DFT insights into structural effects of Ni-Cu/CeO catalysts for CO selective reaction towards water-gas shift.

The water-gas shift (WGS) reaction is a key step in hydrogen production, particularly to meet the high-purity H2 requirement of PEM fuel cells. The catalysts currently employed in large-scale WGS plants require a two-step process to overcome thermodynamic and kinetic limitations. Ni-Cu/CeO2 solids are promising catalysts for the one-step process required for small-scale applications, as the addition of Cu hinders undesired methanation reactions occurring on Ni/CeO2. In this work, we performed calculations on Ni4-xCux/CeO2(111) systems to evaluate the influence of cluster conformation on the selectivity towards water-gas shift. The structure and miscibility of CeO2-supported Ni4-xCux clusters were investigated and compared with those of gas-phase clusters to understand the effect of metal-support interactions. The adsorption of CO onto apical Ni and Cu atoms of Ni4-xCux/CeO2(111) systems was studied, and changes in the C-O bond strength were confirmed at the electronic level by investigating shifts in the 3σ and 1π orbitals. The selectivity towards WGS was evaluated using Brønsted-Evans-Polanyi relations for the C-O activation energy. Overall, a strengthening of the C-O bond and an increase in CO dissociation energy were verified on Cu-containing clusters, explaining the improvement in selectivity of Ni4-xCux/CeO2(111) systems.