A Novel Cerium(IV)‐Based Metal‐Organic Framework for CO2 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 IBU chain containing Ce^IV -MOF, CSUST-3 (CSUST: Changsha University of Science and Technology), was successfully prepared using the kinetic stabilization study of UiO-66(Ce)-NDC (H₂ NDC=2,6-naphthalenedicarboxylic acid). Furthermore, owing to the superior redox activity, Lewis acidity and semiconductor-like behavior owing to Ce⁴⁺ , activated CSUST-3 was demonstrated to be an excellent catalyst for CO₂ chemical fixation. One-pot synthesis of styrene carbonate from styrene and CO₂ was achieved under mild conditions (1 atm CO₂ , 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^-1 h^-1 of H₂ and 22 μmol g^-1 h^-1 of O₂ under simulated sunlight irradiation (Na₂ S-Na₂ SO₃ as sacrificial agent).