A Novel Cerium(IV)-Based Metal-Organic Framework for CO Chemical Fixation and Photocatalytic Overall Water Splitting.

Cerium (IV)-based metal-organic frameworks (MOFs) are highly desirable due to their unique potential in fields such as redox catalysis and photocatalysis. However, due to the high reduction potential of Ce species in solution, it is still a great challenge to synthesize Ce -MOFs with novel structures, which are extremely dominated by the hexanuclear Ce-O cluster inorganic building units (IBUs). Herein, a Ce-O IBU chain containing Ce -MOF, CSUST-3 (CSUST: Changsha University of Science and Technology), was successfully prepared using the kinetic stabilization study of UiO-66(Ce)-NDC (H NDC=2,6-naphthalenedicarboxylic acid). Furthermore, owing to the superior redox activity, Lewis acidity and semiconductor-like behavior owing to Ce , activated CSUST-3 was demonstrated to be an excellent catalyst for CO chemical fixation. One-pot synthesis of styrene carbonate from styrene and CO was achieved under mild conditions (1 atm CO , 80 °C, and solvent free). Moreover, activated CSUST-3 was shown to be a remarkable co-catalyst-free photocatalyst for overall water splitting (OWS), rendering 59 μmol g  h of H and 22 μmol g  h of O under simulated sunlight irradiation (Na S-Na SO as sacrificial agent).