Green and scalable synthesis of a dual-ligand Zn-MOF with unprecedented space–time yield in aqueous media and efficient CH4/N2 separation†

Decades of research unveiled the unlimited potential of metal–organic frameworks (MOFs). Nevertheless, the hazardous and expensive production involving massive amounts of organic solvents has severely limited their widespread industrial adoption. Herein, the advantages of two eco-friendly strategies, base-assisted synthesis and modulated hydrothermal chemistry, were complementarily integrated, with the acetate anion introduced as a mild and efficacious modulator to regulate the coordination and tailor the crystallization pathway(s). The green, rapid, and scalable synthesis of a dual-ligand Zn-MOF was thereby achieved in water media, featuring an unprecedented space–time yield of 24 ton per m³ per day and a batch size exceeding a kilogram (i.e., 1.2 kg). Owing to its strong affinity toward CH₄, the acquired Zn-MOF demonstrated a considerable CH₄/N₂ separation capacity under ambient conditions. This study not only facilitates the green and scalable production of MOFs but also offers a cost-effective adsorbent for CH₄ recovery.