CN105037403B - 一种配位聚合物多孔材料maf‑49及其制备方法和应用 - Google Patents
一种配位聚合物多孔材料maf‑49及其制备方法和应用 Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 39
- 239000013256 coordination polymer Substances 0.000 title claims abstract description 14
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 55
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000005977 Ethylene Substances 0.000 claims abstract description 41
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
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- 150000003751 zinc Chemical class 0.000 claims description 4
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- MBNDVRNZPXEYHL-UHFFFAOYSA-N 5-[(3-amino-1h-1,2,4-triazol-5-yl)methyl]-1h-1,2,4-triazol-3-amine Chemical compound NC1=NNC(CC=2NN=C(N)N=2)=N1 MBNDVRNZPXEYHL-UHFFFAOYSA-N 0.000 abstract 1
- 230000005595 deprotonation Effects 0.000 abstract 1
- 238000010537 deprotonation reaction Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- 241000790917 Dioxys <bee> Species 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000373 single-crystal X-ray diffraction data Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
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Abstract
本发明提供了一例多孔配位聚合物MAF‑49及其制备方法与应用,所述MAF‑49的化学式为[Zn(batz)],其中batz2‑为配体双(5‑氨基‑1H‑1,2,4‑三唑‑3‑基)甲烷H2batz脱去质子后的阴离子,该材料结晶于三方晶系,P3121空间群,a=9.6963Å,c=20.126Å;是由batz2‑配体与三个四配位的Zn2+离子连接形成的具有一维孔道的三维框架结构。该材料具有稳定性好,乙烷吸附强等特点,可用于富集天然气中的乙烷,纯化垃圾填埋气中的甲烷,回收乙烯环氧化产物中的乙烯,还能简便低能耗地分离乙烯乙烷混合物以获得纯度99.95%+的乙烯,具有很高的工业应用价值。
Description
技术领域
本发明属于微孔配位聚合物多孔材料技术领域,更具体地,涉及一种配位聚合物多孔材料MAF-49及其制备方法与应用。
背景技术
多孔配位聚合物(PCP, Porous Coordination Polymer),或金属有机框架(MOF,Metal-Organic Framework),是一类晶态多孔材料。它是通过无机金属中心或簇与有机配体通过配位键相互连接而成的具有周期性网络结构和规则孔道的配合物。与传统的活性炭和无机多孔材料相比,其不仅具有更加丰富多样的结构,且其可控的孔径大小、可修饰的孔道表面与选择性吸附功能是传统多孔材料无法媲美的。通过功能性金属离子或簇的引入或者是在有机配体上引入官能团,都可以赋予或者是改善该材料气体吸附与分离、光电磁以及催化等性能。这些优点使该材料在气体储存与分离、离子交换、光学、电学、磁学等领域具有潜在的应用价值。
例如,作为工业上最重要的工艺之一的乙烯乙烷分离,其能耗非常高(7 GJ t-1),占乙烷生产成本的75-85%。因此,低能耗而且高效的分离方法受到许多科学家的研究和关注。目前,已经有一些多孔配位聚合物能在室温常压条件下分离乙烯乙烷,很大程度上节约了能耗和降低了分离的成本,是一种非常具有发展前景的分离方法。然而,现有材料单次分离得到的乙烯纯度最高为99%,需要多次提纯才能达到聚合级99.95%+要求。
鉴于比,本发明寻求提供一种配位聚合物材料,能够解决现有技术中分离纯化过程中能耗高且分离效率达不到聚合级要求的问题。
发明内容
本发明的目的在于根据现有微孔配位聚合物多孔材料技术的不足,提供了一种配位聚合物多孔材料MAF-49。
本发明的另一个目的在于提供所述多孔材料MAF-49的制备方法与应用。
本发明的上述目的通过以下技术方案实现:
本发明提供了一种配位聚合物多孔材料MAF-49,所述MAF-49的化学式为[Zn(batz)],其中batz2-代表配体双(5-氨基-1H-1,2,4-三唑-3-基)甲烷 H2batz 脱去质子后的阴离子,所述多孔材料MAF-49结晶在三方晶系,P3121空间群,a = 9.6963 Å,c = 20.126Å;
所述MAF-49是通过batz2-与三个四配位的Zn2+离子连接形成的具有一维孔道的三维框架结构,其孔洞率为29%。
本发明配位聚合物多孔材料MAF-49的制备方法由配体H2batz与锌盐在溶剂中反应得到。
优选地,所述配体和锌盐的反应摩尔比为1:1,所述溶剂为氨水与水的混合溶液,反应温度为160 ℃,反应时间为3 d。
本发明提供的MAF-49不仅具有很好的热稳定性和化学稳定性,而且在实用的气体分离应用方面具有非常出色的性能。
优选地,所述小分子气体为甲烷、二氧化碳、乙烷或乙烯。
优选地,所述MAF-49用于吸附甲烷/乙烷混合气体中的乙烷,得到高纯度的甲烷。可应用于天然气中提取乙烷,同时分离得到高纯度的甲烷。
优选地,所述MAF-49用于吸附乙烯/二氧化碳混合气体中的乙烯。可应用于从乙烯的环氧化副产物中资源回收乙烯。
优选地,,所述MAF-49用于吸附二氧化碳和甲烷混合气体中的二氧化碳,得到高纯度的甲烷。可应用于通过优选吸附二氧化碳分离垃圾填埋气得到高纯的甲烷。
优选地,所述MAF-49用于吸附乙烯乙烷混合气体中的乙烷,得到高纯度的乙烯。
特别地,所述多孔材料MAF-49可以作为吸附固定床填料应用于从乙烯/乙烷混合气体中直接分离纯化高纯度乙烯,乙烯的纯度达到聚合纯度度要求99.95%,而且,在工业条件下,即对于15:1的乙烯乙烷混合气,单次分离得到的乙烯纯度高达99.995%,同时具有比较高的工作容量。相比较工业上现有所用的乙烯提纯工艺,不仅能够提高其纯化效率,更重要的是,该配合物合成步骤简单,原料易得,能够大大降低现有的乙烯合成及分离能耗问题。
因此,本发明MAF-49材料作为吸附客体分子,用于制备存储、分离、催化、传感、分子识别或热交换材料,具备极好的应用前景。
与现有技术相比,本发明具有如下有益效果:
(1)本发明提供的的MAF-49热稳定性极好,可以稳定到723 K;化学稳定性也很好,将其浸泡在4 ≤ pH ≤ 12水溶液中,框架结构也不会被破坏;而大多数的PCPs酸碱稳定性都比较差;
(2)在313 K,常压条件下,本发明合成的MAF-49具有很好的甲烷/乙烷、乙烷/二氧化碳和甲烷/二氧化碳分离性能,能分离天然气中的三个主要成分,甲烷、乙烷和二氧化碳,可以得到高纯的甲烷和乙烷。此外,还能应用于分离垃圾填埋气的两个主要成分,甲烷和二氧化碳,得到高纯度的甲烷。
(3)在313 K,常压条件下,本发明合成的MAF-49具有很好的乙烯/二氧化碳分离性能,能应用于资源回收工业上乙烯环氧化的乙烯原料。
(4)在313 K,常压条件下,本发明合成的MAF-49分离体积比1:1的乙烯/乙烷混合气体可以得到纯度为99.95%+的乙烯;
(5)在313 K,常压条件下,本发明合成的MAF-49分离体积比15:1的乙烯/乙烷混合气体可以得到纯度为99.995%+的乙烯,而且1 L 的MAF-49材料可以单次分离得到56 L纯度为99.95%+的乙烯,是目前性能最好的多孔材料的56倍,十分适合工业条件下乙烯的纯化。
附图说明
图1为本发明多孔材料MAF-49的晶体结构;
图2为本发明多孔材料MAF-49的X射线粉末衍射图,包括原合成的粉末,以及各种经过热处理后的粉末;
图3为本发明多孔材料MAF-49的热重曲线图;
图4为本发明多孔材料MAF-49在316 K条件下二氧化碳,甲烷,乙烯和乙烷吸附等温线;
图5为本发明多孔材料MAF-49所制备的吸附固定床在313 K和一个大气压条件下对体积比为1:1:1:1四组气体混合物二氧化碳/甲烷/乙烯/乙烷的气体分离穿透实验曲线;
图6为本发明多孔材料MAF-49所制备的吸附固定床在313 K一个大气压条件下对体积比为1:1乙烯/乙烷混合气体的气体分离穿透实验曲线;
图7为本发明多孔材料MAF-49所制备的吸附固定床在313 K一个大气压条件下对体积比为15:1乙烯/乙烷混合气体的气体分离穿透实验曲线。
具体实施方式
以下结合具体实施例来进一步说明本技术,但实施例并不对本技术做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1多孔材料MAF-49单晶制备
配体H2batz参照现有技术方法合成得到;
将配体H2batz (0.180 g, 1.0 mmol), Zn(OH)2 (0.100 g, 1.0 mmol), 氨水(25%, 4 mL), 水 (4 mL) 一并加入到水热反应釜中,加热到160 ℃ 反应3天得到无色的MAF-49单晶,产率为86%。
实施例2 含客体分子及不含客体的MAF-49的结构表征
单晶X射线衍射数据是在Bruker Smart APEX CCD衍射仪上收集,石墨单色器,用Mo-K射线,以ω扫描方式收集数据,吸收校正采用REQAB程序。利用直接法进行解析,然后用差值傅立叶函数法和最小二乘法求出全部非氢原子坐标,最后用最小二乘法对结构进行修正。化合物的氢原子通过理论加氢法得到。计算工作在PC机上使用SHELXTL程序完成。详细的晶体测定数据见表1。结构见图1。
表1
Complex | MAF-49 | MAF-49·H2O |
Formula | C5H6N8Zn | C5H7N8O0.5Zn |
Formula weight | 243.57 | 252.56 |
Temperature (K) | 195(2) | 195(2) |
Space group | P3121 | P3121 |
a/Å | 9.6963(15) | 9.6767(14) |
c/Å | 20.126(3) | 20.172(3) |
V/Å3 | 1638.7(4) | 1635.8(4) |
Z | 6 | 6 |
D c/g cm-3 | 1.481 | 1.538 |
R int | 0.0192 | 0.0340 |
R 1 [I> 2σ(I)] | 0.0184 | 0.0369 |
wR 2 (all data) | 0.0438 | 0.0994 |
GOF | 1.060 | 1.051 |
Flack | 0.003(10) | -0.02(2) |
Peak and hole (e Å –3) | 0.293 and -0.249 | 0.579 and -0.405 |
R 1=∑||F o| - |F c||/∑|F o|.wR 2 =[∑w(F o 2 - F c 2)2/∑w(F o 2)2]1/2 .
实施例3实施例1所得多孔配位聚合物MAF-49的热稳定性表征
多孔材料的热稳定性通过热重分析法得到。本发明提供的的MAF-49热稳定性极好,可以稳定到723 K。热重曲线图见图3。
同时,本发明将合成得到的MAF-49直接浸泡在4 ≤ pH ≤ 12水溶液中,经过结构测定表征,其框架结构也不会被破坏,显示其良好的酸碱稳定性,相应的粉末衍射表征见图2。
实施例4实施例1所得多孔配位聚合物MAF-49的气体吸附性质表征
将以去除客体的该多孔材料放入石英样品管中,然后在BELSORP-max吸附仪在316K条件下分别测定其甲烷 (CH4),二氧化碳 (CO2),乙烷 (C2H6) 和乙烯 (C2H4) 气体吸附等温线,其吸附等温线图见图4。由图可见,MAF-49具有同时分离四种气体的潜在性能。
实施例5以MAF-49为填料吸附固定床的制作和四组分混合气体分离
将MAF-49粉末样品填充进内径为0.46 cm,长度为10 cm的不锈钢管,尽量压实填密。柱子在He气氛,323 K加热恒温10小时,冷却至313 K,一个大气压下,向柱子通入总流速为0.8 mL min-1,体积比为1:1:1:1 的CH4/CO2/C2H6/C2H4 混合气体,气体的绝对浓度(C o /C i , 各组分出气口摩尔浓度 / 进气口摩尔浓度)用热导检测器 (TCD, 7890A, HP-AL/S毛细管柱) 检测。得到的穿透曲线实验数据图见图5, 图中以比进气量(mmol g-1, 流进柱子气体的总摩尔量/多孔材料的填料量)为横坐标,绝对浓度C o /C i 为纵坐标。由图可见,MAF-49具有同时分离四种气体的性能,能够实现对这四种气体两两分离,在多孔材料中十分罕见。
实施例6 以MAF-49为填料吸附固定床的制作和体积比为1:1的C2H6/C2H4分混合气体分离
将MAF-49粉末样品填充进内径为0.46 cm,长度为10 cm的不锈钢管,尽量压实填密。柱子在He气氛,323 K加热恒温10小时,冷却至313 K,一个大气压下,向柱子通入总流速为0.2 mL min-1,体积比为1:1 的C2H6/C2H4 混合气体,气体的绝对浓度用热导检测器(TCD, 7890A, HP-AL/S毛细管柱) 检测,相对浓度(Composition at outlet, mol%, 各组分出气口摩尔浓度 / (各组分出气口摩尔浓度之和)%)用MS (5975C) 检测。在313 K,常压条件下,本发明合成的MAF-49分离体积比1:1的乙烯/乙烷混合气体可以得到纯度为99.95%+的乙烯,得到的穿透曲线实验数据图见图6。
实施例7 以MAF-49为填料吸附固定床的制作和体积比为1:15的C2H6/C2H4分混合气体分离
将MAF-49粉末样品填充进内径为0.46 cm,长度为10 cm的不锈钢管,尽量压实填密。柱子在He气氛,323 K加热恒温10小时,冷却至313 K,一个大气压下,向柱子通入总流速为1.6 mL min-1,体积比为1:15 的C2H6/C2H4 混合气体,气体的绝对浓度用热导检测器(TCD, 7890A, HP-AL/S毛细管柱) 检测,相对浓度用MS (5975C) 检测。在313 K,常压条件下,本发明合成的MAF-49分离体积比15:1的乙烯/乙烷混合气体可以得到纯度为99.995%+的乙烯,十分适合工业条件下乙烯的纯化,得到的穿透曲线实验数据图见图7。
Claims (10)
1.一种配位聚合物多孔材料MAF-49,其特征在于,所述MAF-49的化学式为[Zn(batz)],其中batz2-代表配体双(5-氨基-1H-1,2,4-三唑-3-基)甲烷 H2batz 脱去质子后的阴离子,所述多孔材料MAF-49结晶在三方晶系,P3121空间群,a = 9.6963 Å,c = 20.126 Å
所述MAF-49是通过batz2-与三个四配位的Zn2+离子连接形成的具有一维孔道的三维框架结构。
2.权利要求1所述的配位聚合物多孔材料MAF-49的制备方法,其特征在于,所述MAF-49由配体H2batz与锌盐在溶剂中反应得到。
3.根据权利要求2所述的配位聚合物多孔材料MAF-49的制备方法,其特征在于,所述配体和锌盐的反应摩尔比为1:1,所述溶剂为氨水与水的混合溶液,反应温度为160 ℃,反应时间为3 d。
4.权利要求1所述的配位聚合物多孔材料MAF-49在制备存储、分离、分子识别或热交换材料中的应用。
5.权利要求1所述的配位聚合物多孔材料MAF-49在分离纯化小分子气体中的应用。
6.根据权利要求5所述的应用,其特征在于,所述小分子气体为甲烷、二氧化碳、乙烷或乙烯。
7.根据权利要求6所述的应用,其特征在于,所述MAF-49用于吸附乙烯乙烷混合气体中的乙烷,得到满足聚合纯度要求的乙烯。
8.根据权利要求6所述的应用,其特征在于,所述MAF-49用于吸附甲烷/乙烷混合气体中的乙烷,得到高纯度的甲烷。
9.根据权利要求6所述的应用,其特征在于,所述MAF-49用于吸附乙烯/二氧化碳混合气体中的乙烯。
10.根据权利要求6所述的应用,其特征在于,所述MAF-49用于吸附二氧化碳和甲烷混合气体中的二氧化碳,得到高纯度的甲烷。
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Title |
---|
Coordination Compounds of Copper(II)with Bis(5-amino-1,2,4-triazol-3-yl)alkanes;M. I. Barmi et al.;《RUSSIAN JOURNAL OF GENERAL CHEMISTRY》;20031231;第73卷(第3期);第482-487页 * |
Microporous Zinc(II) Metal-Organic Framework with 6-Connected pcu Topology: Synthesis, Structure, and Gas Adsorption Properties;Yanli Dong et al.;《Z. Anorg. Allg. Chem》;20150319;第641卷(第8-9期);第1556–1559页 * |
The 3D porous metal–organic frameworks based on bis(pyrazinyl)–trizole: structures, photoluminescence and gas adsorption properties;Jie Pan et al.;《CrystEngComm》;20130612;第15卷;第5673-5680页 * |
张杰鹏等.利用柔性多孔晶体高效储存 / 分离乙炔和二氧化碳.《中国基础科学• * |
研究进展》.2014,第15-17页. * |
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