CN101243034B - 中孔的金属-有机框架 - Google Patents
中孔的金属-有机框架 Download PDFInfo
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- CN101243034B CN101243034B CN2006800303351A CN200680030335A CN101243034B CN 101243034 B CN101243034 B CN 101243034B CN 2006800303351 A CN2006800303351 A CN 2006800303351A CN 200680030335 A CN200680030335 A CN 200680030335A CN 101243034 B CN101243034 B CN 101243034B
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- 239000013337 mesoporous metal-organic framework Substances 0.000 title 1
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 50
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 28
- 150000002894 organic compounds Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 7
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- 238000001354 calcination Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
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- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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Abstract
本发明涉及包含AlIII和至少一种至少二齿的化合物的多孔的金属-有机框架。所述至少一种至少二齿的化合物是六元芳族烃环A,该环A中一个或多个环碳原子可以被氮原子代替,并且该环具有三个取代基X且任选具有一个或多个选自R、NRR′、OR、SR、F、Cl和Br的取代基,其中R、R′各自独立地为氢、可任选被一个或多个氟原子取代的甲基或者可任选被一个或多个氟原子取代的乙基,以及每个X彼此独立地为C(=O)O-、C(=S)O-、C(=O)S-、C(=S)S-或其质子化形式。本发明还涉及制备所述框架的方法和该新的多孔金属-有机框架的用途。
Description
本发明涉及一种多孔的金属-有机框架以及它的制备方法和它的用途。
多孔的金属-有机框架是现有技术中已知的。
它们通常包含至少一种与至少一种金属离子配位的至少二齿的有机化合物。该类金属-有机框架(MOF)例如描述在US-A 5,648,508、EP-A 0 790253、M.O.Keefe,J.Sol.State Chem.152(2000),3-20;H.Li等人,Nature402(1999),276;M.Eddaoudi,Topics in Catalysis 9(1999),105-11 1;B.Chen等人,Science 291(2001),1021-1023,和DE-A 101 11 230中。
现有技术中研究的金属-有机框架具有多种用途。它们可用作例如物质的储存、分离或化学反应。尤其是,它们可用作催化剂载体或者用作催化剂。
在其它的用途研究中或者改善该类金属-有机框架的性能的研究中,已经测试了许多金属离子和至少二齿的有机化合物的联合。最近,也已经考虑其中金属离子是元素周期表中的主族元素的金属-有机框架。
T.Loiseau等人,Chem.Eur.J.10(2004),1373-1382描述了例如多孔的对苯二甲酸铝。然而,这具有较小尺寸的孔。其所处的范围也是已知并且对于基于其它金属如锌的其它金属-有机框架而言是常规的。这对这样的反应特别不利:其中较大体积的反应物在扩散受限的反应中反应。
Z.-Z.Lin等人,Eur.J.Inorg.Chem.2005,77-81描述了一种基于InIII-BTC(BTC=1,3,5-苯三甲酸)的框架。然而,以此方式获得的该框架即便有吸收性的话,也具有差吸收性。这对化合物(尤其是气体)的分离或储存领域中的应用特别不利。
因此一直需要提供具有至少部分优越于现有技术中的已知框架的性能的新金属-有机框架。
因此,本发明的目的是提供一种具有上面所述性能的多孔的金属-有机框架。
该目的通过一种包含至少一种与至少一种金属离子配位的至少二齿的有机化合物的多孔的金属-有机框架而实现,其中所述至少一种金属离子是AlIII,并且所述至少一种至少二齿的有机化合物是六元芳族烃环A,该环A中一个或多个环碳原子可以被氮原子代替,并且该环具有三个取代基X且任选具有一个或多个选自R、NRR′、OR、SR、F、Cl和Br的取代基,其中R、R′各自独立地为氢、可任选被一个或多个氟原子取代的甲基或者可任选被一个或多个氟原子取代的乙基,以及每个X彼此独立地为C(=O)O-、C(=S)O-、C(=O)S-、C(=S)S-或其质子化形式。
已经发现如上所述的框架具有较高比例的大体积孔(中孔)且同样具有较高的比表面积,这在如下所述的用途中产生优点。这一点特别令人吃惊,因为对于建立金属-有机框架而言,当铝被周期表中同一族的它的类似物铟代替时或者仅仅被两个基团X取代的有机化合物用于代替被三个基团X取代的有机化合物时,这些性能无法保留。这在有机化合物是均苯三甲酸根时尤其如此。
此外,本发明框架的X-射线衍射图案几乎没有显示出在5~30°(2θ)、尤其是5~12°范围内的作为上述现有技术中已知框架的特征峰的尖锐信号。
金属-有机框架包含至少一种为六元芳族烃环A的至少二齿的有机化合物,该环A中一个或多个环碳原子可以被氮原子代替,并且该环具有三个取代基X且任选具有一个或多个选自R、NRR′、OR、SR、F、Cl和Br的取代基,其中R、R′各自独立地为氢、可任选被一个或多个氟原子取代的甲基或者可任选被一个或多个氟原子取代的乙基,以及每个X彼此独立地为C(=O)O-、C(=S)O-、C(=O)S-、C(=S)S-或其质子化形式。其它的有机化合物(尤其是一种或多种单齿配体)也可在框架中出现。然而,优选首先提到的有机化合物的摩尔分数必须是框架中有机化合物总量的至少50%、更优选至少75%、特别优选至少90%。
环A优选是苯、吡啶、哒嗪、嘧啶、吡嗪或三嗪环。环A特别优选为苯。
而且,环A具有三个取代基X。这些是羧酸根和/或它们的硫代类似物。在框架中A上的至少部分羧酸根和/或硫代类似物可以质子化形式存在。
此外,环A可具有一个或多个其它的取代基。这些是官能团R、NRR′、OR、SR、F、Cl和Br,其中R和R′可彼此独立地为氢、甲基或乙基。所述甲基和乙基也可以为单氟代或多氟代的。然而,环A优选除了X外不含其它取代基。
有机化合物特别优选是1,2,3-、1,2,4-或1,3,5-苯三甲酸根或者其至少部分质子化的类似物。非常特别优选的是1,3,5-苯三甲酸根。
本发明的金属-有机框架包含孔,尤其是微孔和/或中孔。微孔定义为具有直径为2nm或更小的孔,中孔定义为直径为2~50nm的孔,在每种情形下均根据Pure Applied Chemistry 57(1985),第603-619页,尤其是第606页中给出的定义。微孔和/或中孔的存在可通过吸着测量进行检测,这些测量根据DIN 66131和/或DIN 66134测定金属-有机框架在77K下对氮气的吸收能力。
本发明的金属-有机框架优选的平均孔径为2~10nm,特别优选为3~9nm。特别优选的孔尺寸的离差不超过+/-5nm。而且,最经常存在的孔径优选为3~9nm。
根据Langmuir模型根据DIN 66135(DIN 66131,66134)计算,本发明金属-有机框架在呈粉末形式时的比表面积优选至少为800m2/g。该比表面积更优选至少为1000m2/g,特别优选至少为1300m2/g。该比表面积非常特别优选至少为1500m2/g。
优选至少50%的孔体积通过具有孔径为2~10nm的孔(中孔)形成。该孔体积的比例优选至少为65%,非常特别优选至少为80%。孔体积优选至少为0.8ml/g,更优选至少为1.1ml/g。
MOF成形体可具有低的比表面积。然而,其比表面积优选大于10m2/g,更优选大于50m2/g,甚至更优选大于500m2/g.
除了上述的孔以外,包含本发明的金属-有机框架的成形体还具有其尺寸分布可变的更大的孔。然而,优选大于50%、尤其是大于75%的总孔体积通过孔径为至多1000nm的孔构成。然而,大部分的孔体积优选通过来自两个直径范围的孔形成。因此进一步优选大于25%的总孔体积,尤其是大于50%的总孔体积通过100nm~800nm的直径范围的孔构成,和大于15%的总孔体积,尤其是大于25%的总孔体积通过至多10nm的直径范围的孔构成。孔分布可通过水银孔隙率测定法测定。
本发明进一步提供一种制备根据本发明的框架的方法,其包括至少一种金属化合物与至少一种可与金属离子配位的至少二齿的有机化合物反应的步骤,其中所述金属是AlIII,并且所述至少一种至少二齿的有机化合物是六元芳族烃环A,该环A中一个或多个环碳原子可以被氮原子代替,且该环具有三个取代基X且任选具有一个或多个选自R、NRR′、OR、SR、F、Cl和Br的取代基,其中R、R′各自独立地为氢、可任选被一个或多个氟原子取代的甲基或者可任选被一个或多个氟原子取代的乙基,以及每个X彼此独立地为C(=O)O-、C(=S)O-、C(=O)S-、C(=S)S-或其质子化形式。
上述反应优选在非水有机溶剂中在不大于2巴的压力(绝对压力)下搅拌进行。
上述压力更优选不大于1230毫巴(绝对压力)。甚至更优选反应在大气压下进行。
本发明的金属-有机框架还可以在作为溶剂的水中并添加碱进行制备。
然而,非水有机溶剂的使用使得可以免除使用碱。然而同样业可以加入碱。有机溶剂自身还可以作为碱。
当在合成中使用铝盐时,优选的起始原料是氯化铝或硝酸铝的水合物,特别优选氯化铝的水合物。
而且,用于制备本发明多孔的金属-有机框架的金属化合物可优选为非离子的和/或AlIII阳离子的抗衡离子可衍生自质子溶剂。适当选择的非离子化合物的使用使得可以避免金属在形成多孔的金属-有机框架的反应中以盐形式存在,并因此可以避免在除去金属盐的相应阴离子时的任何困难,只要没有其它干扰盐在反应中由金属化合物产生。如果抗衡离子是溶剂阴离子,当适当选择时,这可在反应后作为溶剂存在,该溶剂可与所用的非水有机溶剂相同或不同。在后者的情形下,优选该溶剂与非水有机溶剂至少部分混溶。
非离子化合物或金属阳离子的衍生自质子溶剂的抗衡离子可以是例如金属醇盐,例如甲醇盐、乙醇盐、丙醇盐、丁醇盐。氧化物或氢氧化物同样也是可行的。
非水有机溶剂优选是C1-6链烷醇、二甲基亚砜(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、甲乙酮(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、乙二醇、N-甲基吡咯烷酮(NMP)、γ-丁内酯、脂环族醇类如环己醇、酮类如丙酮或乙酰丙酮、环酮类如环己酮、环丁烯砜(Sulfolen)或其混合物。
C1-6链烷醇是具有1~6个碳原子的链烷醇。实例是甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、戊醇、己醇和其混合物。
任选卤代的C1-200链烷烃是具有1~200个碳原子并且其中一个或多个至所有的氢原子可以被卤素、优选氯或氟、尤其是氯替代的链烷烃。实例是氯仿、二氯甲烷、四氯甲烷、二氯乙烷、己烷、庚烷、辛烷和其混合物。
优选的溶剂是DMF、DEF和NMP。特别优选的是DMF。
术语″非水的″优选是指基于溶剂的总重量,具有的最大水含量为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%重量的溶剂。
在反应过程中的最大水含量优选为10%重量,更优选5%重量,甚至更优选1%重量。
术语″溶剂″包含纯溶剂和不同溶剂的混合物。
而且,至少一种金属化合物与至少一种至少二齿的有机化合物的反应的工艺步骤之后优选接着进行煅烧步骤。此处设定的温度通常为大于250℃,优选为300~400℃。
煅烧步骤可除去存在于孔中的配体。
此外或作为可选方案,从多孔的金属-有机框架的孔中除去配体可通过用非水溶剂处理形成的框架来进行。此处,配体以″萃取方法″的方式除去,和如果合适的话,在该框架中被溶剂分子替代。如果有煅烧步骤的话,萃取方法优选在该煅烧之前进行。
上述处理优选进行至少30分钟,可通常进行至多两天。这可在室温或升高的温度下进行。优选在升高的温度下进行,例如在至少40℃、优选60℃下进行。其它优选的是反应在溶剂的沸点下(回流)进行。
上述处理可在简单的容器中通过制浆并搅拌该框架进行。也可以使用萃取装置如Soxlet 10装置,尤其是工业萃取装置。
合适的溶剂是上述提到的那些,即C1-6链烷醇、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、环丁烯砜(Sulfolen)、乙二醇、NMP或其混合物。
用于萃取的溶剂可以与用于至少一种金属化合物与至少一种至少二齿的有机化合物的反应的溶剂相同或不同。尤其是,它在用于萃取的溶剂是无水时不是绝对需要的。
优选的萃取剂是甲醇、乙醇、丙酮、MEK或其混合物。特别优选甲醇。
本发明进一步提供一种制备本发明金属-有机框架的方法,其中AlIII通过阳极氧化用于反应。
通过电化学路线制备金属-有机框架描述在WO-A 2005/049892中。
本发明的金属-有机框架可以粉末形式存在或以聚集体形式存在。该框架可以其本身使用或将该框架转化成成形体。此处优选的方法是挤出或压片。在制备成形体中,该框架可包含制备过程中添加的其它材料如粘合剂、润滑剂或其它添加剂。对于该框架同样也可以包含其它的组分,例如吸附剂如活性炭或类似物质。
这些成形体可能的几何形状基本上没有限制。实例尤其是丸片如盘状丸片、丸剂、球、颗粒、挤出物如棒状挤出物、蜂巢、栅格和空心体。
原则上所有合适的方法都可以用于制备这些成形体。尤其是优选下述方法:
-单独或与至少一种粘合剂和/或至少一种浆糊剂和/或至少一种模板化合物捏合/盘磨框架以形成混合物;通过至少一种合适的方法(例如挤出)成形所得的混合物;任选洗涤和/或干燥和/或煅烧该挤出物;任选修整。
-将框架施加到至少一种任选多孔的载体材料上。所得的材料然后可通过上述方法进一步加工以形成成形体。
-将框架施加到至少一种任选多孔的底材上。
捏合/盘磨和成形可通过任何合适的方法如例如UllmannsEnzyklopdie der Technischen Chemie,第4版,第2卷,第313页及随后页(1972)中所述进行。
例如,捏合/盘磨和/或成形可优选通过活塞压机、辊压机在存在或不存在至少一种粘合剂材料的情况下,配混、压丸、压片、挤出、共挤出、发泡、纺丝、涂布、造粒(优选喷雾造粒)、喷雾、喷雾干燥或这些方法中的两种或更多种的组合。
非常特别优选的是制备丸片和/或片剂。
捏合和/或成形可在升高的温度下(例如在室温~300℃),和/或在升高的压力(例如在大气压至几百巴),和/或在保护气氛(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)的存在下进行。
根据其它实施方案,捏合和/或成形在添加至少一种粘合剂下进行,所用的粘合剂原则上可以是确保用于捏合和/或成形组合物的希望粘度的任何化学化合物。因此出于本发明的目的,粘合剂可以是增粘或降粘的化合物。
优选的粘合剂包括例如氧化铝或包含氧化铝的粘合剂,如描述在例如WO 94/29408中的那些,如描述在例如EP 0 592 050 A1中的二氧化硅,如描述在例如WO 94/13584中的二氧化硅和氧化铝的的混合物,如描述在例如JP 03-037156 A中的粘土矿物(例如蒙脱石、高岭土、膨润石、埃洛石(Hallosit)、地开石、珍珠陶土和蠕陶土),如描述在例如EP 0 102 544 B1中的烷氧基硅烷(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,如果合适的话,除了上述化合物以外也可以例如使用有机化合物和/或亲水聚合物(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/或聚环氧乙烷。
作为浆糊剂,优选尤其使用水或至少一种醇,例如具有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),或者水和至少一种前述提到的醇的混合物或多元醇(如乙二醇),优选水混溶性的多元醇,其单独使用或作为与水和/或至少一种提到的一元醇的混合物使用。
可用于捏合和/或成形的其它添加剂尤其是胺或胺的衍生物(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)。这类其它添加剂描述在例如EP 0 389 041 A1、EP 0200 260 A1或WO 95/19222中。
在成形和捏合中添加添加剂(如模板化合物、粘合剂、浆糊剂、增粘物质)的顺序原则上不重要。
在本发明方法的其它优选实施方案中,将通过捏合和/或成形获得的成形体进行至少一种通常在25~300℃、优选50~300℃、特别优选100~300℃的温度下进行的干燥操作。它同样可以在减压下或在保护气氛下或通过喷雾干燥进行干燥。
在特别优选的实施方案中,至少一种作为添加剂添加的化合物在该干燥操作过程中至少部分从成形体中除去。
本发明进一步提供本发明多孔的金属-有机框架用于吸收至少一种物质以为了将其储存、分离、控制释放或化学反应的用途,还作为载体材料例如作为金属、金属氧化物、金属硫化物或其它框架结构的载体材料的用途,以及在催化中的用途。
上述至少一种物质可以是气体或液体。该物质优选是气体。
对本发明而言,术语″气体″和″液体″简化使用,但气体混合物和液体混合物或液体溶液同样包含在术语″气体″或″液体″中。
优选的气体是氢气、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、胺类、甲醛、稀有气体(尤其是氦气、氖气、氩气、氪气和氙气)。
特别优选本发明的金属-有机框架在储存氢气中的用途和在与大体积反应物的扩散受限的反应中的用途。还优选储存在其它金属-有机框架或其它多孔材料如沸石中通常不能储存或不能满意储存的较大物质。实例是染料(颜料)或小的蛋白质,如酶。
上述反应可以是氢化、液相中的氧化、液相中的易位、烷氧基化、醚化、酯化、烷基化、水解或可比反应。扩散受限的反应中的典型大反应物可例如是多元醇、取代苯、染料或其它化合物。
上述至少一种物质如上述也可以是液体。该类液体的实例是消毒剂、无机或有机溶剂、燃料(尤其是汽油或柴油)、液压机液体、散热器液体、制动液或油(尤其是机油)。该液体也可以是卤代的脂族或芳族、环状或无环烃或其混合物。尤其,该液体可以是丙酮、乙腈、苯胺、苯甲醚、苯、苯甲腈、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、二甲基亚砜、二烷、冰醋酸、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、甲乙酮、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、三氯乙烷、三乙胺、三甘醇、三甘醇二甲醚、水或其混合物。
而且,上述至少一种物质可以是有气味的物质。
有气味的物质优选是包含至少一种元素氮、磷、氧、硫、氟、氯、溴或碘的挥发性的有机或无机化合物,或者是不饱和或芳族烃或者是饱和或不饱和醛或酮。更优选的元素是氮、氧、磷、硫、氯、溴,特别优选是氮、氧、磷和硫。
尤其是,有气味的物质是氨、硫化氢、硫氧化物、氧氮化物、臭氧、环状或无环胺类、硫醇类、硫醚类和醛类、酮类、酯类、醚类、酸类或醇类。特别优选是氨、硫化氢、有机酸类(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),还有包含氮或硫的环状或无环的烃以及饱和或不饱和的醛类,如己醛、庚醛、辛醛、壬醛、癸醛、辛烯醛或壬烯醛,尤其是挥发性的醛类(如丁醛、丙醛、乙醛和甲醛),还有燃料如汽油、柴油(组分)。
有气味的物质也可以是例如用于制备香水的香料。香料或可释放该类香料的油的实例是:精油、罗勒油、香叶油、薄荷油、卡南加油、小豆蔻油、熏衣草油、胡椒薄荷油、肉豆蔻油、春黄菊油、桉树油、迷迭香油、柠檬油、梨莓油、橙油、香柠檬油、麝香葡萄鼠尾草油、胡荽油、柏树油、1,1-二甲氧基-2-苯乙烷、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、氧化玫瑰、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、乙酸茴香酯、环己氧基乙酸烯丙酯、乙基里哪醇、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、四氢藏花乙酯、香叶基腈、顺式-3-己烯-1-醇、顺式-3-己烯基乙酸酯、顺式-3-己烯基.甲基碳酸酯、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、[5.2.1.0]三环癸烷甲酸乙酯、香叶醇、香茅醇、柠檬醛、里哪醇、乙酸里哪醇酯、紫罗兰酮、苯乙醇和其混合物。
对本发明而言,挥发性的有气味的物质优选具有300℃的沸点或低于300℃的沸点。有气味的物质更优选是易挥发性的化合物或混合物。有气味的物质特别优选具有250℃的沸点或低于250℃的沸点,更优选低于230℃的沸点,特别优选低于200℃的沸点。
同样优选有气味的物质具有高挥发性。蒸气压可以用作挥发性的量度。对本发明而言,挥发性的有气味的物质优选具有大于0.001kPa的蒸气压(20℃)。有气味的物质更优选是易挥发性的化合物或混合物。有气味的物质特别优选具有大于0.01kPa的蒸气压(20℃),更优选大于0.05kPa的蒸气压(20℃)。特别优选的有气味的物质具有大于0.1kPa的蒸气压(20℃)。
实施例
实施例1:Al-BTC MOF的大气压制备/表征
在玻璃烧瓶中将7.8g的1,3,5-苯三甲酸和22.9g的Al(NO3)3*9H2O悬浮在520.5g的DMF中,并在130℃下回流搅拌4天。冷却后,滤出固体,用2×100ml的DMF和4×100ml的甲醇洗涤并在真空干燥箱中在200℃下干燥16小时。随后将样品在马弗炉(100l/h的空气)中在330℃下后处理3天(以大约75℃/h加热)。获得8.4g表面积为1791m2/g(通过Langmuir方法使用N2测定)的Al-BTC MOF。X-射线衍射(XRD)图案显示在图1中。对于所有的衍射图案,将样品在N2钟罩下未研磨地制备并涂布有Styroflex薄膜以使其密封。样品的衍射图案使用Cu阳极以0.02°的步宽和3.6秒的步速率在Siemens的D5000仪器上记录。该衍射图案显示,对MOF不典型,几乎没有任何反射,并且具有非常无定形的外观。孔分布显示在图8中。在图8中,孔体积V(ml/g)描述为孔径d(nm)的函数。此处,中孔的不寻常的高比例(对于MOF)是明显的。
实施例2:Al-BTC MOF的水热制备/表征
将2.46g的1,3,5-苯三甲酸和8.7g的Al(NO3)3*9H2O悬浮在33mL的DMF中。将该混合物在Berghoff高压釜(特氟隆衬里)中在170℃下加热1天。冷却后,滤出固体,用DMF和甲醇洗涤并在真空干燥箱中在200℃下干燥5小时。随后将样品在马弗炉(100L/h的空气)在330℃下后处理3天(以大约75℃/h加热)。获得2.5g表面积为1516m2/g(通过Langmuir方法使用N2测定)的Al-BTC MOF。XRD显示在图2中。该衍射图案显示,对MOF不典型,几乎没有任何反射并具有非常无定形的外观。
透射电镜照片(TEM)显示在图3和图4中。这些清楚表明存在结晶性亚结构。
透射电镜照片通过将样品与少量的乙醇混合并在2个玻璃显微镜载片之间摩擦来记录。这于是薄薄地铺展开,并用已经施加了Formvar/碳薄膜的试样载体栅格将其轻轻地擦掉。显微照片使用来自FEI的200kV FEGTEM记录。仪器名称:Tecnai G2。
实施例3:Al-BTC MOF的制备/表征
在玻璃烧瓶中将15.6g的1,3,5-苯三甲酸和45.8g的Al(NO3)3*9H2O悬浮在520.5g的DMF中,并在130℃下回流搅拌4天。冷却后,滤出固体,用2×100ml的DMF和4×100ml的甲醇洗涤并在真空干燥箱中在200℃下干燥16小时。随后将样品在马弗炉(100l/h的空气)在330℃下后处理3天(以大约75℃/h加热)。获得17.7g表面积为1696m2/g(通过Langmuir方法使用N2测定)的Al-BTC MOF。衍射图案(XRD)与实施例2没有明显不同。
实施例4:Al-BTC MOF的制备/表征
在玻璃烧瓶中将7.8g的1,3,5-苯三甲酸和14.7g的AlCl3*6H2O悬浮在520.5g的DMF中,并在130℃下回流搅拌4天。冷却后,滤出固体,用2×100ml的DMF和4×100ml的甲醇洗涤并在真空干燥箱中在200℃下干燥16小时。随后将样品在马弗炉(100l/h的空气)在330℃下后处理3天(以大约75℃/h加热)。获得10.9g表面积为1451m2/g(通过Langmuir方法使用N2测定)的Al-BTC MOF。衍射图案(XRD)显示在图5中。
实施例5:Al-BTC MOF的制备/表征
在玻璃烧瓶中将23.1g的1,3,5-苯三甲酸和29.4g的AlCl3*6H2O悬浮在520.5g的DMF中,并在130℃下回流搅拌4天。冷却后,滤出固体,用2×100ml的DMF和4×100ml的甲醇洗涤并在真空干燥箱中在200℃下干燥16小时。随后将样品在马弗炉(100l/h的空气)在330℃下后处理3天(以大约75℃/h加热)。获得12.3g表面积为2033m2/g(通过Langmuir方法使用N2测定)的Al-BTC MOF。衍射图案显示在图6中。
实施例6:Al-BTC MOF的制备/表征
在玻璃烧瓶中将15.6g的1,3,5-苯三甲酸和29.4g的AlCl3*6H2O悬浮在520.5g的DMF中,并在130℃下回流搅拌4天。冷却后,滤出固体,用2×100ml的DMF和4×100ml的甲醇洗涤并在真空干燥箱中在200℃下干燥16小时。随后将样品在马弗炉(100l/h的空气)在330℃下后处理3天(以大约75℃/h加热)。获得20.1g表面积为1898m2/g(通过Langmuir方法使用N2测定)的Al-BTC MOF。衍射图案显示在图7中。
实施例7:在Al-BTC MOF中储存氢气
将314mg来自实施例1的框架首先在200℃下抽空。然后借助于Quantachrome Autosorb 1仪器在77K下吸收氢气。在p/p0=6.5*10-3获得大约100ml/g的氢气吸收。
Claims (12)
1.一种包含至少一种与AlIII配位的至少二齿的有机化合物的多孔的金属-有机框架,其中所述至少一种至少二齿的有机化合物是六元芳族烃环A,该环A中一个或多个环碳原子可以被氮原子代替,并且该环具有三个取代基X且任选具有一个或多个选自R、NRR′、OR、SR、F、Cl和Br的取代基,其中R、R′各自独立地为氢、可任选被一个或多个氟原子取代的甲基或者可任选被一个或多个氟原子取代的乙基,以及每个X彼此独立地为C(=O)O-、C(=S)O-、C(=O)S-、C(=S)S-或其质子化形式,其特征在于该金属-有机框架呈粉末形式时具有的根据Langmuir方法测定的比表面积至少为800m2/g。
2.根据权利要求1的框架,其中A是苯、吡啶、哒嗪、嘧啶、吡嗪或三嗪。
3.根据权利要求1或2的框架,其中所述至少一种至少二齿的有机化合物是1,3,5-、1,2,3-、1,2,4-苯三甲酸根或其质子化形式。
4.根据权利要求1或2的框架,其具有的所述至少一种至少二齿的有机化合物的摩尔分数是框架中出现的单齿有机化合物和所述至少二齿的有机化合物的总量的至少50%。
5.根据权利要求1或2的框架,其中至少50%的孔体积通过孔径为2~10nm的孔形成。
6.根据权利要求1或2的框架,其孔体积至少为0.8mL/g。
7.根据权利要求1或2的框架,其呈粉末形式时具有的根据Langmuir方法测定的比表面积至少为1000m2/g。
8.一种制备根据权利要求1的框架的方法,其包括AlIII化合物与至少一种可与AlIII配位的至少二齿的有机化合物反应的步骤,其中所述至少一种至少二齿的有机化合物是六元芳族烃环A,该环A中一个或多个环碳原子可以被氮原子代替,且该环具有三个取代基X且任选具有一个或多个选自R、NRR′、OR、SR、F、Cl和Br的取代基,其中R、R′各自独立地为氢、可任选被一个或多个氟原子取代的甲基或者可任选被一个或多个氟原子取代的乙基,以及每个X彼此独立地为C(=O)O-、C(=S)O-、C(=O)S-、C(=S)S-或其质子化形式。
9.根据权利要求8的方法,其中在反应后将所形成的框架用有机溶剂后处理和/或煅烧。
10.根据权利要求8或9的方法,其中AlIII通过阳极氧化用于反应。
11.根据权利要求1的框架用于吸收至少一种物质以为了将其储存、分离、控制释放或化学反应的用途,还作为载体材料的用途。
12.根据权利要求11的用途,用于储存氢气。
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PCT/EP2006/065346 WO2007023119A1 (de) | 2005-08-22 | 2006-08-16 | Mesoporöses metallorganisches gerüstmaterial |
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KR20080038191A (ko) | 2008-05-02 |
DE102005039654A1 (de) | 2007-03-01 |
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ATE489353T1 (de) | 2010-12-15 |
JP2009504797A (ja) | 2009-02-05 |
US20080188677A1 (en) | 2008-08-07 |
JP5455367B2 (ja) | 2014-03-26 |
CN101243034A (zh) | 2008-08-13 |
CA2618869A1 (en) | 2007-03-01 |
KR101423784B1 (ko) | 2014-07-25 |
WO2007023119A1 (de) | 2007-03-01 |
EP1917228A1 (de) | 2008-05-07 |
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