Rich oxygen vacancies in core–shell structured Co3O4-CuO-ZnO@ZIF-8 for boosting CO2 hydrogenation to methanol

• Flower-like Co 3 O 4 -CuO-ZnO@ZIF-8 catalyst was synthesized by a two-step hydrothermal process. • The productivity of CH 3 OH over Co 3 O 4 -CuO-ZnO@ZiF-8 catalyst at 200 °C and 2 MPa was 449.71 mmol kg −1 ·h −1 . • The good performance of the catalyst is attributed to the large specific surface area and abundant oxygen vacancies . Converting carbon dioxide (CO 2 ) into high-quality methanol to alleviate the energy crisis is a promising strategy. However, as a traditional catalyst for CO 2 hydrogenation to methanol, Cu/ZnO exhibits low CO 2 conversion and low methanol selectivity at low temperature. In order to improve the catalytic performance of CO 2 hydrogenation to methanol, Co 3 O 4 was introduced to form Co 3 O 4 -CuO-ZnO with flower-like structure, and then diamond-shaped ZIF-8 particles with large specific surface area and rich oxygen vacancies were synthesized on the surface of Co 3 O 4 -CuO-ZnO by hydrothermal method. A series of characterizations showed that the synthesis of ZIF-8 greatly increased the specific surface area of the catalyst. The oxygen vacancy is the site of CO 2 adsorption and activation, and stabilizes the reaction intermediate, which promotes the conversion of CO 2 and the formation of methanol. The introduction of Co promotes the formation of the alloy phase, enhances the interaction between the metals, makes the active center more dispersed, reduces the sintering of the catalyst, and thus exhibits better catalytic performance. Among co-precipitated CuO-ZnO, hydrothermal CuO-ZnO, CuO-ZnO@ZIF-8, Co 3 O 4 -CuO-ZnO and Co 3 O 4 -CuO-ZnO@ZIF-8 catalysts, Co 3 O 4 -CuO-ZnO@ZIF-8 exhibits the best catalytic performance (CO 2 conversion 16.06% and CH 3 OH selectivity 94.58%). Based on the above design, ZIF-8 and Co 3 O 4 synergistic CuO-ZnO catalyst effectively improved CO 2 conversion and CH 3 OH selectivity.