CN113024751A - 一种磁性共价有机框架mTFBD-PPD的制备方法、产品及其应用 - Google Patents
一种磁性共价有机框架mTFBD-PPD的制备方法、产品及其应用 Download PDFInfo
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Abstract
本发明公开了一种磁性共价有机框架mTFBD‑PPD的制备方法、产品及其应用,属于毒素吸附剂制备技术领域;所述制备方法包括:将3,3',5,5'‑四醛基‑4,4'‑二羟基联苯与碱溶解于水中,得到溶液;将对苯二胺与磁性纳米粒子分散于有机溶剂中,得到分散液;将所述溶液与所述分散液混合,反应得到所述磁性共价有机框架mTFBD‑PPD;本发明将共价有机框架材料与磁性纳米颗粒结合制备得到的新型吸附剂mTFBD‑PPD,具有比表面积大、热稳定性良好、选择性强和可快速分离、重复使用等特点,将其用于腹泻性贝类毒素的吸附中,可有效提高吸附率。
Description
技术领域
本发明属于毒素吸附剂制备技术领域,具体涉及一种磁性共价有机框架mTFBD-PPD的制备方法、产品及其应用。
背景技术
腹泻性贝类毒素(Diarrheal shellfishpoisoning,DSP)是一类聚醚和亲脂化合物,可引起明显的胃肠功能障碍症状,如恶心、呕吐、腹泻等,通过刺激肠细胞分泌Na+引起腹泻,导致肠腔内积液,导致腹部绞痛,引起一些慢性毒性作用,对生物的多种功能造成影响。
产生DSP的毒藻被海洋中的贝类、鱼类及其他海洋动物摄食,消费者食用后导致腹泻性贝类中毒,常用的加热处理不易破坏其化学结构和毒性,因此不能通过一般烹饪来降低DSP的毒性。
采用吸附法消减腹泻性贝毒是应对危害的主要措施,多孔的合成树脂HP20可以将海洋亲脂性毒素吸附在上,进行提取和分析。但大孔树脂吸附毒素时间长,效率低,重复利用过程繁琐。
发明内容
为解决现有技术中的上述问题,本发明提供了一种磁性共价有机框架mTFBD-PPD的制备方法、产品及其应用。
为实现上述目的,本发明提供了如下技术方案:
本发明提供了一种磁性共价有机框架mTFBD-PPD的制备方法,包括以下步骤:将3,3',5,5'-四醛基-4,4'-二羟基联苯与碱溶解于水中,得到溶液;将对苯二胺与氨基修饰的磁性纳米粒子分散于有机溶剂中,得到分散液;将所述溶液与所述分散液混合,反应得到所述磁性共价有机框架mTFBD-PPD。
进一步地,所述碱为KOH、NaOH或Ba(OH)2。
进一步地,所述碱及对苯二胺的用量均为3,3',5,5'-四醛基-4,4'-二羟基联苯量的1.5~2.5当量。
进一步地,所述氨基修饰的磁性纳米粒子为氨基修饰的纳米Fe3O4。
进一步地,所述氨基修饰的磁性纳米粒子的用量为3,3',5,5'-四醛基-4,4'-二羟基联苯的50wt%。
进一步地,所述分散液中氨基修饰的磁性纳米粒子的浓度为12.5~25g/L。
进一步地,所述有机溶剂为N,N-二甲基甲酰胺。
进一步地,所述反应温度为130~150℃,反应时间为20~30h。
进一步地,所述反应完毕后,还包括在磁力条件下进行收集,之后分别采用二甲基甲酰胺、无水乙醇和丙酮洗涤,真空干燥的步骤。
进一步地,所述真空干燥的温度为80℃。
本发明还提供了一种根据上述制备方法制备得到的磁性共价有机框架mTFBD-PPD。
本发明还提供了一种上述磁性共价有机框架mTFBD-PPD在腹泻性贝类毒素吸附中的应用。
与现有技术相比,本发明具有以下有益效果:
本发明将共价有机框架材料与磁性纳米颗粒结合制备得到的新型吸附剂mTFBD-PPD,既具有共价有机框架的有序的纳米孔结构,又能在外部磁场的作用下实现快速分离,具有比表面积大、热稳定性良好、选择性强和可快速分离、重复使用等特点,将其用于腹泻性贝类毒素的吸附中,可有效提高吸附率。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为实施例1制备得到的磁性共价有机框架mTFBD-PPD的结构示意图。
图2为TFBD、实施例1制备得到的MNP-NH2及磁性共价有机框架mTFBD-PPD的红外谱图。
图3为实施例1制备得到的MNP-NH2及磁性共价有机框架mTFBD-PPD的XRD谱图。
图4为实施例1制备得到的磁性共价有机框架mTFBD-PPD的扫描电镜图。
图5为实施例1制备得到的磁性共价有机框架mTFBD-PPD的热重分析图。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。
另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
实施例1
磁性共价有机框架mTFBD-PPD的制备,包括以下步骤:
(1)氨基修饰的磁性纳米Fe3O4(amino-modified Fe3O4nanoParticles,MNP-NH2)的制备:
将11.68g FeCl3·6H2O和4.30g FeCl2·4H2O添加到装有200mL超纯水的圆底烧瓶中。将该混合物在氮气气氛下搅拌加热至85℃。随后,在剧烈搅拌条件下将20mLNH3·H2O(30%)缓慢倒入混合物中。0.5小时后,将所得反应体系冷却至室温。收集Fe3O4纳米颗粒,分别用去离子水和乙醇洗涤3次。然后将产物在60℃的真空烘箱中干燥过夜。随后取1.0g干燥后的Fe3O4添加到装有40mL去离子水和160mL无水乙醇的烧杯中。超声分散15分钟后,将混合物转移至圆底烧瓶中,并加入1mLNH3·H2O。搅拌30分钟后,滴加1.0mLTEOS(正硅酸乙酯),然后剧烈搅拌45min,然后引入0.07mLAPTES(3-氨丙基三乙氧基硅烷)。再经过4小时反应后,将所得混合物从混合溶液中分离出来,用水和乙醇洗涤,然后在45℃的真空烘箱中干燥,得到MNP-NH2。
(2)将1.0g的3,3',5,5'-四醛基-4,4'-二羟基联苯(3,3',5,5'-tetraformyl-4,4'-biphenyldiol,TFBD)和TFBD的2当量的KOH溶解在水中,超声溶解均匀至得到澄清溶液;将TFBD的2当量的对苯二胺(p-Phenylenediamine,PPD)与0.50g的步骤(1)所得的MNP-NH2于烧杯中超声均匀分散在20mLN,N-二甲基甲酰胺(N,N-Dimethylformamide,DMF)中,得到分散液;将上述所得溶液与所得分散液混合,140℃油浴反应24h,在外部磁力条件下收集反应所得产物,并分别用二甲基甲酰胺、无水乙醇和丙酮重复洗涤,80℃真空干燥得到所述磁性共价有机框架mTFBD-PPD。
磁性共价有机框架mTFBD-PPD的合成路线图如图1所示。
采用红外光谱仪对所得磁性共价有机框架mTFBD-PPD表面的官能团进行分析,结果如图2所示。由图2可见:mTFBD-PPD在1692cm-1处的吸收强度消失,在1618cm-1出现C=N的吸收峰,说明两个单体之间发生了希夫碱反应。Si-O-Si不对称振动在1090cm-1处的峰值为MNPs的存在提供了有力的证据。Fe-O的特征吸收带出现在580cm-1附近,红外图谱显示合成了目标化合物。
磁性共价有机框架mTFBD-PPD的XRD谱图如图3所示,观察到31°和35°处的特征图谱,这与已发表的晶体Fe3O4数据(JCPDS文件,No.19-0629)一致,说明MNPs的成功掺入,在约25°时的宽谱图,这可以归因于其堆叠的分层共轭芳族体系。
采用扫描电镜对磁性共价有机框架mTFBD-PPD的形貌进行了表征,如图4所示,图4分别是标尺为5μm、2μm、1μm和500nm的SEM图像,清楚地显示了mTFBD-PPD材料具有颗粒状态,表面有粗糙的突触。
实施例2
磁性共价有机框架mTFBD-PPD的制备,步骤如下:
步骤(1)同实施例1;
步骤(2):将1.0g的TFBD及TFBD的1.5当量的NaOH溶解在水中,超声溶解均匀至得到澄清溶液;将TFBD的1.5当量的PPD与0.50g的MNP-NH2于烧杯中超声均匀分散在30mLN,N-二甲基甲酰胺DMF中,得到分散液;将上述所得溶液与所得分散液混合,130℃油浴反应30h,在外部磁力条件下收集反应所得产物,并分别用二甲基甲酰胺、无水乙醇和丙酮重复洗涤,80℃真空干燥得到所述磁性共价有机框架mTFBD-PPD。
实施例3
磁性共价有机框架mTFBD-PPD的制备,包括以下步骤:
步骤(1)同实施例1;
步骤(2):将1.0g的TFBD及TFBD的2.5当量的Ba(OH)2溶解在水中,超声溶解均匀至得到澄清溶液;将TFBD的2.5当量的PPD与0.50g的MNP-NH2于烧杯中超声均匀分散在40mLDMF中,得到分散液;将上述所得溶液与所得分散液混合,150℃油浴反应20h,在外部磁力条件下收集反应所得产物,并分别用二甲基甲酰胺、无水乙醇和丙酮重复洗涤,80℃真空干燥得到所述磁性共价有机框架mTFBD-PPD。
对比例1
同实施例1,区别在于,不包括步骤(1),将步骤(2)中的MNP-NH2替换为磁性纳米Fe3O4。
对比例2
TFBD-PPD的制备:
将1.0g的TFBD及TFBD的2当量的KOH溶解在水中,超声溶解均匀至得到澄清溶液;将TFBD的2当量的PPD于烧杯中超声均匀分散在20mL DMF中,得到分散液;将上述所得溶液与所得分散液混合,140℃油浴反应24h,离心收集反应所得产物,并分别用二甲基甲酰胺、无水乙醇和丙酮重复洗涤,80℃真空干燥得到所述TFBD-PPD。
对比例3
磁性共价有机框架mTFBD-PPD的制备,包括以下步骤:
步骤(1)同实施例1;
步骤(2)为:将1.0g的TFBD及TFBD的2当量的KOH溶解在水中,超声溶解均匀至得到澄清溶液;将TFBD的2当量的PPD于烧杯中超声均匀分散在10mL DMF中,得到分散液A,将上述所得溶液与所得分散液A混合,140℃油浴反应24h,之后将0.50g的MNP-NH2于烧杯中超声均匀分散在10mL DMF中,得到分散液B,将分散液B置于上述反应体系中,继续140℃油浴反应24h,在外部磁力条件下收集反应所得产物,并分别用二甲基甲酰胺、无水乙醇和丙酮重复洗涤,80℃真空干燥得到所述磁性共价有机框架mTFBD-PPD。
效果验证
1.对实施例1~3及对比例1~3制备得到的产品的比表面积进行测定,结果如表1所示:
表1
2.对腹泻性贝类毒素的吸附作用
分别采用实施例1~3、对比例1~3制备得到的产品及市售大孔树脂HP20(购自:北京索莱宝科技有限公司)对腹泻性贝类毒素进行吸附,具体方法为:初始浓度为1μg mL-1的腹泻性贝类毒素溶液2mL,分别添加10mg的上述样品,在19℃、190r/min振荡条件下吸附2h,反应结束后,在外部磁力作用下分离出mTFBD-PPD,离心得到TFBD-PPD、大孔树脂HP20,将上清通过腹泻性贝类毒素Elisa试剂盒进行检测,计算腹泻性贝类毒素的脱除率。分离得到的样品:mTFBD-PPD、TFBD-PPD、大孔树脂HP20的质量及腹泻性贝类毒素的脱除率如表2所示。
表2
由表2可以得出:TFBD-PPD和大孔树脂HP20不能从反应体系中完全分离,在过程中会造成材料的损失,从而影响吸附效率和材料的可重用性;在离心过程中使部分毒素脱离吸附剂,导致吸附率的降低,采用本发明制备得到的mTFBD-PPD,将COF材料加入磁性,减少了分离过程中吸附剂上毒素的损失,提高了吸附率。
3.热稳定性检测
对实施例1~3及对比例1~3制备得到的产品的热稳定性进行检测,方法如下:
检测方法:N2氛围,30℃/(10.0K/min)/800℃;
结果见表3,实施例1的mTFBD-PPD的热重分析图如图5所示。
表3
由表3和图5可以看出,本发明制备得到的mTFBD-PPD的热稳定性显著高于对比例,mTFBD-PPD在30-400℃失重4.12~4.19%,可归因于其孔内和/或内部的残留吸附的水和残留溶剂的挥发。在400-800℃重量显著下降,失重38.45~38.69%,这表明mTFBD-PPD的基本骨架遭到破坏和分解,残留质量主要为热稳定性更强的MNP-NH2。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围内。
Claims (10)
1.一种磁性共价有机框架mTFBD-PPD的制备方法,其特征在于,包括以下步骤:将3,3',5,5'-四醛基-4,4'-二羟基联苯与碱溶解于水中,得到溶液;将对苯二胺与氨基修饰的磁性纳米粒子分散于有机溶剂中,得到分散液;将所述溶液与所述分散液混合,反应得到所述磁性共价有机框架mTFBD-PPD。
2.根据权利要求1所述的制备方法,其特征在于,所述碱为KOH、NaOH或Ba(OH)2。
3.根据权利要求1所述的制备方法,其特征在于,所述碱及对苯二胺的用量均为3,3',5,5'-四醛基-4,4'-二羟基联苯量的1.5~2.5当量。
4.根据权利要求1所述的制备方法,其特征在于,所述氨基修饰的磁性纳米粒子为氨基修饰的纳米Fe3O4。
5.根据权利要求1所述的制备方法,其特征在于,所述氨基修饰的磁性纳米粒子的用量为3,3',5,5'-四醛基-4,4'-二羟基联苯的50wt%。
6.根据权利要求1所述的制备方法,其特征在于,所述有机溶剂为N,N-二甲基甲酰胺。
7.根据权利要求1所述的制备方法,其特征在于,所述反应温度为130~150℃,反应时间为20~30h。
8.根据权利要求1所述的制备方法,其特征在于,所述反应完毕后,还包括在磁力条件下进行收集,之后分别采用二甲基甲酰胺、无水乙醇和丙酮洗涤,真空干燥的步骤。
9.一种根据权利要求1~8任一项所述的制备方法制备得到的磁性共价有机框架mTFBD-PPD。
10.一种权利要求9所述的磁性共价有机框架mTFBD-PPD在腹泻性贝类毒素吸附中的应用。
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---|
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