skip to main content

DOE PAGESDOE PAGES

This content will become publicly available on February 12, 2019

Title: Kinetically Controlled Formation and Decomposition of Metastable [(BiSe) 1+δ] m[TiSe 2] m Compounds

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[TiSe 2] 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[TiSe 2] 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,more » 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.« less
Authors:
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)
Publication Date:
Report Number(s):
LA-UR-17-30767
Journal ID: ISSN 0002-7863; TRN: US1801678
Grant/Contract Number:
AC52-06NA25396; AC05-76RL01830; AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 9; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; heterostructure; materials chemistry; kinetic product; solid state chemistry
OSTI Identifier:
1422968

Lygo, Alexander C., Hamann, Danielle M., Moore, Daniel B., Merrill, Devin R., Ditto, Jeffrey, Esters, Marco, Orlowicz, Jacob, Wood, Suzannah R., and Johnson, David C.. Kinetically Controlled Formation and Decomposition of Metastable [(BiSe)1+δ]m[TiSe2]m Compounds. United States: N. p., Web. doi:10.1021/jacs.7b13398.
Lygo, Alexander C., Hamann, Danielle M., Moore, Daniel B., Merrill, Devin R., Ditto, Jeffrey, Esters, Marco, Orlowicz, Jacob, Wood, Suzannah R., & Johnson, David C.. Kinetically Controlled Formation and Decomposition of Metastable [(BiSe)1+δ]m[TiSe2]m Compounds. United States. doi:10.1021/jacs.7b13398.
Lygo, Alexander C., Hamann, Danielle M., Moore, Daniel B., Merrill, Devin R., Ditto, Jeffrey, Esters, Marco, Orlowicz, Jacob, Wood, Suzannah R., and Johnson, David C.. 2018. "Kinetically Controlled Formation and Decomposition of Metastable [(BiSe)1+δ]m[TiSe2]m Compounds". United States. doi:10.1021/jacs.7b13398.
@article{osti_1422968,
title = {Kinetically Controlled Formation and Decomposition of Metastable [(BiSe)1+δ]m[TiSe2]m Compounds},
author = {Lygo, Alexander C. and Hamann, Danielle M. and Moore, Daniel B. and Merrill, Devin R. and Ditto, Jeffrey and Esters, Marco and Orlowicz, Jacob and Wood, Suzannah R. and Johnson, David C.},
abstractNote = {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.},
doi = {10.1021/jacs.7b13398},
journal = {Journal of the American Chemical Society},
number = 9,
volume = 140,
place = {United States},
year = {2018},
month = {2}
}