Supercritical CO2 Activation Enables an Exceptional Methanol Synthesis Activity Over the Industrial Cu/ZnO/Al2O3 Catalyst

Abstract The ternary Cu/ZnO/Al2O3 catalyst is widely used in the industry for renewable methanol synthesis. The tenuous trade‐off between the strong metal–support interaction (SMSI)‐induced Cu–ZnOx interface and the accessible Cu surface strongly affects the activity of the final catalyst. Successes in the control of oxide migration on adsorbate‐induced SMSI catalysts have motivated this to develop a supercritical CO2 activation strategy to synchronously perfect the Cu0–O–Znδ+ interface and Cu0–Cu+ surface sites through the manipulation of the adsorbate diffusion kinetics, which involves *OC2H5 and “side‐on” fixed CO2 species. This findings illustrate that the adsorbate on ZnOx can facilitate its secondary uniform nucleation and induce a ZnxAl2Oy spinel phase and that CO2 adsorption on metallic Cu0 produces an activated CuxO amorphous shell. Such a structural evolution unlocks a dual‐response pathway in methanol synthesis, thus enabling Cu/ZnO/Al2O3 with a twofold increase in catalytic activity. This atomic‐level design of active sites and understanding of supercritical CO2‐induced structural evolution will guide the future development of high‐performance supported metal catalysts.