A Green Scalable Method to Prepare Zr Oxide Dicarboxylate Metal–Organic Frameworks

We report the synthesis of a series of isoreticular hydrophobic microporous zirconium dicarboxylate metal–organic frameworks (MOFs), MIL‐140(Zr)s, under green ambient pressure conditions. Their pore sizes and hydrophilic/hydrophobic balance can be finely adjusted with a view to potential applications. MIL‐140A(Zr) has a pore size of 3.2 Å, made from benzene dicarboxylate ligands, and MIL‐140B(Zr) has a pore size of 4 Å built from naphthalene dicarboxylate ligands, the latter with a more hydrophobic balance. We report herein the synthesis optimization, scale‐up, and shaping of this MOF series, avoiding the use of chemicals, organic solvents that are toxic or/and Carcinogenic, Mutagenic, Reprotoxic (CMR), and corrosive starting chemicals. The activation process required no additional washing/purification steps. Finally, we considered their use for the removal of traces of acetic acid for cultural heritage preservation applications in the presence of moisture from indoor air at museums, archives, and private collections. After a scale‐up of MIL‐140B(Zr) at a 50 g scale using a 5 L double‐wall batch reactor, we evaluated the performance of acetic acid capture under humid conditions. The performance of shaped MIL‐140B(Zr) in comparison with benchmark zeolites and activated carbons was also evaluated.