CN109621889A - 介孔磁性硅基微囊藻毒素吸附剂的制备方法 - Google Patents
介孔磁性硅基微囊藻毒素吸附剂的制备方法 Download PDFInfo
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Abstract
本发明涉及一种介孔磁性硅基微囊藻毒素吸附剂的制备方法。该方法包括以下步骤:步骤一,将FeCl3·6H2O,加入到乙二醇中溶解,加入全部NaAc和聚乙二醇4000,搅拌形成粘稠液体;将混合溶液转移到水热合成釜中,放入烘箱反应;反应结束后用磁铁分离出黑色沉淀,用去离子水和无水乙醇洗涤后烘干得到Fe3O4磁性纳米粒子;步骤二,Fe3O4分散于HCl中,磁性分离出Fe3O4用纯水洗涤;将其分散于无水乙醇、水中,加入模板剂和氨水,将TEOS加入,反应后用磁铁收集产物;加入乙醇中去除模板剂,再清洗后烘干,得到介孔Fe3O4@SiO2。本发明方法能够减少试剂污染,同时使材料具有更好的吸附性能。
Description
技术领域
本发明涉及一种用于水质检测和处理的材料制备,具体是一种介孔磁性硅基微囊藻毒素吸附剂的制备方法。
背景技术
湖泊中蓝藻爆发会产生对人体有毒害作用的微囊藻毒素,近年来,对微囊藻毒素的吸附处理方法有较多的研究。目前采用介孔磁性硅基吸附材Fe3O4@SiO2进行水中微囊藻毒素的吸附研究,主要集中于制备方法及富集实验。
一、在制备Fe3O4@SiO2材料过程中,目前的方法中均包含采用75℃用丙酮回流48小时去除模板剂CTAB的步骤。该方法实践中有以下问题:
1)、该方法耗时长,操作繁琐,需要搭建回流装置,无法批量处理。
2)、由于在75℃下回流,高于丙酮的沸点(56.5℃),因此回流冷凝的效果较差。
3)、大量采用丙酮试剂对环境及人体都有损害。
二、在制备Fe3O4@SiO2@Cu2+介孔材料时,目前是采用0.56gFe3O4@SiO2+0.17gCuNO3·3H2O进行制备,实践中发现,得到的介孔材料吸附效率难以有效提高,现有文献记载的回收率为78%。因此需要调变两者比例,使其吸附性能达到最佳。
发明内容
本发明所要解决的技术问题是,提供一种改进的介孔磁性硅基微囊藻毒素吸附剂的制备方法,使其在制备Fe3O4@SiO2介孔材料时,能够高效便捷地去除模板剂,减少试剂污染,同时使材料具有更好的吸附性能。
本发明的介孔磁性硅基微囊藻毒素吸附剂的制备方法包括以下步骤:
步骤一,磁性纳米粒子的制备:
采用水热合成法制备,根据质量比Fe:NaAc:聚乙二醇4000=1:13:3.6的比例称取FeCl3·6H2O、NaAc和聚乙二醇;将FeCl3·6H2O,加入到乙二醇中,其中铁元素的质量与乙二醇的体积之为0.25~0.3g:40ml,搅拌使固体溶解,加入全部NaAc和聚乙二醇4000,继续搅拌使之形成均一的粘稠液体;然后将混合溶液转移到水热合成釜中,密封后放入烘箱,180~200℃下反应7~9h;反应结束后用磁铁分离出黑色沉淀,用去离子水和无水乙醇充分洗涤后,在55~65℃下烘箱烘干得到Fe3O4磁性纳米粒子;
步骤二,硅基Fe3O4@SiO2磁性复合微球的制备:
称取Fe3O4分散于0.1mol/L HCl中,其中铁元素质量与0.1mol/L HCl溶液体积之比为0.070~0.074g:50ml,充分分散后磁性分离出Fe3O4并用纯水充分洗涤;再将其均匀分散于装有无水乙醇、水的三颈烧瓶中,其中铁元素质量与乙醇体积、水的体积之比为0.070~0.074g:60ml:80ml;同时加入模板剂和质量浓度28%的氨水,铁元素质量:模板剂质量:质量浓度28%的氨水体积=0.072g:0.2g:1ml;连续搅拌0.5~1h后,再将TEOS逐滴加入,其中铁元素质量与TEOS体积之比为0.070~0.074g:0.5ml;继续搅拌充分反应后,用磁铁收集产物并用纯水、无水乙醇分别洗涤去除非磁性产物;最后将纯净的产物加入乙醇中,其中铁元素质量与乙醇体积之比为0.070~0.074g:150ml,在55~65℃下振荡去除模板剂,再用纯水和乙醇分别清洗后,入烘箱里55~65℃烘干,最终得到介孔Fe3O4@SiO2。
进一步的,所述模板剂为CTAB。
进一步的,还包括步骤三,Fe3O4@SiO2@Cu2+磁性纳米粒子的制备:
将介孔Fe3O4@SiO2分散于蒸馏水中,介孔Fe3O4@SiO2质量与蒸馏水体积之比为0.140.16g:20ml,制得混合液A;将0.10gCuNO3·3H2O溶于20mL蒸馏水并向其中加入1.0mL氨水,CuNO3·3H2O质量、蒸馏水体积、氨水体积之比为0.09~0.11:20ml:1.0ml,制得溶液B;将混合液A和溶液B混合均匀,其中Fe3O4与CuNO3·3H2O的质量比为1.4~1.6:1,混合后转移至水热反应釜中,密封后放入烘箱135~145℃下加热9~11h,冷却至室温,磁性分离,用纯水和分别乙醇清洗后,55~65℃下烘干,获得最终产物。
本发明的优点体现在:1、通过选择合适的模板剂和萃取液,提高了模板剂的去除操作效率和去除效果,有利于提高材料对微囊藻毒素的回收率;2、通过优化Fe3O4与CuNO3·3H2O的比例,使最终材料对微囊藻毒素的回收率大幅提高,可达90%以上。
具体实施方式
下面结合实施例对本发明的方法作进一步说明。
实施例一,制备介孔Fe3O4@SiO2微囊藻毒素吸附剂:
1)磁性纳米粒子的制备
磁性纳米粒子采用水热合成法制备,称取1.35g的FeCl3·6H2O,加入到40mL乙二醇中,搅拌使固体溶解,加入3.60gNaAc和1.00g聚乙二醇4000,继续搅拌使之形成均一的粘稠液体。然后将混合溶液转移到50mL的水热合成釜中,密封后放入烘箱,190℃下反应8h。反应结束后用磁铁分离出黑色沉淀,用去离子水和无水乙醇充分洗涤,60℃下烘箱干燥6h,得到Fe3O4磁性纳米粒子。
2)硅基Fe3O4@SiO2磁性复合微球的制备
准确称取0.10g Fe3O4分散于50mL 0.1mol/L HCl中,超声10min,磁性分离出Fe3O4并用纯水充分洗涤后,再将其均匀分散于装有60mL无水乙醇、80mL水的三颈烧瓶中,同时加入0.2g模板剂CTAB和1mL氨水(质量分数28%),连续搅拌0.5h后,再将0.5mL TEOS逐滴加入上述溶液,继续搅拌6h。搅拌停止后,用磁铁收集产物并用纯水、无水乙醇各洗2-3次去除非磁性产物。最后将纯净的产物加入150mL乙醇中,60℃下振荡3h,重复此步骤1次以去除模板剂,再用纯水清洗2次,乙醇清洗2次,烘箱里60℃烘6h,最终得到介孔Fe3O4@SiO2。
用制备得到的介孔Fe3O4@SiO2对太湖蓝藻爆发时候的水样各500mL(加标浓度为25.0ug/L)进行吸附测试,观察可知,原本浑浊且呈绿色的水样变成为微黄色且澄清,说明水中的藻类分解的物质被吸附材料吸附掉。将材料用乙腈-磷酸溶液解吸后用HPLC进行测试,测试结果如下表。
由表可知,当加入的Fe3O4@SiO2为25.0mg时,回收率达到88.8~92.0%,因此,该方法制备得到的材料对于微囊藻毒素的吸附效果是显著的。
实施例二,制备Fe3O4@SiO2@Cu2+磁性纳米粒子:
利用水热合成法制备Fe3O4@SiO2@Cu2+MNPs:称取0.15g实施例一获得的介孔Fe3O4@SiO2分散于20mL蒸馏水中;再称取0.10gCuNO3·3H2O溶于20mL蒸馏水并向其中加入1.0mL氨水;分别超声30min。将上述两种液体混合转移至水热反应釜中,密封后放入烘箱140℃下加热10h,冷却至室温,磁性分离,用二次水洗3次,无水乙醇洗3次后,60℃下干燥6h,获得最终产物。
得到的Fe3O4@SiO2@Cu2+对水中微囊藻毒素进行富集并用HPLC进行测定,检出限为0.06ug/L。测定方法如下:
1)磁性固相萃取
称取10.0mg的磁性纳米粒子,加入到500mL样品溶液中,旋涡振荡使含有MC-LR的样品与磁性吸附剂充分接触混合,振荡60min。在此过程中,MC-LR被吸附到磁性纳米粒子表面。振荡萃取结束后,将磁铁置于样品瓶底部外侧,使吸附了MC-LR的吸附剂被吸附到样品瓶内侧的底部,将上清液吸出。随后加入洗脱液乙腈-0.1%(v/v)磷酸水(3:1,v/v)2mL,超声混合30min,立即离心,取出含有MC-LR的上清液,用氮气吹扫浓缩,定容至200uL,进行高效液相色谱分析。
2)高效液相色谱测定
色谱柱:SpursilC18色谱柱(250mm×4.6mm,5μm,DikmaTechnologies);柱温:30℃;检测波长:238nm;流速:1.0mL/min;流动相为乙腈-0.1%(v/v)磷酸水溶液(35:65,v/v);进样量:10μL。实验依据保留时间定性。
依据该方法对太湖蓝藻爆发时的水样各500mL进行富集后检测,测试结果见下表。
由表可知,10.0mg的Fe3O4@SiO2@Cu2+对水样中微囊藻毒素进行测试,标准偏差及相对标准偏差均符合质控要求。
Claims (3)
1.一种介孔磁性硅基微囊藻毒素吸附剂的制备方法,其特征是:包括以下步骤,
步骤一,磁性纳米粒子的制备:
采用水热合成法制备,根据质量比Fe:NaAc:聚乙二醇4000=1:13:3.6的比例称取FeCl3·6H2O、NaAc和聚乙二醇;将FeCl3·6H2O,加入到乙二醇中,其中铁元素的质量与乙二醇的体积之为0.25~0.3g:40ml,搅拌使固体溶解,加入全部NaAc和聚乙二醇4000,继续搅拌使之形成均一的粘稠液体;然后将混合溶液转移到水热合成釜中,密封后放入烘箱,180~200℃下反应7~9h;反应结束后用磁铁分离出黑色沉淀,用去离子水和无水乙醇充分洗涤后, 在55~65℃下烘箱烘干得到Fe3O4磁性纳米粒子;
步骤二,硅基Fe3O4@SiO2磁性复合微球的制备:
称取 Fe3O4分散于0.1mol/L HCl中,其中铁元素质量与0.1mol/L HCl溶液体积之比为0.070~0.074g:50ml,充分分散后磁性分离出Fe3O4并用纯水充分洗涤;再将其均匀分散于装有无水乙醇、水的三颈烧瓶中,其中铁元素质量与乙醇体积、水的体积之比为0.070~0.074g:60ml:80ml;同时加入模板剂和质量浓度28%的氨水,铁元素质量:模板剂质量:质量浓度28%的氨水体积=0.072g:0.2g:1ml;连续搅拌0.5~1h后,再将TEOS逐滴加入,其中铁元素质量与TEOS体积之比为0.070~0.074g:0.5ml;继续搅拌充分反应后,用磁铁收集产物并用纯水、无水乙醇分别洗涤去除非磁性产物;最后将纯净的产物加入乙醇中,其中铁元素质量与乙醇体积之比为0.070~0.074g:150ml,在55~65℃下振荡去除模板剂,再用纯水和乙醇分别清洗后,入烘箱里55~65℃烘干,最终得到介孔Fe3O4@SiO2。
2.根据权利要求1所述的介孔磁性硅基微囊藻毒素吸附剂的制备方法,其特征是:所述模板剂为CTAB。
3.根据权利要求1或2所述的介孔磁性硅基微囊藻毒素吸附剂的制备方法,其特征是:
还包括步骤三,Fe3O4@SiO2@Cu2+ 磁性纳米粒子的制备:
将介孔Fe3O4@SiO2分散于蒸馏水中,介孔Fe3O4@SiO2质量与蒸馏水体积之比为0.140.16g:20ml,制得混合液A;将0.10gCuNO3·3H2O溶于20 m L蒸馏水并向其中加入1.0mL氨水,CuNO3·3H2O质量、蒸馏水体积、氨水体积之比为0.09~0.11:20ml:1.0ml,制得溶液B;将混合液A和溶液B混合均匀,其中Fe3O4与CuNO3·3H2O的质量比为1.4~1.6:1,混合后转移至水热反应釜中,密封后放入烘箱135~145℃下加热9 ~11h,冷却至室温,磁性分离,用纯水和分别乙醇清洗后,55~65℃下烘干,获得最终产物。
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