Green CO₂/CS₂ Catalytic Fixation into High-Value Chemicals Promoted by a [Ce₂] Cluster-Based Metal-Organic Framework

The capture and transformation of excessive CO₂ and CS₂ waste into high-value-added chemicals are significant and challenging. Herein, the 2D lamellar metal-organic framework (MOF) {[Ce₂(DATP)₂(CH₃COO)₂(H₂O)₂]}_n (compound 1) (H₂DATP = 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine) has been harvested and characterized structurally, demonstrating exceptional thermal stability up to 424 °C and remarkable chemical robustness across a broad pH range from 1 to 13. Importantly, 1 as a heterogeneous catalyst exhibits superior performance for facilitating the cycloaddition of CO₂ with aziridine to produce oxazolidinone with a yield of 99% at 0.5 MPa and 50 °C for 12 h, as well as that of CS₂ with aziridine into thiazolidine-2-thione with a yield of 97% under ambient conditions for 7 h. Notably, the catalytic activity of compound 1 does not significantly decrease after five cycles, which has been confirmed by Powder X-ray diffraction (PXRD) analysis. The reaction mechanisms have been comprehensively investigated through an integrated approach combining substrate activation studies, real-time ¹H NMR spectroscopy, and density functional theory (DFT) calculations. This work marks a bifunctional MOF-based catalyst that facilitates CS₂ conversion under ambient temperature and pressure and also demonstrates excellent catalytic performance in CO₂ conversion.