CO‐Induced Reconstruction of Cu–ZnZrO <i> _x </i> Catalyst Enables Synergistic CO ₂ /CO Co‐Hydrogenation to Methanol

Abstract Catalytically active phase depends strongly on reaction conditions. In CO 2 hydrogenation, efforts have largely emphasized CO 2 activation while overlooking how to design active phase for the co‐conversion of CO 2 and the kinetically distinct byproduct CO. Here, it is found that adding CO to CO 2 –H 2 feeds boosts methanol productivity by up to 2.2‐fold via a pronounced synergistic promotion of both CO 2 and CO hydrogenation over a Cu–ZnZrO x catalyst. In situ spectroscopy reveals that CO accelerates Zn reduction and migration onto Cu, increasing Zn 0 /Cu ratio, Zn 2+ /Cu, and Cu + /Cu fraction, while reducing exposed surface Cu from 42% to 19%. This CO‐induced restructuring enriches Zn exposure, drives CuZn alloy formation, and creates abundant CuZn alloy–ZnO x interfaces that stabilize Cu + sites. These interfaces enable a cooperative dual‐pathway mechanism: CO 2 is hydrogenated mainly via the formate route at alloy–ZnO x sites, whereas CO follows the formyl route on Cu sites. Additionally, in situ‐formed water accelerates conversion of the rate‐determining CH 3 O * intermediate in the CO pathway. Together, CO‐driven evolution of active sites, synergistic dual‐pathway catalysis, and water‐assisted promotion yield highly efficient methanol synthesis from mixed CO–CO 2 feeds.