A Comparison of Two Isoreticular Metal–Organic Frameworks with Cationic and Neutral Skeletons: Stability, Mechanism, and Catalytic Activity. Issue 11 (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 international edition. Volume 59:Issue 11(2020)
• Page Start: 4385
• Page End: 4390
• Publication Date: 2020-01-29
• Subjects: electrostatic interactions -- formic acid dehydrogenation -- heterogeneous catalysis -- metal–organic frameworks (MOFs) -- stability; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201916649
• Languages: English
• ISSNs: 1433-7851

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 : MOFing compares to you : Cationic PFC‐8 and neutral PFC‐9 have identical dative bonds, topology, and space group. Unlike neutral PFC‐9, the positively charged structure PFC‐8 can survive in various extremely harsh conditions (12 m HCl 301 days; aqua regia (86 days); seawater 30 days). Pd nanoparticles (NPs) immobilized in PFC‐8 gave high catalytic activity for formic acid (FA) dehydrogenation.