CN101248034A - 生产包含主族金属离子的金属-有机框架材料的方法 - Google Patents
生产包含主族金属离子的金属-有机框架材料的方法 Download PDFInfo
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- CN101248034A CN101248034A CNA2006800307530A CN200680030753A CN101248034A CN 101248034 A CN101248034 A CN 101248034A CN A2006800307530 A CNA2006800307530 A CN A2006800307530A CN 200680030753 A CN200680030753 A CN 200680030753A CN 101248034 A CN101248034 A CN 101248034A
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- dioctyl phthalate
- metal
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Images
Classifications
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0026—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof of one single metal or a rare earth metal; Treatment thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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Abstract
本发明涉及通过使至少一种金属化合物与至少一种至少二齿有机化合物反应来制备多孔金属-有机框架的方法,其中所述金属为Be、Mg、Ca、Sr、Ba、Al、Ga或In。本发明还涉及这类多孔金属-有机框架的用途。
Description
本发明涉及制备多孔金属-有机框架的方法和所制备的框架的用途。
多孔金属-有机框架在现有技术中是已知的。这些通常包含配位于至少一种金属离子的至少一种至少二齿有机化合物。例如在US-A 5,648,508;EP-A 0 790 253;M.O.Keeffe,J.Sol.State Chem.,152(2000),3-20;H.Li等人,Nature 402(1999),276;M.Eddaoudi,Topics in catalysis 9(1999),105-111;B.Chen等人,Science 291(2001),1021-1023和DE-A 101 11 230中描述了这类金属-有机框架(MOF)。
已经开发了多种制备这类多孔金属-有机框架的方法。通常,使金属盐与至少二齿有机化合物如二羧酸在超计大气压和升温下在适合的溶剂中反应。
但是,这样经常遇到困难。作为使用金属盐的后果,必须由框架分离出在形成金属-有机框架后保留在反应介质中的金属阳离子的抗衡离子(例如硝酸根),这是一个问题。
使用高压和高温对用于合成多孔金属-有机框架的设备有严格要求。通常,仅仅在相当小的设备中的批量合成是可能的,并且已有描述。扩大规模被证明是非常昂贵的。
取决于用于制备框架的金属和有机化合物,反应条件难以转换,这是另一困难。例如,当金属-有机框架中的金属组分为周期表的第二或第三主族的主族金属时,就是如此。这里,用于制备的反应条件往往与用于金属组分为过渡金属如锌或铜的类似框架的反应条件显著不同。
这类可包含第二或第三主族的主族金属的多孔金属-有机框架也在它们的性能上不同于上述类似框架,这可能是现有技术中经常将改进的制备方法用于它们的制备的原因。
例如,T.Loiseau等人,Chem.Eur.J.2004,(10),1373-1382描述了多孔对苯二甲酸铝的制备。其具有相当高的热稳定性。因此,据报道,该材料仅在温度超过500℃才会分解。通过使硝酸铝(作为九水合物)与1,4-苯二甲酸在去离子水中反应来进行该合成。在超计大气压下在220℃进行该反应。与其它金属-有机框架相比,发现在该制备中用作有机化合物的配体不仅作为该金属-有机框架中的框架结构单元(building block)出现,还作为配体留在该框架的孔中。配体在多孔金属-有机框架中的这种额外结合在源于过渡金属的类似框架中通常不出现。为了解决这个问题,Loiseau等人建议加热该材料,直至除去捕获在孔中的配体。该步骤具有的缺点在于:实际的合成之后必须跟随经常是耗时和严格的后处理步骤,而这强烈地依赖于配体的沸点或蒸汽压。对于沸点特别高的配体,这种操作也可能完全失败。
Z.Lin等人,Inorganic Chemistry 44(2005),73-76描述了其中铟构成金属组分和1,3,5-苯三甲酸用作有机化合物的金属-有机框架。同样,这里也将水用作溶剂。此外,Lin等人指出,必须向反应中加入大大过量的碱(吡啶),以便设定足够的pH。
L.Pan等人,Inorg.Chem.40(2001),1271-1283描述了含钙、锶和钡的多孔金属-有机框架,并且同样建议使用水或水/三乙胺。3,5-吡唑二甲酸被用作配体。
Z.Fei等人,Inorg.Chem.44(2005),5200-5202描述了锶-咪唑羧酸盐。
H.-F.Zhu等人,Crystal Growth & Design 5(2005),177-182描述了钙和钡一起与1,3,5-苯三甲酸在水中产生的金属-有机框架。
J.Sun等人,Angew.Chem.114(2002),4651-4653尤其描述了在DMF中制备对苯二甲酸铟。其中,在超计大气压下和160℃进行反应。
B.Gomez-Lor等人,Inorganic Chemistry 41(2002),2429-2432同样描述了对苯二甲酸铟,该反应在水中进行,将三乙胺用作碱。
使用水的缺点在于有机化合物往往在水中溶解性差以及经常获得低的框架产率和/或其比表面积低。
另一缺点是使用高压。这里,构造设备的困难生产通常不允许搅拌来混合各种起始材料从而制备金属-有机框架。
因此,仍需制备其中金属组分为元素周期表的第二或第三主族的金属的多孔金属-有机框架的改进方法。
因此,本发明的目的是提供制备这类金属-有机框架的改进方法。
该目的通过制备多孔金属-有机框架的方法来实现,该方法包括以下步骤:
使至少一种金属化合物与至少一种可配位于所述金属的至少二齿有机化合物在非水有机溶剂存在下反应,其中所述金属为BeII、MgII、CaII、SrII、BaII、AlIII、GaIII或InIII,所述有机化合物具有至少两个独立选自氧、硫和氮的原子且所述有机化合物通过它们可配位于所述金属,所述反应在搅拌和不超过2巴(绝对)的压力下进行。
已经发现使用非水有机溶剂和提及的其它条件使得实现至少部分更有效地制备多孔金属-有机框架成为可能,尤其是使得简单的规模扩大成为可能。
其中的一个优点是所述反应可在搅拌下进行,这对于规模扩大也是有利的。
所述反应在不超过2巴(绝对)的压力下进行。但是,所述压力优选不超过1230毫巴(绝对)。所述反应非常特别优选在大气压下进行。
所述反应可在室温下进行。但是,优选在高于室温的温度下进行。该温度优选高于100℃。此外,该温度优选不超过180℃,更优选不超过150℃。
上述金属-有机框架通常在添加了进一步碱的作为溶剂的水中进行。碱尤其用于使得用作至少二齿有机化合物的多元羧酸在水中易溶。由于使用非水有机溶剂,并非必须使用这种碱。然而,可选择用于本发明方法的溶剂,使其具有碱性反应,但是这对于实施本发明的方法不是绝对必须的。
同样可以使用碱。但是,优选不使用额外的碱。
此外,用于制备多孔金属-有机框架的金属化合物可优选为非离子的和/或金属阳离子的抗衡离子可源自质子溶剂。只要金属化合物在形成多孔金属-有机框架的反应中不进一步产生干扰盐,使用适合的非离子化合物就可以避免在反应中存在金属盐,金属盐会导致除去金属盐的相应阴离子方面的困难。如果抗衡离子为溶剂阴离子,则当适当选择时,其可在反应后作为溶剂存在。这种溶剂可以与所用的非水有机溶剂相同或与其不同。对于后一种情况,优选该溶剂与非水有机溶剂至少部分地溶混。如果在金属化合物的反应中形成水,则其比例应该位于下文描述的限度内。这可以通过使用足够量的非水有机溶剂来实现。
非离子化合物或可源自质子溶剂的金属阳离子的抗衡离子例如可为金属醇盐,如甲醇盐、乙醇盐、丙醇盐、丁醇盐,尤其是铝醇盐。氧化物或氢氧化物同样是可能的。
所用的金属为BeII、MgII、CaII、SrII、BaII、AlIII、GaIII或InIII。金属优选MgII、CaII、SrII、BaII、AlIII或InIII。非常特别优选AlIII和MgII。尤其优选AlIII。
所述至少一种至少二齿有机化合物具有至少两个选自氧、硫和氮的原子,该有机化合物通过它们可配位于金属。这些原子可以是骨架的一部分或官能团。
作为通过它们可形成上述配位键的官能团,可以通过举例尤其提及以下的官能团:-CO2H、-CS2H、-COSH、-NO2、-SO3H、-Ge(OH)3、-Sn(OH)3、-Si(SH)4、-Ge(SH)4、-Sn(SH)3、-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,其中R例如优选为具有1、2、3、4或5个碳原子的亚烷基,例如亚甲基、亚乙基、亚正丙基、亚异丙基、亚正丁基、亚异丁基、亚叔丁基或亚正戊基,或为包含1或2芳族环的芳基,例如包含2个C6环,如果合适的话,它们可以是稠合的并且各自相互独立地被至少一个取代基适当取代和/或可相互独立地包含至少一个诸如N、O和/或S的杂原子。根据同样优选的实施方案,可以提及其中上述基团R不存在的官能团。在这方面,可以尤其提及-CH(SH)2、-C(SH)3、-CH(NH2)2、-C(NH2)3、-CH(OH)3、-CH(CN)2或-C(CN)3。
所述至少两个官能团原则上可以结合至任何适合的有机化合物,只要确保带有这些官能团的有机化合物能够形成所述配位键并且适合于制备所述框架。
包含至少两个官能团的有机化合物优选衍生自饱和或不饱和的脂族化合物或芳族化合物或同时为脂族和芳族的化合物。
脂族化合物或同时为脂族和芳族的化合物的脂族部分可以为直链的和/或支化的和/或环状的,每个化合物有多个环也是可能的。更优选地,脂族化合物或同时为脂族和芳族的化合物的脂族部分包含1至15,更优选1至14,更优选1至13,更优选1至12,更优选1至11,特别优选1至10个碳原子,例如1、2、3、4、5、6、7、8、9或10个碳原子。这里特别优选的尤其是甲烷、乙烷、丁烷、2-丁烯、金刚烷、乙炔、乙烯或丁二烯。
芳族化合物或同时为芳族和脂族的化合物的芳族部分可具有一个或多个环,例如两个、三个、四个或五个环,这种情况下所述环可以彼此分开存在和/或至少两个环可以稠合形式存在。芳族化合物或同时为脂族和芳族的化合物的芳族部分更优选具有一个、两个或三个环,特别优选一个或两个环。此外,所提及的化合物的每个环可独立地包含至少一个杂原子,如N、O、S、B、P、Si,优选N、O和/或S。更优选地,芳族化合物或同时为芳族和脂族的化合物的芳族部分包含一个或两个C6环,这两个环能相互独立存在或以稠合形式存在。具体地,作为芳族化合物,可以提及苯、芘、二氢芘、萘和/或联苯和/或联吡啶和/或吡啶。
可以提及的实例尤其为反式粘康酸、富马酸和亚苯基二丙烯酸。
对本发明而言,可以提及例如二羧酸,例如,
草酸、琥珀酸、酒石酸、1,4-丁烷二甲酸、1,4-丁烯二甲酸、4-氧代吡喃-2,6-二甲酸、1,6-己烷二甲酸、癸烷二甲酸、1,8-十七烷二甲酸、1,9-十七烷二甲酸、十七烷二甲酸、乙炔二甲酸、1,2-苯二甲酸、1,3-苯二甲酸、2,3-吡啶二甲酸、吡啶-2,3-二甲酸、1,3-丁二烯-1,4-二甲酸、1,4-苯二甲酸、对苯二甲酸、咪唑-2,4-二甲酸、2-甲基喹啉-3,4-二甲酸、喹啉-2,4-二甲酸、喹喔啉-2,3-二甲酸、6-氯喹喔啉-2,3-二甲酸、4,4’-二氨基苯基甲烷-3,3’-二甲酸、喹啉-3,4-二甲酸、7-氯-4-羟基喹啉-2,8-二甲酸、二亚氨基二甲酸、吡啶-2,6-二甲酸、2-甲基咪唑-4,5-二甲酸、噻吩-3,4-二甲酸、2-异丙基咪唑-4,5-二甲酸、四氢吡喃-4,4-二甲酸、苝-3,9-二甲酸、苝二甲酸、Pluriol E 200-二甲酸、3,6-二氧杂辛烷二甲酸、3,5-环己二烯-1,2-二甲酸、辛烷二甲酸、戊烷-3,3-二甲酸、4,4’-二氨基-1,1’-二苯基-3,3’-二甲酸、4,4’-二氨基二苯基-3,3’-二甲酸、联苯胺-3,3’-二甲酸、1,4-双-(苯基氨基)-苯-2,5-二甲酸、1,1’-联萘二甲酸、7-氯-8-甲基喹啉-2,3-二甲酸、1-苯胺基蒽醌-2,4’-二甲酸、聚四氢呋喃-250-二甲酸、1,4-双(羧基甲基)哌嗪-2,3-二甲酸、7-氯喹啉-3,8-二甲酸、1-(4-羧基)苯基-3-(4-氯)苯基吡唑啉-4,5-二甲酸、1,4,5,6,7,7-六氯-5-降冰片烯-2,3-二甲酸、苯基茚满二甲酸、1,3-二苄基-2-氧代咪唑啉-4,5-二甲酸、1,4-环己烷二甲酸、萘-1,8-二甲酸、2-苯甲酰基苯-1,3-二甲酸、1,3-二苄基-2-氧代咪唑啉-4,5-顺式二甲酸、2,2’-联喹啉-4,4’-二甲酸、吡啶-3,4-二甲酸、3,6,9-三氧杂十一烷二甲酸、羟基二苯甲酮二甲酸、Pluriol E 300-二甲酸、Pluriol E 400-二甲酸、Pluriol E 600-二甲酸、吡唑-3,4-二甲酸、2,3-吡嗪二甲酸、5,6-二甲基-2,3-吡嗪二甲酸、4,4’-二氨基(二苯基醚)二亚氨基二甲酸、4,4’-二氨基二苯基甲烷二亚氨基二甲酸、4,4’-二氨基(二苯基砜)-二亚氨基二甲酸、1,4-萘二甲酸、2,6-萘二甲酸、1,3-金刚烷二甲酸、1,8-萘二甲酸、2,3-萘二甲酸、8-甲氧基-2,3-萘二甲酸、8-硝基-2,3-萘二甲酸、8-磺基-2,3-萘二甲酸、蒽-2,3-二甲酸、2’,3’-二苯基-对三联苯-4,4”-二甲酸、(二苯基醚)-4,4’-二甲酸、咪唑-4,5-二甲酸、4(1H)-氧硫代苯并吡喃-2,8-二甲酸、5-叔丁基-1,3-苯二甲酸、7,8-喹啉二甲酸、4,5-咪唑二甲酸、4-环己烯-1,2-二甲酸、三十六烷二甲酸、十四烷二甲酸、1,7-庚烷二甲酸、5-羟基-1,3-苯二甲酸、2,5-二羟基-1,4-二甲酸、吡嗪-2,3-二甲酸、呋喃-2,5-二甲酸、1-壬烯-6,9-二甲酸、二十碳烯二甲酸、4,4’-二羟基二苯基甲烷-3,3’-二甲酸、1-氨基-4-甲基-9,10-二氧代-9,10-二氢蒽-2,3-二甲酸、2,5-吡啶二甲酸、环己烯-2,3-二甲酸、2,9-二氯荧红环-4,11-二甲酸、7-氯-3-甲基喹啉-6,8-二甲酸、2,4-二氯二苯甲酮-2’,5’-二甲酸、1,3-苯二甲酸、2,6-吡啶二甲酸、1-甲基吡咯-3,4-二甲酸、1-苄基-1H-吡咯-3,4-二甲酸、蒽醌-1,5-二甲酸、3,5-吡唑二甲酸、2-硝基苯-1,4-二甲酸、庚烷-1,7-二甲酸、环丁烷-1,1-二甲酸、1,14-十四烷二甲酸、5,6-脱氢降冰片烷-2,3-二甲酸、5-乙基-2,3-吡啶二甲酸或樟脑二甲酸;
三羧酸,如
2-羟基-1,2,3-丙烷三甲酸、7-氯-2,3,8-喹啉三甲酸、1,2,3-、1,2,4-苯三甲酸、1,2,4-丁烷三甲酸、2-膦酰基-1,2,4-丁烷三甲酸、1,3,5-苯三甲酸、1-羟基-1,2,3-丙烷三甲酸、4,5-二氢-4,5-二氧代-1H-吡咯并[2,3-F]喹啉-2,7,9-三甲酸、5-乙酰基-3-氨基-6-甲基苯-1,2,4-三甲酸、3-氨基-5-苯甲酰基-6-甲基苯-1,2,4-三甲酸、1,2,3-丙烷三甲酸或金精三甲酸;
或四羧酸,如
1,1-二环氧苝并[1,12-BCD]噻吩-3,4,9,10-四甲酸(1,1-Dioxidperylo[1,12-BCD]thiophen-3,4,9,10-tetracarbonsure)、苝四甲酸如苝-3,4,9,10-四甲酸或苝-1,12-砜-3,4,9,10-四甲酸、丁烷四甲酸如1,2,3,4-丁烷四甲酸或内消旋-1,2,3,4-丁烷四甲酸、癸烷-2,4,6,8-四甲酸、1,4,7,10,13,16-六氧杂环十八烷-2,3,11,12-四甲酸、1,2,4,5-苯四甲酸、1,2,11,12-十二烷四甲酸、1,2,5,6-己烷四甲酸、1,2,7,8-辛烷四甲酸、1,4,5,8-萘四甲酸、1,2,9,10-癸烷四甲酸、二苯甲酮四甲酸、3,3’,4,4’-二苯甲酮四甲酸、四氢呋喃四甲酸或环戊烷四甲酸,如环戊烷-1,2,3,4-四甲酸。
非常特别优选使用具有1、2、3、4或更多个环的未取代的或任选至少单取代的芳族二羧酸、三羧酸或四羧酸,其中每个环可以包含至少一个杂原子,以及2个或更多个环可以包含相同或不同的杂原子。此类优选羧酸的实例是一环二羧酸、一环三羧酸、一环四羧酸、二环二羧酸、二环三羧酸、二环四羧酸、三环二羧酸、三环三羧酸、三环四羧酸、四环二羧酸、四环三羧酸和/或四环四羧酸。适合的杂原子是例如N、O、S、B、P、Si,优选的杂原子是N、S和/或O。适合的取代基尤其是-OH、硝基、氨基或烷基或烷氧基。
作为至少二齿有机化合物,特别优选使用乙炔二甲酸(ADC),樟脑二甲酸,富马酸,琥珀酸,苯二甲酸,萘二甲酸,联苯二甲酸如4,4’-联苯二甲酸(BPDC),吡嗪二甲酸如2,5-吡嗪二甲酸,联吡啶二甲酸如2,2’-联吡啶二甲酸,如2,2’-联吡啶-5,5’-二甲酸,苯三甲酸如1,2,3-、1,2,4-苯三甲酸或1,3,5-苯三甲酸(BTC),苯四甲酸,金刚烷四甲酸(ATC),金刚烷二苯甲酸盐(ADB),苯三苯甲酸盐(BTB),甲烷四苯甲酸盐(MTB),金刚烷四苯甲酸盐或二羟基对苯二甲酸如2,5-二羟基对苯二甲酸(DHBDC)。
非常特别优选尤其使用间苯二甲酸、对苯二甲酸、2,5-二羟基对苯二甲酸、1,2,3-苯三甲酸、1,3,5-苯三甲酸、2,6-萘二甲酸、1,4-萘二甲酸、1,2,3,4-和1,2,4,5-苯四甲酸、樟脑二甲酸或2,2’-联吡啶-5,5’-二甲酸。
除了这些至少二齿有机化合物,金属-有机框架还可包含一种或多种单齿配体。
所述至少一种至少二齿有机化合物优选不包含硼或磷原子。此外,金属-有机框架的骨架优选不包含硼或磷原子。
非水有机溶剂优选为C1-6烷醇,二甲亚砜(DMSO),N,N-二甲基甲酰胺(DMF),N,N-二乙基甲酰胺(DEF),乙腈,甲苯,二烷,苯,氯苯,甲基乙基酮(MEK),吡啶,四氢呋喃(THF),乙酸乙酯,任选卤代的C1-200链烷烃,环丁砜,二醇,N-甲基吡咯烷酮(NMP),γ-丁内酯,脂环醇如环己醇,酮类如丙酮或乙酰丙酮,环酮如环己酮、环丁烯砜(sulfolen)或其混合物。
C1-6烷醇是具有1至6个碳原子的醇。实例为甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、戊醇、己醇及其混合物。
任选卤代的C1-200链烷烃为具有1至200碳原子的链烷烃,其中一个或多个直至所有的氢原子可以被卤素代替,优选氯或氟,尤其是氯。实例为氯仿、二氯甲烷、四氯甲烷、二氯乙烷、己烷、庚烷、辛烷及其混合物。
优选的溶剂为DMF、DEF和NMP。特别优选DMF。
术语“非水”优选指这样的溶剂,基于溶剂总重量,具有10重量%、更优选5重量%、甚至更优选1重量%、还更优选0.1重量%、特别优选0.01重量%的最大水含量。
在反应过程中最大水含量优选为10重量%、更优选5重量%,甚至更优选1重量%。
术语“溶剂”包括纯溶剂和各种溶剂的混合物。
此外,优选在所述至少一种金属化合物与所述至少一种至少二齿有机化合物反应的工艺步骤之后跟随煅烧步骤。这里设定的温度通常在250℃以上,优选300至400℃。
煅烧步骤尤其可在多孔铝框架的制备中除去存在于孔中的配体。
作为补充或替代,将配体从多孔金属-有机框架的孔中除去可通过用非水溶剂处理形成的框架来实现。这时,配体以“萃取方法”的方式被去除,并且,如果合适的话,其在框架中被溶剂分子代替。当配体为高沸点化合物时,这种温和的方法尤其有用。
所述处理优选进行至少30分钟,并且通常可进行多至2天。这可在是室温或升高温度下发生。优选在升高温度下进行,例如在至少40℃、优选60℃下进行。还优选在所用溶剂的沸点(回流条件下)进行萃取。
所述处理可在简单容器中通过将框架浆化和搅拌进行。也可以使用诸如索格利特抽提器的萃取设备,尤其是工业萃取设备。
适合的溶剂为以上提到的那些,即,例如C1-6烷醇,二甲亚砜(DMSO),N,N-二甲基甲酰胺(DMF),N,N-二乙基甲酰胺(DEF),乙腈,甲苯,二烷,苯,氯苯,甲基乙基酮(MEK),吡啶,四氢呋喃(THF),乙酸乙酯,任选卤代的C1-200链烷烃,环丁砜,二醇,N-甲基吡咯烷酮(NMP),γ-丁内酯,脂环醇如环己醇,酮类如丙酮或乙酰丙酮,环酮如环己酮或其混合物。
优选甲醇、乙醇、丙醇、丙酮、MEK及其混合物。
非常特别优选的萃取剂为甲醇。
用于萃取的溶剂可与用于所述至少一种金属化合物和所述至少一种至少二齿有机化合物反应的溶剂相同或不同。特别地,尽管不是必须的,但是优选在“萃取”中使用的溶剂为无水的。
本发明的金属-有机框架包含孔,尤其是微孔和/或中孔。微孔定义为具有2nm或更小的直径的孔,中孔定义为直径在2至50nm范围,每种情况都对应于Pure Applied Chem.57(1985)第603-619页,尤其是第606页给出的定义。微孔和/或中孔的存在可借助吸附测量检查,这些测量根据DIN 66131和/或DIN 66134在77 K下确定该MOF对氮气的吸收能力。
根据DIN 66135(DIN 66131,66134)通过Langmuir模型计算的粉末形式的金属-有机框架的比表面积优选大于5m2/g,更优选在10m2/g以上,更优选大于50m2/g,甚至更优选大于500m2/g,甚至更优选大于1000m2/g并且特别优选大于1250m2/g。
MOF成形体可具有较低的比表面积;但是,其优选大于10m2/g,更优选大于50m2/g,甚至更优选大于500m2/g。
金属-有机框架的孔径大小可通过选择适合的配体和/或所述至少二齿有机化合物来进行控制。通常是所述有机化合物越大,孔径就越大。基于晶体材料,所述孔径大小优选为0.2nm至30nm,特别优选0.3nm至9nm的范围。
但是,其大小分布可变化的较大孔也出现在MOF成形体中。但是优选大于50%的总孔体积,尤其是大于75%的总孔体积由孔直径高达1000nm的孔形成。但是,孔体积的主要部分优选在两个直径范围中的孔形成。因此,进一步优选大于25%的总孔体积,尤其是大于50%的总孔体积由直径范围100nm至800nm内的孔形成,并且大于15%的总孔体积,尤其是大于25%的总孔体积由直径至多10nm的孔形成。可通过水银孔隙率检测法确定孔径大小分布。
金属-有机框架可为粉末形式或作为附聚体存在。所述框架可直接使用或转化成成形体。优选的方法是挤出或压片。在成形体的生产中,所述框架可包含其它材料,例如粘合剂、润滑剂或在生产过程中加入的其它添加剂。所述框架也可以包含其它成分,例如吸附剂,如活性炭等。
这些成形体的可能几何形状基本上不受任何限制。实例尤其为丸如盘状丸、片、球、颗粒、挤出物如杆状挤出物、蜂巢、网格和中空体。
所有适合的方法原则上都可能用于生产这些成形体。具体地,尤其以下方法是优选的:
-将框架单独捏合或者与至少一种粘合剂和/或至少一种粘稠剂(anteigungsmittel)和/或至少一种模板化合物一起捏合以得到混合物;通过至少一种适合的方法如挤出使得到的混合物成形;任选地洗涤和/或干燥和/或煅烧挤出物;任选地修整。
-将框架施用至至少一种任选多孔的载体材料。然后将所获得的材料通过上述方法进一步加工以得到成形体。
-将框架施用至至少一种任选多孔的基材。
捏合和成形可通过任何适合的方法来进行,如例如UllmannsEnzyklopdie der Technischen Chemie,第四版,第2卷,第313及以后页(1972)中所描述的。
例如,捏合和/或成形可以优选借助于如下方式进行:在存在或不存在至少一种粘合剂材料下借助于活塞压机、轧压机,配混,压丸,压片,挤出,共挤出,发泡,纺丝,涂敷,制粒,优选喷雾制粒,喷雾,喷雾干燥或这些方法中的两种或更多种方法的组合。
非常特别优选生产丸和/或片。
捏合和/或成形可以在升高的温度下,例如在室温至300℃的温度下,和/或升高的压力下,例如在大气压至几百巴的压力下,和/或在保护气体气氛中,例如在至少一种稀有气体、氮气或其两种或更多种的混合物存在下进行。
根据本发明方法的另一实施方案,捏合和/或成形在添加至少一种粘合剂下进行,其中使用的粘合剂原则上是能够确保将组合物捏合和/或成形所需的粘度的任何化合物。因此,粘合剂对本发明而言可以是增粘化合物或降粘化合物。
优选的粘合剂包括例如氧化铝,或例如在WO 94/29408中描述的包含氧化铝的粘合剂,例如在EP 0 592 050 A1中描述的包含二氧化硅的粘合剂,例如在WO 94/13584中描述的包含二氧化硅和氧化铝的混合物的粘合剂,如在JP 03-037156A中描述的包含粘土矿物的粘合剂,例如蒙脱土、高岭土、膨润土、多水高岭土、地开石(Dickit)、珍珠陶土和富硅高岭土,如在EP 0 102 544 B1中描述的包含烷氧基硅烷的粘合剂,例如四烷氧基硅烷,如四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、四丁氧基硅烷,和例如三烷氧基硅烷,如三甲氧基硅烷、三乙氧基硅烷、三丙氧基硅烷、三丁氧基硅烷,烷氧基钛酸酯,例如四烷氧基钛酸酯,如四甲氧基钛酸酯、四乙氧基钛酸酯、四丙氧基钛酸酯、四丁氧基钛酸酯,和例如三烷氧基钛酸酯,如三甲氧基钛酸酯、三乙氧基钛酸酯、三丙氧基钛酸酯、三丁氧基钛酸酯,烷氧基锆酸酯,例如四烷氧基锆酸酯,如四甲氧基锆酸酯、四乙氧基锆酸酯、四丙氧基锆酸酯、四丁氧基锆酸酯,和例如三烷氧基锆酸酯,如三甲氧基锆酸酯、三乙氧基锆酸酯、三丙氧基锆酸酯、三丁氧基锆酸酯,硅溶胶,两亲性物质和/或石墨。特别优选石墨。
作为增粘化合物,合适的话,除了上述化合物以外,还可以例如使用有机化合物和/或亲水性聚合物如纤维素或纤维素衍生物如甲基纤维素和/或聚丙烯酸酯和/或聚甲基丙烯酸酯和/或聚乙烯醇和/或聚乙烯吡咯烷酮和/或聚异丁烯和/或聚四氢呋喃和/或聚氧化乙烯。
作为粘稠剂,优选使用尤其是水或至少一种醇,如具有1-4个碳原子的一元醇,如甲醇、乙醇、正丙醇、异丙醇、1-丁醇、2-丁醇、2-甲基-1-丙醇或2-甲基-2-丙醇,或水与至少一种上面提及的醇的混合物,或多元醇如二醇,优选水溶混性多元醇,这些醇既可以单独形式也可以作为与水和/或至少一种上述提及的一元醇的混合物的形式。
可以用于捏合和/或成形的其它添加剂尤其是胺或胺衍生物,如四烷基铵化合物或氨基醇和含碳酸根的化合物如碳酸钙。此类其它的添加剂例如在EP 0 389 041 A1、EP 0 200 260 A1或WO 95/19222中有描述。
添加剂如模板化合物、粘合剂、粘稠剂、增粘物质在成形和捏合中的添加顺序原则上不是关键的。
在另一优选实施方案中,将通过捏合和/或成形得到的成形体进行至少一次干燥操作,该操作一般在25-300℃,优选在50-300℃,特别优选在100-300℃的温度下进行。同样可以在减压下或在保护气体气氛下进行干燥或通过喷雾干燥来进行。
在特别优选的实施方案中,至少一种作为添加剂加入的化合物在该干燥操作期间至少部分地从成形体中除去。
本发明还提供了可通过本发明用于其制备的方法获得的多孔金属-有机框架。这里,该框架优选具有上述就框架概述中指明的比表面积(通过Langmuir方法确定)。
本发明还提供了包含至少一种选自BeII、MgII、CaII、SrII、BaII、AlIII、GaIII和InIII的金属和至少一种至少二齿有机化合物的多孔金属-有机框架的用途,其中该有机化合物具有至少两个独立选自氧、硫和氮的原子,且该有机化合物通过它们配位于所述金属,尤其是可通过本发明的方法获得的框架的用途,该用途是用于为了存储、分离、控制释放或化学反应而吸收至少一种物质,以及用作金属、金属氧化物、金属硫化物或其它框架结构的载体材料。
所述至少一种物质可为气体或液体。所述物质优选为气体。
对本发明而言,术语“气体”和“液体”是出于简洁的目的而使用,但是气体混合物和液体混合物或液体溶液同样也包括在术语“气体”或“液体”中。
优选的气体为氢气,烃,尤其是甲烷、乙烷、乙烯、乙炔、丙烷、正丁烷和异丁烷,一氧化碳,二氧化碳,氮氧化物,氧气,硫氧化物,卤素,卤代烃,NF3,SF6,氨,硼烷,膦(phosphane),硫化氢,胺,甲醛,稀有气体,尤其是氦、氖、氩、氪和氙。
特别优选使用其中金属为AlIII或MgII的本发明金属-有机框架来存储氢气。
但是,所述至少一种物质也可以为液体。这类液体的实例为消毒剂,无机或有机溶剂,燃料,尤其是汽油或柴油,液压液体,散热器液体,制动液或油,尤其是机油。此外,所述液体也可以为卤代的脂族或芳族、环状或非环状烃,或其混合物。具体地,液体可为丙酮、乙腈、苯胺、茴香醚、苯、苄腈、溴苯、丁醇、叔丁醇、喹啉、氯苯、氯仿、环己烷、二甘醇、乙醚、二甲基乙酰胺、二甲基甲酰胺、二甲亚砜、二烷、冰乙酸、乙酸酐、乙酸乙酯、乙醇、碳酸亚乙酯、二氯乙烷、乙二醇、乙二醇二甲醚、甲酰胺、己烷、异丙醇、甲醇、甲氧基丙醇、3-甲基-1-丁醇、二氯甲烷、甲基乙基酮、N-甲基甲酰胺、N-甲基吡咯烷酮、硝基苯、硝基甲烷、哌啶、丙醇、碳酸亚丙酯、吡啶、二硫化碳、环丁砜、四氯乙烯、四氯化碳、四氢呋喃、甲苯、1,1,1-三氯乙烷、三氯乙烯、三乙胺、三甘醇、三甘醇二甲醚、水或其混合物。
所述至少一种物质也可为有气味物质。
该有气味物质优选挥发性有机或无机化合物,其包含氮、磷、氧、硫、氟、氯、溴或碘中的至少一种元素,或者是不饱和的或芳族烃,或者饱和的或不饱和的醛,或者酮。更优选的元素为氮、氧、磷、硫、氯、溴;并且特别优选氮、氧、磷和硫。
具体地,该有气味物质是氨、硫化氢、硫氧化物、氮氧化物、臭氧、环状或非环状胺、硫醇、硫醚,以及醛、酮、酯、醚、酸或醇。特别优选氨、硫化氢、有机酸(优选乙酸、丙酸、丁酸、异丁酸、戊酸、异戊酸、己酸、庚酸、月桂酸、壬酸)和包含氮或硫的环状或非环状烃,以及饱和或不饱和醛,如己醛、庚醛、辛醛、壬醛、癸醛、辛烯醛或壬烯醛,尤其是挥发性醛,如丁醛、丙醛、乙醛和甲醛,以及燃料,如汽油、柴油(成分)。
所述有气味物质也可是芳香物质,其例如用于生产香水。芳香物质或释放这种芳香物质的油的实例为:精油、罗勒油、香叶油、薄荷油(Minzl)、依兰油、小豆蔻油、薰衣草油、薄荷油(Pfefferminzl)、肉豆蔻油、春黄菊油、桉树油、迷迭香油、柠檬油、椴木油、橙皮油、香柠檬油、Muskatellersalbeil、芫荽油、柏木油、1,1-二甲氧基-2-苯基乙烷、2,4-二甲基-4-苯基四氢呋喃、二甲基四氢苯甲醛、2,6-二甲基-7-辛烯-2-醇、1,2-二乙氧基-3,7-二甲基-2,6-辛二烯、苯乙醛、玫瑰醚、2-甲基戊酸乙酯、1-(2,6,6-三甲基-1,3-环己二烯-1-基)-2-丁烯-1-酮、乙基香兰素、2,6-二甲基-2-辛烯醇、3,7-二甲基-2-辛烯醇、乙酸叔丁基环己酯、乙酸大茴香酯、环己氧基乙酸烯丙酯、乙基芳樟醇、丁子香酚、香豆素、乙酰乙酸乙酯、4-苯基-2,4,6-三甲基-1,3-二烷、4-亚甲基-3,5,6,6-四甲基-2-庚酮、四氢藏花酸乙酯(Ethyltetrahydrosafranat)、香叶基腈、顺式-3-己烯-1-醇、乙酸顺式-3-己烯基酯、碳酸顺式-3-己烯基甲基脂、2,6-二甲基-5-庚烯-1-醛、4-(三环[5.2.1.0]亚癸基)-8-丁醛、5-(2,2,3-三甲基-3-环戊烯基)-3-甲基戊-2-醇、对叔丁基-α-甲基氢化肉桂醛、乙基[5.2.1.0]三环癸烷甲酸乙酯、香叶醇、香茅醇、柠檬醛、芳樟醇、乙酸里哪酯、紫罗酮、苯基乙醇及其混合物。
对于本发明而言,挥发性有气味物质优选具有300℃以下的沸点或沸点范围。有气味物质更优选为容易挥发的化合物或混合物。有气味物质特别优选具有250℃以下,更优选230℃以下,特别优选200℃以下的沸点或沸点范围。
同样优选具有高挥发性的有气味物质。蒸汽压可用作对挥发性的衡量。对于本发明而言,挥发性有气味物质优选具有大于0.001kPa(20℃)的蒸汽压。有气味物质更优选为容易挥发的化合物或混合物。有气味物质特别优选具有大于0.01kPa(20℃)的蒸汽压,更优选具有大于0.05kPa(20℃)的蒸汽压。特别优选蒸汽压大于0.1kPa(20℃)的有气味物质。
实施例
实施例1在DMF中大气压制备Al-BDC MOF
将5.8g的对苯二甲酸(BDC)和26g的Al(NO3)3*9H2O悬浮在100mlDMF中,将该混合物在133℃,回流下搅拌16小时。随后滤出固体,用20ml甲醇洗涤并在真空干燥箱中在200℃干燥16小时。最后将粉末在马弗炉(100L/h空气)中在330℃后处理3天(以约75℃/h加热)。
获得7.7g浅棕色粉末,表面积为1267m2/g(通过Langmuir方法确定)。衍射图(XRD)显示在图1中。对于所有的衍射图,样品均在N2钟罩下制备,并覆有Styroflex膜以密闭,未研磨。样品的衍射图在来自Siemens的D5000仪器上记录,采用Cu阳极,布幅0.02°,步速3.6s。
实施例2在DMF中大气压制备Al-BDC MOF
将19.9g的对苯二甲酸(BDC)和23.3g的Al2(SO4)3*18H2O悬浮在100ml DMF中,将该混合物在130℃,回流下搅拌16小时(350rpm)。随后滤出固体,用3×20ml DMF和20ml甲醇洗涤并在真空干燥箱中在200℃干燥16小时。最后将粉末在马弗炉(100L/h空气)中在330℃后处理3天(以约75℃/h加热)。
获得15.7g产物,表面积为1398m2/g(通过Langmuir方法确定)。
实施例3在DEF中大气压制备Al-BDC MOF
将19.9g的对苯二甲酸(BDC)和23.3g的Al2(SO4)3*18H2O悬浮在100ml DEF中,将该混合物在130℃的油浴外部温度下搅拌16小时(290rpm)。随后让混合物在室温下静置约60小时。随后滤出固体,用7×20ml DMF和2×20ml甲醇洗涤并在真空干燥箱中在200℃干燥16小时。最后将粉末在马弗炉(100L/h空气)中在330℃后处理3天(以约75℃/h加热)。
获得16g产物,表面积为1425m2/g(通过Langmuir方法确定)。衍射图(XRD)显示在图3中。
对比例4在水中大气压制备Al-BDC MOF
将5.8g的对苯二甲酸(BDC)和23.3g的Al2(SO4)3*18H2O悬浮在100ml水中,将该混合物在100℃,回流下搅拌3天(500rpm)。让混合物在室温下静置约60小时。随后滤出固体,用3×20ml水和3×20ml甲醇洗涤并在真空干燥箱中在200℃干燥16小时。最后将粉末在马弗炉(100L/h空气)中在330℃后处理3天(以约75℃/h加热)。
仅获得1.5g产物,表面积为1416m2/g(通过Langmuir方法确定)。
对比例5 在超计大气压和无后处理情况下在水中制备Al-BDC MOF
将5.76g的对苯二甲酸(BDC)和26g的Al(NO3)3*9H2O悬浮在100ml水中,将该混合物在环境条件下搅拌30分钟。随后让混合物在Berghoff高压釜(Teflon衬垫)中在220℃维持3天。过滤后,用5×20ml水洗涤固体并在马弗炉(100L/h空气)中在330℃干燥3天。
仅获得4.6g产物,表面积为319m2/g(通过Langmuir方法确定)。衍射图(XRD)显示在图2中。
对比例6在超计大气压下在DMF中制备Al-BDC MOF
将5.8g的对苯二甲酸(BDC)和26g的Al(NO3)3*9H2O悬浮在100mlDMF中,将该混合物在环境条件下搅拌10分钟。随后让混合物在Berghoff高压釜(Teflon衬垫)中在170℃维持1天。过滤后,用DMF洗涤固体数次,随后用丙酮洗涤数次。产物首先在真空干燥箱中在130℃预干燥20小时,并在马弗炉(100L/h空气)中在330℃干燥3天。
获得7.8g产物,表面积为1196m2/g(通过Langmuir方法确定)。不能进行规模扩大。
实施例7在DMF中大气压制备Al-BDC MOF(规模扩大)
将292.9g的对苯二甲酸(BDC)和250.1g的Al2(SO4)3*18H2O悬浮在1257g DMF中,在搅拌下在130℃加热24小时。随后过滤悬浮液,并用DMF洗涤滤饼数次。滤饼首先在空气中预干燥2天,随后在马弗炉中在空气气氛中和320℃下干燥72小时。
获得192g产物,表面积为1483m2/g(通过Langmuir方法确定)。
实施例8大气压制备Al-BDC MOF
将19.9g的对苯二甲酸(BDC)和23.3g的Al2(SO4)3*18H2O悬浮在100g NMP中,在搅拌下在130℃加热24小时。随后过滤悬浮液,并用NMP洗涤滤饼数次。滤饼首先在空气中预干燥2天,随后在马弗炉中在空气气氛中和320℃下干燥72小时。
获得15.1g产物,表面积为1134m2/g(通过Langmuir方法确定)。
实施例9借助来自实施例3的框架的异丁烯聚合
将5g框架置于300ml钢高压釜中,并与100g甲苯混合。将82ml的液体异丁烯注入该封闭的高压釜中。将高压釜维持在170℃ 3小时。冷却后,通过GC分析液相(GC面积%,):尤其是包含68%的C4,26%的C8。此外,也发现了高级烯烃,例如2.3%的C16和1.7%的C20。
实施例10通过来自实施例7的框架存储H2
在测量前将来自实施例7的Al-MOF在80℃在小于1毫巴的压力下抽真空5小时。将161.96g的干燥产物转移至空容器中。其随后被冷却至77K并将容器抽真空。通过气体计量装置将氢气一次一点儿地引入,通过重量分析确定每种情况下的吸收量。在50.3巴,Al-MOF实现了约3重量%的氢吸收。
实施例11通过来自实施例7的框架存储甲烷
在测量前将来自实施例7的Al-MOF在80℃在小于1毫巴的压力下抽真空5小时。将161.96g的干燥产物转移至空容器中。随后使其温度到25℃并抽真空。通过气体计量装置将甲烷一次一点儿地引入,通过重量分析确定每种情况下的吸收量。以此方式,在填充MOF的瓶中,在50.4巴可存储40.3g/L的甲烷,在99.7巴甚至可存储79.8g/L的甲烷。
实施例12在DMF中大气压制备Al-BDC MOF(规模扩大)
将398.7g的对苯二甲酸(BDC)和466.5g的Al2(SO4)3*18H2O悬浮在2000ml DMF中,在搅拌下在115℃加热24小时。随后过滤悬浮液,并用3×400ml的DMF和400ml甲醇洗涤滤饼数次。然后用N2将滤饼吹干96小时。获得375g产物。
将15g干燥产物用甲醇在索格利特萃取器中萃取48小时并滤出。用3×25ml甲醇洗涤滤饼并在真空干燥箱中在110℃干燥24小时。
萃取后材料的表面积为1522m2/g(通过Langmuir方法确定)。
实施例13在DMF中大气压制备Al-BTC MOF
将7.8g的苯三甲酸(BTC)和22.9g的Al(NO3)3*9H2O悬浮在520.5gDMF中,在搅拌下在130℃加热4天。随后过滤悬浮液,并用2×100ml的DMF和4×100ml甲醇洗涤滤饼。然后在真空干燥箱中在200℃干燥滤饼16小时。最后将粉末在马弗炉(100L/h空气)中在330℃后处理3天(以约75℃/h加热)。
获得8.4g产物,表面积为1791m2/g(通过Langmuir方法确定)。
实施例14在DMF中大气压制备Al-BDC MOF
将7.8g的苯三甲酸(BTC)和14.7g的AlCl3*6H2O悬浮在520.5g DMF中,在搅拌下在130℃加热4天。随后过滤悬浮液,并用2×100ml的DMF和4×100ml甲醇洗涤滤饼。然后在真空干燥箱中在200℃干燥滤饼16小时。最后将粉末在马弗炉(100L/h空气)中在330℃后处理3天(以约75℃/h加热)。
获得10.9g产物,表面积为1451m2/g(通过Langmuir方法确定)。
对比例15在水中大气压制备Al-BTC MOF
将7.8g的苯三甲酸(BTC)和22.9g的Al(NO3)3*9H2O悬浮在130.8g水中,在搅拌下在100℃加热4天。随后过滤悬浮液,并用水洗涤滤饼。将滤饼在真空干燥箱中在150℃干燥2天。
仅获得0.6g产物。
对比例16在H2O中水热制备Al-BTC MOF
将7.8g的苯三甲酸(BTC)和22.9g的Al(NO3)3*9H2O悬浮在130.8g水中,在Berghoff高压釜(Teflon衬垫)中在130℃加热4天。随后过滤悬浮液,并用水洗涤滤饼。将滤饼在真空干燥箱中在150℃干燥2天。
仅获得0.4g产物。
实施例17/实施例18在DMF中制备Al-BDC MOF
将250.1g的对苯二甲酸(BDC)和292.9g的Al2(SO4)3*18H2O悬浮在1257g的DMF中,在搅拌下在130℃加热24小时。随后将悬浮液过滤,用DMF洗涤滤饼。在真空干燥箱中在120℃干燥滤饼2小时。
然后,将一半的干燥滤饼在干燥箱中在250℃煅烧24小时。重量损失38.6%。形成表面积634m2/g的产物。
将另一半在马弗炉中在320℃煅烧3小时。重量损失59.8%。形成表面积1368m2/g的产物。
实施例19在DEF中大气压制备Al-樟脑二酸MOF
将7.4g的(+)-樟脑二酸和24g的Al(SO4)3*18H2O悬浮在520.5g DEF中,在搅拌下在130℃加热4天。随后过滤悬浮液,用2×100ml的DEF和4×100ml甲醇洗涤滤饼。将滤饼在真空干燥箱中在200℃干燥16小时。获得11.8g产物,表面积为429m2/g(通过Langmuir方法确定)。衍射图(XRD)显示在图4中。将1.5g的产物在索格利特抽提器中在沸腾甲醇中萃取16小时,随后在室温下减压干燥。表面积提高至555m2/g。
实施例20在DEF中大气压制备Al-丁烷四甲酸MOF
将8.7g的1,2,3,4-丁烷四甲酸和48g的Al(SO4)3*18H2O悬浮在520.5gDEF中,在搅拌下在130℃加热4天。随后过滤悬浮液,用2×100ml的DEF和4×100ml甲醇洗涤滤饼。将滤饼在真空干燥箱中在200℃干燥16小时。获得14.9g产物,表面积为518m2/g(通过Langmuir方法确定)。
实施例21在DEF中大气压制备Al-巯基琥珀酸MOF
将5.6g的巯基琥珀酸和27.8g的Al(NO3)3*9H2O悬浮在520.5g DEF中,在搅拌下在130℃加热3天。随后过滤悬浮液,用2×100ml的DEF和4×100ml甲醇洗涤滤饼。将滤饼在真空干燥箱中在200℃干燥16小时。获得7.8g产物,表面积为488m2/g(通过Langmuir方法确定)。衍射图(XRD)显示在图5中。
实施例22在DMF中大气压制备Al-1,4-萘二甲酸MOF
将8g的1,4-萘二甲酸和27.8g的Al(NO3)3*9H2O悬浮在520.5g DMF中,在搅拌下在130℃加热3天。随后过滤悬浮液,用3×100ml甲醇洗涤滤饼。将滤饼在真空干燥箱中在200℃干燥16小时。获得8.7g产物。然后,将1.5g产物在索格利特萃取器中用甲醇萃取16小时,并在室温下减压干燥16小时。
获得752m2/g的比表面积。
实施例23在DEF中大气压制备Mg-2,6-萘二甲酸MOF
将4.9g的2,6-萘二甲酸和8.16g的Mg(NO3)2*6H2O悬浮在1686gDEF中,在搅拌下在105℃加热24小时。随后过滤悬浮液,首先用DMF,然后用氯仿洗涤滤饼。让滤饼在空气中干燥。获得4.8g产物。将干燥产物在马弗炉中以330℃煅烧2天。
获得3.6g产物。衍射图(XRD)显示在图6中。该产物为具有典型MOF衍射图的晶体物质。
实施例24制备Al-1,2,4,5-苯四甲酸MOF
将9.4g的1,2,4,5-苯四甲酸和30.5g的Al(NO3)3*9H2O悬浮在1L搅拌烧瓶中的520.5g DMF中,在搅拌下加热至130℃,在这些条件下维持72小时。滤出沉淀的产物,用2×100ml DMF和4×100ml甲醇洗涤,在真空干燥箱中在200℃干燥16小时。最后将产物在马弗炉中空气气氛下在330℃煅烧72小时。
获得12.8g产物,N2表面积为930m2/g(通过Langmuir方法确定)。
实施例25制备Al-巯基琥珀酸MOF
将13.6g的巯基琥珀酸和67.6g的Al(NO3)3*9H2O悬浮在2L搅拌烧瓶中的1246g DMF中,在搅拌下加热至130℃,在这些条件下维持72小时。滤出沉淀的产物,用1×200ml DMF和3×200ml甲醇洗涤,在真空干燥箱中在200℃干燥16小时。
获得17.7g淡黄色产物,N2表面积为551m2/g(通过Langmuir方法确定)。
实施例26制备Al-对苯二甲酸MOF
将239kg的对苯二甲酸和279kg的Al2(SO4)3*18H2O悬浮在1500kgDMF中,在搅拌下加热至130℃,在这些条件下维持18小时。滤出沉淀的产物,用3×500L丙酮洗涤。随后将滤饼在500L甲醇中在60℃再悬两次,每次3小时,随后再次滤出甲醇。然后,将滤饼在减压下干燥,开始是50℃,后来是100℃。
获得249kg白色物质。在随后的在马弗炉中空气气氛下在360℃处理48小时之后,该物质具有的N2表面积为1400m2/g。XRD显示在图7中。
实施例27制备Al-间苯二甲酸MOF
将7.23g的间苯二甲酸和7.0g的AlCl3*6H2O悬浮在搅拌烧瓶中的300ml DMF中,在搅拌下加热至130℃,在这些条件下维持20.5小时。滤出沉淀的产物,用3×50ml DMF和4×50ml甲醇洗涤,并在真空干燥箱中在110℃干燥16小时。
获得3.94g黄色产物,具有的N2表面积为1242m2/g(通过Langmuir方法确定;活化温度:150℃)。根据元素分析,该物质包含42.8%的C、8.8%的Al和4.5%的H。XRD显示在图8中。
实施例28制备Al-4,5-咪唑二甲酸MOF
将5.17g的4,5-咪唑二甲酸和5.33g的AlCl3*6H2O悬浮在搅拌烧瓶中的300ml DMF中,在搅拌下加热至130℃,在这些条件下维持20.5小时。滤出沉淀的产物,用3×50ml DMF和4×50ml甲醇洗涤,并在真空干燥箱中在110℃干燥72小时。
获得3.94g淡橙色产物,具有的N2表面积为703m2/g(通过Langmuir方法确定;活化温度:150℃)。根据元素分析,该物质包含35.3%的C、8.5%的Al和3.7%的H。
实施例29 制备Al-环己烷二甲酸MOF
将1.33g的环己烷二甲酸(顺/反混合物)和5.95g的Al(NO3)3*9H2O悬浮在搅拌烧瓶中的111g DMF中,在搅拌下加热至130℃,在这些条件下维持17小时。滤出沉淀的产物,用2×50ml DMF和4×50ml甲醇洗涤,并在真空干燥箱中在130℃干燥16小时。
获得3.94g白色产物,具有的N2表面积为410m2/g(通过Langmuir方法确定)。XRD显示在图9中。
实施例30制备Mg-萘二甲酸MOF
将6.66g的2,6-萘二甲酸和10.98g的Mg(NO3)2*6H2O悬浮在搅拌烧瓶中的137g DMF中,在搅拌下加热至130℃,在这些条件下维持48小时。通过N2流经由蒸馏附件分离出反应中形成的水。滤出沉淀的产物,用DMF洗涤两次,用氯仿洗涤两次。将滤饼首先在室温下干燥,最后在250℃煅烧48小时。
干燥后获得7.8g产物,煅烧后获得5.4g产物。煅烧后的形式具有的N2表面积(通过Langmuir方法确定)为294m2/g。图10显示了干燥形式产物的XRD,图11显示了煅烧形式产物的XRD。
实施例31制备Ca-5-叔丁基间苯二甲酸MOF
将4.95g的5-叔丁基间苯二甲酸和9.75g的CaCl2*6H2O悬浮在搅拌烧瓶中的312.3g DMF中,在搅拌下加热至130℃,在这些条件下维持20小时。滤出沉淀的产物,用1×50ml DMF和3×50ml甲醇洗涤,并在真空干燥箱中在200℃干燥10小时。
获得4.9g产物。N2表面积为5m2/g(通过Langmuir方法确定)-该产物显然为仅具有低空隙度或非常窄的孔的MOF。XRD显示在图12中。
Claims (13)
1.一种制备多孔金属-有机框架的方法,其包括以下步骤:
使至少一种金属化合物与至少一种可配位于所述金属的至少二齿有机化合物在非水有机溶剂存在下反应,其中所述金属为BeII、MgII、CaII、SrII、BaII、AlIII、GaIII或InIII,所述有机化合物具有至少两个独立选自氧、硫和氮的原子且所述有机化合物通过它们可配位于所述金属,所述反应在搅拌和不超过2巴(绝对)的压力下进行。
2.根据权利要求1的方法,其中所述反应在不超过1230毫巴(绝对)下进行,优选在大气压下进行。
3.根据权利要求1或2的方法,其中所述反应在没有额外碱下进行。
4.根据权利要求1至3中任一项的方法,其中所述至少二齿有机化合物为二羧酸、三羧酸或四羧酸。
5.根据权利要求1至4中任一项的方法,其中所述金属为AlIII。
6.根据权利要求1至5中任一项的方法,其中所述非水有机溶剂为C1-6烷醇、DMSO、DMF、DEF、乙腈、甲苯、二烷、苯、氯苯、MEK、吡啶、THF、乙酸乙酯、任选卤代的C1-200链烷烃、环丁砜、二醇、NMP、γ-丁内酯、脂环醇、酮、环酮、环丁烯砜或其混合物。
7.根据权利要求1至6中任一项的方法,其中在所述反应后用有机溶剂后处理所形成的框架。
8.根据权利要求1至7中任一项的方法,其中在所述反应后进行煅烧步骤。
9.根据权利要求1至8中任一项的方法,其中所述金属化合物为非离子的和/或所述金属阳离子的抗衡离子源自质子溶剂。
10.可通过根据权利1至8中任一项的方法获得的多孔金属-有机框架。
11.根据权利要求10的框架,其具有的通过Langmuir方法确定的比表面积为大于10m2/g。
12.根据权利要求10的多孔金属-有机框架用于为了存储、分离、控制释放或化学反应而吸收至少一种物质的用途,以及作为载体材料的用途。
13.根据权利要求12的用途,其中所述金属为AlIII或MgII,并且所述框架用于存储氢气。
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DE502006008395D1 (de) | 2011-01-05 |
DE102005039623A1 (de) | 2007-03-01 |
JP5455368B2 (ja) | 2014-03-26 |
CN101248034B (zh) | 2012-07-04 |
KR20080039985A (ko) | 2008-05-07 |
EP1922299A1 (de) | 2008-05-21 |
CA2620113A1 (en) | 2007-03-01 |
KR101422854B1 (ko) | 2014-07-24 |
JP2009506991A (ja) | 2009-02-19 |
US9878906B2 (en) | 2018-01-30 |
ES2356258T3 (es) | 2011-04-06 |
EP1922299B1 (de) | 2010-11-24 |
US20100166644A1 (en) | 2010-07-01 |
ATE489354T1 (de) | 2010-12-15 |
WO2007023134A1 (de) | 2007-03-01 |
CA2620113C (en) | 2015-05-05 |
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