Vertex Strategy in Layered 2D MOFs: Simultaneous Improvement of Thermodynamics and Kinetics for Record C₂H₂/CO₂...

Developing adsorbents with multiple merits in capacity, selectivity, mass transfer, and stability toward C₂H₂/CO₂ separation is crucial and challenging for producing high-purity C₂H₂ for advanced polymers and the electronic industry. Here, we demonstrate a vertex strategy to create adsorbents combining these merits through rationally designing the vertex groups of a wavy-shaped framework in layered 2D metal-organic frameworks (MOFs) to finely regulate the local conformation and stacking interactions, which creates the optimal inter- and intralayer space to realize simultaneous improvement of adsorption thermodynamics and kinetics. Two new hydrolytically stable MOFs, ZUL-330 and ZUL-430, were prepared, and diverse experiments and modeling on both adsorption equilibrium and diffusion were performed. Record separation selectivities coupled with extraordinary dynamic C₂H₂ capacities were achieved for C₂H₂/CO₂ mixtures with different proportions (50/50 or 10/5, v/v), along with a small diffusion barrier and fast mass transfer. Consequently, polymer-grade (99.9%) and electronic-grade (99.99%) C₂H₂ were obtained with excellent productivities of up to ∼6 mmol cm^-3.