Tailor-Made Pyrazolide-Based Metal–Organic Frameworks for Selective Catalysis

Abstract

The predesignable porous structures in metal-organic frameworks (MOFs) render them quite attractive as a host-guest platform to address a variety of important issues at the frontiers of science. In this work, a perfluorophenylene functionalized metalloporphyrinic MOF, namely, PCN-624, has been rationally designed, synthesized, and structurally characterized. PCN-624 is constructed by 12-connected [Ni(OH)(HO)Pz] (Pz = pyrazolide) nodes and fluorinated 5,10,15,20-tetrakis(2,3,5,6-tetrafluoro-4-(1 H-pyrazol-4-yl)phenyl)-porphyrin (TTFPPP) linker with an ftw-a topological net. Notably, PCN-624 exhibits extinguished robustness under different conditions, including organic solvents, strong acid, and base aqueous solutions. The pore surface of PCN-624 is decorated with pendant perfluorophenylene groups. These moieties fabricate densely fluorinated nanocages resulting in the selective guest capture of the material. More importantly, PCN-624 can be employed as an efficient heterogeneous catalyst for the selective synthesis of fullerene-anthracene bisadduct. Owing to the high chemical robustness of PCN-624, it can be recycled over five times without significant loss of its catalytic activity. All of these results demonstrate that MOFs can serve as a powerful platform with great flexibility for functional design to solve various synthetic problems.

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 …”

A Phthalocyanine‐Based Layered Two‐Dimensional Conjugated Metal–Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction

“…[1,2] Due to the diversity in composition/ structure,h igh surface area, and chemical/thermal stability, MOFs have been applied in many areas including gas separation/storage,s ensors,a nd catalysis. [3][4][5][6][7][8] Recently, MOFs have been rising as af ascinating family of electrocatalysts providing insight in both homogeneous and heterogeneous chemistry:t he well-defined structures and readily accessible active sites can be tuned at the molecular level to improve the catalytic performance and they also enable the MOFs to serve as model systems for the fundamental understanding of catalytic mechanisms.R ecently,v arious MOFs,s uch as [Cu 2 (OH)(bpy) 2 (btc) 3 ], [Fe 2 (Fe(tcpp))Cl], [Cu 3 (btc) 2 (H 2 O) 3 ], and [Co(mim) 2 ], have been explored as oxygen reduction reaction (ORR) electrocatalysts. [2,[9][10][11][12] However,g reat challenges still remain for conventional MOFs including electrical insulators and the blockage of metal centers by organic ligands;this leads to inferior activity (halfwave potential E 1/2 < 0.8 Vv s. RHE) and dramatically limits their broader applications in electrocatalysis.P yrolysis of MOFs to provide metal-and heteroatom-doped porous carbons has been widely demonstrated to improve the catalytic activity.…”

A Phthalocyanine‐Based Layered Two‐Dimensional Conjugated Metal–Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction

“…Metal–organic frameworks (MOFs), one class of highly ordered crystalline coordination polymers with well‐defined porous networks, are formed by metal ions or clusters and organic ligands . Due to the diversity in composition/structure, high surface area, and chemical/thermal stability, MOFs have been applied in many areas including gas separation/storage, sensors, and catalysis . Recently, MOFs have been rising as a fascinating family of electrocatalysts providing insight in both homogeneous and heterogeneous chemistry: the well‐defined structures and readily accessible active sites can be tuned at the molecular level to improve the catalytic performance and they also enable the MOFs to serve as model systems for the fundamental understanding of catalytic mechanisms.…”