CN112321744B - 海藻酸钠-类酞菁光敏剂、光催化复合材料及其制备方法和应用 - Google Patents
海藻酸钠-类酞菁光敏剂、光催化复合材料及其制备方法和应用 Download PDFInfo
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 56
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Abstract
本发明属于光催化材料技术领域，公开了海藻酸钠‑类酞菁光敏剂、光催化复合材料及其制备方法和应用。所述光敏剂为磷类酞菁与海藻酸钠以化学键酯基链接的海藻酸钠‑磷类酞菁二元分子光敏剂，所述海藻酸钠‑磷类酞菁二元分子光敏剂和聚丁烯‑芳纶纤维相互作用制备得到了聚丁烯‑芳纶光催化复合材料。本发明提供的复合材料，成本低，磷类酞菁的合成路线简单产率高、原料对环境友好；并且所述光敏剂和光催化材料能在光降解有机污染物的同时，利用海藻酸钠凝胶的特性吸附无机重金属离子。
Description
技术领域
本发明属于光催化材料技术领域，特别涉及海藻酸钠-类酞菁光敏剂、光催化复合材料及其制备方法和应用。
背景技术
为了应对日益严峻的海洋污染事故，开发纳米材料作为光催化剂，在自然光源下对污染物进行光降解，是一种在自然水体中适宜的污染物处置方法。
已有大量的文献或专利报道了各种复合纳米光催化剂，能够对污染物产生光降解，比如中国专利申请202010316341.5公开了一种掺杂有石墨烯和氧化铁纳米粒子的聚丙烯纤维的制备方法，可以用于处理污水中的有机污染物和微生物；中国专利申请201710533592.7公开了一种基于石墨烯-酞菁光敏剂的聚丙烯光催化材料，实现了光催化剂的材料化，但其中的石墨烯-酞菁光敏剂合成路线复杂，产率低，且不能对无机重金属进行有效吸附。上述专利申请中的光催化剂或光催化材料大部分需要添加石墨烯等碳纳米材料，其光催化效果受到纳米材料的结构形态影响，而海洋污染物通常处于复杂环境，这不利于发挥这些材料的效能；另一个限制是石墨烯和碳纳米管等纳米材料的工业化产能有限，成本高，这造成上述材料实际上无法进入到应用中。
再比如中国专利申请201910126835.4和201811046804.X公开了一种包裹石墨烯纳米材料的海藻酸钠凝胶球作为光催化剂，中国专利申请201410277219.6公开了一种将酞菁包裹在海藻酸钙内形成凝胶的方法，但上诉技术都仅仅是一种物理包裹，并未涉及到酞菁分子与海藻酸盐的化学键链接，其产品稳定性容易受到工艺条件的影响，该技术方案也未将其与合适的吸附材料结合制备成可在海洋水体中应用的光催化材料。而且酞菁是一类重要的光敏剂分子，可以在自然阳光的照射下敏化产生单线态氧等活性氧分子，活性氧分子具有强氧化性可以氧化大部分有机污染物为无毒小分子物质，但大部分酞菁光敏剂分子需要重金属的中心原子来加强旋轨耦合效应以此提高光敏化效能。因此，提供高分子结构稳定态的光敏剂和光催化复合材料，提高其光敏化效率，同时可以有效的吸附铅汞等重金属污染物，具有重要意义。
发明内容
为了解决现有技术中的光催化剂结构稳定态差、光敏化效率低以及不能有效的吸附铅汞等重金属污染物的问题，本发明提供了一种海藻酸钠-类酞菁光敏剂。
为了解决上述技术问题，本发明采用以下技术方案：
海藻酸钠-类酞菁光敏剂，所述光敏剂为磷类酞菁与海藻酸钠以化学键酯基链接的海藻酸钠-磷类酞菁二元分子光敏剂；所述二元分子光敏剂的结构式下所示：
其中，结构式中的R为COOH或者H，聚合度n＝100-10000。
作为优选，海藻酸钠-类酞菁光敏剂的制备方法如下，以DMAP为脱水剂，海藻酸钠与羧基磷类酞菁按照特定重量比例混合于吡啶中，在反应温度100-150℃下反应2-6h，得到海藻酸钠-磷类酞菁光敏剂二元分子光敏剂。
其中，所述海藻酸钠的G/M比为1:1-3，其分子量10-30KDa；所述海藻酸钠与羧基磷类酞菁按照0.1-10％的重量比混合与吡啶中；所述DMAP与所述羧基磷类酞菁的摩尔比1:1。
作为优选，所述羧基磷类酞菁的制备方法如下：以钼酸铵为催化剂，偏苯三酸酐或均苯四甲酸，金属锂片在尿素中熔融反应4-8h，制备得到羧基取代的无金属酞菁；所述无金属酞菁和三溴化磷在吡啶溶剂中回流反应4-10h，制备得到羧基磷类酞菁光敏剂；
更为优选地，所述偏苯三酸酐或均苯四甲酸，与金属锂片、尿素的摩尔比2-3:1:20；所述钼酸铵的摩尔分数为0.1-1％；所述无金属酞菁和三溴化磷的摩尔比1:1-1.5。
1)但大部分酞菁光敏剂分子需要重金属的中心原子来加强旋轨耦合效应以此提高光敏化效能，本发明选用的磷类酞菁不含有重金属原子，对环境更加友好；海藻酸钠高分子结构中含有大量的羟基和羧基，因此可以和羧基取代的磷类酞菁以氢键的形式牢固结合，这种海藻酸钠-磷类酞菁结构中，可以通过海藻酸钠的高分子结构稳定酞菁分子的光化学激发态，提高其光敏化效率，光解有机污染物，同时海藻酸钠在海水中遇到钙镁离子可以迅速形成凝胶，这种凝胶依靠静电和络合作用可以有效的吸附铅汞等重金属污染物。因此，本发明提供的能在光降解有机污染物的同时，利用海藻酸钠凝胶的特性吸附无机重金属离子。
本发明的另一个发明目的是，提供聚丁烯-芳纶光催化复合材料，使上述海藻酸钠-磷类酞菁光敏剂制备而成的水凝胶分子进入溶胀的聚丁烯-芳纶纤维的缝隙中，缝隙收缩后海藻酸钠-磷类酞菁分子固定在聚丁烯-芳纶纤维表面，得到聚丁烯-芳纶光催化复合材料。
作为优选，将所述海藻酸钠-磷类酞菁光敏剂制备成质量分数为1-5％的水溶胶，将聚丁烯-芳纶纤维在其中加热到60-90℃，维持此温度4-8小时，使得海藻酸钠-磷类酞菁凝胶分子进入因溶胀造成的聚丁烯-芳纶纤维束的缝隙中，冷却干燥后，缝隙收缩即可将海藻酸钠-磷类酞菁分子固定在聚丁烯-芳纶纤维表面，制得聚丁烯-芳纶光催化复合材料。
本发明提供的海藻酸钠-磷类酞菁光敏剂在所述聚丁烯-芳纶纤维上的负载量为1-100克/每平方米。
本发明的最后一个发明目的是，将聚丁烯-芳纶光催化复合材料应用在降解海洋水体中泄漏的有害污染物中。具体的，所述有害污染物可以包括可被单线态氧等氧化剂氧化降解的有机污染物、重金属离子及其化合物，因此本发明所提供的聚丁烯-芳纶光催化吸附材料可以在处置海洋等水体表面有机/无机污染物方面中加以应用。
本发明提供了海藻酸钠-类酞菁光敏剂、光催化复合材料及其制备方法和应用；所述光敏剂为磷类酞菁与海藻酸钠以化学键酯基链接的海藻酸钠-磷类酞菁二元分子光敏剂，所述海藻酸钠-磷类酞菁二元分子光敏剂和聚丁烯-芳纶纤维相互作用制备得到了聚丁烯-芳纶光催化复合材料。本发明提供的制备方法，成本低，磷类酞菁的合成路线简单产率高，具备工业化生产的条件，整体材料的成本降低，具备实际应用价值；光敏剂及光催化材料中不含有其他纳米催化剂中常见的Ti/Sn等金属离子，对环境友好；并且所述光敏剂和光催化材料能在光降解有机污染物的同时，利用海藻酸钠凝胶的特性吸附无机重金属离子。
附图说明
图1为实施例2制备的海藻酸钠-磷类酞菁光敏剂和实施例3制备的海藻酸钠-磷类酞菁光敏剂的Uv-vis光谱图；
图2为实施例5制备的海藻酸钠-磷类酞菁光催化复合材料在模拟水体中对Pb2+(a)和4-氯酚(b)的降解效率图。
具体实施方式
本发明公开了海藻酸钠-类酞菁光敏剂、光催化复合材料及其制备方法和应用。本领域技术人员可以借鉴本文内容，适当改进工艺参数实现。特别需要指出的是，所有类似的替换和改动对本领域技术人员来说是显而易见的，它们都被视为包括在本发明当中。本发明的方法及应用已经通过较佳实施例进行了描述，相关人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和应用进行改动或适当变更与组合，来实现和应用本发明技术。
为了使本领域技术人员能够更好的理解本发明，下面结合具体实施方式对本发明作进一步的详细说明。
实施例1海藻酸钠-磷类酞菁光敏剂及其制备方法
海藻酸钠-类酞菁光敏剂，所述光敏剂为磷类酞菁与海藻酸钠以化学键酯基链接的海藻酸钠-磷类酞菁二元分子光敏剂；所述二元分子光敏剂的结构式下所示：
其中，R为COOH或者H，聚合度n＝100-10000。
所述海藻酸钠-磷类酞菁二元分子光敏剂的制备方法如下：
偏苯三酸酐，金属锂条在尿素(三者摩尔比2:1:20)中熔融反应4h，加入摩尔分数为0.1％的钼酸铵为催化剂，反应冷却后将反应物溶解在15％的NaOH中，释放出多余的氨，然后过滤，将滤液用HCl酸化到pH1，搅拌2h，析出四羧基无金属酞菁，反应收率约85％；四羧基无金属酞菁和三溴化磷(两者的摩尔比1:1)在吡啶溶剂中回流6h，反应结束后以碱液破坏掉过量的三溴化磷并使羧基磷类酞菁溶解，过滤后，以HCl将滤液酸化到pH1，使四羧基磷类酞菁析出，反应收率约60％；海藻酸钠(G/M比1:3，分子量20KDa)与0.1％的四羧基磷类酞菁混合于20倍重量的吡啶中，以DMAP为脱水剂，100℃反应6h，反应结束后首先蒸出吡啶，DMAP与四羧基磷类酞菁摩尔比为1:1，然后以碱溶液溶解产物，过滤后造粒干燥，制备出四羧基磷类酞菁二元分子光敏剂，产率约70％。
实施例2海藻酸钠-磷类酞菁光敏剂的制备方法
偏苯三酸酐，金属锂条在尿素(三者摩尔比2.5:1:20)中熔融反应6h，加入摩尔分数为0.5％的钼酸铵为催化剂，反应冷却后将反应物溶解在15％的NaOH中，释放出多余的氨，然后过滤，将滤液用HCl酸化到pH1，搅拌2h，析出四羧基无金属酞菁，反应收率约85％；四羧基无金属酞菁和三溴化磷(两者摩尔比1:1.2)在吡啶溶剂中回流8h，反应结束后以碱液破坏掉过量的三溴化磷并使羧基磷类酞菁溶解，过滤后，以HCl将滤液酸化到pH1，使四羧基磷类酞菁析出，反应收率约70％；海藻酸钠(G/M比1:3，分子量20KDa)与0.5％的四羧基磷类酞菁混合于20倍重量的吡啶中，以DMAP为脱水剂，DMAP与四羧基磷类酞菁按摩尔比1:1添加，120℃反应4h，反应结束后首先蒸出吡啶，然后以碱溶液溶解产物，过滤后造粒干燥，制备出四羧基磷类酞菁二元分子光敏剂，产率约80％。
实施例3海藻酸钠-磷类酞菁光敏剂的制备方法
均苯四甲酸，金属锂条在尿素(三者的摩尔比3:1:20)中熔融反应8h，加入摩尔分数为1％的钼酸铵为催化剂，反应冷却后将反应物溶解在15％的NaOH中，释放出多余的氨，然后过滤，将滤液用HCl酸化到pH1，搅拌2h，析出八羧基无金属酞菁，反应收率约70％；八羧基无金属酞菁和三溴化磷(两者的摩尔比1:1.5)在吡啶溶剂中回流10h，反应结束后以碱液破坏掉过量的三溴化磷并使羧基磷类酞菁溶解，过滤后，以HCl将滤液酸化到pH1，使八羧基磷类酞菁析出，反应收率约60％；海藻酸钠(G/M比1:3，分子量20KDa)与1％的八羧基磷类酞菁混合于20倍重量的吡啶中，以DMAP为脱水剂，DMAP与八羧基磷类酞菁按摩尔比1:1添加，150℃反应2h，反应结束后首先蒸出吡啶，然后以碱溶液溶解产物，过滤后造粒干燥，制备出海藻酸钠-八羧基磷类酞菁二元分子光敏剂，产率约80％。
实施例2制备的海藻酸钠-磷类酞菁光敏剂(a，DMSO溶液中测试)和实施例3制备的海藻酸钠-磷类酞菁光敏剂(b纤维表面的漫反射测试)的Uv-vis光谱图见图1所示，图1显示，在纤维表面670nm处有二元分子中酞菁的的典型Q带吸收峰，其位置和形状与溶液中的纯二元分子的Q带吸收峰基本相同，表明二元分子光催化剂已经稳定完好的结合在纤维材料表面。
实施例4光催化复合材料的制备
将实施例1制备的海藻酸钠-四羧基磷类酞菁光敏剂50克在搅拌下缓缓加入5L水中，搅拌1小时，加热到60℃后，加入1m2面积的聚丁烯-芳纶纤维(厚度5-10mm，单重25-50克)，使聚丁烯-芳纶纤维完全浸没，搅拌方式改为底层，每分钟2-5转，保持60℃4小时后，将聚丁烯-芳纶纤维提出，离心沥掉多余的海藻酸钠-四羧基磷类酞菁光敏剂溶胶，降温冷却到室温冷却6小时，然后在80℃下干燥定型，即可得到海藻酸钠-四羧基磷类酞菁光催化复合吸附材料，经重量法测试，负载海藻酸钠-四羧基磷类酞菁光敏剂约5克/平方米。
实施例5光催化复合材料的制备
将实施例2制备的海藻酸钠-四羧基磷类酞菁光敏剂150克在搅拌下缓缓加入5L水中，搅拌1小时，加热到80℃后，加入1m2面积的聚丁烯-芳纶纤维(厚度5-10mm，单重25-50克)，使聚丁烯-芳纶纤维完全浸没，搅拌方式改为底层，每分钟2-5转，保持80℃6小时后，将聚丁烯-芳纶纤维提出，离心沥掉多余的海藻酸钠-四羧基磷类酞菁光敏剂溶胶，降温冷却到室温冷却6小时，然后在80℃下干燥定型，即可得到海藻酸钠-四羧基磷类酞菁光催化复合吸附材料，经重量法测试，负载海藻酸钠-四羧基磷类酞菁光敏剂约10克/平方米。将上述海藻酸钠-磷类酞菁光催化复合材料在模拟水体中对Pb2+(a)和4-氯酚(b)的降解效率见图2，图2显示，在6小时内，光催化材料对Pb2+离子的吸附率接近90％，8小时内光催化材料对4-氯酚的降解效率可达90％，这表明了其对重金属和酚类均有良好的降解吸附能力。
实施例6光催化复合材料的制备
将实施例3制备的海藻酸钠-八羧基磷类酞菁光敏剂250克在搅拌下缓缓加入5L水中，搅拌2小时，加热到90℃后，加入1m2面积的聚丁烯-芳纶纤维(厚度5-10mm，单重25-50克)，使聚丁烯-芳纶纤维完全浸没，搅拌方式改为底层，每分钟2-5转，保持90℃6小时后，将聚丁烯-芳纶纤维提出，离心沥掉多余的海藻酸钠-四羧基磷类酞菁光敏剂溶胶，降温冷却到室温冷却6小时，然后在80℃下干燥定型，即可得到海藻酸钠-四羧基磷类酞菁光催化复合吸附材料，经重量法测试，负载海藻酸钠-八羧基磷类酞菁光敏剂约15克/平方米。
实施例7光催化复合材料的光催化性能和吸附重金属性能测试
对实施例4-6制备的光催化复合材料的光催化性能和吸附重金属性能进行室外模拟海洋水体的测试，其最大降解率结果如表1所示，测试条件如下：
模拟水体面积1m2，体积0.3立方米，聚丁烯-芳纶光催化材料0.5m2，室外日照时间累计12小时，特征污染物：柴油浓度0.5g/平方米，4氯酚浓度0.2g/立方米，Pb2+浓度0.1g/立方米，检测方法：TOC(柴油)/HPLC(4氯酚)/ICP-OES(Pb2+)，其中，降解率＝初始浓度-终了浓度/初始浓度×100％，文献参考值1为现有专利申请201710533592.7所公开的可见光光催化吸附材料。
表1光催化材料对污染物的最大降解率
| 柴油 | 4-氯酚 | Pb<sup>2+</sup> | |
| 实施例4光催化复合材料 | 83％ | 80％ | 86％ |
| 实施例5光催化复合材料 | 85％ | 80％ | 90％ |
| 实施例6光催化复合材料 | 85％ | 78％ | 90％ |
| 文献参考值1光催化吸附材料 | 85％ | 75％ | - |
表1数据显示，本发明提供的光敏剂和光催化材料能在光降解有机污染物的同时，利用海藻酸钠凝胶的特性吸附无机重金属离子，光催化材料对无机和有机污染物的去除率较高，光敏化效率较高。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种海藻酸钠-磷类酞菁光敏剂，其特征在于，所述光敏剂的制备方法为，以DMAP为脱水剂，海藻酸钠与羧基磷类酞菁按照特定重量比例混合于吡啶中，在反应温度100-150℃下反应2-6h，得到海藻酸钠-磷类酞菁光敏剂二元分子光敏剂，所述海藻酸钠的分子量为10-30KDa，所述羧基磷类酞菁是四羧基磷类酞菁或八羧基磷类酞菁。
2.如权利要求1所述的海藻酸钠-磷类酞菁光敏剂，其特征在于，所述海藻酸钠的G/M比为1:1-3；所述DMAP与所述羧基磷类酞菁的摩尔比为1:1。
3.如权利要求1所述的海藻酸钠-磷类酞菁光敏剂，其特征在于，所述羧基磷类酞菁的制备方法如下：以钼酸铵为催化剂，偏苯三酸酐或均苯四甲酸，金属锂片在尿素中熔融反应4-8h，制备得到羧基取代的无金属酞菁；所述无金属酞菁和三溴化磷在吡啶溶剂中回流反应4-10h，制备得到羧基磷类酞菁光敏剂。
4.如权利要求3所述的海藻酸钠-磷类酞菁光敏剂，其特征在于，所述偏苯三酸酐或均苯四甲酸，与金属锂片、尿素的摩尔比为2-3:1:20；所述钼酸铵的摩尔分数为0.1-1％；所述无金属酞菁和三溴化磷的摩尔比为 1:1-1.5。
5.聚丁烯-芳纶光催化复合材料，其特征在于，使权利要求1所述的海藻酸钠-磷类酞菁光敏剂制备而成的水凝胶分子进入溶胀的聚丁烯-芳纶纤维的缝隙中，缝隙收缩后海藻酸钠-磷类酞菁分子固定在聚丁烯-芳纶纤维表面，得到聚丁烯-芳纶光催化复合材料。
6.如权利要求5所述的聚丁烯-芳纶光催化复合材料，其特征在于，将所述海藻酸钠-磷类酞菁光敏剂制备成质量分数为1-5％的水溶胶，将聚丁烯-芳纶纤维在其中加热到60-90℃，维持此温度4-8小时，使得海藻酸钠-磷类酞菁凝胶分子进入因溶胀造成的聚丁烯-芳纶纤维束的缝隙中，冷却干燥后，缝隙收缩即可将海藻酸钠-磷类酞菁分子固定在聚丁烯-芳纶纤维表面，制得聚丁烯-芳纶光催化复合材料。
7.如权利要求5所述的聚丁烯-芳纶光催化复合材料，其特征在于，所述海藻酸钠-磷类酞菁光敏剂在所述聚丁烯-芳纶纤维上的负载量为1-100克/每平方米。
8.如权利要求5-7任一项所述的聚丁烯-芳纶光催化复合材料在降解海洋水体中泄漏的有害污染物中的应用。
9.如权利要求8所述的应用，其特征在于，所述有害污染物包括可被氧化剂单线态氧氧化降解的有机污染物、重金属离子及其化合物。
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