CN113499759B - 一种具有核壳结构的FeOH@MSN-PDMAEMA纳米吸附剂 - Google Patents
一种具有核壳结构的FeOH@MSN-PDMAEMA纳米吸附剂 Download PDFInfo
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Abstract
本发明提供一种可实现水中磷酸根离子高效、快速吸附的无机‑有机杂化的核壳结构纳米颗粒,由内核介孔硅纳米颗粒(MSN)和外层聚甲基丙烯酸N,N‑二甲基氨基乙酯(PDMAEMA)聚合物凝胶构成,并在纳米颗粒孔道中负载FeOH。MSN是一种重要的吸附剂,具有比表面积大、孔道结构有序、骨架结构稳定且易于表面改性等优点。但是,在实际应用中,仅依靠MSN的自身性能还远远不能满足要求,所以对MSN进行表面改性是当今研究热点之一。本发明通过在MSN表面包覆PDMAEMA阳离子聚合物形成凝胶层,并在其孔道内负载带正电的FeOH,首次利用PDMAEMA和FeOH对磷酸根离子吸附的协同作用,达到高效、快速吸附磷酸根离子的功效。
Description
技术领域
本发明属于污水处理领域,具体涉及无机–有机核壳结构纳米颗粒,更具体涉及作为水中磷酸根离子吸附剂的FeOH@MSN-PDMAEMA核壳结构纳米颗粒。
背景技术
介孔硅纳米颗粒(MSN)是一种极具潜力的水污染治理吸附剂,由于其孔道和表面结构易于调控、高的比表面积和孔隙率等特点,能有效地吸附分散或溶解在液体中的小分子或离子污染物。FeOH是一种价廉物美的吸附剂,对磷有很高的亲和力,而且选择性很强。MSN的高孔隙率使其成为FeOH的理想载体介质,FeOH负载到MSN上以后会提高其的吸附能力,增强对磷酸根离子的亲和力。
无机-有机核壳复合材料同时具有无机材料的刚度和强度以及有机材料的高韧性、可塑性等优良性质,同时容易剪裁成具有特殊结构的材料,所以无机-有机核壳复合材料在光学、催化、微电子、生物和制药等领域都有巨大的应用价值。
聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)是一种新型的阳离子聚合物,具有温度和pH双重敏感性,在酸性条件下可与溶液中的磷酸根离子相互作用。
本发明通过FeOH@MSN-PDMAEMA核壳结构纳米颗粒的组装设计,以MSN为核,先对其进行表面改性,然后在其表面通过化学键作用包覆PDMAEMA阳离子聚合物,形成凝胶外壳,再在其孔道中负载FeOH,实现酸性条件下对磷酸根离子的高效、快速吸附,从而完成了本发明。
发明内容
本发明的一个目的是提供一种可实现污水中磷酸根离子高效、快速吸附的核壳结构纳米颗粒。
本发明的另一个目的是提供这种核壳结构纳米颗粒的制备方法。
本发明的再一个目的是提供这种核壳结构纳米颗粒在污水处理领域的用途。
本发明提供的核壳结构纳米颗粒由内核MSN、外层PDMAEMA聚合物凝胶和孔道负载的FeOH构成。
本发明的颗粒中,内核MSN为有序结构的介孔硅纳米颗粒。所述MSN由模板法制成。
本发明的颗粒中,外层PDMAEMA聚合物凝胶由甲基丙烯酸N,N-二甲基氨基乙酯(DMAEMA)进行交联反应而形成。
本发明的颗粒中,内核MSN与外层PDMAEMA聚合物凝胶之间通过化学键进行连接。
本发明选用PDMAEMA聚合物凝胶,是因为其在酸性条件下带正电荷,可与经过表面改性带负电荷的MSN通过化学键连接,形成MSN-PDMAEMA核壳结构。外层PDMAEMA聚合物凝胶在交联剂的存在下,分子发生交联作用,形成的网络状凝胶结构稳定包裹在MSN的表面。
本发明提供的核壳结构颗粒的制备方法包括以下步骤:
1)将模板剂溶于去离子水中,加入NaOH溶液,搅拌反应后快速加入硅源,反复离心分离,烘干,研磨成粉末,然后高温煅烧;
2)将步骤1)所得粉末分散于无水乙醇中,超声分散,加入硅烷偶联剂和氨水,升温回流后离心分离,然后烘干,得到表面改性的MSN,记为mMSN;
3)将步骤2)所得mMSN分散于无水乙醇中,超声分散,加入DMAEMA,通氮除氧;
4)将步骤3)所得混合液中逐滴加入交联剂,升温反应,反复离心分离后冷冻干燥得到MSN-PDMAEMA;
5)将步骤4)所得固体和六水氯化铁超声分散于甲醇中,旋蒸除去溶剂后复溶,搅拌条件下加入NaOH溶液,进行反复离心分离后冷冻干燥得到FeOH@MSN-PDMAEMA。
本发明方法的步骤1)中,煅烧时间为250min,煅烧温度为500-600℃。
本发明方法的步骤2)中采用的硅烷偶联剂为KH570。
本发明方法的步骤4)中采用的交联剂优选AIBN。
在一个优选方案中,本发明的核壳结构吸附颗粒的制备方法包括以下步骤:
1.模板法制备MSN
称取1.00-1.50g十六烷基三甲基溴化铵(CTAB)固体溶于600mL去离子水中,加入3-5mL 2mol/L的NaOH溶液,搅拌反应30min后快速加入7-8mL的硅酸四乙酯(TEOS),反应2h,反复离心分离,50℃下烘干,先研磨成粉末,然后在500-600℃的条件下煅烧250min。
MSN表面改性制mMSN
称取1.0-3.0gMSN,分散于20mL无水乙醇中,超声分散5min-10min,加入2-4mL硅烷偶联剂和1.5mL氨水,升温至69℃后回流6h,反复离心分离,50℃下烘干。
PDMAEMA的包覆
称取0.5-3.0g表面改性的mMSN分散于50mL无水乙醇中,超声分散2-5min,加入1.0-5.0mLDMAEMA,通氮除氧30min。
壳层PDMAEMA凝胶合成
称取0.01-1.00g交联剂偶氮二异丁腈(AIBN),分散于少量无水乙醇中。取所得MSN-PDMAEMA混合液,逐滴加入交联剂偶氮二异丁腈(AIBN),缓慢升温至75℃,无氧反应6h,反复离心分离,冷冻干燥。
FeOH@MSN-PDMAEMA的制备
称取0.1-1.0g MSN-PDMAEMA粉末和2mmol六水氯化铁超声分散2-3min于20mL甲醇中,旋蒸除去溶剂,20mL甲醇复溶,搅拌条件下加入6mmol NaOH溶液,室温搅拌,反复离心分离,冷冻除水。
本发明以MSN为核,通过硅烷偶联剂对其进行表面改性,使其颗粒表面带上C=C,再通过化学键使带正电的PDMAEMA聚合物凝胶包覆在MSN表面,然后在交联剂的作用下,PDMAEMA在壳层发生交联反应,最后在MSN孔道中负载FeOH,形成无机-有机杂化的核壳结构纳米颗粒。该核壳结构纳米颗粒具有高效、快速吸附污水中磷酸根离子的作用。
本发明对MSN进行表面改性,再包覆阳离子聚合物凝胶层,同时在MSN孔道中部分负载FeOH,首次利用PDMAEMA和FeOH对磷酸根离子吸附的协同作用,制备了高效、快速吸附污水中磷酸根离子的吸附剂,并且对环境友好。
附图说明
图1是MSN、mMSN、MSN-PDMAEMA和FeOH@MSN-PDMAEMA的红外光谱图;图2是MSN、mMSN、MSN-PDMAEMA的TG曲线图;图3是MSN、FeOH@MSN-PDMAEMA的TEM图像;图4是FeOH@MSN-PDMAEMA的C、Si、O、Fe元素EDS图和STEM图;图5是FeOH@MSN-PDMAEMA的吸附曲线。
Claims (7)
1.一种实现水中磷酸根离子吸附的无机-有机杂化的核壳结构纳米颗粒,由内核介孔硅纳米颗粒、外层聚甲基丙烯酸N,N-二甲基氨基乙酯聚合物凝胶和孔道负载的FeOH构成,该核壳结构纳米颗粒的制备方法,包括以下步骤:
1)将模板剂溶于去离子水中,加入NaOH溶液,搅拌反应后快速加入硅源,反复离心分离,烘干,研磨成粉末,然后高温煅烧250min;
2)将步骤1)所得粉末散于无水乙醇中,超声分散,加入硅烷偶联剂和氨水,升温回流后离心分离,然后烘干,得到表面改性的介孔硅纳米颗粒,记为mMSN;
3)将步骤2)所得mMSN分散于无水乙醇中,超声分散,加入甲基丙烯酸N,N-二甲基氨基乙酯,通氮除氧;
4)将步骤3)所得混合液中逐滴加入交联剂,升温反应,反复离心分离后冷冻干燥得到MSN-PDMAEMA;
5)将步骤4)所得固体和六水氯化铁超声分散于甲醇中,旋蒸除去溶剂后复溶,搅拌条件下加入NaOH溶液,进行反复离心分离后冷冻干燥得到FeOH@MSN-PDMAEMA。
2.如权利要求1所述的纳米颗粒,其中所述模板剂为十六烷基三甲基溴化铵。
3.如权利要求1所述的纳米颗粒,其中所述硅源为硅酸四乙酯。
4.如权利要求1所述的纳米颗粒,其中所述煅烧温度为500-600℃。
5.如权利要求1所述的纳米颗粒,其中所述硅烷偶联剂为γ-甲基丙烯酰氧基丙基三甲氧基硅烷。
6.如权利要求1所述的纳米颗粒,其中所述交联剂为偶氮二异丁腈。
7.权利要求1所述核壳结构纳米颗粒在水中磷酸根离子吸附领域的用途。
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