Controlled Reactive Metal−Support Interactions in NiIn/CeO ₂ Catalysts for Enhanced Methanol Synthesis from CO ₂

ABSTRACT Reactive metal‐support interactions (RMSIs) frequently occur under high‐temperature reaction conditions, leading to intricate reconstructions of metal‐oxide interfaces and alloy formation. Such uncontrollable features severely impede the optimization of catalytic performance. In this study, we demonstrate precise control over RMSIs by leveraging the high mobility of InO x on CeO 2 support under hydrogen reducing conditions—directly visualized by in situ environmental electron microscopy—in combination with the quantitative tuning of InO x content via atomic layer deposition. The resulting optimized catalyst delivers an exceptional space‐time yield of 1.67 g MeOH ·g cat −1 ·h −1 at 280°C in the CO 2 hydrogenation reaction, surpassing previously reported Ni‐based catalysts and even Pd‐based noble metal catalysts in the literature. In situ spectroscopic characterization reveals that the controlled RMSIs enables the optimization of InO x /NiIn interface, which promotes the selective conversion of HCOO* to CH 3 O* and subsequently to methanol, thereby significantly enhancing the methanol production. These findings highlight the critical role of precisely regulated RMSIs in the rational design of high‐performance catalysts.