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Title: Kinetically Controlled Formation and Decomposition of Metastable [(BiSe)1+δ]m[TiSe2]m Compounds

Journal Article · · Journal of the American Chemical Society
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Oregon, Eugene, OR (United States)
  2. Univ. of Oregon, Eugene, OR (United States) ; Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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We report that preparing homologous series of compounds allows chemists to rapidly discover new compounds with predictable structure and properties. Synthesizing compounds within such a series involves navigating a free energy landscape defined by the interactions within and between constituent atoms. Historically, synthesis approaches are typically limited to forming only the most thermodynamically stable compound under the reaction conditions. Presented here is the synthesis, via self-assembly of designed precursors, of isocompositional incommensurate layered compounds [(BiSe)1+δ]m[TiSe2]m with m = 1, 2, and 3. The structure of the BiSe bilayer in the m = 1 compound is not that of the binary compound, and this is the first example of compounds where a BiSe layer thicker than a bilayer in heterostructures has been prepared. Specular and in-plane X-ray diffraction combined with high-resolution electron microscopy data was used to follow the formation of the compounds during low-temperature annealing and the subsequent decomposition of the m = 2 and 3 compounds into [(BiSe)1+δ]1[TiSe2]1 at elevated temperatures. These results show that the structure of the precursor can be used to control reaction kinetics, enabling the synthesis of kinetically stable compounds that are not accessible via traditional techniques. Lastly, the data collected as a function of temperature and time enabled us to schematically construct the topology of the free energy landscape about the local free energy minima for each of the products.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC52-06NA25396; AC05-76RL01830; AC02-06CH11357
OSTI ID:
1422968
Report Number(s):
LA-UR-17-30767; TRN: US1801678
Journal Information:
Journal of the American Chemical Society, Vol. 140, Issue 9; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

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Cited By (1)

Non-linear enhancement of thermoelectric performance of a TiSe 2 monolayer due to tensile strain, from first-principles calculations journal January 2019

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