CN108043459B - 一种铜金属有机骨架膜在催化降解有机染料中的应用 - Google Patents
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 15
- 230000015556 catabolic process Effects 0.000 title claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 150000001879 copper Chemical class 0.000 claims abstract description 12
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- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 4
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- 239000002245 particle Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
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- 238000005265 energy consumption Methods 0.000 abstract description 3
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- 229910052802 copper Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000013085 Cu(II)-based metal-organic framework Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
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- 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
- 229940012189 methyl orange Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
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- 238000007146 photocatalysis Methods 0.000 description 1
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Abstract
本发明公开了一种铜金属有机骨架膜在催化降解有机染料中的应用。有机骨架膜制备的具体步骤如下:(1)将铜盐溶解于有机溶剂中,搅拌至完全溶解,然后向其中加入bpd,充分搅拌后室温静置,再过滤,将得到的滤液命名为溶液A;(2)将溶液A置于可密封容器中;选取载体,经过预处理后浸泡在上述溶液A中;(3)先将溶剂B装入敞口容器中,然后将敞口容器竖立放入可密封容器中,再密封好可密封容器,室温静置,得到铜金属有机骨架膜。该金属有机骨架膜层连续,MOFs晶粒尺寸均一。本发明制备过程简单,不需要能耗,生产过程稳定性好。所制备金属有机骨架膜具有较高的催化性能,能有效降解有机染料,因此它在染料废水污染处理方面有着潜在的应用价值。
Description
技术领域
本发明涉及金属有机骨架膜技术领域,具体的说,涉及一种铜金属有机骨架膜在催化降解有机染料中的应用。
背景技术
金属有机骨架(MOFs)是近年来发展迅猛的一类新型微孔介孔多功能材料,在催化、分子识别、分离、分子器件等方面具有广阔的应用前景。膜分离技术是一种新型的分离技术,因其环境友好、分离体积小、能耗低、分离性能好、无二次污染、操作简单等优势,近年来得到迅速的发展,受到越来越多的重视。金属有机骨架材料和膜分离技术各具优点,如果把两者结合起来,实现“强强联合”,制成MOFs晶体膜,可为它们的应用提供新的可能,并为实际工业过程提供新的解决方案。目前在有关MOFs膜的研究中,尤其以应用于气体分离的MOFs膜最为常见,而应用于水处理的MOFs膜却鲜有报道。近几年来,研究工作者利用MOFs对水相中多种物质进行了分离和催化降解研究,MOFs显示出其他材料无法比拟的良好的处理效果,为废水净化技术提供了新的方向。因此,将对有机染料具有催化降解功能的MOFs材料,制成兼具催化降解和杂质过滤功能的MOFs晶体膜,在污水处理等环保领域极具潜在应用价值。
发明内容
本发明的目的是提供一种Cu(II)金属有机骨架膜的制备方法,以提供一种能够催化降解有机染料的MOFs膜。
本发明的目的可以通过以下技术方案来实现。
一种具有催化性能的铜金属有机骨架膜的制备方法,具体步骤如下:
(1)将铜盐溶解于有机溶剂中,搅拌至完全溶解,然后向其中加入1,4-二(4-吡啶基)-2,3-偶氮-1,3-丁二烯bpd,充分搅拌后室温静置,再过滤,将得到的滤液命名为溶液A;
(2)将溶液A置于可密封容器中;选取载体,经过预处理后浸泡在上述溶液A中;
(3)先将溶剂B装入敞口容器中,然后将敞口容器竖立放入可密封容器中,再密封好可密封容器,室温静置6~9天,得到铜金属有机骨架膜。
本发明中,步骤(1)中,铜盐为硝酸盐、硫酸盐或盐酸盐,有机溶剂为DMF。
本发明中,步骤(1)中,铜盐和1,4-二(4-吡啶基)-2,3-偶氮-1,3-丁二烯bpd的摩尔比为1:2~4:1;铜盐在有机溶剂中的摩尔浓度为0.03~0.06mol/L。
本发明中,步骤(1)中,溶液室温静置的时间为10~30min。
本发明中,步骤(2)中,载体选自Al2O3、石墨片或铜网中任一种。
本发明中,步骤(2)中,载体的预处理方法如下:将载体置于无水乙醇超声清洗10~ 30min,之后50~80℃烘干备用。
本发明中,步骤(3)中,溶剂B为无水乙醚、无水甲醇或者无水乙醇。
本发明还提供一种上述制备方法得到的具有催化性能的铜金属有机骨架膜。优选的,载体上的晶体为球状,粒径在1~2μm之间。
和现有技术相比,本发明的有益效果在于:金属有机骨架膜制备过程简单,不需要能耗,生产过程稳定性好。所制备金属有机骨架膜具有较高的催化性能,能有效降解有机染料,因此它在染料废水污染处理方面有着潜在的应用价值。
附图说明
图1为实施例1制得MOFs晶体膜的SEM图。
图2为实施例1~3制得样品催化降解有机染料甲基橙的曲线。
具体实施方式
下面结合实施例对本发明做进一步详细、完整的说明:
实施例1
室温条件下,将2mmol Cu(NO3)2·3H2O溶解于40mL DMF中,搅拌至完全溶解,然后再向溶液中加入2mmol bpd,充分搅拌,将溶液静置10min后过滤,将得到的滤液A,将滤液A置于可密封的容器广口瓶中。选取20×10mm的Al2O3,将其置于无水乙醇超声清洗10min,之后50℃下烘干后浸泡在上述可密封的容器广口瓶中。取10ml玻璃试管,装8ml乙醚,然后竖立放入广口瓶中,密封好广口瓶。大概7天左右,可得到Cu(II)金属有机骨架膜,电镜图如图1,晶体颗粒呈均匀的球状,颗粒直径约为2μm。
实施例2
重复实施例1的操作步骤,不同之处在于载体为20×10mm的石墨片,结果显示组成金属有机骨架膜的晶体仍然是球状,只是颗粒直径变为约1μm。
实施例3
重复实施例1的操作步骤,不同之处在于载体为20×10mm的铜网,结果和实施例1相比,组成金属有机骨架膜的晶体中大部分为球状颗粒,其中出现了部分细小的块状颗粒,粒径约为1μm。
图1为实施例1所得样品的SEM图,球状的晶体在载体上形成了一层致密的膜,MOFs晶体粒径约为1μm。图2为实施例1~3制得样品催化降解有机染料甲基橙的曲线。甲基橙溶液的初始体积为125mL,浓度为12ppm,在常温下,取一片面积为20×10mm的铜网的金属有机骨架膜,固定在甲基橙溶液中。从图可以看出,三种载体中石墨片作为载体时,MOFs晶体膜的催化效果是最好的,降解率能达到65%;Al2O3片作为载体时的MOFs晶体膜次之,降解率为38%;铜网作为载体时MOFs晶体膜的光催化效果最差,降解率仅为 24%。
以上所述仅为本发明的优选实施例,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包括在本发明的保护范围之内。
Claims (5)
1.一种铜金属有机骨架膜在催化降解有机染料中的应用,其特征在于,所述铜金属有机骨架膜的制备方法具体步骤如下:
(1)将铜盐溶解于有机溶剂中,搅拌至完全溶解,然后向其中加入1,4-二(4-吡啶基)-2,3-偶氮-1,3-丁二烯bpd,充分搅拌后室温静置,再过滤,将得到的滤液命名为溶液A;
并且,铜盐和1,4-二(4-吡啶基)-2,3-偶氮-1,3-丁二烯bpd的摩尔比为1:2~4:1;铜盐在有机溶剂中的摩尔浓度为0.03~0.06mol/L;
(2)将溶液A置于可密封容器中;选取载体,经过预处理后浸泡在上述溶液A中;所述载体为石墨片;
(3)先将溶剂B装入敞口容器中,然后将敞口容器竖立放入可密封容器中,再密封好可密封容器,室温静置6~9天,得到铜金属有机骨架膜;
所述载体上的晶体为球状,粒径在1~2μm之间。
2.根据权利要求1所述的应用,其特征在于,步骤(1)中,铜盐为硝酸盐、硫酸盐或盐酸盐,有机溶剂为DMF。
3.根据权利要求1所述的应用,其特征在于:步骤(1)中,溶液室温静置的时间为10~30min。
4.根据权利要求1所述的应用,其特征在于,步骤(2)中,载体的预处理方法如下:将载体置于无水乙醇超声清洗10~30min,之后50~80℃烘干备用。
5.根据权利要求1所述的应用,其特征在于:步骤(3)中,溶剂B为无水乙醚、无水甲醇或者无水乙醇。
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