A new material built with alternating Cu sulfide and (Al,Mg) hydroxide molecular sheets: hydrothermal synthesis and selected characteristics

Abstract

Two-dimensional materials with new physical phenomena are gaining popularity due to their unique properties. In recent years, a new family of layered compounds inspired by the minerals valleriite and tochilinite which are composed of alternating quasi-atomic sheets of transition metal chalcogenides (sulfides and selenides of Fe, Fe–Cu and other metals) and hydroxides of Mg, Al, Fe, Li, etc., assembled via electrostatic interaction, has arisen as a new synthetic platform for 2D materials. In this work, we synthesized a new promising material composed of alternating quasi two-dimensional sulfide Cu_4−xS₂ (x = 1–1.5) and hydroxide (Mg_1−yAl_y)(OH)₂ (y ∼ 0.25) sheets as multilayer flakes with a lateral size of 1–2 μm and a thickness of several tens of nm. The reliable formation of the material was ensured by an excess of aqueous sodium sulfide along with some quantity of Al salt, which was necessary for the self-assembly of the sulfide and hydroxide sheets driven by their opposite electric charges. A series of samples with varying Al/Mg ratios were examined using TEM, EDS, SAED, XRD, XPS, Raman and UV-vis-NIR spectroscopy. Using the Rietveld refinement procedure, the crystal lattice was determined to resemble the space group Pm1 with cell parameters a = b = 3.89 Å and a = b = 3.03 Å for sulfide and hydroxide parts, respectively, and the common parameter c = 12.03 Å. XPS and Raman spectra agree with the chalcocite-like sulfide layers containing Cu⁺ cations, monosulfide anions and few, if any, S–S bonds. UV-vis-NIR spectra show indirect transitions of 0.8 eV and considerable absorption in the near-infrared region. Thermogravimetry and differential scanning calorimetry studies under an Ar atmosphere suggest a slightly endothermic process and a phase transition at 90 °C accompanied, as suggested by conductivity measurements, by a metal–semiconductor transition; the main destruction with a loss up to 15 wt% occurs at ∼510 °C, due to decomposition of hydroxide layers similar to layered valleriite and tochilinite. The (thermo)electrical data show that, contrary to valleriite, which is an n-type semiconductor with mediocre thermoelectric performance, the proposed material is a heavily doped p-type semiconductor exhibiting good thermoelectric efficiency. The new member of the valleriite family of heterolayered quasi-2D materials demonstrates therefore essentially novel promising properties.