CN112159517B - 朝格尔碱基共轭微孔聚合物光催化剂及其制备方法和应用 - Google Patents
朝格尔碱基共轭微孔聚合物光催化剂及其制备方法和应用 Download PDFInfo
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- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 12
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Abstract
本发明公开了一种朝格尔碱基共轭微孔聚合物及其制备方法，该材料以二碘代朝格尔碱以及咔唑或芳香族二炔、三炔化合物为原料，通过氧化偶联或Sonogashira偶联共聚反应制备而成。该共轭微孔聚合物具有V型刚性骨架结构，物理、化学稳定性高，气体吸附能力强，比表面积大，可见光吸收能力强，可应用于光催化污染物降解、水分解和CO2还原领域。
Description
技术领域
本发明属于光电功能材料技术领域，具体涉及一种朝格尔碱基共轭微孔聚合物、制备方法及其光催化应用。
背景技术
共轭微孔聚合物的有机骨架完全由苯环、碳-碳三键以π电子共轭形式连接，为其在光电、储能和传感等领域的应用提供了基础。自2007年Cooper报道了第一个基于聚芳炔的共轭微孔聚合物至今，众多具有不同结构和性质的共轭微孔聚合物被不断地开发出来。虽然该类材料不具有长程序性，由于其合成的反应条件比较温和，非常适合使用功能化单体构建功能化的新型共轭微孔聚合物，通过改变共轭结构之间链接的长度或共轭单体的构型可以有效实现孔结构与比表面积的调节。专利CN110394187A公开了一种氮、铁掺杂共轭微孔碳材料的制备方法及其应用，该材料制备简单，便于控制，具有较好的氧还原催化活性。然而，该材料主要用作燃料电池正极，且以金属元素为催化活性位点。专利CN109942570A公开了一种基于吩噻嗪的共轭微孔聚合物，并将该材料用于吲哚的光催化有氧硒化，但该共轭微孔聚合物主要体现为紫外吸收，对可见光的吸收利用不足。
发明内容
本发明的目的是提供一种朝格尔碱基共轭微孔聚合物及其制备方法，该聚合物制备工艺简单，结构可控，具有较高的比表面积和良好的可见光响应性，可应用于光催化污染物降解、水分解、CO2还原转换等多个领域。
实现本发明目的的技术解决方案是：一种朝格尔碱基共轭微孔聚合物，具有式I或II结构：
其中，
为以下结构
较佳的，所述的朝格尔碱基共轭微孔聚合物，其特征在于，所述的聚合物是粉末状，孔径分布范围主要在0.5～2nm。
较佳的，具有式I结构的朝格尔碱基共轭微孔聚合物的制备方法：配置0.1～0.2mol/L的二碘代朝格尔碱的N，N-二甲基甲酰胺溶液，以二碘代朝格尔碱与咔唑的摩尔比为1:4，将咔唑加入上述二碘代朝格尔碱溶液，以二碘代朝格尔碱与碳酸钾，碘化亚铜和1,10-菲咯啉的摩尔比为100:400:10:1，将碳酸钾，碘化亚铜和1,10-菲咯啉分散入上述溶液，氮气保护，150℃反应24h，冷却至室温，除去溶剂，通过柱层析(乙酸乙酯/石油醚＝1:3)纯化产物，得到咔唑基共轭微孔聚合物单体。配置0.009～0.01mol/L的咔唑基共轭微孔聚合物单体的氯仿溶液，以咔唑基共轭微孔聚合物单体与FeCl3的摩尔比为1:10，将FeCl3加入到上述咔唑基共轭微孔聚合物单体的氯仿溶液中，氮气保护，60℃反应24h，然后向反应混合物中加入50mL甲醇，所得混合物再搅拌1小时，过滤收集沉淀物，依次用甲醇，二氯甲烷和丙酮洗涤。将该沉淀物用盐酸处理2小时，过滤，并依次用水、甲醇，二氯甲烷和丙酮洗涤。采用甲醇和四氢呋喃的混合溶液进行索氏提取，纯化24h，干燥，得到共轭微孔聚合物。
较佳的，具有式I结构的朝格尔碱基共轭微孔聚合物的制备方法：以N,N-二甲基甲酰胺和三乙胺体积比1:1的混合溶剂为介质，配置0.1～0.15mol/L的二碘代朝格尔碱溶液，以二碘代朝格尔碱与1,3,5-三乙炔基苯的摩尔比为1.5:1，加入三炔基单体，以二碘代朝格尔碱与Pd(pph3)4和CuI的摩尔比为30:1:1，将Pd(pph3)4和CuI分散入上述溶液，氮气保护下，80℃反应24h，进行Sonogashira偶联反应，收集反应后的沉淀物，将沉淀物在盐酸中搅拌1h，水洗，再在丙酮，甲苯，甲醇的混合溶液中搅拌1h，干燥，用甲醇和四氢呋喃的混合溶液进行索氏提取，得到共轭微孔聚合物。
较佳的，具有式II结构的朝格尔碱基共轭微孔聚合物的制备方法：以N,N-二甲基甲酰胺和三乙胺体积比1:1的混合溶剂为介质，配置0.1～0.15mol/L的二碘代朝格尔碱溶液，以二碘代朝格尔碱与1,4-二乙炔基苯的摩尔比为1.5:1，加入二炔基单体，以二碘代朝格尔碱与Pd(pph3)4和CuI的摩尔比为30:1:1，将Pd(pph3)4和CuI分散入上述溶液，氮气保护下，80℃反应24h，进行Sonogashira偶联反应，收集反应后的沉淀物，将沉淀物在盐酸中搅拌1h，水洗，再在丙酮，甲苯，甲醇的混合溶液中搅拌1h，干燥，用甲醇和四氢呋喃的混合溶液进行索氏提取，得到共轭微孔聚合物。
本发明还提供了上述朝格尔碱基共轭微孔聚合物的应用，所述的共轭微孔聚合物应用于光催化CO2还原反应中。
与现有技术相比，本发明的有益效果是：
(1)本发明的共轭微孔聚合物基于具有V型骨架结构的朝格尔碱，具有较大的比表面积和良好的物理、化学稳定性。
(2)本发明的基于朝格尔碱的共轭微孔聚合物具有优异的CO2吸附能力，在光催化CO2还原转换中，具有较高的反应物吸附和活化能力。
(3)本发明的基于朝格尔碱的共轭微孔聚合物具有较窄带隙，可见光吸收能力强，因此具有较大的应用潜力。
下面结合附图对本发明作进一步详细描述。
附图说明
图1为实施例1所制备共轭微孔聚合物的红外光谱图。
图2为实施例1所制备共轭微孔聚合物的13C固体核磁谱图。
图3为实施例1所制备共轭微孔聚合物的光催化CO2还原性能。
图4为实施例1所制备共轭微孔聚合物的扫描电镜图。
图5为实施例2所制备共轭微孔聚合物的红外光谱图。
图6为实施例2所制备共轭微孔聚合物的13C固体核磁谱图。
图7为实施例2所制备共轭微孔聚合物的光催化CO2还原性能。
图8为实施例3所制备共轭微孔聚合物的红外光谱图。
图9为实施例3所制备共轭微孔聚合物的13C固体核磁谱图。
图10为实施例3所制备共轭微孔聚合物的光催化CO2还原性能。
图11为实施例3所制备共轭微孔聚合物的紫外-可见漫反射光谱。
具体实施方式
下面的实施例可以使本专业技术人员更全面地理解本发明。
朝格尔碱是一个有百年研究历史的化合物，其衍生物都具有类似的V型分子框架，分子中心为亚甲基二氮芳辛桥，芳香烃分别连接在二氮芳辛桥中心两侧。之前，人们对朝格尔碱的关注主要集中于分子识别，手性催化、主客体化学等方面。最近，朝格尔碱骨架在电子转移、推拉方面的效应被应用于新型固态荧光和非线性光学活性材料，其V型刚性结构被用于多孔有机聚合物的构建。此外，由于氮元素存在而带来的碱性特质，朝格尔碱基材料在CO2分离和储存方面显示出巨大优势。因此，将朝格尔碱结构引入聚合物骨架，协同共轭基元扩展构筑共轭微孔聚合物，将在光催化污染物降解、分解水产氢产氧、CO2还原转换等领域发挥巨大应用价值。
实施例1
本实施例的反应方程式如下：
将2.369g二碘代朝格尔碱(5.0mmol)溶于40mL无水N，N-二甲基甲酰胺，依次加入3.344g咔唑(20mmol)，2.764g碳酸钾(20mmol)，0.095g碘化亚铜(0.5mmol)和0.009g 1,10-菲咯啉(0.05mmol)，氮气保护，150℃反应24h。冷却至室温，除去溶剂，通过柱层析(乙酸乙酯/石油醚＝1:3)纯化产物，得到淡棕色咔唑基共轭微孔聚合物单体。
将0.203g(0.367mmol)咔唑基共轭微孔聚合物单体分散在25mL无水氯仿中，然后加入0.595g(3.67mmol)氯化铁，氮气保护下，60℃反应24h。然后向反应混合物中加入50mL甲醇，所得混合物再搅拌1小时，过滤收集沉淀物，依次用甲醇，二氯甲烷和丙酮洗涤。将该沉淀物用盐酸处理2小时，过滤，并依次用水、甲醇，二氯甲烷和丙酮洗涤。采用甲醇和四氢呋喃的混合溶液进行索氏提取，纯化24h。干燥，得到土黄色粉末状共轭微孔聚合物。
图1为实施例1所制备的共轭微孔聚合物的红外光谱图。其中在1318cm-1和1060cm-1处为环外C-N的伸缩振动吸收峰，此为朝格尔碱结构中桥联结构上的碳氮键，1400-1720cm-1为共轭微孔聚合物结构中苯环骨架的特征吸收峰。
图2为实施例1所制备共轭微孔聚合物的13C固体核磁谱图。在58ppm处为中间桥联骨架上C-N键的出峰位置，表明结构中朝格尔碱的存在，在128ppm处为咔唑上苯环结构的三取代基的位置，表明材料的成功聚合。
图3为实施例1所制备共轭微孔聚合物的光催化CO2还原性能。6h的产量为424μmolg-1h-1。
图4为实施例1所制备共轭微孔聚合物的扫描电镜图，可以看出微观结构为絮状结构。
实施例2
本实施例的反应方程式如下：
以20ml N,N-二甲基甲酰胺和20ml三乙胺混合溶液为反应介质，加入0.356g二碘代朝格尔碱(0.75mmol)，0.075g 1,3,5-三乙炔基苯(0.5mmol)，0.029g Pd(pph3)4(0.025mmol)和0.005g CuI(0.025mmol)，氮气保护下，80℃反应24h。收集反应后的沉淀物，将沉淀物在盐酸溶液中搅拌1h后，水洗，再在丙酮，甲苯，甲醇的混合溶液中搅拌1h，干燥，用甲醇和四氢呋喃的混合溶液进行索氏提取，得到黄色粉末状共轭微孔聚合物。
图5为实施例2所制备共轭微孔聚合物的红外光谱图。其中在1316cm-1和1097cm-1处为环外C-N的伸缩振动吸收峰，此为朝格尔碱结构中桥联结构上的碳氮键，1400-1720cm-1为共轭微孔聚合物结构中苯环骨架的特征吸收峰,在2190cm-1处为结构中炔基的特征峰。
图6为实施例2所制备共轭微孔聚合物的13C固体核磁谱图。在57ppm与65ppm处为中间桥联骨架上C-N键的出峰位置，表明结构中朝格尔碱的存在，在87ppm处为咔唑上苯环结构的三取代基的位置。
图7为实施例2所制备共轭微孔聚合物的光催化CO2还原性能。6h的产量为761μmolg-1h-1。
实施例3
本实施例的反应方程式如下：
以20ml N,N-二甲基甲酰胺和20ml三乙胺混合溶液为反应介质，加入0.356g二碘代朝格尔碱(0.75mmol)，0.063g 1,4-二乙炔基苯(0.5mmol)，0.029g Pd(pph3)4(0.025mmol)和0.005g CuI(0.025mmol)，氮气保护下，80℃反应24h。收集反应后的沉淀物，将沉淀物在盐酸溶液中搅拌1h后，水洗，再在丙酮，甲苯，甲醇的混合溶液中搅拌1h，干燥，用甲醇和四氢呋喃的混合溶液进行索氏提取，得到黄色粉末状共轭微孔聚合物。
图8为实施例3所制备共轭微孔聚合物的红外光谱图。其中在1316cm-1和1097cm-1处为环外C-N的伸缩振动吸收峰，此为朝格尔碱结构中桥联结构上的碳氮键，1400-1720cm-1为共轭微孔聚合物结构中苯环骨架的特征吸收峰,在2190cm-1处为结构中炔基的特征峰。
图9在57ppm与65ppm处为中间桥联骨架上C-N键的出峰位置，表明结构中朝格尔碱的存在，在89ppm处为咔唑上苯环结构的三取代基的位置。
图10为实施例3所制备共轭微孔聚合物的光催化CO2还原性能。6h的产量为346μmol g-1h-1。
图11为实施例3所制备共轭微孔聚合物的紫外-可见漫反射光谱，该材料在波长200-650nm之间都有良好的吸收，吸收范围延伸到可见光区域。
Claims (6)
1.一种朝格尔碱基共轭微孔聚合物，其特征在于，具有式I结构：
其中，
为以下结构
2.一种如权利要求1所述的朝格尔碱基共轭微孔聚合物，其特征在于，所述的聚合物是粉末状，孔径分布范围主要在0.5～2nm。
3.一种如权利要求1所述的朝格尔碱基共轭微孔聚合物的制备方法，其特征在于，包括：
(1)以碘化亚铜为催化剂，碱性条件下，将二碘代朝格尔碱与咔唑发生取代反应制备单体III的步骤，
(2)以FeCl3为催化剂，将单体III发生氧化偶联自聚反应制备目标产物的步骤，
4.如权利要求3所述的方法，其特征在于，步骤(1)中，二碘代朝格尔碱与咔唑的摩尔比为1:4；二碘代朝格尔碱与碘化亚铜的摩尔比为10：1；反应温度为150℃，反应在氮气保护下进行。
5.如权利要求3所述的方法，其特征在于，步骤(2)中，单体与FeCl3的摩尔比为1:10；
反应温度为60℃，反应在氮气保护下进行。
6.一种如权利要求1所述的朝格尔碱基共轭微孔聚合物在光催化还原CO2中的应用。
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