CN115209986A - 制备金属-有机骨架复合材料的方法 - Google Patents
制备金属-有机骨架复合材料的方法 Download PDFInfo
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- CN115209986A CN115209986A CN202180017754.6A CN202180017754A CN115209986A CN 115209986 A CN115209986 A CN 115209986A CN 202180017754 A CN202180017754 A CN 202180017754A CN 115209986 A CN115209986 A CN 115209986A
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- metal
- organic framework
- monolith
- composite
- organic
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- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 170
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- 238000000576 coating method Methods 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000011148 porous material Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000011247 coating layer Substances 0.000 claims abstract description 16
- 239000003463 adsorbent Substances 0.000 claims abstract description 15
- 230000000052 comparative effect Effects 0.000 claims abstract description 14
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- -1 uiO-66 Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 23
- 125000000524 functional group Chemical group 0.000 claims description 23
- 229910021645 metal ion Inorganic materials 0.000 claims description 20
- 239000013110 organic ligand Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
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- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003618 dip coating Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
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- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 229910052878 cordierite Inorganic materials 0.000 claims description 11
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 11
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
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- 229920000728 polyester Polymers 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
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- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 4
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- 239000013291 MIL-100 Substances 0.000 claims description 4
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000002207 thermal evaporation Methods 0.000 claims description 4
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 claims description 4
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 4
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920000307 polymer substrate Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- JZKNMIIVCWHHGX-UHFFFAOYSA-N adamantane-1,2,2,3-tetracarboxylic acid Chemical compound C1C(C2)CC3CC1(C(=O)O)C(C(O)=O)(C(O)=O)C2(C(O)=O)C3 JZKNMIIVCWHHGX-UHFFFAOYSA-N 0.000 claims description 2
- NLWFONQBVVTGEM-UHFFFAOYSA-N adamantane;benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1.C1C(C2)CC3CC1CC2C3 NLWFONQBVVTGEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- 235000012255 calcium oxide Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
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- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims 2
- PAMBMUOTYPLTQG-UHFFFAOYSA-N 2-[2,3-bis(2-carboxyphenyl)phenyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC(C=2C(=CC=CC=2)C(O)=O)=C1C1=CC=CC=C1C(O)=O PAMBMUOTYPLTQG-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
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- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 6
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Abstract
本发明提供制备吸附床的方法,所述吸附床用作微反应器或催化和/或分离装置。所述吸附床包含金属‑有机骨架复合材料。在本发明的方法中,将粉末形式的一种或多种金属‑有机骨架在液体中混合以制造金属‑有机骨架悬浮液或其它类型的金属‑有机骨架涂料。用所述悬浮液或涂料涂布整料以提供金属‑有机骨架复合材料,所述金属‑有机骨架复合材料具有至少一个沉积在所述整料上并与其结合的金属‑有机骨架涂料层。制造的金属‑有机骨架复合材料具有约1m2/g至约300m2/g的BET表面积和/或相对于所述金属‑有机骨架整料为约40%至约100%的比较BET表面积和约1nm至约50nm的孔径。
Description
技术领域
本发明一般涉及金属-有机骨架的制剂,具体地涉及制备具有至少一个沉积在整料上的金属-有机骨架涂料层的金属-有机骨架复合材料的方法。
背景技术
对于吸附应用,具有由孔和通道限定的大的内表面积的材料是有益的。产生这种微孔或中孔活性材料的策略包括使用金属-有机骨架。与其它类型的材料相比,金属-有机骨架提供多种优势,包括显著的孔隙率和内表面积、高的体积对表面积之比、优异的分离和催化性能以及流体存储。此外,金属-有机骨架的孔径和通道结构可在大范围内调节。此外,金属-有机骨架能够容易地进行功能化。
尽管具有这些好处,但是金属-有机骨架的合适制剂对于各种应用来说至关重要。先前的方法包括合成粉末形式的金属-有机骨架并将粉末成形为例如用于工业应用的膜、薄膜、丸、整料和泡沫体前体。但这些装置极易受固有的易碎性和较差的加工性的影响。此外,与有机聚合物不同,金属-有机骨架晶体不溶于任何溶剂中且通常不是热塑性的,这意味着传统的基于溶剂或熔融的加工技术不适用于金属-有机骨架。最近,已经提出了纯金属-有机骨架整料的油墨直写(3-D打印)。然而,该方法的一个关键挑战是,必须将材料制成具有理想流变性能的悬浮液以具有连续流过细喷嘴而不会堵塞的能力(剪切思考)。
因此,需要制备金属-有机骨架装置的方法,所述方法能够保持金属-有机骨架的结构完整性而不降低这种材料所提供的表面积和孔隙率的优势。
发明内容
本文提供制备吸附床的方法,所述方法包括如下步骤:(a)将粉末形式的金属-有机骨架混合在液体中以制造悬浮液;(b)提供整料;(c)将所述整料在所述悬浮液中进行浸涂以制造金属-有机骨架复合材料,所述金属-有机骨架复合材料具有至少一个沉积在所述整料上并与其结合的金属-有机骨架涂料层;和(d)干燥所述金属-有机骨架复合材料以制造具有约5m2/g至约100m2/g的BET表面积和约1nm至约50nm的孔径的吸收床。
此外,本文提供制备吸附床的方法,所述方法包括如下步骤:(a)将粉末形式的金属-有机骨架混合在液体中以制造悬浮液;(b)提供整料;(c)将所述整料在所述悬浮液中进行浸涂以制造金属-有机骨架复合材料,所述金属-有机骨架复合材料具有至少一个沉积在所述整料上并与其结合的金属-有机骨架涂料层;和(d)干燥所述金属-有机骨架复合材料以制造吸收床,所述吸收床具有相对于所述金属-有机骨架整料为约1%至约10%的比较BET表面积和在所述有机-金属骨架和具有大孔的吸收床中约1nm至约50nm的孔径。
本文还提供制备可用作吸附床的金属-有机骨架复合材料的方法,所述方法包括如下步骤:(a)将金属-有机骨架粉末悬浮在液体中以制造悬浮液,其中所述金属-有机骨架粉末占所述悬浮液的约10重量%至约90重量%,并且所述悬浮液不包含酸;(b)将所述悬浮液冲刷到基底上以制造包含沉积在整料上的金属-有机骨架涂料的金属-有机骨架复合材料;和(c)用一种或多种沸石加热所述金属-有机骨架复合材料以将所述金属-有机骨架涂料粘合到所述整料上,其中所述金属-有机骨架复合材料具有约5m2/g至约100m2/g的BET表面积和/或相对于所述金属-有机骨架整料为约1%至约10%的比较BET表面积和约1nm至约50nm的孔径。
此外,提供制备金属-有机骨架复合材料的方法,所述方法包括如下步骤:(a)将金属-有机骨架粉末与液体混合以形成金属-有机骨架涂料;(b)通过热沉积将所述金属-有机骨架涂料施加到整料上以制造金属-有机骨架复合材料,其中在液体中金属-有机骨架在所述金属-有机骨架涂料中的重量百分比(重量%)在约30重量%至约60重量%的范围内;和(c)在低于250℃的温度下干燥所述金属-有机骨架复合材料,以制造具有约5m2/g至约100m2/g的BET表面积和/或相对于所述金属-有机骨架整料为约1%至约10%的比较BET表面积和约2nm至约50nm的孔径的金属-有机骨架复合材料。
在一个方面,金属-有机骨架为HKUST-1,液体为乙醇,并且整料为氧化铝洗涂的堇青石。在一个方面,金属-有机骨架为Mg-MOF-74,液体为乙醇,并且整料为陶瓷。在一个方面,所述方法还包括在约40℃至约150℃的温度下使金属-有机骨架复合材料熟化约30分钟或更多的时间的步骤。在一个方面,所述方法还包括在约100℃至约300℃的温度下将金属-有机骨架复合材料煅烧约1小时或更多的时间的步骤。在一个方面,所述方法还包括用任选的溶剂洗涤金属-有机骨架复合材料。在一个方面,任选的溶剂选自:水、甲醇、乙醇、二甲基甲酰胺、丙酮、乙醚、乙腈、酮类、酰胺类、酯类、醚类、腈类、芳族烃类、脂族烃类及其组合物。在一个方面,吸附床为用于气体和流体的通道反应器。
在一个方面,整料选自:陶瓷、金属、聚合物基底和/或纤维素纤维。在一个方面,整料为陶瓷。在一个方面,聚合物基底包括聚乙烯酰胺、聚丙烯酸酯、聚碳酸酯、聚酰胺、聚酯、聚醚、聚乙烯胺、聚乙烯醇、聚乙烯酯和/或其组合物。
在一个方面,金属-有机骨架选自:HKUST-1、UiO-66、ZIF-8、ZIF-7、MIL-100、MOF-74、M2(m-dobdc)、MOF-274、Cu(Qc)2及其组合物。
本文还提供用于气体和流体的通道反应器,所述通道反应器包含至少一层沉积在整料上并与其结合以得到金属-有机骨架复合材料的金属-有机骨架涂料,所述金属-有机骨架复合材料具有约5m2/g至约200m2/g的BET表面积和/或相对于所述金属-有机骨架整料为约1%至约10%的比较BET表面积和约1nm至约50nm的孔径。在一个方面,通道反应器的整料为堇青石。在一个方面,对堇青石进行氧化铝洗涂。在一个方面,通道反应器的整料主要为氧化铝。
附图说明
图1A和图1B为涂布有配制的HKUST-1金属-有机骨架涂料的陶瓷材料的400cpsi方形通道整料的照片图像。
图2为具有涂布有Mg-MOF-74的方形通道的陶瓷材料的整料的显微照片。
图3显示了涂布前陶瓷整料的显微照片。
具体实施方式
在更详细地描述本发明的制备金属-有机骨架复合材料的方法之前,下面列出术语以帮助更好地理解本发明。
本文中的具体实施方式和权利要求书中的所有数值相对于指示值都可以由“约”或“大约”来修饰,并考虑了本领域技术人员所预期的实验误差和偏差。除非另有说明,否则室温为约25℃。
为简洁起见,本文中仅明确公开了特定的范围。然而,从任何下限开始的范围能够与任何上限组合以列举未明确列举的范围,同样,从任何下限开始的范围能够与任何其它下限组合以列举未明确列举的范围,以相同的方式,从任何上限开始的范围能够与任何其它上限组合以列举未明确列举的范围。此外,在一个范围内即使未明确列举也包括其端点之间的每个点或单个值。因此,每个点或单个值都能够用作其本身与任何其它点或单个值或任何其它下限或上限组合的下限或上限,以列举未明确列举的范围。
如在本发明和权利要求书中所使用的,单数形式“一个”、“一种”、“该”和“所述”包括复数形式,除非上下文另有明确规定。
如本文中的诸如短语“A和/或B”中所使用的术语“和/或”旨在包括“A和B”、“A或B”、“A”和“B”。
术语“水性介质”是指包含5体积%或更多水的液体。合适的水性介质可以主要包含水或水与水混溶性有机溶剂的混合物或者基本上由水或水与水混溶性有机溶剂的混合物构成。
术语“预结晶的”是指一种材料,特别是金属-有机骨架材料,它是预先合成的(预形成的)并且通常与在其中形成所述材料的反应介质分离。
如本文中所使用的,术语“金属-有机骨架材料”或“MOF材料”是指金属或准金属和能够与所述金属或准金属配位的有机配体。在特定实施方案中,有机配体和金属(或准金属)的MOF配位网络形成多孔三维结构。
通常,金属-有机骨架(MOF)是在宽范围的领域中具有潜在应用的一类高度多孔的材料,所述领域包括气体存储、气体和液体分离、异构体分离、废物去除和催化等。与纯无机特征的沸石相比,MOF使用有机配体,所述有机配体能够充当“支柱”以将金属原子或金属原子的簇桥接在一起。如同沸石,MOF具有微孔。MOF的孔形状和孔径能够通过选择有机配体和金属来调节。因为能够对有机配体进行改性,所以MOF整体上结构多样,这不同于沸石。影响MOF的结构的因素包括例如如下中的一种或多种:配体齿合度;配位基团的大小和类型;远离或靠近配位基团的另外取代;配体的尺寸和几何形状;配体的疏水性或亲水性;金属和/或金属盐的选择;溶剂的选择;以及诸如温度、浓度等的反应条件。
MOF作为结晶粉末材料来合成或商业获得。如上所述,对于许多工业和商业产品,粉末形式的MOF能够成形为具有所需的限定形状的较大的粘着体。将粉末形式的MOF固结成大主体的传统方法如造粒和挤出通常无法提供期望的物理和机械性能。更具体地,因为MOF结构具有压力敏感性和相对较低的压碎强度,所以通过压实来加工粉末形式的MOF能够导致BET表面积低于粉末形式的MOF。此外,特定的加工条件能够导致初始MOF结构的全部或部分相变,如X射线粉末衍射和BET表面积分析所证实的。这些因素中的各个因素对于制造成形体形式的MOF和/或将成形体在各种应用中用作装置都能够成为问题。
尽管希望将金属-有机骨架(“MOF”)粉末固结成更粘着(成形)主体,但是MOF的性质,特别是它们对压力和剪切的弱点,能够在用于固结粉末形式的MOF,特别是在挤出过程中的压力(例如约100psi到几千psi)和剪切下导致各种问题。MOF粉末的这种加工能够使MOF结构内的至少一部分孔坍塌,并导致BET表面积的不希望的且通常显著的降低。此外,用于将粉末形式的MOF固结成成形体的条件能够导致MOF结构的至少部分甚至有时完全转化为另一种材料,例如另一种结晶相。具有较差压碎强度的固结的MOF可存在问题。例如,较差的压碎强度值可导致产生细粉,这可能对特定的应用是有害的。
本文提供制备可用作微反应器或催化和/或分离装置的吸附床的方法。本发明的吸附床包含金属-有机骨架复合材料。在本发明的方法中,将一种或多种粉末形式的金属-有机骨架混合在液体中以制造金属-有机骨架悬浮液或诸如悬浮液的其它类型的金属-有机骨架涂料。用悬浮液或金属-有机骨架涂料涂布整料以提供具有至少一个沉积在和/或结合到整料上的金属-有机骨架涂料层的金属-有机骨架复合材料。如本文中所述,整料的形状能够是二维或三维的。所制造的金属-有机骨架复合材料具有约5m2/g至约100m2/g的BET表面积和/或相对于金属-有机骨架整料为约1%至约10%的比较BET表面积和约1nm至约50nm的孔径。
本文公开的金属-有机骨架能够在它们的孔隙率方面进行表征。MOF能够包括微孔、中孔、大孔及其任何组合。微孔在本文中定义为具有约2nm或更低的孔径,并且中孔在本文中定义为具有约2nm至约50nm的孔径。在某些情况下能够存在粒子间纹理孔隙率。
期望地,根据本发明的方法制备的金属-有机骨架涂料和金属-有机骨架复合材料保留了形成它们的预结晶金属-有机骨架粉末的至少大部分的BET表面积。具体地,这些金属-有机骨架复合材料的特征能够在于,BET表面积相对于预结晶金属-有机骨架粉末材料的BET表面积为约1%、2%、3%、4%、5%、6%、7%、8%、9%或10%或更大。
如本文中所提供的,MOF能够为单独的或与其它MOF组合的ZIF(或沸石咪唑酯骨架)、MIL(或来自拉瓦锡研究所的材料)和IRMOF(或等网状金属有机骨架)。在特定实施方案中,MOF选自:HKUST-1、MOF-74、MIL-100、ZIF-7、ZIF-8、ZIF-90、UiO-66、UiO-67、MOF-808或MOF-274。
MOF能够通过有机配体或一种或两种以上有机配体的组合与如下所述的金属或准金属的组合来制备。例如,MOF-274为Mg2+、Mn2+、Fe2+、Zn2+、Ni2+、Cu2+、Co2+或其组合与4,4'-二羟基-(1,1'-联苯)-3,3'-二羧酸的组合。此外,MOF-274能够包括与其结构内的金属位点配位的胺。
如本文中所使用的,“等温线”是指在系统的温度保持恒定的同时作为浓度的函数的吸附物的吸附。在一个实施方案中,吸附物为CO2并且能够作为CO2压力来测量浓度。如本文中所述,等温线可用多孔材料进行并使用各种数学模型来计算表观表面积。S.Brunauer,P.H.Emmett,and E.Teller.J.Am.Chem.Soc.1938,60,309-319;K.Walton和R.Q.Snurr,J.Am.Chem.Soc.2007,129,8552-8556;I.Langmuir,J.Am.Chem.Soc.1916,38,2221。
有机配体
如本文中所使用的,有机配体为单齿、双齿或多齿的配体。有机配体能够为单一类型的配体或其组合。通常,有机配体能够与金属离子配位,原则上能够使用适合这种配位的所有化合物。有机配体包括能够与金属盐的金属离子、或金属或准金属配位的至少两个中心。在一个方面,有机配体包括:i)具有1至10个碳原子的烷基基团亚结构;ii)具有1至5个芳族环的芳基基团亚结构;iii)由具有1至10个碳原子的烷基基团或具有1至5个芳族环的芳基基团构成的烷基或芳基胺亚结构,其中所述亚结构具有至少两个官能团“X”,所述官能团“X”与所述亚结构共价结合,并且其中X能够与金属或准金属配位。
在一个方面,各个X独立地选自以下的中性或离子形式:CO2H、OH、SH、NH2、CN、HCO、CS2H、NO2、SO3H、Si(OH)3、Ge(OH)3、Sn(OH)3、Sn(SH)3、PO3H、CH(RSH)2、C(RSH)3、CH(RNH2)2、C(RNH2)3、CH(ROH)2、C(ROH)3、CH(RCN)2、C(RCN)3、CH(SH)2、C(SH)3、CH(NH2)2、C(NH2)2、CH(OH)2、C(OH)3、CH(CN)2、C(CN)3、含氮杂环、含硫杂环及其组合物,其中R为具有1至5个碳原子的烷基基团或由1至2个苯环构成的芳基基团。
在一个方面,有机配体包括:取代或未取代的单核或多核的芳族二羧酸、芳族三羧酸和芳族四羧酸;和取代或未取代的包含至少一个杂原子的具有一个或多个核的芳族二羧酸、芳族三羧酸和芳族四羧酸。
在一个方面,有机配体为:苯三羧酸酯(BTC)(一种或多种异构体)、ADC(乙炔二羧酸酯)、NDC(萘二羧酸酯)(任何异构体)、BDC(苯二羧酸酯)(任何异构体)、ATC(金刚烷四羧酸酯)(任何异构体)、BTB(苯三苯甲酸酯)(任何异构体)、MTB(甲烷四苯甲酸酯)、ATB(金刚烷三苯甲酸酯)(任何异构体)、联苯-4,4'-二羧酸酯、苯-1,3,5-三(1H-四唑)、咪唑、或其衍生物、或其组合物。
具有多齿官能团的配体能够包括:相应的抗衡阳离子如H+、Na+、K+、Mg2+、Ca2+、Sr2+、铵离子、烷基取代的铵离子和芳基取代的铵离子;或抗衡阴离子如F-、Cl-、Br-、I-、ClO-、ClO2 -、ClO3 -、ClO4 -、OH-、NO3 -、NO2 -、SO4 2-、SO3 2-、PO4 3-、CO3 2-和HCO3-。
在一个方面,有机配体包括单齿官能团。单齿官能团定义为与亚结构结合的部分,其能够包括如前限定的有机配体或胺配体亚结构L,其只能与金属离子形成一个键。根据该定义,配体能够包含一个或多个单齿官能团。例如,环己胺和4,4'-联吡啶为含有单齿官能团的配体,因为各个官能团只能与一个金属离子结合。
因此,环己胺为含有单齿官能团的单官能配体,并且4,4'-联吡啶为含有两个单齿官能团的双官能配体。含有单齿官能团的配体的具体实例为作为单官能配体的吡啶、作为双官能配体的氢醌和作为三官能配体的1,3,5-三氰基苯。
具有单齿官能团的配体能够与含有多齿官能团的配体共混以在合适的金属离子和任选的模板剂的存在下制备MOF。单齿配体也能够用作模板剂。为了占据所得MOF中的孔,能够将模板剂添加到反应混合物中。单齿配体和/或模板剂能够包括如下物质和/或其衍生物:
A.烷基或芳基胺或膦及其相应的铵盐或盐,所述烷基胺或膦能够包括具有1至20个碳原子的直链、支化的或环状脂族基团(及其相应的铵盐),所述芳基胺或膦能够包括包含杂环的1至5个芳族环。单官能胺的实例为甲胺、乙胺、正丙胺、异丙胺、正丁胺、仲丁胺、异丁胺、叔丁胺、正戊胺、新戊胺、正己胺、吡咯烷、3-吡咯啉、哌啶、环己胺、吗啉、吡啶、吡咯、苯胺、喹啉、异喹啉、1-氮杂菲和8-氮杂菲。双官能和三官能胺的实例为1,4-二氨基环己烷、1,4-二氨基苯、4,4'-联吡啶、咪唑、吡嗪、1,3,5-三氨基环己烷、1,3,5-三嗪和1,3,5-三氨基苯。
B.包含含有1至20个碳原子的烷基或环烷基基团或含有1至5个苯环的芳基基团的醇。单官能醇的实例为甲醇、乙醇、正丙醇、异丙醇、烯丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、正戊醇、异戊醇、仲戊醇、新戊醇、正己醇、环己醇、苯酚、苯甲醇和2-苯基乙醇。双官能和三官能醇的实例为1,4-二羟基环己烷、氢醌、儿茶酚、间苯二酚、1,3,5-三羟基苯和1,3,5-三羟基环己烷。
C.包含含有1至20个碳原子的烷基或环烷基基团或含有1至5个苯环的芳基基团的醚。醚的实例为乙醚、呋喃和吗啉。
D.包含含有1至20个碳原子的烷基或环烷基基团或含有1至5个苯环的芳基基团的硫醇。单官能硫醇的实例为硫代甲烷、硫代乙烷、硫代丙烷、硫代环己烷、噻吩、苯并噻吩和硫代苯。双官能和三官能硫醇的实例为1,4-二硫代环己烷、1,4-二硫代苯、1,3,5-三硫代环己烷和1,3,5-三硫代苯。
E.包含含有1至20个碳原子的烷基或环烷基基团或含有1至5个苯环的芳基基团的腈。单官能腈的实例为乙腈、丙腈、丁腈、正戊腈、苄腈和对甲苯腈。双官能和三官能腈的实例为1,4-二腈基环己烷、1,4-二腈基苯、1,3,5-三腈基环己烷和1,3,5-三腈基苯。
F.选自如下中的无机阴离子:硫酸根、硝酸根、亚硝酸根、亚硫酸根、亚硫酸氢根、磷酸根、磷酸氢根、磷酸二氢根、二磷酸根、三磷酸根、亚磷酸根、氯离子、氯酸根、溴离子、溴酸根、碘离子、碘酸根、碳酸根、碳酸氢根、硫氰离子和异腈离子;以及上述无机阴离子的相应酸和盐。
G.有机酸和相应的阴离子(和盐)。有机酸能够包括含有具有1至20个碳原子的直链、支化的或环状脂族基团的烷基有机酸或能够含有杂环的具有1至5个芳族环的芳基有机酸及其相应的芳基有机阴离子和盐。
H.其它有机和无机物如氨、二氧化碳、甲烷、氧气、乙烯、己烷、苯、甲苯、二甲苯、氯苯、硝基苯、萘、噻吩、吡啶、丙酮、1-2-二氯乙烷、二氯甲烷、四氢呋喃、乙醇胺、三乙胺或三氟甲基磺酸。
此外,模板剂能够包括不含官能团的其它脂族和芳族烃。在一个方面,模板剂包括:环烷烃如环己烷、金刚烷或降冰片烯;和/或芳烃如苯、甲苯或二甲苯。
金属离子
如上所述,MOF能够通过将金属离子、有机配体和任选的合适的模板剂组合来合成。合适的金属离子包括具有不同配位几何形状和氧化态的金属和准金属。在一个方面,以与具有多齿官能团的配体和合适模板剂组合的方式使用具有明显不同的配位几何形状的金属离子,来制造MOF。MOF能够使用优选八面体配位的金属离子如钴(II)和/或优选四面体配位的金属离子如锌(II)来制备。MOF能够使用如下金属离子中的一种或多种以及相应金属盐的抗衡离子来制备:Mg2+、Ca2+、Sr2+、Ba2+、Sc3+、Y3+、Ti4+、Zr4+、Hf4+、V5+、V4+、V3+、V2+、Nb3+、Ta3+、Cr3+、Mo3+、W3+、Mn3+、Mn2+、Re3+、Re2+、Fe3+、Fe2+、Ru3+、Ru2+、Os3+、Os2+、Co3+、Co2+、Rh2+、Rh+、Ir2+、Ir+、Ni2+、Ni+、Pd2+、Pd+、Pt2+、Pt+、Cu2+、Cu+、Ag+、Au+、Zn2+、Cd2+、Hg2+、Al3+、Ga3+、In3+、Tl3 +、Si4+、Si2+、Ge4+、Ge2+、Sn4+、Sn2+、Pb4+、Pb2+、As5+、As3+、As+、Sb5+、Sb3+、Sb+、和Bi5+、Bi3+、Bi+、Be2+。术语“金属离子”是指金属和准金属离子。在一个方面,适用于制造MOF的金属离子可包括如下离子以及相应的金属盐的抗衡阴离子:Sc3+、Ti4+、V4+、V3+、V2+、Cr3+、Mo3+、Mg2+、Mn3+、Mn2+、Fe3+、Fe2+、Ru3+、Ru2+、Os3+、Os2+、Co3+、Co2+、Rh2+、Rh+、Ir2+、Ir+、Ni2+、Ni+、Pd2+、Pd+、Pt2+、Pt+、Cu2+、Cu+、Ag+、Au+、Zn2+、Cd2+、Al3+、Ga3+、In3+、Ge4+、Ge2+、Sn4+、Sn2+、Pb4+、Pb2+、Sb5+、Sb3+、Sb+、和/或Bi5+、Bi3+、Bi+、Be2+。在一个方面,用于制造MOF的金属离子包括如下离子以及相应金属盐的抗衡离子:Sc3+、Ti4+、V4+、V3+、Cr3+、Mo3+、Mn3+、Mn2+、Fe3+、Fe2+、Co3+、Co2+、Ni2+、Ni+、Cu2+、Cu+、Ag+、Zn2+、Cd2+、Al3+、Sn4+、Sn2+、和/或Bi5+、Bi3+、Bi+。在一个方面,用于制造MOF的金属离子选自如下离子以及相应金属盐的抗衡离子:Mg2+、Mn3+、Mn2+、Fe3+、Fe2+、Co3+、Co2+、Ni2+、Ni+、Cu2+、Cu+、Pt2+、Ag+和Zn2+。
金属-有机骨架的制备
刚性和稳定的金属-有机骨架(“MOF”)的合成能够在极其温和的反应条件下进行。在大多数情况下,(在开口烧杯中)在0℃至100℃的合成反应温度范围内将试剂合并到水性或非水性溶液中。在其它情况下,溶液反应在25℃至300℃的温度下在密闭容器中进行。在任何一种情况下,都会形成大的单晶或微晶微孔固体。
在MOF的制备中,能够以金属离子与含有多齿官能团的配体的摩尔比为1:10至10:1的量添加反应物。在一个方面,金属离子与含有多齿官能团的配体的比例为1:3至3:1,例如1:2至2:1。模板剂的用量能够影响MOF的制造,事实上,模板剂在特定情况下能够用作发生反应的溶剂。因此能够大大过量使用模板剂而不干扰反应和MOF的制备。此外,当与金属离子组合来使用含有单齿官能团的配体和使用含有多齿官能团的配体时,能够过量使用含有单齿官能团的配体。在特定情况下,含有单齿官能团的配体能够用作发生反应的溶剂。此外,在特定情况下,模板剂和含有单齿官能团的配体能够相同。作为含有单齿官能团的配体的模板剂的一个实例为吡啶。
MOF的制备能够在水性或非水性体系中进行。溶剂能够为极性的或非极性的,并且溶剂能够为模板剂或含有单齿官能团的任选配体。非水溶剂的实例包括:正烷烃如戊烷、己烷、苯、甲苯、二甲苯、氯苯、硝基苯、氰基苯、苯胺、萘、石脑油;正醇如甲醇、乙醇、正丙醇、异丙醇;丙酮;1,2,-二氯乙烷;二氯甲烷;氯仿;四氯化碳;四氢呋喃;二甲基甲酰胺;二甲亚砜;噻吩;吡啶;乙醇胺;三乙胺;乙二胺等。
为了形成适合单晶X射线结构表征的微孔材料的大单晶,溶液反应能够在粘性材料如聚合物添加剂的存在下进行。具体的添加剂能够包括聚环氧乙烷、聚甲基甲基丙烯酸、硅胶、琼脂、脂肪和胶原蛋白,它们能够帮助实现高收率和纯结晶产物。微孔材料的大单晶的生长导致微孔骨架的明确表征。微孔材料的大单晶能够用于磁性和电子传感应用。
本发明的方法
本文提供制备吸附床的方法,所述方法包括如下步骤:(a)将粉末形式的金属-有机骨架混合在液体中以制造悬浮液;(b)提供整料;(c)将所述整料在胶体悬浮液中进行浸涂以制造金属-有机骨架复合材料,所述金属-有机骨架复合材料具有至少一个沉积在所述整料上并与其结合的金属-有机骨架涂料层;和(d)干燥所述金属-有机骨架复合材料以制造具有约1m2/g至约300m2/g的BET表面积和约1nm至约50nm的孔径的吸收床。
如本文中所述,将金属-有机骨架与液体混合的步骤能够制造用于将金属-有机骨架涂料层施加到整料上的悬浮液或胶体悬浮液。然后通过浸涂、洗涂或溶剂热沉积将涂料施加到整料上以制造具有至少一个沉积在整料上的金属-有机骨架涂料层的金属-有机骨架复合材料。能够用多层的相同或不同的金属-有机骨架涂布整料,以提供特别用作吸附床和微反应器的复合材料。除了涂布整料之外,用悬浮液涂布平面基底可用于制造高表面积载体或卷起的箔。
更特别地,本发明的方法还能够包括如下步骤:(a)将粉末形式的金属-有机骨架混合在液体中以制造胶体悬浮液;(b)提供整料;(c)将所述整料在所述胶体悬浮液中进行浸涂以制造金属-有机骨架复合材料,所述金属-有机骨架复合材料具有至少一个沉积在所述整料上并与其结合的金属-有机骨架涂料层;和(d)干燥所述金属-有机骨架复合材料以制造吸收床,所述吸收床具有相对于所述金属-有机骨架整料为约40%至约100%的比较BET表面积和约1nm至约50nm的孔径。
为了通过洗涂而将涂料施加到整料上,将金属-有机骨架粉末混合在液体中以制造悬浮液。金属-有机骨架粉末为所述悬浮液的约10重量%至约90重量%、约20重量%至约80重量%、约25重量%至约75重量%和/或约30重量%至约50重量%,并且所述悬浮液不包含酸。将悬浮液冲刷到基底上以制造具有沉积在整料上的金属-有机骨架涂料层的金属-有机骨架复合材料。然后能够用一种或多种沸石将金属-有机复合材料进行加热以将金属-有机骨架涂料粘附到整料上。所得金属-有机骨架复合材料具有约5m2/g至约100m2/g或1m2/g至约300m2/g的BET表面积和/或相对于金属-有机骨架整料约40%至约100%的比较BET表面积以及约1nm至约50nm的孔径。
此外,金属-有机骨架复合材料能够通过热沉积来制备。在此,将金属-有机骨架粉末与液体混合以形成金属-有机骨架涂料。然后通过热沉积将金属-有机骨架涂料施加到整料上,以制造金属-有机骨架复合材料。在液体中金属-有机骨架在所述金属-有机骨架涂料中的重量百分比(重量%)在约30重量%至约60重量%的范围内。
任选地,在本文所述的任何方法中,金属-有机骨架复合材料能够在低于约250℉的温度下干燥以制造金属-有机骨架复合材料。
在一个方面,金属-有机骨架为HKUST-1,液体为乙醇,并且整料为氧化铝洗涂的堇青石。在一个方面,金属-有机骨架为Mg-MOF-74,液体为乙醇,并且整料为陶瓷。在一个方面,所述方法还包括在约40℃至约150℃的温度下使金属-有机骨架复合材料熟化约30分钟或更多的时间的步骤。在一个方面,所述方法还包括在约100℃至约300℃的温度下将金属-有机骨架复合材料煅烧约1小时或更多的时间的步骤。
在一个方面,所述方法还包括用任选的溶剂洗涤金属-有机骨架复合材料。在一个方面,任选的溶剂选自:水、甲醇、乙醇、N,N-二甲基甲酰胺、丙酮、乙醚、乙腈、酮类、酰胺类、酯类、醚类、腈类、芳族烃类、脂族烃类及其组合物。在一个方面,吸附床为用于气体和流体的通道反应器。
在一个方面,整料选自:陶瓷、金属、聚合物基底和/或纤维素纤维。在一个方面,整料为陶瓷。在一个方面,聚合物基底包括聚乙烯酰胺、聚丙烯酸酯、聚甲基丙烯酸酯、聚碳酸酯、聚酰胺、聚酯、聚醚、聚乙烯胺、聚乙烯醇、聚(乙烯酯)、聚酰胺、聚(酰胺酸)和/或其组合物。在一个方面,所述液体包含聚乙酸乙烯酯和水,并且聚乙酸乙烯酯与水的比例为约1:1至约1:3。
在一个方面,金属-有机骨架选自:HKUST-1、UiO-66、ZIF-8、ZIF-7、MIL-100、MOF-74、M2(m-dobdc)、MOF-274、Cu(Qc)2及其组合物。
本文还提供用于气体和流体的通道反应器,所述通道反应器包含一层或多层的沉积和/或结合在整料上以得到金属-有机骨架复合材料的金属-有机骨架涂料,所述金属-有机骨架复合材料具有约5m2/g至约100m2/g的BET表面积和/或相对于所述金属-有机骨架整料为约1%至约10%的比较BET表面积和约1nm至约50nm的孔径。在一个方面,通道反应器的整料为堇青石。在一个方面,对堇青石进行氧化铝洗涂。
整料
本发明的整料能够为整料或蜂窝结构的基底。整料可由单一类型的材料或不同的材料制成,这些材料包括陶瓷、金属,或者所述整料能够为聚合物基底或纤维素纤维。例如,整料能够包含如下陶瓷中的一种或多种:堇青石、氧化铝、堇青石-α氧化铝、氮化硅、锆石莫来石、锂辉石、氧化铝-二氧化硅氧化镁、硅酸锆石、硅线石、硅酸镁、锆石、透锂长石、铝硅酸盐及其组合物。在一个方面,陶瓷整料由堇青石、氧化铝或其组合物制成。
整料能够包括片、网、箔、薄片、粉末、线、棒或其组合形式的铝、钛、不锈钢、Fe-Cr合金或Cr-Al-Fe合金。在一个方面,整料包括片、网或箔形式的铝、不锈钢、Cr-Al-Fe合金或其组合。在一个方面,整料包含混有约1重量%至约10重量%的二氧化硅和/或约1重量%至约5重量%选自二氧化硅、二氧化钛、氧化镁和氧化钙的氧化物的约80重量%至约97重量%的氧化铝。
整料能够包含如下物质的聚合物和/或共聚物或其组合物:聚烯烃类、聚酯类、聚氨酯类、聚碳酸酯类、聚醚醚酮类、聚苯醚类、聚醚砜类、三聚氰胺类、聚酰胺类、聚丙烯酸酯类、聚苯乙烯类、聚丙烯腈类、聚酰亚胺类、聚糠醇、苯酚糠醇、三聚氰胺甲醛类、间苯二酚甲醛类、甲酚甲醛、苯酚甲醛、聚乙烯醇二醛、聚氰脲酸酯类、聚丙烯酰胺类、各种环氧树脂类、琼脂和琼脂糖。在一个方面,塑性整料能够由聚烯烃、聚酯、聚氨酯、三聚氰胺、聚丙烯或聚酰胺的聚合物和/或共聚物制成。
整料能够包含纤维素纤维(即,纸)。整料能够为陶瓷丸或碳丸。整料能够为平面基底或由波纹金属箔和波纹塑料片分别层叠而制成的基底。
整料的选择将取决于整料复合材料的期望性能。例如,在减轻系统重量是关键或压降是关键的应用中,金属蜂窝和纤维素纤维蜂窝比陶瓷蜂窝能够更有优势。在传热是关键的应用中,金属蜂窝比陶瓷能够更有优势。
聚合物粘合剂
金属-有机骨架涂料层能够任选地包含一种或多种聚合物粘合剂。聚合物粘合剂能够为极性或非极性聚合物并且包括:酯类、酰胺类、乙酸酯类、酸酐类、酰亚胺类、醚类、酰胺酸类、乙烯基类、丙烯酸酯类的均聚物和共聚物;C2至C20烯烃如乙烯和/或丙烯和/或丁烯与一种或多种极性单体如乙酸酯类、酸酐类、酯类、醇类和/或丙烯酸类的共聚物。聚合物粘合剂的其它实例包括聚酯类、聚酰胺类、乙烯乙酸乙烯酯共聚物、聚氯乙烯、聚乙烯醇(PVA)、聚乙酸乙烯酯、聚乙烯醇和乙酸酯的混合物、聚乙烯胺、聚纤维素醚或其衍生物。在一个方面,聚合物粘合剂包括聚乙烯醇或其衍生物,例如聚乙烯醇、聚乙酸乙烯酯、聚丁酸乙烯酯或聚丙酸乙烯酯。
聚合物粘合剂能够选自:聚乙烯、聚丙烯、聚烯烃共聚物、聚异戊二烯、聚丁二烯、聚丁二烯共聚物类、氯化橡胶、丁腈橡胶、聚氯丁二烯、乙烯-丙烯-二烯弹性体、聚苯乙烯、聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯腈、聚(乙烯基酯)类、聚(卤乙烯)类、聚酰胺类、纤维素聚合物类、聚酰亚胺类、丙烯酸树脂类、乙烯基丙烯酸树脂类和苯乙烯丙烯酸树脂类、聚乙烯醇、热塑性聚酯类、热固性聚酯类、聚(苯醚)、聚(苯硫醚)、氟化聚合物如聚(四氟乙烯)聚偏二氟乙烯、聚(氟乙烯)和氯/氟共聚物如乙烯三氟氯乙烯共聚物、聚酰胺、酚醛树脂和环氧树脂、聚氨酯、有机硅聚合物及其组合物。
在一个方面,聚合物粘合剂为两种或更多种聚合物的聚合物共混物。聚合物粘合剂能够包括聚合物的混合物,其中第一聚合物在聚合物混合物中的重量百分比(重量%)在约10重量%至约99重量%的范围内,例如在20重量%至95重量%、30重量%至90重量%、40重量%至90重量%或50重量%至90重量%的范围内,其中重量的其余部分为第二聚合物或聚合物的组合。在一个方面,聚合物粘合剂包含聚乙烯醇和聚乙酸乙烯酯的聚合物共混物。
任选的添加剂
此外,金属-有机骨架涂料层能够包含添加剂如填料,抗氧化剂(例如位阻酚类,如得自Ciba-Geigy的IRGANOXTM 1010或IRGANOXTM1076),光氧化抑制剂(例如位阻胺光稳定剂(HALS),如得自BASF的123),亚磷酸酯(例如得自Ciba-Geigy的IRGAFOSTM168),防粘添加剂,增粘剂如聚丁烯类、萜烯树脂类、脂族和芳族烃树脂类,碱金属和甘油硬脂酸盐和氢化松香,紫外线稳定剂;热稳定剂、抗粘连剂、脱模剂、抗静电剂、颜料;着色剂、染料、蜡、二氧化硅、填料和滑石。
其它任选的添加剂包括二氧化硅,例如沉淀的二氧化硅和源自诸如飞灰的副产物的二氧化硅,所述飞灰为例如二氧化硅-氧化铝、二氧化硅-钙粒子或煅制二氧化硅。在一个方面,二氧化硅为微粒物质并且具有10μm或更小比如5μm或更小或1μm或更小的平均粒度。在一个方面,二氧化硅为无定形二氧化硅。
能够任选地包含在金属-有机涂料层中的其它添加剂包括无机化合物,例如:二氧化钛、水合二氧化钛、水合氧化铝或氧化铝衍生物、硅和铝化合物的混合物、硅化合物、粘土矿物、烷氧基硅烷和两亲物质。添加剂还能够包括用于粘附粉末材料的任何合适化合物,例如硅、铝、硼、磷、锆和/或钛的氧化物。此外,添加剂能够包括镁的氧化物和铍的氧化物。此外,作为添加剂,能够使用四烷氧基硅烷,例如四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷和四丁氧基硅烷,类似的四烷氧基钛和四烷氧基锆化合物以及三甲氧基铝、三乙氧基铝、三丙氧基铝和三丁氧基铝。
悬浮液
如上所述,本发明的方法包括将金属-有机骨架混合和/或悬浮在液体中以制造悬浮液。在本发明的方法中,金属-有机骨架保持分散在液体中。优选的有机溶剂包括乙醇、甲醇、DMF(二甲基甲酰胺)和水。在一个方面,溶剂能够为两种或更多种有机溶剂的混合物。悬浮液能够为液体或气体的形式。
金属-有机骨架与有机溶剂的重量百分比对于各种金属-有机骨架是可变的。MOF与有机溶剂的不同重量百分比将取决于液体中金属-有机骨架的粒度、溶剂溶解度、孔体积、粘度和胶体稳定性。悬浮液的pH可为约5至约9或约6至约8。
具有金属-有机骨架层的MOF复合材料能够任选地经历熟化,例如MOF复合材料的干燥或沉降。干燥温度不能超过250℉,并且能够为约5℉至约250℉、约20℉至约200℉或约20℉至约150℉。熟化能够持续约1分钟至约72小时,例如约30分钟至约72小时、约1小时至约48小时或约1小时至约24小时。在一个方面,熟化能够在空气或具有20%至100%、例如70%至100%的相对湿度的加湿空气中进行。用加湿气体处理能够使材料水合,这能够有利于固化特定的聚合物粘合剂。在一个方面,熟化能够在除湿的空气或惰性气体中进行,例如在相对湿度为0%至10%或0%至5%的空气中进行。
MOF复合材料能够任选地经历活化。活化可在约50℉至约250℉的温度下进行。活化能够持续约1小时(“h”)至约6h,例如约1h至约4h。活化能够帮助除去溶剂。活化能够在空气、惰性气体或含氧气的混合物中进行。此外,活化能够在减压或加压下进行,例如在真空或高于大气压的压力下进行。
在一个方面,MOF复合材料能够在干燥空气或具有不同湿度水平的空气下煅烧,或者它们在包括惰性气体如氮气和/或氧气的气体混合物存在下进行热处理。在一个方面,所使用的气体混合物能够包括5体积%或更多、例如10体积%或更多的氧气。在一个方面,气体混合物不含或基本上不含氧气并且仅包含惰性气体。煅烧温度能够为约50℃至约250℉。
MOF复合材料的性能
用本发明的方法制备的MOF复合材料能够具有约5m2/g至约200m2/g、约5m2/g至约150m2/g、约5m2/g至约100m2/g,约5m2/g至约75m2/g、约20m2/g至约100m2/g、约40m2/g至约100m2/g、约20m2/g至约80m2/g或约30m2/g至约70m2/g的BET表面积(使用ASTM D3663测得的)。
此外,用本发明的方法制备的MOF复合材料能够具有原始MOF的约1%至约10%如约1%至约9%或约2%至约8%的比较BET表面积(使用ASTM D3663测得的)。
用本发明的方法制备的涂布有MOF的MOF复合材料的平均孔宽度(使用ASTM D4365测得的)为约1nm至约2.5nm、约1nm至约2.2nm、约1nm至约2nm、约1.2nm至约2.5nm、约1.5nm至约2.5nm或约1.5nm至约2nm。
MOF复合材料包含约1重量%至10重量%、2重量%至8重量%或3重量%至6重量%的金属-有机骨架。在任何方面,MOF复合材料可包含3.15重量%、4.5重量%或6.1重量%的金属-有机骨架。
应用
本发明的金属-有机骨架复合材料能够用于其中多孔体或具有通道的主体提供优于固体主体或粉末的优点并且操作温度不超过400℃且操作压力不超过150巴的任何应用中。具体地,这些应用能够包括但不限于通道反应器、吸附床、干燥剂或其它流体存储器、离子交换剂和分子筛。
此外,MOF复合材料能够用于催化以下的各种反应,其中引入其中的通道和/或孔的存在已知或被认为会增加反应的活性和/或选择性和/或收率。
另一个应用为化合物、特别是气体化合物的存储。MOF复合材料的孔径和孔隙率能够导致优异的诸如CO2、CH4或H2的气体化合物的储存或隔离以及气体的分离,所有这些都是能源工业中特别重要的。
在接下来的如下非限制性实施例中对本发明的特征进行描述。
实施例
通过将堇青石整料在金属-有机骨架(MOF)的悬浮液中进行浸涂来完成对堇青石整料的涂布。使用了两种金属-有机骨架:HKUST-1(Cu3(btc)2;btc3-=1,3,5-苯三羧酸根);和Mg-MOF-74(Mg2(dobdc);dobdc4-=2,5-二羟基-1,4-苯二羧酸根)。HKUST-1涂料的悬浮液是通过将HKUST-1粉末悬浮在乙醇中制备的(40重量%HKUST-1的乙醇溶液)。使用的整料为一英寸,每平方英寸具有400个通道(“CPSI”),OFA为55%。将整料浸涂两次,在各个浸涂步骤之后进行干燥步骤,以获得具有图1A和图1B中所示的HKUST-1涂料层的金属-有机骨架整料。HKUST-1金属-有机骨架涂料在这些图中显示为蓝色。所述图还显示了整个整料的相对均匀的厚度。如图所示,整料具有方形通道,在通道的直角处具有分层厚度,导致通道在浸涂后“更圆”。
用于浸涂HKUST-1的悬浮液是通过将HKUST-1粉末悬浮在乙醇中制备的(40重量%HKUST-1的乙醇溶液)。金属-有机骨架复合材料的布鲁厄-埃米特-特勒(Brunauer-Emmett-Teller)表面积(本文中称为“BET表面积”)为42m2/g,其包括整料本身的质量。整料本身实际上没有表面积,从而观察到的金属-有机骨架复合材料的表面积能够完全归因于MOF涂料。MOF即HKUST-1的BET表面积为约1500m2/g。金属-有机骨架涂料为整个金属-有机骨架复合材料的质量的6.1%。鉴于纯金属-有机骨架的BET,复合材料的预期BET表面积为92m2/g,其中假设金属-有机骨架具有与我们实验观察到的42m2/g相同数量级的表面积。此外,由N2等温线计算的孔径表明,整料复合材料的平均孔宽度为1.697nm,这为金属-有机骨架HKUST-1的孔宽度,表明孔隙率源自金属-有机骨架HKUST-1,并且已保留在本发明的方法中。
金属-有机骨架HKUST-1在乙醇中的涂料也浸涂到具有方形通道和每平方英寸400个通道的氧化铝整料上。整料的BET表面积为26m2/g并且平均孔宽度为1.622nm,这再次与整料上的HKUST-1涂料一致。金属-有机骨架复合材料产生了4.5重量%的HKUST-1,这提供了67m2/g的预期BET,再次接近实验获得的值。
用不同的整料进行其它浸涂实验,所述整料包含涂布在应用陶瓷整料上的Mg-MOF-74。图2为所述金属-有机复合材料的显微照片。
图3显示了涂布前的两种整料。当与上面涂布的整料的图像相比时,整料的颜色变化和厚度变化表明,金属-有机涂料是成功的。
Claims (26)
1.一种制备金属-有机骨架复合材料的方法,所述方法包括如下步骤:
将粉末形式的金属-有机骨架混合在液体中以制造胶体悬浮液;
提供整料;
将所述整料在所述胶体悬浮液中进行浸涂以制造金属-有机骨架复合材料,所述金属-有机骨架复合材料具有至少一个沉积在所述整料上并与其结合的金属-有机骨架涂料层;和
干燥所述金属-有机骨架复合材料以制造具有约5m2/g至约100m2/g的BET表面积和约1nm至约50nm的孔径的金属-有机骨架复合材料。
2.一种制备吸附床的方法,所述方法包括如下步骤:
将粉末形式的金属-有机骨架混合在液体中以制造悬浮液;
提供整料;
将所述整料在胶体悬浮液中进行浸涂以制造金属-有机骨架复合材料,所述金属-有机骨架复合材料具有至少一个沉积在所述整料上并与其结合的金属-有机骨架涂料层;和
干燥所述金属-有机骨架复合材料以制造吸收床和/或微反应器,所述吸收床和/或微反应器具有相对于所述整料的表面积为约40%至约100%比例的比较BET表面积和约1nm至约50nm的孔径。
3.一种制备用作吸附床的金属-有机骨架复合材料的方法,所述方法包括如下步骤:
将金属-有机骨架粉末悬浮在液体中以制造悬浮液,其中所述金属-有机骨架粉末占所述悬浮液的约10重量%至约90重量%,并且所述悬浮液不包含酸;
将所述悬浮液冲刷到基底上以制造包含沉积在整料上的金属-有机骨架涂料的金属-有机骨架复合材料;和
用一种或多种沸石加热所述金属-有机骨架复合材料以将所述金属-有机骨架涂料粘合到所述整料上,其中所述金属-有机骨架复合材料具有约5m2/g至约100m2/g的BET表面积和/或相对于所述金属-有机骨架整料为约40%至约100%的比较BET表面积和约1nm至约50nm的孔径。
4.一种制备金属-有机骨架复合材料的方法,所述方法包括如下步骤:
将金属-有机骨架粉末与液体混合以形成金属-有机骨架涂料;
通过热沉积将所述金属-有机骨架涂料施加到整料上以制造金属-有机骨架复合材料,其中在所述液体中所述金属-有机骨架在所述金属-有机骨架涂料中的重量百分比在约30重量%至约60重量%的范围内;和
在低于250℃的温度下干燥所述金属-有机骨架复合材料,以制造具有约1m2/g至约300m2/g的BET表面积和/或相对于金属-有机骨架整料为约40%至约100%的比较BET表面积和约1nm至约50nm的孔径的金属-有机骨架复合材料。
5.根据权利要求4所述的方法,其中所述金属-有机骨架复合材料具有约1m2/g至约100m2/g的BET表面积。
6.根据前述权利要求中的任一项所述的方法,其中所述整料选自陶瓷、金属、聚合物基底和/或纤维素纤维。
7.根据前述权利要求中的任一项所述的方法,其中所述整料为陶瓷。
8.根据前述权利要求中的任一项所述的方法,其中所述聚合物基底包括聚乙烯酰胺、聚丙烯酸酯、聚碳酸酯、聚酰胺、聚酯、聚醚、聚乙烯胺、聚乙烯醇、聚乙烯酯和/或其组合物。
9.根据前述权利要求中的任一项所述的方法,其中所述金属-有机骨架为HKUST-1,所述液体为乙醇,并且所述整料包含氧化铝。
10.根据前述权利要求中的任一项所述的方法,其中所述金属-有机骨架为Mg-MOF-74,所述液体为乙醇,并且所述整料为陶瓷。
11.根据前述权利要求中的任一项所述的方法,其中所述金属-有机骨架选自:HKUST-1、UiO-66、ZIF-8、ZIF-7、MIL-100、MOF-74、M2(m-dobdc)、MOF-274、Cu(Qc)2及其组合物。
12.根据前述权利要求中的任一项所述的方法,其中所述金属-有机骨架包含有机配体,所述有机配体包含以下中的一种或多种:
具有1至10个碳原子的烷基基团亚结构;或
具有1至5个芳族环的芳基基团亚结构;
其中一个或多个亚结构各自具有至少两个X基团,并且其中X为以与金属或准金属配位的方式构造的官能团。
13.根据权利要求12所述的方法,其中各个X独立地选自以下的中性或离子形式:CO2H、OH、SH、OH2、NH2、CN、HCO、CS2H、NO2、SO3H、Si(OH)3、Ge(OH)3、Sn(OH)3、Si(SH)4、Ge(SH)4、Sn(SH)3、PO3H、AsO3H、AsO4H、P(SH)3、As(SH)3、CH(RSH)2、C(RSH)3、CH(RNH2)2、C(RNH2)3、CH(ROH)2、C(ROH)3、CH(RCN)2、C(RCN)3、CH(SH)2、C(SH)3、CH(NH2)2、C(NH2)2、CH(OH)2、C(OH)3、CH(CN)2、C(CN)3、含氮杂环、含硫杂环及其组合,其中R为具有1至5个碳原子的烷基基团或由1至2个苯环构成的芳基基团。
14.根据前述权利要求中的任一项所述的方法,其中所述有机配体选自:1,3,5-苯三羧酸酯、1,4-苯二羧酸酯、1,3-苯二羧酸酯、联苯-4,4'-二羧酸酯、苯-1,3,5-三(1H-四唑)、乙炔-1,2-二羧酸酯、萘二羧酸酯、金刚烷四羧酸酯、苯三苯甲酸酯、甲烷四苯甲酸酯、金刚烷三苯甲酸酯、联苯-4,4'-二羧酸酯、咪唑、2,5-二羟基-1,4-苯二羧酸、4,4'-二羟基-(1,1'-联苯)-3,3'-二羧酸及其衍生物、及其组合物。
15.根据前述权利要求中的任一项所述的方法,其中所述金属-有机骨架材料包含选自以下的金属离子:Be2+、Mg2+、Ca2+、Sr2+、Ba2+、Sc3+、Y3+、Ti4+、Zr4+、Hf4+、V5+、V4+、V3+、V2+、Nb3+、Ta3+、Cr3+、Mo6+、Mo3+、W6+、W3+、W、Mn3+、Mn2+、Re3+、Re2+、Fe3+、Fe2+、Ru3+、Ru2+、Os3+、Os2+、Co3+、Co2 +、Rh2+、Rh+、Ir2+、Ir+、Ni2+、Ni+、Pd2+、Pd+、Pt2+、Pt+、Cu2+、Cu+、Ag+、Au+、Zn2+、Cd2+、Hg2+、Al3+、Ga3 +、In3+、Tl3+、Si4+、Si2+、Ge4+、Ge2+、Sn4+、Sn2+、Pb4+、Pb2+、As5+、As3+、As+、Sb5+、Sb3+、Sb+、和Bi5+、Bi3+、Bi+、及其组合。
16.根据前述权利要求中的任一项所述的方法,所述方法还包括在约40℃至约150℃的温度下使所述金属-有机骨架复合材料熟化约30分钟或更多的时间的步骤。
17.根据前述权利要求中的任一项所述的方法,所述方法还包括在约100℃至约300℃的温度下将所述金属-有机骨架复合材料热处理约1小时或更多的时间的步骤。
18.根据前述权利要求中的任一项所述的方法,所述方法还包括用任选的溶剂洗涤所述金属-有机骨架复合材料。
19.根据前述权利要求中的任一项所述的方法,其中所述任选的溶剂选自:水、甲醇、乙醇、二甲基甲酰胺、丙酮、乙醚、乙腈、酮类、酰胺类、酯类、醚类、腈类、芳烃类、脂族烃类及其组合物。
20.根据前述权利要求中的任一项所述的方法,其中基于所述悬浮液的总重量,所述悬浮液包含约20重量%至约70重量%的固体。
21.根据前述权利要求中的任一项所述的方法,其中所述吸附床为用于气体和流体的吸收床或通道反应器。
22.根据前述权利要求中的任一项所述的方法,其中所述整料包含混合有约1重量%至约10重量%的二氧化硅和/或约1重量%至约5重量%的选自二氧化硅、二氧化钛、氧化镁和氧化钙的氧化物的约80重量%至约97重量%的氧化铝。
23.一种用于气体和流体的通道反应器,所述通道反应器包含至少一层沉积在整料上并与其结合以得到金属-有机骨架复合材料的金属-有机骨架涂料,所述金属-有机骨架复合材料具有约5m2/g至约100m2/g的BET表面积和/或相对于金属-有机骨架整料为约40%至约100%的比较BET表面积和约1nm至约50nm的孔径。
24.根据权利要求22所述的通道反应器,其中所述整料为堇青石。
25.根据权利要求23所述的通道反应器,其中所述整料包含氧化铝。
26.根据前述权利要求书中的任一项所述的通道反应器或吸附床,其中所述反应器或床可吸附和/或吸收每升约5克至约120克的CO2。
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