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