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How to Look for Compounds: Predictive Screening and in situ Studies in Na−Zn−Bi System
Author(s) -
Gvozdetskyi Volodymyr,
Wang Renhai,
Xia Weiyi,
Zhang Feng,
Lin Zijing,
Ho KaiMing,
Miller Gordon,
Zaikina Julia V.
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101948
Subject(s) - isostructural , stoichiometry , powder diffraction , diffraction , crystallography , materials science , hydride , synchrotron , crystal structure , quenching (fluorescence) , chemistry , in situ , analytical chemistry (journal) , metal , fluorescence , metallurgy , physics , organic chemistry , chromatography , quantum mechanics , nuclear physics , optics
Abstract Here, the combination of theoretical computations followed by rapid experimental screening and in situ diffraction studies is demonstrated as a powerful strategy for novel compounds discovery. When applied for the previously “empty” Na−Zn−Bi system, such an approach led to four novel phases. The compositional space of this system was rapidly screened via the hydride route method and the theoretically predicted NaZnBi (PbClF type, P 4/ nmm ) and Na 11 Zn 2 Bi 5 (Na 11 Cd 2 Sb 5 type, P 1 ‾ ) phases were successfully synthesized, while other computationally generated compounds on the list were rejected. In addition, single crystal X‐ray diffraction studies of NaZnBi indicate minor deviations from the stoichiometric 1 : 1 : 1 molar ratio. As a result, two isostructural (PbClF type, P 4/ nmm ) Zn‐deficient phases with similar compositions, but distinctly different unit cell parameters were discovered. The vacancies on Zn sites and unit cell expansion were rationalized from bonding analysis using electronic structure calculations on stoichiometric “NaZnBi”. In‐situ synchrotron powder X‐ray diffraction studies shed light on complex equilibria in the Na−Zn−Bi system at elevated temperatures. In particular, the high‐temperature polymorph HT ‐Na 3 Bi (BiF 3 type, Fm 3 ‾ m ) was obtained as a product of Na 11 Zn 2 Bi 5 decomposition above 611 K. HT ‐Na 3 Bi cannot be stabilized at room temperature by quenching, and this type of structure was earlier observed in the high‐pressure polymorph HP ‐Na 3 Bi above 0.5 GPa. The aforementioned approach of predictive synthesis can be extended to other multinary systems.