Transuranium Sulfide via the Boron Chalcogen Mixture Method and Reversible Water Uptake in the NaCu TS3Family

Anna A. Berseneva, Vladislav V. Klepov, Koushik Pal, Kelly Seeley, Daniel Koury, Joseph Schaeperkoetter, Joshua T. Wright, Scott T. Misture, Mercouri G. Kanatzidis, Chris Wolverton, Artem V. Gelis, Hans Conrad Zur Loye*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

The behavior of 5f electrons in soft ligand environments makes actinides, and especially transuranium chalcogenides, an intriguing class of materials for fundamental studies. Due to the affinity of actinides for oxygen, however, it is a challenge to synthesize actinide chalcogenides using non-metallic reagents. Using the boron chalcogen mixture method, we achieved the synthesis of the transuranium sulfide NaCuNpS3 starting from the oxide reagent, NpO2. Via the same synthetic route, the isostructural composition of NaCuUS3 was synthesized and the material contrasted with NaCuNpS3. Single crystals of the U-analogue, NaCuUS3, were found to undergo an unexpected reversible hydration process to form NaCuUS3·xH2O (x ≈ 1.5). A large combination of techniques was used to fully characterize the structure, hydration process, and electronic structures, specifically a combination of single crystal, powder, high temperature powder X-ray diffraction, extended X-ray absorption fine structure, infrared, and inductively coupled plasma spectroscopies, thermogravimetric analysis, and density functional theory calculations. The outcome of these analyses enabled us to determine the composition of NaCuUS3·xH2O and obtain a structural model that demonstrated the retention of the local structure within the [CuUS3]- layers throughout the hydration-dehydration process. Band structure, density of states, and Bader charge calculations for NaCuUS3, NaCuUS3·xH2O, and NaCuNpS3 along with X-ray absorption near edge structure, UV-vis-NIR, and work function measurements on ACuUS3 (A = Na, K, and Rb) and NaCuUS3·xH2O samples were carried out to demonstrate that electronic properties arise from the [CuTS3]- layers and show surprisingly little dependence on the interlayer distance.

Original languageEnglish (US)
Pages (from-to)13773-13786
Number of pages14
JournalJournal of the American Chemical Society
Volume144
Issue number30
DOIs
StatePublished - Aug 3 2022

Funding

This research was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under award DE-SC0018739. Specifically, DE-SC0018739 supported all sample synthesis and structure determinations, sample characterization, data collection at MRCAT, and data analysis. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. This research used resources of the Advanced Photon Source, a U.S. Department of Energy Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. K.P. and C.W. acknowledge funding support from the National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD) under the Award 70NANB19H005 by U.S. Department of Commerce which supported DFT calculations. V.V.K. and M.G.K. acknowledge the National Science Foundation Grant DMR-2003476 for UV–vis–NIR measurements and PYSA spectroscopy. We thank Mina Aziziha and Juliano Schorne-Pinto for their assistance in ICP-OES measurements. We are also grateful for assistance with radioactive material transportation by radiation safety officers of the University of South Carolina, Argonne National Laboratory, and Northwestern University.

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry

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