During the utilization of structural and functional advantages of polyoxometalates (POMs) for enhanced applications, a suitable assembly of these clusters in framework materials to act as binding nodes represents a promising approach. In contrast to well-developed coordination/covalent combinations, we have developed a convenient strategy to build porous structures of POMs with smaller-sized counterions as bridging ligands via ionic interactions to reinforce their capability in gas adsorption in parallel to metal–organic frameworks (MOFs)/covalent organic frameworks (COFs). With this goal, a series of POMs-based ionic frameworks (IFs) were constructed with triol-ligand modified Anderson–Evans-type clusters as building blocks, and their sodium counter-cations were used as linkers. The three-dimensional (3D) open-frameworks obtained displayed unusually selective CO₂ capturing capability and efficient separation from their N₂, H₂, and CH₄ mixtures under low pressure at room temperature. Among the synthesized IFs, the cobalt-centered cluster exhibited the best performance for the uptake and selective separation of CO₂ over N₂ and CH₄ in a range of 0–1 bar, while the nickel-centered cluster displayed the highest selectivity over H₂ at 1 bar. Breakthrough experiments based on real binary gas mixtures demonstrated that the cobalt-containing framework illustrated high performance in the actual gas separation and sustained stability against a simulated operating environment.

在利用多金属氧酸盐（POM）的结构和功能优势来增强应用的过程中，将这些簇适当地组装在框架材料中以用作结合节点代表了一种有前途的方法。与发达的配位/共价组合相反，我们已经开发了一种便捷的策略，可通过离子相互作用建立具有较小抗衡离子作为桥连配体的POM的多孔结构，以增强它们在平行于金属-有机骨架（MOF）时的气体吸附能力）/共价有机框架（COF）。为了实现这一目标，使用三醇配体修饰的安德森-埃文斯型簇作为构建基构建了一系列基于POMs的离子框架（IF），并将其钠抗衡阳离子用作连接基。₂在室温下在低压下具有捕获能力并能有效分离N ₂，H ₂和CH ₄混合物。在合成的IFs中，以钴为中心的团簇在0-1 bar范围内对N ₂和CH _4上的CO ₂的吸收和选择性分离表现出最佳性能，而以镍为中心的团簇对H的选择性最高。₂在1巴。基于实际二元气体混合物的突破性实验表明，含钴骨架在实际气体分离中表现出很高的性能，并且在模拟操作环境下具有持续的稳定性。