Comparisons of plutonium, thorium, and cerium tellurite sulfates

Article abstract of DOI:10.1021/ic302216y

The hydrothermal reaction of PuCl₃ or CeCl₃ with TeO₂ in the presence of sulfuric acid under the comparable conditions results in the crystallization of Pu(TeO₃)(SO₄) or Ce₂(Te₂O₅)(SO₄)₂, respectively. Pu(TeO₃)(SO₄) and its isotypic compound Th(TeO₃)(SO₄) are characterized by a neutral layer structure with no interlamellar charge-balancing ions. However, Ce ₂(Te₂O₅)(SO₄)₂ possesses a completely different dense three-dimensional framework. Bond valence calculation and UV-vis-NIR spectra indicate that the Ce compound is trivalent whereas the Pu and Th compounds are tetravalent leading to the formation of significantly different compounds. Pu(TeO₃)(SO₄), Th(TeO₃)(SO₄), and Ce₂(Te₂O ₅)(SO₄)₂ represent the first plutonium/thorium/cerium tellurite sulfate compounds. Our study strongly suggests that the chemistries of Pu and Ce are not the same, and this is another example of the failure of Ce as a surrogate.

Full text of DOI:10.1021/ic302216y

Article
pubs.acs.org/IC
Comparisons of Plutonium, Thorium, and Cerium Tellurite Sulfates
Jian Lin,‡ Justin N. Cross,‡ Juan Diwu,‡ Nathan A. Meredith,‡ and Thomas E. Albrecht-Schmitt*,†
†Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, 310 DLC, Tallahassee, Florida 32306,
United States
‡Department of Civil & Environmental Engineering & Earth Sciences and Department of Chemistry & Biochemistry, University of
Notre Dame, 156 Fitzpatrick Hall, Notre Dame, Indiana 46556, United States
S
* Supporting Information
ABSTRACT: The hydrothermal reaction of PuCl3 or CeCl3 with TeO2 in the
presence of sulfuric acid under the comparable conditions results in the
crystallization of Pu(TeO3)(SO4) or Ce2(Te2O5)(SO4)2, respectively. Pu-
(TeO3)(SO4) and its isotypic compound Th(TeO3)(SO4) are characterized by
a neutral layer structure with no interlamellar charge-balancing ions. However,
Ce2(Te2O5)(SO4)2 possesses a completely different dense three-dimensional
framework. Bond valence calculation and UV−vis−NIR spectra indicate that
the Ce compound is trivalent whereas the Pu and Th compounds are
tetravalent leading to the formation of significantly different compounds.
Pu(TeO3)(SO4), Th(TeO3)(SO4), and Ce2(Te2O5)(SO4)2 represent the first
plutonium/thorium/cerium tellurite sulfate compounds. Our study strongly
suggests that the chemistries of Pu and Ce are not the same, and this is another example of the failure of Ce as a surrogate.
between lanthanide and actinides.2c,e,7 In the boric acid system,
INTRODUCTION
■
the reactions of lanthanide and actinide halides with boric acid
The interest in comparing the chemistry of low oxidation state
under comparable synthetic parameters generate LnIII and AnIII
lanthanide and actinide stems from their similarities in ionic
radii and coordination.1 Lanthanide and actinide cations, such
borates with different coordination geometries and sheet
topologies.7,8 Electronic structure calculations with multi-
as cerium and plutonium, with same oxidation state and
coordination number can possess nearly identical ionic radii.1b
reference, CASSCF, and density functional theory (DFT)
methods suggest that the observed differences in the
In oxo-anion compounds both lanthanide and actinide can be
bonded to 7, 8, 9, or 10 oxygen atoms, yielding different
coordination geometries based on square antiprism, pentagonal
compositions and structures are attributed to real differences
in bonding and not simply a function of changes in ionic radii.7a
In the phosphonate system, the CeIV compound has lower
bipyramid, hexagonal bipyramid, tricapped trigonal prism,
solubility than the NpIV and PuIV.8 In this study, tellurite was
trigonal dodecahedra, distorted dodecahedra, capped triangular
cupola, etc.2 Lanthanides are used to simulate transuranium
chosen because it has stereochemically active lone pair
electrons on the TeIV center, which results in a large variability
elements with low oxidation state to predict their behavior
under long-term storage in repositories and transportation in
of coordination environments and properties.9 Tellurite anions
the environment from contaminated sites.3 For example, CeIV
can be further interconnected to form dimers, trimers, and
has long been used as a surrogate for PuIV owing to their nearly
polymeric structures, which enable a variety of unusual
structures.10 For example, novel infinite tellurite tubes with
lone-pair self-containment have been hydrothermally synthe-
sized.11 Unusual uranyl tellurites containing [Te2O6]4‑ ions and
3D networks have been observed in uranyl tellurites.12 Our
research efforts have successfully given rise to two families of
Pu, Ce, or Zr tellurite halides, which are cationic extended
materials with unusual coordination environments of the metal
centers.13
identical ionic radii.4 In many cases, however, lanthanides are
not proper mimics of transuranium elements both in solution
and in the solid state.5 Surprising coordination geometry
differences were observed in CeIV- and PuIV-maltol complexes
with respect to ligand orientation.6 Studies about differences
between lanthanide and actinides are still limited, and the
rationale of using lanthanides as the surrogates of trans-
uraniunm elements is still questionable.
Differentiating between low oxidation state lanthanides and
actinides using geometrically versatile ligands as a structural
probe provides a promising approach to study the differences
between lanthanides and actinides. These ligands can bind
metals in a variety of ways to form clusters, chains, sheets, or
frameworks leading to a rich study of the coordination
chemistry of lanthanide and actinides. Borate and phosphonate
have been studied as the ligands to differentiate the differences
Herein, we report the preparation, structure elucidation, and
absorption spectra of plutonium, thorium, and cerium tellurite
sulfate Pu(TeO3)(SO4), Th(TeO3)(SO4), and Ce2(Te2O5)-
(SO4)2 which were prepared hydrothermally. The reaction of
CeCl3 with TeO2 under comparable conditions as PuCl3
Received: October 11, 2012
Published: March 25, 2013
© 2013 American Chemical Society
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Article
produces completely different crystal structures with the PuIV in
Pu(TeO3)(SO4) and CeIII in Ce2(Te2O5)(SO4)2. More
significantly, the reaction chemistry of Ce and Pu is shown to
be different as PuIII oxidizes to PuIV even under inert conditions
whereas CeIII remains CeIII in air and CeIV reduces to CeIII in
air.
(frames). Each set had a different φ angle for the crystal, and each
exposure covered a range of 0.5° in ω. A total of 1464 frames were
collected with an exposure time per frame of 20−60 s, depending on
the crystal. The SAINT software was used for data integration
including Lorentz and polarization corrections. Semiempirical
absorption corrections were applied using the program SADABS or
TWINABS. Selected crystallographic information is listed in Table 1.
Atomic coordinates and additional structural information are provided
in the Supporting Information (CIFs).
EXPERIMENTAL SECTION
■
Synthesis. Th(NO3)4·5H2O (98%, International Bio-Analytical
Industries), CeCl3 (99.5%, Alfa-Aesar), CeO2 (99.99%, Alfa-Aesar),
TeO2 (99.99%, Alfa-Aesar), and NH4OH (28.0−30.0%, Alfa-Aesar)
were all used as received. Weapons-grade plutonium (94% 239Pu, 6%
240Pu) in the form of PuCl3 was used as received from LANL.
Reactions were run in PTFE-lined Parr 4749 autoclaves with a 23 mL
internal volume for the thorium/cerium and 10 mL internal volume
autoclaves for plutonium. Distilled water with was used in all reactions.
Caution! 239Pu (t1/2 = 24 065 years), and 240Pu (t1/2 = 6 537 years)
represent serious health risks owing to their α and γ emission. All studies
with plutonium were conducted in a laboratory dedicated to studies on
transuranium elements. This laboratory is located in a nuclear science
facility and is equipped with HEPA filtered hoods and negative pressure
gloveboxes that are ported directly into the hoods. A series of counters
continually monitor radiation levels in the laboratory. The laboratory is
licensed by the Nuclear Regulatory Commission. All experiments were
carried out with approved safety operating procedures. All free-flowing
solids are worked with in gloveboxes, and products are only examined when
coated with either water or Krytox oil and water. There are significant
limitations in accurately determining yield with plutonium compounds
because this requires drying, isolating, and weighing a solid, which poses
certain risks, as well as manipulation difficulties given the small quantities
employed in the reactions.
Table 1. Crystallographic Data for Pu(TeO3)(SO4),
Th(TeO3)(SO4), and Ce2(Te2O5)(SO4)2
Pu(TeO3)(SO4) Th(TeO3)(SO4) Ce2(Te2O5)(SO4)2
formula mass
color
513.66
red
503.70
403.78
colorless
tablet
colorless
prism
habit
block
space group
a (Å)
P21/c
P21/c
P21/c
7.4789(5)
13.5521(10)
5.4927(4)
90.000
109.097(1)
90.000
526.07(6)
4
7.5329(8)
13.8290(15)
5.6448(6)
90.000
9.597(3)
6.9391(18)
8.248(2)
90.00
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
Z
109.587(1)
90.000
106.452(3)
90.00
554.01(10)
4
526.8(2)
4
T (K)
100(2)
0.710 73
27.440
6.485
100(2)
0.710 73
27.470
100(2)
0.710 73
27.690
5.091
λ (Å)
max 2θ (deg)
ρcalcd (g cm−3
)
6.039
μ (cm−1
)
18.339
0.0207
32.432
14.429
0.0405
0.1138
Pu(TeO3)(SO4). PuCl3 (0.0295 mmol, 0.0100 g), TeO2 (0.0589
mmol, 0.0094 g), argon-sparged 1 M H2SO4 solution (0.0589 mmol,
59 μL), and argon-sparged water (241 μL) were loaded into a 10 mL
autoclave. The autoclave was sealed and heated to 230 °C in a box
furnace in an argon-filled glovebox for 3 days. The autoclave was then
cooled to room temperature at a rate of 5 °C/h. The products were
rinsed with DI water, and pale red tablets were isolated.
a
R(F)
0.0187
b
2
Rw(Fo )
0.0468
0.0475
a
b
R(F) = Σ∥Fo| − |Fo∥/Σ|Fo|. Rw(F2o)=[Σ[w(F2o − Fc2)2]/ΣwF4o]1/2
.
Th(TeO3)(SO4). Amorphous Th(OH)4 was precipitated with
NH4OH from a 1.25 mL solution of Th(NO3)4·5H2O (0.25 mmol,
0.1425 g) in water.14 The precipitate was washed several times with DI
water and dried at 90 °C in a 23 mL autoclave. TeO2 (0.5 mmol,
0.0798 g), 1 M H2SO4 solution (500 μL), and argon-sparged water
(2042 μL) were loaded into the autoclave. The autoclave was sealed
and heated to 230 °C for 3 days followed by slow cooling to room
temperature at a rate of 5 °C/h. The products were washed with DI
water to remove soluble solids, followed by rinsing with methanol. The
products consist of colorless block crystals of Th(TeO3)(SO4).
Ce2(Te2O5)(SO4)2. Ce2(Te2O5)(SO4)2 can be synthesized using
CeIIICl3 or CeIVO2 as the starting material. CeCl3 (0.25 mmol, 0.0616
g), TeO2 (2 mmol, 0.3192 g), 1 M H2SO4 (500 μL), and argon-
sparged water (2042 μL) were loaded into a 23 mL PTFE-lined
autoclave linear. Ce2(Te2O5)(SO4)2 can also be synthesized using
CeO2 (1 mmol, 0.1682 g), TeO2 (2 mmol, 0.3192 g), and 1 M H2SO4
(2 mL). The autoclave was sealed and heated to 230 °C for 3 days
followed by slow cooling to room temperature at a rate of 5 °C/h. The
products were washed with DI water to remove soluble solids,
followed by rinsing with methanol. Ce2(Te2O5)(SO4)2 crystallize into
colorless tablet crystals. Photographs of all three sets of crystals can be
found in Supporting Information.
Crystallographic Studies. Single crystals of all compounds were
mounted on CryoLoops with Krytox oil and optically aligned on a
Bruker APEXII Quazar X-ray diffractometer using a digital camera.
Initial intensity measurements were performed using an IμSX-ray
source, a 30 W microfocused sealed tube (Mo Kα, λ = 0.710 73 Å)
with high-brilliance and high-performance focusing Quazar multilayer
optics. Standard APEXII software was used for determination of the
unit cells and data collection control. The intensities of reflections of a
sphere were collected by a combination of four sets of exposures
UV−Vis−NIR Spectroscopy. UV−vis−NIR data were acquired
from single crystals using a Craic Technologies microspectropho-
tometer. Crystals were placed on quartz slides under Krytox oil, and
the data was collected from 200 to 1400 nm.
RESULTS AND DISCUSSION
■
Synthesis. The reaction of PuCl3 or CeCl3 with TeO2
under comparable conditions generates two compounds with
distinct structures and different oxidation state of the metal
centers. Both plutonium and cerium metals can be trivalent and
tetravalent.15 In Pu(TeO3)(SO4) and Th(TeO3)(SO4), Pu and
Th are tetravalent even though Pu(TeO3)(SO4) was
synthesized using PuIIICl3 as the starting material. The redox
potential for PuIV/PuIII is 0.76 V/NHE in 1 M H2SO4.16 PuIV is
the favored valence under ambient conditions, and oxygen from
air can easily oxidize PuIII to PuIV.1a To avoid oxygen, the Pu
reaction was performed in an argon-filled glovebox and all
solutions used were sparged with argon, which suggests the
valence transition could be attributed to the pH conditions and
possibly a solubility driven mechanism.2a,b,8 The presence of
Th(TeO3)(SO4), which is isotypic to Pu(TeO3)(SO4), further
confirms the valence of Pu because Th occurs exclusively in the
tetravalent state in nature.1a The redox potential for CeIV/CeIII
is 1.44 V/NHE in 1 M H2SO4, and CeIII is the preferred valence
state in an acidic environment.17 The reactions of both trivalent
cerium chloride and tetravalent cerium oxide with TeO2 in
sulfuric acid yield the same product, Ce2(Te2O5)(SO4)2 with
trivalent metal centers.
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Structures and Topological Descriptions. Materials with
layered structures are typically anionic/cationic in nature with
cations/anions as the interlamellar charge-balancing ions.18 In
this study, however, isotypic compounds Pu(TeO3)(SO4) and
Th(TeO3)(SO4) possess neutral layers with no charge-
balancing ions between the layers. Figure 1a shows the
Table 2. Selected Bond Distances for Pu(TeO3)(SO4),
Th(TeO3)(SO4), and Ce2(Te2O5)(SO4)2
Pu(TeO3)
(SO4)
Th(TeO3)
(SO4)
Ce2(Te2O5)
(SO4)2
An(1)−
2.113(4)
2.321(4)
2.379(4)
2.408(4)
2.480(4)
2.452(4)
2.524(4)
2.578(4)
2.443(4)
2.216(3)
2.416(3)
2.436(3)
2.481(3)
2.521(3)
2.520(3)
2.587(3)
2.662(3)
2.489(3)
Ce(1)−O(2)
Ce(1)−O(3)
Ce(1)−O(3)
Ce(1)−O(4)
Ce(1)−O(5)
Ce(1)−O(6)
Ce(1)−O(6)
Ce(1)−O(7)
Ce(1)−O(7)
2.442(13)
2.466(8)
2.506(8)
2.467(8)
2.511(7)
2.559(7)
2.593(7)
2.700(8)
2.539(7)
O(1)
An(1)−
O(2)
An(1)−
O(2)
An(1)−
O(3)
An(1)−
O(3)
An(1)−
O(4)
An(1)−
O(6)
An(1)−
O(7)
An(1)−
O(7)
S(1)−O(4)
S(1)−O(5)
S(1)−O(6)
S(1)−O(7)
1.463(4)
1.443(4)
1.493(4)
1.504(4)
1.852(4)
1.463(3)
1.437(4)
1.488(3)
1.515(3)
1.833(3)
S(1)−O(4)
S(1)−O(5)
S(1)−O(6)
S(1)−O(7)
1.455(8)
1.458(8)
1.488(8)
1.494(7)
2.02(2)
Te(1)−
Te(1A)−
O(1)
O(1)
Te(1)−
1.890(4)
1.900(4)
1.885(3)
1.900(3)
Te(1A)−
1.93(2)
O(2)
O(2)
Te(1)−
Te(1A)−
1.850(11)
2.18(2)
O(3)
O(3)
Te(1B)−
O(1)
Te(1B)−
2.005(18)
1.867(12)
1.88(2)
O(2)
Te(1B)−
O(3)
Te(1C)−
O(1)
Te(1C)−
2.17(3)
O(2)
Te(1C)−
1.804(14)
O(3)
2‑
O atoms (O1, O2, O3) from the TeO3 anions participate in
the coordination with the metal centers. The AnO9 polyhedra
edge-share with three other AnO9 polyhedra, forming the An-
oxo sheets (cf. Figure 1c).
Figure 1. (a) View of AnTeO3SO4 showing the neutral charged layers
extending down the c axis. (b) Depiction of one AnTeO3SO4 layer
which is composed An-oxo sheet, TO32‑, and SO42‑ polyhedra. (c) An-
The reaction of CeCl3 with TeO2 under comparable
conditions as PuCl3 yields a completely different structure
with a dense three-dimensional framework (cf. Figure 2a). This
2‑
oxo sheet. An polyhedra are shown in blue-violet, TO3 polyhedra in
2‑
light-blue, SO4 polyhedra in gray.
3D framework is broken down into CeIII−SO4 layers and
2‑
tellurite layers (cf. Figure 2b). Within the CeIII−SO4 layer,
2‑
depiction of the layers that extend along the c axis. Within
2‑
2‑
2‑
SO4 polyhedra share one edge and two corners with the Ce
each layer, paired TeO3 and SO4 polyhedra either corner-
share or edge-share with metal centers alternatively, forming
zigzagging layered structures (cf. Figure1b). The metal center is
a nine-coordinate tricapped trigonal prism where four O atoms
are donated from sulfate and five O atoms are donated from
tellurite moieties (cf. Figure 3). The average An−O bond
lengths in Pu(TeO3)(SO4) and Th(TeO3)(SO4) are 2.411 and
2.481 Å, respectively. Selected bond distances are given in
Table 2. Bond valence calculations resulted in values of 3.929
for Pu and 4.069 for Th, which suggest the tetravalent nature of
center. All O atoms (O4, O5, O6, and O7) of SO42‑ participate
in the coordination. The Ce center is a nine-coordinate
tricapped trigonal prism where six O atoms are donated from
2‑
SO4 anions and three O atoms from tellurite anions (cf.
Figure 3). The average metal−oxygen bond length is 2.531 Å,
and selected bond distances are given in Table 2. Bond valence
calculations resulted in value 2.813 for Ce which confirm the
trivalent state of Ce in this compound.19 The CeO9 polyhedra
also share three edges with three other Ce centers, but form a
remarkably different zigzagging skeleton from that of
AnTeO3SO4 (cf. Figure 2c). The Ce-SO42‑ layers are connected
together by tellurite layers. Within the tellurite layer, Te atoms
the metal centers.19 Three O atoms (O4, O6, O7) from SO4
2‑
anions coordinate with the metal ions, and the remaining O5
atom points into interlamellar space. Contrasting sulfate, all the
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Figure 3. Tricapped trigonal prism coordination geometries of the
PuIV, ThIV, and CeIII centers. The PuIV center is blue-violet sphere, the
ThIV center is green sphere, the CeIII center is yellow sphere, and the
O atoms are in red spheres.
Figure 4. (a) UV−vis−NIR spectra of Pu(TeO3)(SO4), Th(TeO3)-
(SO4), and Ce2(Te2O5)(SO4)2. The spectrum of Pu(TeO3)(SO4)
5
5
showing the assigned peaks for different f−f transitions (the F2 + I6
peaks centered at 1100 nm are signature peaks of the PuIV; at
wavelengths <909 nm, multiple J values contribute).
Figure 2. (a) View of Ce2(Te2O5)(SO4)2 showing the dense 3D
of Ce2(Te2O5)(SO4)2 likely corresponds to delocalization of
the 4f1 electrons.2g Te−O charge transfer could also contribute
to the absorption.
frameworks. (b) Depiction of one Ce2(Te2O5)(SO4)2 3D framework
2‑
which is composed cerium sheet, tellurite layer, and SO4 polyhedra.
2‑
(c) Cerium-oxo sheet. Ce polyhedra are shown in yellow, TO3
polyhedra in light-blue, SO4 polyhedra in gray.
2‑
CONCLUSIONS
■
are highly disordered which are delocalized into three
independent Te atoms with a total occupancy of 1. Three of
the O atoms (O1, O2, and O3) bonded to tellurium are also
disordered and with one of them being half occupied.
In this study, the tellurite-sulfate system was selected to
differentiate between low oxidation state lanthanides and
actinides. The hydrothermal reaction of PuCl3 with TeO2 in
sulfuric acid forms PuIV(TeO3)(SO4), characterizing a neutral
layer structure with no charge-balancing ions between the
layers. The reaction of CeCl3 with TeO2 in sulfuric acid under
comparable conditions yields CeIII2(Te2O5)(SO4)2. This
compound possesses a completely different dense three-
dimensional framework from Pu(TeO3)(SO4). Bond valence
calculation and UV−vis−NIR spectrum suggest the tetravalent
oxidation state of Pu in Pu(TeO3)(SO4). The presence of
Th(TeO3)(SO4), which is isotypic to Pu(TeO3)(SO4), further
confirms PuIV in Pu(TeO3)(SO4). Cerium in Ce2(Te2O5)-
(SO4)2, however, is trivalent based on the bond valence
calculation, and if CeIV is used as a starting material it will
reduce to CeIII to form Ce2(Te2O5)(SO4)2, which stands as a
marked contrast from the Pu reaction. Pu(TeO3)(SO4),
Th(TeO3)(SO4), and Ce2(Te2O5)(SO4)2 represent the first
UV−Vis−NIR Absorption Spectroscopy. The absorption
spectra for Pu(TeO3)(SO4), Th(TeO3)(SO4), and
Ce2(Te2O5)(SO4)2 were obtained from single crystals of each
compound and are shown in Figure 4. The existence of PuIV in
Pu(TeO3)(SO4) can be confirmed by the UV−vis−NIR
5
5
spectrum. The F2 + I6 peaks centered near 1100 nm are
signature peaks of PuIV. At wavelengths less than 900 nm, the
transitions are due to multiple J states and have not been
deconvoluted, but the transitions match well with the spectra
reported by Carnall.20 ThIV has empty 5f orbital and does not
exhibit any f−f transitions in the absorption spectra. The peaks
ranging from 200 to 400 nm are ascribed to the Te−O charge
transfer based on the measurement of TeO2 crystal. CeIII has
one 4f electron, and the absorption near 300 nm in the spectra
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identical with Ce and is another example of the failure of Ce as
a surrogate.21 Investigations are underway to prepare
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hope would be that future theory will be able to account for the
differences in structure and valence.
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ASSOCIATED CONTENT
* Supporting Information
X-ray crystallographic files in CIF format and photographs of
the crystals. This material is available free of charge via the
Internet at http://pubs.acs.org.
8510.
■
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AUTHOR INFORMATION
Corresponding Author
*E-mail: talbrechtschmitt@gmail.com.
Notes
■
The authors declare no competing financial interest.
(16) Gupta, R.; Guin, S. K.; Aggarwal, S. K. RSC Adv. 2012, 2, 1810−
ACKNOWLEDGMENTS
■
1819.
This material is based upon work supported as part of the
Materials Science of Actinides, an Energy Frontier Research
Center funded by the U.S. Department of Energy, Office of
Science, Office of Basic Energy Sciences under Award Number
DE-SC0001089. This work was supported by a Chinese
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