CN110302838B - 表面修饰PNH的磁性Fe2O3纳米小球及其在水处理中的应用 - Google Patents

表面修饰PNH的磁性Fe2O3纳米小球及其在水处理中的应用 Download PDF

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CN110302838B
CN110302838B CN201910539497.7A CN201910539497A CN110302838B CN 110302838 B CN110302838 B CN 110302838B CN 201910539497 A CN201910539497 A CN 201910539497A CN 110302838 B CN110302838 B CN 110302838B
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路建美
徐庆锋
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Suzhou University
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Abstract

本发明公开了表面修饰PNH的磁性Fe2O3纳米小球及其在水处理中的应用，首先2,2‑联吡啶‑5,5'‑二羧酸与氯化亚砜反应，得到2,2‑联吡啶‑5,5'‑二酰氯；然后在三乙胺存在下，将2,2‑联吡啶‑5,5'‑二酰氯、1,4,8,11‑四氮杂环十四烷反应，得到多氮杂环聚合物；将多氮杂环聚合物加入铁盐水溶液中，反应得到表面修饰PNH的磁性Fe2O3纳米小球。具有强吸光能力，提高其在可见光催化降解四环素的能力，使得污染物离开水体，去除污染物。

Description

表面修饰PNH的磁性Fe2O3纳米小球及其在水处理中的应用
技术领域
本发明属于金属有机配合物材料领域，具体涉及一种催化降解有机污染物的复合材料、其制备方法及其对水体中抗生素的有效去除应用。
背景技术
光催化技术因其在环境修复和能源再生等方面的强大优势而被广泛使用，研究的很多材料如TiO2，SnO2等都显示出良好的催化活性，但是大部分材料只对紫外（UV）光有响应。
发明内容
本发明提供了一种可降解抗生素的复合材料，其制备方法以及对水体中的抗生素有效去除的应用，以四环素为例，4h之内可以降解90%的四环素。
本发明采用如下技术方案：
一种表面修饰PNH的磁性Fe2O3纳米小球，其制备方法包括以下步骤：
（1）2,2-联吡啶-5,5'-二羧酸与氯化亚砜反应，得到2,2-联吡啶-5,5'-二酰氯；然后在三乙胺存在下，将2,2-联吡啶-5,5'-二酰氯、1,4,8,11-四氮杂环十四烷反应，得到多氮杂环聚合物；
（2）将多氮杂环聚合物加入铁盐水溶液中，反应得到表面修饰PNH的磁性Fe2O3纳米小球。
本发明公开了降解水中有机污染物的方法，包括以下步骤：
（1）2,2-联吡啶-5,5'-二羧酸与氯化亚砜反应，得到2,2-联吡啶-5,5'-二酰氯；然后在三乙胺存在下，将2,2-联吡啶-5,5'-二酰氯、1,4,8,11-四氮杂环十四烷反应，得到多氮杂环聚合物；
（2）将多氮杂环聚合物加入铁盐水溶液中，反应得到表面修饰PNH的磁性Fe2O3纳米小球；
（3）将表面修饰PNH的磁性Fe2O3纳米小球加入含有有机污染物的水中，再加入双氧水，光照完成水中有机污染物的降解。
上述技术方案中，步骤（1）中，2,2-联吡啶-5,5'-二羧酸溶于氯化亚砜中，于110~115℃反应10~12 h，得到2,2-联吡啶-5,5'-二酰氯；2,2-联吡啶-5,5'-二酰氯和1,4,8,11-四氮杂环十四烷的反应时间为24~48 h，反应温度为45~50℃。优选的，2,2-联吡啶-5,5'-二酰氯和1,4,8,11-四氮杂环十四烷反应结束后，反应体系依次经过KOH水溶液、氯仿、乙醇洗涤后置于DMF中于140~150℃加热12 h，然后过滤，得到的固体分别经过水和乙醇洗涤后干燥，得到淡黄色多氮杂环聚合物PNH。
上述技术方案中，步骤（2）中，反应温度为140~180℃，反应时间为10~20 h，反应结束后，产物依次用乙醇和去离子水洗涤，烘干得到表面修饰PNH的磁性Fe2O3纳米小球Fe2O3@PNH。
上述技术方案中，2,2-联吡啶-5,5'-二羧酸、1,4,8,11-四氮杂环十四烷的摩尔比为1∶（2~2.1）；多氮杂环聚合物和铁盐的质量比为1∶（0.5~2）。
本发明中，铁盐为FeCl3。在降解水中有机污染物时，光照为可见光照射。
本发明将原料2,2-联吡啶-5,5'-二羧酸分散于氯化亚砜溶液中，2,2-联吡啶-5,5'-二羧酸完全溶于氯化亚砜中，然后在110℃的条件下反应12h，接着趁热旋干溶剂，得到产物2,2-联吡啶-5,5'-二酰氯；
将原料1,4,8,11-四氮杂环十四烷和2,2-联吡啶-5,5'-二酰氯分别溶于氯仿溶液中，冰浴条件下，将2,2-联吡啶-5,5'-二酰氯的氯仿溶液滴加入1,4,8,11-四氮杂环十四烷的氯仿溶液中，加入三乙胺，然后在常温下搅拌半小时，然后置于45℃反应24h，反应结束后，反应体系依次经过KOH水溶液、氯仿、乙醇洗涤后置于DMF中于140℃加热12 h，趁热过滤，得到的固体经过水和乙醇洗涤数次后置于60℃干燥箱中真空干燥12h，得到淡黄色多氮杂环聚合物PNH；
将FeCl3溶于水中，将淡黄色多氮杂环聚合物置于反应釜中，通过PNH完全吸附水溶液中Fe3+，在140℃反应10h，反应结束后，产物通过乙醇和去离子水洗涤，烘干得到Fe2O3@PNH。
本发明首次通过聚合物吸附重金属离子经水热合成形成聚合物包裹的纳米粒子光催化剂，并能够有效用于污染物的去除；本发明公开了上述表面修饰PNH的磁性Fe2O3纳米小球在水处理中的应用。
本发明中，所述水处理为降解水中有机污染物；进一步优选的，有机污染物为抗生素，比如四环素。
本发明采用的是Fe2O3，Fe2O3拥有较窄的带隙（2.0~2.2 eV），对可见光有很好的响应，吸收边缘在600 nm左右，而且它在水性介质中拥有良好的化学稳定性，合成成本低廉，原料丰富和无毒的特点，在降解污染技术中有很强的运用。
附图说明
图1为实施例一中PNH的固体碳谱；
图2为实施例一中PNH的扫描电镜和投射电镜图，a为b的放大图；
图3为实施二中Fe2O3的扫描电镜和投射电镜图，a为b的放大图；
图4为实施例三中Fe2O3@PNH的扫描电镜和投射电镜图，a为b的放大图；
图5为实施例中PNH、Fe2O3和Fe2O3@PNH的X射线衍射图；
图6为实施例六中四环素的紫外吸收图；
图7为实施例六中Fe2O3@PNH催化降解四环素的效果图。
具体实施方式
本发明利用2,2'-联吡啶-5,5'-二羧酸中联吡啶基团对Fe3+极强的配位能力，聚合物PNH预吸附水溶液中Fe3+，并通过简单的水热过程一步合成了有机聚合物包裹的磁性纳米颗粒Fe2O3@PNH，具有强吸光能力，提高其在可见光催化降解四环素的能力，使得污染物离开水体，去除污染物。本发明表面修饰PNH的磁性Fe2O3纳米小球（Fe2O3@PNH）可以作为光催化降解有机污染物的复合材料，其制备方法如下：
（1）多氮杂环聚合物（PNH）的制备
2,2-联吡啶-5,5'-二羧酸溶于氯化亚砜中，回流反应，得到的2,2-联吡啶-5,5'-二酰氯，溶剂旋干后加入氯仿，然后滴加1,4,8,11-四氮杂环十四烷和三乙胺的氯仿溶液，然后回流反应得到PNH；
（2）Fe2O3@PNH的制备
铁盐溶于水中，然后加入PNH进行反应，反应结束后，产物用乙醇和去离子水分别洗涤，然后真空干燥得到Fe2O3@PNH。
反应过程如下：
Figure DEST_PATH_IMAGE001
实施例一
2,2-联吡啶-5,5'-二羧酸（3 g）溶于氯化亚砜（80 ml）中，在110 ℃反应8 h，然后旋干溶剂，得到2,2-联吡啶-5,5'-二酰氯；再将得到的2,2-联吡啶-5,5'-二酰氯溶于氯仿（120ml）中，再于冰浴下滴加入含有1,4,8,11-四氮杂环十四烷（1.17 g）和三乙胺（10 ml）的氯仿溶液中，然后撤去冰浴，常温搅拌30 min之后，45 ℃反应2天；反应结束后将粗产物经过KOH水溶液、氯仿和乙醇洗涤后置于DMF溶液中在140℃下加热12小时，然后过滤，将固体分别经过水和乙醇洗涤后于60℃干燥12小时后得到PNH，为淡黄色固体。
图1为上述PNH的固体碳谱图，其中蓝色和绿色的线代表两种原料，蓝色曲线为2,2-联吡啶-5,5'-二酰氯的碳谱数据，绿色的曲线是1,4,8,11-四氮杂环十四烷碳谱数据，红色的是聚合物PNH的碳谱数据。通过分析SSC13-NMR可以得到，2,2-联吡啶-5,5'-二羧酸在δ=121 pm, 124 pm, 139 pm, 152 ppm, 157 pm, 174 pm出现明显的尖峰，1,4,8,11-四氮杂环十四烷在δ=29 ppm 和53 ppm的位置出峰，PNH的峰包含两个单体的峰并且在一定程度上出现了偏移，结果表明2,2-联吡啶-5,5'-二羧酸和1,4,8,11-四氮杂环十四烷发生了明显的化学反应。；图2为上述PNH的扫描电镜图和投射电镜图，证明PNH成功合成且为无序的块状。
实施例二
称取50 mg的FeCl3溶于水（10ml）中，溶液置于高压反应釜中，140 ℃反应10 h，产物用乙醇和去离子水分别洗涤3次，置于60 ℃干燥箱中真空干燥12 h，反应得到纯的Fe2O3。图3为Fe2O3的扫描电镜和投射电镜图，证明Fe2O3为不规则的颗粒。
实施例三
称取50 mg 的FeCl3溶于水（10ml）中，加入50 mg 的PNH，常温搅拌6 h后置于高压反应釜中，140 ℃反应10 h，产物用乙醇和去离子水分别洗涤3次，再置于60 ℃干燥箱中真空干燥12 h，得到产物Fe2O3@PNH，为表面修饰PNH的磁性Fe2O3纳米小球。
图4为Fe2O3@PNH的扫描电镜图和投射电镜图，证明Fe2O3@PNH为规则的球形。图5为PNH、Fe2O3和Fe2O3@PNH的X射线衍射图，证明本发明成功合成了Fe2O3和Fe2O3@PNH且主要表现为Fe2O3的晶型。
实施例四
称取50 mg 的FeCl3溶于水中，加入25 mg 的PNH，常温搅拌6 h后混合溶液置于高压反应釜中，140 ℃反应10 h，产物用乙醇和去离子水分别洗涤3次，置于60 ℃干燥箱中真空干燥12 h，反应得到系列Fe2O3@PNH的产物。
实施例五
称取50 mg 的FeCl3溶于水中，加入100 mg 的PNH，常温搅拌6 h后混合溶液置于高压反应釜中，140 ℃反应10 h，产物用乙醇和去离子水分别洗涤3次，置于60 ℃干燥箱中真空干燥12 h，反应得到系列Fe2O3@PNH的产物。
实施例六
将2 mg Fe2O3@PNH（实施例三制备）分散在30 ml、50 ppm的四环素水溶液中，加入10 ul的 H2O2，将悬浊液在黑暗中搅拌2小时以实现吸附-解吸附平衡；然后用氙灯源（滤光器> 420 nm）照射悬浮液，通过0.45 um过滤器过滤收集2 mL上清液，并通过UV-vis光谱仪在λ= 354 nm处以分析四环素浓度。
图6为四环素的紫外吸收图；图7为Fe2O3@PNH催化降解四环素的效果图；结果显示Fe2O3@PNH在4 h之内可以降解掉90%的四环素，而聚合物在光照条件下只表现出微弱的吸附性能，而纯的Fe2O3在吸附-解吸附平衡后，表现出了一定的降解能力，但是只有35%，降解效果远远低于Fe2O3@PNH复合材料。
本发明Fe2O3@PNH在水性介质中拥有良好化学稳定性，合成成本低廉，原料丰富和无毒性，可成为光催化降解和水分解应用最有前景的材料之一。

Claims (5)

1.一种表面修饰PNH的磁性Fe2O3纳米小球，其特征在于，所述表面修饰PNH的磁性Fe2O3纳米小球的制备方法包括以下步骤：
（1）2,2-联吡啶-5,5'-二羧酸与氯化亚砜反应，得到2,2-联吡啶-5,5'-二酰氯；然后在三乙胺存在下，将2,2-联吡啶-5,5'-二酰氯、1,4,8,11-四氮杂环十四烷反应，得到多氮杂环聚合物；
（2）将多氮杂环聚合物加入铁盐水溶液中，反应得到表面修饰PNH的磁性Fe2O3纳米小球；
步骤（1）中，2,2-联吡啶-5,5'-二羧酸溶于氯化亚砜中，于110~115℃反应10~12 h，得到2,2-联吡啶-5,5'-二酰氯；2,2-联吡啶-5,5'-二酰氯和1,4,8,11-四氮杂环十四烷的反应时间为24~48 h，反应温度为45~50℃；2,2-联吡啶-5,5'-二酰氯和1,4,8,11-四氮杂环十四烷反应结束后，反应体系依次经过KOH水溶液、氯仿、乙醇洗涤后置于DMF中于140~150℃加热12 h，然后过滤，再将得到的固体干燥，得到多氮杂环聚合物；
步骤（2）中，反应温度为140~180℃，反应时间为10~20 h；
2,2-联吡啶-5,5'-二羧酸、1,4,8,11-四氮杂环十四烷的摩尔比为1∶（2~2.1）；多氮杂环聚合物和铁盐的质量比为1∶（0.5~2）；铁盐为FeCl3。
2.根据权利要求1所述表面修饰PNH的磁性Fe2O3纳米小球，其特征在于，步骤（2）中，反应结束后，产物依次用乙醇和去离子水洗涤，再烘干得到表面修饰PNH的磁性Fe2O3纳米小球。
3.权利要求1所述表面修饰PNH的磁性Fe2O3纳米小球在水处理中的应用。
4.根据权利要求3所述的应用，其特征在于，所述水处理在双氧水存在下、光照下进行。
5.根据权利要求3所述的应用，其特征在于，所述水处理为降解水中有机污染物。
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