Ab iomimetic catalyst ……f CO 2 photoreduction was developed through self-assembling porphyrins a hydrogen-bonded organic framework, as reported by Tian-Fu Liu, Rong Cao,a nd coworkers in their Research Article (e202203955). Thec ombination of photosensitizers and redox centers in the structure not only allows for adequate photon input and efficient utilization of the photogenerated charge,b ut also changes the microenvironment surrounding the active sites.
h h h h h h a a a a af f f f f f f f f ft t t t t t D D D D D De e eu u ut t ts sc c ch h he er r C . . Ein biomimetischer Katalysator … …f ürd ie CO durch Selbstorganisation von Porphyrinen in einer wasserstoffgebundenen organischen Gerüststruktur entwickelt, wie Tian-Fu Liu, Rong Cao und Mitarbeiter in ihrem Forschungsartikel berichten (e202203955). Die Kombination von Photosensibilisatoren und Redoxzentren in der Struktur ermçglicht nicht nur einen hohen Photonen-Input und eine effiziente Nutzung der photogenerierten Ladung, sondern verändert auch die Mikroumgebung der aktiven Zentren.
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), H2O2 (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.
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