饱和甘汞电极为参比电极，铂丝为辅助电极，磷酸缓冲溶液(pH＝7.4)为测定介质，在-0.4V至-0.7V测量电压范围下，采用示差脉冲伏安法法对氯霉素标准溶液进行电化学扫描，可见氯杂石墨烯Cl-RGO较之裸玻碳电极(GC)具有增强的电流响应强度(图3)，表明本发明制备的Cl-RGO可大大提高检测的灵敏度。
进一步通过梯度进样，记录电压-电流曲线，可见随氯霉素浓度的增大，响应电流强度也增大(图4)。将氯霉素浓度与-0.56V处测定电流值利用软件Origin8进行拟合，在氯霉素浓度为1-46μM范围内得一线性工作曲线，线性回归常数为0.9922，线性回归方程为y＝-0.31x-82.88，y代表电流强度，x代表氯霉素浓度，检测下限为0.5μM。据此即可通过测定电流强度计算得到氯霉素的浓度(图4)。
实施例4
电化学传感器的稳定性和实际样品中氯霉素浓度的电化学测定。
将实施例3中制备的电化学传感器直接暴露于空气中保存一个月，每隔5天扫描氯霉素标准溶液，电流强度几乎没有衰减，可见该电化学传感器具有良好的稳定性和可重复使用性(图5)。
实际样品中氯霉素浓度的电化学测定，具体做法如下：将市售氯霉素滴眼液用PBS(pH＝7.4)缓冲溶液稀释300倍后按照实施例3中步骤直接测定电流值y，代入线性回归方程y＝-0.31x-82.88中可计算出氯霉素滴眼液中氯霉素含量x为25.5μM，结果与说明书中浓度25.7mM几乎一致，可见该电化学传感器具有应用于实际样品分析中的前景。
Claims (10)
1.一种氯杂石墨烯的制备方法，包括：
将氧化石墨烯按质量体积比10-30mg:20-40mL超声均匀分散于盐酸中，氮气保护下于80-180℃回流反应2-12h；冷却至室温后进行离心分离，洗涤、干燥，即得氯杂石墨烯；其中，氯杂石墨烯中氯含量为1-3％。
2.根据权利要求1所述的一种氯杂石墨烯的制备方法，其特征在于：所述氧化石墨烯的制备方法包括：将石墨粉与浓硝酸和浓硫酸在冰水浴中混合，搅拌下加入高锰酸钾，逐步升温至45℃和90℃各反应1小时，冷却，静置过夜；将所得沉淀洗涤、干燥即得氧化石墨烯。
3.根据权利要求2所述的一种氯杂石墨烯的制备方法，其特征在于：所述石墨粉、高锰酸钾、浓硫酸和浓硝酸的比例为0.5-1g:2-5g:15-30mL:1.5-3mL。
4.根据权利要求1所述的一种氯杂石墨烯的制备方法，其特征在于：所述盐酸的浓度为2-12M。
5.根据权利要求1所述的一种氯杂石墨烯的制备方法，其特征在于：所述得到的氯杂石墨烯用于制备电化学传感器检测氯霉素。
6.根据权利要求5所述的一种氯杂石墨烯的制备方法，其特征在于：所述电化学传感器的制备方法包括：将氯杂石墨烯超声分散在乙醇中得到浓度为1-2mg/mL的催化剂分散液，移取10-20μL转移至玻碳电极活性表面，经红外灯干燥即得电化学传感器。
7.根据权利要求5所述的一种氯杂石墨烯的制备方法，其特征在于：所述电化学传感器检测氯霉素的方法包括：电化学传感器为工作电极，饱和甘汞电极为参比电极，铂丝为辅助电极，测试底液为磷酸盐缓冲液；采用示差脉冲伏安分析法，通过对氯霉素标准溶液进行测试，以氯霉素浓度为横坐标，电流强度为纵坐标，建立标准工作曲线，通过电流强度的数值计算样品中氯霉素的浓度。
8.根据权利要求7所述的一种氯杂石墨烯的制备方法，其特征在于：所述磷酸盐缓冲液pH＝7.4，浓度为5-10mM。
9.根据权利要求7所述的一种氯杂石墨烯的制备方法，其特征在于：测试电压范围为-0.4V至-0.7V。
10.根据权利要求5所述的一种氯杂石墨烯的制备方法，其特征在于：所述电化学传感器的工作浓度范围为1-46μM，检测下限为0.5μM。
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