CN108837813A - 一种介孔硅藻As(V)离子表面印迹材料的制备方法和应用 - Google Patents

一种介孔硅藻As(V)离子表面印迹材料的制备方法和应用 Download PDF

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CN108837813A
CN108837813A CN201810682109.6A CN201810682109A CN108837813A CN 108837813 A CN108837813 A CN 108837813A CN 201810682109 A CN201810682109 A CN 201810682109A CN 108837813 A CN108837813 A CN 108837813A
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李聪
钟溢健
王蓝青
梁效铭
解庆林
陈南春
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Abstract

本发明公开了一种介孔硅藻As(V)离子表面印迹材料的制备方法和应用,该离子印迹材料是以硅藻土为载体,As(V)离子为模板，氨丙基三甲氧基硅烷为功能单体，环氧氯丙烷为交联剂，盐酸为洗脱剂，通过表面离子印迹技术制备了介孔硅藻As(V)离子印迹材料。本发明的介孔硅藻As(V)离子印迹材料具有步骤简单、操作方便、生产效率高等优点,并且对水中As(V)离子具有良好的吸附性和选择性。

Description

一种介孔硅藻As(V)离子表面印迹材料的制备方法和应用
技术领域
发明属于材料技术领域,涉及一种基于介孔硅藻的印迹材料,具体涉及一种介孔硅藻As(V)离子表面印迹材料的制备方法和应用。
背景技术
砷是普遍存在于自然界中的一种类金属元素,在地壳中含量排名第20，主要以硫化物和合金的形式存在。砷普遍应用在电子、农业、木材防腐、冶金和医药等领域,因此导致环境中砷含量尤其是水中的砷超标。根据化合价不同,砷又可分为五价砷和三价砷。其中三价砷毒性是五价砷毒性的60倍，但环境中五价砷存在更加稳定。砷中毒可能会引起消化***，呼吸***，血液***等一系列的问题，严重的可能会导致癌症。因此，除砷技术已经成为了研究热点之一。
离子印迹技术是分子印迹技术的一个重要分支，与分子印迹一样具有构效预知性、特异识别性和广泛适用性等优点。传统的离子印迹聚合物存在着，识别位点“包埋”在聚合物内部,使得模板离子与识别位点结合困难,结合速率低，所制备的印迹聚合物，机械性能差等缺点。而表面离子印迹技术能够实现印迹聚合物与印迹离子之间快速的结合与分离,降低了非特异吸附对选择性的影响。
用表面离子印迹技术制备印迹材料，载体的选择至关重要，所需的载体要具备一定的机械稳定性和热稳定性，而且具有较好的经济效应。硅藻土具有独特的有序排列的孔道结构、孔隙率高、孔体积大、质量轻、机械稳定性和热稳定性较好，并且其分布广泛，价格低廉，是理想的载体材料。此外，现有的表面离子印迹聚合物所有的载体大都集中于硅胶、碳纳米管、介孔硅等，在天然矿物类方面的研究较少，因此，在硅藻表面实现离子印迹材料具有一定的意义。
发明内容
本发明的目的在于提供一种介孔硅藻As(V)离子表面印迹材料的制备方法和应用，并且该印迹材料对水中As(V)离子具有良好的吸附性和选择性。一种介孔硅藻As(V)离子表面印迹材料的制备方法和应用，其特征在于包括以下步骤:
(1)活化硅藻土：称30g硅藻土用2mol/L的盐酸70℃水浴加热回流8～12h，之后抽滤，用去离子水洗至中性，最后80℃烘干。
(2)称取0.2～0.25mmol的砷酸钠固体在三口瓶中，然后加入10mL超纯水使其充分溶解，再量取80～100mL的甲醇加入三口瓶中，混匀之后，滴加2mL的氨基丙基三甲氧基硅烷，反应1～2h，接着加入活化后的硅藻土4g，60℃冷凝回流20h，之后加入2.7mL的环氧氯丙烷，继续反应2～4h，冷却后抽滤，用无水乙醇洗涤2～3次。
(3)最后用0.5～1mol/L的盐酸在常温下洗脱2～4h，再用去离子水洗涤至中性，80℃烘干，得到介孔硅藻As(V)离子印迹材料。
本发明利用表面离子印迹技术,以比表面积大,机械稳定性和热稳定性较好、表面含有大量硅轻基的硅藻为基质，氨丙基三甲氧基硅烷为功能单体，环氧氯丙烷为交联剂，通过聚合反应制备了介孔硅藻As(V)离子印迹材料，并应用于水中As(V)离子方面的研究。该印迹材料水中2mg/L As(V)离子的去除率可以达到97％以上，具有较好的吸附性。并且对Cd(Ⅱ)、Pb(Ⅱ)和Cr(Ⅵ)的选择性系数均可达到1.5以上，具有良好的选择性。
附图说明
图1为本发明实施例1介孔硅藻As(V)离子印迹材料扫描电镜图，(a)为非印迹材料，(b)为印迹材料。
图2为本发明实施例1介孔硅藻As(V)离子印迹材料红外光谱图。a，b，c，d，e分别代表硅藻原土，酸化后的硅藻土，硅藻接枝单体，交联之后，印迹材料。
图3为本发明实施例1介孔硅藻As(V)离子印迹材料X射线光电子能谱图。
图4为本发明实施例1介孔硅藻As(V)离子印迹材料与非As(V)离子印迹材料对As(V)离子去除率随pH变化的关系示意图。
具体实施方式
以下结合具体实施例对发明作进一步详细的描述。
实施例1：
一种介孔硅藻As(V)离子表面印迹材料的制备方法和应用，包括如下步骤：
(1)活化硅藻土：称30g硅藻土用2mol/L的盐酸70℃水浴加热回流12h，之后抽滤，用去离子水洗至中性，最后80℃烘干；
(2)称取0.25mmol的砷酸钠固体在三口瓶中，然后加入10mL超纯水使其充分溶解，再量取80mL的甲醇加入三口瓶中，混匀之后，滴加2mL的氨基丙基三甲氧基硅烷，反应2h，接着加入活化后的硅藻土4g，60℃冷凝回流20h，之后加入2.7mL的环氧氯丙烷，继续反应4h，冷却后抽滤，用无水乙醇洗涤2～3次；
(3)最后用1mol/L的盐酸在常温下洗脱2h，再用去离子水洗涤至中性，80℃烘干，得到介孔硅藻As(V)离子印迹材料；
(4)将步骤(3)的得到的印迹材料记作As-IIP，作为对比非印迹材料记作As-NIP。同时取一系列0.1gAs-IIP和As-NIP分别加入到100mL离心管中,加入25mLpH＝3～11浓度为2mg/LAs(V)离子溶液,吸附时间60min,吸附温度25℃,在回旋式水浴恒温振荡器中以150r/min的转速振荡至吸附平衡；
(5)将步骤(4)所得溶液用0.45μm滤膜过滤，用原子荧光光度计测定滤液中的As(V)浓度,并得出As-IIP和As-NIP对As(V)的去除率。结果如图4所示，其中As-IIP对As(V)的去除率可以达到97％以上，实施例2：
一种介孔硅藻As(V)离子表面印迹材料的制备方法和应用，包括如下步骤：
(1)活化硅藻土：称30g硅藻土用2mol/L的盐酸70℃水浴加热回流12h，之后抽滤，用去离子水洗至中性，最后80℃烘干；
(2)称取0.25mmol的砷酸钠固体在三口瓶中，然后加入10mL超纯水使其充分溶解，再量取80mL的甲醇加入三口瓶中，混匀之后，滴加2mL的氨基丙基三甲氧基硅烷，反应2h，接着加入活化后的硅藻土4g，60℃冷凝回流20h，之后加入2.7mL的环氧氯丙烷，继续反应4h，冷却后抽滤，用无水乙醇洗涤2～3次；
(3)最后用1mol/L的盐酸在常温下洗脱2h，再用去离子水洗涤至中性，80℃烘干，得到介孔硅藻As(V)离子印迹材料；
(4)将步骤(3)的得到的印迹材料记作As-IIP，作为对比非印迹材料记作As-NIIP。同时取一系列0.1gAs-IIP和As-NIP分别加入到100mL离心管中,加入25mLpH＝5浓度为10mg/L的As(V)/Cd(Ⅱ)、As(V)/Pb(Ⅱ)、As(V)/Cr(Ⅵ)一系列二元竞争混合溶液，吸附时间60min,吸附温度25℃,在回旋式水浴恒温振荡器中以150r/min的转速振荡至吸附平衡；
(5)将步骤(4)所得溶液用0.45μm滤膜过滤，用原子荧光光度计测定滤液中的As(V)浓度,用原子吸收测定相应混合离子的浓度，并得出As-IIP和As-NIP在不同二元体系下对As(V)的去除率和相应混合离子的去除率。结果显示介孔硅藻As(V)离子表面印迹材料对As(V)表现出良好的选择性,其中As(V)相对于竞争吸附离子Cd(Ⅱ)、Pb(Ⅱ)和Cr(Ⅵ)的选择性系数分别为2.64，2.45，9.67均大于1.5，具有良好的选择性。

Claims (2)

1.一种介孔硅藻As(V)离子表面印迹材料的制备方法和应用，其特征在于包括以下步骤:
(1)活化硅藻土：称30g硅藻土用2mol/L的盐酸70℃水浴加热回流8～12h，之后抽滤，用去离子水洗至中性，最后80℃烘干；
(2)称取0.2～0.25mmol的砷酸钠固体在三口瓶中，然后加入10mL超纯水使其充分溶解，再量取80～100mL的甲醇加入三口瓶中，混匀之后，滴加2mL的氨基丙基三甲氧基硅烷，反应1～2h，接着加入步骤(1)活化后的硅藻土4g，60℃冷凝回流20h，之后加入2.7mL的环氧氯丙烷，继续反应2～4h，冷却后抽滤，用无水乙醇洗涤2～3次；
(3)最后在步骤(2)中加入0.5～1mol/L的盐酸在常温下洗脱2～4h，再用去离子水洗涤至中性，80℃烘干，得到介孔硅藻As(V)离子印迹材料。
2.根据权利要求1所述的介孔硅藻As(V)离子表面印迹材料的应用，其特征在于，该离子印迹材料可以很好的应用于水中As(V)离子的去除。
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CN110294524A (zh) * 2019-05-09 2019-10-01 太致新材料(上海)有限公司 一种多功能高效净水剂
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CN110201650A (zh) * 2019-06-09 2019-09-06 桂林理工大学 一种硅藻土基Cr（Ⅵ）离子印迹吸附材料的制备方法
CN110201648A (zh) * 2019-06-09 2019-09-06 桂林理工大学 一种硅藻土表面As（Ⅴ）离子印迹吸附材料的制备方法
CN110201649A (zh) * 2019-06-09 2019-09-06 桂林理工大学 一种硅藻土表面As（Ⅲ）离子印迹吸附材料的制备方法
CN111760561A (zh) * 2020-07-23 2020-10-13 桂林理工大学 一种基于MCM-41分子筛表面的As(Ⅲ)离子印迹材料的制备方法
CN113856649A (zh) * 2021-10-09 2021-12-31 上海理工大学 一种硅基介孔五价砷阴离子印迹聚合物的制备方法
CN113856649B (zh) * 2021-10-09 2024-01-12 上海理工大学 一种硅基介孔五价砷阴离子印迹聚合物的制备方法
CN115739048A (zh) * 2022-11-17 2023-03-07 广西师范大学 一种正砷酸根离子印迹材料及其制备方法和应用

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