CN102241695A - 类分子筛金属双咪唑多孔配位聚合物及其制备方法 - Google Patents
类分子筛金属双咪唑多孔配位聚合物及其制备方法 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 150000002460 imidazoles Chemical class 0.000 title claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000013259 porous coordination polymer Substances 0.000 title abstract 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract 3
- 229920000642 polymer Polymers 0.000 claims description 40
- 239000003446 ligand Substances 0.000 claims description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000013256 coordination polymer Substances 0.000 abstract description 4
- 229920001795 coordination polymer Polymers 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000011701 zinc Substances 0.000 description 14
- 239000010949 copper Substances 0.000 description 11
- 238000007789 sealing Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 235000011089 carbon dioxide Nutrition 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000001757 thermogravimetry curve Methods 0.000 description 4
- 230000000274 adsorptive effect Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000005394 sealing glass Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000013159 zeolitic imidazolate framework-69 Substances 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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Abstract
本发明公开了类分子筛金属双咪唑配位聚合物及其制备方法和应用。本发明的新型类分子筛配位聚合物是下述化学式的化合物:{[M(BIm)]×xDMF×yC2H6O×zH2O}∞,其中M=Zn,x=0.9,y=0,z=0;M=Cu,x=1.2,y=0,z=0;M=Mn,x=2.0,y=0,z=0;M=Ni,x=0.4,y=1.2,z=1.0,Bim为双-4-咪唑亚甲基联胺,DMF为N,N-二甲基甲酰胺,H2O为水。化合物采用溶剂热法或缓慢扩散法制备,所得的晶体纯度较高。本发明的配位聚合物具有很好的热稳定性,并在0oC常压条件下对CO2具有极强的吸附性能,从而可以作为吸附材料得到应用。
Description
技术领域
本发明属于过渡金属配合物材料技术领域,涉及微孔金属有机配位聚合物材料,特别是一类新型类分子筛金属双咪唑多孔配位聚合物和制备方法及其应用,所属微孔配位聚合物是具有微孔的三维类分子筛配位聚合物及对CO2具有较高的吸附能力。
背景技术
分子筛因其催化、吸附、分离等性能,在石油化工、精细化工和药物化学等领域得到广阔的应用。近年来,类分子筛金属咪唑多孔配位聚合物引起人们极大的兴趣,不仅因为他们具有分子筛的网络结构,更主要是其极其稳定性及在催化,分离,气体储存等方面的潜在应用(例如:a) Tian, Y. Q.; Cai, C. X.; Ji, Y.; You, X. Z.; Peng, S. M.;
Lee, G. H., Angew . Chem. Int. Ed. 2002,
41, 1384; b) Huang, X. C.; Lin, Y. Y.; Zhang, J. P.; Chen, X. M., Angew . Chem. Int. Ed. 2006, 45,
1557; c) Park, K. S.; Ni, Z.; Côté, A. P.; Choi, J.
Y.; Huang, R.; Uribe-Romo, F. J.; Chae,
H. K.; O’Keeffe, M.;
Yaghi, O. M., Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 10186; d) Tran, U.
P. N.; Le, K. K. A.; Phan, N. T. S., ACS Catalysis
2011, 1, 120-127; e) Jiang, H.-L.;
Akita, T.; Ishida, T.; Haruta, M.; Xu, Q., J. Am. Chem. Soc. 2011, 133,1304-1306;
f) Venna, S. R.; Carreon,
M. A., J. Am. Chem. Soc. 2010, 132, 76-78; g) Zhang, J.;
Wu, T.; Zhou, C.; Chen, S.; Feng, P.; Bu, X., Angew . Chem. Int. Ed. 2009, 48,
2542; h) Wu, T.; Zhang, J.; Zhou, C.; Wang, L.; Bu, X.; Feng,
P., J. Am. Chem. Soc. 2009, 131, 6111-6113; i) Li, K.; Olson, D. H.; Seidel, J.; Emge,
T. J.; Gong, H.; Zeng, H.; Li, J. , J. Am. Chem.
Soc. 2009, 131, 10368-10369; j) Banerjee,
R.; Furukawa, H.; Britt, D.; Knobler, C.; O’Keeffe, M.; Yaghi, O. M., J. Am. Chem. Soc. 2009, 131,
3875.)。尽管一些具有分子筛结构的金属咪唑多孔配位已经被化学家合成(只有9种),但相对于拥有194种的庞大分子筛家族还是比较少(见 Baerlocher, C.; Meier, W. M.; Olson, D. H., Atlas of Zeolite Framework Types. 2007;或网站: http://www.iza-structure.org/.),因此合成新型的具有分子筛结构的配位聚合物仍然是一大难题。在194种的分子筛家族中,具有手性的螺旋孔道结构的分子筛只有六种。BSV分子筛是其中比较特殊的一种,具有左手螺旋和右手螺旋两种互为镜像的三维孔道。类似于BSV分子筛具有左手螺旋和右手螺旋两种三维螺旋孔道的配位聚合物迄今还没有报道。由于可能用于发展手性催化,手性分离材料,这类化合物的合成与探索,特别是通过合理设计具有三维螺旋孔道的配位聚合物,对开发高性能材料将会产生极大的影响,将为整个分子筛材料科学注入强大的生命力。
发明内容
本发明的目的在于提供具有三维螺旋孔道的一种类分子筛配位聚合物,它包括了含有锌-双-4-咪唑亚甲基联胺,铜-双-4-咪唑亚甲基联胺,锰-双-4-咪唑亚甲基联胺,镍-双-4-咪唑亚甲基联胺的四种具有相同类分子筛结构的配位聚合物。
本发明的另一目的在于提供该类分子筛多孔配位聚合物的制备方法。
本发明的再一目的在于提供一种类分子筛多孔配位聚合物在制备作为CO2吸附储存材料方面的应用。
本发明的技术方案如下:具有下述通式的类分子筛多孔配位聚合物:{[M(BIm)]×xDMF×yC2H6O×zH2O}∞其中M选自Zn、Cu、Mn或Ni,且满足:M = Zn,x = 0.9,y = 0,z = 0;当 M =
Cu,x = 1.2,y = 0,z = 0;当M = Mn,x = 2.0,y = 0,z = 0;当M =
Ni,x = 0.4 y
= 1.2,z = 1.0;聚合物结构示意图如图15所示。
BIm是双-4-咪唑亚甲基联胺,DMF为 N,N-二甲基甲酰胺, BIm及DMF结构式如图16所示。
本发明所述配位聚合物主要红外吸收峰如下:锌-双-4-咪唑亚甲基联胺(溴化钾压片,cm-1):2927.0w, 2835.3w, 1660.8s,1616.1vs,1586.0s,1506.1m,1469.1w,1455.8w, 1384.5vs, 1352.1w,1326.6w,1280.6w,1264.7m,1214.4m,1114.8s,1041.3m, 1019.3m,971.1m,841.1m,841.1m,659.4m,627.3w,496.4m; 铜-双-4-咪唑亚甲基联胺(溴化钾压片,cm-1):2917.4w, 2853.4w, 1654.8s, 1610.5vs, 1577.3s, 1500.0w, 1458.1w, 1384.3vs, 1252.2m, 1201.7w, 1114.4s, 1050.4m, 1017.9m, 968.2w, 840.8m, 818.0m, 653.3m, 619.3w, 561.5w, 504.8w; 锰-双-4-咪唑亚甲基联胺(溴化钾压片,cm-1):2920.64w, 1655.6s, 1604.7vs, 1584.1s, 1568.4s, 1515.78m, 1495.4m, 1467.7w, 1415.1w, 1386.8m, 1349.5s, 1276.5w, 1252.2s, 1206.9m, 1111.2s, 1028.2m, 1005.2m, 963.3m, 855.18w, 838.5m, 816.5m, 791.3m, 754.6m, 733.1w, 695.6w, 659.8s, 627.2m, 487.9m;镍-双-4-咪唑亚甲基联胺:(溴化钾压片,cm-1): 2920.6w, 1654.7s, 1600.3vs, 1570.3s, 1498.1m, 1458.9w, 1437.9w, 1408.9w, 1384.9m, 1355.8m, 1327.6w, 1258.7s, 1198.8m, 1111.2s, 1044.7m,1014.3s, 964.3m, 840.9m, 818.2m, 660.6m, 640.2w, 499.9m。
本发明类分子筛金属双咪唑多孔配位聚合物的晶体属于立方晶系,空间群为:Ia-3d,晶胞参数为:锌-双-4-咪唑亚甲基联胺:a = b = c = 34.6471(2) Å,a= b = g = 90°,V = 41591.1(4) Å3 ; 铜-双-4-咪唑亚甲基联胺:a = b = c = 34.2896(3) Å,a = b = g =90°,V = 40316.8(6) Å3;锰-双-4-咪唑亚甲基联胺:a = b = c =
35.7950(4) Å, a =b = g = 90°,V =
45863.4(9) Å3;镍-双-4-咪唑亚甲基联胺:a = b
= c = 33.8514(19),a = b
= g = 90°,V =
38791(4) Å3。这四种配位聚合物具有同样的骨架结构,不同之处在于金属原子不一样。四种配位聚合物,除了镍-双-4-咪唑亚甲基联胺中的金属原子采取六配位八面体构型之外(额外一个水分子配位),其余三个配位聚合物的金属原子都采取五配位的平面四角锥的配位构型。其结构是基于配体BIm与金属离子的桥联配位,形成具有左手螺旋和右手螺旋为镜像的三维孔道的三维骨架;孔道中填充了DMF或乙醇溶剂分子。其骨架结构具有跟BSV分子筛一样的三维拓扑网络结构。
本发明类分子筛配位聚合物的合成方法,包括以下步骤:方法一:有机配体BIm与金属盐(Zn(NO3)2×6H2O,Cu(NO3)2·3H2O, Ni(NO3)2·6H2O或Mn(NO3)2的50%水溶液)的混合物溶于DMF或 DMF/乙醇的混合溶剂,溶剂热条件下反应,随后过滤溶液,收集晶体,用DMF洗涤,干燥。所述的BIm与金属盐的摩尔比为1:1~1.1:1,优选1:1。
所述的DMF和乙醇的体积比为4:1~3:1,优选4:1。
所述的加热温度为100~120°C。
方法二:有机配体与Zn(NO3)2×6H2O 溶于DMF,在室温下用三乙胺/正己烷的混合溶剂缓慢扩散,随后过滤,收集沉淀,用DMF洗涤,干燥。
所述的三乙胺和正己烷的体积比为2:70~5:70, 优选3:70。
本发明热分析实验表明此类配位聚合物的配位骨架具有很高的热稳定性(图1,2,3和4),气体吸附试验表明它在摄氏0度常压条件下对二氧化碳具有较强的吸附性能,每克达70.2毫升,或每克吸附138.0毫克二氧化碳。因此该类配位聚合物可作为潜在的储二氧化碳材料,在材料科学领域具有良好的应用前景。
附图说明
图1 本发明的锌-双-4-咪唑亚甲基联胺的热分析图。
图2本发明的铜-双-4-咪唑亚甲基联胺的热分析图。
图3本发明的锰-双-4-咪唑亚甲基联胺的热分析图。
图4本发明的镍-双-4-咪唑亚甲基联胺的热分析图。
图5 本发明的锌-双-4-咪唑亚甲基联胺粉末衍射图。
图6本发明的铜-双-4-咪唑亚甲基联胺粉末衍射图。
图7本发明的锰-双-4-咪唑亚甲基联胺粉末衍射图。
图8本发明的镍-双-4-咪唑亚甲基联胺的粉末衍射图。
图9本发明的锌-双-4-咪唑亚甲基联胺的配位环境图。
图10本发明的铜-双-4-咪唑亚甲基联胺的配位环境图。
图11本发明的锰-双-4-咪唑亚甲基联胺的配位环境图。
图12本发明的镍-双-4-咪唑亚甲基联胺的配位环境图。
图13本发明的类分子筛金属(锌,铜,锰,镍)双咪唑配位聚合物的三维多孔结构。
图14本发明的锌-双-4-咪唑亚甲基联胺的二氧化碳吸附脱附图。
图
15
是本发明聚合物结构示意图。
图
16
是本发明
BIm
及
DMF
结构示意图。
配位聚合物的合成具体实施方式。
实施例1:将0.021mmol BIm与0.021 mmol Zn(NO3)2·6H2O溶于2.0 mL DMF溶剂,并加入到一端封闭的硬质玻璃管内,随后加热熔融封闭。把封闭好的玻璃管放入烘箱中恒温摄氏100度加热24小时,收集晶体,用DMF洗涤,干燥得目标产品,产率:50%。
实施例2:将1.94 mmol BIm与1.94 mmol Zn(NO3)2·6H2O溶于90 mL DMF 溶剂,分装到10个小的玻璃瓶中,每个9.0 mL,然后放置到一个装有三乙胺/正己烷混合溶剂(73 mL,体积比3/70)的广口瓶中(500 mL),放慢扩散3天得到产品。用DMF洗涤,干燥得目标产品,产率:90%。
实施例3:将0.021mmol BIm与0.021mmol Cu(NO3)2·3H2O溶于2.0 mL DMF/乙醇(体积比,4:1)溶剂,并加入到一端封闭的硬质玻璃管内,随后加热熔融封闭。把封闭好的玻璃管放入烘箱中恒温摄氏100度加热24小时,收集晶体,用DMF洗涤,干燥得目标产品,产率:60%。
实施例4:将0.21 mmol BIm与0.21mmol Mn(NO3)2·6H2O溶于2.0 mL DMF/乙醇 (体积比4:1)溶剂,并加入到一端封闭的硬质玻璃管内,随后加热熔融封闭。把封闭好的玻璃管放入烘箱中恒温摄氏120度加热24小时,收集晶体,用DMF洗涤,干燥得目标产品,产率:50%。
实施例5:将0.21 mmol BIm 与 0.21 mmol Ni(NO3)2·6H2O溶于2.0 mL DMF/乙醇溶剂(体积比,4:1),并加入到一端封闭的硬质玻璃管内,随后加热熔融封闭。把封闭好的玻璃管放入烘箱中恒温摄氏120度加热24小时,收集晶体,用DMF洗涤,干燥得目标产品,产率:55%。
实施例6:对类分子筛金属咪唑多孔配位聚合物的表征和吸附性能研究:(1)
粉末衍射表征纯度,图5为锌-双-4-咪唑亚甲基联胺,图6为铜-双-4-咪唑亚甲基联胺,图7为锰-双-4-咪唑亚甲基联胺粉末衍射图,图8为镍-双-4-咪唑亚甲基联胺的粉末衍射图。粉末衍射数据收集在bruker D8 advance 衍射仪上完成,仪器的操作电压为40 KV,电流为40 mA,使用石墨单色化的铜靶X射线 (Cu Ka,λ= 1.5418 Å ), 在5°到30°范围内连续扫描完成。单晶结构粉末衍射谱模拟转化使用Mercury软件。
(2)晶体结构的测定:在显微镜下选取合适大小的单晶,在安捷伦公司的Gmini A衍射仪上 (Cu
Ka,λ= 1.5418 Å),射线通过石墨单色器单色。数据处理使用衍射仪的程序CrysAlisPro.1;结构使用直接法解出初始模型,然后用基于F 2的最小二乘法精修结构。所有的非氢原子都进行各项异性精修,用理论加氢的方法确定氢原子的位置。客体分子处于高度无序状态,使用PLATON软件的SQEEZE 程序处理。晶体结构图见:图9是本发明的锌-双-4-咪唑亚甲基联胺,图10是铜-双-4-咪唑亚甲基联胺,图11是锰-双-4-咪唑亚甲基联胺,图12是镍-双-4-咪唑亚甲基联胺的配位环境图,图13是该类分子筛金属(锌,铜,锰或镍)双咪唑配位聚合物的三维多孔结构。晶体学衍射点数据收集与结构精修的部分参数列在表1。
(3)对实施例1配位聚合物的吸附性能研究:二氧化碳吸附实验使用美国麦克公司生产的Micromeritics ASAP
2010型体积吸附装置完成。使用高纯的二氧化碳气体,190.1mg锌-双-4-咪唑亚甲基联胺样品在0度下完成吸附脱附实验,结果见图14(四方块代表等温吸附点,三角形代表等温脱附点)。如图14本发明的类分子筛金属双咪唑配位聚合物表现出对二氧化碳完全可逆的吸附和脱附。在常压及零度情况下每克能吸附70.2毫升CO2,相当于1千克的配位聚合物能吸附138.7克的CO2。吸附的重量比达到13.8%。超过了一般的类分子筛金属咪唑配位聚合物对二氧化碳的吸附能力,如对二氧化碳吸附能力最强的ZIF-69每千克在常压及摄氏0度情况下能吸附126.1克 (Banerjee, R.; Phan, A.; Wang, B.;
Knobler, C.; Furukawa, H.; O’Keeffe, M.; Yaghi,O. M. Science 2008, 319, 939–943)。
表1 类分子筛金属咪唑多孔配位聚合物的晶体学数据
锌-双-4-咪唑亚甲基联胺 | 铜-双-4-咪唑亚甲基联胺 | 锰-双-4-咪唑亚甲基联胺 | 镍-双-4-咪唑亚甲基联胺 | |
经验分子式 | C384H288N288Zn48 | C384H288N288Cu48 | C384H288N288Mn48 | C384H384N288Ni48O48 |
分子量 | 12074.78 | 11986.94 | 11574.14 | 12619.87 |
晶系 | cubic | cubic | cubic | cubic |
温度(K) | 293.3 | 293.3 | 293.3 | 100.0 |
空间群 | Ia-3d | Ia-3d | Ia-3d | Ia-3d |
晶胞参数 | ||||
a (Å) | 34.6471(2) | 34.2896(3) | 35.7950(4) | 33.8514(19) |
b (Å) | 34.6471(2) | 34.2896(3) | 35.7950(4) | 33.8514(19) |
c (Å) | 34.6471(2) | 34.2896(3) | 35.7950(4) | 33.8514(19) |
α (deg) | 90 | 90 | 90 | 90 |
β (deg) | 90 | 90 | 90 | 90 |
γ (deg) | 90 | 90 | 90 | 90 |
V (Å3) | 41591.1(4) | 40316.8(6) | 45863.4(9) | 38791(4) |
Z | 2 | 2 | 2 | 2 |
理论密度 (g cm-3) | 0.964 | 0.987 | 0.838 | 1.080 |
吸收系数(mm-1) | 1.858 | 1.722 | 5.518 | 1.689 |
总衍射点 | 10396 | 15159 | 15968 | 14980 |
独立衍射点 | 2132 | 3325 | 3099 | 2627 |
Rint | 0.0650 | 0.0278 | 0.0788 | 0.1054 |
R 1 [I>2σ(I)]a | 0.0388 | 0.0407 | 0.0513 | 0.1289 |
wR 2 [I>2σ(I)]b | 0.0791 | 0.1148 | 0.1117 | 0.3104 |
R 1 [all data] | 0.0766 | 0.0510 | 0.1183 | 0.1852 |
wR 2 [all data] | 0.0888 | 0.1214 | 0.1302 | 0.3708 |
a R 1=å(||F0 |-
|Fc ||)/å|F0 |; b wR 2=[åw(F0 2- Fc 2)2/åw(F0 2)2]1/2
Claims (8)
1.具有下述化学通式的类分子筛金属双咪唑多孔配位聚合物:
{[M(BIm)]×xDMF×yC2H6O×zH2O}∞,其中:
M = Zn,x = 0.9,y = 0,z = 0;
M = Cu,x = 1.2,y = 0,z = 0;
M = Mn,x = 2.0,y = 0,z = 0;
M = Ni,x = 0.4,y = 1.2,z = 1.0
BIm是双-4-咪唑亚甲基联胺,DMF为 N,N-二甲基甲酰胺。
2.如权利要求1所述的多孔配位聚合物:类分子筛金属双咪唑多孔配位聚合物的晶体属于立方晶系,空间群为:Ia-3d,
晶胞参数为:
锌-双-4-咪唑亚甲基联胺:a = b = c = 34.6471(2) Å, a
= b = g = 90°,
V = 41591.1(4) Å3 ;
铜-双-4-咪唑亚甲基联胺:a = b = c = 34.2896(3) Å,a = b
= g = 90°,V = 40316.8(6) Å3;
锰-双-4-咪唑亚甲基联胺:a = b= c = 35.7950(4) Å, a =
b = g = 90°,V = 45863.4(9) Å3;
镍-双-4-咪唑亚甲基联胺:a = b = c = 33.8514(19),a = b
= g = 90°,V = 38791(4) Å3;
其中镍-双-4-咪唑亚甲基联胺中的金属原子采取六配位八面体构型;锌-双-4-咪唑亚甲基联胺、铜-双-4-咪唑亚甲基联胺、锰-双-4-咪唑亚甲基联胺聚合物的金属原子都采取五配位的平面四角锥的配位构型,其结构是基于配体BIm与金属离子的桥联配位,形成具有左手螺旋和右手螺旋为镜像的三维孔道的三维骨架;孔道中填充了DMF或乙醇溶剂分子,其骨架结构具有跟BSV分子筛一样的三维拓扑网络结构。
3.权利要求1所述的配位聚合物的制备方法,其特征在于按如下步骤操作:有机配体BIm与相应金属盐按摩尔比为1:1~1.1:1混合后溶于DMF或 DMF/乙醇的混合溶剂,溶剂热条件下反应,随后过滤溶液,收集晶体,用DMF洗涤,干燥;所说的金属盐分别为Zn(NO3)2×6H2O、Cu(NO3)2·3H2O、Mn(NO3)2或 Ni(NO3)2·6H2O。
4.根据权利要求3所述配位聚合物的制备方法,其特征在于所述的DMF和乙醇的体积比为4:1~3:1。
5.根据权利要求4所述配位聚合物的制备方法,其特征在于所述溶剂热条件的加热温度为100~120°C。
6.权利要求1所述的配位聚合物的制备方法,其中锌-双-4-咪唑亚甲基联胺按以下步骤操作:有机配体Bim与Zn(NO3)2×6H2O按摩尔比为1:1~1.1:1溶于DMF,在室温下用三乙胺/正己烷的混合溶剂缓慢扩散,随后过滤,收集沉淀,用DMF洗涤,干燥。
7.一种权利要求6所述的配位聚合物的制备方法,其特征所述的三乙胺和正己烷的体积比为3:70~5:70。
8.一种权利要求1所述的配位聚合物在0摄氏度常压条件作为二氧化碳吸附剂的应用。
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CN110330516B (zh) * | 2019-07-31 | 2021-06-25 | 商丘师范学院 | 一种三元咪唑配体锌配合物及其制备方法 |
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CN112795023A (zh) * | 2019-10-28 | 2021-05-14 | 暨南大学 | 一种超稳定的金属有机框架材料及其制备方法与应用 |
CN114671896A (zh) * | 2022-04-29 | 2022-06-28 | 闽都创新实验室 | 一类基于三氮烯桥连唑的晶体及其制备方法和作为含能材料的应用 |
CN114671896B (zh) * | 2022-04-29 | 2024-01-02 | 闽都创新实验室 | 一类基于三氮烯桥连唑的晶体及其制备方法和作为含能材料的应用 |
CN115947950A (zh) * | 2022-12-07 | 2023-04-11 | 电子科技大学长三角研究院(湖州) | 一种微米级单晶ZIFs及制备方法 |
CN115947950B (zh) * | 2022-12-07 | 2024-02-27 | 电子科技大学长三角研究院(湖州) | 一种微米级单晶ZIFs及制备方法 |
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CN102241695B (zh) | 2014-12-24 |
WO2012155417A1 (zh) | 2012-11-22 |
US20140088312A1 (en) | 2014-03-27 |
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