Abstract
Heteroanionic materials are a burgeoning class of compounds that offer new properties via the targeted selection of anions. However, understanding the design principles and achieving successful syntheses of new materials in this class are in their infancy. To obtain mechanistic insight and a panoramic view of the reaction progression from beginning to end of the formation of a heteroanionic material, we selected BiOCuSe, a well-known thermoelectric compound, and utilized in situ synchrotron powder diffraction as a function of temperature and time. BiOCuSe is a layered material, which crystallizes in a common mixed anion structure type: ZrSiAsFe. Two reactions of starting materials (Bi2O2Se + Cu2Se and Bi2O3 + Bi + 3Cu + 3Se) were studied to determine the effect of precursors on the reaction pathway. Our in situ investigation shows that the ternary-binary Bi2O2Se + Cu2Se reaction proceeds without intermediates to directly form BiOCuSe, while the binary-elemental Bi2O3 + Bi + 3Cu + 3Se reaction generates many intermediates before the final product forms. These intermediates include CuSe, Bi3Se4, Bi2Se3, and Cu2Se. While the stoichiometric loading of the precursors necessarily dictates the identity of the first intermediates, kinetics also plays a contributing role in stabilizing unexpected intermediates such as CuSe and Bi3Se4. Understanding and establishing a link between the selection of precursors and the reaction pathways improves the potential for rational synthesis of heteroanionic materials and solid-state reactions in general.
Original language | English (US) |
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Pages (from-to) | 12090-12099 |
Number of pages | 10 |
Journal | Journal of the American Chemical Society |
Volume | 143 |
Issue number | 31 |
DOIs | |
State | Published - Aug 11 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 the International Institute for Nanotechnology (IIN). Use of the Advanced Photon Source (17-BM-B) 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
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry