CN114561025A - 一种吡啶鎓修饰的UiO-66类型化合物、制备方法及应用 - Google Patents
一种吡啶鎓修饰的UiO-66类型化合物、制备方法及应用 Download PDFInfo
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
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Abstract
本发明公开一种吡啶鎓修饰的UiO‑66类型化合物，是由含有吡啶鎓取代基的线性二羧酸配体和金属氧簇Zr6O4(OH)4构筑而成，主体框架带正电荷，卤素离子作为抗衡阴离子分散在框架中，具有高稳定性、较高的比表面积和显著的多孔特征，可在无助催化剂、无溶剂及温和条件下有效催化CO2与环氧化物合成环状碳酸酯，可循环使用且产物易分离提纯。
Description
技术领域
本发明涉及一种新的化合物、制备方法及应用，尤其是一种吡啶鎓修饰的UiO-66类型化合物、制备方法及应用。
背景技术
环境中过多的CO2气体导致全球气候变暖，进而引发冰川融化、海平面升高等一系列问题，严重威胁到人类的生存。有效的解决方法是减少CO2的排放的同时将环境中的CO2捕获、存储以及转化为有用的物质，例如将CO2和环氧化合物在催化剂的作用下合成优良溶剂环状碳酸酯，应用于工业生产中。传统的合成方法是均相催化工艺，存在产物不易分离及催化剂难以再生利用的问题，因此人们开发出高效的MOFs等多相催化剂。MOFs是金属-有机框架材料，具有比表面积大、组成和结构可调控等特点，在催化CO2与环氧化合物合成环状碳酸酯的反应中表现出优异的性能，然而，因多数MOFs的不稳定性，限制了实际应用。由对苯二甲酸和金属氧簇Zr6O4(OH)4构筑而成的UiO-66是为数不多的几种水稳型MOFs之一，其在pH 1-11范围内具有良好的水热稳定性，然而，其作为CO2与环氧化合物合成环状碳酸酯反应的催化剂使用时，必须在四丁基溴化铵等助催化剂的协同作用下才能表现出催化活性，而助催化剂的引入不仅增加了成本，也导致产物不易分离。
发明内容
本发明是为了解决现有技术所存在的上述技术问题，提供一种吡啶鎓修饰的UiO-66类型化合物、制备方法及应用。
本发明的技术解决方案是：一种吡啶鎓修饰的UiO-66类型化合物，是由含有吡啶鎓取代基的线性二羧酸配体和金属氧簇Zr6O4(OH)4构筑而成。
a. 将异烟酸甲酯、丙酮、金属钠和无水乙醚置于三颈烧瓶中，氮气保护，室温搅拌3h，抽滤得到固体1-(吡啶-4-基) -1,3-丁二酮钠盐，洗涤，烘干；所述异烟酸甲酯、丙酮、金属钠和无水乙醚的用量比为0.1mol：0.1mol：0.1mol：50mL；
b. 将1-(吡啶-4-基) -1,3-丁二酮钠盐、二硫化碳、无水碳酸钾和N,N-二甲基甲酰胺置于三颈烧瓶中室温搅拌1 h，再加入溴乙酸乙酯室温反应24h，然后升温至80℃反应3h，将所得混合液倒入冰水中固体析出，过滤收集固体并经柱层析分离得到固体3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸乙酯；所述1-(吡啶-4-基) -1,3-丁二酮钠盐、二硫化碳、无水碳酸钾、N,N-二甲基甲酰胺和溴乙酸乙酯的用量比为10mmol：10mmol：60mmol：20mL：20mmol；
c. 将3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸乙酯在溶有KOH的乙醇/水混合溶液中水解，调pH 值至2，沉淀析出，抽滤烘干，得到3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸；
d. 将3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸、苯甲酸、氯化锆、N,N-二甲基甲酰胺置于反应釜中，120℃加热反应36 h，抽滤，所得沉淀经二氯甲烷浸泡和加热活化得到固体，命名为Pyridyl-MOF-1，所述3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸、苯甲酸或冰醋酸、氯化锆和N,N-二甲基甲酰胺的用量比为0.3mmol：9mmol：0.3mmol：10mL；
e. 将Pyridyl-MOF-1置于CH3I溶剂中加热反应24h，然后过滤，所得固体置于KBr水溶液中浸泡24h，然后分离得到吡啶鎓修饰的UiO-66类型化合物。
一种上述的吡啶鎓修饰的UiO-66类型化合物在催化CO2与环氧化物合成环状碳酸酯反应中的应用。
本发明的吡啶鎓修饰的UiO-66类型化合物主体框架带正电荷，卤素离子作为抗衡阴离子分散在框架中，具有高稳定性、较高的比表面积和显著的多孔特征，可在无助催化剂、无溶剂及温和条件下有效催化CO2与环氧化物合成环状碳酸酯，可循环使用且产物易分离提纯。
附图说明
图1是本发明实施例 (Br-)CH3-Pyridinium-MOF-1的PXRD谱图。
图2是本发明实施例(Br-)CH3-Pyridinium-MOF-1的扫描电镜图像及粒径分布分析图。
图3是本发明实施例(Br-)CH3-Pyridinium-MOF-1的N2吸附曲线。
图4是本发明实施例(Br-)CH3-Pyridinium-MOF-1的CO2吸附曲线和等量吸附热曲线。
图5是本发明实施例(Br-)CH3-Pyridinium-MOF-1催化环氧氯丙烷与CO2反应的循环测试结果示意图。
具体实施方式
实施例1：
本发明的吡啶鎓修饰的UiO-66类型化合物的制备方法，依次按照如下步骤进行：
a. 将异烟酸甲酯（0.1mol）、丙酮（0.1mol）、金属钠（0.1mol）和无水乙醚（50mL）置于三颈烧瓶中，氮气保护，室温搅拌3h，抽滤得到黄色固体1-(吡啶-4-基) -1,3-丁二酮钠盐，用乙酸乙酯洗涤，烘干，产率75%；
b. 将1-(吡啶-4-基) -1,3-丁二酮钠盐（10mmol）、二硫化碳（10mmol）、无水碳酸钾（60mmol）和N,N-二甲基甲酰胺（20mL）置于三颈烧瓶中，室温搅拌1 h，加入溴乙酸乙酯（20mmol）室温反应24h，然后升温至80℃反应3h，所得混合液倒入冰水中固体析出，过滤收集固体并经柱层析分离得到浅黄色固体3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸乙酯（3-Methyl-4-pyridin-4-yl- thieno[2,3-b]thiophene-2,5-dicarboxylic aciddiethyl ester），产率25%；
c. 将3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸乙酯（2g）在5%的KOH乙醇/水混合溶液中水解，调pH 值至2，浅黄色沉淀析出，抽滤烘干，得到3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸（3-Methyl-4-pyridin-4-yl-thieno[2,3-b]- thiophene-2,5-dicarboxylic acid，简写为H2MPTDC），产率95%；
d. 将3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸（0.3mmol）、苯甲酸（9mmol）、氯化锆（0.3mmol）、N,N-二甲基甲酰胺（10mL）置于反应釜中，120℃加热反应36 h，抽滤，所得沉淀经二氯甲烷浸泡和加热活化得到淡黄色固体Pyridyl-MOF-1，产率60%；
e. 将2.5g Pyridyl-MOF-1置于15g碘甲烷溶剂中40℃加热反应24h，过滤收集固体，将所获得固体置于KBr水溶液中浸泡24h，然后经加热活化得到吡啶鎓修饰的UiO-66类型化合物，命名为(Br-)CH3-Pyridinium-MOF-1，产率90%。
实验：
实验例1：
对实施例1所得到的暗黄色固体(Br-)CH3-Pyridinium-MOF-1进行X射线粉末衍射表征，结果如图1所示。图1中曲线分别是Pyridyl-MOF-1和(Br-)CH3-Pyridinium-MOF-1；Simulated data from Zr-DMTDC曲线是来自于文献已报道的具有UiO-66结构的Zr-DMTDC的模拟信号。Zr-DMTDC由3，4-二甲基噻吩并噻吩二甲酸与ZrO4(OH)4(COO)6簇构筑而成。Pyridyl-MOF-1与Zr-DMTDC结构相比，相当于将Zr-DMTDC中羧酸配体上的一个取代甲基替换为吡啶基团，将Pyridyl-MOF-1上的吡啶烷基化后变成吡啶鎓就形成了(Br-)CH3-Pyridinium-MOF-1。结果显示，Pyridyl-MOF-1和(Br-)CH3-Pyridinium-MOF-1的衍射花样与Zr-DMTDC的模拟数据吻合较好，说明Pyridyl-MOF-1和(Br-)CH3-Pyridinium-MOF-1与Zr-DMTDC是同构的，均具有UiO-66拓扑结构。
实验例2：
通过扫描电子显微镜（SEM）对实施例1所制备的吡啶鎓修饰的UiO-66类型化合物(Br-)CH3-Pyridinium-MOF-1进行形貌表征，结果如图2所示。SEM成像结果表明(Br-)CH3-Pyridinium-MOF-1在后合成修饰的过程中保持了较为均一的微纳米结构，尺寸主要分布在100nm左右，证明了产物的相纯度和结构稳定性。
实验例3：
通过全自动比表面积和微孔分析仪对实施例1所制备的化合物 (Br)CH3-Pyridinium-MOF-1进行表征。N2吸附热曲线图如图3所示，N2 等温吸附曲线呈现出典型微孔材料的 I 型可逆吸附，Brunauer–Emmett–Teller (BET) 表面积为600.0m2 g-1，孔体积为0.32 cm3 g-1，平均孔径为0.46nm。结果表明，化合物(Br-)CH3-Pyridinium-MOF-1具有较高的比表面积和显著的多孔特征。
实验例4：
对实施例1所制备的化合物(Br-)CH3-Pyridinium-MOF-1在不同温度条件下的CO2吸附进行了测试，结果如图4所示。图4中左图为CO2的等温吸附曲线。数据分析表明，在273K和100kPa下，每克化合物(Br-)CH3-Pyridinium-MOF-1可吸附48.9 cm3 CO2，吸附质量百分比为9.5wt%；在298 K和100 kPa下, 每克化合物(Br-)CH3-Pyridinium-MOF-1可吸附33.6 cm3 CO2，吸附质量百分比为6.0 wt%。
根据以上数据，计算得到化合物(Br-)CH3-Pyridinium-MOF-1对CO2的吸附焓曲线如图4右图所示，化合物(Br-)CH3-Pyridinium-MOF-1对CO2分子的吸附焓Qst值位于15.0-48.8kJ mol-1之间。初始阶段较高的吸附热归因于离子型框架结构较强的极化作用，增强了化合物(Br-)CH3-Pyridinium-MOF-1与CO2分子之间的相互作用。
实验例5：
以环氧氯丙烷和CO2反应生成碳酸环氯丙烯酯为反应模型，评价本发明实施例1所制备的(Br-)CH3- Pyridinium-MOF-1的催化性能。
向平行反应装置中的5组试管中分别加入1.85g环氧氯丙烷（20 mmol）和100 mg实施例1所制备的(Br-)CH3-Pyridinium-MOF-1（0.05 mmol，物质的量基于催化剂中的活性组分Br-计算）。向试管中充入CO2，排尽空气并保持反应试管内的CO2压力为1atm。5组试管反应温度分别设置为室温、50℃，70℃、90℃和90℃，1-4组反应时间12h，第5组反应时间24h。反应完毕后，离心分离催化剂和产物，并对产物进行气相色谱分析，结果如表1所示。
表1 (Br-)CH3-Pyridinium-MOF-1催化环氧氯丙烷与CO2合成环状碳酸酯反应结果
从表1可以看出，12h时间内，在无溶剂和助催化剂的条件下，温度从室温升高到90℃，反应的选择性从99.9%逐渐下降到95.1%，转化率则逐渐升高至59.2%，产率也逐渐升高。当温度为90℃，反应时间延长至24h，则总的转化率为93.5%，选择性91.6%，产率高达85.6%。以上结果表明，本发明的(Br-)CH3-Pyridinium-MOF-1的催化效率与反应温度和时间存在正相关性，提高温度和延长时间能够有效提升目标产物的产率，其在90℃条件下表现出良好的催化活性，可以有效催化CO2与环氧氯丙烷反应生成环状碳酸酯。
实验例6：
向反应装置中的试管中加入1.85g环氧氯丙烷（20 mmol）和100 mg 实施例1所制备的 (Br-)CH3-Pyridinium-MOF-1（0.1 mmol，物质的量计算基于催化剂中的活性组分Br-）。向试管中充入CO2，排尽空气并保持反应试管内的CO2压力为1atm，反应温度为90℃，反应时间24h。反应完毕后，离心分离催化剂和产物，并对产物进行气相色谱分析。
为了评价催化剂(Br-)CH3-Pyridinium-MOF-1的稳定性和可重复性，在90℃和24h的反应条件下，对上述回收的催化剂进行了三次重复使用实验，结果如图5所示。结果表明：催化反应的转化率和选择性均无明显降低，表明该催化剂结构稳定，可重复用于CO2与环氧氯丙烷反应生成环状碳酸酯的反应。
Claims (3)
1.一种吡啶鎓修饰的UiO-66类型化合物，其特征在于：是由含有吡啶鎓取代基的线性二羧酸配体和金属氧簇Zr6O4(OH)4构筑而成。
2.一种如权利要求1所述的吡啶鎓修饰的UiO-66类型化合物的制备方法，其特征在于依次按照如下步骤进行：
a. 将异烟酸甲酯、丙酮、金属钠和无水乙醚置于三颈烧瓶中，氮气保护，室温搅拌3h，抽滤得到固体1-(吡啶-4-基) -1,3-丁二酮钠盐，洗涤，烘干；所述异烟酸甲酯、丙酮、金属钠和无水乙醚的用量比为0.1mol：0.1mol：0.1mol：50mL；
b. 将1-(吡啶-4-基) -1,3-丁二酮钠盐、二硫化碳、无水碳酸钾和N,N-二甲基甲酰胺置于三颈烧瓶中室温搅拌1 h，再加入溴乙酸乙酯室温反应24h，然后升温至80℃反应3h，将所得混合液倒入冰水中固体析出，过滤收集固体并经柱层析分离得到固体3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸乙酯；所述1-(吡啶-4-基) -1,3-丁二酮钠盐、二硫化碳、无水碳酸钾、N,N-二甲基甲酰胺和溴乙酸乙酯的用量比为10mmol：10mmol：60mmol：20mL：20mmol；
c. 将3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸乙酯在溶有KOH的乙醇/水混合溶液中水解，调pH 值至2，沉淀析出，抽滤烘干，得到3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸；
d. 将3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸、苯甲酸、氯化锆、N,N-二甲基甲酰胺置于反应釜中，120℃加热反应36 h，抽滤，所得沉淀经二氯甲烷浸泡和加热活化得到固体，命名为Pyridyl-MOF-1；所述3-甲基-4-(吡啶-4-基)-[2,3-b]并噻吩二羧酸、苯甲酸、氯化锆和N,N-二甲基甲酰胺的用量比为0.3mmol：9mmol：0.3mmol：10mL；
e. 将Pyridyl-MOF-1置于CH3I溶剂中加热反应24h，然后过滤，所得固体置于KBr水溶液中浸泡24h，然后分离得到权利要求1所述的吡啶鎓修饰的UiO-66类型化合物。
3.一种如权利要求1所述的吡啶鎓修饰的UiO-66类型化合物在催化CO2与环氧化物合成环状碳酸酯反应中的应用。
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