Synthesis and Modification of Formate Zr‐MOF (ZrFA) Toward Scalable and Cost‐Cutting Gas Separation

The mass production of metal-organic frameworks (MOFs) with affordable cost is highly demanding yet limited for commercial applications, e.g., purification of polymer-grade ethylene (C₂H₄) via acetylene (C₂H₂) and carbon dioxide (CO₂) removal faces the challenge of developing low-cost and large-scale physisorbents with efficiency and recyclability. Herein, we developed a viable synthetic protocol to scale-up a series of ultramicroporous Zr-MOFs (ZrFA/ZrFA-D/ZrFA-D-Cu(I)) with the simplest monocarboxylate, formate (FA), through consecutive production by recycling solvent/modulator. Besides a size-exclusion effect disfavoring C₂H₄ adsorption, introduction of defective and Cu(I) sites was found to enhance gas affinity and uptake capacity. A comprehensive evaluation of C₂H₄ separation and economic efficiency has been proposed, suggesting the improvement of C₂H₂ uptake capacity is effective for the binary C₂H₂/C₂H₄ separation, while the separation process of the ternary C₂H₂/CO₂/C₂H₄ mixtures depends on subtle tradeoff of complex factors and limited by challenging CO₂/C₂H₄ separating. Notably, the large-scale separation has been testified to significantly improve separation efficiency, and the low-cost preparation benefits high economic efficiency. The distinct C₂H₂/C₂H₄/CO₂ adsorption mechanism in ZrFA/ZrFA-D/ZrFA-D-Cu(I) has been elucidated by the theoretical calculations. This work may shed a light on the future C₂H₄ purification technology by pushing MOF-syntheses toward low-cost, scale-up, and recyclable production.