CN112592474B - 一种苯并三噻吩类共价有机框架材料及其制备方法与应用 - Google Patents
一种苯并三噻吩类共价有机框架材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种苯并三噻吩类共价有机框架材料及其制备方法与应用，其是以苯并三噻吩和2,5‑二乙氧基对苯二甲酰肼为反应单体，二甲基亚砜为溶剂，醋酸为催化剂，经冷冻、解冻、抽真空、保温反应，制得所述共价有机框架材料。本发明制备条件温和，操作方便，成本低廉，所得苯并三噻吩类共价有机框架材料具有明确的孔隙、有序的孔道结构、大的表面积及低密度等多种结构特点，将其应用于光催化还原二氧化碳反应中，具有选择性强等优点，在光催化领域具有较大的应用潜力。
Description
技术领域
本发明属于光催化材料制备领域，具体涉及一种苯并三噻吩连接的新型共价有机框架材料及其合成方法与其在光催化二氧化碳还原为一氧化碳中的应用。
背景技术
随着科学技术的发展以及人类生活水平的提高，空气中的二氧化碳含量持续增加，由其导致的温室效应现象加剧引发了一系列的冰川融化，台风、龙卷风持续威力时间加长等气候反常现象，引起了人们环境保护意识的提高。太阳能作为一种取之不尽、用之不竭的能量，在光照下将二氧化碳有选择性的转化成一氧化碳、甲烷这种清洁能源，不仅可以降低化石能源这种不可再生能源的消耗，还可以产生无污染的清洁能源，这对环境及能源发展都是意义非凡的。
发明内容
针对现有无机半导体材料在光催化领域的局限性，本发明提供了一种制备简单方便，成本低廉，具有良好的经济效益以及环境效益的苯并三噻吩类新型共价有机框架及其制备方法，该材料可在光照下选择性将二氧化碳还原为一氧化碳。
为实现上述目的，本发明采用如下技术方案：
一种苯并三噻吩类共价有机框架材料（BTT-COF），其是由苯并三噻吩和2,5-二乙氧基对苯二甲酰肼基团重复连接构成；其具体单元结构式为：
所述苯并三噻吩类共价有机框架材料的制备方法，是以苯并三噻吩和2,5-二乙氧基对苯二甲酰肼为反应单体，二甲基亚砜为溶剂，醋酸为催化剂，将其共同置于玻璃试管中，先在液氮浴中快速冷冻后解冻，抽真空，以除去玻璃试管中的氧气，再用火焰密封玻璃试管，避免氧气在反应过程中对胺基原料的氧化副反应，然后将玻璃试管升温至80℃-120℃，保温反应3-5天，得到所述共价有机框架材料BTT-COF。
其中，所用苯并三噻吩和2,5-二乙氧基对苯二甲酰肼的摩尔比为3:2。
所述醋酸的浓度为3～6mol/L。
在光照条件下、二氧化碳气氛中，将所得苯并三噻吩类共价有机框架材料与其用量10-20wt%的金属配合物在有机溶剂中搅拌超声2~5分钟，使其活性位点与金属离子结合，进而可高选择性的将二氧化碳光催化还原为一氧化碳。所适用的金属配合物如Ni[(ClO)4]2。
本发明的有益效果在于：
1）本发明通过使用苯并三噻吩和2,5-二乙氧基对苯二甲酰肼为反应单体，在二甲基亚砜/醋酸水溶液体系下经反应得到一种以亚胺连接的新型共价有机框架材料，该材料具有较多微孔结构与杂原子，可与金属离子配合，实现高效光催化还原二氧化碳。
2）本发明所用到的设备和化学试剂易于获取，工艺操作简便，适用性强，工业应用价值高，易于推广利用。
附图说明
图1为本发明制备BTT-COF的合成工艺示意图；
图2为实施例1所用苯并三噻吩及所制备的BTT-COF的X射线粉末衍射图；
图3为实施例1所用苯并三噻吩、2,5-二乙氧基对苯二甲酰肼和所制备BTT-COF的傅里叶变换红外光谱图；
图4为实施例1所制备BTT-COF的氮气吸附曲线；
图5为实施例1所制备BTT-COF光催化还原CO2的产量随时间变化情况图。
具体实施方式
为了使本发明的目的、技术方案及优势更加清楚明白便于理解，以下结合实施例，对本发明进行进一步详细说明。可以理解，此处所描述的具体实施仅用于解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以结合。
实施例1
将苯并三噻吩（13.22mg，0.02 mmol）和2,5-二乙氧基对苯二甲酰肼（16.92 mg，0.063mmol）置于Pyrex玻璃试管中（体积约5 mL、长20 cm、直径1 cm），加入0.8 mL的无水二甲基亚砜，超声处理1分钟使其分散均匀，然后加入0.3 mL的6 M乙酸后，将Pyrex玻璃试管在液氮浴中快速冷冻并解冻，抽真空三次，以除去氧气，并进行火焰密封，然后升至室温后，将Pyrex玻璃试管置于120 ℃的烘箱中反应3天，反应结束后抽滤收集沉淀物，分别用DMF、甲醇、二氯甲烷洗涤三次，所得黄色粉末60℃真空干燥过夜，即得共价有机框架材料BTT-COF。
图2为所用苯并三噻吩和所制备BTT-COF的X射线粉末衍射图。由图中可以观察到，共价有机框架材料中单体的特征衍射峰消失，并在2.7度出现（100）晶面特征峰，说明共价有机框架材料的成功合成。
图3为所用苯并三噻吩、2,5-二乙氧基对苯二甲酰肼和所制备BTT-COF的红外光谱图。由图中结果显示，在1600 cm-1处出现的特征峰归属于共价有机框架中的C=N基团，表明共价有机框架材料的成功合成。
图4为所制备BTT-COF的氮气吸附曲线，由图中可知，所制备BTT-COF的BET比表面积达到426平方米/克。
实施例2
称取10 mg实施例1制备的BTT-COF，加入2mg Ni[(ClO)4]2和15 mg 2,2'-联吡啶，一并投入石英玻璃反应器中，再加入5 mL乙腈/水/三乙醇胺（3:1:1 v/v/v）混合溶液。将反应器抽真空后，通入CO2并保持通气15分钟，使反应器充满CO2并密封。用300 W氙灯模拟可见光，在303~323 K下照射反应器4小时，每间隔1小时用气密注射器（100 μL）采集反应器中生成的气体。用岛津GC-2014气相色谱对气体成分进行检测，并根据CO和H2的含量绘制BTT-COF光催化还原CO2的性能-时间曲线。
结果显示，10 mg BTT-COF在光照条件下处理4小时，其CO产量可以达到880微摩尔，表明其具有良好的催化效率。
尽管本发明的内容已经通过上述优选实施例作了详细介绍，但应当认识到上述的描述不应该被认为是对本发明的限制。在本领域技术人员阅读了上述内容后，对于本发明的多种修改和替代都是显而易见的。因此，本发明的保护范围应由所附的权利要求来限定。
Claims (3)
1.一种苯并三噻吩类共价有机框架材料在光催化还原二氧化碳中的应用，其特征在于：所述共价有机框架材料是由苯并三噻吩和2,5-二乙氧基对苯二甲酰肼基团重复连接构成；其具体单元结构式为：
其是以苯并三噻吩和2,5-二乙氧基对苯二甲酰肼为反应单体，二甲基亚砜为溶剂，醋酸为催化剂，将其共同置于玻璃试管中，先在液氮浴中快速冷冻后解冻，抽真空，以除去氧气，再用火焰密封玻璃试管，然后将玻璃试管升温至80℃-120℃，保温反应3-5天，得到所述共价有机框架材料；
其应用方法是在光照条件下、二氧化碳气氛中，将所得苯并三噻吩类共价有机框架材料与其用量10-20wt%的金属配合物在有机溶剂中搅拌超声2~5分钟，使其活性位点与金属离子结合，进而高选择性的将二氧化碳光催化还原为一氧化碳，所适用的金属配合物为Ni[(ClO)4]2。
2.根据权利要求1所述的应用，其特征在于：所用苯并三噻吩和2,5-二乙氧基对苯二甲酰肼的摩尔比为3:2。
3.根据权利要求1所述的应用，其特征在于：所述醋酸的浓度为3～6mol/L。
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