Computational Insights into Ru, Pd and Pt fcc Nano-Catalysts from Density Functional Theory Calculations: The Influence of Long-Range Dispersion Corrections

Ruthenium, palladium and platinum fall within the group of noble metals that are widely used in catalysis, especially for the electrocatalytic production of hydrogen. The dominant phase of the bulk Ru metal is hexagonal close-packed (hcp), which has been studied extensively. However, significantly less attention has been paid to the face-centred cubic (fcc) phases, which have been observed in nanoparticles. In this study, we have carried out density functional theory calculations with long-range dispersion corrections [DFT-D2, DFT-D3 and DFT-D3-(BJ)] to investigate the lattice parameters, surface energies and work functions of the (001), (011) and (111) surfaces of Ru, Pd and Pt in the fcc phase. When investigating the surface properties of the three metals, we observed that the DFT-D2 method generally underestimated the lattice parameters by up to 2.2% for Pt and 2.8% for Ru. The surface energies followed the observed trend (111) < (001) < (011) for both Ru and Pd with all three methods, which is comparable to experimental data. For Pt the same trend was observed with DFT-D2 and DFT-D3(BJ), but it deviated to Pt (111) < Pt (011) < Pt (001) for the DFT-D3 method. DFT-D2 overestimated the surface energies for all three Miller Indexes by 82%, 73%, and 60%, when compared to experimental values. The best correlation for the surface energies was obtained with the DFT-D3 and DFT-D3(BJ) methods, both of which have deviate by less than 15% deviation for all surfaces with respect to experiment. The work function followed the trend of Φ (111) < Φ (001) < Φ (011) for all three metals and calculated by all three methods. Five different types of Ru, Pd and Pt nanoparticles were considered, including icosahedral, decahedral, cuboctahedral, cubic and spherical particles of different sizes. The bulk, surface and nanoparticle calculations showed that the DFT-D2 method for Pt overestimated the exchange-correlation, leading to higher energy values that can be contributed erroneously to a more stable structure. The calculations showed that as soon as the surface-to-bulk ratio > 1, the energy per atom resembles bulk energy values.