CN108620129B - 球形Fc-(COOH)2@COFETTA-TPAL纳米复合材料的制备方法 - Google Patents
球形Fc-(COOH)2@COFETTA-TPAL纳米复合材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种制备包裹了电活性二茂铁二甲酸分子(Fc‑(COOH)2)的球形共价有机框架材料(COFETTA‑TPAL)纳米复合材料(Fc‑(COOH)2@COFETTA‑TPAL)的新方法。通过将四‑(4‑氨基苯)乙烯(ETTA)、对苯二甲醛(TPAL)和Fc‑(COOH)2共同溶解于1,4‑二氧六环溶剂中，超声混合后再加入乙酸，最后将混合液转移到反应釜中并置于120℃烘箱中反应2天，获得土黄色固体Fc‑(COOH)2@COFETTA‑TPAL纳米复合材料。利用溶剂热一锅合成法制备的Fc‑(COOH)2@COFETTA‑TPAL纳米复合材料为球形，尺寸均匀，直径约为200nm。Fc‑(COOH)2分子被很好地装载在COFETTA‑TPAL的孔洞中。较好地维持了COFETTA‑TPAL材料的晶体结构，同时保留了Fc‑(COOH)2与COFETTA‑TPAL的电活性性能。研究发现该纳米复合材料能催化H2O2发生歧化反应，可代替过氧化物酶，制备过程简单、原材料廉价易得。
Description
技术领域
本发明涉及一种制备均匀球形Fc-(COOH)2@COFETTA-TPAL纳米复合材料的方法，属于材料化学领域。
背景技术
共价有机框架材料（COF）是继无机类沸石多孔材料和金属有机骨架材料（MOF）后发展起来的一类新材料，是一种结构较为稳定的新型晶型多孔高分子材料，具有明确的孔径分布，较大的比表面积和许多特殊的官能团，易于装载种功能小分子或蛋白质分子等。COFETTA-TPAL是由四-(4-氨基苯)乙烯（ETTA）与对苯二甲醛（TPAL）在高温下经过氨醛缩合反应而获得的。它是一种典型的二维片层堆叠多孔材料，在高温下也比较稳定，从而克服了无机多孔材料组成单一、孔道分布不均以及晶型不好等缺陷，同时也克服了MOF材料的多孔结构在水里易塌陷等缺点。但由于它不溶于水和大多数有机溶剂(如正已院、甲醇、丙酮、四氢呋喃、DMF、二甲亚砜等)，因此通常情况下所合成的COFETTA-TPAL往往团聚在一起，且性能比较单一，也进一步限制了该材料的广泛使用。
发明内容
本发明的目的在于提供一种制备均匀球形且同事具有Fc-(COOH)2与COFETTA-TPAL的电活性性能的Fc-(COOH)2@ COFETTA-TPAL纳米复合材料的方法。
实现本发明的技术方案：
本发明在合成COFETTA-TPAL的基础上，通过在其孔洞中包裹电活性二茂铁二甲酸分子（Fc(COOH)2）制备Fc-(COOH)2@COFETTA-TPAL纳米复合材料。
一种Fc-(COOH)2@COFETTA-TPAL纳米复合材料的制备方法，包括以下步骤：
（1）将四-(4-氨基苯)乙烯（ETTA）、对苯二甲醛（TPAL）和二茂铁二甲酸（Fc-(COOH)2）溶解于1,4-二氧六环溶剂中，超声混合，得混合溶液；
（2）向混合溶液中加入6 M乙酸溶液，再转移到反应釜中在90~120℃条件下反应一段时间；
（3）用N,N-二甲基甲酰胺（DMF）和四氢呋喃（THF）依次作为溶剂对所得沉淀物进行离心洗涤，然后将沉淀物在四氢呋喃和二氯乙烷的混合溶液中浸泡一段时间，以便更充分地除去沉淀物中所吸附的有机单体分子和杂质，沉淀物再进行真空冷冻干燥，并经过研磨得到土黄色固体，即Fc-(COOH)2@COFETTA-TPAL纳米复合材料。
优选的，步骤（1）中，四-(4-氨基苯)乙烯溶液的浓度为10~15 mg/mL，对苯二甲醛溶液的浓度为6.85~10.25 mg/mL，二茂铁二甲酸溶液的浓度为5~25 mg/mL。
优选的，步骤（2）中，乙酸溶液的浓度为6 M。
优选的，步骤（2）中，混合溶液在反应釜中于温度为90~120℃条件下反应的时间为2天。
优选的，步骤（3）中，四氢呋喃和二氯乙烷的混合溶液中四氢呋喃与二氯乙烷的体积比为1:1。
优选的，步骤（3）中，沉淀物在四氢呋喃和二氯乙烷的混合溶液中浸泡时间为10~12 h。
通过上述方法，成功制备了球形Fc-(COOH)2@COFETTA-TPAL纳米复合材料，尺寸均匀，直径约为200 nm。Fc-(COOH)2很好地被装载在COFETTA-TPAL的孔洞中。维持了COFETTA-TPAL的晶体结构，同时保留了Fc-(COOH)2与COFETTA-TPAL的电化学活性。
本发明的技术效果是：通过包裹电活性分子Fc(COOH)2，最终合成了具有球状形貌的Fc-(COOH)2@COFETTA-TPAL纳米复合材料，从而有效避免了二维片层COFETTA-TPAL材料团聚，并将其用于比率电化学传感分析。该复合材料Fc-(COOH)2@COFETTA-TPAL具有一定的催化H2O2的歧化能力，在电化学检测中可代替过氧化物酶，从而实现对H2O2的快速灵敏检测。
附图说明
图1为球形Fc-(COOH)2@COFETTA-TPAL纳米复合材料的扫描电子显微镜图。
图2分别是COFETTA-TPAL(曲线a)和球形Fc-(COOH)2@COFETTA-TPAL(曲线b) 纳米复合材料的X-射线衍射图谱。
图3分别是COFETTA-TPAL(曲线a)和Fc-(COOH)2@COFETTA-TPAL(曲线b)纳米复合材料修饰电极的循环伏安曲线图。
图4是球形Fc-(COOH)2@COFETTA-TPAL纳米复合材料修饰电极检测H2O2的微分脉冲伏安曲线(曲线a：未加H2O2；曲线b：加入50μ M H2O2)图。
具体实施方式
实施例1
（1）将22 mg ETTA（10 mg/mL）、15 mg（6.85 mg/mL） TPAL和11 mg（5 mg/mL）的二茂铁二甲酸溶解于2 mL 1, 4-二氧六环溶剂中，并超声混合15 min；
（2）向混合溶液中加入0.2 mL 6 M的乙酸溶液。将混合液转移到反应釜中置于90℃烘箱中，反应2天；
（3）用N,N-二甲基甲酰胺（DMF）和四氢呋喃（THF）作为溶剂依次对所得沉淀物进行离心，直至上层清液为无色，然后将沉淀物置于THF和二氯乙烷体积比为1:1混合溶液中浸泡10 h，以便更充分地除去沉淀物所吸附的有机单体分子和杂质。最后将沉淀物放在真空冷冻干燥机中干燥24 h后，经过研磨得到土黄色固体Fc-(COOH)2@COFETTA-TPAL复合材料。
实施例2
（1）将30 mg ETTA（13.64 mg/mL）、20.5 mg（9.32 mg/mL）的TPAL和22 mg（10 mg/mL）的二茂铁二甲酸溶解于2 mL的1,4-二氧六环溶剂中，并超声混合15 min；
（2）向混合溶液中加入0.2 mL 6 M乙酸溶液。将混合液转移到反应釜中置于100℃烘箱中，反应2天；
（3）用N,N-二甲基甲酰胺（DMF）和四氢呋喃（THF）作为溶剂依次对所得沉淀物进行离心洗涤，直至上层清液为无色，然后将沉淀物置于THF和二氯乙烷体积比为1:1混合溶液中浸泡11 h，以便更充分地除去沉淀物所吸附的有机单体分子和杂质。最后将沉淀物放在真空冷冻干燥机中干燥24 h后，经过研磨得到土黄色固体Fc-(COOH)2@COFETTA-TPAL复合材料。
实施例3
（1）将33 mg ETTA（15 mg/mL）、22.5 mg TPAL（10.25 mg/mL）和55 mg（25 mg/mL）的二茂铁二甲酸溶解于2 mL 1,4-二氧六环溶剂中，并超声混合15 min；
（2）向混合溶液中加入0.2 mL 6 M乙酸溶液。将混合液转移到反应釜中置于120℃烘箱中，反应2天；
（3）用N, N-二甲基甲酰胺（DMF）和四氢呋喃（THF）作为溶剂依次对所得沉淀物进行离心，直至上层清液为无色，然后将沉淀物置于THF和二氯乙烷体积比为1：1混合溶液中浸泡12 h，以便更充分地除去沉淀物所吸附的有机单体分子和杂质。最后将沉淀物放在真空冷冻干燥机中干燥24 h后，经过研磨得到土黄色固体Fc-(COOH)2@COFETTA-TPAL复合材料。
上述用溶剂热一锅法制备的Fc-(COOH)2@COFETTA-TPAL纳米复合材料为球形，尺寸均匀，直径约为200 nm。Fc-(COOH)2被很好地装载在COFETTA-TPAL的孔洞中。维持了COFETTA-TPAL的晶体结构，同时保留了Fc-(COOH)2与COFETTA-TPAL的电活性性能。
Claims (7)
1.一种Fc-(COOH)2@COFETTA-TPAL纳米复合材料的制备方法，包括以下步骤：
（1）将四-(4-氨基苯)乙烯、对苯二甲醛和二茂铁二甲酸溶解于1,4-二氧六环溶剂中，超声混合，得混合溶液；四-(4-氨基苯)乙烯溶液的浓度为10~15 mg/mL，对苯二甲醛溶液的浓度为6.85~10.25 mg/mL，二茂铁二甲酸溶液的浓度为5~25 mg/mL；
（2）向混合溶液中加入乙酸溶液，再转移到反应釜中在90~120℃条件下反应一段时间；
（3）用N,N-二甲基甲酰胺和四氢呋喃依次作为溶剂对所得沉淀物进行离心洗涤，然后将沉淀物在四氢呋喃和二氯乙烷的混合溶液中浸泡一段时间，沉淀物再进行真空冷冻干燥，并经过研磨得到土黄色固体，即Fc-(COOH)2@COFETTA-TPAL纳米复合材料。
2.根据权利要求1所述的方法，其特征在于：步骤（2）中，乙酸溶液的浓度为6 M。
3.根据权利要求1所述的方法，其特征在于：步骤（2）中，混合溶液在反应釜中反应的时间为2天。
4.根据权利要求1所述的方法，其特征在于：步骤（3）中，四氢呋喃和二氯乙烷的混合溶液中四氢呋喃与二氯乙烷的体积比为1:1。
5.根据权利要求1所述的方法，其特征在于：步骤（3）中，沉淀物在四氢呋喃和二氯乙烷的混合溶液中浸泡时间为10~12 h。
6.根据权利要求1~5任一权利要求所述的方法得到的Fc-(COOH)2@COFETTA-TPAL纳米复合材料。
7.根据权利要求6所述的Fc-(COOH)2@COFETTA-TPAL纳米复合材料在检测H2O2中的应用。
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