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We report here a simple hydrothermal synthesis of 100–200 nm flakes of tochilinite (Fe1−xS)·n(Mg,Fe)(OH)2 constructed by interchanging atomic sulfide and hydroxide sheets as a representative of a new platform of multifunctional two-dimensional materials. The reliable formation of tochilinites was ensured by an excess of sodium sulfide, with the assembly of the metal sulfide and hydroxide sheets driven by their opposite electric charges. X-ray photoelectron spectroscopy found that the hydroxide layers involved Fe3+ cations from 10 to 40% of total iron tuned by addition of Al and Li entering the layers; the Fe1−xS sheets comprised comparable amounts of high-spin Fe3+ and Fe2+ centers, and minor S–S bonding. The room-temperature Mössbauer spectra fitted with several doublets (chemical shift of 0.35–0.4 mm s−1 and varying quadrupole splitting) transformed to three six-line patterns (hyperfine fields of ∼290, 350 and 480 kOe) due to magnetic ordering at 4.2 K, albeit the paramagnetic behavior observed in SQUID experiments. A series of UV-vis absorption maxima were explained in terms of both the high-index all-dielectric Mie resonance, in line with the permittivity measurement data, and the ligand-metal charge transfer resembling that in Fe–S clusters in proteins. Prospective properties and applications of the materials are discussed. [ABSTRACT FROM AUTHOR]

We introduce here a multifunctional material composed of alternating atomic sulfide sheets close to the composition of CuFeS2 and Mg-based hydroxide ones (valleriite), which are assembled due to their electric charges of opposite sign. Valleriite particles 50-200 nm in lateral size and 10-20 nm in thickness were synthesized via a simple hydrothermal pathway using various concentrations of precursors and dopants, and examined with XRD, TEM, EDS, X-ray photoelectron spectroscopy, reflection electron energy loss spectroscopy (REELS), Mössbauer, Raman and UV-vis-NIR spectroscopies, and magnetization, dynamic light scattering, and zeta potential measurements. The electronic, magnetic and optical characteristics are found to be critically dependent on the charge (electron density) at the narrow-gap sulfide layers containing Cu+ and Fe3+ cations, and can be tuned via the composition of the hydroxide part. Particularly, substitution of Mg2+ with Al3+ increases the negative charge of the hydroxide layers and reduces the content of Fe3+-OH centers (10-45% of total iron); the effects of Cr and Co dopants entering both layers are more complicated. Mössbauer doublets of paramagnetic Fe3+ detected at room temperature transform into several Zeeman sextets at 4.2 K; the hyperfine fields up to 500 kOe and complex magnetic behavior, but not pure paramagnetism or antiferromagnetism, were observed for valleriites with the higher positive charge of the sulfide sheets, probably due to the depopulation of the minority-spin 3d states of S-bonded Fe3+ ions. Aqueous colloids of valleriite show optical absorption at 500-750 nm, which, along with the peaks at the same energies in REELS, may arise due to quasi-static dielectric resonance involving the vacant Fe 3d band and being dependent on the composition of both layers too. These and other findings call attention to valleriites as a new rich family of 2D materials for a variety of potential applications. [ABSTRACT FROM AUTHOR]

We report here the application of the low-temperature X-ray photoelectron spectroscopy (cryo-XPS) of fast-frozen dispersions as a quasi in situ technique for a case study of metal sulfides reacted in acidic aqueous solutions under non-oxidizing and moderate oxidizing conditions. The sulfide surfaces are known to tend to be depleted in metals, producing essentially sulfur-enriched surfaces and extended underlayers on Fe- and Cu-bearing sulfides, which have previously been examined using depth-sensitive HAXPES and cryo-XPS. The current study is focused on zinc and lead sulfides (natural sphalerite and galena), for whom both the experiment and theoretical DFT simulations suggest a low stability of sulfur-excessive structures. Cryo-XPS revealed the complicated behavior of the minerals under non-oxidative etching conditions, in particular, a notable concentration of polysulfide for PbS in dilute perchloric acid and a very minor one in hydrochloric acid. Oxidative etching with Fe3+ cations produced polysulfide anions and then elemental sulfur, which both volatized in the ultra-high vacuum at room temperature; the species can, nonetheless, be distinguished by considering the binding energies, electrostatic charging and evaporation rates. The cryo-XPS also detected interfacial products, e.g., ferrous chloride. DFT found that S-excessive centers are unstable in the undersurface regions of both materials, but are less unfavorable for ZnS surfaces, in agreement with the experimental data. It was concluded that cryo-XPS allows us to greatly reduce distortions of the interface composition in comparison with conventional techniques. [ABSTRACT FROM AUTHOR]

Previously, we found a series of fluid nanoscale intermediates preceding nucleation of gold sulfide in the reaction between aqueous HAuCl4 and sodium sulfide. Here, the effects of temperature, addition of an inert electrolyte and some other factors on characteristics of the “dense liquid” intermediates and the formation of solid nuclei were studied using UV-vis absorption spectroscopy, DLS, zeta-potential measurements, and SAXS. It was revealed, in particular, that the negatively-charged interfaces of the dense liquid species critically impede their fusion into large enough dense droplets in which nucleation can take place. The nucleation and following coagulation of poorly crystalline gold sulfide proceed not instantly but progressively as the dense liquid droplets arise, with the process being sharply accelerated by the injection of NaCl or temperature increase. [ABSTRACT FROM AUTHOR]

Phenomena preceding precipitation of gold(i) sulfide in the reaction of aqueous tetrachloroauric acid with sodium sulfide have been studied applying several time-resolved in situ techniques. As can be deduced from UV-vis absorption spectroscopy, soluble species (“pre-nucleation clusters”) emerge within several seconds and slightly change with time; the spectra, along with the previous data for the immobilized products, are indicative of disordered matter with Au(i)–S bonding and the gap of about 1.5 eV. In situ tapping-mode atomic force microscopy (AFM) directly imaged “soft” droplet-like species from 20–50 nm to about 200 nm in the lateral size and the continuous film condensed on the highly oriented pyrolytic graphite (HOPG) support. Small-angle X-ray scattering (SAXS) revealed quasi-particles (“liquid clusters”) growing to about 12 nm for 30 min, and slowly afterwards. Dynamic light scattering (DLS) was preferentially due to the larger species, although the liquid clusters within 20 nm comprise more than 80% of the total volume of the fluid products. The entities, which exist in solution for many hours before sudden gold sulfide sedimentation, are considered as “dense liquid” intermediates involved in a non-classical nucleation pathway. [ABSTRACT FROM AUTHOR]

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, Au2S or their mixtures have been studied applying in situand ex situtechniques (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 Na2S/HAuCl4ratios of 0.5 to 1.5. It was concluded that the peak is due to longitudinal plasmon resonance of gold nanoplates. Au2S 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 situtransformation and role in the reaction mechanisms are discussed. [ABSTRACT FROM AUTHOR]

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.