CN113181887B - 一种pam/mof/cof复合材料及其制备方法、应用 - Google Patents
一种pam/mof/cof复合材料及其制备方法、应用 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 6
- 150000002466 imines Chemical class 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 125000002091 cationic group Chemical group 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- VDBJCDWTNCKRTF-UHFFFAOYSA-N 6'-hydroxyspiro[2-benzofuran-3,9'-9ah-xanthene]-1,3'-dione Chemical compound O1C(=O)C2=CC=CC=C2C21C1C=CC(=O)C=C1OC1=CC(O)=CC=C21 VDBJCDWTNCKRTF-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000356 contaminant Substances 0.000 claims 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- 150000003384 small molecules Chemical class 0.000 claims 1
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000975 dye Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- NSDSIQGBHACTLY-UHFFFAOYSA-N Reactive Blue 5 Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S(O)(=O)=O)C=C1NC(C=1)=CC=C(S(O)(=O)=O)C=1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S(O)(=O)=O)=C1 NSDSIQGBHACTLY-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
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- ROHGQIQUQCTSOK-UHFFFAOYSA-K trisodium;1-amino-4-[3-[[4-chloro-6-(3-sulfonatoanilino)-1,3,5-triazin-2-yl]amino]-4-sulfonatoanilino]-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S([O-])(=O)=O)C=C1NC(C=1)=CC=C(S([O-])(=O)=O)C=1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S([O-])(=O)=O)=C1 ROHGQIQUQCTSOK-UHFFFAOYSA-K 0.000 description 2
- SQKKZLOTNDUUEU-UHFFFAOYSA-M (z)-n-[(z)-(1,3-dimethylbenzimidazol-3-ium-2-yl)methylideneamino]-3-methyl-1,3-benzothiazol-2-imine;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC=C2N(C)C(C=NN=C3N(C4=CC=CC=C4S3)C)=[N+](C)C2=C1 SQKKZLOTNDUUEU-UHFFFAOYSA-M 0.000 description 1
- NJIRSTSECXKPCO-UHFFFAOYSA-M 3-[n-methyl-4-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]anilino]propanenitrile;chloride Chemical compound [Cl-].C1=CC(N(CCC#N)C)=CC=C1\C=C\C1=[N+](C)C2=CC=CC=C2C1(C)C NJIRSTSECXKPCO-UHFFFAOYSA-M 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- KXXFHLLUPUAVRY-UHFFFAOYSA-J [Na+].[Na+].[Na+].[Cu++].[O-]C(=O)C1=CC=C(C=C1N=N[C-](N=NC1=C([O-])C(NC2=NC(F)=NC(NCCOCCS(=O)(=O)C=C)=N2)=CC(=C1)S([O-])(=O)=O)C1=CC=CC=C1)S([O-])(=O)=O Chemical compound [Na+].[Na+].[Na+].[Cu++].[O-]C(=O)C1=CC=C(C=C1N=N[C-](N=NC1=C([O-])C(NC2=NC(F)=NC(NCCOCCS(=O)(=O)C=C)=N2)=CC(=C1)S([O-])(=O)=O)C1=CC=CC=C1)S([O-])(=O)=O KXXFHLLUPUAVRY-UHFFFAOYSA-J 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JGIGXKSJLSQJGQ-UHFFFAOYSA-K trisodium 5-[[4-chloro-6-(N-methylanilino)-1,3,5-triazin-2-yl]amino]-4-hydroxy-3-[(2-sulfonatophenyl)diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].CN(c1ccccc1)c1nc(Cl)nc(Nc2cc(cc3cc(c(N=Nc4ccccc4S([O-])(=O)=O)c(O)c23)S([O-])(=O)=O)S([O-])(=O)=O)n1 JGIGXKSJLSQJGQ-UHFFFAOYSA-K 0.000 description 1
- WTPOYMNMKZIOGO-UHFFFAOYSA-K trisodium;2,5-dichloro-4-[4-[[5-[[4-chloro-6-(4-sulfonatoanilino)-1,3,5-triazin-2-yl]amino]-2-sulfonatophenyl]diazenyl]-3-methyl-5-oxo-4h-pyrazol-1-yl]benzenesulfonate Chemical compound [Na+].[Na+].[Na+].CC1=NN(C=2C(=CC(=C(Cl)C=2)S([O-])(=O)=O)Cl)C(=O)C1N=NC(C(=CC=1)S([O-])(=O)=O)=CC=1NC(N=1)=NC(Cl)=NC=1NC1=CC=C(S([O-])(=O)=O)C=C1 WTPOYMNMKZIOGO-UHFFFAOYSA-K 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
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- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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Abstract
本发明公开了一种用于污染物吸附的PAM/MOF/COF复合材料及其制备方法、应用。先合成MOF晶体材料，再合成PAM/MOF材料，最后引入亚胺类COF材料，形成用于污染物吸附PAM/MOF/COF复合材料。本发明能够得到高度结晶的分级孔结构的PAM/MOF/COF复合材料，在吸附污染物小分子的时候会有层层递进的效果，而且片层中间会形成纳米限域效应，提升催化性能。PAM核层作为吸附点，MOF作为过滤层，进行污染物的过滤和吸附。PAM还起到稳定MOF晶体的作用，提高复合材料的均匀稳定性。COF的稳定外壳结构使MOF在进行过滤和吸附过程中不会造成结构坍塌，维持原有骨架的形状。本发明的PAM/MOF/COF复合材料用于污染物吸附，吸附效率提升达20％以上。
Description
技术领域
本发明属于新材料技术领域，具体涉及一种PAM/MOF/COF复合材料及其制备方法、应用。
背景技术
聚丙烯酰胺(PAM)，是一种线型高分子聚合物，化学式为(C3H5NO)n。在常温下为坚硬的玻璃态固体。具有热稳定性良好、能以任意比例溶于水等特点。聚丙烯酰胺作为润滑剂、悬浮剂、粘土稳定剂、驱油剂、降失水剂和增稠剂，在钻井、酸化、压裂、堵水、固井及二次采油、三次采油中得到了广泛应用，是一种极为重要的油田化学品。金属-有机框架材料(MOF)是近十年来发展迅速的一种配位聚合物，具有三维的孔结构，一般以金属离子为连接点，有机配位体支撑构成空间3D延伸。MOF在催化、储能和分离中都有广泛应用。共价有机骨架(COF)是一类结晶性的有机多孔材料，基于可逆化学反应将功能单元以共价键的形式连接成高度有序的二维层叠层结构或特定的三维拓扑结构。
有机污染物排放会导致严重的水质恶化和水资源短缺。全球每年会产生数亿吨高浓度的残留染液，这些染液进入自然水体被稀释后会产生大量有色废水，摧毁水生态系统。其中，很多活性染料的化学稳定性极高(半衰期甚至长达几十年)，几乎无法自然降解，对水环境的危害很高，因此处理难度大，处理过程复杂。现有技术中有采用Zr-MOF材料来吸附处理活性染料和阳离子染料污染物的方法，但是，该方法存在吸附容量小的缺点。
发明内容
为解决上述技术问题，本发明采用的技术方案是：一种PAM/MOF/COF复合材料，包括有由内至外依次设置的PAM、MOF、COF，所述MOF为UiO-66-NH2晶体，所述COF为亚胺类COF材料，所述PAM包裹在MOF内部形成核壳结构，所述亚胺类COF材料通过化学键连接MOF。
作为上述技术方案的优选，所述亚胺类COF材料为TAPB-COF或TPE-COF。
PAM/MOF/COF复合材料的制备方法，包括以下步骤：
步骤1，聚丙烯酰胺表面活化：将一定比例的PAM和氢氧化钠在80℃-120℃温度下搅拌反应3-4小时，然后洗涤、干燥；
步骤2，通过原位方法组装成均匀稳定的UiO-66-NH2晶体；
步骤3，将UiO-66-NH2晶体加入到高压釜中，在110-130℃温度下搅拌22-26小时，合成具有核壳结构的UiO-66-NH2-聚丙烯酰胺复合材料；
步骤4，将亚胺类COF材料加入到高压釜容器中，在8-16小时内温度保持在100-200℃，得到高度结晶分级孔结构的PAM/MOF/COF复合材料。
作为上述技术方案的优选，所述步骤1中反应温度为90℃，搅拌3时间。
作为上述技术方案的优选，所述步骤3中温度为120℃，搅拌24时间。
作为上述技术方案的优选，所述步骤4中温度为150℃，并搅拌8时间。
PAM/MOF/COF复合材料的应用，将PAM/MOF/COF复合材料用于吸附具有线型结构小分子有机污染物。
作为上述技术方案的优选，所述线型结构小分子有机污染物包括有亚甲基兰、阳离子艳红5GN、阳离子嫩黄7GL中的一种或多种。
作为上述技术方案的优选，所述PAM/MOF/COF复合材料在饱和的NaCl的甲醇溶液中进行脱附，脱附后的PAM/MOF/COF复合材料重复使用。
作为上述技术方案的优选，所述PAM/MOF/COF复合材料重复使用次数为8-12次。
本发明的有益效果是：本发明的PAM/MOF/COF复合材料，PAM核层作为吸附点，MOF/COF作为过滤层，进行污染物进行逐层吸附，提高过滤性能。MOF/COF之间依靠化学键实现连接，结构稳定，机械强度高。由于COF材料的加入，使得表面积进一步增加和更小的带隙，良好的光催化活性可降解有机污染物，实现逐层吸附和过滤的功能。
附图说明
图1是PAM/MOF/COF复合材料的制备流程图；
图2是UiO-66-NH2晶体的扫描图；
图3是UiO-66-NH2-聚丙烯酰胺复合材料的xrd分析图；
图4中高度结晶分级孔的PAM/MOF/COF结构图；
图5是对混合染料的选择性吸附图；
图6是吸附MB的PAM/MOF/COF在NaCl甲醇溶液中的脱附图；
图7是8次循环后及不同PH值下PAM/MOF/COF的X射线衍射图谱。
具体实施方式
下面将结合附图对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
如图1-2所示，(1)将一定比例的PAM和氢氧化钠在80℃-120℃温度下搅拌3-4小时反应一段时间，然后洗涤、干燥。氢氧化钠活化聚丙烯酰胺表面，以减轻其惰性，暴露出官能团，提高了聚丙烯酰胺与UiO-66-NH2晶体之间的亲和力,在PAM上化学接枝UiO-66-NH2。
(2)通过原位方法组装成均匀稳定的UiO-66-NH2晶体，图2是UiO-66-NH2晶体的扫描图。
(3)将UiO-66-NH2晶体加入到高压釜中，在120℃温度下搅拌22-26小时，合成具有核壳结构的UiO-66-NH2-聚丙烯酰胺复合材料。图3是UiO-66-NH2-聚丙烯酰胺复合材料的xrd分析图，表明其中含有PAM内核。
(4)将TAPB-COF材料加入到高压釜容器中，在100-200℃温度下搅拌8-16小时，得到图4中高度结晶分级孔结构的PAM/MOF/COF复合材料。
将上述制得的PAM/MOF/COF复合材料进行扫描电镜分析，如图4所示，表明得到了高度结晶分级孔结构的PAM/MOF/COF复合材料。
将该PAM/MOF/COF复合材料用于有机染料的吸附对比测试：
A、通过将固态的染料溶解在蒸馏水中得到的小尺寸亚甲基蓝(MB)、阳离子艳红5GN(BR14)、阳离子嫩黄7GL(BY24)和大尺寸的活性艳红K-2BP(RR24)、活性黄K-6G(RY2)、活性艳蓝K-GR(RB5)水溶液。分别将MB、BY24和BR14同与其颜色不同的活性染料进行混合得到(MB+RY2)、(MB+RR24)、(BY24+RR24)、(BY24+RB5)、(BR14+RY2)和(BR14+RB5)共6组双染料混合水溶液。其中：亚甲基蓝(C.I.Basic Blue 9，MB)、甲基橙(MO)、阳离子艳红5GN(C.I.Basic Red 14，BR14)、阳离子嫩黄7GL(C.I.Basic Yellow 24，BY24)、活性艳红K-2BP(C.I.Reactive Red 24，RR24)、活性黄K-6G(C.I.Reactive Yellow 2，RY2)和活性艳蓝K-GR(C.I.Reactive Blue 5，RB5)
B、PAM/MOF/COF可以从(MB+RY2)、(MB+RR24)、(BY24+RR24)、(BY24+RB5)、(BR14+RY2)和(BR14+RB5)的混合水溶液中对具有线型结构的MB、BY24和BR14进行高效地选择性吸附，如图5所示，其对MB的吸附效率分别为99.78％(从21.29mg/L下降至0.046mg/L)、93.74％(从17.89mg/L下降至1.12mg/L)，而对BY24的吸附效率分别为79.29％(从112.92mg/L下降至23.39mg/L)、87.72％(从133.21mg/L下降至16.36mg/L)，对BR14的吸附效率分别为97.34％(从53.80mg/L下降至1.43mg/L)、＞79.46％(从44.02mg/L下降至低于9.04mg/L)。此外，PAM/MOF/COF对活性染料RY2、RR24和RB5的吸附能力微弱，这很可能归因于活性染料相对复杂的非线型结构和较大的分子尺寸，使其无法通过PAM/MOF/COF复合材料的特定尺寸的刚性孔道入口。
C、复合材料在30mL质量浓度为20mg/L的MB水溶液中饱和吸附MB后，将其浸泡在30mL饱和的NaCl的甲醇溶液中，如图6所示，其可以逐渐解吸出MB分子，并最终在240min后达到脱附平衡，显示出很好的可再生能力。
D、8次循环及不同pH值下复合材料的X射线衍时图谱，如图7所示。可以看出，经受8次的吸附－脱附循环以及在浓盐酸和NaOH调节的pH值为2～14的水溶液中放置48h之后，复合材料的结晶性几乎毫无变化，说明骨架结构依然十分完整，显示出了十分可靠的耐水解稳定性和可循环使用能力。
进行吸附能力和水稳定性测试，测试结果如下表所示：
| 比表面积 | 吸附种类(6)种 | 吸附能力 | 水稳定性 | |
| PAM/MOF/COF | 2838.5m2/g | 3 | 97.6％ | 96％ |
| MOF/COF | 2306.2m2/g | 2 | 93％ | 90％ |
| COF | 827.6m2/g | 1 | 76％ | 82％ |
| MOF | 747.4m2/g | 1 | 78％ | 62％ |
值得一提的是，本发明专利申请涉及的UiO-66-NH2晶体等技术特征应被视为现有技术，UiO-66-NH2晶体的制备原理，这些技术特征的具体结构、工作原理以及可能涉及到的控制方式、空间布置方式采用本领域的常规选择即可，不应被视为本发明专利的发明点所在，本发明专利不做进一步具体展开详述。
以上详细描述了本发明的较佳具体实施例，应当理解，本领域的普通技术人员无需创造性劳动就可以根据本发明的构思做出诸多修改和变化，因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。
Claims (9)
1.PAM/MOF/COF复合材料的制备方法，其特征在于，包括以下步骤：
步骤1，聚丙烯酰胺表面活化：将一定比例的PAM和氢氧化钠在80℃-120℃温度下搅拌反应3-4小时，然后洗涤、干燥；
步骤2，通过原位方法组装成均匀稳定的UiO-66-NH2晶体；
步骤3，将UiO-66-NH2晶体加入到高压釜中，在110-130℃温度下搅拌22-26小时，合成具有核壳结构的UiO-66-NH2-聚丙烯酰胺复合材料；
步骤4，将亚胺类COF材料加入到高压釜容器中，在8-16小时内温度保持在100-200℃，得到高度结晶分级孔结构的PAM/MOF/COF复合材料；
所述亚胺类COF材料为TAPB-COF或TPE-COF。
2.如权利要求1所述的PAM/MOF/COF复合材料的制备方法，其特征在于，所述步骤(1)中反应温度为90℃，搅拌3时间。
3.如权利要求1所述的PAM/MOF/COF复合材料的制备方法，其特征在于，所述步骤(3)中温度为120℃，搅拌24时间。
4.如权利要求1所述的PAM/MOF/COF复合材料的制备方法，其特征在于，所述步骤(4)中温度为150℃，并搅拌8时间。
5.一种PAM/MOF/COF复合材料，其特征在于，由权利要求1-4中任一一项的制备方法制成，所述PAM/MOF/COF复合材料包括有由内至外依次设置的PAM、MOF、COF，所述MOF为UiO-66-NH2晶体，所述COF为亚胺类COF材料，所述PAM包裹在MOF内部形成核壳结构，所述亚胺类COF材料通过化学键连接MOF。
6.如权利要求5所述的PAM/MOF/COF复合材料的应用，其特征在于，将PAM/MOF/COF复合材料用于吸附具有线型结构小分子有机污染物。
7.如权利要求6所述的PAM/MOF/COF复合材料的应用，其特征在于，所述线型结构小分子有机污染物包括有亚甲基兰、阳离子艳红5GN、阳离子嫩黄7GL中的一种或多种。
8.如权利要求6所述的PAM/MOF/COF复合材料的应用，其特征在于，所述PAM/MOF/COF复合材料在饱和的NaCl的甲醇溶液中进行脱附，脱附后的PAM/MOF/COF复合材料重复使用。
9.如权利要求6所述的PAM/MOF/COF复合材料的应用，其特征在于，所述PAM/MOF/COF复合材料重复使用次数为8-12次。
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