CN115069097A - 一种界面聚合法制备纳米材料复合膜的方法 - Google Patents
一种界面聚合法制备纳米材料复合膜的方法 Download PDFInfo
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Abstract
本发明公开一种界面聚合法制备纳米材料复合膜的方法,本方法将界面聚合反应的水相溶液与氧化石墨烯混悬液、纳米颗粒混悬液混合,在基膜上通过真空抽滤层层自组装得到纳米材料初生膜,进一步的将烘干后的初生膜浸入界面聚合油相溶液中进行聚合反应,从而得到稳定的纳米材料复合膜。本发明提供的复合膜具有良好的水通量,并且与传统的氧化石墨烯膜相比具有较低的溶胀度。本方法操作简单、控制参数少且反应条件温和,可用于水中污染物的去除。
Description
技术领域
本发明属于功能膜材料技术领域,具体涉及一种界面聚合法制备纳米材料复合膜的方法。
背景技术
随着城市化和工业化的发展,水资源污染已成为全球关注的话题。传统工业废水、医药工业废水中含有的氟化物、重金属、高浓度的酚类以及抗生素等指标仍然较高。膜技术作为一种新型分离技术,在水处理和净水产业生产过程中得到了越来越广泛的应用。膜分离技术具有能耗低、易于操作、环境友好等优点。
氧化石墨烯(Graphene oxide,GO)表面分散有羟基、羧基、环氧基等基团,具有较好的分散性和易于功能化等优点,可以作为活性位点,成为优良的吸附材料。沸石骨架中的交换性阳离子可以与水中的重金属进行交换,其较大的比表面积对重金属具有独特的吸附作用。金属有机框架(Metal-organic frameworks, MOFs)也称为多孔配位聚合物,是由有机配体和金属离子/簇组成的具有周期性网状拓扑结构的多孔晶体。具有比表面积大、孔径可调、孔隙率高、结构组成多样性及化学可修饰性等优点,在水体无机污染物、有机染料的去除等方面被广泛研究。
公开号CN111821867A的中国专利公开了一种自支撑还原氧化石墨烯纳滤膜及其制备方法和应用,该方法将氧化石墨烯溶液均匀涂覆在基膜上,进一步将氧化石墨烯还原用于水处理,但该方法制备的氧化石墨烯膜较为致密,水通量仅为6 L·m-2·h-1,且氧化石墨烯膜极易溶胀,易从基膜上脱落。
公开号为CN113441016A的中国专利公开了一种基于分步旋涂法的界面聚合制备复合纳滤膜的方法,该方法采用聚偏氟乙烯微孔滤膜为基膜,使用含多胺类单体的水相与含多酰氯单体的有机相,在分步旋涂的条件下进行界面聚合反应制备聚酰胺分离层,应用于有机染料的分离。但旋涂法较为浪费材料,且不适用于大面积膜制备。
公开号为CN106076132A的中国专利公开了一种氧化石墨烯改性聚酰胺复合纳滤膜及其制备方法,该制备方法以超滤膜为基膜,将氧化石墨烯或改性氧化石墨烯加入油相溶液中,经界面聚合法制膜,但超薄聚酰胺层与氧化石墨烯层结合不紧密,且GO负载量较低,吸附作用较低。
目前制备方法得到的氧化石墨烯膜相对致密,水通量较低;此外氧化石墨烯膜浸入水或盐溶液时,容易吸收水分子,导致膜溶胀而发生损坏。本方法利用界面聚合原理制备得到新型吸附功能膜。
发明内容
本发明的目的在于克服传统氧化石墨烯膜易溶胀等缺点,设计一种通量较高、具有较强稳定性的氧化石墨烯复合膜。本发明将纳米颗粒嵌入GO层中,采用界面聚合法将GO与纳米颗粒通过外在化学反应牢固的结合在一起,制得GO复合膜,并用于水中污染物的去除。
本发明采用以下技术方案:一种界面聚合法制备纳米材料复合膜的方法,其特征在于,包含以下步骤:
步骤一:配制氧化石墨烯混悬液、纳米颗粒混悬液用于制备复合膜;
步骤二:配制界面聚合反应的水相溶液与油相溶液;
步骤三:将氧化石墨烯混悬液、纳米颗粒混悬液与水相溶液混合,采用真空抽滤层层自组装法制备纳米材料初生膜。
步骤四:将纳米材料初生膜浸入油相溶液中进行聚合反应,取出晾干,得到稳定的界面聚合纳米材料复合膜;步骤一中纳米颗粒为NaY沸石以及UiO、ZIF、MIL、PCN系列金属有机框架中的一种或几种。
进一步的,所述步骤一中氧化石墨烯与纳米颗粒混悬液质量比为0.1-1:0.1-5。
进一步的,所述步骤二中,水相溶液为哌嗪、间苯二胺、对苯二胺中的一种或几种,浓度为2-10wt%;油相溶液为均苯三甲酰氯、对苯二甲酰氯、间苯二甲酰氯、环己烷三酰氯中的一种或几种,浓度为0.01-10 wt%。
进一步的,所述步骤三中,吸附剂氧化石墨烯混悬液、纳米颗粒混悬液与水相溶液的体积比为0.1-1:0.1-5:0.1-5。
进一步的,所述步骤四中,将纳米材料初生膜在油相溶液中浸泡2~60min,充分反应后取出晾干。
与现有技术相比,本发明的有益效果如下:
本发明的膜中嵌入了纳米颗粒,增加了GO层间距,与纯GO膜相比水通量增大了约20倍,同时界面聚合原理使得GO与ZaY结合更加紧密,达到抑制膜溶胀的效果。与传统的高成本氧化石墨烯膜相比,纳米颗粒的加入降低了氧化石墨烯的用量,从而降低了成本。UiO-66-NH2复合膜中纳米材料本身的-NH2进行界面聚合反应,相比其他混合基质膜UiO-66-NH2复合膜具有更大的吸附材料利用率。本方法制备工艺简便、条件温和、不需要复杂的仪器设备即可制备。
附图说明
图1是 GO/NaY/Nylon复合膜表面电镜图;
图2是GO/NaY/Nylon复合膜截面电镜图;
图3是GO/NaY/Nylon复合膜红外图;
图4是GO/NaY/Nylon复合膜水通量随时间变化的曲线图;
图5是GO/NaY/Nylon复合膜与GO膜在不同溶液中的溶胀度示意图。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。水相溶液为哌嗪、间苯二胺、对苯二胺中的一种或几种,油相溶液为均苯三甲酰氯、对苯二甲酰氯、间苯二甲酰氯、环己烷三酰氯中的一种或几种。
实施例1:GO/NaY/Nylon复合膜的制备
准确量取1 mL GO混悬液(10 mg·mL-1)、1 mL NaY混悬液(10 mg·mL-1)和3 mL哌嗪溶液(2 wt%)于烧杯中,超声15 min混合,得到GO、NaY质量比为1:1的混合液。将膜过滤装置置于真空泵上,以尼龙膜为支撑层,采用逐层过滤的方式进行抽滤,得到氧化石墨烯初生膜。将初生膜放入60°C烘箱中,烘干2 h,得到稳定且干燥的初生膜。随后将初生膜完全浸入0.15 wt%均苯三甲酰氯溶液中,聚合反应1 h后取出,放于室温条件下晾干,得到稳定的氧化石墨烯复合膜。
实施例2:GO/ZIF-8/Nylon复合膜的制备
准确量取1 mL GO混悬液(10 mg·mL-1)、5 mL ZIF-8混悬液(10 mg·mL-1)和3 mL哌嗪溶液(2 wt%)于烧杯中,超声20 min混合,得到GO、ZIF-8质量比为1:5的混合液。将膜过滤装置置于真空泵上,以尼龙膜为支撑层,采用逐层过滤的方式进行抽滤,得到氧化石墨烯初生膜。将初生膜放入55°C烘箱中,烘干2 h,得到稳定且干燥的初生膜。随后将初生膜完全浸入0.15 wt%均苯三甲酰氯溶液中,聚合反应1 h后取出,放于室温条件下晾干2 h,得到稳定的氧化石墨烯复合膜。
实施例3:GO/UiO-66-NH2/Nylon复合膜的制备
准确称取0.5 g UiO-66-NH2粉末,分散于50mL去离子水中,超声20 min混合均匀得到UiO纳米颗粒混悬液(10 mg·mL-1)。准确量取1 mL GO混悬液(10 mg·mL-1)、3 mLUiO-66-NH2混悬液和3 mL哌嗪溶液(2 wt%)于烧杯中,超声20 min混合均匀,得到GO、UiO-66-NH2质量比为1:3的混合液。将膜过滤装置置于真空泵上,以尼龙膜为支撑层,采用逐层过滤的方式进行抽滤,得到纳米材料初生膜。将初生膜放入55°C烘箱中,烘干2h,得到稳定且干燥的初生膜。随后将初生膜完全浸入0.15 wt%均苯三甲酰氯溶液中,聚合反应1h后取出,放于室温条件下晾干,得到纳米材料复合膜。
实施例4:GO/MIL-101/Nylon复合膜的制备
准确称取0.5 g MIL-101粉末,分散于50mL去离子水中,超声20 min混合均匀得到MIL纳米颗粒混悬液(10 mg·mL-1)。准确量取1 mL GO混悬液(10 mg·mL-1)、4 mL MIL-101混悬液和3 mL哌嗪溶液(2 wt%)于烧杯中,超声20 min混合均匀,得到GO、MIL-101质量比为1:4的混合液。将膜过滤装置置于真空泵上,以尼龙膜为支撑层,采用逐层过滤的方式进行抽滤,得到纳米材料初生膜。将初生膜放入55°C烘箱中,烘干2h,得到稳定且干燥的初生膜。随后将初生膜完全浸入0.15 wt%均苯三甲酰氯溶液中,聚合反应1h后取出,放于室温条件下晾干,得到纳米材料复合膜。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (5)
1.一种界面聚合法制备纳米材料复合膜的方法,其特征在于,包含以下步骤:
步骤一:配制氧化石墨烯混悬液、纳米颗粒混悬液用于制备复合膜;
步骤二:配制界面聚合反应的水相溶液与油相溶液;
步骤三:将氧化石墨烯混悬液、纳米颗粒混悬液与水相溶液混合,采用真空抽滤层层自组装法制备纳米材料初生膜;
步骤四:将纳米材料初生膜浸入油相溶液中进行聚合反应,取出晾干,得到稳定的界面聚合纳米材料复合膜;
所述步骤一中纳米颗粒为NaY沸石以及UiO、ZIF、MIL、PCN系列金属有机框架中的一种或几种。
2.根据权利要求1所述的一种界面聚合法制备纳米材料复合膜的方法,其特征在于,所述步骤一中氧化石墨烯与纳米颗粒质量比为0.1-1:0.1-5。
3.根据权利要求1所述的一种界面聚合法制备纳米材料复合膜的方法,其特征在于,所述步骤二中,水相溶液为哌嗪、间苯二胺、对苯二胺中的一种或几种,浓度为2-10wt%;油相溶液为均苯三甲酰氯、对苯二甲酰氯、间苯二甲酰氯、环己烷三酰氯中的一种或几种,浓度为0.01-10 wt%。
4.根据权利要求1所述的一种界面聚合法制备纳米材料复合膜的方法,其特征在于,所述步骤三中,氧化石墨烯混悬液、纳米颗粒混悬液与水相溶液的体积比为0.1-1:0.1-5:0.1-5。
5.根据权利要求1所述的一种界面聚合法制备纳米材料复合膜的方法,其特征在于,所述步骤四中,将纳米材料初生膜在油相溶液中浸泡2~60 min,充分反应后取出晾干。
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