Ga and Zn increase the oxygen affinity of Cu

The direct hydrogenation of CO or CO2 to methanol, a highly vivid research area in the context of sustainable development, is typically carried out with Cu-based catalysts. Specific elements (so-called promoters) improve the catalytic performance of these systems under a broad range of reaction conditions (from pure CO to pure CO2). Some of these promoters, such as Ga and Zn, can alloy with Cu and their role remains a matter of debate. In that context, we used periodic DFT calculations on slab models and ab initio thermodynamics to evaluate both metal alloying and surface formation by considering multiple surface facets, different promoter concentrations and spatial distributions as well as adsorption of several species (O*, H*, CO* and ) for different gas phase compositions. Both Ga and Zn form an fcc-alloy with Cu due to the stronger interaction of the promoters with Cu than with themselves. While the Cu鈥揋a-alloy is more stable than the Cu鈥揨n-alloy at low promoter concentrations (