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Panoramic Solid-state Synthesis Using In-situ Powder X-ray Diffraction Techniques

The in-situ PXRD capabilities at IMSERC have provided essential data for my doctoral work

Becca McClain, PhD
Chemistry Department

In-situ techniques provide unparalleled mechanistic insights into reactions

More details about this work at McClain, R. et al. "Mechanistic insight of KBiQ2 (Q = S, Se) using panoramic synthesis towards synthesis-by-design" Chemical Science 2020 [10.1039/d0sc04562d].

This work made use of the StadiMP instrument at IMSERC. If you would like to perform similar measurements, follow these detailed operational steps . Read more about the in-situ diffractions techniques available at IMSERC.

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 (PXRD) is employed to observe crystalline phase evolution over the course of the reaction, thereby constructing a “panoramic” view of the reaction. In-situ diffraction studies were conducted in the K-Bi-Q (Q = S, Se) system to understand the formation of known phases in this system as well as to correlate future observations of analogues.

Powder diffraction patterns collected at IMSERC as a function of temperature

Three new phases, K3BiS3, β-KBiS2, and β-KBiSe2, were discovered using in-situ X-ray diffraction up to 800°C. Panoramic synthesis showed that K3BiQ3 serves an important mechanistic role as a structural intermediate in both systems in the reaction to form the KBiQ2 structure. The formation of the β-KBiQ2 structures, both of which crystallize in the NaCrS2 structure type, show a boundary where the structure can be disordered or ordered with regards to the alkali metal and pnictogen. A cation radius tolerance for six-coordinate cation site sharing of ∽1.3 is proposed. The mechanistic insight this technique provides in the K-Bi-Q system is progress towards the overarching goal of synthesis-by-design.

Compositional diagram of various intermediate phases and products formed during the in-situ measurement