Addressing the pressing challenge of high energy consumption and solvent waste in the industrial-scale production of metal-organic frameworks(MOFs),we report a rapid,green,and scalable mechanochemical strategy for the...Addressing the pressing challenge of high energy consumption and solvent waste in the industrial-scale production of metal-organic frameworks(MOFs),we report a rapid,green,and scalable mechanochemical strategy for the mass preparation of the highly efficient CO2 adsorbent,UTSA-16(Zn).Unlike conventional solvothermal methods,this protocol using zinc acetate and potassium citrate dramatically shortens the synthesis time from 48 h to just 6 h.This achieves a re markable 48-fold enhancement in space-time yield while reducing solvent consumption by approximately 90%.Crucially,we identify that the in-situ accumulation of acidic byproducts during grinding inhibits framework assembly.Precise pH modula tion using 0.2 equiv.of triethylamine(TEA)is essential to buffer the reaction environment,preventing defect formation and ensuring high product crystallinity.The resulting material is structurally isomorphous to its hydrothermally synthesized counterpart,possessing a consistent pore environment with a high BET surface area of 817 m2/g.In terms of performance,the mechanochemically derived UTSA-16(Zn)exhibits exceptional CO2 uptake(3.68 mmol/g at 296 K and 0.1 MPa)and an ultra-high ideal adsorbed solution theory(IAST)selectivity of 388 for CO2/N2 mixtures,driven by a significant difference in isosteric heats of adsorption.Dynamic breakthrough experiments further validate a robust dynamic CO2 capacity of 1.94 mmol/g and stable recyclability under simulated flue gas conditions.This work not only provides a practical manufacturing route for UTSA-16(Zn)but also underscores the pivotal role of pH regulation in the green synthesis of advanced porous ma terials.展开更多
摘要Addressing the pressing challenge of high energy consumption and solvent waste in the industrial-scale production of metal-organic frameworks(MOFs),we report a rapid,green,and scalable mechanochemical strategy for the mass preparation of the highly efficient CO2 adsorbent,UTSA-16(Zn).Unlike conventional solvothermal methods,this protocol using zinc acetate and potassium citrate dramatically shortens the synthesis time from 48 h to just 6 h.This achieves a re markable 48-fold enhancement in space-time yield while reducing solvent consumption by approximately 90%.Crucially,we identify that the in-situ accumulation of acidic byproducts during grinding inhibits framework assembly.Precise pH modula tion using 0.2 equiv.of triethylamine(TEA)is essential to buffer the reaction environment,preventing defect formation and ensuring high product crystallinity.The resulting material is structurally isomorphous to its hydrothermally synthesized counterpart,possessing a consistent pore environment with a high BET surface area of 817 m2/g.In terms of performance,the mechanochemically derived UTSA-16(Zn)exhibits exceptional CO2 uptake(3.68 mmol/g at 296 K and 0.1 MPa)and an ultra-high ideal adsorbed solution theory(IAST)selectivity of 388 for CO2/N2 mixtures,driven by a significant difference in isosteric heats of adsorption.Dynamic breakthrough experiments further validate a robust dynamic CO2 capacity of 1.94 mmol/g and stable recyclability under simulated flue gas conditions.This work not only provides a practical manufacturing route for UTSA-16(Zn)but also underscores the pivotal role of pH regulation in the green synthesis of advanced porous ma terials.