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

While impregnation approaches are attractive, scalable routes for preparing supported oxide catalysts, achieving competitive methanol productivities over impregnated ZnO/ZrO2 remains challenging as they underperform state-of-the art systems with isolated zinc sites. Herein, by targeting the optimal active site structure, ZnO/ZrO2 systems prepared by impregnation achieve stable methanol space-time yields of 0.73 g(MeOH) h(-1) g(cat)(-1) during CO2 and hybrid CO-CO2 hydrogenation at suitable conditions. Notably, controlling the catalyst formulation using 5 mol% Zn and a high surface area m-ZrO2 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/ZrO2 systems.