Inverse In₂O_3-x/Ni interfaces via Ni₃InC_0.5 surface reconstruction for efficient CO₂ hydrogenation to methanol

Catalyst surface reconstruction under reaction conditions is ubiquitous and crucial for creating unusual active sites, thereby enhancing catalytic performance. Here, we report the surface reconstruction of supported Ni₃InC_0.5 nanoparticles, leading to the formation of defective In₂O_3-x overlayers and inverse In₂O_3-x/Ni interfaces, driven by CO₂-induced selective surface oxidation during CO₂ hydrogenation. The synergy between In₂O_3-x overlayers and inverse In₂O_3-x/Ni interfaces facilitates CO₂ adsorption and activation, as well as the following hydrogenation of HCOO^* and CH_xO^* intermediates, enabling efficient methanol synthesis from CO₂. Accordingly, the optimized LDH-NiInCAl catalyst achieves an impressive CO₂ conversion of 19% with 65% methanol selectivity and 508.4 $\mathrm{mg}{g}_{\mathrm{cat}}^{-1}{h}^{-1}$ methanol space-time yield at 260 °C, 5 MPa, and 12000 $\mathrm{mL}{g}_{\mathrm{cat}}^{-1}{h}^{-1}$ , outperforming commercial Cu/ZnO/Al₂O₃ catalysts. This work showcases how structural evolution and surface reconstruction enhance catalytic performance, providing new insights into the dynamic structure-activity relationship.