Chemically-induced structural variations of a family of Cs2[(AnO2)2(TO4)3] (An = U, Np; T = S, Se, Cr, Mo) compounds: Thermal behavior, calorimetry studies and spectroscopy characterization of Cs uranyl sulfate and selenate

Vladislav V. Gurzhiy; Ilya V. Kornyakov; Jennifer Szymanowski; Daniel Felton; Olga S. Tyumentseva; Maria G. Krzhizhanovskaya; Sergey V. Krivovichev; Peter C. Burns

doi:10.1016/j.jssc.2019.121077

Chemically-induced structural variations of a family of Cs₂[(AnO₂)₂(TO₄)₃] (An = U, Np; T = S, Se, Cr, Mo) compounds: Thermal behavior, calorimetry studies and spectroscopy characterization of Cs uranyl sulfate and selenate

Vladislav V. Gurzhiy, Ilya V. Kornyakov, Jennifer Szymanowski, Daniel Felton, Olga S. Tyumentseva, Maria G. Krzhizhanovskaya, Sergey V. Krivovichev, Peter C. Burns

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

Cs₂[(AnO₂)₂(TO₄)₃] (where An = U, Np; T = S, Se, Cr, Mo) is a remarkable family of actinide-bearing compounds due to the surprising persistence of its structure type despite the substitutions in actinide and oxyanion sites. Cesium uranyl sulfate and selenate compounds have been analysed using high-temperature powder X-ray diffraction, Raman and luminescence spectroscopy techniques; in addition, high-temperature oxide-melt calorimetry studies had been carried out to derive the enthalpies of formation of both compounds. The crystal structures of all six known isotypic compounds have been compared to reveal specific geometric parameters, which results in differences of thermal behavior and spectra. Chemical alteration in the An and T sites results in changes of the Cs⁺ coordination environment, which in turn leads to an increase of its influence on the layered structural units and the stability of the structure itself. These substitution mechanisms may be regarded as an example of the chemical composition selectivity for the preparation of compounds with the desired properties.

Original language	English
Article number	121077
Journal	Journal of Solid State Chemistry
Volume	282
DOIs	https://doi.org/10.1016/j.jssc.2019.121077
State	Published - Feb 2020

Funding

This work is supported by the Department of Energy , Basic Energy Sciences , Heavy Elements Program under grant number: D E-FG02-07ER15880 , St. Petersburg State University (to IVK, 3.42.712.2017 ) and by the Russian Science Foundation (to VVG, no. 18-17-00018 ). The ICP-OES analyses were conducted at the Center for Environmental Science and Technology (CEST), at the University of Notre Dame. Raman spectroscopy and high-temperature calorimetry data were collected in the Materials Characterization Facility supported by the Center for Sustainable Energy at the University of Notre Dame (ND Energy). Powder XRD data at non-ambient temperatures and luminescence spectra were collected in the X-ray Diffraction Centre and Center for Optical and Laser materials research of the St. Petersburg State University, respectively. Appendix A This work is supported by the Department of Energy, Basic Energy Sciences, Heavy Elements Program under grant number: DE-FG02-07ER15880, St. Petersburg State University (to IVK, 3.42.712.2017) and by the Russian Science Foundation (to VVG, no. 18-17-00018). The ICP-OES analyses were conducted at the Center for Environmental Science and Technology (CEST), at the University of Notre Dame. Raman spectroscopy and high-temperature calorimetry data were collected in the Materials Characterization Facility supported by the Center for Sustainable Energy at the University of Notre Dame (ND Energy). Powder XRD data at non-ambient temperatures and luminescence spectra were collected in the X-ray Diffraction Centre and Center for Optical and Laser materials research of the St. Petersburg State University, respectively.

Keywords

Calorimetry
Cesium
Chromate
Crystal structure
Isomorphism
Molybdate
Neptunium
Selenate
Sulfate
Uranium
X-ray diffraction

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Gurzhiy, V. V., Kornyakov, I. V., Szymanowski, J., Felton, D., Tyumentseva, O. S., Krzhizhanovskaya, M. G., Krivovichev, S. V., & Burns, P. C. (2020). Chemically-induced structural variations of a family of Cs₂[(AnO₂)₂(TO₄)₃] (An = U, Np; T = S, Se, Cr, Mo) compounds: Thermal behavior, calorimetry studies and spectroscopy characterization of Cs uranyl sulfate and selenate. Journal of Solid State Chemistry, 282, Article 121077. https://doi.org/10.1016/j.jssc.2019.121077

@article{a84548f3f7514786ad4ca7e6df6cc6f7,

title = "Chemically-induced structural variations of a family of Cs2[(AnO2)2(TO4)3] (An = U, Np; T = S, Se, Cr, Mo) compounds: Thermal behavior, calorimetry studies and spectroscopy characterization of Cs uranyl sulfate and selenate",

abstract = "Cs2[(AnO2)2(TO4)3] (where An = U, Np; T = S, Se, Cr, Mo) is a remarkable family of actinide-bearing compounds due to the surprising persistence of its structure type despite the substitutions in actinide and oxyanion sites. Cesium uranyl sulfate and selenate compounds have been analysed using high-temperature powder X-ray diffraction, Raman and luminescence spectroscopy techniques; in addition, high-temperature oxide-melt calorimetry studies had been carried out to derive the enthalpies of formation of both compounds. The crystal structures of all six known isotypic compounds have been compared to reveal specific geometric parameters, which results in differences of thermal behavior and spectra. Chemical alteration in the An and T sites results in changes of the Cs+ coordination environment, which in turn leads to an increase of its influence on the layered structural units and the stability of the structure itself. These substitution mechanisms may be regarded as an example of the chemical composition selectivity for the preparation of compounds with the desired properties.",

keywords = "Calorimetry, Cesium, Chromate, Crystal structure, Isomorphism, Molybdate, Neptunium, Selenate, Sulfate, Uranium, X-ray diffraction",

author = "Gurzhiy, \{Vladislav V.\} and Kornyakov, \{Ilya V.\} and Jennifer Szymanowski and Daniel Felton and Tyumentseva, \{Olga S.\} and Krzhizhanovskaya, \{Maria G.\} and Krivovichev, \{Sergey V.\} and Burns, \{Peter C.\}",

note = "Publisher Copyright: {\textcopyright} 2019 Elsevier Inc.",

year = "2020",

month = feb,

doi = "10.1016/j.jssc.2019.121077",

language = "English",

volume = "282",

journal = "Journal of Solid State Chemistry",

issn = "0022-4596",

publisher = "Elsevier",

}

Gurzhiy, VV, Kornyakov, IV, Szymanowski, J , Felton, D, Tyumentseva, OS, Krzhizhanovskaya, MG, Krivovichev, SV & Burns, PC 2020, 'Chemically-induced structural variations of a family of Cs₂[(AnO₂)₂(TO₄)₃] (An = U, Np; T = S, Se, Cr, Mo) compounds: Thermal behavior, calorimetry studies and spectroscopy characterization of Cs uranyl sulfate and selenate', Journal of Solid State Chemistry, vol. 282, 121077. https://doi.org/10.1016/j.jssc.2019.121077

Chemically-induced structural variations of a family of Cs₂[(AnO₂)₂(TO₄)₃] (An = U, Np; T = S, Se, Cr, Mo) compounds: Thermal behavior, calorimetry studies and spectroscopy characterization of Cs uranyl sulfate and selenate. / Gurzhiy, Vladislav V.; Kornyakov, Ilya V.; Szymanowski, Jennifer et al.
In: Journal of Solid State Chemistry, Vol. 282, 121077, 02.2020.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Chemically-induced structural variations of a family of Cs2[(AnO2)2(TO4)3] (An = U, Np; T = S, Se, Cr, Mo) compounds

T2 - Thermal behavior, calorimetry studies and spectroscopy characterization of Cs uranyl sulfate and selenate

AU - Gurzhiy, Vladislav V.

AU - Kornyakov, Ilya V.

AU - Szymanowski, Jennifer

AU - Felton, Daniel

AU - Tyumentseva, Olga S.

AU - Krzhizhanovskaya, Maria G.

AU - Krivovichev, Sergey V.

AU - Burns, Peter C.

PY - 2020/2

Y1 - 2020/2

N2 - Cs2[(AnO2)2(TO4)3] (where An = U, Np; T = S, Se, Cr, Mo) is a remarkable family of actinide-bearing compounds due to the surprising persistence of its structure type despite the substitutions in actinide and oxyanion sites. Cesium uranyl sulfate and selenate compounds have been analysed using high-temperature powder X-ray diffraction, Raman and luminescence spectroscopy techniques; in addition, high-temperature oxide-melt calorimetry studies had been carried out to derive the enthalpies of formation of both compounds. The crystal structures of all six known isotypic compounds have been compared to reveal specific geometric parameters, which results in differences of thermal behavior and spectra. Chemical alteration in the An and T sites results in changes of the Cs+ coordination environment, which in turn leads to an increase of its influence on the layered structural units and the stability of the structure itself. These substitution mechanisms may be regarded as an example of the chemical composition selectivity for the preparation of compounds with the desired properties.

AB - Cs2[(AnO2)2(TO4)3] (where An = U, Np; T = S, Se, Cr, Mo) is a remarkable family of actinide-bearing compounds due to the surprising persistence of its structure type despite the substitutions in actinide and oxyanion sites. Cesium uranyl sulfate and selenate compounds have been analysed using high-temperature powder X-ray diffraction, Raman and luminescence spectroscopy techniques; in addition, high-temperature oxide-melt calorimetry studies had been carried out to derive the enthalpies of formation of both compounds. The crystal structures of all six known isotypic compounds have been compared to reveal specific geometric parameters, which results in differences of thermal behavior and spectra. Chemical alteration in the An and T sites results in changes of the Cs+ coordination environment, which in turn leads to an increase of its influence on the layered structural units and the stability of the structure itself. These substitution mechanisms may be regarded as an example of the chemical composition selectivity for the preparation of compounds with the desired properties.

KW - Calorimetry

KW - Cesium

KW - Chromate

KW - Crystal structure

KW - Isomorphism

KW - Molybdate

KW - Neptunium

KW - Selenate

KW - Sulfate

KW - Uranium

KW - X-ray diffraction

UR - https://www.scopus.com/pages/publications/85075830028

U2 - 10.1016/j.jssc.2019.121077

DO - 10.1016/j.jssc.2019.121077

M3 - Article

AN - SCOPUS:85075830028

SN - 0022-4596

VL - 282

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

M1 - 121077

ER -

Gurzhiy VV, Kornyakov IV, Szymanowski J , Felton D, Tyumentseva OS, Krzhizhanovskaya MG et al. Chemically-induced structural variations of a family of Cs₂[(AnO₂)₂(TO₄)₃] (An = U, Np; T = S, Se, Cr, Mo) compounds: Thermal behavior, calorimetry studies and spectroscopy characterization of Cs uranyl sulfate and selenate. Journal of Solid State Chemistry. 2020 Feb;282:121077. doi: 10.1016/j.jssc.2019.121077