CN114181154B - 一种嵌套笼状间位氮配体锌配合物及其制备方法和应用 - Google Patents
一种嵌套笼状间位氮配体锌配合物及其制备方法和应用 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000011701 zinc Substances 0.000 title claims abstract description 33
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000010668 complexation reaction Methods 0.000 title description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 55
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 33
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 25
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- 238000012360 testing method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims abstract description 6
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000872 buffer Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000010025 steaming Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims 1
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Abstract
本发明公开了一种嵌套笼状间位氮配体锌配合物及其制备方法和应用,其化学式为[Zn(L)2ZrF6],其中L为1,3‑二咪唑基苯配体。将咪唑、碳酸钾和碘化铜混合并研磨均匀后滴加1,3‑二溴苯,反应结束后,洗涤过滤,旋蒸得到配体L;将Zn(BF4)2/(NH4)2ZrF6水溶液滴加于试管,再将N,N‑二甲基甲酰胺/乙醇/水混合物加入试管作为缓冲层,最后将L的N,N‑二甲基甲酰胺溶液加入试管,形成三层界面溶液;室温放置反应后,过滤,洗涤,干燥得到间位氮配体锌配合物。本发明制备工艺简单,成本低,条件温和,且为内外双层嵌套空笼结构,内笼表面及内外笼层间与乙炔有较强的相互作用,能高效的分离乙炔/二氧化碳。
Description
技术领域
本发明属于高分子化学、聚合物自组装及超分子材料技术领域,具体涉及一种嵌套笼状间位氮配体锌配合物及其制备方法和应用。
背景技术
乙炔是一种非常重要的有机化工基础原料,在其生产过程中,通常会产生少量的二氧化碳等杂质,因此在应用之前需要对乙炔进行纯化。由于乙炔和二氧化碳的沸点(乙炔沸点189.3K,二氧化碳沸点194.7K)、分子尺寸(乙炔分子尺寸为二氧化碳分子尺寸为/>)非常相近,同时具有相同的动力学尺寸/>传统的吸附材料难以有效地对乙炔和二氧化碳的混合物进行分离。金属有机骨架材料因其具有特殊的孔道结构,并可对孔道尺寸和孔道环境进行调整和修饰,在乙炔/二氧化碳分离领域表现出极大的潜力[Metal–organic frameworks for C2H2/CO2 separation,Dalton Trans.,2020,49,16598-16607]。研究表明,通过结构设计及调变在金属有机骨架材料中引入六氟酸根基团,可利用其与乙炔形成的氢键作用,达到极高的乙炔分离效率。
发明内容
针对现有金属有机骨架材料在乙炔吸附分离方面的性能不够理想的问题,本发明提供一种具有新型晶体结构及功能孔道类型的金属有机骨架材料嵌套笼状间位氮配体锌配合物及其制备方法和应用。
为解决上述技术问题,本发明采用的技术方案为:
一种嵌套笼状间位氮配体锌配合物,其化学式为[Zn(L)2ZrF6],其中L为1,3-二咪唑基苯配体(Ⅰ),结构式如下所示:
所述的嵌套笼状间位氮配体锌配合物晶体属于立方晶系,空间群,其晶胞参数为a=16.5467(6),b=16.5467(6),/>α=90°,β=90°,γ=90°,
本发明的嵌套笼状间位氮配体锌配合物的制备方法包括如下步骤:
(1)制备配体L:将咪唑、碳酸钾和碘化铜混合并研磨均匀并滴加1,3-二溴苯,装入聚四氟内衬反应器中,氮气吹扫后放入烘箱加热反应;反应结束后,降至室温,用水洗涤抽滤后保留滤渣,经萃取,过滤,旋蒸得到配体L;
(2)将Zn(BF4)2/(NH4)2ZrF6水溶液滴加于试管底层,再将N,N-二甲基甲酰胺/乙醇/水混合物缓冲溶液沿管壁缓慢加入试管作为缓冲层,最后将L的N,N-二甲基甲酰胺溶液缓慢加入试管,形成三层界面溶液;Zn(BF4)2/(NH4)2ZrF6水溶液中两种反应物的浓度为0.08~0.10mol/L,摩尔比为1:1;
(3)将步骤(2)制备分层溶液加盖,室温放置反应,反应结束后,经过滤,洗涤,干燥,得到间位氮配体锌配合物。
作为一种优选方案,步骤(1)和步骤(2)中所用水为去离子水,步骤(1)中咪唑、碳酸钾、碘化铜和1,3-二溴苯的摩尔比为100:35:0.3:12。
作为一种优选方案,步骤(1)中加热反应的温度为200℃,反应时间为18-24h。
作为一种优选方案,步骤(2)中Zn(BF4)2/(NH4)2ZrF6水溶液中Zn(BF4)2和(NH4)2ZrF6的浓度均为0.08~0.10mol/L,摩尔比为1:1。
作为一种优选方案,,步骤(2)中配体L在N,N-二甲基甲酰胺溶液中的浓度为0.04~0.06mol/L。
作为一种优选方案,步骤(2)中配体L的N,N-二甲基甲酰胺溶液、N,N-二甲基甲酰胺/乙醇/水混合物缓冲溶液和Zn(BF4)2/(NH4)2ZrF6水溶液的体积比为2:3:2。
作为一种优选方案,步骤(2)中N,N-二甲基甲酰胺/乙醇/水混合物缓冲溶液中N,N-二甲基甲酰胺、乙醇和水的体积比为3:3:1。
作为一种优选方案,步骤(3)中室温放置反应5~7d。
所述的嵌套笼状间位氮配体锌配合物在乙炔/二氧化碳混合气分离中的应用,能高效的分离乙炔/二氧化碳。
本发明具有以下有益效果:
本发明通过双齿间位氮配体合成了一种新型嵌套笼状锌基三维晶体结构,合成方法简单,产率达85%以上。该配合物三维结构为内外双层嵌套空笼结构,内笼表面及内外笼层间与乙炔有较强的相互作用,选择性好,能高效的分离乙炔/二氧化碳,以满足工业化乙炔纯化的要求。
附图说明
图1为本发明实施例1配合物的不对称单元。
图2为本发明实施例1配合物的配体L连接图。
图3为本发明实施例1配合物的金属连接图。
图4为本发明实施例1配合物在c方向的结构图。
图5为本发明实施例1配合物的粉末X射线衍射图,图中,1-本发明配合物的粉末X射线衍射图,2-模拟图。
图6为本发明实施例1配合物在298K温度下乙炔和二氧化碳的等温吸附曲线。
图7为本发明实施例1配合物在298K温度下50%乙炔/50%二氧化碳混合气的固定床分离性能曲线。
具体实施方式
下面结合具体实施例对本发明作进一步的解释说明,但具体实施例并不对本发明作任何限定。除非特别说明,实施例中所涉及的试剂均为本领域常用的试剂。
实施例1
(1)配体L的制备
咪唑(6.81g,100mmol)、碳酸钾(4.84g,35mmol)和碘化铜(57.14mg,0.3mmol)均匀研磨后装入聚四氟内衬反应器,滴加1,3-二溴苯(2.83g,12mmol)后氮气吹扫10分钟后装入不锈钢反应釜,紧固,放入烘箱200℃反应24小时。反应结束后,降至室温,用水抽滤洗涤(3*500mL),除去无机盐及未反应的咪唑;将上述滤渣,二氯甲烷萃取(3*100mL),加硫酸镁(静置3-4小时)干燥除去萃取残留的水分,过滤,旋蒸,得到产品,产率81%。
(2)嵌套笼状间位氮配体锌配合物的制备
将12mg Zn(BF4)2·H2O和12mg(NH4)2ZrF6溶于0.5mL水并滴加于内径6mm×高150mm的试管底层,再将0.75mL的体积比为3:3:1的N,N-二甲基甲酰胺/乙醇/水混合物沿管壁缓慢加入试管作为缓冲层,最后将6mg的L配体溶于0.5mL的N,N-二甲基甲酰胺溶液后同样缓慢加入试管,从而分为明显的三层;将制备的分层溶液试管加盖,25℃室温放置5天,反应结束后,经过滤,洗涤,干燥,得到嵌套笼状间位氮配体锌配合物,产率87%。
对比例1
(1)配体L的制备
同实施例1。
(2)嵌套笼状间位氮配体锌配合物的制备
Zn(BF4)2·H2O和(NH4)2ZrF6的用量均为20mg,其余步骤同实施例1,试管底部有大量无色沉淀,无晶体析出。
对比例2
(1)配体L的制备
同实施例1。
(2)嵌套笼状间位氮配体锌配合物的制备
步骤(2)中缓冲溶液使用N,N-二甲基甲酰胺/水体积比为1:1的混合物,其余步骤同实施例1,无晶体析出。
本发明制得的配合物在298K和1bar条件下,乙炔吸附量为58mL/g,而二氧化碳基本无吸附(附图6)。鉴于此,通过固定床分离装置测试了配合物50%乙炔/50%二氧化碳混合气的分离性能,298K温度下,乙炔突破时间为100分钟(附图7)。与文献中相似材料进行对比发现,本发明配合物对乙炔吸附量与其相当,但得益于对二氧化碳几乎无吸附,使得本发明配合物表现出极为优异的乙炔/二氧化碳分离性能。
*Angew.Chem.Int.Ed.2021,60,15995–16002(doi:10.1002/anie.202102810)
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (8)
1.一种嵌套笼状间位氮配体锌配合物在乙炔/二氧化碳混合气分离中的应用,其特征在于:所述间位氮配体锌配合物的化学式为[Zn(L)2ZrF6],其中L为1,3-二咪唑基苯配体(Ⅰ),结构式如下所示:
所述的间位氮配体锌配合物晶体属于立方晶系,空间群,其晶胞参数为a=16.5467(6),b=16.5467(6),/>α=90°,β=90°,γ=90°,/>
所述的嵌套笼状间位氮配体锌配合物的制备方法,包括如下步骤:
(1)制备配体L:将咪唑、碳酸钾和碘化铜混合并研磨均匀后滴加1,3-二溴苯,装入聚四氟内衬反应器中,氮气吹扫后放入烘箱;反应结束后,降至室温,用水洗涤抽滤后保留滤渣,经萃取,过滤,旋蒸得到配体L;
(2)将Zn(BF4)2/(NH4)2ZrF6水溶液滴加于试管底层,再将N,N-二甲基甲酰胺/乙醇/水混合物缓冲溶液沿管壁缓慢加入试管作为缓冲层,最后将L的N,N-二甲基甲酰胺溶液缓慢加入试管,形成三层界面溶液;
(3)将步骤(2)制备的三层界面溶液加盖,室温放置反应,反应结束后,经过滤,洗涤,干燥,得到间位氮配体锌配合物。
2.根据权利要求1所述的应用,其特征在于,步骤(1)中咪唑、碳酸钾、碘化铜和1,3-二溴苯的摩尔比为100:35:0.3:12。
3.根据权利要求1所述的应用,其特征在于,步骤(1)中加热反应的温度为200℃,反应时间为18-24h。
4.根据权利要求1所述的应用,其特征在于,步骤(2)中Zn(BF4)2/(NH4)2ZrF6水溶液中Zn(BF4)2和(NH4)2ZrF6的浓度均为0.08~0.10mol/L,摩尔比为1:1。
5.根据权利要求1所述的应用,其特征在于,步骤(2)中配体L在N,N-二甲基甲酰胺溶液中的浓度为0.04~0.06mol/L。
6.根据权利要求1所述的应用,其特征在于,步骤(2)中配体L的N,N-二甲基甲酰胺溶液、N,N-二甲基甲酰胺/乙醇/水混合物缓冲溶液和Zn(BF4)2/(NH4)2ZrF6水溶液的体积比为2:3:2。
7.根据权利要求1所述的应用,其特征在于,步骤(2)中N,N-二甲基甲酰胺/乙醇/水混合物缓冲溶液中N,N-二甲基甲酰胺、乙醇和水的体积比为3:3:1。
8.根据权利要求1所述的应用,其特征在于,步骤(3)中室温放置反应5~7d。
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