Quantum-Chemical Analysis of the Mechanism of Degradation of Binary Platinum Nanoclusters with Sulfur-Containing Compounds

We propose a quantum-chemical model of poisoning of binary Pt 42 Me 13 platinum nanoclusters (where Me is a transition metal, namely, Fe, Co, or Ni) with core-shell structure by hydrogen sulfide and sulfur dioxide in media of low-temperature fuel cells. This model is based on the evaluation of the adsorption characteristics of interaction of H 2 S and SO 2 molecules with the surfaces of nanoclusters. It is shown that their susceptibility to the formation of strong chemisorption bonds with H 2 S and SO 2 molecules depends on the type of nanocluster core and the sites of adsorption on their surfaces. By using the quantum-chemical method of density functional, we establish the regularities of influence of the cores of binary nanoclusters of transition metals Fe, Co, or Ni on the geometric and energy characteristics of the adsorption of molecules. We also propose the mechanism of interaction of H 2 S and SO 2 molecules with binary platinum nanoclusters based on the changes in the electronic properties of the surface platinum atoms or in the distribution of active adsorption centers on the surface of nanoclusters depending on the type of the core. The accumulated results confirm the prospects of the density functional method in the theoretical evaluation of the influence of chemical composition and the structure of binary nanoparticles on their properties in the reactions of low-temperature fuel cells.