Thermally Driven Hydrogenation of CO ₂ to Light Olefins Over Hollow Cubic In ₂ O ₃ ‐La‐ZIF‐8 Tandem Catalyst

ABSTRACT Thermally driven hydrogenation of CO 2 to light olefins (C 2 = –C 4 = ) using metal oxide‐zeolite tandem catalysts is an effective strategy for achieving carbon neutrality. However, progress in this area is constrained by zeolite pore transport limitations, acid‐site inactivation, and surface carbon poisoning. To address these issues, we replaced conventional zeolites with La‐modified ZIF‐8 and combined it with hollow cubic In 2 O 3 to develop a novel In 2 O 3 ‐La‐ZIF‐8 tandem catalyst. Our study investigates the effects of the hydrothermal reaction temperature used for synthesizing In 2 O 3 and the La content in ZIF‐8 on catalytic performance. We also found that the oxygen vacancy (O V ) concentration in In 2 O 3 can be substantially regulated by adjusting the hydrothermal temperature. The In 2 O 3 sample with the highest O V concentration not only promotes the formation of reaction intermediates but also markedly reduces the energy barrier of the rate‐determining step in methanol synthesis. Comprehensive characterization and simulation analyses indicate that La incorporation enhances the thermal stability of ZIF‐8, improves its ability to adsorb and activate reaction intermediates, and effectively adjusts its acid‐base properties. Under a reaction pressure of 3.0 MPa and a temperature of 360°C, the hollow cubic In 2 O 3 ‐La‐ZIF‐8 tandem catalyst achieves 23.5% CO 2 conversion with 65.3% C 2 = –C 4 = selectivity.