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

doi:10.1039/d0sc04562d

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^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

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 language	English (US)
Pages (from-to)	1378-1391
Number of pages	14
Journal	Chemical Science
Volume	12
Issue number	4
DOIs	https://doi.org/10.1039/d0sc04562d
State	Published - Jan 28 2021

Funding

This work was supported by the National Science Foundation through the MRSEC program (NSF-DMR 1720139) at the Materials Research Center. Use was made of the IMSERC Facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and International Institute for Nanotechnology (IIN). Use of the computational resources were provided by the Quest high performance computing facility at Northwestern University. The authors thank Dr Kyle M. McCall for helpful discussions. Use of the Advanced Photon Source (11-BM-B and 11-ID-B beamline) at Argonne National Laboratory was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. This work was supported by the National Science Foundation through the MRSEC program (NSF-DMR 1720139) at the Materials Research Center. Use was made of the IMSERC Facility at Northwestern University, which has received support from the So and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and International Institute for Nanotechnology (IIN). Use of the computational resources were provided by the Quest high performance computing facility at Northwestern University. The authors thank Dr Kyle M. McCall for helpful discussions. Use of the Advanced Photon Source (11-BM-B and 11-ID-B beamline) at Argonne National Laboratory was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357.

ASJC Scopus subject areas

General Chemistry

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10.1039/d0sc04562d

Cite this

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

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.",

author = "Rebecca McClain and Malliakas, {Christos D.} and Jiahong Shen and Jiangang He and Chris Wolverton and Gonz{\'a}lez, {Gabriela B.} and Kanatzidis, {Mercouri G.}",

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AU - McClain, Rebecca

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AU - He, Jiangang

AU - Wolverton, Chris

AU - González, Gabriela B.

AU - Kanatzidis, Mercouri G.

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

Abstract

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CSD 2003740: Experimental Crystal Structure Determination

CSD 2003741: Experimental Crystal Structure Determination

CSD 2003742: Experimental Crystal Structure Determination

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

Abstract

Funding

ASJC Scopus subject areas

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CSD 2003740: Experimental Crystal Structure Determination

CSD 2003741: Experimental Crystal Structure Determination

CSD 2003742: Experimental Crystal Structure Determination

Cite this

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