CN115591584B - 一种对芬太尼具有快速响应的铁MOFs/纳米碳材料及其制备方法与应用 - Google Patents
一种对芬太尼具有快速响应的铁MOFs/纳米碳材料及其制备方法与应用 Download PDFInfo
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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Abstract
本发明属于电化学快速检测技术领域，公开了一种对芬太尼具有快速响应的铁MOFs/纳米碳材料及其制备方法与应用。本发明通过将对芬太尼具有高效催化活性的纳米碳与铁MOFs复合，构筑超灵敏的电极材料。铁MOFs的吸附作用和类芬顿效应可促进这类电极材料对芬太尼检测的灵敏度和响应速率，使其在电化学快检技术中表现出优异的性能，实现了比现有技术低一个数量级的超级检测限，同时具备优异的检测重复性和电化学环境下、空气中的稳定性。本发明制备的这类全新的铁MOFs/纳米碳电极材料有望成为芬太尼快检技术中的潜在应用材料。
Description
技术领域
本发明属于电化学快速检测技术领域，特别涉及一类对芬太尼具有快速响应的铁MOFs/纳米碳材料及其制备方法与应用。
背景技术
芬太尼原本是一种强效的阿片类止痛剂，适用于各种疼痛及外科、妇科等手术后和手术过程中的镇痛，但过量摄入时会让人嗜睡、困惑和恶心，此后是上瘾、低血压，最后是因为呼吸抑制而死亡。适量使用时芬太尼是药物，滥用则是毒品。欧洲毒品和毒瘾监测中心指出，血液中芬太尼浓度超过60nM就有致死效应。除了毒性大，芬太尼还有数以亿计的可能化学变体，即所谓的类似物，如枸橼酸芬太尼、卡芬太尼、舒芬太尼等。作为一类新型合成毒品，由于其毒性强、品种多、变异快、查缉难，现场快速检测芬太尼已成为当前国际禁毒领域面临的一大难题。
电化学检测具有快速、小型化、灵敏度高、成本低等优势，是极具发展潜力的现场快速检测技术。通过两步失氢失电子和一步水加成的过程，芬太尼最终被氧化分解为两种物质。该过程产生的氧化峰则是定性定量检测的依据。纳米洋葱、多壁碳纳米管、TiO2/石墨烯、锌MOF修饰的丝网印刷碳糊电极(Mat. Sci.Eng.C-Mater.,2018,110,110684；J.Anal.Chem.,2020,75,.1209；Int.J. Electrochem.Sci.,2021,16；New J.Chem.,2020,44,9271)都是近年来用于电化学检测芬太尼的催化剂。因此，基于纳米碳的电化学检测是切实可行的芬太尼快检技术之一。然而，现有技术的检测限仍有待进一步降低。
发明内容
为了克服现有技术的缺点与不足，本发明的首要目的在于提供一种对芬太尼具有快速响应的铁MOFs/纳米碳材料的制备方法。
本发明的再一目的在于提供上述制备方法制备得到的对芬太尼具有快速响应的铁MOFs/纳米碳材料。
本发明的又一目的在于提供上述铁MOFs/纳米碳材料在芬太尼快速检测技术中的应用；本发明提出运用类芬顿技术提高芬太尼的电催化氧化效率，降低检测限。
本发明的首要目的通过下述方案实现：
一种对芬太尼具有快速响应的铁MOFs/纳米碳材料的制备方法，包括以下步骤：
(1)将铁盐和有机配体加入溶剂中，充分溶解后转移至反应釜中进行反应，反应完成后依次用甲醇、去离子水、乙醇、丙酮洗涤，80℃下真空干燥12h，得到铁MOFs；
(2)取10mg步骤(1)中得到的铁MOFs与1-100mg纳米碳置于溶剂中超声反应得到分散液，然后取分散液滴涂玻碳电极，自然晾干，在玻碳电极上面得到铁MOFs/纳米碳材料。
步骤(1)中所述铁盐为FeCl3·6H2O、Fe(NO3)3·9H2O、FeCl3、Fe(NO3)2中的一种，所述有机配体为苯甲酸、对苯二甲酸、均苯三甲酸、反丁烯二酸、六氨基苯、双(3,5-二羧基苯基)偶氮中的一种，所述溶剂为N,N-二甲基甲酰胺(DMF)、N,N-二乙基甲酰胺(DEF)、1-甲基-2-吡咯烷酮(NMP)、乙醇(EtOH)、水(H2O)、氢氟酸(HF)、盐酸(HCl)中的一种或多种混合。
步骤(1)中所述的铁盐与有机配体的摩尔比为1:1-1:20；所述铁盐和有机配体加入溶剂中形成的混合溶液中铁盐的浓度为1-100mg/mL。
步骤(1)中所述反应的温度为60-200℃，反应的时间为6-80h。
步骤(2)中所使用的铁MOFs是步骤(1)中所制备的铁MOFs中的一种或两种，并且两种铁MOFs的质量比1:1。
步骤(2)中所述的纳米碳为单壁碳纳米管、双壁碳纳米管、多壁碳纳米管、石墨烯和富勒烯中的一种或两种；当纳米碳为两种时，其质量比为1:1。
步骤(2)中所述的溶剂为DMF、THF、CH2Cl2、CHCl3、EtOH和H2O 中的至少一种，溶剂的用量为5-20mL。
步骤(2)中所述超声的功率为40W，超声的时间为10-120min。
一种由上述的制备方法制备得到的铁MOFs/纳米碳材料。
上述的制备方法制备得到的铁MOFs/纳米碳材料在芬太尼快检技术中的应用，其特征在于：所述铁MOFs/纳米碳材料对芬太尼具有10nM超低检测限。
本发明的原理：
本发明制备了一种对芬太尼具有快速响应的铁MOFs/纳米碳材料。已报道的研究中，都是依赖于碳材料本身的催化活性，掺杂其他物质只是调控碳材料的电子结构。而在本发明中，发明人通过实验的研究和改进合成的方法，提供了一条创新性的材料设计思路，属于新材料的开发与应用。发明人提出非均相类芬顿催化剂与纳米碳复合，利用Fe(III)/Fe(II)循环加快芬太尼的氧化分解，与纳米碳的催化氧化作用产生协同效应，大大降低纳米碳本身的检测限。该铁 MOFs/纳米碳材料的基本物化性质情况可通过红外光谱(FTIR)、X射线衍射仪 (XRD)、扫描电镜(SEM)、透射电镜(TEM)和X射线光电子能谱仪(XPS)的表征得以确认。最后通过三电极体系下的电化学测试评估该铁MOFs/纳米碳材料在芬太尼快检技术中的应用前景。
本发明相对于现有技术，具有如下的优点及有益效果：
本发明在对芬太尼具有催化氧化作用的纳米碳上复合非均相类芬顿催化剂，两者的协同作用使得这类铁MOFs/纳米碳材料在电化学快检技术中表现出优异的性能，实现了比现有技术更低的检测限，同时具备优异的检测重复性和电化学环境下、空气中的稳定性。本发明制备的这类全新的铁MOFs/纳米碳材料有望成为芬太尼快检技术中的潜在应用材料。
附图说明
图1为实施例1中铁MOFs-1的SEM图；
图2为实施例2中铁MOFs-2的SEM图；
图3为实施例3中铁MOFs-3的SEM图；
图4为实施例4中铁MOFs-4的SEM图；
图5为实施例5中铁MOFs-5的XPS图；
图6为实施例6中铁MOFs-6的XPS图；
图7为实施例3中铁MOFs-3/多壁碳纳米管的动力学测试图；
图8为实施例5中铁MOFs-5/富勒烯的动力学测试图；
图9为实施例7中铁MOFs-7/多壁碳纳米管的检测限测试图；
图10为实施例2中铁MOFs-2/单壁碳纳米管的检测限测试图；
图11为实施例4中铁MOFs-4/富勒烯的检测限测试图；
图12为实施例1,2,4,5,7中铁MOFs/纳米碳材料的实际样品检测统计图。
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，但本发明的实施方式不限于此。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例中所用试剂如无特殊说明均可从市场常规购得。
实施例1
将20mg FeCl3·6H2O和30mg均苯三甲酸溶于50mL去离子水中，充分溶解后转移至反应釜中，在120℃下反应72h，离心收集固体，依次用甲醇、去离子水、乙醇、丙酮洗涤，80℃下真空干燥12h，得到铁MOFs-1。称取10 mg铁MOFs-1和10mg多壁碳纳米管于1mL乙醇中以40W超声功率超声分散30min得到分散液，取5μL所得分散液滴涂于玻碳电极中，自然晾干，在玻碳电极上面得到铁MOFs/纳米碳材料；该修饰了铁MOFs/纳米碳的玻碳电极可用于芬太尼检测的电极材料。
如图1所示为本实施例中铁MOFs-1的SEM图，该图表明铁MOFs-1具有八面体结构，属于立方晶系。
实施例2
将30mg Fe(NO3)2溶于100mL去离子水/DMF中，充分溶解得到溶液1；将30mg六氨基苯溶于100mL 1-甲基-2-吡咯烷酮中，充分溶解得到溶液2，将溶液1和溶液2混合后转移至反应釜中，在100℃下反应7h，离心收集固体，依次用甲醇、去离子水、乙醇、丙酮洗涤，80℃下真空干燥12h，得到铁 MOFs-2。称取10mg铁MOFs-2和20mg单壁碳纳米管于1mL乙醇中以40W 超声功率超声分散30min，取5μL悬浮液滴涂于玻碳电极中，自然晾干，在玻碳电极上面得到铁MOFs/纳米碳材料；该修饰了铁MOFs/纳米碳的玻碳电极可用于芬太尼检测的电极材料。
如图2所示为本实施例中铁MOFs-2的SEM图，该图表明铁MOFs-2具有菱形十二面体结构，属于立方晶系。如图10所示为本实施例中铁MOFs-2/ 单壁碳纳米管的检测限测试图，从图中可以看出该材料对芬太尼的检测限为 0.01μM，即10nM，线性范围为0.01-5μM，5-50μM。
实施例3
将30mg FeCl3·6H2O和50mg对苯二甲酸溶于80mL DMF中，充分溶解混合后转移至反应釜中，在150℃下反应12h，离心收集固体，依次用甲醇、去离子水、乙醇、丙酮洗涤，80℃下真空干燥12h，得到铁MOFs-3。称取10 mg铁MOFs-3和15mg多壁碳纳米管于1mL乙醇中以40W超声功率超声分散30min，取5μL悬浮液滴涂于玻碳电极中，自然晾干，在玻碳电极上面得到铁MOFs/纳米碳材料；该修饰了铁MOFs/纳米碳的玻碳电极可用于芬太尼检测的电极材料。
如图3所示为本实施例中铁MOFs-3的SEM图，该图表明铁MOFs-3呈现球形纳米颗粒形貌。如图7所示为本实施例中铁MOFs-3/多壁碳纳米管的动力学测试图，从图中可以看出氧化峰电流和还原峰电流均随着扫速的增大而增大，其中还原反应具有更大动力学速率。
实施例4
将10mg FeCl3·6H2O和20mg反丁烯二酸溶于60mL水中，充分溶解混合后转移至反应釜中，在65℃下反应12h，离心收集固体，依次用甲醇、去离子水、乙醇、丙酮洗涤，80℃下真空干燥12h，得到铁MOFs-4。称取10mg 铁MOFs-4和25mg富勒烯于1mL乙醇中以40W超声功率超声分散30min，取5μL悬浮液滴涂于玻碳电极中，自然晾干，在玻碳电极上面得到铁MOFs/ 纳米碳材料；该修饰了铁MOFs/纳米碳的玻碳电极可用于芬太尼检测的电极材料。
如图4所示为本实施例中铁MOFs-4的SEM图，该图表明铁MOFs-4呈现纳米棒状形貌。如图11所示为本实施例中铁MOFs-4/富勒烯的检测限测试图，从图中可以看出该材料对芬太尼的检测限为0.25μM，即250nM，线性范围为0.25-25μM。
实施例5
将10mg Fe(NO3)3·9H2O、40mg双(3,5-二羧基苯基)偶氮和8mL乙酸溶于 50mL DMF中，充分溶解混合后转移至反应釜中，在150℃下反应24h，离心收集固体，依次用甲醇、去离子水、乙醇、丙酮洗涤，80℃下真空干燥12h，得到铁MOFs-5。称取10mg铁MOFs-5和80mg富勒烯于10mL乙醇中以40W 超声功率超声分散30min，取5μL悬浮液滴涂于玻碳电极中，自然晾干，在玻碳电极上面得到铁MOFs/纳米碳材料；该修饰了铁MOFs/纳米碳的玻碳电极可用于芬太尼检测的电极材料。
如图5所示为本实施例中铁MOFs-5的XPS图，从图中可以看出铁MOFs-5 的Fe离子呈+3价，且两个卫星峰清晰可见。如图8所示为本实施例中铁 MOFs-5/富勒烯的动力学测试图，从图中可以看出氧化峰电流和还原峰电流均随着扫速的增大而增大，其中还原反应具有更大动力学速率。
实施例6
将13mg Fe(NO3)3·9H2O和40mg对苯二甲酸溶于50mL DMF中，充分溶解混合后转移至反应釜中，在120℃下反应20h，离心收集固体，依次用甲醇、去离子水、乙醇、丙酮洗涤，80℃下真空干燥12h，得到铁MOFs-6。称取10mg铁MOFs-6和90mg多壁碳纳米管于10mL乙醇中以40W超声功率超声分散30min，取5μL悬浮液滴涂于玻碳电极中，自然晾干，在玻碳电极上面得到铁MOFs/纳米碳材料；该修饰了铁MOFs/纳米碳的玻碳电极可用于芬太尼检测的电极材料。
如图6所示为本实施例中铁MOFs-6的XPS图，从图中可以看出铁MOFs-6 的Fe离子呈+3价，且两个卫星峰清晰可见。
实施例7
将28mg FeCl3·6H2O和70mg对苯二甲酸溶于50mL DMF中，缓慢滴加 10mL NaOH(aq)，转移至反应釜中，在100℃下反应12h，离心收集固体，依次用甲醇、去离子水、乙醇、丙酮洗涤，80℃下真空干燥12h，得到铁MOFs-7。称取10mg铁MOFs-7和100mg多壁碳纳米管于10mL乙醇中以40W超声功率超声分散30min，取5μL悬浮液滴涂于玻碳电极中，自然晾干，在玻碳电极上面得到铁MOFs/纳米碳材料；该修饰了铁MOFs/纳米碳的玻碳电极可用于芬太尼检测的电极材料。
如图9所示为本实施例中铁MOFs-7/多壁碳纳米管的检测限测试图，从图中可以看出该材料对芬太尼的检测限为0.25μM，即250nM，线性范围为 0.25-25μM。
综上所述，本发明首次提出了用于电化学检测芬太尼的新型电催化剂的设计思路，并且通过该思路制备了一系列全新的铁MOFs/纳米碳材料，实现了超低的检测限。首先，纳米碳材料的高导电性和催化活性是电化学检测芬太尼的基础，系统研究多种纳米碳基催化剂有助于全面分析芬太尼电极材料的优缺点。其次，利用铁MOFs的吸附作用和类芬顿效应，促进电极材料对芬太尼的捕获，提高氧化还原反应的效率。最后，通过优化反应参数，可得到超低检测限、重复性稳定性优异的铁MOFs/纳米碳电极材料。实验证明，该思路制备的铁MOFs/纳米碳电极材料在芬太尼快检技术中具有一定潜在应用价值。
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 (8)
1.一种铁MOFs/纳米碳材料在芬太尼快检技术中的应用，其特征在于：所述铁MOFs/纳米碳材料对芬太尼具有10nM超低检测限；
所述铁MOFs/纳米碳材料按照以下方法制备得到：
（1）将铁盐和有机配体加入溶剂中，充分溶解后转移至反应釜中进行反应，反应完成后依次用甲醇、去离子水、乙醇、丙酮洗涤，80℃下真空干燥12 h，得到铁MOFs；
（2）取10 mg步骤（1）中得到的铁MOFs与1-100 mg纳米碳置于溶剂中超声反应得到分散液，然后取分散液滴涂玻碳电极，自然晾干，在玻碳电极上面得到铁MOFs/纳米碳材料。
2.根据权利要求1所述的应用，其特征在于：步骤（1）中所述铁盐为FeCl3·6H2O、Fe(NO3)3·9H2O、FeCl3、Fe(NO3)2中的一种，所述有机配体为苯甲酸、对苯二甲酸、均苯三甲酸、反丁烯二酸、六氨基苯、双（3,5-二羧基苯基）偶氮中的一种，所述溶剂为N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、1-甲基-2-吡咯烷酮、乙醇、水中的一种或多种混合。
3. 根据权利要求1所述的应用，其特征在于：步骤（1）中所述的铁盐与有机配体的摩尔比为1:1-1:20；所述铁盐和有机配体加入溶剂中形成的混合溶液中铁盐的浓度为1-100mg/mL。
4. 根据权利要求1所述的应用，其特征在于：步骤（1）中所述反应的温度为60-200℃，反应的时间为6-80 h。
5.根据权利要求1所述的应用，其特征在于：步骤（2）中所使用的铁MOFs是步骤（1）中所制备的铁MOFs中的一种或两种，并且两种铁MOFs的质量比1:1。
6.根据权利要求1所述的应用，其特征在于：步骤（2）中所述的纳米碳为单壁碳纳米管、双壁碳纳米管、多壁碳纳米管、石墨烯和富勒烯中的一种或两种；当纳米碳为两种时，其质量比为1:1。
7. 根据权利要求1所述的应用，其特征在于：步骤（2）中所述的溶剂为DMF、THF、CH2Cl2、CHCl3、EtOH和H2O中的至少一种，溶剂的用量为5-20 mL。
8. 根据权利要求1所述的应用，其特征在于：步骤（2）中所述超声的功率为40W，超声的时间为10-120 min。
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