No abstract

The effects of the molar ratio of sodium sulfide to chloroauric acid in the range of 0.5 to 5 and the time factor on the formation of the nanoparticles (NPs) of metallic Au, Au(2)S or their mixtures have been studied applying in situ and ex situ techniques (UV-Vis absorption spectroscopy, potentiometry, TEM, SPM, SERS, XPS). The products and intermediates have been compared with those for the reduction of chloroaurate with citrate ions and combinations of citrate and sulfide ions. An increase in the concentration of sulfide ions accelerates the reduction of Au(iii) complexes but hinders the nucleation and growth of Au NPs, resulting in a prolonged period before the appearance of plasmon peaks. The electrochemical potential is not directly associated with the plasmon intensities, although the potential sharply decreases simultaneously with a blue shift of the near-IR peak emerging with the Na(2)S/HAuCl(4) ratios of 0.5 to 1.5. It was concluded that the peak is due to longitudinal plasmon resonance of gold nanoplates. Au(2)S NPs, the nucleation of which is effectively inhibited, and probably some structures and fragments visible in TEM and AFM, including 2-5 nm Au NPs, crystallize in part outside the solutions. The evidence of partially liquid mesoscale structures comprising intermediate gold species as precursors of nanoparticles is presented, and their origin, ex situ transformation and role in the reaction mechanisms are discussed.

The depletion of oxidized metal sulfide surfaces in metals due to the preferential release of cations is a common, but as yet poorly understood phenomenon. Herein, X-ray photoelectron spectroscopy using excitation energies from 1.25 keV to 6 keV, and Fe K- and S K-edge X-ray absorption near-edge spectra in total electron and partial fluorescence yield modes was employed to study natural chalcopyrite oxidized in air and etched in an acidic ferric sulfate solution. The metal-depleted undersurface formed was found to consist of a thin, 1-4 nm, outer layer containing polysulfide species, a layer with a pronounced deficiency of metals, mainly iron, and an abundant disulfide content but negligible polysulfide content (about 20 nm thick after the chemical etching), and a defective underlayer which extended down to about a hundred nm. DFT+U was used to simulate chalcopyrite with increasing numbers of removed Fe atoms. It was found that the structure with disulfide anion near double Fe vacancies, and the 'defective' structure comprising Cu in the position of Fe and Cu vacancy are most energetically favorable, especially when using a higher Hubbard-type parameter U, and have a large density of states at the Fermi level, whereas polysulfide anions are stable only near the surface. We propose a mechanism explaining the formation of the layered undersurface and 'passivation' of metal sulfides by (i) arrested decomposition of a nearly stoichiometric sulfide surface, and (ii) faster interfacial transfer and solid diffusion of cations towards the surface; (iii) stability limits for specific defect structures, promoting their expansion in depth rather than through compositional changes, excluding surface layers; (iv) decay of surface polysulfide layer yielding elemental sulfur.