Cu_2−xS and Cu_2−xSe (0 ≤ x ≤ 0.2) alloys stand out as highly promising materials for thermoelectric applications, owing to the phonon–liquid electron–crystal (PLEC) convention. In this study, we undertake a comprehensive investigation to reassess the synthesis conditions, with a focus on achieving pure-phased systems through a direct reaction between elements at elevated temperatures. Simultaneously, we present experimental evidence showcasing the feasibility of doping these systems with Ag, Ni, and Zn. The study demonstrates that obtaining single-phased systems requires multi-step processes, and the dissolution of chosen impurities appears doubtful, as evidenced by numerous foreign phase segregations. Additionally, it is revealed that the partial dissolution of individual impurities deteriorates the operational parameters of these chalcogenides. For the optimal Cu_1.97S composition, it reduces the thermoelectric figure-of-merit ZT from 1.5 to approximately 1.0, 0.65, and 0.85 for Ag-, Ni-, and Zn-doped systems, respectively, while marginally improving their stability. For metal-like Cu_1.8Se, the ZT parameter remains at a low level, ranging between 0.09 and 0.15, showing slight destabilization during subsequent operating cycles. The article concludes with an in-depth analysis of the basic thermoelectric performance exhibited by these doped systems, contributing valuable insights into the potential enhancements and applications of Cu_2−xS and Cu_2−xSe alloys in the field of thermoelectric materials.

Since pentlandites are among the most promising catalysts for hydrogen evolution reactions (HER), in this study, we investigated the influence of different cobalt, iron, and nickel substitutions in the cationic sublattice and the form of the material (powder, ingot, sintered pellet) on catalytic performance. This complements previous results regarding a multi-component approach in these chalcogenides. It was shown that in the case of sulfur-rich pentlandites with a non-equimolar ratio of Co, Fe, and Ni, the impact of intrinsic material properties is smaller than the surface-related effects. Among powder forms, catalysts based on a combination of Fe and Co perform the best. However, in volumetric forms, extremely high contents of individual metals are favorable, albeit they are associated with active precipitations of foreign phases. The presence of these phases positively affects the recorded currents but slows down the reaction kinetics. These findings shed light on the nuanced interplay between material composition, form, and HER properties, offering insights for tailored catalyst design.