CN115532241B - Ionic liquid modified composite material and preparation method and application thereof - Google Patents
Ionic liquid modified composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 41
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 35
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZOMSMJKLGFBRBS-UHFFFAOYSA-N bentazone Chemical compound C1=CC=C2NS(=O)(=O)N(C(C)C)C(=O)C2=C1 ZOMSMJKLGFBRBS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 12
- 229960004853 betadex Drugs 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 8
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 8
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 6
- 239000012498 ultrapure water Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical group OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002211 L-ascorbic acid Substances 0.000 claims description 5
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- AKIOUZFROHTEEN-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-1,2-dihydroimidazol-1-ium chloride Chemical compound [Cl-].CCCC[NH+]1C=CN(C)C1C AKIOUZFROHTEEN-UHFFFAOYSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000447 pesticide residue Substances 0.000 abstract description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract 1
- 239000005476 Bentazone Substances 0.000 description 15
- CNBGNNVCVSKAQZ-UHFFFAOYSA-N benzidamine Natural products C12=CC=CC=C2C(OCCCN(C)C)=NN1CC1=CC=CC=C1 CNBGNNVCVSKAQZ-UHFFFAOYSA-N 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HHHYPTORQNESCU-UHFFFAOYSA-M 1-butyl-2,3-dimethylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1C HHHYPTORQNESCU-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- TYOCDPIZUIQUSO-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1C TYOCDPIZUIQUSO-UHFFFAOYSA-N 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- RVKZDIDATLDTNR-UHFFFAOYSA-N sulfanylideneeuropium Chemical compound [Eu]=S RVKZDIDATLDTNR-UHFFFAOYSA-N 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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Abstract
一种离子液体修饰复合材料及其制备方法、应用，属于农药残留吸附处理技术领域。该复合材料具体通过以下步骤得到：将氧化石墨烯、离子液体、β‑环糊精、水和碳纳米管混合，磁力搅拌30‑60min，随后超声溶解30‑60min，进行预聚合反应，得到预聚体；将所述预聚体、交联剂和还原剂混合，磁力搅拌10‑15min，溶解均匀后进行聚合反应，反应结束后，将所获得的产物过滤后用超纯水洗涤3‑5次，冷冻干燥24h。与现有的苯达松富集与吸附技术相比，本发明的复合材料吸附效果更好，且操作简单，具有良好的应用前景。
An ionic liquid modified composite material and its preparation method and application belong to the technical field of pesticide residue adsorption treatment. The composite material is specifically obtained through the following steps: mixing graphene oxide, ionic liquid, β-cyclodextrin, water and carbon nanotubes, stirring magnetically for 30-60 minutes, then ultrasonically dissolving for 30-60 minutes, and performing a pre-polymerization reaction to obtain a pre- polymer; mix the prepolymer, cross-linking agent and reducing agent, magnetically stir for 10-15min, dissolve evenly and carry out polymerization reaction, after the reaction is over, filter the obtained product and wash it with ultrapure water for 3-5 times, freeze-dried for 24 hours. Compared with the existing bentazon enrichment and adsorption technology, the composite material of the invention has better adsorption effect, simple operation and good application prospect.
Description
技术领域technical field
本发明属于农药残留吸附处理技术领域，具体涉及一种离子液体修饰复合材料及其制备方法、应用。The invention belongs to the technical field of pesticide residue adsorption treatment, and in particular relates to an ionic liquid modified composite material and its preparation method and application.
背景技术Background technique
苯达松又名灭草松，化学名称为3-异丙基- (1H) -苯并-2,1,3-噻二嗪-4-酮-2,2-二氧化物，纯品为无色晶体，低毒，熔点在 138℃左右，密度为 1.47g·cm-3。易溶于甲醇、乙腈等有机溶剂，化学性质较为稳定，在酸、碱介质中不容易发生水解，但在紫外光下易发生分解。它属于苯并噻二唑（简称 BTH）类的广谱性除草剂，用于处理苗期杂草的茎叶，通过植物体绿色部分的吸收而发挥其除草作用。苯达松在进入中国市场的这三十多年期间，在国内登记生产企业中原药十九家、制剂六十多家，销量一直是趋于递增的态势。同时，苯达松的大量使用也带来了残留和降解方面的新问题。Bentazone, also known as bentazone, has a chemical name of 3-isopropyl-(1H)-benzo-2,1,3-thiadiazin-4-one-2,2-dioxide, and its pure product is Colorless crystal, low toxicity, melting point around 138℃, density 1.47g·cm -3 . It is easily soluble in organic solvents such as methanol and acetonitrile, and its chemical properties are relatively stable. It is not easy to be hydrolyzed in acid and alkali media, but it is easy to decompose under ultraviolet light. It belongs to the broad-spectrum herbicide of benzothiadiazole (abbreviated as BTH). It is used to treat the stems and leaves of weeds at the seedling stage, and exerts its weeding effect through the absorption of the green part of the plant. During the more than 30 years since Bentaxone entered the Chinese market, there are 19 original medicines and more than 60 preparations registered in the domestic production enterprises, and the sales volume has been tending to increase. At the same time, the extensive use of bentazone has also brought new problems in residue and degradation.
苯达松在土壤中的移动性强，蓄积性低，易溶于水，在水溶液不易被水解。相关研究表明，土壤对苯达松的吸附固定能力普遍较低，因此，施用苯达松，会随着土壤中的径流等流入附近水域或地下水中，因此苯达松的易溶于水对农田附近水域是一个及其严重的、具有毁灭性的污染。Bentazon has strong mobility in soil, low accumulation, is easily soluble in water, and is not easily hydrolyzed in aqueous solution. Relevant studies have shown that the adsorption and fixation capacity of bentazone to soil is generally low. Therefore, the application of bentazone will flow into nearby waters or groundwater along with the runoff in the soil. The nearby waters are an extremely serious and devastating pollution.
发明内容Contents of the invention
针对现有技术存在的问题，本发明的目的在于设计提供一种离子液体修饰复合材料及其制备方法、应用的技术方案。本发明提供的离子液体@β-环糊精-氧化石墨烯-碳纳米管复合材料，对水中苯达松具有优异的选择吸附性能，是一种简便而高效的富集与吸附水中苯达松的方法。Aiming at the problems existing in the prior art, the object of the present invention is to design and provide a technical solution for an ionic liquid modified composite material and its preparation method and application. The ionic liquid @β-cyclodextrin-graphene oxide-carbon nanotube composite material provided by the present invention has excellent selective adsorption performance for bendazone in water, and is a simple and efficient method for enriching and adsorbing bendazone in water Methods.
本发明具体通过以下技术方案实现：The present invention is specifically realized through the following technical solutions:
本发明一方面提供了一种离子液体@β-环糊精-氧化石墨烯-碳纳米管复合材料的制备方法，其包括以下步骤：One aspect of the present invention provides a method for preparing an ionic liquid @β-cyclodextrin-graphene oxide-carbon nanotube composite material, which includes the following steps:
1）将氧化石墨烯、离子液体、β-环糊精、水和碳纳米管混合，磁力搅拌30-60min，随后超声溶解30-60min，进行预聚合反应，得到预聚体；1) Mix graphene oxide, ionic liquid, β-cyclodextrin, water and carbon nanotubes, stir magnetically for 30-60 minutes, then ultrasonically dissolve for 30-60 minutes, and perform prepolymerization to obtain a prepolymer;
2）将所述预聚体、交联剂和还原剂混合，磁力搅拌10-15min，溶解均匀后进行聚合反应，反应结束后，将所获得的产物过滤后用超纯水洗涤3-5次，冷冻干燥24h，即得到离子液体@β-环糊精-氧化石墨烯-碳纳米管复合材料。2) Mix the prepolymer, cross-linking agent and reducing agent, stir magnetically for 10-15 minutes, dissolve evenly and carry out polymerization reaction. After the reaction, filter the obtained product and wash it with ultrapure water for 3-5 times , freeze-dried for 24 hours, and the ionic liquid @β-cyclodextrin-graphene oxide-carbon nanotube composite material was obtained.
进一步，所述离子液体为1-丁基-2,3-二甲基咪唑氯盐。Further, the ionic liquid is 1-butyl-2,3-dimethylimidazolium chloride.
进一步，所述交联剂为戊二醛、表氯醇或柠檬酸中的一种。Further, the crosslinking agent is one of glutaraldehyde, epichlorohydrin or citric acid.
进一步，所述还原剂为L-抗坏血酸。Further, the reducing agent is L-ascorbic acid.
进一步，所述氧化石墨烯、离子液体、β-环糊精、水和碳纳米管的用量比为(30～50)mL:(5～15)g:（5～10）g:（80～120）g：(0.15～0.20)g，氧化石墨烯浓度为2mg/mL。Further, the dosage ratio of the graphene oxide, ionic liquid, β-cyclodextrin, water and carbon nanotubes is (30～50)mL:(5～15)g:(5～10)g:(80～ 120) g: (0.15-0.20) g, the concentration of graphene oxide is 2 mg/mL.
进一步，所述预聚体、交联剂和还原剂的用量比为（120～160）g:(4～6)mL:(2.5～3.5)g。Further, the dosage ratio of the prepolymer, crosslinking agent and reducing agent is (120-160) g:(4-6) mL:(2.5-3.5) g.
进一步，所述聚合反应的温度为80～90℃，时间为12～24h。Further, the temperature of the polymerization reaction is 80-90° C., and the time is 12-24 hours.
进一步，所述冷冻干燥条件为-40～-50℃，8～15Mpa。Further, the freeze-drying conditions are -40～-50°C, 8～15Mpa.
本发明第二方面提供了通过上述任一制备方法得到的离子液体@β-环糊精-氧化石墨烯-碳纳米管复合材料。The second aspect of the present invention provides the ionic liquid @β-cyclodextrin-graphene oxide-carbon nanotube composite material obtained by any of the above preparation methods.
本发明第三方面提供了离子液体@β-环糊精-氧化石墨烯-碳纳米管复合材料在吸附水溶液中苯达松的应用。The third aspect of the present invention provides the application of ionic liquid @β-cyclodextrin-graphene oxide-carbon nanotube composite material in the adsorption of bendazone in aqueous solution.
本发明的有益效果是：本发明中离子液体@β-环糊精/氧化石墨烯-碳纳米管复合材料的制备工艺步骤简单，复合材料既具有氧化石墨烯较大的比表面积和β-环糊精的包合作用，又具有离子液体选择性吸附化合物的优势，本发明制备的复合材料明显提高了β-环糊精-氧化石墨烯-碳纳米管复合材料对苯达松的吸附性能。与现有的苯达松富集与吸附技术相比，该方法吸附效果更好，且操作简单，具有良好的应用前景。The beneficial effects of the present invention are: the preparation process steps of the ionic liquid @β-cyclodextrin/graphene oxide-carbon nanotube composite material in the present invention are simple, and the composite material not only has a large specific surface area of graphene oxide and β-ring The inclusion of dextrin also has the advantage of selective adsorption of compounds by ionic liquids, and the composite material prepared by the invention obviously improves the adsorption performance of the β-cyclodextrin-graphene oxide-carbon nanotube composite material on bendazone. Compared with the existing bentazone enrichment and adsorption technology, this method has better adsorption effect, simple operation and good application prospect.
附图说明Description of drawings
图1离子液体@β-环糊精-氧化石墨烯-碳纳米管（IL@β-CD-GO-CNT）与β-环糊精-氧化石墨烯-碳纳米管（β-CD-GO-CNT）复合材料的红外光谱对比图；Fig. 1 Ionic liquid @β-cyclodextrin-graphene oxide-carbon nanotubes (IL@β-CD-GO-CNT) and β-cyclodextrin-graphene oxide-carbon nanotubes (β-CD-GO- CNT) infrared spectrum comparison chart of composite materials;
图2 离子液体@β-环糊精-氧化石墨烯-碳纳米管（IL@β-CD-GO-CNT）与β-环糊精-氧化石墨烯-碳纳米管（β-CD-GO-CNT）复合材料扫描电镜图；Figure 2 Ionic liquid @β-cyclodextrin-graphene oxide-carbon nanotubes (IL@β-CD-GO-CNT) and β-cyclodextrin-graphene oxide-carbon nanotubes (β-CD-GO- CNT) SEM images of composite materials;
图3离子液体@β-环糊精-氧化石墨烯-碳纳米管（IL@β-CD-GO-CNT）与β-环糊精-氧化石墨烯-碳纳米管（β-CD-GO-CNT）复合材料XPS光谱；Fig.3 Ionic liquid@β-cyclodextrin-graphene oxide-carbon nanotubes (IL@β-CD-GO-CNT) and β-cyclodextrin-graphene oxide-carbon nanotubes (β-CD-GO- CNT) composite material XPS spectrum;
图4离子液体@β-环糊精-氧化石墨烯-碳纳米管（IL@β-CD-GO-CNT）与β-环糊精-氧化石墨烯-碳纳米管（β-CD-GO-CNT）复合材料拉曼光谱图；Figure 4. Ionic liquid@β-cyclodextrin-graphene oxide-carbon nanotubes (IL@β-CD-GO-CNT) and β-cyclodextrin-graphene oxide-carbon nanotubes (β-CD-GO- CNT) composite material Raman spectrum;
图5离子液体@β-环糊精-氧化石墨烯-碳纳米管（IL@β-CD-GO-CNT）与β-环糊精-氧化石墨烯-碳纳米管（β-CD-GO-CNT）复合材料热重图；Figure 5. Ionic liquid @β-cyclodextrin-graphene oxide-carbon nanotubes (IL@β-CD-GO-CNT) and β-cyclodextrin-graphene oxide-carbon nanotubes (β-CD-GO- CNT) composite thermogravimetric map;
图6 苯达松含量检测HPLC色谱图：（a）标准品溶液；(b)典型样品溶液；Figure 6 HPLC chromatogram of bentazone content detection: (a) standard solution; (b) typical sample solution;
图7 离子液体@β-环糊精-氧化石墨烯-碳纳米管（IL@β-CD-GO-CNT）与β-环糊精-氧化石墨烯-碳纳米管（β-CD-GO-CNT）复合材料吸附苯达松结果。Fig.7 Ionic liquid@β-cyclodextrin-graphene oxide-carbon nanotubes (IL@β-CD-GO-CNT) and β-cyclodextrin-graphene oxide-carbon nanotubes (β-CD-GO- CNT) composites adsorbed bentazone results.
具体实施方式Detailed ways
现在结合附图和以下实施例对本发明作进一步详细的说明,但应了解的是,这些实施例仅为例示说明之用,而不应被解释为本发明实施的限制。The present invention will now be further described in detail with reference to the accompanying drawings and the following examples, but it should be understood that these examples are for illustrative purposes only, and should not be construed as limitations on the implementation of the present invention.
实施例1： 离子液体@β-环糊精-氧化石墨烯-碳纳米管复合材料（IL@β-CD-GO-CNT）的合成Example 1: Synthesis of ionic liquid@β-cyclodextrin-graphene oxide-carbon nanotube composite (IL@β-CD-GO-CNT)
（1）将氧化石墨烯（2mg/mL）40mL、1-丁基-2,3-二甲基咪唑氯盐10g、β-环糊精8g、水100mL和碳纳米管0.15g混合，磁力搅拌30min，随后超声溶解30min，进行预聚合反应，得到预聚体；(1) Mix 40mL of graphene oxide (2mg/mL), 10g of 1-butyl-2,3-dimethylimidazolium chloride salt, 8g of β-cyclodextrin, 100mL of water and 0.15g of carbon nanotubes, and stir magnetically 30min, and then ultrasonically dissolved for 30min to carry out prepolymerization to obtain a prepolymer;
（2）将上述A中得到的预聚体150g与5.6mL戊二醛、2.8g L-抗坏血酸混合，磁力搅拌10min，溶解均匀后转入特氟龙内衬的高压釜中进行聚合反应（90℃，12h），反应结束后，将所获得的产物过滤后用超纯水洗涤3次，在-50℃，10Mpa下冷冻干燥即得到离子液体@β-环糊精/氧化石墨烯-碳纳米管复合材料。(2) Mix 150 g of the prepolymer obtained in A above with 5.6 mL of glutaraldehyde and 2.8 g of L-ascorbic acid, stir it magnetically for 10 min, dissolve it evenly, and transfer it to a Teflon-lined autoclave for polymerization (90 ℃, 12h), after the reaction, the obtained product was filtered and washed 3 times with ultrapure water, and freeze-dried at -50°C, 10Mpa to obtain the ionic liquid @β-cyclodextrin/graphene oxide-carbon nano Tube composites.
β-环糊精-氧化石墨烯-碳纳米管复合材料（β-CD-GO-CNT）的合成区别仅在以上（1）步中不加入1-丁基-2，3-二甲基咪唑氯盐。通过由复合材料的红外光谱（图1）、扫描电镜图（图2）、XPS光谱（图3）、拉曼光谱图（图4）和热重变化图（图5），可以明显看出离子液体负载后基团的特征和材料形貌的变化。The only difference in the synthesis of β-cyclodextrin-graphene oxide-carbon nanotube composites (β-CD-GO-CNT) is that 1-butyl-2,3-dimethylimidazole is not added in the above (1) step Chlorine salt. Through the infrared spectrum (Figure 1), scanning electron microscope (Figure 2), XPS spectrum (Figure 3), Raman spectrum (Figure 4) and thermogravimetric change diagram (Figure 5) of the composite material, it can be clearly seen that the ion Characterization of groups and changes in material morphology after liquid loading.
实施例2：离子液体@β-环糊精-氧化石墨烯-碳纳米管复合材料（IL@β-CD-GO-CNT）的合成Example 2: Synthesis of ionic liquid@β-cyclodextrin-graphene oxide-carbon nanotube composite (IL@β-CD-GO-CNT)
（1）将氧化石墨烯（2mg/mL）30mL、1-丁基-2，3-二甲基咪唑氯盐5g、β-环糊精5g、水80mL和碳纳米管0.15g混合，磁力搅拌30min，随后超声溶解30min，进行预聚合反应，得到预聚体；(1) Mix 30mL of graphene oxide (2mg/mL), 5g of 1-butyl-2,3-dimethylimidazolium chloride salt, 5g of β-cyclodextrin, 80mL of water and 0.15g of carbon nanotubes, and stir magnetically 30min, and then ultrasonically dissolved for 30min to carry out prepolymerization to obtain a prepolymer;
（2）将上述A中得到的预聚体160g与6mL柠檬酸、2.5g L-抗坏血酸混合，磁力搅拌10min，溶解均匀后转入特氟龙内衬的高压釜中进行聚合反应（80℃，24h），反应结束后，将所获得的产物过滤后用超纯水洗涤3次，在-45℃，8Mpa下冷冻干燥即得到离子液体@β-环糊精/氧化石墨烯-碳纳米管复合材料。(2) Mix 160g of the prepolymer obtained in A above with 6mL of citric acid and 2.5g of L-ascorbic acid, stir magnetically for 10min, dissolve evenly, and transfer to a Teflon-lined autoclave for polymerization (80°C, 24h), after the reaction, the obtained product was filtered and washed three times with ultrapure water, and then freeze-dried at -45°C and 8Mpa to obtain the ionic liquid @β-cyclodextrin/graphene oxide-carbon nanotube composite Material.
实施例3：离子液体@β-环糊精-氧化石墨烯-碳纳米管复合材料（IL@β-CD-GO-CNT）的合成Example 3: Synthesis of ionic liquid@β-cyclodextrin-graphene oxide-carbon nanotube composite (IL@β-CD-GO-CNT)
（1）将氧化石墨烯（2mg/mL）50mL、1-丁基-2，3-二甲基咪唑氯盐15g、β-环糊精10g、水120mL和碳纳米管0.2g混合，磁力搅拌30min，随后超声溶解30min，进行预聚合反应，得到预聚体；(1) Mix 50mL of graphene oxide (2mg/mL), 15g of 1-butyl-2,3-dimethylimidazolium chloride salt, 10g of β-cyclodextrin, 120mL of water and 0.2g of carbon nanotubes, and stir magnetically 30min, and then ultrasonically dissolved for 30min to carry out prepolymerization to obtain a prepolymer;
（2）将上述A中得到的预聚体140 g与4mL表氯醇、3.5g L-抗坏血酸混合，磁力搅拌10min，溶解均匀后转入特氟龙内衬的高压釜中进行聚合反应（85℃，24h），反应结束后，将所获得的产物过滤后用超纯水洗涤3次，在-50℃,10Mpa下冷冻干燥即得到离子液体@β-环糊精/氧化石墨烯-碳纳米管复合材料。(2) Mix 140 g of the prepolymer obtained in the above A with 4 mL of epichlorohydrin and 3.5 g of L-ascorbic acid, stir magnetically for 10 min, dissolve evenly, and transfer to a Teflon-lined autoclave for polymerization (85 ℃, 24h), after the reaction, the obtained product was filtered and washed 3 times with ultrapure water, and freeze-dried at -50°C, 10Mpa to obtain the ionic liquid @β-cyclodextrin/graphene oxide-carbon nano Tube composites.
实施例4Example 4
IL@β-CD-GO-CNT复合材料吸附水中的苯达松Adsorption of bendazone in water by IL@β-CD-GO-CNT composite
将称取20mg的实施例1制得的IL@β-CD-GO-CNT复合材料与离心管中，加入含有0.5mg/mL苯达松（BTZ）的水溶液20mL，置于40℃振荡器中100rpm振荡1h。取上层水相应用HPLC检测苯达松的含量，HPLC检测条件为：岛津液相色谱仪，包括LC-20AD分离色谱系统，SIL-20A自动进样系统，CTO-20A柱温箱，SPD-20A紫外/可见检测器，色谱柱WondaCractODS-2（4.6mm×250mm, 5μm），以乙腈：0.1%磷酸（52；48）为流动相，检测波长为250nm，柱温35℃，进样量10μl；典型苯达松标准品和样品溶液检测色谱图如图6所示。Weigh 20 mg of the IL@β-CD-GO-CNT composite material prepared in Example 1 and a centrifuge tube, add 20 mL of an aqueous solution containing 0.5 mg/mL bentazone (BTZ), and place it in a shaker at 40 °C Shake at 100rpm for 1h. Take the upper aqueous phase and apply HPLC to detect the content of bentazone. The HPLC detection conditions are: Shimadzu liquid chromatography, including LC-20AD separation chromatography system, SIL-20A automatic sampling system, CTO-20A column thermostat, SPD- 20A UV/visible detector, chromatographic column WondaCractODS-2 (4.6mm×250mm, 5μm), with acetonitrile: 0.1% phosphoric acid (52; 48) as mobile phase, detection wavelength 250nm, column temperature 35℃, injection volume 10μl ; Typical bentazone standard substance and sample solution detection chromatogram as shown in Figure 6.
IL@β-CD-GO-CNT复合材料吸附前后检测结果显示，与初始水溶液中苯达松的浓度相比，可确定IL@β-CD-GO-CNT复合材料吸附苯达松含量达到30mg/g，且吸附量约为IL修饰前的β-CD-GO-CNT复合材料的2倍(图7)。The test results before and after the adsorption of IL@β-CD-GO-CNT composite materials show that compared with the concentration of bentazone in the initial aqueous solution, it can be determined that the content of bentazone adsorbed by IL@β-CD-GO-CNT composite materials reaches 30 mg/ g, and the adsorption amount was about twice that of the β-CD-GO-CNT composite before IL modification (Fig. 7).
另外，实施例2-3制得的IL@β-CD-GO-CNT复合材料进行与实施例4相同的吸附试验，IL@β-CD-GO-CNT复合材料吸附苯达松含量分别达到29.5和30.2mg/g。In addition, the IL@β-CD-GO-CNT composite material prepared in Example 2-3 was subjected to the same adsorption test as in Example 4, and the bentazone content of the IL@β-CD-GO-CNT composite material reached 29.5% respectively. and 30.2mg/g.
上述较佳实施例仅用于说明本发明的内容,但这并非是对本发明的限制，本领域的相关技术人员，在不脱离本发明的范围的情况下,还可以做出相应的调整和变型，因此所有等同替换或等效变型的方式形成的技术方案均属于本发明的保护范围。The above-mentioned preferred embodiments are only used to illustrate the content of the present invention, but this is not a limitation of the present invention. Those skilled in the art can also make corresponding adjustments and modifications without departing from the scope of the present invention. , so all technical solutions formed by means of equivalent replacement or equivalent modification belong to the protection scope of the present invention.
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