CN113248691B - 一种联噻吩线性有机共轭聚合物及其制备方法和应用 - Google Patents
一种联噻吩线性有机共轭聚合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种联噻吩线性有机共轭聚合物及其制备方法和应用，所述聚合物由3,3’‑双((2,5,8,11‑四氧杂环丁烷‑13‑基)氧基)‑2,2'‑联噻吩作为电子受体，与不同的电子供体通过Stille偶联构筑的D‑A型共轭聚合物。该联噻吩线性有机聚合物在水中具有良好的分散性以及具有较大的可见光吸收，能够应用于光催化水制氢。
Description
技术领域
本发明涉及共轭聚合物材料技术领域，更具体地，涉及一种联噻吩线性有机共轭聚合物及其制备方法和应用。
背景技术
近年来，随着社会经济的迅速发展和人口的不断增加，传统的非可再生资源(如石油、天然气和煤炭等)正以极快的速度消耗，资源短缺问题已成为当今世界的重大难题之一。于此同时，传统能源造成的环境污染和生态失衡等一系列问题也极大的限制了全球工业化的发展甚至极大的威胁人类的生存环境，寻找可替代的绿色能源成为全球的研究热点之一。在众多的绿色能源中，新兴能源-氢能以其燃烧产物无污染、优异的稳定性、较高的导热性和发热值等优点，成为当今世界能源舞台上一种举足轻重的能源。
目前，常见的制氢方式包括水解法制氢、水煤气法制氢、石油裂解产氢、光解水产氢等。其中，光解水产氢充分利用太阳能将水分解生成氢气，具有成本低、无二次污染等优点，是一种可循环利用的产氢技术，极大的吸引了研究人员的关注。1972年，首次报告发现TiO2单晶电极紫外光下催化分解水产生氢气，标志着光催化制氢领域的开启。此后，文献(Kawai T,Sakata T.Conversion of carbohydrate into hydrogen fuel by aphotocatalytic process[J].Nature,1980,286:474-476.)报道了线型共轭聚合物聚对苯撑在紫外光区有制氢性能，首个应用于光催化制氢领域的有机共轭聚合物。由于有机共轭材料的结构多样性，使得越来越多的有机共轭聚合物作为光催化剂应用在光解水制氢领域。
发明内容
本发明的目的是提供一种联噻吩线性有机共轭聚合物，所述联噻吩线性有机共轭聚合物能够应用于光催化水制氢。
本发明的另一目的在于提供所述联噻吩线性有机共轭聚合物的制备方法。
本发明的另一目的是提供所述连噻吩线性有机共轭聚合物的应用。
本发明的上述目的通过以下技术方案实现：
一种联噻吩线性有机共轭聚合物，所述共轭聚合物化学结构式如式(Ⅰ)所示：
其中，m为1～10，n为2～10000；
其中
单元选自以下结构式中的任意一种：
其中R是C4～C20的烷基。
本发明所述联噻吩线性有机共轭聚合物由3,3’-双((2,5,8,11-四氧杂环丁烷-13-基)氧基)-2,2'-联噻吩作为电子受体，与不同的电子供体反应得到的线性有机共轭聚合物。所述线性有机共轭聚合物采用苯并双噻吩和并噻吩作为给电子基团，由于其具有良好的平面性，与联噻吩单元构成全平面结构，有利于光催化水产氢过程中催化剂内电荷转移，其次，联噻吩侧链为烷氧基团，使聚合物亲水性增加，提高在催化剂在水中的溶解性，有利于光催化水制氢的速率。
优选地，所述
单元选自以下结构式中的任意一种：
所述
单元为
时，光催化水制氢效果更好。
优选地，所述联噻吩线性有机共轭聚合物的制备方法，包括如下步骤：在惰性气氛下，联噻吩与
单元的单体形成的混合物中加入以三(二亚苄基丙酮)二钯和三(邻甲基苯基)磷作为的催化剂、有机溶剂，加热反应即得线性有机共轭聚合物。
优选地，所述联噻吩与
单元的单体的摩尔比为1:(1～2)。
当所述联噻吩与
单元的单体的摩尔比在这个范围时，效果最好。
优选地，所述联噻吩与催化剂三(二亚苄基丙酮)二钯的摩尔比为1：(0.01～0.1)。
优选地，所述联噻吩与三(邻甲基苯基)磷的摩尔比为1：(0.01～0.2)。
优选地，所述加热反应温度为120～160℃，反应时间为12～60h。
优选地，所述有机溶剂选为氯苯、甲苯或N,N-二甲基甲酰胺中的一种或多种。
一种光催化剂，包含所述联噻吩线性有机共轭聚合物。
所述光催化剂在光催化分解水制氢中的应用。
与现有技术相比，本发明的有益效果是：
本发明所述连噻吩线性有机共轭聚合物由3,3’-双((2,5,8,11-四氧杂环丁烷-13-基)氧基)-2,2'-联噻吩作为电子受体，与不同的电子供体反应得到的线性有机共轭聚合物。由于其具有良好的平面性，与联噻吩单元构成全平面结构，有利于光催化水产氢过程中催化剂内电荷转移，其次，联噻吩侧链为烷氧基团，使聚合物亲水性增加，提高在催化剂在水中的溶解性，有利于光催化水制氢的速率。
附图说明
图1为实施例1～2的光催化剂P1、P2的红外光谱图；
图2为实施例1～2的光催化剂P1、P2的紫外-可见吸收(Uv-vis)光谱图；
图3为实施例1～2中P1、P2的热失重分析图；
图4为实施例1～2中P1、P2的光催化水制氢效率图；
图5为实施例1～2中P1、P2的核磁共振碳谱图。
具体实施方式
为了更清楚、完整的描述本发明的技术方案，以下通过具体实施例进一步详细说明本发明，应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明，可以在本发明权利限定的范围内进行各种改变。
实施例1
聚合物P1的合成
代表性合成路线如下：
聚合物P1的合成：
准确称取单体M1(0.275mmol，0.1419g)和单体M2(0.275mmol，0.2027g)，加入48mL厚壁耐压瓶中，在惰性气体环境下加入10mL甲苯，5wt％钯催化剂，密封。在120℃的条件下避光反应48h。反应液冷却至室温后，滴入不断搅拌的甲醇溶液中，过滤得到粗产物。粗产物依次用100mL甲醇、石油醚、二氯甲烷、氯苯溶剂进行索氏抽提各24h，剩余固体用甲醇冲洗，真空干燥24h，得到固体产物P1，所述P1的m为4，n为500。
本实施例所述光催化剂由共轭聚合物P1组成。
实施例2
聚合物P2的合成
代表性合成路线如下：
聚合物P2的合成：
准确称取单体M3(0.306mmol 0.1425g)和单体M2(0.306mmol 0.2254g)，加入48mL厚壁耐压瓶中，在惰性气体环境下加入10mL甲苯，5wt％的钯催化剂，密封。在120℃的条件下避光反应48h。反应液冷却至室温后，滴入不断搅拌的甲醇溶液中，过滤得到粗产物。粗产物依次用100mL甲醇、石油醚、二氯甲烷、氯苯溶剂进行索氏抽提各24h，剩余物固体用甲醇冲洗，真空干燥24h，得到固体产物P2，所述P2的m为4，n为500。
本实施例所述光催化剂由共轭聚合物P2组成。
实施例3
本实施例的制备方法同实施例1，其主要的区别在于，M1单体替换成D3单体
得到P3共轭聚合物，所述P3的m为4，n为500。
本实施例的光催化剂由共轭聚合物P3组成。
实施例4
本实施例的制备方法同实施例1，其主要的区别在于，M1单体替换成D4单体
得到P4共轭聚合物，所述P4的m为4，n为500。
本实施例的光催化剂由共轭聚合物P4组成。
实施例5
本实施例的制备方法同实施例1，其主要的区别在于，M1单体替换成D5单体
得到P5共轭聚合物，所述P5的m为4，n为500。
本实施例的光催化剂由共轭聚合物P5组成。
实施例6
本实施例的制备方法同实施例1，其主要的区别在于，M1单体替换成D6单体
得到P6共轭聚合物，所述P6的m为4，n为500。
本实施例的光催化剂由共轭聚合物P6组成。
实施例7
本实施例的制备方法同实施例1，其主要的区别在于，共轭聚合物的m为1，n为2。
本实施例的光催化剂由共轭聚合物P7组成。
实施例8
本实施例的制备方法同实施例1，其主要的区别在于，共轭聚合物的m为10，n为100。
本实施例的光催化剂由共轭聚合物P8组成。
实施例9
本实施例的制备方法同实施例1，其主要的区别在于，共轭聚合物的m为10，n为1000。
本实施例的光催化剂由共轭聚合物P9组成。
实施例10
本实施例的制备方法同实施例1，其主要的区别在于，共轭聚合物的m为10，n为10000。
本实施例的光催化剂由共轭聚合物P10组成。
测试表征
上述实施例和对比例均经过性能测试
产氢速率的测试步骤：
称取5mg上述实施例1～6的聚合物，加入50mL抗坏血酸溶液(0.2mol/L)，超声震荡15分钟至聚合物完全分散，使用泊菲莱Labsolar 6A全玻璃自动在线微量气体分析系统测试，在全光谱照射下6小时，得到产氢速率结果，测试结果见表1。
表1实施例1～6所述光催化剂析氢速率(μmol·g-1·h-1)
图1为实施例1～2中P1、P2的红外光谱图。从图1可以看出，该线性有机共轭聚合物均成功制备。
图2为实施例1～2中P1、P2的紫外-可见吸收光谱图。从图2可以看出，该线性有机共轭聚合物在可见光范围内具有良好的吸收。
图3为实施例1～2中P1、P2的热失重分析图。从图3可以看出，该线性有机共轭聚合物具有良好的热力学稳定性。
图4为实施例1～2中P1、P2的光催化水制氢效率图。从图4可以看出，该线性有机共轭聚合物具有一定的光催化水产氢性能。
图5为实施例1～2中P1、P2的核磁共振碳谱图。从图5看，在70ppm处有C-O键的伸缩振动峰，114ppm是联噻吩连接处C-C键的特征峰，137ppm处是C-S键的伸缩振动峰，说明成功合成出目标聚合物。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。
Claims (9)
1.一种联噻吩线性有机共轭聚合物，其特征在于，所述聚合物化学结构式如式(Ⅰ)所述：
其中，m为10，n为10000；
其中
单元结构式为
2.根据权利要求1所述联噻吩线性有机共轭聚合物的制备方法，其特征在于，包括如下步骤：在惰性气氛下，联噻吩与
单元的单体的混合物中加入以三(二亚苄基丙酮)二钯和三(邻甲基苯基)磷作为的催化剂、有机溶剂，加热反应所得即为线性有机共轭聚合物。
3.根据权利要求2所述联噻吩线性有机共轭聚合物的制备方法，其特征在于，所述联噻吩与
单元的单体的摩尔比为1:(1～2)。
4.根据权利要求2所述联噻吩线性有机共轭聚合物的制备方法，其特征在于，所述联噻吩与催化剂三(二亚苄基丙酮)二钯的摩尔比为1:(0.01～0.1)。
5.根据权利要求2所述联噻吩线性有机共轭聚合物的制备方法，其特征在于，所述联噻吩与三(邻甲基苯基)磷的摩尔比为1:(0.01～0.2)。
6.根据权利要求2所述联噻吩线性有机共轭聚合物的制备方法，其特征在于，所述加热反应温度为120～160℃，反应时间为12～60h。
7.如权利要求2所述联噻吩线性有机共轭聚合物的制备方法，其特征在于，所述有机溶剂选为氯苯、甲苯或N,N-二甲基甲酰胺中的一种或多种。
8.一种光催化剂，其特征在于，包含权利要求1所述联噻吩线性有机共轭聚合物。
9.权利要求8所述光催化剂在光催化分解水制氢中的应用。
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