Heterogeneous Catalytic Interface Engineering of Oxygen Vacancies on Cu-Zn Sites for Low-Temperature Methanol...

Despite the synthesis of methanol from CO₂-containing syngas at low temperature represents an efficient route for chemical energy storage, the limited activity and stability of Cu/ZnO-based catalysts remain major obstacles. Here, we demonstrate that the introduction of Ba induces oxygen-vacancy-mediated heterogeneous catalytic interfaces at Cu-Zn sites, markedly enhancing both the activity and durability of low-temperature methanol synthesis. By precisely regulating the concentration of interfacial oxygen vacancies, a turnover frequency (TOF) as high as 21.2 × 10^-3 s^-1 and a methanol space-time yield (STY) of 655.17 g kg_cat^-1 h^-1 are achieved. Simultaneously, Ba incorporation increases the exposed Cu⁰ surface area, improves Cu dispersion, suppresses Cu particle sintering, and enriches surface basic sites. Density functional theory calculations further reveal that oxygen vacancies preferentially form at the Cu-Zn interfacial region and act as the primary active sites for low-temperature methanol synthesis. These findings establish that interfacial oxygen-vacancy engineering is an effective strategy for advancing methanol production at low temperatures.