High–Entropy Oxides: A New Frontier in Photocatalytic CO2 Hydrogenation

This is the author accepted manuscript.Herein, we investigate the potential of nanostructured high–entropy oxides (HEOs) for photocatalytic CO2 hydrogenation, a process with significant implications for environmental sustainability and energy production. Several cerium–oxide–based rare–earth HEOs with fluorite structures were prepared for UV–light driven photocatalytic CO2 hydrogenation towards valuable fuels and petrochemical precursors. The cationic composition profoundly influences the selectivity and activity of the HEOs, where the Ce0.2Zr0.2La0.2Nd0.2Sm0.2O2–δ catalyst showed outstanding CO2 activation (14.4 molCO kgcat −1 h−1 and 1.27 molCH3OH kgcat −1h−1) and high methanol and CO selectivity (7.84 % CH3OH and 89.26% CO) at ambient conditions with 4–times better performance in comparison to pristine CeO2. Systematic tests showed the effect of a high–entropy system compared to mid–entropy oxides. XPS, in–situ DRIFTS as well as DFT calculation elucidate the synergistic impact of Ce, Zr, La, Nd, and Sm, resulting in an optimal Ce3+/Ce4+ ratio. The observed formate–routed mechanism and a surface with high affinity to CO2 reduction offer insights into the photocatalytic enhancement. While our findings lay a solid foundation, further research is needed to optimize these catalysts and expand their applications.Croatian Science FoundationSlovenian Research AgencyRepublic of SloveniaMinistry of Education, Science and SportEuropean UnionEuropean Regional Development FundNational Research, Development and Innovation FundMinistry of Human CapacitiesMinistry for Innovation and Technolog