Design of technical ZnO/ZrO2 catalysts for CO2 hydrogenation to green methanol.

[Display omitted] • Impregnated ZnO/ZrO 2 catalysts rival state-of-the-art benchmarks in CO 2 hydrogenation. • Stable methanol productivity > 0.7 g h−1 g cat −1 attained in CO 2 and CO 2 + CO feeds. • Tuning content to 5 mol% Zn on high-surface m -ZrO 2 support maximized Zn dispersion. • Facile vacancy generation and retention of isolated zinc sites during reaction. • Successful translation of performance and architecture from powder to technical form. While impregnation approaches are attractive, scalable routes for preparing supported oxide catalysts, achieving competitive methanol productivities over impregnated ZnO/ZrO 2 remains challenging as they underperform state-of-the art systems with isolated zinc sites. Herein, by targeting the optimal active site structure, ZnO/ZrO 2 systems prepared by impregnation achieve stable methanol space–time yields of 0.73 g MeOH h−1 g cat −1 during CO 2 and hybrid CO-CO 2 hydrogenation at suitable conditions. Notably, controlling the catalyst formulation using 5 mol% Zn and a high surface area m -ZrO 2 support fosters high zinc dispersion. In situ electron paramagnetic resonance and operando X-ray spectroscopy studies affirm the retention of isolated zinc species and facile generation of associated oxygen vacancies during the reaction. Analysis of pore structure and composition within the shaped bodies evidences abundant mesopores and a uniform zinc distribution, ensuring similar performance when translating from powder to technical forms. This work bridges fundamental understanding with practical demonstration of ZnO/ZrO 2 systems. [ABSTRACT FROM AUTHOR]