CN116693872A - 一种Cu的金属有机框架材料的制备方法及气体分离应用 - Google Patents
一种Cu的金属有机框架材料的制备方法及气体分离应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000000926 separation method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 26
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 5
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Abstract
一种基于Cu的金属‑有机框架材料的制备方法及气体分离应用,属于晶态材料的技术领域。化学分子式为[Cu2(H2O)2(BCBA)],其中有机配体(H4BCBA)为5‑(3,6‑双(4‑羧基苯基)‑9H‑咔唑‑9‑基)间苯二甲酸。该金属‑有机框架的合成为封闭条件下,有机配体H4BCBA和硝酸铜在N,N‑二甲基甲酰胺与三氟乙酸的混合溶液中,经由溶剂热反应得到金属‑有机框架材料的晶体。该金属‑有机框架材料对乙炔及二氧化碳有较高的吸附量且框架与乙炔气体分子作用力更强,可以实现乙炔/二氧化碳混合气体的高效分离。
Description
技术领域
本发明技术涉及金属-有机配位聚合物材料,属于晶态材料的技术领域。具体涉及一种Cu的金属有机框架材料(Metal-Organic Frameworks,MOFs)的制备方法。特征是该MOF可以实现乙炔/二氧化碳混合气体的高效分离。
背景技术
乙炔气体是石油化工和电子工业生产中的重要基础原料之一,通常用于制造乙醛、乙酸、合成橡胶、合成纤维等产品。此外,乙炔气体也可作焊接气用于焊接和金属切割。石化工业中,甲烷在氧气存在下偶联得到粗制乙炔,而粗制产品中往往含有大量的副产物,其中包括二氧化碳(CO2)。由于乙炔和二氧化碳分子呈线性形状,具有相似的沸点(-84℃和-78.5℃)、相似的三维尺寸和相同的动力学直径实现两者的高效分离纯化十分困难。与此同时,乙炔气体对热量、压力等物理因素较为敏感,在室温无氧条件下,压缩压力大于0.2MPa即会发生爆炸,使得工业生产中乙炔纯化过程面临诸多挑战。传统工业中主要采用高能耗的低温精馏技术分离乙炔/二氧化碳混合气,所涉及到的分离设备投资较大,维护复杂。因此,开发新的乙炔/二氧化碳分离技术和优化现有分离工艺对于乙炔产业具有十分重要的意义。由于能耗相对较低、分离选择性较高以及过程简单等优点,基于多孔材料的吸附分离技术有望解决传统分离过程中的诸多难题,为乙炔纯化带来新的契机。
传统多孔材料,如沸石分子筛、粘土、活性炭等,在常温常压条件下通常选择性较低,吸附容量较低吸附剂的分离性能取决于吸附剂的孔结构和孔表面性质以及被吸附气体的物理化学性质。金属有机框架材料(Metal organic frameworks,MOFs)是一种新型晶态多孔功能材料,它是由金属/金属簇节点和有机配体基于配位键形成的多孔网状骨架结构材料。由于其结构多样化、尺寸可调控、比表面积大等特点,已被广泛应用于气体存储与分离、药物释缓、荧光检测、催化等领域。近年来,许多MOFs被应用于低碳烃吸附分离中,例如乙烷/乙烯、乙炔/乙烯中纯化乙烯,丙烷/丙烯、丙炔/丙烯中纯化丙烯,也包括乙炔/二氧化碳分离。尽管众多研究结果表明MOFs作为吸附剂材料分离低碳烃混合物具有独特的优势,并获得了良好的效果,但如何兼顾高的分离选择性、相对低廉的制备成本、较快的合成效率,依然是乙炔/二氧化碳吸附分离材料筛选制备中面临的难点之一。
发明内容
本发明的目的在于提供了一种咔唑羧酸配体构筑的Cu基金属有机框架材料的制备方法,该MOF材料可以在较短时间内完成制备,方便大规模合成且可用于乙炔/二氧化碳混合气的高效分离。
本发明的一种新型咔唑-羧酸Cu的金属-有机框架材料,其特征在于,铜基金属有机框架材料为有机配体和铜盐通过溶剂热法反应制备的晶体材料。化学分子式为[Cu2(H2O)2(BCBA)],其中有机配体5-(3,6-双(4-羧基苯基)-9H-咔唑-9-基)间苯二甲酸(H4BCBA),分子式为C34H21NO8,结构式如下所示:
从晶体结构的角度解析,该金属-有机框架的晶体结构属于六方晶系,空间群为P21/n,晶胞参数为:α=90°,β=102.697(5)°,γ=90°。
从拓扑学角度看,每个BCBA4-配体都可以看作是具有四面体构型的4-连接的节点,与此同时Cu2簇可以看作是4-连接的顶点,这两种类型的结构单元交替连接形成了一个(4,4)-连接具有nou拓扑的网络,其施莱夫利符号(symbol)为{4.65}2{42.84}{64.82}。
该金属-有机框架材料沿a轴方向存在大小为(垂直两个方向上孔道最小的尺寸)的五边形孔道。较大的孔结构使得该金属-有机框架适用于气体存储。
本发明金属-有机框架材料的合成方法,包括以下步骤:
配体合成:首先将4-硼酸甲酯(分子式C8H9BO4)、3,6-二溴-9H-咔唑(分子式C12H7Br2N)、碳酸钾、四(三苯基膦)钯(分子式Pd[P(C6H5)3]4)及1,4-二氧六环加入到反应器中,密封,抽真空,氮气保护,加热反应得到4,4'-(9H-咔唑-3,6-二基)二苯甲酸二甲酯(分子式C28H21NO4)。将上述合成的产物及5-碘间苯二甲酸二甲酯(分子式C10H9IO4)、碳酸钾及N,N-二甲基甲酰胺(DMF)加入到反应器中,密封,抽真空,氮气保护,加热反应,反应结束后加入去离子水,过滤干燥后得到5-(3,6-双(4-(甲氧基羰基)苯基)-9H-咔唑-9-基)间苯二甲酸酯(分子式C38H29NO8)。最后将5-(3,6-双(4-(甲氧基羰基)苯基)-9H-咔唑-9-基)间苯二甲酸酯在2M氢氧化钠、1,4-二氧六环及四氢呋喃(THF)中反应,反应结束后减压蒸馏去除有机溶剂,加入去离子水,用2M盐酸水溶液调节pH至沉淀析出完全,抽滤洗涤干燥后得到5-(3,6-双(4-羧基苯基)-9H-咔唑-9-基)间苯二甲酸(H4BCBA)。配体合成线路图见附图1。
Cu-MOF合成:密封条件下,有机配体5-(3,6-双(4-羧基苯基)-9H-咔唑-9-基)间苯二甲酸(H4BCBA),与硝酸铜(Cu(NO3)2)在N,N-二甲基甲酰胺(DMF)、三氟乙酸(TFA)的混合溶液中,经由溶剂热反应得到该金属-有机框架的晶体。有机配体5-(3,6-双(4-羧基苯基)-9H-咔唑-9-基)间苯二甲酸(H4BCBA)与Cu(NO3)2的摩尔比为1:(2~6),每0.04mmol的Cu(NO3)2对应1mL~4mL的DMF,0.01mL~0.1mL的TFA。热反应的温度为80℃-135℃,反应时间为12~48小时。
本发明的金属-有机框架结构新颖、框架稳定、孔道尺寸大、比表面积大,在气体存储中具有潜在的应用。
附图说明
图1为该咔唑-羧酸配体的合成路线图。
图2为该咔唑-羧酸配体的1H核磁共振谱图。
图3为该金属-有机框架的配体及金属离子配位模式图。
图4为该金属-有机框架的三维结构示意图。
图5为该金属-有机框架材料在77K条件下N2吸附解吸曲线图。
图6为该金属-有机框架材料在298K条件下乙炔和二氧化碳单组分吸附曲线图。
图7为该金属-有机框架材料在298K条件下分离乙炔/二氧化碳(50/50)混合气的IAST选择性示意图。
具体实施方式
下面结合实施例对本发明作进一步说明,但本发明并不限于以下实施例。
实施例1
将有机配体H4BCBA(0.04mmol)与Cu(NO3)2(0.04mmol)在2.0mL的N,N-二甲基甲酰胺中混合均匀,加入0.01mL三氟乙酸,封入小瓶中。在100℃下经由热反应48小时得到该金属-有机框架的晶体。
实施例2
将有机配体H4BCBA(0.04mmol)与Cu(NO3)2(0.04mmol)在2.0mL的N,N-二甲基甲酰胺中混合均匀,加入0.01mL三氟乙酸,封入小瓶中。在90℃下经由热反应48小时得到该金属-有机框架的晶体。
上述实施例所得的产品的测试结果相同,具体见下述:
晶体结构的确定:
选取大小合适的单晶,在室温下,利用Agilent Technologies SuperNova X-射线单晶衍射仪收集数据。数据收集使用经滤镜单色器单色化的Cu-Kα(λ=)靶射线。数据的吸收校正使用SCALE3ABSPACK软件完成。晶体结构使用SHELXTL-97程序通过直接法解析得到。先用差值函数法和最小二乘法确定全部非氢原子坐标,并用理论加氢法得到氢原子位置,然后用SHELXTL-97对晶体结构进行精修。结构图见图2和图3。晶体学数据见表1。
表1金属有机框架材料的晶体学数据
图1展示了该咔唑-羧酸配体的合成路线。
图2的配体的1H核磁共振谱图表明:将5-(3,6-双(4-(甲氧基羰基苯基)-9H-咔唑-9-基)间苯二甲酸酯脱去保护基团后水解酯基得到了5-(3,6-双(4-羧基苯基)-9H-咔唑-9-基)间苯二甲酸。
图3的配位环境图表明:从拓扑学角度看,每个BCBA4-配体都可以看作是具有四面体构型的4-连接的节点,与此同时Cu2簇可以看作是4-连接的顶点,这两种类型的结构单元交替连接形成了一个(4,4)-连接具有nou拓扑的网络,其施莱夫利符号(symbol)为{4.65}2{42.84}{64.82}。
图4的结构图表明:该金属-有机框架材料沿a轴方向存在大小为 (垂直两个方向上孔道最小的尺寸)的五边形孔道。
图5中的氮气吸附曲线表明:该Cu-MOF在77K下N2吸附表现为经典I型曲线,利用专业的商品化的物理吸附仪或化学吸附仪,先将吸附剂在一定温度下以真空或吹扫气的形式对其进行彻底脱气,再在恒定温度下,控制吸附质与载气的分压,使吸附体系逐步达到平衡。这种通过控制吸附质分压与相应的平衡吸附量的关系所得到的实验曲线即为吸附等温线。习惯上,将由实验得到的吸附和脱附过程得到的等温线统称为吸附等温线。Ⅰ型等温线:Langmuir等温线,相应于朗格缪单层可逆吸附过程,是窄孔进行吸附,而对于微孔来说,可以说是体积充填的结果。样品的外表面积比孔内表面积小很多,吸附容量受孔体积控制。平台转折点对应吸附剂的小孔完全被凝聚液充满。这类等温线在接近饱和蒸气压时,由于微粒之间存在缝隙,会发生类似于大孔的吸附,等温线会迅速上升。该MOF材料的N2吸附表现的经典Ⅰ型等温线对应结构中的微孔通道,进一步证实了该材料实现气体吸附的结构基础。
图6为298K下金属-有机框架材料的气体吸附等温线图。从图中可以看出,该材料在298K时对C2H2和CO2的最大吸附量分别为65.92cm3·g-1和22.187cm3·g-1。该Cu-MOF对两种气体具有较高的吸附容量,同时框架与乙炔气体分子作用力更强,具体表现为298K,低压区等压力下乙炔吸附量更大。这一现象为该材料应用于乙炔/二氧化碳混合气分离纯化奠定了基础。
图7为CO2与C2H2(50:50)在298K下的IAST选择性吸附图,理想吸附溶液理论(IAST)是一种热力学理论,它可以通过一系列单一气体的吸附等温曲线来预测混合气体的选择性,大大降低了实验中测试混合气体选择性的难度。根据IAST对MOF进行了吸附选择性计算,定量地获得了CO2/C2H2混合物的分离性能。
Claims (9)
1.一种Cu基微孔金属-有机框架材料,其特征在于,化学分子式为[Cu2(H2O)2(BCBA)],H4BCBA为有机配体5-(3,6-双(4-羧基苯基)-9H-咔唑-9-基)间苯二甲酸,分子式为C34H21NO8,H4BCBA化学结构式为:
2.按照权利要求1所述的Cu基微孔金属-有机框架材料,其特征在于,从框架连接构筑的角度,该金属-有机框架的晶体结构属于单斜晶系,空间群为P21/n,晶胞参数为 α=90°,β=102.697(5)°,γ=90°。
3.按照权利要求1所述的Cu基微孔金属-有机框架材料,其特征在于,从拓扑学角度看,每个BCBA4-配体都可以看作是具有四面体构型的4-连接的节点,与此同时Cu2簇可以看作是4-连接的顶点,这两种类型的结构单元交替连接形成了一个(4,4)-连接具有nou拓扑的网络,其施莱夫利符号(symbol)为{4.65}2{42.84}{64.82}。
4.按照权利要求1所述的Cu基微孔金属-有机框架材料,其特征在于,该金属-有机框架材料沿a轴方向存在大小为的五边形孔道,上述尺寸为垂直两个方向上孔道最小的尺寸;较大的孔结构使得该金属-有机框架适用于气体存储。
5.制备权利要求1-4所述的Cu基微孔金属-有机框架材料,其特征在于,密封条件下,有机配体5-(3,6-双(4-羧基苯基)-9H-咔唑-9-基)间苯二甲酸(H4BCBA),与硝酸铜(Cu(NO3)2)在N,N-二甲基甲酰胺(DMF)、三氟乙酸(TFA)的混合溶液中,经由溶剂热反应得到该金属-有机框架的晶体。
6.按照权利要求5所述的方法,其特征在于,有机配体5-(3,6-双(4-羧基苯基)-9H-咔唑-9-基)间苯二甲酸(H4BCBA)与Cu(NO3)2的摩尔比为1:(2~6),优选1:2;
所选用的铜源为硝酸铜、醋酸铜、硫酸铜、氯化铜中的一种或几种或者其他铜盐,优选硝酸铜。
7.按照权利要求5所述的方法,其特征在于,每0.04mmol的Cu(NO3)2对应1mL~4mL的DMF,0.01mL~0.1mL的TFA。热反应的温度为80℃-135℃,反应时间为12~48小时。
8.按照权利要求1-7所述的任意一项所述的Cu基微孔金属-有机框架材料的应用,用于选择性分离乙炔和二氧化碳混合气。
9.按照权利要求8所述的应用,该Cu-MOF材料经过DMF洗涤以后,在经过溶剂交换并真空脱除客体分子后得到的材料用于选择性分离乙炔/二氧化碳混合气的最终分离材料,在分离过程中优先吸附乙炔;其中用于交换的溶剂特征在于尺寸较小,沸点较低。
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