Supercritical CO Activation Enables an Exceptional Methanol Synthesis Activity Over the Industrial Cu/ZnO/AlO Catalyst.

The ternary Cu/ZnO/AlO catalyst is widely used in the industry for renewable methanol synthesis. The tenuous trade-off between the strong metal-support interaction (SMSI)-induced Cu-ZnO 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 CO activation strategy to synchronously perfect the Cu-O-Zn interface and Cu-Cu surface sites through the manipulation of the adsorbate diffusion kinetics, which involves OCH and "side-on" fixed CO species. This findings illustrate that the adsorbate on ZnO can facilitate its secondary uniform nucleation and induce a ZnAlO spinel phase and that CO adsorption on metallic Cu produces an activated CuO amorphous shell. Such a structural evolution unlocks a dual-response pathway in methanol synthesis, thus enabling Cu/ZnO/AlO with a twofold increase in catalytic activity. This atomic-level design of active sites and understanding of supercritical CO-induced structural evolution will guide the future development of high-performance supported metal catalysts.