Structure Inhomogeneity of Gold Nanoparticles and Its Effect on H₂ Dissociative Chemisorption

Significant differences in hydrogen adsorption on amorphous and crystalline gold nanoparticles deposited on highly oriented pyrolytic graphite (HOPG) were revealed. Crystalline nanoparticles were synthesized via the impregnation-precipitation method followed by annealing at 700 K, whereas amorphous ones were obtained using the laser electrodispersion method. The morphology and electronic structure of single nanoparticles were investigated with high spatial resolution using scanning tunneling microscopy and spectroscopy (STM/STS) in ultra-high vacuum both before and after exposure to molecular hydrogen at doses of 400-6000 L. Experiments performed at room temperature showed that the surface coverage by the adsorbate in both cases begins at the Au-HOPG interface, spreads towards the center of the particle, and corresponds to the island growth model. However, amorphous nanoparticles have fewer growth sites at the periphery compared to crystalline ones. The local electronic structure of amorphous nanoparticles is more inhomogeneous compared to crystalline ones, demonstrating variation across different points on the nanoparticle surface. It was shown that dissociative chemisorption of hydrogen takes place on amorphous gold nanoparticles with a size of 4-6 nm. Chemisorption is completely inhibited when the nanoparticle size is reduced to 2 nm or less.