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CN101421034B - 用于水分吸附和脱附的吸附剂 - Google Patents

用于水分吸附和脱附的吸附剂 Download PDF

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CN101421034B
CN101421034B CN2007800135115A CN200780013511A CN101421034B CN 101421034 B CN101421034 B CN 101421034B CN 2007800135115 A CN2007800135115 A CN 2007800135115A CN 200780013511 A CN200780013511 A CN 200780013511A CN 101421034 B CN101421034 B CN 101421034B
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CN101421034A (zh
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张钟山
郑成和
黄璄圭
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Korea Research Institute of Chemical Technology KRICT
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Abstract

本发明涉及一种利用具有高比表面积并且具有分子或纳米尺度孔窗尺寸的多孔无机-有机杂化材料得到的吸附剂。具体地说，本发明涉及一种水分吸附剂，该水分吸附剂即使在低于100℃时也能轻易吸附-脱附，其吸附量高，并且当被加热到低于100℃时也表现出高的脱附量。本发明的吸附剂可用于加湿器、除湿器、冷却器和加热器。本发明亦涉及到一种使用所述吸附剂来控制湿度的技术。

Description

用于水分吸附和脱附的吸附剂
技术领域
本发明涉及一种在低于100℃时能轻易吸附和脱附水分，并且吸附量在吸附条件和脱附条件下相差很大的吸附剂。更具体而言，本发明涉及一种利用具有纳米尺度孔窗尺寸和非常大的孔隙体积与比表面积的多孔无机-有机杂化材料得到的吸附剂。
背景技术
能够吸附和脱附水分的吸附剂具有多种用途。举例来说，除湿器可以利用在低温条件下吸水而在高温加热条件下脱水的吸附剂。此外，当吸附剂被用于加热器中时，加热器可以在高温时释放出在低温时从外界环境吸附的水分，从而像加湿器一样加湿。同样的，加入了吸附剂的冷却器也可以在低温条件下吸水来降低房间的湿度。其吸收的水分可以通过高温加热而被释放到外界。应用这些理念的空调机和湿度控制器(恒湿器)在美国专利6978635、6959875与6675601中被提出。但是，对于在这些设备中使用的吸附剂并没有详细的说明。提到了硅胶、沸石或者离子交换剂被用在这些设备中，或者只是陈述了将吸附剂用于这些设备。而且，这些吸附剂由于具有吸附量小和脱附温度高于100℃的缺点，导致运行成本的升高。
因此，非常需要研发一种即使在低温下也能脱附水分，并且吸附量和脱附后的残留水量相差很大的吸附剂。但是，当吸附量很高时，往往存在脱附困难的问题；当吸附量小的时候，吸附量和脱附后的残留水量之差又很小。通过确认使用一种具有非常大的比表面积的无机-有机杂化材料，吸附量大，并且大部分吸附的水分能在100℃以下脱附，从而完成了本发明。
在本发明中，用于水分吸附剂的无机-有机杂化材料可以定义为一种由中心金属离子和配位到中心金属离子的有机配体形成的多孔配位化合物。该无机-有机杂化材料在框架结构中同时包含有机物质和无机物质，其代表一种有着分子尺寸或者纳米尺寸的孔隙结构的晶态化合物。无机-有机杂化材料是一个很宽泛的术语，一般被称作多孔配位聚合物(Angew.Chem.Int.Ed.，43，2334，2004)或者金属-有机框架物(Chem.Soc.Rev.，32，276，2003)。最近，对此类材料的研究通过分子配位键和材料化学之间的组合而有了新进展，而且最近一直在积极地研究这些材料，因为这些材料因其高比表面积和分子尺度或者纳米量级的孔隙而可以用作多用途的纳米材料。
这些材料可以有多种方法合成。通常的合成方法包括室温溶剂扩散，在水溶剂存在的情况下的高温水热合成，或者使用有机溶剂的溶剂热合成(Microporous Mesoporous Maters.，73，15，2004；Accounts of ChemicalResearch，38，217，2005)。
类似于包括沸石或者介孔材料在内的无机多孔材料的合成，无机-有机杂化材料的合成可以如下实施：在水或者合适的溶剂处在比合成中使用的溶剂的沸点更高的温度的条件下，在自生压力下进行。换句话说，类似于沸石或者介孔材料，无机-有机杂化材料是把反应物质装入比如高压釜等高压反应器后在高温条件下持续数天而合成得到的。提供高温的热源一般是传统的电加热。比如说，一个装有反应前体(包括金属盐、有机配体和水或者其他溶剂)的高压釜，用电加热器或者电热烘箱在恒定温度加热。但是，先前的用电加热的技术方案由于其反应时间长，并不经济。而且，这种方法无法提供尺寸小于500纳米或者更优选小于100纳米的无机-有机杂化材料，因为当反应时间缩短以获得小晶体颗粒时，会得到非晶态的无机-有机杂化材料。
因此，在本发明中，为了克服上述的问题，以微波作为加热源而获得无机-有机杂化材料。因为微波加热可以得到小颗粒，当被用作吸附剂时，这种小颗粒具有易扩散的优点。而且，这种小颗粒容易制成薄膜(thinfilm)、厚膜(thick film)或者膜片(membrane)。另一方面，微波加热合成可以提高水分吸附剂的性能，因为吸附剂的亲水性和疏水性都得到了提高。所以，无机-有机杂化材料可以在将包含金属盐、有机配体和如水或有机溶剂等溶剂的前体密封之后在自生压力下使用微波加热而得到。而且，无机-有机杂化材料可由微波加热连续合成。
发明内容
技术问题：
因此，本发明的目的是研发一种对于水有高吸附量，并且在较低的温度下容易脱附水分的吸附剂；以及研发一种使用无机-有机杂化材料的具有出色的吸附量和吸附特性的吸附剂。所以，本发明的目的就是研发容易吸附和脱附水分的吸附剂，并使用如此得到的吸附剂来控制湿度。并且，本发明的另一目的是提供该吸附剂的制备方法。
技术方案：
本发明涉及一种水分吸附剂，特别是使用有着纳米尺度孔隙的多孔无机-有机杂化材料的吸附剂。
本发明通过使用即使在低温也能轻易脱水并且高温吸附量与低温吸附量相差很大的无机-有机杂化材料，提供了一种吸附剂。
本发明的吸附剂具有大于1000m2/g的比表面积，大于1.0mL/g的孔隙体积，孔窗尺寸为0.5nm～2nm，并且吸附剂的框架结构由有机物质与无机物质组成。优选的是吸附剂具有的(100℃吸附量)/(室温吸附量)的比值小于0.2。
如果比表面积和孔隙体积小于上文所述的数值，则作为水分吸附剂的效率很低。虽然效率随着比表面积和孔隙体积的增大而增大，但一般方法能达到的实际极限是约10000m2/g的比表面积与10mL/g的孔隙体积。如果孔窗尺寸小于0.5nm，则吸附和脱附所需时间会很长，因为吸附和脱附的速度较低。相反地，如果孔窗尺寸大于2nm，则吸附剂的结构变得不稳定，吸附剂也会有不稳定的缺点。
此外，一种先前报道的吸附剂具有在低温下脱附效率低的缺点，因为在100℃以下脱附的吸附水少于50％，而且其(100℃吸附量)/(室温吸附量)的比值在0.5到1.0之间。另一方面，本发明的吸附剂在100℃以下脱附了至少80％的吸附水。
具体而言，本发明的吸附剂是金属对苯二甲酸盐类物质，所述金属为铬、铝、铁等。
本发明的吸附剂的制备方法是将金属前体、选自苯二甲酸、苯三甲酸等的有机物质与溶剂添加到反应器中；密封反应器；之后将反应器加热至高温。反应温度由微波加热保持，而反应压力由自生压力保持。
附图说明
图1与图2展示了实施例中得到的对苯二甲酸铬的扫描电子显微镜(SEM)图像。图1与图2分别是从实施例1与实施例3得到的对苯二甲酸铬的扫描电子显微镜图像。
图3展示了实施例中得到的对苯二甲酸铬的X射线衍射(XRD)图样。图3a与图3b分别是从实施例2与实施例3得到的对苯二甲酸铬的X射线衍射图样。
图4展示了从实施例2得到的对苯二甲酸铬的氮气与苯吸附等温曲线。
图5展示了从实施例3得到的对苯二甲酸铬制成的吸附剂的水分脱附特性。该图显示大部分吸附的水分在低于70℃的温度脱附。
具体实施方式
本发明将被更详细的描述如下：
用作本发明的吸附剂的无机-有机杂化材料由包括以下步骤的方法合成：
1.制备包括混合金属前体、能被用作配体的有机物质和溶剂的反应混合物的步骤；和
2.用频率在0.3GHz～300GHz的微波进行辐射从而加热至100℃之上的步骤。
由以上方法合成的无机-有机杂化材料具有纳米级别的孔窗尺寸，并且粒径均一。该无机-有机杂化材料的平均粒径小于500nm，优选为10nm～500nm，更优选为小于200nm，进一步优选为小于100nm，最优选为小于50nm。本发明得到的无机-有机杂化材料处于粉末、厚膜、薄膜或膜片的形态。
膜片或薄膜状的多孔无机-有机杂化材料可以通过将基质浸泡在以上提到的反应混合物中，之后进行微波辐射来合成。
本发明的无机-有机杂化材料以微波作为加热源进行合成，频率为300MHz～300GHz的任何微波都适用于加热该反应混合物。使用已被广泛商用的频率在2.45GHz或0.915GHz的微波是简单而且有效的。
金属物质，作为多孔无机-有机杂化材料的成分之一，可以是如Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Mg、Ca、Sr、Ba、Sc、Y、Al、Ga、In、Tl、Si、Ge、Sn、Pb、As、Sb和Bi等任意的金属材料。容易形成配位化合物的过渡金属适用于本发明。在过渡金属中，Cr、Ti、V、Mn、Fe、Co、Ni和Cu更加合适，Cr是最合适的。容易形成配位化合物的主族元素和镧系元素也可被用作金属成分。在主族元素中Al和Si是合适的金属成分，而Ce和La是镧系元素中合适的金属成分。金属单质本身或者任何的含有金属成分的化合物都可以用作金属前体。
无机-有机杂化材料的另一个成分是有机物质，被称为连接物。任何有机分子，只要它含有能够配位到金属中心的官能团，都可以作为多孔无机-有机杂化材料的另一个成分，即连接物。能够配位到金属的官能团为：羧酸基、羧酸根、氨基(-NH2)、亚氨基、酰胺基(-CONH2)、磺酸基(SO3H)、磺酸根(-SO3 -)、二硫代甲酸基(-CS2H)、二硫代甲酸根(-CS2 -)、吡啶、吡嗪等。有多个配位点的多齿配位体，例如二齿配体与三齿配体，适合用来制备稳定的多孔无机-有机杂化材料。只要具有配位点，诸如阳离子化合物、阴离子化合物和中性化合物等任何的有机分子都是适用的，无论它带有何种电荷。举例来说，例如联吡啶和吡嗪等中性分子和比如对苯二甲酸根、萘二甲酸根、苯三甲酸根、戊二酸根与丁二酸根等阴离子分子都是适用的。如对苯二甲酸根等含有芳香环的离子、如甲酸根等不含有芳香环的离子和如环己基二甲酸根等含有非芳香环的离子都是合适的羧酸根阴离子。不仅仅是含有配位点的有机物质，而且含有能在反应条件下转换为适合配位的状态的潜在位点的有机物质，都可以用作有机前体。举例来说，例如对苯二甲酸等有机酸就可以使用，因为在反应条件下它可以被转换为对苯二甲酸根从而配位到金属中心。典型的有机物质包括苯二甲酸、萘二甲酸、苯三甲酸、萘三甲酸、吡碇二甲酸、联吡碇二甲酸、甲酸、乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、环己基二甲酸等等。上述酸的阴离子也是适用的。吡嗪和联吡啶是可以被用作有机配体的中性物质。两种以上的上述有机部分的混合物也是适用的。
对苯二甲酸铬、对苯二甲酸钒、对苯二甲酸铁是典型的多孔无机-有机杂化材料的实例，而对苯二甲酸铬则是为人熟知的多孔无机-有机杂化材料之一。具有巨大比表面积与较大的孔窗尺寸的立方晶系的对苯二甲酸铬具有极大的商业吸引力，并且具有高效率。
除了金属组分和有机配体，合适的溶剂也是合成多孔无机-有机杂化材料所必需的。对于溶剂来说，水、如甲醇、乙醇和丙醇等醇类、如丙酮和丁酮等酮类以及如己烷、庚烷、辛烷等烃类都是适用的。上述溶剂的混合物也可使用，而水是最适合的溶剂。
有时，如HF等含氟物质是合成无机-有机杂化材料所必需的。氟化氨、LiF、NaF、KF、CsF等也可以使用。因为对合成无机-有机杂化材料而言一般优选酸性条件，所以HF是优选的含氟成分。
反应温度没有任何实际限制。但是，温度高于100℃比较合适，100～250℃的温度更合适，150～220℃的温度最合适。当反应温度过低时，反应速率过低，生产率也过低。而反应温度过高时，因为反应速率过快，会形成密实无孔的物质和通过副反应产生杂质。而且，当反应温度过高时，制造高压反应器的成本很高。反应压力没有任何限制条件。在反应温度和自生压力条件下进行反应是比较方便的。并且，可以通过加入惰性气体，比如氮气或氦气，使反应在增压的情况下进行。
反应可以在分批模式或者连续模式下进行。分批模式操作适合小规模的生产，因为单位时间的生产量低；而连续模式适用于多孔无机-有机杂化材料的大规模生产，虽然投资成本高。分批模式操作的反应时间为1分钟～8小时。当反应时间过长时，副产品会混杂在产品当中，并且因为晶体生长，造成很难得到纳米颗粒。相反地，反应时间过短时，转化率就低。反应时间在1分钟到60分钟之间更为合适。对于连续反应而言，停留时间在1分钟到60分钟之间是合适的。停留时间过长时，副产品会混杂在产品当中，很难得到纳米颗粒。停留时间较长时，单位时间的生产量低。相反地，停留时间较短时，反应转化率就低。停留时间在1分钟到20分钟之间更为合适。分批模式反应期间，可以对反应混合物进行搅拌，100rpm～1000rpm的搅拌速度是合适的。反应可以在静态进行，并且静态的反应因其低投资成本和易操作性而更为合适。
因为使用微波的反应速度非常快，并且均匀的或者成核的反应混合物有利于反应，所以可取的是对预处理过的反应混合物进行微波辐射。当对未经预处理的反应混合物进行微波辐射时，即使工艺会简化，但反应速度低，或者会有杂质混入，或者晶体尺寸不均匀。
预处理可由超声波处理或者剧烈混合来完成。预处理温度适于在室温与反应温度之间。预处理温度太低会造成预处理效果太小，而预处理温度太高，则需要非常复杂的预处理用设备，而且可能伴生杂质。长于1分钟的预处理时间是适合的。对于超声波预处理来说，预处理时间在1分钟与5小时之间更为合适，而对于剧烈搅拌来说，5分钟以上的预处理更为合适。如果预处理时间过短，则预处理效果太小，而预处理时间过长，预处理的效率又较低。使用超声波的预处理在预处理时间和反应混合物的均匀性方面是有效的。
而且，多孔无机-有机杂化材料的厚膜、薄膜或膜片可以通过将基质浸泡在以上提到的反应混合物中之后进行微波辐射来制得；也可以通过包括在制备多孔无机-有机杂化材料之后进行丝网印刷的利用粘合剂的方法来制得。多孔无机-有机杂化材料的厚膜、薄膜或膜片对于吸附剂与水分之间的相互作用的容易性来说是必要的，使用它们可以大幅改善吸附和脱附的性能。基质可以是氧化铝、硅、玻璃、氧化铟锡(ITO)、氧化铟锌(IZO)或者耐热聚合物。任何的经表面处理的上述基质更为合适。
以下的具体的实施例是以描述本发明为目的的，它们不应该被解释为对如所附权利要求所限定的本发明的范围的限制。
实施例1(Cr-BDCA-1)
以Cr(NO3)3·9H2O，、HF水溶液、1，4-苯二甲酸(BDCA)与水，配制摩尔组成为Cr∶HF∶BDCA∶H2O＝1∶1∶1∶275的反应混合物。将该反应混合物装入特氟隆反应器中，并用超声波预处理一分钟，以使混合物均匀化并促进成核。将装有预处理过的反应混合物的特氟隆反应器放入微波烘箱(CEM，Mars-5)中。在微波辐射(2.45GHz)下在3分钟内反应温度到达210℃，然后，在该反应温度在微波辐射下使合成进行1分钟。通过冷却至室温、离心、用去离子水洗涤然后干燥从而回收多孔无机-有机杂化材料，即对苯二甲酸铬，缩写Cr-BDCA-1。XRD结果显示出位于3.3、5.2、5.9、8.5、9.1(2θ)的特征衍射峰，确认得到的是立方晶系的对苯二甲酸铬。图1显示了本实施例中得到的Cr-BDCA-1的SEM(扫描电子显微镜)图像，其显示了具有1.3nm的平均孔窗尺寸的晶体，该晶体大小非常均一，为30nm～40nm。这些结果说明，通过充分预处理和微波辐射，可以在短反应时间内非常高效地制得多孔无机-有机杂化材料。
实施例2(Cr-BDCA-2)
进行多孔无机-有机杂化材料的合成，除了省略超声预处理和反应时间改为2分钟外，其他条件与实施例1相同。图3a的X射线衍射图谱显示得到的材料的结构与实施例1相同，SEM图像确认制得的多孔无机-有机杂化材料具有40nm～50nm的均一尺寸。该多孔无机-有机杂化材料在真空条件下在150℃进行抽气后，在相对压力0.5的条件下(P/Po＝0.5，液氮温度)，具有的氮气吸附量为1050mL/g或者46.9mmol/g。并且，该多孔无机-有机杂化材料在30℃和相对压力为0.5(P/Po＝0.5)的条件下，具有较高的苯吸附量(16mmol/g)。此时，该多孔无机-有机杂化材料的平均孔窗尺寸为1.3nm。氮气与苯的吸附等温曲线示于图4中。
本实施例的无机-有机杂化材料的比表面积与孔隙体积分别为3700m2/g和1.9mL/g。所以，本实施例合成的纳米晶体多孔无机-有机杂化材料，即对苯二甲酸铬，具有非常高的吸附量，晶态的多孔无机-有机杂化材料可被成功用作吸附剂、催化剂、催化剂载体等。
实施例3(Cr-BDCA-3)
进行多孔无机-有机杂化材料的合成，除了反应时间改为40分钟外，其他条件与实施例2相同。图3b的X射线衍射图谱显示得到的材料的结构与实施例1相同，SEM图像(图2)确认制得的多孔无机-有机杂化材料具有200nm的均一尺寸，尽管晶体尺寸已经比实施例2中的尺寸增大了许多。此材料的比表面积与孔隙体积分别为3900m2/g和2.1mL/g。
实施例4(Fe-BDCA-1)
进行多孔无机-有机杂化材料的合成，除了以FeCl3替换Cr(NO3)3·9H2O外，其他条件与实施例2相同。X射线衍射图谱显示得到的材料的结构与实施例1相同，SEM图像确认制得的多孔无机-有机杂化材料具有50nm～100nm的均一尺寸。
实施例5(V-BDCA-1)
制备多孔无机-有机杂化材料，除了以VCl3替换Cr(NO3)3·9H2O外，其他条件与实施例2相同。X射线衍射图谱显示得到的材料的结构与实施例1相同，SEM图像确认制得的多孔无机-有机杂化材料具有50nm～80nm的均一尺寸。
实施例6(Cr-BDCA-1薄膜)
以Cr(NO3)3·9H2O、HF水溶液、1，4-苯二甲酸(BDCA)与水，配制摩尔组成为Cr∶HF∶BDCA∶H2O＝1∶1∶1∶275的反应混合物。将该反应混合物装入特氟隆反应器，并将氧化铝板竖直放入反应混合物中。将装有反应混合物和氧化铝板的特氟隆反应器放入微波烘箱中(CEM，Mars-5)，在微波辐射(2.45GHz)下在3分钟内反应温度到达210℃，然后，在该反应温度在微波辐射下使合成进行30分钟。通过冷却至室温、离心、用去离子水洗涤然后干燥从而回收多孔无机-有机杂化材料，即对苯二甲酸铬，缩写Cr-BDCA-1(粉末与薄膜)。该薄膜的X射线衍射图谱与实施例3的图谱非常相似。这些结果说明可以直接制得多孔无机-有机杂化材料的薄膜。
实施例7(Cr-BDCA：水分吸附与脱附特性)
将由实施例3得到的Cr-BDCA放入一个盛有饱和氯化铵水溶液的干燥器的上部。将此Cr-BDCA放置三天来充分吸收水分，之后使用TGA(热重分析仪)测量水分的脱附量与脱附温度。如图5所示，分别在60℃、65℃、70℃脱附了相当于总重量的约37％、43％、45％的水分，超过300℃时发生了由于Cr-BDCA结构破坏所造成的质量减少。由图5可知，Cr-BDCA的水分吸收量是很大的，Cr-BDCA的总重量的约45％～50％是水。而且，Cr-BDCA具有很高的脱附量，因为在70℃以下的温度有超过90％的吸附水分发生脱附。
实施例8(Cr-BDCA：水分吸附实验)
将实施例3所获得的Cr-BDCA在真空下在150℃进行干燥以后，对其进行了重量分析方式的水分吸附实验。在相对湿度21.4％时，基于吸附剂重量的吸附量为0.04g/g，非常低。因此，由此可知Cr-BDCA在低湿度下不易吸收水分。由此可知，Cr-BDCA将基于这些特性和在100℃以下的温度的易脱附性，在加湿和除湿工艺中显示出优异的性能。
比较例1(硅胶水分吸附与脱附特性)
像实施例7一样，对水分的吸附和脱附特性进行了分析，不同之处是以硅胶替换了Cr-BDCA。在70℃时脱附量仅有15％，达到30％水分脱附需要115℃的高温。
工业实用性
如上所述，由本发明所合成的多孔无机-有机杂化材料在100℃以下的较低温度时具有很高的水分吸附与脱附量，体现出了此种杂化材料在除湿器、加湿器、冷却器与加热器中的实用性。更特别的是，正是由于比较低的脱附温度，使用此种多孔无机-有机杂化材料的设备的运行成本会降低许多。

Claims (10)

1.一种多孔无机-有机杂化材料作为水分吸附剂的应用，所述无机-有机杂化材料：
1)由金属前体与选自有机化合物的配体之间的反应合成；且
2)具有大于1000m2/g且极限是10000m2/g的比表面积；且
3)具有大于1.0mL/g的孔隙体积；且
4)孔窗尺寸为0.5nm～2nm。
2.如权利要求1所述的应用，其中，所述多孔无机-有机杂化材料平均粒度小于500nm。
3.如权利要求1或2所述的应用，其中，所述金属前体为一种或多种的金属或者一种或多种的金属化合物，所述金属选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Mg、Ca、Sr、Ba、Sc、Y、Al、Ga、In、Tl、Si、Ge、Sn、Pb、As、Sb或者Bi；所述金属化合物含有选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Mg、Ca、Sr、Ba、Sc、Y、Al、Ga、In、Tl、Si、Ge、Sn、Pb、As、Sb或者Bi中的一种或多种成分。
4.如权利要求1或2所述的应用，其中，所述有机化合物是含有选自羧酸基、羧酸根、氨基(-NH2)、亚氨基、酰胺基(-CONH2)、磺酸基(-SO3H)、磺酸根(-SO3 -)、二硫代甲酸基(-CS2H)、二硫代甲酸根(-CS2 -)、吡啶或者吡嗪中的一种或者多种官能团的分子或者分子混合物。
5.如权利要求4所述的应用，其中，含有羧酸基官能团的所述有机化合物选自苯二甲酸、萘二甲酸、苯三甲酸、萘三甲酸、吡碇二甲酸；联吡碇二甲酸、甲酸、乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸和环己基二甲酸。
6.如权利要求5所述的应用，其中，所述多孔无机-有机杂化材料是选自对苯二甲酸铬、对苯二甲酸铁或者对苯二甲酸钒中的一种。
7.如权利要求6所述的应用，其中，所述多孔无机-有机杂化材料是对苯二甲酸铬。
8.如权利要求7所述的应用，其中，所述多孔无机-有机杂化材料是具有孔隙的立方晶系的对苯二甲酸铬。
9.如权利要求1或2所述的应用，其中，所述多孔无机-有机杂化材料呈厚膜状、薄膜状或者膜片状。
10.如权利要求9所述的应用，其中，厚膜状、薄膜状或者膜片状的所述多孔无机-有机杂化材料通过以下方法制备：将氧化铝、硅、玻璃、氧化铟锡(ITO)、氧化铟锌(IZO)或者耐热性聚合物浸入所述反应混合物中，然后微波加热；或者将表面处理过的氧化铝、硅、玻璃、氧化铟锡(ITO)、氧化铟锌(IZO)或者耐热聚合物浸入所述反应混合物中，然后微波加热。
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JP2012152738A (ja) 2012-08-16
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US20090130411A1 (en) 2009-05-21
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