Pore‐Environment Engineering with Multiple Metal Sites in Rare‐Earth Porphyrinic Metal–Organic Frameworks

Abstract

Multi-component metal-organic frameworks (MOFs) with precisely controlled pore environments are highly desired owing to their potential applications in gas adsorption, separation, cooperative catalysis, and biomimetics. A series of multi-component MOFs, namely PCN-900(RE), were constructed from a combination of tetratopic porphyrinic linkers, linear linkers, and rare-earth hexanuclear clusters (RE ) under the guidance of thermodynamics. These MOFs exhibit high surface areas (up to 2523 cm g ) and unlimited tunability by modification of metal nodes and/or linker components. Post-synthetic exchange of linear linkers and metalation of two organic linkers were realized, allowing the incorporation of a wide range of functional moieties. Two different metal sites were sequentially placed on the linear linker and the tetratopic porphyrinic linker, respectively, giving rise to an ideal platform for heterogeneous catalysis.

Metal–Organic Frameworks Encapsulating Active Nanoparticles as Emerging Composites for Catalysis: Recent Progress and Perspectives

“…For examples, SO 3 H group functions as Brønsted acid sites, while NH 2 group acts as base sites. Furthermore, the chemical environments of pore walls including hydrophilic/hydrophobic properties are easily tuned for effective adsorption of substrates and reagents, thus increasing the catalytic efficiency . Hence, MOFs themselves possess many intriguing features to become new generation of heterogeneous catalysts, and moreover, they provide an ideal platform for molecular architecture toward catalyzing the specific reactions …”

Ultramicroporous Building Units as a Path to Bi‐microporous Metal–Organic Frameworks with High Acetylene Storage and Separation Performance

“…[4] Adsorption-based separation will be an important technology for the future C 2 H 2 /CO 2 separation. There has been as harp increase in the study on crystalline porous materials in the past 30 years,especially on metal-organic frameworks (MOFs) [6,7] because of the diverse selection of organic ligands and metal ions/clusters. How to simultaneously increase adsorption capacity, selectivity,a sw ell as the stability of the adsorbents is ab ottleneck.…”

Molecular Pivot‐Hinge Installation to Evolve Topology in Rare‐Earth Metal–Organic Frameworks

“…[25] Fori nstance,the connectivity of 12-c RE 9 clusters in the structure of PCN-905-SO 2 can be further increased to eighteen, as seen in the structure of gea-MOF-1 and PCN-918. [25] Fori nstance,the connectivity of 12-c RE 9 clusters in the structure of PCN-905-SO 2 can be further increased to eighteen, as seen in the structure of gea-MOF-1 and PCN-918.…”