CN113896185A - 一种杏壳基氮掺杂石墨烯量子点的制备方法及其应用 - Google Patents
一种杏壳基氮掺杂石墨烯量子点的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了杏壳基氮掺杂石墨烯量子点的制备方法,步骤为:将杏壳洗净、烘干放入粉碎机中粉碎,用氯化锌溶液浸泡,将杏壳放入恒温烘箱中烘干,然后进行高温活化处理,再冷却并洗涤过滤,放入恒温烘箱中再次烘干;将杏壳碳放入容器中,容器放入含有浓硝酸的反应釜中,反应釜放入烘箱中加热反应,然后原位过滤,即得杏壳基氮掺杂石墨烯量子点溶液。本发明利用废弃生物质原料制备石墨烯量子点荧光探针,能快速无干扰检测维生素C。与现有制备氮石墨烯量子点的方法相比,本发明的制备方法,操作简便,价格低廉且环保,符合绿色可持续发展的理念,符合工业中的大规模生产要求。此外,以其为荧光探针与现有荧光传感技术相比,稳定高、抗干扰能力强。
Description
技术领域
本发明涉及光学材料和医学检测技术领域,具体的说涉及一种杏壳基氮掺杂石墨烯量子点的制备方法及其应用。
背景技术
石墨烯量子点(GQDs)即具有石墨烯的特殊结构也有碳量子点的量子限域效应及边界效应,因其特殊性能备受科学家的广泛关注。在最近几年,石墨烯量子点在光学领域如光电器件、数据存储器、传感器、生物成像、抗菌系统以及对环境的检测等领域有广泛的应用。自上而下法制备石墨烯量子点,所利用的碳源主要包括碳纳米管、氧化石墨烯、碳纤维、炭黑、石墨烯、石墨粉、煤炭等,但由于受到碳源成本、环境保护和生态平衡等因素制约不宜大量生产规模。以废弃生物质为原材料制备石墨烯量子点,可减少环境污染,且能有效利用资源、降低成本,更加满足可持续发展的需要。
在我国北方,山杏是重要的生态经济树种之一,具有很高的年产量。据调查,我国目前杏仁年产量为30-40kt。而就河北省而言,河北省省内的苦杏仁产量约占全国总产量的30%,而较为集中的地区为承德市,其山杏经济林资源246万亩。其中生产的杏仁主要被用于生产各种生活食品,如饼干、饮料等,杏壳占杏核质量的70%左右,在生产加工过程中未被利用,据统计,我国每年加工杏核产生的杏壳为180万吨,约占山杏年产量的72%,被利用完剩下的杏核不但会造成环境污染,而且还造成资源的浪费。所以,以杏壳为原料制备杏壳碳,既节省成本不造成环境污染、又不浪费资源。由于其低生产成本,杏壳碳制GQDs适用于大规模工业应用并可能成功地作为传统无机量子点的一种高性价比、绿色环保的替代品。
维生素C也就是抗坏血酸(AA),是人体所必需的营养成分之一。因AA的高还原性使其成为有效的抗氧化剂。AA的缺少或过度使用都会则会直接导致疾病的产生。它在维持动物和人体新陈代谢等机体各项功能方面起着十分重要的作用。与此同时它还能与自由基发生反应,也可以被用于治疗普通的感冒,癌症和精神疾病等的辅助药物。由于AA与人体健康水平相关联,所以研发一种能应用于实际生活中医疗检测血清中AA的方法至关重要,使人们可以及时的评估人体的生理情况,并且及时纠正AA缺乏症,在临床医学中具有重要的意义。在化学领域,检测AA的方法有很多,包括经典的碘量法、电化学法、滴定分析法、分光光度法、高效液相色谱法(HPLC)。石墨烯量子点荧光纳米传感器由于其低毒、无标记且易操作为检测AA提供了方便,并且拓展了其在生物和化学传感中的应用价值。
因此,提供一种以废弃的杏壳为原材料,通过硝酸蒸汽切断的方法制备得到荧光石墨烯量子点,将其作为荧光探针,快速完成尿液中维生素C的检测的方案是本领域技术人员亟需解决的技术问题。
发明内容
有鉴于此,本发明提供了一种以废弃杏壳为原材料,自上而下的制备荧光氮掺杂石墨烯量子点(N-GQDs)的方法,并可灵敏地、高选择性地检测AA。本发明使用杏壳作为起始原料,通过粉碎、碳化、活化制备杏壳基活性炭材料之后,使用硝酸蒸汽作为剪刀制备出了水溶性好的N-GQDs。石墨烯量子点富含羟基和羧基等含氧官能团不仅使其具有极佳的水溶性,而且以Fe3+为荧光淬灭剂形成Fe3+-N-GQDs体系,加入生物小分子AA作为还原剂,实现对AA的turn-on检测,并实施了尿液中AA的检测,获得较高的回收率。
为了实现上述目的,本发明采用如下技术方案:
一种杏壳基氮掺杂石墨烯量子点的制备方法,包括以下步骤:
(1)将杏壳洗净、烘干放入粉碎机中粉碎,再用氯化锌溶液浸泡,然后将杏壳放入50-200℃恒温烘箱中烘干10-30h,将烘干之后的杏壳进行高温活化处理,高温活化处理后进行冷却至25-75℃并用蒸馏水洗涤过滤,再放入恒温烘箱中烘干2-10h,得到成品杏壳碳;
(2)将制备好的0.05-0.5g杏壳碳放入容器中,然后将容器放入含有1-3ml浓硝酸的反应釜中,再将反应釜放入120-180℃的烘箱中加热反应1-6h,将反应后的容器原位过滤,收集黄色滤液,即得杏壳基氮掺杂石墨烯量子点溶液。
进一步,步骤(1)中所述粉碎粒度为200-2500目。
采用上述进一步方案的有益效果在于:使杏壳充分粉粹,利于其与氯化锌的接触,提高杏壳碳的比表面积。
进一步,步骤(1)中所述氯化锌溶液的质量浓度为20-80%,所述浸泡时间为6-36h。
采用上述进一步方案的有益效果在于:氯化锌作为活化剂,通过氯化锌溶液浸泡方式,利于其与杏壳的充分接触。
进一步,步骤(1)中所述高温活化处理温度为700-1200℃,处理时间为1-4h。
采用上述进一步方案的有益效果在于:高温活化处理在此温度区间和时间下,已可有效得到杏壳碳,降低能耗。
进一步,步骤(2)中所述浓硝酸的质量浓度为68%。
本发明还提供了上述制备方法得到的杏壳基氮掺杂石墨烯量子点在荧光检测维生素C中的应用,包括以下步骤:
1)将所述杏壳基氮掺杂石墨烯量子点溶液用水稀释获得检测液,以10nm为间隔的激发波长激发杏壳基氮掺杂石墨烯量子点,狭缝为5-10nm进行荧光测试,得到荧光发射峰强度最大波长;
2)取稀释的杏壳基氮掺杂石墨烯量子点溶液石英比色皿中,首先加入10-100μMFe3+溶液,得到测试体系,测定不同AA浓度下的荧光强度,以荧光强度对AA浓度绘制传感曲线图。
优选的,步骤1)中所述所述杏壳基氮掺杂石墨烯量子点溶液与水的体积比为0.1-1:1-1.9。
更优选的,所述水为超纯水,其电阻率≥18.2MΩ。
采用上述进一步方案的有益效果在于:在分析检测中,干扰越少越好,因此测试液采用超纯水。
本发明的有益效果在于:本发明的利用废弃杏壳为原材料制备氮掺杂石墨烯量子点的方法利用N-GQDs的荧光“开关”模式专一性检测维生素C,采用基于节约环保的杏壳为原材料制备杏壳碳,并采取氯化锌活化法增加杏壳碳比表面积,经炭化、浸泡、烘干、洗涤等过程制备杏壳碳,再利用硝酸切断法将大比表面杏壳碳制备成石墨烯量子点。
本发明制备方法简便且原材料低廉,同时也可以保护生态环境、变废为宝、节约资源,既有利于工业上石墨烯量子点的大规模制备又体现了绿色环保的经济理念。
本发明制备的氮掺杂石墨烯量子点表面的富氧官能团特别是酚羟基和羧基是其对铁离子具有较好选择性的主要因素。此外,N-GQDs表面的羧基对铁离子也具有较大的贡献。本发明中铁离子加入到N-GQDs溶液之后形成了Fe-N-GQDs配合物,这个配合物利于光生电子从N-GQDs到Fe3+的转移,从而淬灭荧光,加入目标维生素C后,利用铁离子作为氧化剂,通过加入具有还原作用及配位作用的维生素C改变氮掺杂石墨烯量子点的配位环境,进而恢复N-GQDs的荧光发射,达到开关模式检测维生素C的目的。
本发明利用废弃生物质原料制备石墨烯量子点荧光探针,能快速无干扰检测维生素C。与现有制备氮石墨烯量子点的方法相比,本发明的制备方法,操作简便,价格低廉且环保,符合绿色可持续发展的理念,符合工业中的大规模生产要求。此外,以其为荧光探针与现有荧光传感技术相比,稳定高、抗干扰能力强。
附图说明
图1为本发明中由杏壳制备杏壳碳的实物照片;
图2为本发明中制备杏壳碳的氮气吸附等温线;
图3为本发明实施例2制备的N-GQDs的X射线光电子能谱图;
图4为本发明实施例3Fe3+-N-GQDs对AA的传感应用图,不同浓度AA下的Fe3+-N-GQDs溶液的荧光光谱图(AA浓度从上到下依次是:0,1,3,10,20,30,40,50,60,70,80,90和100μM);
图5为本发明实施例3Fe3+-N-GQDs对AA检测的工作曲线,F0和F分别是350nm激发下,AA缺乏和存在下的荧光强度;
图6为本发明实施例3Fe3+-N-GQDs在50μM不同生物小分子存在下的淬灭性能,从左到右分别为:L-半胱氨酸、D-果糖、无水乙醇、葡萄糖、甘氨酸、尿酸、油酸、L-异亮氨酸、L-精氨酸、L-丝氨酸、L-丙氨酸。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。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前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种杏壳基氮掺杂石墨烯量子点的制备方法
(1)将杏壳洗净、烘干放入粉碎机中粉碎至1000目,再用质量浓度为60%氯化锌溶液浸泡24h,然后将杏壳放入60℃恒温烘箱中烘干24h,将烘干之后的杏壳850℃高温活化处理1h,高温活化处理后冷却至25℃并用蒸馏水洗涤过滤,再放入恒温烘箱中烘干8h,得到成品杏壳碳;
(2)将制备好的0.05g杏壳碳放入容器中,然后将容器放入含有1.5ml质量浓度为68%的浓硝酸的反应釜中,再将反应釜放入150℃的烘箱中加热反应3h,将反应后的容器原位过滤,收集黄色滤液,即得杏壳基氮掺杂石墨烯量子点溶液。
实施例2
(1)将杏壳洗净、烘干放入粉碎机中粉碎至2000目,再用质量浓度为60%氯化锌溶液浸泡36h,然后将杏壳放入80℃恒温烘箱中烘干36h,将烘干之后的杏壳750℃温活化处理1h,高温活化处理后冷却至25℃并用蒸馏水洗涤过滤,再放入恒温烘箱中烘干10h,得到成品杏壳碳;
(2)将制备好的0.1g杏壳碳放入容器中,然后将容器放入含有2ml质量浓度为68%的浓硝酸的反应釜中,再将反应釜放入180℃的烘箱中加热反应4h应后的容器原位过滤,收集黄色滤液,即得杏壳基氮掺杂石墨烯量子点溶液。
实施例3
AA检测
将0.2mL N-GQDs溶液用1.8mL超纯水(≥18.2,MΩ)稀释获得检测液。以10nm为间隔的激发波长激发N-GQDs,狭缝为5nm,10nm进行荧光测试。当激发波长是350nm时,它的荧光发射峰强度最大。选择350nm为激发波长用于以下荧光检测AA实验。其次,取制备的N-GQDs稀释溶液于石英比色皿中,首先加入Fe3+溶液,得到测试体系,测定不同AA浓度下的荧光强度,以荧光强度对AA浓度绘制传感曲线图。
Fe3+-N-GQDs对AA的响应线性范围浓度范围是0-100μM,拟合的线性关系式是:F/F0=0.9865+0.02935*CAA,相关系数R=0.997,本发明的传感器对AA的线性范围较宽,展现了其优势。
实施例4
Fe3+-N-GQDs对AA的选择性测试
将Fe3+-N-GQDs检测液放入石英比色皿中,然后分别加入80μM的干扰物质L-半胱氨酸、D-果糖、无水乙醇、葡萄糖、甘氨酸、尿酸、油酸、多巴胺、L-异亮氨酸、L-精氨酸、L-丝氨酸、L-丙氨酸。以上干扰物质加入以后,荧光几乎没有恢复,表明干扰较小,而当80μMAA加入到Fe3+-N-GQDs后,荧光增强大为提高。这些结果表明所制备的Fe3+-N-GQDs对AA具有好的选择性。
实施例5
检测尿液中的维生素C
样品取自人体尿液,用其配制已知浓度的AA标准溶液。将Fe3+-GQDs检测液放入石英比色皿中。然后分别加入10,30,40μM的AA,测定荧光强度,利用工作曲线计算AA的含量。利用本发明的荧光传感器检测到的AA的浓度为9.339μM,28.845μM,37.084,μMAA的回收率各是93.39%,96.15%和92.71%(表1)。从表1中可以看出:本发明制备的N-GQDs可以应用于尿液中AA的检测。
表1 N-GQDs荧光探针用于尿液中AA检测(n=3)
本发明所述的制备方法,以废弃杏壳为原材料,通过洗涤、粉碎、活化等工艺制备了大比表面杏壳碳,然后利用简易的硝酸蒸气切断策略,在密闭反应釜的空间内,氧化切断杏壳碳,获得氮掺杂石墨烯量子点(N-GQDs),利用N-GQDs的荧光“开关”模式实现了对维生素C的检测。
图1是杏壳制备杏壳碳的实物照片。
图2,是制备杏壳碳的氮气吸附曲线,可见杏壳碳对氮气吸附量较大,含有大量的空隙结构,BET比表面积为1487.413m2/g,平均孔径为2.21nm。
图3,中N-GQDs的XPS全谱图显示了一个弱的N1s(405,eV)的特征峰和两个明显的C1s(284,eV)和O1s(532,eV)的特征峰,表明该量子点由大量的C、O及微量的N元素构成,其中氮含量和氧含量分别约为6.02%和36.45%。N-GQDs高的氧含量使其具有较好的水溶性,为其应用提供了可能。
图4和5表明随着维生素C浓度的增加,淬灭的量子点荧光逐渐恢复,且恢复的荧光强度比(F/F0)在0-100μM范围内成一定的线性关系。线性方程为F/F0=0.9865+0.02935*CAA,(R=0.997),式中F为加入AA后的荧光强度,F0为未加入AA时的荧光强度。
图6表明Fe3+-N-GQDs对维生素C具有较好的选择性。
尽管上面已经示出和描述了本发明的实施例,可以理解的是,上述实施例是示例性的,不能理解为对本发明的限制,本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。
Claims (9)
1.一种杏壳基氮掺杂石墨烯量子点的制备方法,其特征在于,包括以下步骤:
(1)将杏壳洗净、烘干放入粉碎机中粉碎,再用氯化锌溶液浸泡,然后将杏壳放入50-200℃恒温烘箱中烘干10-30h,将烘干之后的杏壳进行高温活化处理,高温活化处理后进行冷却至25-75℃并用水洗涤过滤,再放入恒温烘箱中烘干2-8h,得到成品杏壳碳;
(2)将制备好的0.05-0.5g杏壳碳放入容器中,然后将容器放入含有1-3ml浓硝酸的反应釜中,再将反应釜放入120-180℃的烘箱中加热反应1-6h,将反应后的容器原位过滤,收集黄色滤液,即得杏壳基氮掺杂石墨烯量子点溶液。
2.根据权利要求1所述一种杏壳基氮掺杂石墨烯量子点的制备方法,其特征在于,步骤(1)中所述粉碎粒度为200-2500目。
3.根据权利要求1所述一种杏壳基氮掺杂石墨烯量子点的制备方法,其特征在于,步骤(1)中所述氯化锌溶液的质量浓度为20-80%,所述浸泡时间为6-36h。
4.根据权利要求1所述一种杏壳基氮掺杂石墨烯量子点的制备方法,其特征在于,步骤(1)中所述高温活化处理温度为700-1200℃,处理时间为1-4h。
5.根据权利要求1所述一种杏壳基氮掺杂石墨烯量子点的制备方法,其特征在于,步骤(2)中所述浓硝酸的质量浓度为68%。
6.一种权利要求1-5任一项所述制备方法得到的杏壳基氮掺杂石墨烯量子点在荧光检测维生素C中的应用。
7.根据权利要求6所述一种杏壳基氮掺杂石墨烯量子点在荧光检测维生素C中的应用,其特征在于,包括以下步骤:
1)将所述杏壳基氮掺杂石墨烯量子点溶液用水稀释获得检测液,以10nm为间隔的激发波长激发杏壳基氮掺杂石墨烯量子点,狭缝为5-10nm进行荧光测试,得到荧光发射峰强度最大波长;
2)取稀释的杏壳基氮掺杂石墨烯量子点溶液石英比色皿中,首先加入10-100μM Fe3+溶液,得到测试体系,测定不同AA浓度下的荧光强度,以荧光强度对AA浓度绘制传感曲线图。
8.根据权利要求7所述一种杏壳基氮掺杂石墨烯量子点在荧光检测维生素C中的应用,其特征在于,步骤1)中所述所述杏壳基氮掺杂石墨烯量子点溶液与水的体积比为0.1-1:1-1.9。
9.根据权利要求7所述一种杏壳基氮掺杂石墨烯量子点在荧光检测维生素C中的应用,其特征在于,所述水为超纯水,其电阻率≥18.2MΩ。
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