A Comparison of Two Isoreticular Metal–Organic Frameworks with Cationic and Neutral Skeletons: Stability, Mechanism, and Catalytic Activity. (29th January 2020)

• Record Type: Journal Article
• Authors: Huang, Ge; Yang, Li; Yin, Qi; Fang, Zhi‐Bin; Hu, Xiao‐Jing; Zhang, An‐An; Jiang, Jun; Liu, Tian‐Fu; Cao, Rong
• Is Part Of: Angewandte Chemie. Volume 132:Number 11(2020)
• Page Start: 4415
• Page End: 4420
• Publication Date: 2020-01-29
• Subjects: Ameisensäure-Dehydrierung -- Elektrostatische Wechselwirkungen -- Heterogene Katalyse -- Metall-organische Gerüste (MOFs) -- Stabilität; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201916649
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Although many ionic metal–organic frameworks (MOFs) have been reported, little is known about how the charge of the skeleton affects the properties of the MOF materials. Herein we report how the chemical stability of MOFs can be substantially improved through embedding electrostatic interactions in structure. A MOF with a cationic skeleton is impervious to extremely acidic, oxidative, reductive, and high ionic strength conditions, such as 12 m HCl (301 days), aqua regia (86 days), H2 O2 (30 days), and seawater (30 days), which is unprecedented for MOFs. DFT calculations suggested that steric hinderance and the repulsive interaction of the cationic framework toward positively charged species in microenvironments protects the vulnerable bonds in the structure. Diverse functionalities can be bestowed by substituting the counterions of the charged framework with identically charged functional species, which broadens the horizon in the design of MOFs adaptable to a demanding environment with specific functionalities. Abstract : Bleib positiv : Kationisches PFC‐8 und neutrales PFC‐9 weisen identische dative Bindungen, Topologie und Raumgruppen auf. Im Gegensatz zu neutralem PFC‐9 bleibt die positiv geladene Struktur PFC‐8 unter verschiedenen harschen Bedingungen stabil (in 12 m HCl für 301 Tage; in Königswasser für 86 Tage; in Seewasser für 30 Tage). In PFC‐8 immobilisierte Pd‐Nanopartikel ermöglichen eine hohe katalytische Aktivität zur Ameisensäure‐Dehydrierung.