Defect Chemistry in Rare-Earth High-Entropy Oxides for Solar-Driven CO₂ Conversion

Up to date, the development of highly efficient, visible light-active catalysts remains a formidable challenge due to the enhanced rising of atmospheric CO₂ concentration. This study discusses a class of ceria-based high-entropy oxides designed to optimize charge carrier dynamics, surface reactivity, and CO₂ activation efficiency. Due to the advantages of high configurational entropy and multi-element synergy, these materials achieved improved photocatalytic performance, surpassing conventional ceria-based systems. Structural and spectroscopic analyses reveal that Pr³⁺/Pr⁴⁺ redox pairs and abundant oxygen vacancies create an electronically disordered yet thermodynamically stable environment, which enhances charge separation and suppresses electron-hole recombination. Photocatalytic experiments demonstrated that Ce_0.2Zr_0.2La_0.2Pr_0.2Sm_0.2O_2-δ (CZLPS) achieves the highest CO₂ conversion rate, reaching a conversion of 20.3% under visible light irradiation, significantly surpassing pure ceria (1.4%), with a calculated space-time yield (STY) of 10.15 mol_COkg^-1h^-1 under the same conditions. First-principles density functional theory (DFT) simulations were employed to investigate the CO₂ reduction mechanism on CZLPS catalysts. The study elucidates the Gibbs free energy changes (ΔG) for each step of the reaction pathways leading to CO and HCOOH formation, highlighting the Zr site of CZLPS as the most active for the CO₂RR, which is responsible for the outstanding catalytic activity.