Ga and Zn increase the oxygen affinity of Cu-based catalysts for the CO x hydrogenation according to ab initio atomistic thermodynamics.

The direct hydrogenation of CO or CO 2 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 CO 2 ). 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-Ga-alloy is more stable than the Cu-Zn-alloy at low promoter concentrations (<25%), further increasing the promoter concentration reverses this trend, due to the unfavoured Ga-Ga-interactions. Under CO 2 hydrogenation conditions, a substantial amount of O* can adsorb onto the alloy surfaces, resulting in partial dealloying and oxidation of the promoters. Therefore, the CO 2 hydrogenation conditions are actually rather oxidising for both Ga and Zn despite the large amount of H 2 present in the feedstock. Thus, the growth of a GaO x /ZnO x overlayer is thermodynamically preferred under reaction conditions, enhancing CO 2 adsorption, and this effect is more pronounced for the Cu-Ga-system than for the Cu-Zn-system. In contrast, under CO hydrogenation conditions, fully reduced and alloyed surfaces partially covered with H* and CO* are expected, with mixed CO/CO 2 hydrogenation conditions resulting in a mixture of reduced and oxidised states. This shows that the active atmosphere tunes the preferred state of the catalyst, influencing the catalytic activity and stability, indicating that the still widespread image of a static catalyst under reaction conditions is insufficient to understand the complex interplay of processes taking place on a catalyst surface under reaction conditions, and that dynamic effects must be considered.