CN114471476A - 磁性多孔有机骨架材料及其制备方法与应用 - Google Patents
磁性多孔有机骨架材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种磁性多孔有机骨架材料及其制备方法和应用，所述方法以氨基改性的Fe3O4作为磁性吸附材料的核，间苯三酚和对苯二甲醛单体结合形成的Ph‑POP多孔有机骨架作为磁性吸附材料的壳，形成具有共轭结构的苯环和丰富的‑OH‑功能化结构，可以和目标分子之间形成多种作用力以便同时萃取不同极性的酰胺类除草剂。本发明合成的磁性多孔有机骨架材料具有较大的比表面积和孔隙率，磁性强，稳定性好，可重复利用，可以满足快速分离分析的需求。
Description
技术领域
本发明涉及吸附剂制备技术领域，具体涉及一种磁性多孔有机骨架材料及其制备方法与应用。
背景技术
随着现代农业的发展，除草剂是当今农药使用的第一大品种，其种类繁多，应用广泛。大规模使用所造成的环境污染，生态破坏以及在水体中的残留等问题日益受到关注。除草剂是农药中毒性最低的一类化合物，但由于品种繁多，使用面积巨大以及不规范使用等原因，除草剂导致的急性危害仍不可忽视。主要表现为对皮肤、眼、呼吸道的刺激，以及急性中毒等。目前酰胺类除草剂是市场的主流产品之一，在近代农田化学除草剂应用中占有重要的位置，大量使用可减少作物损失，进入环境以后，容易转化为二烷基苯醌亚胺，增大动物癌变的风险。报道表明乙草胺可能破坏水体中斑马鱼幼虫的甲状腺内分泌，丁草胺可以诱导姐妹染色单体交换和染色体畸变。美国环保局已将乙草胺、甲草胺和丁草胺等列为B-2类致癌物。水体中的酰胺类除草剂可通过食物链进入人体，影响人体的健康。考虑到对人体健康的保护，对酰胺类除草剂在水体中的残留进行检测分析，具有非常重要的意义。因此，迫切需要建立一种高效简便、快捷灵敏的样品预处理方法体系。
目前常用的检测酰胺类除草剂的方法包括气相色谱法、气相色谱-质谱法和液相色谱-质谱法(HPLC-MS)等，随着质谱技术的飞速发展，相对于HPLC-MS方法，液相色谱串联质谱(HPLC-MS/MS)技术进一步提高了选择性、准确性，同时降低检出限，受到研究者们的青睐。
对于复杂基质样品中酰胺类除草剂浓度低、基质复杂、种类繁多、性质差异大，分析检测困难。研究同时、高效、高通量的样品预处理技术是其亟待解决的关键问题。样品中酰胺类除草剂的预处理方法多采用液液萃取、固相萃取、固相微萃取、超声萃取和QuEChERS法等。近年来，磁固相萃取技术因其独特的化学性质、良好的生物相容性和磁性可分离性，在样品前处理领域得到广泛关注。一方面因为，磁性吸附材料可在外加磁场作用下能够快速分离；另一方面，磁性吸附材料都具有核-壳结构，多孔有机聚合物(POPs)因高度交联的刚性对称骨架，较高的力学和热稳定性、巨大的表面积和合适的孔径分布作为磁性吸附材料的外壳结构(分子间作用力和疏水作用为吸附提供了大的表面积和活性位点)不仅起到富集作用，同时可以选择不同类型的多孔材料作为外壳可以实现分离和富集不同酰胺类除草剂的目的。综合这些优势，磁性多孔吸附材料有望具有巨大的潜力。然而，本发明的发明人研究发现，目前磁性吸附材料存在制备时间长、反应条件苛刻等缺陷，且吸附材料在除草剂吸附分离应用中效果不理想，因此，需要研究一种制备简单，对酰胺类除草剂富集提取性能好、脱附快速的材料。
发明内容
本发明的目的在于提供一种磁性多孔有机骨架材料及其制备方法与应用，以解决水体中酰胺类除草剂检测、分离困难，现有磁性吸附材料成本高、吸附脱附性能不理想的问题。本发明针对磁性多孔有机骨架材料类POPs吸附剂在应用后期分离困难的技术缺陷，提供磁性改进，形成具有磁性的核-壳材料，在确保富集性能高的基础上，实现材料在脱附过程的快速分离，降低材料的应用成本。
本发明提供的具体技术方案是：一种磁性多孔有机框架材料的制备方法；包括以下步骤：
(a)采用溶剂热法制备磁性Fe3O4颗粒，制备的Fe3O4颗粒经洗涤、真空干燥后待用；
(b)将Fe3O4颗粒置于乙醇和水的混合溶液中，并加入正硅酸乙酯和氨水，反应得到磁性纳米粒子Fe3O4@SiO2；
(c)将磁性纳米粒子Fe3O4@SiO2加入到乙醇溶液中，超声分散，再加入3-氨基丙基三乙氧基硅(APTES)，加热回流，最后产物经无水乙醇洗涤后，得到表面氨基修饰的Fe3O4@SiO2-NH2磁性纳米粒子，Fe3O4@SiO2与APTES的比例为0.1g：0.5-1.2mL；
(d)将Fe3O4@SiO2-NH2磁性纳米粒子、间苯三酚、对苯二甲醛、盐酸置于1，4-二氧六环的溶液中，超声混合，反应溶液加热回流反应20-28h；所得产物经磁分离后进行洗涤、干燥，即得到所述的磁性多孔有机框架材料Fe3O4@SiO2-NH2@Ph-POP；Fe3O4@SiO2-NH2磁性纳米粒子、间苯三酚、对苯二甲醛的质量比为4-15：5：4。
步骤(a)所述Fe3O4颗粒通过以下步骤制得：
(a-1)将FeCl3·6H2O、无水乙酸钠和PEG-4000溶于乙二醇中，搅拌均匀，FeCl3·6H2O、无水乙酸钠和PEG-4000的质量比为2.03：5.2-5.6：1.2-1.8；
(a-2)将反应液转移到反应釜中180-220℃反应5-9h，产物经无水乙醇洗涤后，真空40℃干燥过夜。
步骤(b)中，乙醇和水的混合溶液中乙醇与水的体积比为3-5:1；所述加热反应，反应温度为28-32℃，反应时间为20-28h。
步骤(d)中，Fe3O4@SiO2-NH2磁性纳米粒子、间苯三酚、对苯二甲醛的质量比为2：1：0.8。
步骤(d)中，反应溶液加热至100℃回流搅拌；产物经磁分离后，分别用水和乙醇进行洗涤，然后分散于N,N-二甲基甲酰胺(DMF)中加热回流1-3h除去未反应原料；所得产物经无水乙醇洗涤后，室温真空干燥20-28h得到磁性多孔有机框架材料。
上述方法制备的磁性多孔有机框架材料。
上述方法制备的磁性多孔有机框架材料作为吸附剂应用于水体中酰胺类除草剂的富集提取。
所述应用包括：将磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP加入到含有酰胺类除草剂的水样中，震荡后磁分离除去水样，然后向磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP中加入洗脱剂回收待测物，并进行液相色谱串联质谱(HPLC-MS/MS)测定。
吸附剂的吸附时间为5～15min，洗脱时间为2～10min，洗脱剂为乙腈。
本发明的有益效果在于：
(1)本发明成功制备了一种磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP，合成方法简单，吸附性能优异，重复性高，可以应用于水体中除草剂残留的富集检测。
(2)现有的固相萃取(SPE)介质多为微米级材料，多采用癸酸、聚吡咯等聚合物为磁性外壳，形成的材料仅依靠材料表面密布的微孔及数量有限的活性基团作用对目标物的吸附，提取效率有限。不同于传统的SPE介质，本发明磁性多孔材料的高比表面积可提供数量巨大的结合位点，为高效提取提供了本质的保证。磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP拥有较大的比表面积(提高其吸附动力学)和特异性的吸附作用(提高其专属性)，给高效分离、提取和富集奠定了基础。
(3)本发明以氨基改性的Fe3O4作为磁性吸附材料的核，间苯三酚和对苯二甲醛单体结合形成的Ph-POP多孔有机骨架作为磁性吸附材料的壳，形成具有共轭结构的苯环和丰富的-OH-功能化结构，可以和目标分子之间形成多种作用力，如静电引力作用、π-π共轭作用、氢键等，可同时萃取不同极性的酰胺类除草剂。同时Ph-POP成环后因羟基之间强烈的分子内氢键的形成，增强了大环的稳定性，减小环张力，使其孔隙率分布更大，具有更强的吸附亲和力和渗透性，吸附动力学速度更快，也更加便于与HPLC-MS/MS分析法衔接。本发明合成的磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP具有较大的比表面积和孔隙率，同时具有磁性强、稳定性好、可重复利用等优点，可以满足快速分离分析的需求。
附图说明
图1本发明磁性多孔有机框架材料的合成流程图。
图2为本发明实施例1所合成的四氧化三铁纳米粒子(a)和磁性多孔有机骨架材料(b)的扫描电镜图；四氧化三铁纳米粒子(c)和磁性多孔有机骨架材料(d)的透射电镜图。
图3为本发明实施例1磁性多孔有机骨架材料的N2吸附-脱附表征。
图4为本发明实施例1磁性多孔有机骨架材料的磁力性质表征。
图5为本发明实施例1所得磁性多孔有机骨架材料(Fe3O4@SiO2-NH2@Ph-POP)对水体中8类酰胺类除草剂为例的5个回收-再利用循环后的吸附效果图。
具体实施方式
以下结合附图和实施例对本发明进一步详细说明。在下述实施例中未详细描述的过程和方法是本领域公知的常规方法，实施例中所用原料或试剂除另有说明外均为市售品，可通过商业渠道购得。
实施例1
磁性多孔有机骨架材料的制备过程如图1所示。
(1)Fe3O4磁性纳米粒子的制备：精准称取2.03g FeCl3·6H2O溶于60mL乙二醇中，充分搅拌溶解后，向其中分别加入5.4g无水乙酸钠和1.5g PEG-4000，充分搅拌后得到棕色浑浊溶液，转移到反应釜中200℃反应7h，产物经无水乙醇洗涤三次得到Fe3O4磁性纳米粒子，真空40℃干燥过夜；
(2)采用溶胶-凝胶方法制备Fe3O4@SiO2：向步骤(1)中Fe3O4纳米粒子的乙醇和水的混合溶液加入正硅酸乙酯和氨水，反应得到磁性纳米粒子Fe3O4@SiO2，Fe3O4纳米粒子、正硅酸乙酯和氨水的比例为0.1g:1mL:1.5mL；乙醇和水的体积比为4:1，反应条件为30℃，24h。
(3)氨基改性磁性纳米粒子制备Fe3O4@SiO2-NH2：将磁性纳米粒子Fe3O4@SiO2加入到乙醇溶液，超声分散，再加入APTES，加热回流，最后产物经无水乙醇洗涤三次，得到表面氨基修饰的Fe3O4@SiO2-NH2磁性纳米粒子，Fe3O4@SiO2与APTES的比例为0.1g：0.8mL。
(4)核-壳结构Fe3O4@SiO2-NH2@Ph-POP的磁性多孔有机骨架材料的制备：先将250mg Fe3O4@SiO2-NH2磁性纳米粒子加入装有20mL 1,4-二氧六环圆底烧瓶中，超声10min后，依次将125mg间苯三酚(0.99mmol)、100mg对苯二醛(0.75mmo1)和0.5mL盐酸加入到圆底烧瓶中，反应溶液加热至100℃回流搅拌，反应24h；产物经磁分离后，分别用水和乙醇洗涤三次，然后分散于DMF中加热回流2h以除去未反应的间苯三酚和对苯二醛；所得产物经无水乙醇洗涤后室温真空干燥24h得到磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP。对所得材料进行表征，结果如图2-4所示。
将其用于水体中酰胺类除草剂的富集提取，具体为：称取16mg磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP加入到10ml含有酰胺类除草剂50ng/mL的水样中，涡旋10min，磁分离除去水样，向磁性多孔有机骨架材料中加入2.5mL乙腈溶液，超声8min，移出乙腈氮吹至干，用1ml甲醇复溶，过0.2μm滤膜后，注入HPLC-MS/MS中分析，通过计算回收率来评价磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP对31种酰胺类除草剂的富集效果，回收率为75.41-105.07％，以其中8种酰胺类除草剂为例，回收率如表1所示。
表1磁性多孔有机骨架材料对8种酰胺类除草剂的回收率
| 化合物 | 回收率(％) |
| 敌稗 | 91.22 |
| 异噁酰草胺 | 95.25 |
| 草氟胺 | 93.69 |
| 苯噻酰草胺 | 96.66 |
| 乙草胺 | 94.80 |
| 噻吩草胺 | 92.34 |
| 异丙甲草胺 | 94.34 |
| 庚酰草胺 | 93.78 |
实施例2
(1)Fe3O4磁性纳米粒子的制备：精准称取2.03g FeCl3·6H2O溶于60mL乙二醇中，充分搅拌溶解后，向其中分别加入5.4g无水乙酸钠和1.5g PEG-4000，充分搅拌后得到棕色浑浊溶液，转移到反应釜中200℃反应7h，产物经无水乙醇洗涤三次得到Fe3O4磁性纳米粒子，真空40℃干燥过夜；
(2)采用溶胶-凝胶方法制备Fe3O4@SiO2：向步骤(1)中Fe3O4纳米粒子的乙醇和水的混合溶液加入正硅酸乙酯和氨水，反应得到磁性纳米粒子Fe3O4@SiO2，Fe3O4纳米粒子、正硅酸乙酯和氨水的比例为0.1g:1mL:1.5mL；乙醇和水的体积比为4:1，反应条件为30℃，24h。
(3)氨基改性磁性纳米粒子制备Fe3O4@SiO2-NH2：将磁性纳米粒子Fe3O4@SiO2加入到乙醇溶液，超声分散，再加入APTES，加热回流，最后产物经无水乙醇洗涤三次，得到表面氨基修饰的Fe3O4@SiO2-NH2磁性纳米粒子，Fe3O4@SiO2与APTES的比例为0.1g：0.5mL。
(4)核-壳结构Fe3O4@SiO2-NH2@Ph-POP的磁性多孔有机骨架材料的制备：取100mgFe3O4@SiO2-NH2磁性纳米粒子加入装有20mL 1,4-二氧六环圆底烧瓶中，超声10min后，依次将125mg间苯三酚(0.99mmol)、100mg对苯二醛(0.75mmo1)和0.5mL盐酸加入到圆底烧瓶中，反应溶液加热至100℃回流搅拌，反应20h；产物经磁分离后，分别用水和乙醇洗涤三次，然后分散于DMF中加热回流2h以除去未反应的间苯三酚和对苯二醛；所得产物经无水乙醇洗涤后室温真空干燥24h得到磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP。对其进行表征，其具有实施例1所得材料类似的性能，将其用于水体中31种酰胺类除草剂的富集提取(方法同实施例1)，回收率为69.04-97.56％，以其中8种酰胺类除草剂为例，回收率如表2所示。
表2磁性多孔有机骨架材料对8种酰胺类除草剂的回收率
| 化合物 | 回收率(％) |
| 敌稗 | 80.13 |
| 异噁酰草胺 | 77.11 |
| 草氟胺 | 74.60 |
| 苯噻酰草胺 | 76.22 |
| 乙草胺 | 75.91 |
| 噻吩草胺 | 81.84 |
| 异丙甲草胺 | 82.65 |
| 庚酰草胺 | 78.52 |
实施例3
(1)Fe3O4磁性纳米粒子的制备：精准称取2.03g FeCl3·6H2O溶于60mL乙二醇中，充分搅拌溶解后，向其中分别加入5.4g无水乙酸钠和1.5g PEG-4000，充分搅拌后得到棕色浑浊溶液，转移到反应釜中200℃反应7h，产物经无水乙醇洗涤三次得到Fe3O4磁性纳米粒子，真空40℃干燥过夜；
(2)采用溶胶-凝胶方法制备Fe3O4@SiO2：向步骤(1)中Fe3O4纳米粒子的乙醇和水的混合溶液加入正硅酸乙酯和氨水，反应得到磁性纳米粒子Fe3O4@SiO2，Fe3O4纳米粒子、正硅酸乙酯和氨水的比例为0.1g:1mL:1.5mL；乙醇和水的体积比为4:1，反应条件为30℃，24h。
(3)氨基改性磁性纳米粒子制备Fe3O4@SiO2-NH2：将磁性纳米粒子Fe3O4@SiO2加入到乙醇溶液，超声分散，再加入APTES，加热回流，最后产物经无水乙醇洗涤三次，得到表面氨基修饰的Fe3O4@SiO2-NH2磁性纳米粒子，Fe3O4@SiO2与APTES的比例为0.1g：1.2mL。
(4)核-壳结构Fe3O4@SiO2-NH2@Ph-POP的磁性多孔有机骨架材料的制备：取375mgFe3O4@SiO2-NH2磁性纳米粒子加入装有20mL 1,4-二氧六环圆底烧瓶中，超声10min后，依次将125mg间苯三酚(0.99mmol)、100mg对苯二醛(0.75mmo1)和0.5mL盐酸加入到圆底烧瓶中，反应溶液加热至100℃回流搅拌，反应28h；产物经磁分离后，分别用水和乙醇洗涤三次，然后分散于DMF中加热回流2h以除去未反应的间苯三酚和对苯二醛；所得产物经无水乙醇洗涤后室温真空干燥24h得到磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP。对其进行表征，其具有实施例1所得材料类似的性能，将其用于水体中31种酰胺类除草剂的富集提取(方法同实施例1)，回收率为73.23-98.89％，以其中8种酰胺类除草剂为例，回收率如表3所示。
表3磁性多孔有机骨架材料对8种酰胺类除草剂的回收率
| 化合物 | 回收率(％) |
| 敌稗 | 85.41 |
| 异噁酰草胺 | 81.30 |
| 草氟胺 | 83.77 |
| 苯噻酰草胺 | 86.61 |
| 乙草胺 | 87.53 |
| 噻吩草胺 | 84.32 |
| 异丙甲草胺 | 85.71 |
| 庚酰草胺 | 88.68 |
实施例4
称取实施例1中制得的磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP 16mg加入到10ml含有酰胺类除草剂50ng/mL的水样中，涡旋10min，磁分离除去水样，向磁性多孔有机骨架材料中加入2.5mL乙腈溶液，超声8min，移出乙腈氮吹至干，用1ml甲醇复溶，过0.2μm滤膜后，进样分析酰胺类除草剂的回收率。将上述磁性多孔有机骨架材料使用3mL乙腈洗涤后，重复上述吸附实验，计算回收率。结果如图5所示，该材料经5个回收-再利用循环后，对31种酰胺类除草剂仍保持较好的富集效率，以其中8种酰胺类除草剂为例，回收率仍保持在75％以上，结果如图5所示，表明该材料具有较好的稳定性和重复性。
显然，本发明的保护范围不仅局限于上述内容。基于本发明中的实施例，熟悉本技术领域的人员还可据此做出多种变化，但任何与本发明等同或相类似的变化都属于本发明保护的范围。
Claims (9)
1.一种磁性多孔有机框架材料的制备方法；其特征在于，包括以下步骤：
（a）采用溶剂热法制备磁性Fe3O4颗粒，制备的Fe3O4颗粒经洗涤、真空干燥后待用；
（b）将Fe3O4颗粒置于乙醇和水的混合溶液中，并加入正硅酸乙酯和氨水，反应得到磁性纳米粒子Fe3O4@SiO2；
（c）将磁性Fe3O4@SiO2加入到乙醇溶液中，超声分散，再加入3-氨基丙基三乙氧基硅(APTES)，加热回流，最后产物经无水乙醇洗涤后，得到表面修饰氨基的Fe3O4@SiO2-NH2磁性纳米粒子，Fe3O4@SiO2与APTES的比例为0.1g：0.5-1.2mL；
（d）将Fe3O4@SiO2-NH2磁性纳米粒子、间苯三酚、对苯二甲醛、盐酸置于1，4-二氧六环的溶液中，超声混合，反应溶液加热回流反应20-28h；所得产物经磁分离后进行洗涤、干燥，即得到所述的磁性多孔有机框架材料Fe3O4@SiO2-NH2@Ph-POP；Fe3O4@SiO2-NH2磁性纳米粒子、间苯三酚、对苯二甲醛的质量比为4-15：5：4。
2.根据权利要求1所述的制备方法，其特征在于，步骤（a）所述Fe3O4颗粒通过以下步骤制得：
（a-1）将FeCl3·6H2O、无水乙酸钠和PEG-4000溶于乙二醇中，搅拌均匀，FeCl3·6H2O、无水乙酸钠和PEG-4000的质量比为2.03：5.2-5.6：1.2-1.8；
（a-2）将反应液转移到反应釜中180-220℃反应5-9h，产物经无水乙醇洗涤后，真空40℃干燥过夜。
3.根据权利要求1所述的制备方法，其特征在于，步骤（b）中，所述Fe3O4颗粒、正硅酸乙酯和氨水的比例为0.1g：0.5-1.5mL：1-2mL；乙醇和水的混合溶液中乙醇与水的体积比为3-5:1。
4.根据权利要求1所述的制备方法，其特征在于，步骤（b）中，反应温度为28-32℃，反应时间为20-28h。
5.根据权利要求1所述的制备方法，其特征在于，步骤（d）中，反应溶液加热至100℃回流搅拌；产物经磁分离后，分别用水和乙醇进行洗涤，然后分散于N,N-二甲基甲酰胺中加热回流1-3h除去未反应原料；所得产物经无水乙醇洗涤后，室温真空干燥20-28h得到磁性多孔有机框架材料。
6.权利要求1-5任一所述方法制备的磁性多孔有机框架材料。
7.权利要求1-5任一所述方法制备的磁性多孔有机框架材料作为吸附剂应用于水体中酰胺类除草剂的富集提取。
8.根据权利要求7所述的应用，其特征在于，所述应用包括：将磁性多孔有机骨架材料Fe3O4@SiO2-NH2@Ph-POP加入到含有酰胺类除草剂的水样中，震荡后磁分离除去水样，然后向磁性多孔有机骨架材料中加入洗脱剂回收待测物，并进行液相色谱串联质谱测定。
9.根据权利要求8所述的应用，其特征在于，吸附剂的吸附时间为5～15min，洗脱时间为2～10min，洗脱剂为乙腈。
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| CN117225377B (zh) * | 2023-08-10 | 2024-05-03 | 石家庄市疾病预防控制中心（石家庄市卫生检测中心） | 一种核壳结构共价有机骨架材料、其制备方法及应用 |
| CN116832791B (zh) * | 2023-08-10 | 2024-09-10 | 石家庄市疾病预防控制中心（石家庄市卫生检测中心） | 一种磁性共价有机骨架材料、其制备方法及应用 |
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