An atomically economical and environmentally benign approach for the scalable synthesis of rare‐earth <scp>metal‐organic framework</scp> catalysts

Abstract Metal–organic frameworks (MOFs), as an emerging class of porous materials, demonstrated substantial potential for applications in chemical engineering processes. However, their production often generates significant waste including ionic residues and organic solvents, posing considerable environmental concerns. Herein, we report the environmentally benign MOF synthesis with metal oxides precursors, yielding water as the exclusive by‐product. This approach not only enhances atom economy but also promotes solvent recycling by preventing anion accumulation, significantly reducing waste generation. The synthesis can be easily scaled up in a 10‐L reactor with an impressive space–time yield of 608 kg·m −3 ·day −1 . Furthermore, MOF‐76(Y) was implemented in a reactor for catalytic cycloaddition reaction at kg‐scale. Through optimization of the interfacial contact between CO 2 and the reaction liquid phase, a yield of 96.7% was achieved under mild conditions. This work demonstrates a rare example of scalable and sustainable synthesis of MOF materials coupled with catalysis implementation at kilogram scale.