CN110052244A - 一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法 - Google Patents
一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法 Download PDFInfo
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- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 title claims abstract description 54
- 229940107698 malachite green Drugs 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 239000011365 complex material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 150000003628 tricarboxylic acids Chemical class 0.000 claims abstract description 11
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
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- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 9
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 9
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical class C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 5
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 150000003891 oxalate salts Chemical class 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
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- 235000005074 zinc chloride Nutrition 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
本发明涉及一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,步骤如下:在N,N‑二甲基甲酰胺中加入硝酸盐、含氮二羧酸配体和三羧酸配体,超声10~50min使反应物完全溶解后倒入聚四氟乙烯不锈钢反应釜中,在80~130℃条件下反应12~36h;将得到的材料洗涤,干燥,即得金属有机配合物材料。本方法制得的金属有机配合物为介孔材料,热稳定性高,水相稳定性好,拥有介孔特性且表面存在特殊基团,具有高的吸附容量以及较多活性位点,对孔雀石绿具有很强的吸附性能,具有较高富集孔雀石绿的能力,在室温干燥的环境中放置半年后,仍可对孔雀石绿进行富集,极大地节约了使用的生产成本,具有广阔的应用前景。
Description
技术领域
本发明属于功能化材料制备技术领域,尤其是一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法。
背景技术
金属有机配合物是由金属离子或团簇与有机配体连接构成的一维、二维或三维配位聚合物。近20多年来,金属有机配合物材料因其具有多种多样精美有趣的结构而吸引了一大批科研工作者在其合成上的不断发展创新。同时,作为多孔材料的一种,金属有机配合物材料的多样结构使得其应用十分广泛。金属有机配合物材料将无机化学和有机化学巧妙的结合起来,产生了传统多孔材料不具备的特性。
孔雀石绿(Malachite Green)是一种三芳基甲烷染料,是在有浓硫酸或者氯化锌存在条件下,一份苯甲醛与二份二甲基苯胺缩合而成的深绿色晶体。孔雀石绿有多种存在形式,主要是以至少百分之五十的草酸盐或盐酸盐的形式存在于醋酸盐和盐酸盐的混合物中。孔雀石绿可以有效的预防鱼和鱼卵中真菌的生长,所以孔雀石绿在水产养殖中被广泛应用。但是国内外的研究表明,孔雀石绿会在鱼体内和环境中长时间残留,具有强毒性,还会导致哺乳动物出现致畸、致癌、致突变的“三致”作用。因此去除和检测非法添加的孔雀石绿具有重大的意义。
目前,用于富集孔雀石绿的材料多种多样,包括石墨烯、纳米银、磁性分子印迹聚合物和生物吸附剂等。孔雀石绿的检测方法众多,包括液相色谱法、毛细管电泳法、紫外分光光度法、酶联免疫法、表面增强拉曼光谱法和化学发光传感法等。因此,制作一种同时具有高吸附容量与高灵敏荧光响应的孔雀石绿富集、传感材料具有非常重要的意义。
通过检索,尚未发现与本发明专利申请相关的专利公开文献。
发明内容
本发明的目的在于克服以上提到的不足之处,提供一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,该方法制备的金属有机配合物材料对孔雀石绿有很高的吸附容量和灵敏的荧光响应,可用于孔雀石绿快速、高效富集与高灵敏检测。
本发明解决其技术问题是采取以下技术方案实现的:
一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,步骤如下:
⑴在N,N-二甲基甲酰胺中加入硝酸盐、含氮二羧酸配体和三羧酸配体,超声10~50min使反应物完全溶解后倒入聚四氟乙烯不锈钢反应釜中,在80~130℃条件下反应12~36h;
其中,所述N,N-二甲基甲酰胺:硝酸盐的比例mL:mol为10~20:2~4,所述硝酸盐、含氮二羧酸配体和三羧酸配体的摩尔比例为2:1:1~4:1.5:1;
⑵将步骤⑴反应得到的材料洗涤,干燥,即得用于孔雀石绿富集和传感的金属有机配合物材料。
而且,所述步骤⑴中硝酸盐为硝酸锂、硝酸镉、硝酸铬、硝酸锌或硝酸铜。
而且,所述步骤⑴中含氮二羧酸配体为2,6-萘二羧酸、偶氮苯-3,3-二羧酸、偶氮苯-4,4-二羧酸、2-氨基对苯二甲酸或2-硝基对苯二甲酸。
而且,所述步骤⑴中三羧酸配体为1,3,5-三(4-羧基苯基)苯、1,3,5-三(4′-羧基[1,1′-联苯]-4-基)苯、1,3,5-苯三甲酸或金精三羧酸。
而且,所述步骤⑵中洗涤条件为用N,N-二甲基甲酰胺洗涤2~5次,然后用甲醇洗涤2~5次。
而且,所述步骤⑵中干燥的具体条件为80~140℃过夜烘干。
本发明取得的优点和积极效果是:
1、本方法制得的金属有机配合物为介孔材料,热稳定性高,水相稳定性好,拥有介孔特性且表面存在特殊基团,具有高的吸附容量以及较多活性位点,对孔雀石绿具有很强的吸附性能,具有较高富集孔雀石绿的能力,对孔雀石绿的富集效率高,性能稳定,可重复利用至少四次,在室温干燥的环境中放置半年后,仍可对孔雀石绿进行富集,极大地节约了使用的生产成本,具有广阔的应用前景。
2、本发明方法合成过程简单,条件易于控制,所制得的材料具有较好的热稳定性与化学稳定性,可以用于孔雀石绿的富集,实现了对孔雀石绿更加高效简便地富集。
3、本发明方法制得的金属有机配合物材料在荧光传感检测中十分灵敏,而且操作简便,可以快速检测孔雀石绿。
4、本发明方法的金属有机配合物材料的制备仅需一步反应即可得到,反应过程简单,提高了工作效率。
附图说明
图1为本发明方法制得的金属有机配合物材料的照片,从图1中可看出本发明颗粒长度约为2~3mm(底部为圆形抽滤滤膜,直径50mm);
图2为本发明方法制得的金属有机配合物材料的孔径分布图,从图中可以看出本发明材料孔径约为4.8nm,为介孔材料;
图3为本发明方法制得的金属有机配合物材料的热重图,从图中可看出本发明材料热稳定相良好;
图4为本发明方法制得的金属有机配合物材料吸附孔雀石绿其吸附量随吸附时间变化图,从图中可以看出在前一小时内快速吸附,吸附率达50%,在两小时内,吸附率达75%,最终对于母液为1300mg/L的孔雀石绿,吸附率达到92.6%;
图5为本发明方法制得的金属有机配合物材料的荧光传感孔雀石绿图,从图中可以看出随着孔雀石绿浓度的增加,检测出的荧光强度逐渐降低,孔雀石绿对本发明金属有机配合物材料有猝灭效果,从而实现对孔雀石绿的传感。
具体实施方式
下面结合通过具体实施例对本发明作进一步详述,以下实施例只是描述性的,不是限定性的,不能以此限定本发明的保护范围。
本发明中所使用的原料,如无特殊说明,均为常规的市售产品;本发明中所使用的方法,如无特殊说明,均为本领域的常规方法。
实施例1
一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,步骤如下:
⑴在N,N-二甲基甲酰胺溶液中加入硝酸铜、含氮二羧酸配体和1,3,5-苯三甲酸,超声30min使反应物完全溶解后装入聚四氟乙烯的不锈钢反应釜中,在80℃反应12h。
其中,所述N,N-二甲基甲酰胺:硝酸铜的比例mL:mol为10~20:2.2,硝酸铜、含氮二羧酸配体和1,3,5-均苯三甲酸配体的摩尔比例为2.2:1:1;
⑵将步骤⑴反应得到的材料用N,N-二甲基甲酰胺洗涤2次,甲醇洗涤3次,100℃,过夜烘干,即得该金属有机配合物材料。
所述步骤⑴中含氮二羧酸配体为2,6-萘二羧酸、偶氮苯-3,3-二羧酸、偶氮苯-4,4-二羧酸、2-氨基对苯二甲酸或2-硝基对苯二甲酸。
实施例2
一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,步骤如下:
⑴在N,N-二甲基甲酰胺溶液中加入硝酸镉、含氮二羧酸配体和1,3,5-三(4-羧基苯基)苯,超声30min使反应物完全溶解后装入聚四氟乙烯的不锈钢反应釜中,在120℃反应36h。
其中,所述N,N-二甲基甲酰胺:硝酸镉的比例mL:mol为10~20:3,硝酸镉、含氮二羧酸配体和1,3,5-三(4-羧基苯基)苯的摩尔比例为3:1:1;
⑵将步骤⑴反应得到的材料用N,N-二甲基甲酰胺洗涤3次,甲醇洗涤3次,80℃,过夜烘干,即得该金属有机配合物材料。
所述步骤⑴中含氮二羧酸配体为2,6-萘二羧酸、偶氮苯-3,3-二羧酸、偶氮苯-4,4-二羧酸、2-氨基对苯二甲酸或2-硝基对苯二甲酸。
实施例3
一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,步骤如下:
⑴在N,N-二甲基甲酰胺溶液中加入硝酸镉、2,6-萘二羧酸和三羧酸配体,超声30min使反应物完全溶解后装入聚四氟乙烯的不锈钢反应釜中,在130℃反应12h。
其中,所述N,N-二甲基甲酰胺:硝酸镉的比例mL:mol为10~20:4,硝酸镉、2,6-萘二羧酸和三羧酸配体的摩尔比例为4:1.5:1;
⑵将步骤⑴反应得到的材料用N,N-二甲基甲酰胺洗涤3次,甲醇洗涤3次,80℃,过夜烘干,即得该金属有机配合物材料。
所述步骤⑴中三羧酸配体为1,3,5-三(4-羧基苯基)苯、1,3,5-三(4′-羧基[1,1′-联苯]-4-基)苯、1,3,5-均苯三甲酸或金精三羧酸。
实施例4
一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,步骤如下:
⑴在N,N-二甲基甲酰胺溶液中加入硝酸盐、偶氮苯-3,3-二羧酸和1,3,5-三(4-羧基苯基)苯,超声30min使反应物完全溶解后装入聚四氟乙烯的不锈钢反应釜中,在80~130℃反应24h。
其中,所述N,N-二甲基甲酰胺:硝酸盐的比例mL:mol为10~20:3.5,硝酸盐、含氮二羧酸配体和三羧酸配体的摩尔比例为3.5:1:1;
⑵将步骤⑴反应得到的材料用N,N-二甲基甲酰胺洗涤3次,甲醇洗涤3次,100℃,过夜烘干,即得该金属有机配合物材料。
所述步骤⑴中硝酸盐为硝酸锂、硝酸镉、硝酸铬、硝酸锌或硝酸铜。
本发明金属有机配合物材料的相关检测结果:
1、本发明方法制得的金属有机配合物材料的照片见图1、图2,从图中可看出本发明颗粒大小较均一,颗粒长度约为2~3mm;
2、本发明方法制得的金属有机配合物材料的热重检测,结果如图3所示,从图3中可看出本发明材料热稳定性良好。
3、本发明方法制得的金属有机配合物材料富集孔雀石绿后的紫外分光光度检测:
检测步骤如下:
取30mg本发明金属有机配合物材料于100mL离心管中,加入pH值为5的1300ppm的孔雀石绿水溶液,室温25℃下置于摇床内吸附,在20,30,45,60,80,100,130,160,380,1010min分别用紫外分光光度计测量吸光值,计算获得不同时间的吸附量。
结果见图4,从图中可以看出在前一小时内快速吸附,吸附率达50%,在两小时内,吸附率达75%,最终对于母液为1300mg/L的孔雀石绿,吸附率达到92.6%。
4、本发明方法制得的金属有机配合物材料传感孔雀石绿的荧光分光光度检测:
检测步骤如下:
配置本发明金属有机配合物材料成0.1mg/mL的水溶液,分别配置浓度为2.74×10-3M,2.74×10-4M,2.74×10-5M,2.74×10-6M,2.74×10-7M,2.74×10-8M的孔雀石绿水溶液,分别取本发明金属有机配合物材料的0.1mg/mL的水溶液0.9mL和孔雀石绿的水溶液0.1mL,在荧光激发波长276nm下检测,获得各自对应的荧光发射光谱。
结果见图5,从图中可以看出随着孔雀石绿浓度的增加,检测出的荧光强度逐渐降低,孔雀石绿对本发明金属有机配合物材料有猝灭效果,从而实现对孔雀石绿的传感。
尽管为说明目的公开了本发明的实施例,但是本领域的技术人员可以理解:在不脱离本发明及所附权利要求的精神和范围内,各种替换、变化和修改都是可能的,因此,本发明的范围不局限于实施例所公开的内容。
Claims (6)
1.一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,其特征在于:步骤如下:
⑴在N,N-二甲基甲酰胺中加入硝酸盐、含氮二羧酸配体和三羧酸配体,超声10~50min使反应物完全溶解后倒入聚四氟乙烯不锈钢反应釜中,在80~130℃条件下反应12~36h;
其中,所述N,N-二甲基甲酰胺:硝酸盐的比例mL:mol为10~20:2~4,所述硝酸盐、含氮二羧酸配体和三羧酸配体的摩尔比例为2:1:1~4:1.5:1;
⑵将步骤⑴反应得到的材料洗涤,干燥,即得用于孔雀石绿富集和传感的金属有机配合物材料。
2.根据权利要求1所述的用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,其特征在于:所述步骤⑴中硝酸盐为硝酸锂、硝酸镉、硝酸铬、硝酸锌或硝酸铜。
3.根据权利要求1所述的用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,其特征在于:所述步骤⑴中含氮二羧酸配体为2,6-萘二羧酸、偶氮苯-3,3-二羧酸、偶氮苯-4,4-二羧酸、2-氨基对苯二甲酸或2-硝基对苯二甲酸。
4.根据权利要求1所述的用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,其特征在于:所述步骤⑴中三羧酸配体为1,3,5-三(4-羧基苯基)苯、1,3,5-三(4′-羧基[1,1′-联苯]-4-基)苯、1,3,5-苯三甲酸或金精三羧酸。
5.根据权利要求1所述的用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,其特征在于:所述步骤⑵中洗涤条件为用N,N-二甲基甲酰胺洗涤2~5次,然后用甲醇洗涤2~5次。
6.根据权利要求1至5任一项所述的用于孔雀石绿富集和传感的金属有机配合物材料的制备方法,其特征在于:所述步骤⑵中干燥的具体条件为80~140℃过夜烘干。
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