Role of Foreign Phases, Synergistic Effects, and Morphology in the HER Performance of Trimetallic Pentlandites with Non-Equimolar Co:Fe:Ni Ratio

Abstract

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.