A Novel Cerium(IV)‐Based Metal‐Organic Framework for CO 2 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(IV) species in solution, it is still a great challenge to synthesize Ce(IV)-MOFs with novel structures, which are extremely dominated by the hexanuclear Ce-O cluster inorganic building units (IBUs). Herein, a Ce-O chain IBU containing Ce(IV)-MOF CSUST-3 (CSUST: Changsha University of Science and Technology) was successfully prepared guided by the kinetic stabilization study of UiO-66(Ce)-NDC (H 2 NDC = 2,6-naphthalenedicarboxylic acid). Furthermore, owing to the superior redox activity, Lewis acidity and semiconductor-like behavior incurred by Ce 4+ , activated CSUST-3 was demonstrated to be an excellent catalyst for CO 2 chemical fixation by virtue of one-pot synthesis of styrene carbonate from styrene and CO 2 under mild conditions (1 atm CO 2 , 80 °C, and solvent-free), as well as to be a remarkable co-catalyst-free photocatalyst for overall water splitting (OWS), which exhibits 59 μmol∙g -1 ∙h -1 of H 2 and 22 μmol∙g -1 ∙h -1 of O 2 under simulated sunlight irradiation (Na 2 S-Na 2 SO 3 as sacrificial agent).