Identifying the Recognition Site for Selective Trapping of 99TcO4- in a Hydrolytically Stable and Radiation Resistant Cationic Metal-Organic Framework

Article abstract of DOI:10.1021/jacs.7b08632

Effective and selective removal of ⁹⁹TcO₄^- from aqueous solution is highly desirable for both waste partitioning and contamination remediation purposes in the modern nuclear fuel cycle, but is of significant challenge. We report here a hydrolytically stable and radiation-resistant cationic metal-organic framework (MOF), SCU-101, exhibiting extremely fast removal kinetics, exceptional distribution coefficient, and high sorption capacity toward TcO₄^-. More importantly, this material can selectively remove TcO₄^- in the presence of large excesses of NO₃^- and SO₄^2-, as even 6000 times of SO₄^2- in excess does not significantly affect the sorption of TcO₄^-. These superior features endow that SCU-101 is capable of effectively separating TcO₄^- from Hanford low-level waste melter off-gas scrubber simulant stream. The sorption mechanism is directly unraveled by the single crystal structure of TcO₄^--incorporated SCU-101, as the first reported crystal structure to display TcO₄^- trapped in a sorbent material. A recognition site for the accommodation of TcO₄^- is visualized and is consistent with the DFT analysis results, while no such site can be resolved for other anions.

Full text of DOI:10.1021/jacs.7b08632

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Communication
Identifying the Recognition Site for Selective Trapping
of 99TcO4- in a Hydrolytically Stable and Radiation
Resistant Cationic Metal-Organic Framework
Lin Zhu, Daopeng Sheng, Chao Xu, Xing Dai, Mark A. Silver, Jie Li, Peng Li, Yaxing
Wang, Yanlong Wang, Lanhua Chen, Chengliang Xiao, Jing Chen, Ruhong Zhou, chao
zhang, Omar K. Farha, Zhifang Chai, Thomas E. Albrecht-Schmitt, and Shuao Wang
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 06 Oct 2017
Downloaded from http://pubs.acs.org on October 6, 2017
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-
Identifying the Recognition Site for Selective Trapping of TcO
4
in a Hydrolytically Stable and Radiation Resistant Cationic Metal-
Organic Framework
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, §
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Lin Zhu, Daopeng Sheng, Chao Xu, Xing Dai, Mark A. Silver, Jie Li, Peng Li, Yaxing
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,1
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Wang, Yanlong Wang, Lanhua Chen, Chengliang Xiao,* Jing Chen, Ruhong Zhou, Chao Zhang,
3
,5
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,1
Omar K. Farha, Zhifang Chai, Thomas E. AlbrechtꢀSchmitt, and Shuao Wang*
1
School for Radiological and Interdisciplinary Sciences (RADꢀX) and Collaborative Innovation Center of Radiation Mediꢀ
cine of Jiangsu Higher Education Institutions, Soochow University, Suzhou 215123, China
2
Nuclear Chemistry and Chemical Engineering Division, Institute of Nuclear and New Energy Technology, Tsinghua Uniꢀ
versity, Beijing 100084, China
3
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA
4
School of Materials Science and Engineering, Anhui University of Science and Technology, Huainan 232001, China
5
Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
6
Department of Chemistry and Biochemistry, Florida State University, 95 Chieftain Way, Tallahassee, Florida 32306, USA
Supporting Information
9
9
ꢀ
it is highly desirable to develop functional materials that can
remove TcO during used fuel reprocessing or remediation of
4
4
ABSTRACT: Effective and selective removal of TcO4 from
aqueous solution is highly desirable for both waste partitioning
and contamination remediation purposes in the modern nuclear
fuel cycle, but is of significant challenge. We report here a
hydrolytically stable and radiation resistant cationic metalꢀorganic
framework (MOF), SCUꢀ101, exhibiting extremely fast removal
ꢀ
contaminated water systems.
Traditional polymeric anion exchange resins are commercial
products that exhibit efficient removal of TcO , but their
ꢀ
5ꢀ7
4
poor radiation resistances and chemical stabilities under
8
kinetics, exceptional distribution coefficient, and high sorption
extreme conditions are clear demerits. Furthermore, the
ꢀ
capacity towards TcO . More importantly, this materials can
4
sorption kinetics are relatively slow owing to their randomly
distributed pores that may hinder efficient transport of targeted
anionic species. Crystalline inorganic cationic materials.
possessing ordered extended structures with positive net
charge and unbound or weakly coordinated anions in the open
space ready to exchange, are scarce compared to the neutral
ꢀ
selectively remove TcO in the presence of large excesses of
4
ꢀ
2ꢀ
2ꢀ
NO and SO , as even 6000 times of SO in excess does not
3
4
4
ꢀ
significantly affect the sorption of TcO . These superior features
endow that SCUꢀ101 is capable of effectively separating TcO4
4
ꢀ
from Hanford lowꢀlevel waste melter offꢀgas scrubber simulant
stream. The sorption mechanism is directly unraveled by the
9
ꢀ
and anionic framework materials. Only a handful of such
single crystal structure of TcO ꢀincorporated SCUꢀ101, as the
4
10
11
ꢀ
materials
including
MgꢀAlꢀLDH,
Y (OH) Cl,
2 5
14
first reported crystal structure to display TcO4 trapped in a
12
13
Yb O(OH) Cl, metal sulfides, and NDTBꢀ1 have been
investigated for TcO4 removal, but the majority of these
exhibit low sorption capacity and poor selectivity towards
TcO . The latter property is a critical disadvantage that imꢀ
pedes practical applications, because a large excess of competꢀ
3
6
sorbent material. A recognition site for the accommodation of
ꢀ
ꢀ
TcO is visualized and is consistent with the DFT analysis results,
4
while no such site can be resolved for other anions.
ꢀ
15
4
ꢀ
2ꢀ
ꢀ
ing anions, such as NO3 and SO , often coexist with TcO .
4
4
9
9
5
Tc is a longꢀlived (t1/2 = 2.13×10 y) radioisotope produced
Cationic MOFs, a relatively less investigated subgroup of
MOFs in general, are emerging candidates for removing aniꢀ
onic pollutants with advantages of high surface area, tunable
235
239
during nuclear fission of U or Pu and primarily exists in
the +7 oxidation state as TcO4 anion under aerobic
conditions. The nonꢀcomplexing nature, high water solubility,
and great stability of TcO lead to its extremely high mobility
ꢀ
1
16
pores, and facile functionalities. Up to now, very few cationꢀ
ꢀ
ꢀ
ꢀ
ic MOFs have been tested for TcO
/ReO sequestration and
4
4 4
2
in the environment. Tc is volatile during waste vitrification
their practical applications are still limited by slow sorption
kinetics and poor selectivity.
We recently reported a cationic MOF SCUꢀ100 with open
Ag sites that can efficiently and selectively capture TcO
through a structural transformation process.
clear drawback for this material is that large single crystals
16a,17
processes and can leach from vitrified glass and greatly interꢀ
fere with the separation of uranium and plutonium during biꢀ
phasic solvent extraction, making it one of the most
+
ꢀ
4
3
ꢀ
15a
problematic radionuclides in the nuclear fuel cycle. Therefore
/ReO
4
One
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tion resistance can be further confirmed by the unaffected
disintegrate into microcrystalline materials after anion exꢀ
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change, making chromatographic extraction inapplicable (Figꢀ
ure S1). Moreover, the incomplete phase transition leads to
poor recyclability and limited stability (Figure S2). We
document here a solution to all aforementioned demerits,
anion exchange capacity after irradiation (Figure 2f) and is
likely a consequence of the benzeneꢀrich nature, contrasting
sharply with stateꢀofꢀtheꢀart anion exchange resins that lose
8
anion uptake capacities after irradiation.
based
on
a
stable
cationic
MOF,
1.2
1.0
0.8
0.6
(a)
(b)
1
00
0
min
5 min
0 min
[
(
Ni (tipm) (C O )](NO ) ·2H O (SCUꢀ101, tipm=tetrakis[4ꢀ
1ꢀimidazolyl)phenyl]methane). This compound exhibits fast
2
2
2
4
3 2
2
8
0
0
1
TcO -
290 nm
Purolite A532E
Purolite A530E
SCU-101
4
6
removal kinetics, high sorption capacity, and unique molecular
ꢀ
40
20
0
0
0
0
.4
.2
recognition derived sorption selectivity towards TcO .
4
(a)
(b)
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.0
2
00
250
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0
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150
(C)
(B)
Wavelength (nm)
Contact time (min)
(
c)
(d)
2
50
100
80
(
A)
200
150
100
50
Mg-Al LDH
NDTB-1
SCU-101
60
4
0
0
0
2
(c)
(d)
0
-
2-
3-
-
2-
0
50
100
eq
150
200
250
Blank NO3 CO3
PO4
C
l
O
S
O
4
4
C
(
mg/L
)
(e)
(f)
1
00
100
80
80
60
40
20
0
6
0
40
20
0
0
:1
Molar ratio between SO42-and ReO -
4
1:1
10:1 100:1 1000:1 6000:1
2+
Figure 1. Crystal structure of SCUꢀ101. (a) Coordination environment of Ni
with four tipm ligands and one oxalate group. (b) 3D cationic framework conꢀ
taining three types of channels. Atom colors: Ni=orange; O=red; C=light blue;
N=green. (c) Simplified (4,8)ꢀconnected binodal Flu topology. (d) Simplified
rhombic dodecahedron honeycomb structure.
ꢀ
Figure 2. (a) UVꢀvis absorption spectra of TcO
4
during the anion exchange.
ꢀ
(
b) Sorption kinetics of TcO
A532E. (c) Sorption isotherms of ReO
NDTBꢀ1. (d) Effect of competing anions on the removal percentage of TcO
4
by SCUꢀ101 compared with Purolite A530E and
ꢀ
4
by SCUꢀ101, MgꢀAlꢀLDH, and
ꢀ
4
2
ꢀ
ꢀ
by SCUꢀ101. (e) Effect of SO
(
4
on the anion exchange of ReO
after irradiation as compared with the original
4
by SCUꢀ101.
SCUꢀ101 crystallizes in the triclinic space group, P1, as
ꢀ
f) Removal percentage of ReO
4
blue plate crystals (Figure S5 and Table S1). The size of these
SCUꢀ101 sample.
3
crystals is ca. 400×100×40 ꢁm , large enough for
ꢀ
Anion exchange of TcO4 was initially investigated by
mixing 20 mg of SCUꢀ101 samples with 20 mL of a solution
chromatographic extraction applications. The overall structure
can be best described as a porous 3D cationic nickelꢀtipm
99
ꢀ
2
+
containing 28 ppm TcO . As shown in Figure 2a, the
4
extended framework (Figure S6). Each Ni cation is 6ꢀ
ꢀ
2ꢀ
concentration of TcO4 in aqueous solution as a function of
coordinate and binds to four tipm ligands and one C O4 anion
2
contact time was monitored by its characteristic absorption
(
Figure S7 and Figure 1a). As shown in Figure 1b, there are
2
2
feature at 290 nm in the UVꢀvis spectra. The removal of
three types of channels (A: ~7×9 Å , B: ~11×5 Å , and C:
~
ꢀ
2
ꢀ
TcO occurs at 85% after 5 min and >95% at 10 min. It takes
4
4×2.5 Å ) to accommodate the chargeꢀbalancing NO anions,
3
approximately 10 min to reach the sorption equilibrium,
further verified by liquid scintillation counting measurements
(Figure 2b). Note the sorption kinetics of SCUꢀ101 is much
faster than those of commercial resins (A532E and A530E).
Compared to other cationic MOFs tested for removing anionic
contaminants including SCUꢀ100 (Figure S10 and Table
confirmed by ion chromatography analysis. However, these
anions cannot be located in the electron density map and are
2+
completely disordered. Each tipm ligand bridging four Ni
cations serves as
a
4ꢀconnected node, whereas each
2+
[
Ni C O ] cluster acts as a 8ꢀconnected node, affording a
2
2
4
(4,8)ꢀconnected binodal Flu topology (Figure 1c). The
structure of SCUꢀ101 can be simplified as a honeycomb conꢀ
sisting of a series of rhombic dodecahedra (Figure 1d).
15a,16g
S2),
SCUꢀ101 also exhibits an advance in the removal
rate. For example, it takes more than 24 h to reach the
16a
+ 17
exchange equilibrium for SLUGꢀ21 and UiOꢀ66ꢀNH3
to
After immersing SCUꢀ101 crystals into aqueous solutions
with different pH values ranging from 2 to 14, the structure
remains unchanged (Figure S8). Inductively coupled plasma
optical emission spectrometry measurements show that the
ꢀ
ꢀ
sequester TcO /ReO .
4
4
To comprehensively study the ion exchange properties of
ꢀ
ꢀ
TcO by SCUꢀ101, ReO was used as a surrogate to perform
4
4
2+
batch experiments owing to their almost identical charge
dissolved Ni concentration is only 0.63 ppm at pH 7,
corresponding to 0.9% of the total mass of SCUꢀ101. Such
ꢀ
densities. Sorption kinetics study of ReO4 under the same
condition indeed yields identical anion exchange behavior
value is much lower than that of cationic MOFs
ꢀ
15a,18
with that of TcO . The sorption isotherm curve of SCUꢀ101
4
[
Ag(bipy)]NO and SCUꢀ100 (Figure S9).
Additionally,
3
ꢀ
towards ReO4 can be well fitted to the Langmuir model
SCUꢀ101 survives from ionizing radiation fields and maintains
60
(Figures 2c, S11, and Table S3) and the calculated maximum
its crystallinity even after 200 kGy Co γ irradiation or 200
ꢀ
sorption capacity of SCUꢀ101 is 217 mg ReO4 per gram of
kGy β irradiation (1.2 MeV) (Figure S8). The excellent radiaꢀ
SCUꢀ101, higher than those for LDH, NDTBꢀ1, and UiOꢀ66ꢀ
2
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+
17
19
NH , but only lower than PAFꢀ1ꢀF and SCUꢀ100. The
graphic material. This is very unusual because the singleꢀ
crystallinity of MOF crystals is often ruined after ion
exchange even when the framework structure remains
3
ꢀ
1
2
3
4
5
6
7
8
9
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1
1
1
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1
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1
2
2
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2
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2
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3
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distribution coefficient (K ) of SCUꢀ101 towards ReO
reaches 7.5×10 mL/g, noticeably higher than those of all
reported anion sorbent materials (Table S4). The final ReO4
concentration after uptake by SCUꢀ101 is about four times
d
4
5
ꢀ
unchanged during the process. We therefore collected single
ꢀ
crystal Xꢀray diffraction data directly on TcO incorporated
4
lower than that treated by SCUꢀ100 at similar conditions
SCUꢀ101 crystals (SCUꢀ101ꢀTc). Although the unit cell
parameters, space group, and the structure of the main cationic
framework are almost identical with the original material, we
ꢀ
(
Table S5).Additionally, more than 95.7% of ReO4 could be
exchanged back to the solution using a desorption solution
ꢀ
containing 1 M NaNO , and the material can be fully
were able to resolve the position of TcO4 anions in the
3
regenerated for at least four sorption/desorption cycles (Figure
S4), representing another advance over SCUꢀ100 (Figure S2).
electron density map with a site occupancy factor (SOF) of
ꢀ
~30%. Note that NO3 anions cannot be identified in the
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
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6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ꢀ
Moreover, SCUꢀ101 can remove ReO4 within a wide pH
original structure. Moreover, we also saturated SCUꢀ101 with
ꢀ
ꢀ
2ꢀ
2ꢀ
range from 3 to 12 (Figure S12), which is also a clear
advantage compared to the purely inorganic cationic materials.
a variety of other anions including Cl , ClO , SO , CrO and
4 4 4
3ꢀ
PO4 and attempted to locate their positions but all failed.
These observations offer hints on the intrinsic driving force for
the stabilization of TcO4 in the structure of SCUꢀ101 and
ꢀ
ꢀ
The anion exchange selectivity towards TcO /ReO was
4
4
ꢀ
ꢀ
first studied by the uptake of ReO4 with the presence of one
equivalent of competing anions, including NO , CO , PO ,
ClO4 and SO . The removal percentage is still as high as
ꢀ
2ꢀ
3ꢀ
ꢀ
subsequently the excellent TcO uptake selectivity.
3
3
4
4
ꢀ
2ꢀ
4
(
a)
(b)
~90% in all cases (Figure 2d). This contrasts with other
cationic porous materials reported. Under the same anion
ꢀ
+
exchange condition, the removal of ReO4 by UiOꢀ66ꢀNH3
occurs at 15%, 50%, and 20% of the original concentrations in
3
ꢀ
2ꢀ
ꢀ
4
17
the presence of PO , SO , and ClO , respectively ; the
4
4
removal occurs at 21% and 19% for PAFꢀ1ꢀF in presence of
3
ꢀ
2ꢀ
19
PO4 and SO , respectively . Generally, anions with higher
4
ꢀ
charge densities often successfully outcompete with ReO4
during the exchange process owing to stronger hostꢀguest
electrostatic interactions. Surprisingly, SCUꢀ101 shows much
ꢀ
0.06
(c)
(d)
3ꢀ
2ꢀ
less affinity towards PO and SO4 compared to that of ReO4
4
-0.06
ꢀ
/
TcO , as the removal of which under the same conditions is
4
only 21.7% and 24.2% (Table S6), respectively. This atypical
1
6f
phenomenon follows the antiꢀHofmeister bias and likely
originates from the hydrophobic nature of channels
constructed by benzeneꢀrich tipm ligands. Considering the
ꢀ
2ꢀ
ꢀ
extremely high concentration of NO or SO in certain types
Figure 3. (a) TcO4 trapped in type A channels. (b) Hydrogen bonds formed
ꢀ
3
4
of nuclear waste solutions, we also investigated the uptake of
4
between TcO and SCUꢀ101 framework. (c) Electrostatic potential distribution
ꢀ
ꢀ
of the partial framework. (d) Optimized trapping position of TcO4 in the
framework by theoretical calculations.
ReO4 as a function of their concentrations. As shown in
ꢀ
ꢀ
Figure S13, when the molar ratio of NO and ReO4 is 20:1,
3
ꢀ
the uptake of ReO is still as high as 76%. More impressively,
the removal of ReO is almost unaffected by the concentration
of SO . SCUꢀ101 can still remove 80% of ReO in the
presence of 6000 times of SO4 in excess (Figure 2e), making
ꢀ
4
In the structure of SCUꢀ101ꢀTc, all TcO anions reside only
ꢀ
4
4
ꢀ
in type A channels while disordered NO3 anions are likely
2ꢀ
ꢀ
4
4
trapped in type B and type C channels and are not
2
ꢀ
exchangeable, which is responsible for the nonꢀintegral SOF
it an extremely attractive candidate to selectively remove
ꢀ
of the TcO site (Figures 3a and S19). The bond distances of
ꢀ
4
TcO from waste solutions with high ionic strengths.
4
TcꢀO range from 1.691 to 1.776 Å, comparable with other
To further validate the potential application of SCUꢀ101 in
the partition of nuclear waste, we performed the ion exchange
experiments using a simulated Hanford LAW melter recycle
20
Tc(VII) compounds reported. A close examination of the
ꢀ
ꢀ
coordination environment of TcO4 reveals that TcO4 is
trapped within a very dense hydrogen bond network with H
1
4b
ꢀ
stream. In this type of solution, the concentrations of NO ,
3
atoms of phenyl and imidazolyl groups (Figure 3b). Each
ꢀ
ꢀ
ꢀ
NO , and Cl are all 300 times higher than that of TcO (Table
ꢀ
2
4
TcO coordinates to 13 H atoms, forming 17 hydrogen bonds
ꢀ
4
S7). Notably, SCUꢀ101 can capture 75.2% of TcO4 from the
stream when adding 100 mg of SCUꢀ101 into 10 mL of the
simulated solution.
with an average distance of 3.41 Å (Table S8).
We also analyzed the electrostatic potential (ESP)
distribution of the SCUꢀ101 framework. As shown in Figures
The anion exchange process was confirmed by energyꢀ
dispersive Xꢀray spectroscopy (Figure S14), Fourier transform
infrared spectroscopy spectra (Figure S15), and ion chromaꢀ
tography analysis (Figure S16). The structure of SCUꢀ101
remains intact after anion exchange, verified by powder Xꢀray
diffraction (PXRD) patterns (Figure S17). In addition, the
2+
3
c and S20, those spaces close to Ni centers and oxalate
groups offer the most negative ESP, whereas the intersections
of the crossꢀstacked tipm pair provides large areas of positive
ꢀ
ESP (red areas in arrow direction) to accommodate the TcO4
anion. The subsequent DFT geometry optimizations confirm
ꢀ
this prediction and show that the binding site of TcO4 is
crystal habits of SCUꢀ101 including shape, size, and color
precisely in the corner constructed by two tipm ligands (Figure
ꢀ
does not change even after the exchange of TcO (Figure S18),
4
3
d and Figure S21), consistent with the experimentally
further highlighting the application potential as the chromatoꢀ
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obtained crystal structure (Figure S22). The calculated binding
(13) Neeway, J. J.; Asmussen, R. M.; Lawter, A. R.; Bowden, M. E.;
Lukens, W. W.; Sarma, D.; Riley, B. J.; Kanatzidis, M. G.; Qafoku, N. P.
Chem. Mater. 2016, 28, 3976ꢀ3983.
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energy between TcO and the framework is ꢀ20.42 kcal/mol.
4
In conclusion, SCUꢀ101 is an attractive sorbent material
(14) (a) Wang, S.; Alekseev, E. V.; Diwu. J.; Casey, W. H.; Phillips, B. L.;
ꢀ
for TcO4 removal from either nuclear waste solutions with
Depmeier, W.; AlbrechtꢀSchmitt, T. E. Angew. Chem. Int. Ed. 2010, 49,
1057ꢀ1060. (b) Wang, S.; Yu, P.; Purse, B. A.; Orta, M. J.; Diwu, J.;
Casey, W. H.; Phillips, B. L.; Alekseev, E. V.; Depmeier, W.; Hobbs, D.
T.; AlbrechtꢀSchmitt, T. E. Adv. Funct. Mater. 2012, 22, 2241ꢀ2250.
high ionic strengths or contaminated water systems with low
ꢀ
ꢀ
TcO4 concentrations. The strong TcO4 uptake capability is
ꢀ
elucidated by the single crystal structure of TcO incorporated
4
(15) (a) Sheng, D.; Zhu, L.; Xu, C.; Xiao, C.; Wang, Y.; Wang, Y.; Chen,
materials and first principle theoretic analysis on electrostatic
potential distribution and bonding, which is beneficial to
further development of cationic MOF materials with improved
sequestration capabilities towards anionic pollutants.
L.; Diwu, J.; Chen, J.; Chai, Z.; AlbrechtꢀSchmitt, T. E.; Wang, S. Environ.
Sci. Technol. 2017, 51, 3471ꢀ3479. (b) Li, D.; Kaplan, D. I.; Knox, A. S.;
Crapse, K. P.; Diprete, D. P. J. Environ. Radioactiv. 2014, 136, 56ꢀ63.
(16) (a) Fei, H.; Bresler, M. R.; Oliver, S. R. J. J. Am. Chem. Soc. 2011,
0
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0
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0
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33, 11110ꢀ11113. (b) Yaghi, O. M.; Li, G. M. Angew. Chem. Int. Ed.,
1995, 34, 207ꢀ209. (c) Yaghi, O. M.; Li, H. L. J. Am. Chem. Soc. 1996,
118, 295ꢀ296. (d) Yaghi, O. M.; Li, H. L.; Davis C.; Richardson D.; Groy
T. L. Acc. Chem. Res. 1998, 31, 474ꢀ484. (e) Howarth, A. J.; Katz, M. J.;
Wang, T. C.; PlateroꢀPrats, A. E.; Chapman, K. W.; Hupp, J. T.; Farha, O.
K. J. Am. Chem. Soc. 2015, 137, 7488ꢀ7494. (f) Custelcean, R.; Moyer, B.
A. Eur. J. Inorg. Chem. 2007, 10, 1321ꢀ1340. (g) Desai, A. V.; Manna, B.;
Karmakar, A.; Sahu, A.; Ghosh, S. K. Angew. Chem. Int. Ed. 2016, 55,
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website. (PDF)
7
811ꢀ7815.
AUTHOR INFORMATION
Corresponding Author
(17) Banerjee, D.; Xu, W.; Nie, Z.; Johnson, L. E. V.; Coghlan, C.;
Sushko, M. L.; Kim, D.; Schweiger, M. J.; Kruger, A. A.; Doonan, C. J.;
Thallapally, P. K. Inorg. Chem. 2016, 55, 8241ꢀ8243.
*
*
shuaowang@suda.edu.cn (Shuao Wang)
xiaoc@suda.edu.cn (Chengliang Xiao)
(
18) Zhu, L.; Xiao, C.; Dai, X.; Li, J.; Gui, D.; Sheng, D.; Chen, L.; Zhou,
R.; Chai, Z.; AlbrechtꢀSchmitt, T. E.; Wang, S. Environ. Sci. Technol. Lett.
017, 4, 316ꢀ322
19) Banerjee, D.; Elsaidi, S. K.; Aguila, B.; Li, B.; Kim, D.; Schweiger,
2
(
.
Author Contributions
§
These authors contributed equally.
M. J.; Kruger, A. A.; Doonan, C. J.; Ma, S.; Thallapally, P. K. Chem. Eur.
J. 2016, 22, 17581ꢀ17584.
Notes
(
20) BurtonꢀPye, B. P.; Radivojevic, I.; McGregor, D.; Mbomekalle, I. M.;
Lukens, W. W., Jr.; Francesconi, L. C. J. Am. Chem. Soc. 2011, 133,
8802ꢀ18815.
The authors declare no competing financial interests.
1
ACKNOWLEDGMENT
This work was supported by the National Natural Science Founꢀ
dation
of
China
(21422704,
11605118),
the Science Foundation of Jiangsu Province (BK20150313), the
Priority Academic Program Development of Jiangsu Higher Eduꢀ
cation Institutions (PAPD), and Actinide Science and Technology,
an Energy Frontier Research Center funded by the U.S. Departꢀ
ment of Energy (DEꢀSC0016568).
REFERENCES
(
1) Lee, M. S.; Um, W.; Wang, G.; Kruger, A. A.; Lukens, W. W.;
Rousseau, R.; Glezakou, V. A. Nat. Commun. 2016, 7.
2) Dickson, J. O.; Harsh, J. B.; Flury, M.; Lukens, W. W.; Pierce, E. M.
Environ. Sci. Technol. 2014, 48, 12851ꢀ12857.
3) Natal'ya, N. P.; Ivan, G. T.; Sergei, I. R.; Boris, F. M. Russ. Chem. Rev.
003, 72, 101.
4) Poineau, F.; Mausolf, E.; Jarvinen, G. D.; Sattelberger, A. P.;
(
(
2
(
Czerwinski, K. R. Inorg. Chem. 2013, 52, 3573ꢀ3578.
(5) Wilmarth, W. R.; Lumetta, G. J.; Johnson, M. E.; Poirier, M. R.;
Thompson, M. C.; Suggs, P. C.; Machara, N. P. Solvent. Extr. Ion. Exc.
2
011, 29, 1ꢀ48.
(6) Bonnesen, P. V.; Brown, G. M.; Alexandratos, S. D.; Bavoux, L. B.;
Presley, D. J.; Patel, V.; Ober, R.; Moyer, B. A. Environ. Sci. Technol.
2000, 34, 3761ꢀ3766.
(
7) Long, K. M.; Goff, G. S.; Ware, S. D.; Jarvinen, G. D.; Runde, W. H.
Ind. Eng. Chem. Res. 2012, 51, 10445ꢀ10450.
8) (a) Pillay, K. K. S. J. Radioanal. Nucl. Chem. 1986, 102, 247ꢀ268. (b)
(
Wiley, R. H.; Devenuto, G. J. Appl. Polym. Sci. 1965, 9, 2001ꢀ2007.
(9) Oliver, S. R. Chem. Soc. Rev. 2009, 38, 1868ꢀ1881.
(10) Wang, Y.; Gao, H. J. Colloid Interf. Sci. 2006, 301, 19ꢀ26.
(11) McIntyre, L. J.; Jackson, L. K.; Fogg, A. M. Chem. Mater. 2008, 20,
3
35ꢀ340.
(12) Goulding, H. V.; Hulse, S. E.; Clegg, W.; Harrington, R. W.;
Playford, H. Y.; Walton, R. I.; Fogg, A. M. J. Am. Chem. Soc. 2010, 132,
1
3618ꢀ13620.
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Table of Contents (TOC)
99TcO -
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NO -
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