CN103459029A - 新型im-21有机-无机杂化固体及其制备方法 - Google Patents
新型im-21有机-无机杂化固体及其制备方法 Download PDFInfo
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Abstract
具有有机-无机混合基体的新型结晶杂化固体描述为具有包含锌基金属中心的无机晶格的三维结构，该锌基金属中心通过由-O2C-C6H2-(O)2-CO2类构成的去质子化的有机配体连接在一起。这种新型固体称为IM-21并具有如下给出的X-射线衍射图。
Description
发明领域
本发明涉及具有混合的有机-无机基体和三维结构的新型结晶杂化(hybrid)固体，及其制备方法。形成本发明主题的所述新型固体在说明书的其余部分将称为IM-21。本发明还涉及将所述IM-21固体作为催化剂或吸附剂的用途。
现有技术
多孔固体家族是较多地和持久地受人关注并在材料领域被进行研究的源，其在日常生活中和在工业应用中具有不可否认的重要性。
自从20世纪90年代以来，已经对具有混合的有机-无机基体的杂化化合物赋予极大关注，其也已知为MOF类(金属-有机骨架)或配位聚合物。MOF类是多孔结晶固体，其中金属阳离子(二聚体、三聚体、四聚体、链、平面)的子骨架通过作为多齿配体的有机分子连接在一起以形成二维或三维结构。
由于无机连接体和有机配体的可能的组合的多样性，这类材料可以用来形成大量新型结构。
然而，就大量的已被合成的结构而言，只有一小部分具有可进入的多孔性。然而，可进入孔性是将这些材料用作催化剂或吸附剂的重要性质。多种原因可以用来解释在杂化材料中不存在可进入的多孔性：或者杂化材料的结构过于密集，或者孔开口过小。除了这两种解释之外，在某些情况下，在理论上应该有可进入的孔的杂化材料的结晶结构，具有合成后残存在结构中的溶剂和/或有机配体分子，阻碍了进入孔中。
备受关注的已知杂化材料通常基于由二元或三元羧酸酯或吡啶衍生物构成的有机配体。一些经常遇到的有机配体为：bdc＝苯-1，4-二甲酸酯，btc＝苯-1，3，5-三甲酸酯，ndc＝萘-2，6-二甲酸酯，H4dhtp＝2，5-二羟基对苯二甲酸，bpy＝4，4′-联吡啶，hfipbb＝4，4′-(六氟异丙叉基)-二苯甲酸酯，cyclam＝1，4，8，11-四氮杂环十四烷。
在本发明的上下文中，用作存在于本发明固体中的配体的前体的化合物为2，5-二羟基对苯二甲酸(H4dhtp)。充当连接体的有机实体为锌。
发明描述
本发明涉及具有混合的有机-无机基体的新型结晶杂化固体，其具有三维结构。这种新型固体被称为IM-21。它包含具有基于锌的金属中心的无机骨架，该基于锌的金属中心通过由实体-O2C-C6H2-(O)2-CO2构成的去质子化的有机配体连接在一起。具有式-O2C-C6H2-(O)2-CO2的2，5-二羟基对苯二甲酸的酸和羟化物官能团是去质子化的。
本发明的IM-21结晶杂化固体的X-射线衍射图包括至少记录在表1中的峰。该衍射图是通过使用衍射仪并应用采用铜的Kα1线
的常规粉末法的放射晶体图分析获得的。从由2θ角表示的衍射峰的位置，通过应用Bragg关系计算样品的特征晶面间距，dhkl。测量中的误差—相对于dhkl的Δ(dhkl)—在使用Bragg关系测量2θ中作为绝对误差Δ(2θ)的函数计算。等于±0.2°的绝对误差Δ(2θ)通常是可接受的。用于计算每个dhkl值的相对强度I/I0由相应的衍射峰的高度测量。本发明的IM-21结晶杂化固体的X-射线衍射图包括至少具有表1中给出的dhkl值的峰。在dhkl栏中给出的晶面间距的平均值以埃
计。这些值中的每个都经历在
至
范围内的误差测量Δ(dhkl)。
表1：在1M-21结晶杂化固体的X-射线衍射图上测量的dhkl平均值和相对强度
其中s＝强；m＝中；mw＝中弱；W＝弱。相对强度I/Io使用相对强度标度给出，其中值100归属于X-射线衍射图的最强峰：w＜15；15≤mw＜30；30≤m＜85；s≥85。
IM-21结晶杂化固体归类于六方晶系P，其中晶格参数
和角度α＝β＝90°，γ＝120°。
根据本发明的IM-21结晶杂化固体具有特征在于图1中给出的其X射线衍射图的基本晶体结构或拓扑结构。所述固体的化学组成以Zn2(-O2C-C6H2(O)2-CO2-)为基本模体(motif)。这个模体重复n次，其中n一般大于100。
本发明的IM-21结晶杂化固体具有三维结构，其中充当连接体的基于Zn2+阳离子的金属中心的无机骨架借助于去质子化的对苯二甲酸配体(-O2C-C6H2-(O)2-CO2)键合在一起，所述对苯二甲酸配体在芳环的2位和5位上带有两个去质子化的羟化物官能团。
本发明还涉及制备具有混合的有机-无机基体的所述IM-21结晶杂化固体的方法。该方法包括至少以下步骤：
i)在含水介质中制备反应混合物，基于一摩尔当量的元素锌，该反应混合物按比例含有存在于包含至少N，N-二甲基甲酰胺(DMF)和丙醇(C3H7OH)的溶剂混合物中的至少一种锌前体和2，5-二羟基对苯二甲酸(表示为H4dhtp)，从而所述反应混合物具有以下摩尔组成：
1Zn∶0.1-2H4dhtp∶1-50H2O∶3-10C3H7OH∶50-300DMF
ii)在150℃至290℃范围内的温度下，进行所述反应混合物的溶剂热处理，以获得按所合成的形式的所述IM-21结晶杂化固体；
iii)过滤、洗涤和干燥所述IM-21结晶杂化固体；
iv)热处理从所述步骤iii)获得的所述IM-21结晶杂化固体。
根据用于制备本发明的IM-21结晶杂化固体的方法的所述步骤i)，锌前体有利地选自锌(II)盐，如锌的氯化物、硫酸盐、乙酸盐或硝酸盐。高度优选地，所述使用的前体是硝酸锌。2，5-二羟基对苯二甲酸(-O2C-C6H2-(O)2-CO2H)、二甲基甲酰胺和丙醇(优选丙醇)是市售的化合物。
根据本发明的制备方法的所述步骤i)，基于一摩尔当量的元素锌，反应混合物优选地具有以下摩尔组成：
1Zn∶0.2-0.7H4dhtp∶10-40H2O∶5-9C3H7OH∶100-150DMF
本发明的制备方法的所述步骤ii)的溶剂热处理在自发反应压力条件下进行。所述溶剂热处理优选在160℃至190℃范围内的温度下进行。所述处理的持续时间在8至72小时的范围内，优选在10至30小时的范围内。在所述步骤ii)结束时得到的固体是IM-21结晶杂化固体，其X-射线衍射图包括至少记录于表1中的峰。
将所述步骤ii)结束时获得的IM-21结晶杂化固体过滤并用一种或多种适当的溶剂特别是N，N-二甲基甲酰胺(DMF)和乙醇洗涤。接着，根据所述步骤iii)，所述固体在20℃至200℃范围内，优选在20°至100℃范围内，还更优选在20℃至80℃范围内的温度下，干燥一段时间，该时间可以从1至24小时，通常在4至10小时范围内变化。从所述步骤iii)中得到的IM-21结晶杂化固体是按所合成的形式，即其中所述固体的孔尚未从存在溶剂中释放出来的形式。以其按所合成的形式获得的所述固体的X-射线衍射图包括至少包括在表1中的峰。
为了释放从所述步骤iii)得到的所述IM-21固体的孔，它经历在150℃至500℃范围内的温度下进行的热处理。所述热处理的持续时间优选在1小时至3天的范围内，优选在5至24小时的范围内。从本发明的制备方法的所述步骤iv)中得到的固体是多孔固体：它不含任何溶剂并是脱水的。
在本发明方法的优选实施方案中，在所述步骤iv)之前进行交换步骤，该交换步骤由将至少一种用于进行所述步骤i)的、存在于其按所合成形式的IM-21固体的孔中的溶剂(优选DMF)与优选选自甲醇、乙醇、异丙醇和乙腈的溶剂交换组成。高度优选地，所述溶剂是甲醇。所述交换步骤一般由将从所述步骤iii)中得到的其按所合成形式的所述固体浸渍在所述溶剂中优选甲醇中组成。所述交换在从室温至110℃范围内，优选在50℃至90℃范围内的温度下进行1到15天。将用于交换的溶剂优选定期更新。在所述交换步骤结束时，将在所述溶剂中优选在甲醇中包含交换的IM-21固体的悬浮液过滤，然后有利地干燥。在从室温到100℃范围内，优选在室温的温度下进行干燥达2至12小时范围内的时间。
本发明还涉及所述IM-21杂化固体作为吸附剂或催化剂的用途。特别是，当作为吸附剂使用时，本发明所述的IM-21杂化固体有利地用于分离存在于待纯化的气体混合物如合成气、天然气或燃烧烟中的二氧化碳的方法中。
现在将以下面的实施例示例本发明，但这些实施例实际上没有限定作用。
实施例1(本发明)：制备具有混合的有机-无机基体的IM-21杂化固体
将9.73克(133.1毫摩尔)N，N二甲基甲酰胺(DMF)和0.51克(28.5毫摩尔)的蒸馏水置于内部容积为22.58mL的PTFE容器中。加入0.29克(1毫摩尔)六水合硝酸锌(Sigma Aldrich)。用磁力搅拌器搅拌该混合物5分钟。然后加入0.10克(0.5毫摩尔)的2，5-二羟基对苯二甲酸(H4dhtp)(SigmaAldrich)。将该混合物搅拌5分钟。均质后，加入0.41克(6.9毫摩尔)丙-1-醇(Alfa Aesar)。所得到的混合物的摩尔组成为：1.00硝酸锌∶0.5H4dhtp∶133.1DMF∶34.5H2O∶6.9丙-1-醇。然后，将PTFE容器转移到高压釜中，不搅拌下加热至160℃持续24小时。冷却后，过滤所得的结晶固体，用DMF洗涤然后用乙醇洗涤。在50℃、空气中干燥约6小时后，得到结晶粉末形式的结晶固体，对应于其按所合成的形式的固体；它的X-射线衍射图包括在表1中所包含的线。该固体表示为IM-21按所合成的。
下面的实施例1.1至1.4示例了获得多孔IM-21杂化固体的不同方案。
实施例1.1：将以其按所合成的形式(IM-21按所合成的)的IM-21固体在真空中在300℃下加热12小时。得到多孔固体IM-21。其比表面积通过在77K下的氮吸附评估和通过BET法计算，等于326平方米/克。
实施例1.2：在70℃下，将以其按所合成的形式(IM-21按所合成的)的IM-21固体浸渍在甲醇中持续十天的时间。过滤该固体，然后在真空下在180℃下加热12小时。得到多孔固体IM-21。其比表面积通过在77K下的氮吸附评估和通过BET法计算，等于354平方米/克。
实施例1.3：在70℃下，将以其按所合成的形式(IM-21按所合成的)的IM-21固体浸渍在甲醇中持续十天的时间。过滤固体，然后在真空下在350℃下加热12小时。得到多孔固体IM-21。其比表面积通过在77K下的氮吸附评估和通过BET法计算，等于489平方米/克。
实施例1.4：在70℃下，以其按所合成的形式(IM-21按所合成的)的IM-21固体浸渍在甲醇中持续十天的时间。过滤固体，然后在真空下在450℃下加热12小时。得到多孔固体IM-21。其比表面积通过在77K下的氮吸附评估和通过BET法计算，等于1030平方米/克。
实施例2
使用以下方案制备三批固体：
将9.73克(133.1毫摩尔)N，N二甲基甲酰胺(DMF)和0.51克(28.5毫摩尔)蒸馏水置于内部容积为22.58mL的PTFE容器中。加入0.29克(1毫摩尔)六水合硝酸锌(Sigma Aldrich)。用磁力搅拌器搅拌该混合物5分钟。然后加入0.10克(0.5毫摩尔)的2，5-二羟基对苯二甲酸(H4dhtp)(Sigma Aldrich)。将混合物搅拌5分钟。均质后，加入0.41克(6.9毫摩尔)丙-1-醇(Alfa Aesar)。所得到的混合物的摩尔组成为：1.00硝酸锌∶0.5H4dhtp∶133.1DMF∶34.5H2O∶6.9丙-1-醇。
然后，将包含第一批料的PTFE容器转移到高压釜中，不搅拌下在110℃下加热24小时。
然后，将包含第二批料的PTFE容器转移到高压釜中，不搅拌下在120℃下加热24小时。
然后，将包含第二批料的PTFE容器转移到高压釜中，不搅拌下在140℃下加热24小时。
然后，将包含第二批料的PTFE容器转移到高压釜中，不搅拌下在160℃下加热24小时。
每个批次冷却后，过滤所得的结晶固体，用DMF洗涤然后用乙醇洗涤。在50℃下、在空气中干燥约6小时后，得到结晶粉末形式的结晶固体，对应于其按所合成的形式的固体。X-射线衍射图存在于图2中。还示出了CPO-27的模拟X-射线衍射图以供参考。
在图2中可以清楚地看出，在110℃至140℃范围内的溶剂热处理温度下，得到的固体是CPO-27和IM-21的混合物。在160℃下，得到的固体是纯IM-21。
Claims (13)
1.具有混合的有机-无机基体的IM-21结晶杂化固体，其具有包含基于锌的金属中心的无机骨架的三维结构，该基于锌的金属中心通过由实体-O2C-C6H2-(O)2-CO2构成的去质子化有机配体连接在一起，所述固体具有包括至少在下表中出现的线的X-射线衍射图：
其中s＝强；m＝中；mw＝中弱；W＝弱，相对强度I/Io使用相对强度标度给出，其中值100归属于X-射线衍射图的最强峰：w＜15；15≤mw＜30；30≤m＜85；s≥85。
2.根据权利要求1的IM-21结晶杂化固体，其被归类为六方晶系P，其中晶格参数
和角度α＝β＝90°，γ＝120°。
3.根据权利要求1或权利要求2的IM-21结晶杂化固体，其化学组成以Zn2(-O2C-C6H2(O)2-CO2-)为基本模体。
4.制备具有混合的有机-无机基体的IM-21结晶杂化固体的方法，其包括至少以下步骤：
i)在含水介质中制备反应混合物，基于一摩尔当量的元素锌，该反应混合物按比例含有存在于包含至少N，N-二甲基甲酰胺(DMF)和丙醇(C3H7OH)的溶剂混合物中的至少一种锌前体和2，5-二羟基对苯二甲酸(H4dhtp)，从而所述反应混合物具有以下摩尔组成：
1Zn∶0.1-2H4dhtp∶1-50H2O∶3-10C3H7OH∶50-300DMF
ii)在150℃至290℃范围内的温度下，进行所述反应混合物的溶剂热处理，以获得按所合成的形式的所述IM-21结晶杂化固体；
iii)过滤、洗涤并干燥所述IM-21结晶杂化固体；
iv)热处理从所述步骤iii)获得的所述IM-21结晶杂化固体。
5.根据权利要求4的制备方法，其中基于一摩尔当量的元素锌，所述反应混合物具有以下摩尔组成：
1Zn∶0.2-0.7H4dhtp∶10-40H2O∶5-9C3H7OH∶100-150DMF。
6.根据权利要求4或权利要求5的制备方法，其中所述溶剂热处理在160℃至190℃范围内的温度下进行。
7.根据权利要求4至6之一的制备方法，其中所述溶剂热处理的持续时间在8至72小时范围内。
8.根据权利要求4至7之一的制备方法，其中所述热处理在150℃至500℃范围内的温度下进行。
9.根据权利要求4至8之一的制备方法，其中所述热处理的持续时间在1小时至3天的范围内。
10.根据权利要求4至9之一的制备方法，其中所述步骤iv)结束时得到的固体是多孔固体。
11.根据权利要求4至10之一的制备方法，其中在所述步骤iv)之前进行交换步骤，该交换步骤由将至少一种用于进行所述步骤i)的、存在于以其按所合成的形式的IM-21固体的孔中的溶剂与优选选自甲醇、乙醇、异丙醇和乙腈的溶剂交换组成。
12.根据权利要求11的制备方法，其中所述交换步骤在从室温至110℃范围内的温度下进行1到15天。
13.根据权利要求1至3之一或根据权利要求4至12之一的方法制备的IM-21结晶杂化固体作为吸附剂或催化剂的用途。
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