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

Rebecca McClain, Christos D. Malliakas, Jiahong Shen, Jiangang He, Chris Wolverton, Gabriela B. González, Mercouri G. Kanatzidis

Research output: Contribution to journalArticlepeer-review

Abstract

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 situpowder 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 conductedin situdiffraction 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 Bi2Q3in 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 K3BiQ3serves an important mechanistic role as a structural intermediate in both chalcogen systems (Q = S, Se) in the path to form the KBiQ2structure. Thermal analysis and calculations at the density functional theory (DFT) level show that the cation-ordered β-KBiQ2polymorphs are the thermodynamically stable phase in this compositional space, while Pair Distribution Function (PDF) analysis shows that all α-KBiQ2structures have local disorder due to stereochemically active lone pair expression of the bismuth atoms. The formation of the β-KBiQ2structures, both of which crystallize in the α-NaFeO2structure 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 of1.3 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.

Original languageEnglish
Pages (from-to)1378-1391
Number of pages14
JournalChemical Science
Volume12
Issue number4
DOIs
Publication statusPublished - Jan 28 2021

ASJC Scopus subject areas

  • Chemistry(all)

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