Detrimental 2\(p\)-3\(d\) Hybridisation in Ni Nanosheets Supported on Strontium Dioxide for Catalytic H\(_2\) Production, Necessitating Thickness Optimisation

We employ accurate density functional theory calculations to examine the electronic structure of three Ni/SrO\(_2\) nanostructures containing single-layer, bilayer and four-layer Ni nanosheets. The single Ni layer interacts strongly with the topmost oxygen layer at the Ni/SrO\(_2\) interface, resulting in significant surface reconstruction and strong hybridisation between the O \(2p\) and Ni \(3d\) states. For the bilayer Ni, the layer facing the interface also strongly interacts with the O. However, the second layer retains its geometry. For the four-layer system, none of the Ni layers interacted strongly with O. According to the electronic population analysis, in the thinnest nanosheets, the strong hybridisation with oxygen pulls Ni's \(3d\) states away from the Fermi level deeper into the valence band. In these cases, Ni's electronic population that is labile for catalysis in the vicinity of the Fermi level was as little as half of the bilayer nanosheet. Such reduction in the labile \(3d\) population has a detrimental effect on Ni's catalytic performance in de-hydrogenating formic acid. Our results demonstrate that there is an optimum dimension for Ni nanoparticles below or above which the catalytic performance deteriorates. Consequently, reducing the Ni dimension to maximise the surface in the hope of better catalytic yield might not be the best strategy as detrimental \(p\)-\(d\) hybridisation takes hold. Smaller might not always be better after all!