In situ Raman spectroscopy of uranyl peroxide nanoscale cage clusters under hydrothermal conditions

Haylie L. Lobeck; Hrafn Traustason; Patrick A. Julien; John R. Fitzpatrick; Sara Mana; Jennifer E.S. Szymanowski; Peter C. Burns

doi:10.1039/c9dt01529a

In situ Raman spectroscopy of uranyl peroxide nanoscale cage clusters under hydrothermal conditions

Haylie L. Lobeck
, Hrafn Traustason
, Patrick A. Julien
, John R. Fitzpatrick
, Sara Mana
, Jennifer E.S. Szymanowski
, Peter C. Burns

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

13 Scopus citations

Abstract

Aqueous solutions containing the nanoscale uranyl peroxide cage clusters U₆₀, [(UO₂)(O₂)(OH)]₆₀^60-, and U₆₀Ox₃₀, [{(UO₂)(O₂)}₆₀(C₂O₄)₃₀]^60-, were monitored by in situ Raman spectroscopy during stepwise heating to 180 °C. In solutions containing U₆₀, clusters persist to 120 °C, although conversion of U₆₀ to U₂₄, [(UO₂)(O₂)(OH)]₂₄^24-, occurs above 100 °C. U₆₀Ox₃₀ persisted in solutions heated to 150 °C, although partial conversion to smaller uranyl peroxide clusters species was observed beginning at 100 °C. Upon breakdown of the uranyl peroxide cage clusters, uranium precipitated as a compreignacite-like phase, K₂[(UO₂)₃O₂(OH)₃]₂(H₂O)₇, and metaschoepite, [(UO₂)₈O₂(OH)₁₂](H₂O)₁₀. The role of the countercations, oxalate bridge, and solution pH are examined in order to better understand the mobility of these species at elevated temperatures.

Original language	English
Pages (from-to)	7755-7765
Number of pages	11
Journal	Dalton Transactions
Volume	48
Issue number	22
DOIs	https://doi.org/10.1039/c9dt01529a
State	Published - 2019
Externally published	Yes

Funding

This research was funded by the U.S. Department of Energy, National Nuclear Security Administration, under Award Number DE-NA0003763. We thank the Center for Environmental Science and Technology, Materials Characterization Facility, and Mass Spectrometry and Proteomics Facility at the University of Notre Dame for the instrumentation used in this work. PAJ thanks NSERC and the McGill-GPS Graduate Mobility Award for funding and Dr Tomislav Frišcic for advice and enabling this contribution.

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10.1039/c9dt01529a

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title = "In situ Raman spectroscopy of uranyl peroxide nanoscale cage clusters under hydrothermal conditions",

abstract = "Aqueous solutions containing the nanoscale uranyl peroxide cage clusters U60, [(UO2)(O2)(OH)]6060-, and U60Ox30, [\{(UO2)(O2)\}60(C2O4)30]60-, were monitored by in situ Raman spectroscopy during stepwise heating to 180 °C. In solutions containing U60, clusters persist to 120 °C, although conversion of U60 to U24, [(UO2)(O2)(OH)]2424-, occurs above 100 °C. U60Ox30 persisted in solutions heated to 150 °C, although partial conversion to smaller uranyl peroxide clusters species was observed beginning at 100 °C. Upon breakdown of the uranyl peroxide cage clusters, uranium precipitated as a compreignacite-like phase, K2[(UO2)3O2(OH)3]2(H2O)7, and metaschoepite, [(UO2)8O2(OH)12](H2O)10. The role of the countercations, oxalate bridge, and solution pH are examined in order to better understand the mobility of these species at elevated temperatures.",

author = "Lobeck, \{Haylie L.\} and Hrafn Traustason and Julien, \{Patrick A.\} and Fitzpatrick, \{John R.\} and Sara Mana and Szymanowski, \{Jennifer E.S.\} and Burns, \{Peter C.\}",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2019.",

year = "2019",

doi = "10.1039/c9dt01529a",

language = "English",

volume = "48",

pages = "7755--7765",

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T1 - In situ Raman spectroscopy of uranyl peroxide nanoscale cage clusters under hydrothermal conditions

AU - Lobeck, Haylie L.

AU - Traustason, Hrafn

AU - Julien, Patrick A.

AU - Fitzpatrick, John R.

AU - Mana, Sara

AU - Szymanowski, Jennifer E.S.

AU - Burns, Peter C.

N1 - Publisher Copyright: © The Royal Society of Chemistry 2019.

PY - 2019

Y1 - 2019

N2 - Aqueous solutions containing the nanoscale uranyl peroxide cage clusters U60, [(UO2)(O2)(OH)]6060-, and U60Ox30, [{(UO2)(O2)}60(C2O4)30]60-, were monitored by in situ Raman spectroscopy during stepwise heating to 180 °C. In solutions containing U60, clusters persist to 120 °C, although conversion of U60 to U24, [(UO2)(O2)(OH)]2424-, occurs above 100 °C. U60Ox30 persisted in solutions heated to 150 °C, although partial conversion to smaller uranyl peroxide clusters species was observed beginning at 100 °C. Upon breakdown of the uranyl peroxide cage clusters, uranium precipitated as a compreignacite-like phase, K2[(UO2)3O2(OH)3]2(H2O)7, and metaschoepite, [(UO2)8O2(OH)12](H2O)10. The role of the countercations, oxalate bridge, and solution pH are examined in order to better understand the mobility of these species at elevated temperatures.

AB - Aqueous solutions containing the nanoscale uranyl peroxide cage clusters U60, [(UO2)(O2)(OH)]6060-, and U60Ox30, [{(UO2)(O2)}60(C2O4)30]60-, were monitored by in situ Raman spectroscopy during stepwise heating to 180 °C. In solutions containing U60, clusters persist to 120 °C, although conversion of U60 to U24, [(UO2)(O2)(OH)]2424-, occurs above 100 °C. U60Ox30 persisted in solutions heated to 150 °C, although partial conversion to smaller uranyl peroxide clusters species was observed beginning at 100 °C. Upon breakdown of the uranyl peroxide cage clusters, uranium precipitated as a compreignacite-like phase, K2[(UO2)3O2(OH)3]2(H2O)7, and metaschoepite, [(UO2)8O2(OH)12](H2O)10. The role of the countercations, oxalate bridge, and solution pH are examined in order to better understand the mobility of these species at elevated temperatures.

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U2 - 10.1039/c9dt01529a

DO - 10.1039/c9dt01529a

M3 - Article

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AN - SCOPUS:85066824490

SN - 1477-9226

VL - 48

SP - 7755

EP - 7765

JO - Dalton Transactions

JF - Dalton Transactions

IS - 22

ER -

In situ Raman spectroscopy of uranyl peroxide nanoscale cage clusters under hydrothermal conditions

Abstract

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