Adsorption and Diffusion of Hydrogen on the Surface of the Pt24 Subnanoparticle. A DFT Study

Platinum and platinum based materials are of fundamental importance for modern and developed catalysts, fuel cells, sensors, hydrogen production and storage systems, and nanoelectronic devices. The subnanosize cluster Pt24 was considered as a model of the prospective catalytic system based on the oxide and carbide supported Pt nanoparticles (Pt NPs) or Pt NPs with soft spacers anchored to their surface. Structural, electronic, thermodynamic, and spectral properties of the adsorption complexes of molecular and atomic hydrogen on Pt NPs have been studied using the DFT method (the BLYP functional with the 6-31G(p) basis for H and the CRENBS pseudopotential for Pt atoms). On this basis, the adsorption energies for molecular hydrogen at the Pt NPs along with the energies and activation energies of its dissociation were estimated and the pathways of activationless dissociative adsorption were found. The full map of adsorption energies of atomic hydrogen at the various surface regions of Pt24 was obtained. The s...