Atomically isolated Sb(CN)3 on sp2-c-COFs with balanced hydrophilic and oleophilic sites for photocatalytic C-H activation.
Sci Adv
; 10(5): eadl5432, 2024 Feb 02.
Article
em En
| MEDLINE
| ID: mdl-38295163
ABSTRACT
Activation of carbon-hydrogen (C-H) bonds is of utmost importance for the synthesis of vital molecules. Toward achieving efficient photocatalytic C-H activation, our investigation revealed that incorporating hydrophilic C≡N-Sb(CN)3 sites into hydrophobic sp2 carbon-conjugated covalent organic frameworks (sp2-c-COFs) had a dual effect It simultaneously enhanced charge separation and improved generation of polar reactive oxygen species. Detailed spectroscopy measurements and simulations showed that C≡N-Sb(CN)3 primarily functioned as water capture sites, which were not directly involved in photocatalysis. However, the potent interaction between water molecules and the Sb(CN)3-modified framework notably enhanced charge dynamics in hydrophobic sp2-c-COFs. The reactive species ·O2- and ·OH (ad) subsequently combined with benzyl radical, leading to the formation of benzaldehyde, benzyl alcohol, and lastly benzyl benzoate. Notably, the Sb(CN)3-modified sp2-c-COFs exhibited a 54-fold improvement in reaction rate as compared to pristine sp2-c-COFs, which achieved a remarkable 68% conversion rate for toluene and an 80% selectivity for benzyl benzoate.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Sci Adv
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
China