Mechanistic insight of KBiQ₂ (Q = S, Se) using panoramic synthesis towards synthesis-by-design

Solid-state synthesis has historically focused on reactants and end products; however, knowledge of reaction pathways, intermediate phases and their formation may provide mechanistic insight of solid-state reactions. With an increased understanding of reaction progressions, design principles can be deduced, affording more predictive power in materials synthesis. In pursuit of this goal, in situ powder X-ray diffraction is employed to observe crystalline phase evolution over the course of the reaction, thereby constructing a "panoramic" view of the reaction from beginning to end. We conducted in situ diffraction studies in the K-Bi-Q (Q = S, Se) system to understand the formation of phases occurring in this system in the course of their reactions. Powder mixtures of K₂Q to Bi₂Q₃ in 1 : 1 and 1.5 : 1 ratios were heated to 800 °C or 650 °C, while simultaneously collecting diffraction data. Three new phases, K₃BiS₃, β-KBiS₂, and β-KBiSe₂, were discovered. Panoramic synthesis showed that K₃BiQ₃ serves an important mechanistic role as a structural intermediate in both chalcogen systems (Q = S, Se) in the path to form the KBiQ₂ structure. Thermal analysis and calculations at the density functional theory (DFT) level show that the cation-ordered β-KBiQ₂ polymorphs are the thermodynamically stable phase in this compositional space, while Pair Distribution Function (PDF) analysis shows that all α-KBiQ₂ structures have local disorder due to stereochemically active lone pair expression of the bismuth atoms. The formation of the β-KBiQ₂ structures, both of which crystallize in the α-NaFeO₂ structure type, show a boundary where the structure can be disordered or ordered with regards to the alkali metal and bismuth. A cation radius tolerance for six-coordinate cation site sharing of ∼ 1.3 is proposed. The mechanistic insight the panoramic synthesis technique provides in the K-Bi-Q system is progress towards the overarching goal of synthesis-by-design.