CN113278159B - 分离乙炔/二氧化碳混合气体的铁镍金属有机框架材料及其制备方法 - Google Patents
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Abstract
本发明提供了一种分离乙炔/二氧化碳混合气体的铁镍金属有机框架材料及其制备方法。该铁镍金属有机框架材料化学式为[Fe2Ni(O)(C14H4F4O4)(C27H15O6)4/3(H2O)3]，C14H4F4O4代表3,3',5,5'‑四氟联苯‑4,4'‑二甲酸配体脱去两个甲酸氢原子的分子式，C27H15O6代表1,3,5‑三(4‑羧基苯基)苯配体脱去三个甲酸氢原子的分子式，三方晶系，空间群为R3m，单胞参数为a=33.2～33.3Å，b=33.2～33.3Å，c=23.1～23.2Å，
=90º,
=90º，
=120º，Z=9。其制备方法：将氯化铁、硝酸镍、3,3',5,5'‑四氟联苯‑4,4'‑二羧酸、1,3,5‑三(4‑羧基苯基)苯和有机溶剂置于高压釜中，再加入醋酸，然后在373~393 K下反应，得到所述铁镍金属有机框架材料。该铁镍金属有机框架材料能有效分离乙炔/二氧化碳的混合气体。
Description
技术领域
本发明涉及一种可选择性吸附分离乙炔/二氧化碳混合气体的铁镍金属有机框架材料及其制备方法。
背景技术
金属有机框架材料是由无机金属离子或金属团簇与有机配体通过配位键形成的具有三维周期性网络结构的新型晶态多孔材料。其无机金属离子多为过渡金属、稀土金属和主族金属，如锆、铁、铟、锌、镍和铽等；而有机配体多为含氧、氮和硫等多齿有机配体（如咪唑类，芳香族多元羧酸和多元醇等）。金属有机框架材料结合了无机化合物的刚性和有机高分子材料的柔性特点，具有孔隙率高、比表面积大、热稳定性好、结构多样性和可设计性等优点，在离子交换、磁性、催化、光学、医学、燃料电池以及气体吸附和分离等多个领域具有广阔的应用前景。尤其在气体吸附和分离方面，金属有机框架能利用其本身特有的结构及其对不同气体吸附性能的差异来实现对各组分气体的吸附和分离。
在当今“气体时代”背景下，气体的重要性与日俱增，这就要求气体要有更高的纯度，但在实际生产中，传统的气体分离和纯化需要消耗大量能源，因此急需开发一种高效、环保的气体分离的新技术。在这种背景下，化学家和工程师们将解决问题的关键转向多孔材料，通过低能耗低污染的物理方法来实现气体的吸附和分离。而金属有机框架材料可以利用其自身多孔特性以及孔隙大小的可控性来来实现气体分离的目的，这可以有效解决基于低温分离、蒸馏、化学吸附或溶剂萃取等过程中大量的能耗，大大提高了能源效率，同时在一定程度上可以降低的工厂规模和成本。
乙炔(C2H2)作为石化工业中最关键的原料化学品之一，广泛应用于多种精细化学品的生产中，如丙烯酸甲酯、丁炔二醇、乙烯基衍生物、乙炔醇和电子器件等。作为一种重要化工原材料，工业上需要较高纯度的乙炔，而乙炔在生产过程中会产生二氧化碳杂质，但由于乙炔/二氧化碳尺寸和沸点的相似性，因此它们的分离非常艰难。传统的乙炔/二氧化碳分离是基于丙酮和N-甲基吡咯烷酮的溶剂萃取法，在萃取过程中大量使用了挥发性有机溶剂，会造成严重的环境问题和能源消耗，因此迫切需要开发一种高效、环保的分离乙炔/二氧化碳的新技术。
发明内容
本发明的目的在于提供一种铁镍金属有机框架材料及其制备方法，该金属有机框架材料可作为选择性吸附分离乙炔/二氧化碳混合气体的功能材料。
第一方面，本发明提供一种铁镍金属有机框架材料，其化学式为[Fe2Ni(O)
(C14H4F4O4)(C27H15O6)4/3(H2O)3]，C14H4F4O4代表3,3',5,5'-四氟联苯-4,4'-二甲酸配体脱去
两个甲酸氢原子的分子式，C27H15O6代表1,3,5-三(4-羧基苯基)苯配体脱去三个甲酸氢原子
的分子式，属于三方晶系，空间群为R3m，单胞参数为a = 33.2～33.3Å，b = 33.2～33.3 Å，c = 23.1～23.2 Å，
= 90 º, 
=90º，
= 120 º，Z = 9。
第二方面，本发明提供一种铁镍金属有机框架材料的制备方法，其包括以下步骤：
将氯化铁、硝酸镍、3,3',5,5'-四氟联苯-4,4'-二羧酸、1,3,5-三(4-羧基苯基)苯和有机溶剂置于高压釜中，再加入醋酸，然后在373~393 K下反应，得到所述铁镍金属有机框架材料。
进一步地，所述氯化铁、硝酸镍、3,3',5,5'-四氟联苯-4,4'-二羧酸和1,3,5-三(4-羧基苯基)苯的摩尔比例为(2~4) : (1~3) : (1~3) : (1~3)。优选地，所述氯化铁、硝酸镍、3,3',5,5'-四氟联苯-4,4'-二羧酸和1,3,5-三(4-羧基苯基)苯的摩尔比例为2:1:1:1。
进一步地，所述有机溶剂为N,N-二甲基甲酰胺，所述氯化铁与N,N-二甲基甲酰胺的摩尔比为1:800~1:1200。
进一步地，所述醋酸的浓度为17.5摩尔/升，所述醋酸与N,N-二甲基甲酰胺的体积比为1:5~1:15。
进一步地，所述反应时间为2天。
第三方面，本发明提供一种铁镍金属有机框架材料的应用，所述铁镍金属有机框架材料能够作为选择性吸附分离乙炔/二氧化碳混合气体的功能材料。
有机配体3,3',5,5'-四氟联苯-4,4'-二羧酸和1,3,5-三(4-羧基苯基)苯具有高共轭的苯环、强配位能力的氧原子，以及三核铁簇的稳定结构可以构筑出具有新颖结构和特殊功能的的金属有机框架材料。同时金属有机框架材料的孔隙中有大量氟原子可以修饰孔道环境的吸附位点，以调控与不同气体分子的作用力而达到气体分离的目的。
本发明的优点是：1、铁镍金属有机框架材料可选择性吸附分离乙炔/二氧化碳混合气体，且分离性好，乙炔/二氧化碳混合气体（摩尔比为50:50）的分离系数为2~4；2、铁镍金属有机框架材料的制备方法简单，易操作、原料来源充足、反应的产率较高，纯度高以及稳定性好，使得其适合扩大化生产的要求。
附图说明
图1为本发明的铁镍金属有机框架材料的分子结构图。
图2为本发明的铁镍金属有机框架材料的三维结构图。
图3为本发明的铁镍金属有机框架材料对乙炔/二氧化碳混合气体的分离曲线图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明的金属有机框架材料[Fe2Ni(O)(C14H4F4O4)(C27H15O6)4/3(H2O)3]的合成（C14H4F4O4代表3,3',5,5'-四氟联苯-4,4'-二甲酸配体脱去两个甲酸氢原子的分子式，C27H15O6代表1,3,5-三(4-羧基苯基)苯配体脱去三个甲酸氢原子的分子式），[Fe2Ni(O)(C14H4F4O4)(C27H15O6)4/3(H2O)3]是采用常规溶剂热法得到的，具体反应式为：，
C14H6F4O4(3,3',5,5'-四氟联苯-4,4'-二羧酸)+4/3C27H18O6(1,3,5-三(4-羧基苯基)苯)+2 FeCl3+Ni(NO3)2+4H2O→[Fe2Ni(O)(C14H4F4O4)(C27H15O6)4/3(H2O)3]+ 2HNO3+6HCl
实施例1：将氯化铁、硝酸镍、3,3',5,5'-四氟联苯-4,4'-二羧酸和1,3,5-三(4-羧基苯基)苯按2:1:1:1的摩尔比例混合放入盛有2毫升N,N-二甲基甲酰胺溶剂的体积为20毫升的聚四氟乙烯内衬的高压釜中，再加入0.19毫升浓度为17.5摩尔/升的醋酸，其中氯化铁的量控制在8.1毫克左右，然后恒温在373~393 K下反应2天，得到棕色晶体为铁镍金属有机框架材料，产率约为67％。
实施例2：将氯化铁、硝酸镍、3,3',5,5'-四氟联苯-4,4'-二羧酸和1,3,5-三(4-羧基苯基)苯按2:1:2:1的摩尔比例混合放入盛有2毫升N,N-二甲基甲酰胺溶剂的体积为20毫升的聚四氟乙烯内衬的高压釜中，再加入0.21毫升浓度为17.5摩尔/升的醋酸，其中氯化铁的量控制在8.1毫克左右，然后恒温在373~393 K下反应2天，得到棕色晶体为铁镍金属有机框架材料，产率约为69％。
对实施例1得到的棕色晶体进行测试。单晶X射线衍射仪测试表明该棕色晶体为目标化合物，即铁镍金属有机框架材料。X-射线单晶衍射数据在Agilent SuperNova单晶衍射仪收集。MoKα钼靶（波长为0.71073埃）以ω扫描方式收集衍射数据。通过SHELXL-2018程序利用直接法和全矩阵最小二乘法得到所有非氢坐标，化合物的“晶体学参数”见表1，分子结构图请见图1，三维结构图请见图2。
表1. 铁镍金属有机框架材料[Fe2Ni(O)(C14H4F4O4)(C27H15O6)4/3(H2O)3]的晶体学参数与结构解析
注：R 1＝∑||F o|-|F c||/∑|F o|，wR 2＝[∑w(F o 2-F c 2)2/∑w(F o 2)2]0.5。
上述实施例中的铁镍金属有机框架材料是棕色晶体，该晶体的结构包含由一个羟基桥连两个铁离子和一个镍离子组成的三核簇[Fe2Ni(μ3-OH)]单元，每个三核簇Fe2Ni(μ3-OH)]通过2个3',5,5'-四氟联苯-4,4'-二羧酸配体和4个1,3,5-三(4-羧基苯基)苯配体的桥连形成了三维结构（图2），因此，它是一个三维结构的金属有机框架材料。
如表1所示，本发明的晶体结构参数为：三方晶系，空间群为R3m，单胞参数为a =
33.2～33.3Å，b = 33.2～33.3 Å，c = 23.1～23.2 Å，
= 90 º, 
=90º，
= 120 º，Z
= 9。铁镍金属有机框架材料对于乙炔/二氧化碳混合气体（摩尔比为50:50）的分离系数为2
~4，说明该铁镍金属有机框架材料可以作为一种选择性吸附分离乙炔/二氧化碳混合气体
的材料。在298 K和一个大气压下，以2 毫升/分钟的气体流量把乙炔/二氧化碳混合气体
（摩尔比为50:50）通到装载有铁镍金属有机框架材料的柱子中，用气相色谱检测柱子内流
出气体的成分，测试结果如图3所示，在60分钟左右，铁镍金属有机框架材料对混合气体开
始分离，二氧化碳气体先流出，而乙炔气体被吸附在铁镍金属有机框架材料内，直至110分
钟左右，乙炔才开始从镍配位聚合物材料中流出，220分钟左右乙炔吸附达到饱和。说明该
铁镍金属有机框架材料可以对乙炔/二氧化碳混合气体进行有效分离。
以上实施方式仅用于说明本发明，而并非对本发明的限制，有关技术领域的普通技术人员，在不脱离本发明的精神和范围的情况下，还可以做出各种变化和变型，因此所有等同的技术方案也属于本发明的范畴，本发明的保护范围应由权利要求限定。
Claims (6)
1.一种铁镍金属有机框架材料，其特征在于：化学式为[Fe2Ni(O)(C14H4F4O4)(C27H15O6)4/3(H2O)3]，C14H4F4O4代表3,3',5,5'-四氟联苯-4,4'-二甲酸配体脱去两个甲酸氢原子的分子式，C27H15O6代表1,3,5-三(4-羧基苯基)苯配体脱去三个甲酸氢原子的分子式，属于三方晶系，空间群为R3m，单胞参数为a = 33.2~33.3Å，b = 33.2~33.3 Å，c = 23.1~23.2 Å，α= 90 º, β =90º，γ= 120 º，Z = 9。
2.一种铁镍金属有机框架材料的制备方法，其包括以下步骤：
将氯化铁、硝酸镍、3,3',5,5'-四氟联苯-4,4'-二羧酸、1,3,5-三(4-羧基苯基)苯和有机溶剂置于高压釜中，再加入醋酸，然后在373~393 K下反应，得到所述铁镍金属有机框架材料；所述氯化铁、硝酸镍、3,3',5,5'-四氟联苯-4,4'-二羧酸和1,3,5-三(4-羧基苯基)苯的摩尔比例为2:1:1:1。
3.根据权利要求2所述的方法，其特征在于：所述有机溶剂为N,N-二甲基甲酰胺，所述氯化铁与N,N-二甲基甲酰胺的摩尔比为1:800~1:1200。
4.根据权利要求2所述的方法，其特征在于：所述醋酸的浓度为17.5摩尔/升，所述醋酸与N,N-二甲基甲酰胺的体积比为1:5~1:15。
5.根据权利要求2所述的方法，其特征在于：所述反应时间为2天。
6.根据权利要求1所述的铁镍金属有机框架材料的应用，其特征在于：所述铁镍金属有机框架材料用于分离乙炔/二氧化碳混合气体。
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