Dual active sites over Cu-ZnO-ZrO₂ catalysts for carbon dioxide hydrogenation to methanol

CO₂ hydrogenation to methanol is a significant approach to tackle the problem of global warming and simultaneously meet the demand for the portable fuel. Cu-ZnO catalysts with various kinds of promoters have received wide attention. However, the role of promoter and the form of active sites in CO₂ hydrogenation are still in debate. Here, various molar ratios of ZrO₂ were added into the Cu-ZnO catalysts to tune the distributions of Cu⁰ and Cu⁺ species. A volcano-like trend between the ratio of Cu⁺/ (Cu⁺ + Cu⁰) and the amount of ZrO₂ is presented, among which the CuZn10Zr (the molar ratio of ZrO₂ is 10%) catalyst reaches the highest value. Correspondingly, the maximum value of space-time yield to methanol with 0.65 g_MeOH/(g_cat·hr) is obtained on CuZn10Zr at reaction conditions of 220°C and 3 MPa. Detailed characterizations demonstrate that dual active sites are proposed during CO₂ hydrogenation over CuZn10Zr catalyst. The exposed Cu⁰ takes participate in the activation of H₂, while on the Cu⁺ species, the intermediate of formate from the co-adsorption of CO₂ and H₂ prefers to be further hydrogenated to CH₃OH than decomposing into the by-product of CO, yielding a high selectivity of methanol.