Stability of metal-organic frameworks under gamma irradiation

Article abstract of DOI:10.1039/c6cc06878b

We report the study of the resistance of archetypal MOFs (MILs, HKUST-1, UiO-66, and ZIF-8) under gamma irradiation. The different porous solids were irradiated with doses up to 1.75 MGy. All the MOFs constructed with transition metals (Cu²⁺, Z

Full text of DOI:10.1039/c6cc06878b

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Marcillaud, J. Sabroux and T. Loiseau, Chem. Commun., 2016, DOI: 10.1039/C6CC06878B.
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Stability of Metal-Organic Frameworks under gamma
irradiation
Received 00th January 20xx,
Accepted 00th January 20xx
ab
a
a
a
a
a
a
C. Volkringer* , C. Falaise , P. Devaux , R. Giovine , V. Stevenson , F. Pourpoint , O. Lafon , M.
c
c
c
c
a
Osmond , C. Jeanjacques , B. Marcillaud , J.C. Sabroux and T. Loiseau
DOI: 10.1039/x0xx00000x
www.rsc.org/
2
]
+
6, 7
We report the study of the resistance of archetypal MOFs of [UO
2
per gram of adsorbent).
(MILs, HKUST-1, UiO-66, ZIF-8) under gamma irradiation. The The different studies dedicated to the capture of radionuclides
different porous solids were irradiated to dose up to 1.75 in MOFs led to very promising results. However, many queries
2
+
MGy. All the MOFs constructed with transition metals (Cu , remain before the utilization of MOFs for the capture of
2
Zn , Zr ) exhibit an evident destruction of the framework, radiotoxic molecules during a nuclear accident or other
+
4+
2
, 4
whereas the compounds inserting aluminium remain intact.
processes involving radioactive species, like gas treatment
9-12
One of the main
,
8
medicine or scintillation materials.
Since their discovery, hybrid crystallized porous materials so- questions concerns the resistance of MOF under ionizing
called Metal-Organic Framework (MOF), are very promising radiation generated by radioactive decay. This aspect is rarely
materials to solve societal issues. Indeed, the remarkable studied in hybrid organic-inorganic compounds although some
porosity of this class of solids is currently exploited for the contributions described the stability of Zr/Sn phosphonates
1
3
capture of strategic gases (H
2 2 4
, CO , CH , noble gases, etc.), materials under gamma ray or Hf/Zr MOFs under X-ray have
1
14
drug release, catalysis and many other applications.
been mentioned.
The interest of MOFs in nuclear applications arises after the Due to their lower ionizing power than alpha and beta
Fukushima disaster. At that time, porous materials have particles, gamma rays are more penetrating: they provide the
already been considered by the nuclear industry for the easiest alternative for investigating the radiation damage on
capture of radionuclides during nuclear processes or in the materials.
case of an industrial accident. For example, purely-inorganic In this study, we analysed the effect of gamma irradiation of
zeolites can be used for the adsorption of gaseous iodine different MOFs in order to determine their resistance under
(
mainly silver doped zeolites) and for the capture of cations in strong ionizing radiation. For a better overview, the selected
1
radioactive solution. Activated charcoals are also quite MOFs (ZIF-8, HKUST-1, MILs, UiO-66 ) involves different
5
16
17
18
2
+
2+
3+
4+
efficient for volatile radio-iodine removal and for trapping, in metals and oxidation degrees (Zn , Cu , Al , Zr ), porosities
environmental samplers, airborne iodine derivatives liberated and correspond to prototypical MOFs widely studied in the
2
5, 6, 19-
by nuclear plants.
So far, the studies involving the adsorption of gaseous
3
radionuclides (I , Xe, Kr) in MOFs have shown very high due to their very low stability under air.
literature, especially in the case of radionuclides sorption.
2
1
Other archetypal MOFs, such as MOF-5, were not selected
22
-5
2
uptakes and opened opportunities for radionuclides The different porous solids were submitted to different doses
separation and long-term immobilization. The immobilization in the range 0.5 - 2 MGy, within the gamma irradiation cell
of solubilized radioactive species in MOFs concerns only uranyl called IRMA – IRradiation MAterials – (Figure S4) of the
cations and indicates adsorption capacity comparable to those Institute of Radiological Protection and Nuclear Safety (IRSN)
observed with functionalized mesoporous silica (200-300 mg at Saclay Research Center. This irradiation cell is equipped with
6
0
several Co sources and the dose rates applied for this study
were between 2 and 5 kGy/h. Dosimetry was performed using
a calibrated ionization chamber on each MOF tested in the
irradiation cell.
The solids were synthesized and activated following published
procedures from literature. After gamma irradiation, the solids
were characterized by means of different techniques (PXRD,
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-
1
infrared, N
2
sorption, NMR) in order to define the effect of half as much of the non-irradiated solid (BET of 1328 m².g
3
and microporous volume of 0.545 cm .g ), synthesized from
-1
irradiation and the robustness of the framework.
The first study was carried out with ZIF-8 (imidazolate zinc- the same batch (Figure 2).
3
based MOF), due to its interest in iodine capture. The powder Other MOFs solids have been tested such as UiO-66 and
X-ray diffraction diagrams of ZIF-8 samples irradiated at 0.5, HKUST-1 (Zr-and Cu-based MOFs, respectively). The different
0.75 and 1 MGy, are quite similar to the reference. However structural characterization show that they are also quite
higher irradiation doses (between 1.25 and 1.75 MGy) gave sensitive to the gamma irradiation dose and exhibit a similar
rise to the observation of broader Bragg peaks (Figure 1 and behaviour than ZIF-8. Although the destruction of these MOFs
Figure S5g) together with lower intensities, indicating an is less marked by PXRD or infrared than for ZIF-8, the
important loss of crystallinity.
decomposition of their structure after an irradiation of 1.75
MGy is confirmed by the loss of porosity of approximately
30%, as compared to the initial MOF (See supporting
information).
0
1
kGy
250 kGy
1
500 kGy
750 kGy
1
Figure 1. Evolution of powder X-ray diffraction patterns of non-irradiated and
gamma irradiated zinc-based compound MOF ZIF-8 (copper wavelength) at
different doses (0-1.75 MGy)
1
0
750 kGy
Whereas PXRD technique gives an averaged picture of the
irradiated framework, Nuclear Magnetic Resonance (NMR) is
more informative about the local defects created by the
kGy
1
3
irradiation. The C NMR spectrum of ZIF-8 (Figure S8a) shows
three peaks at 151.2, 124.2 and 13.7 ppm, assigned to the
carbon atoms of the imidazolate ligand organizing the porous
framework. After a dose of 1.75 MGy, all these peaks become
broader and we note the appearance of several new
resonances at 170.5, 146.7, 117.7, 51.9, 14.9 and 11.9 ppm.
1
5
Figure 2. Isotherm curves for the adsorption (solid) and desorption (dash) of
Similar behaviour is also observable for the N NMR spectrum nitrogen (77K) in irradiated and non-irradiated ZIF-8 (top) and MIL-120 (bottom)
(Figure S8b).
The NMR signature of the irradiated material indicates
structural transformation that could be explained by major Then three other MOFs compounds bearing aluminium (MIL-
structural distortion (resonances at 170.5, 14.9 and 11.9 ppm) 53, MIL-100, MIL-120) exhibit a better stability. Whatever the
and/or the breaking of chemical bonds, leading to the gamma dose (up to 1.75 MGy), X-ray diffraction, NMR or IR
presence of free ligand in the pores (signals at 146.7, 117.7, techniques do not indicate any signs of structural
5
1.9 ppm). This last explanation is well supported by nitrogen decomposition or framework collapsing. In the case of MIL-53,
sorption at 77K, which shows an important loss of porosity the porosity is not affected by the gamma radiation and we do
Figure 2). Whereas the non-irradiated ZIF-8 solid exhibits a not observe any modification of the framework swelling of the
(
3
relative high porosity (saturation at 360 cm of N2 per gram of structure. The influence of radiation on the porous solid is
MOF), the irradiated solids have much less affinity for nitrogen quite more pronounced in the case of MIL-100. Surprisingly,
3
-1
at 77K (325-160 cm .g ). This decrease is directly linked to the we observe a slight elevation of the quantity of nitrogen
irradiation process, which induces a lower porosity when adsorbed in the pores (Figure 2), corresponding to a gain of
increasing the gamma dose. For a dose of 1.75 MGy, irradiated BET surface value of 215 m²/g (11%). In the case of MIL-
-
1
ZIF-8 is characterized by
microporous volume of 0.198 cm .g ) which is approximately increase of the specific surface of 190% (273 m²/g). For both
a
BET surface of 598 m².g
3
120(Al), this difference is even more important, with an
-1
(
2
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solids, this improvement of the porosity, without any In the infinite library of Metal-Organic Frameworks, it appears
structural modification, is assigned to the removal of species that the resistance of the solid is mainly dependent on the
trapped within the pores and limiting the accessibility of the strength of the interaction between the metallic cations and
probe molecule. Such poisoning molecules are assigned to the organic ligand. Based on the HSAB (hard and soft acids and
fragment of trimesate ligand or dimethylformamide in the case bases) concept, the association of hard Lewis acid (metallic
2
3, 24
of MIL-100.
The decomposition of extra-framework non- cation) and base (organic linker) induces a strong interaction,
bonded organic molecules by gamma irradiation is even more resulting in a relative good stability versus chemical attack or
pronounced for non-chemically/thermally activated solids, temperature. This explains why MOF constructed from hard
such as as-synthesized MIL-100(Al) (notes MIL-100(Al)-as) Lewis acids such as trivalent aluminium or tetravalent
(
Figure 3). After synthesis, this solid is characterized by a zirconium and carboxylate ligands are generally considered as
2
relative low BET value (858 m /g), mainly due to unreacted the most stable MOFs. For example, MIL-53(Al) and UiO-66(Zr)
1
8, 26
trimesic acid molecules trapped into the pores, easily are the most thermally stable (500°C under air)
, and
-1
27
identifiable by IR spectroscopy (shoulder at 1720 cm ) (Figure exhibit a rather good resistance versus hydrolysis. On the
S7d). The dose of irradiation received by non-activated MIL- other hand, divalent metals based (softer Lewis acid) exhibit a
1
00 (up to 2000 kGy), induces a constant elevation of the lower stability, which is well highlighted by the quick
22
2
accessible porosity, up to a maximum of 1959 m /g (BET decomposition of many compounds just under air.
model) for an irradiation of 2000 kGy (Figure 3). This change As indicated in this study, the radiolytic stability of MOF under
coincides with the departure of free trimesic acid, which is gamma irradiation is not directly related to the Pearson acid
-
confirmed by infrared (disappearance of the band at 1720 cm base concept, but follows another trend. This tendency is not
1
23
)
(Figure S7d). This last study corresponds to the highest based on the ligand since aluminium terephthalate (MIL-53)
irradiation dose received by a MOF and confirms the and trimesate (MIL-100), are quite stable, whereas their
remarkable stability of MIL-100(Al). For information, such dose analogues with zirconium (UiO-66) and copper (HKUST-1) are
corresponds to the exposure received by filter localized for 8 damaged.
2
5
days in the reactor building during a nuclear accident.
The interaction of the highly penetrating gamma radiation
with matter is proportional to the absorption cross section and
the density of the material. Whereas the organic constitution
and the density of the examined MOFs are quite similar, the
main difference relies on the nature of metal utilized for their
synthesis. The probability of beam to interact with a metal is
governed by the cross section of the latter one (see
supplementary information). This interaction can be
modulated by the number of metal atoms in the MOF
structure and the void space in the structure.
The determination of the cross-section of the metals forming
the MOF employed in this study, was realized using NIST-
2
8
60
XCOM database and calculated for Co energies (Table Sx).
The calculated values (Table S1) indicate a gap between
aluminium (2.5 barns/atom) and the transition metals (>5.3
barns/atom). This result implies a lower gamma ray absorption
of MOF constructed with aluminium than those synthesized
with copper, zinc or zirconium. Due to the relative low
interaction of Al-based MOF with gamma ray, no effect of this
radiation is observable for doses up to 1,75 MGy. In the case of
metal showing higher likelihood of absorption of gamma ray,
the radiation interaction with the inorganic sub-network is
transferred to the organic part. This role of metal-oxo cluster
in MOF as radiation antenna was already mentioned by Lin for
the use of anthracene-based UiO-n solids as X-ray
1
4
scintillators.
This phenomenon makes easier the degradation of the
connected ligand through radiolysis mechanisms, involving the
formation of ions, excitons and organic radicals. The particular
low stability of ZIF-8 versus gamma irradiation would be
Figure 3. Influence of gamma irradiation doses (0-2 MGy) over as-synthesized
MIL-100(Al): (bottom) Isotherm curves for the adsorption (solid) and desorption accentuated by the presence of an aliphatic component (-
(
dash) of nitrogen (77 K). (top) Powder X-ray diffractograms
Methyl), which is more sensitive than aromatic rings, to
2
9, 30
gamma irradiation.
Whereas the crystallized framework Al-
based MOFs remain stable under gamma irradiation (at least
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up to 2 MGy), impurities trapped within the pores are directly 8.
impacted by the gamma photons. Such sensibility could be
C. He, D. Liu and W. Lin, Chem. Rev., 2015, 115, 11079-
1108.
F. P. Doty, C. A. Bauer, A. J. Skulan, P. G. Grant and M. D.
Allendorf, Adv. Mater., 2009, 21, 95-101.
P. L. Feng, J. V. Branson, K. Hattar, G. Vizkelethy, M. D.
Allendorf and F. P. Doty, Nucl. Instrum. Methods Phys.
Res. a, 2011, 652, 295-298.
1
9
.
explained by strong interaction between metallic centers
gamma rays antenna) and impurities localized in the pores.
For MIL-100, this affinity was already mentioned in the
(
1
0.
2
3, 24
literature, explaining the difficulty to activate this solid.
In summary, we have demonstrated the high resistance of
aluminium-based MOF under gamma irradiation (comparable
to at least 8 days under strong radioactive conditions during a
nuclear accident), compared to similar materials synthesized
1
1
1.
2.
J. J. Perry, P. L. Feng, S. T. Meek, K. Leong, F. P. Doty and
M. D. Allendorf, J. Mater. Chem., 2012, 22, 10235-10248.
L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. Van
Duyne and J. T. Hupp, Chem. Rev., 2012, 112, 1105-1125.
R. Silbernagel, T. C. Shehee, C. H. Martin, D. T. Hobbs and
A. Clearfield, Chem. Mater., 2016, 28, 2254-2259.
C. Wang, O. Volotskova, K. Lu, M. Ahmad, C. Sun, L. Xing
and W. Lin, J. Am. Chem. Soc., 2014, 136, 6171-6174.
K. S. Park, Z. Ni, A. P. Cote, J. Y. Choi, R. Huang, F. J. Uribe-
Romo, H. K. Chae, M. O'Keeffe and O. M. Yaghi, Proc. Natl.
Acad. Sci. U.S.A., 2006, 103, 10186-10191.
with transitions metals, HKUST-1(Cu), UiO-66(Zr) and ZIF-8(Zn). 13.
This stability is assigned to the lower cross section of
1
1
4.
5.
aluminium, limiting the effect of gamma ray and the
destruction of the hybrid framework. Whereas the porous
network preserves its integrity in the case of Al-MOFs, organic
molecular fragments inserted in the pores are more sensitive
to irradiation. This embrittlement leads to a partial removal of
this species and increase the available porosity of the material.
These results confirm the great potential of MOFs, especially
those constructed with aluminium, in the case of nuclear
1
1
6.
7.
S. S. Y. Chui, S. M. F. Lo, J. P. H. Charmant, A. G. Orpen and
I. D. Williams, Science, 1999, 283, 1148-1150.
T. Loiseau, C. Volkringer, M. Haouas, F. Taulelle and G.
Ferey, C.R. Chimie, 2015, 18, 1350-1369.
accident. However, this significant tolerability gives also 18.
obvious opportunity for other industrial fields involving
radiation environments (such as gamma rays), as for example
J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti,
S. Bordiga and K. P. Lillerud, J. Am. Chem. Soc., 2008, 130,
13850-13851.
1
9.
K. W. Chapman, P. J. Chupas and T. M. Nenoff, J. Am.
Chem. Soc., 2010, 132, 8897-8899.
in medicine or aerospace.
2
0.
D. F. Sava, K. W. Chapman, M. A. Rodriguez, J. A.
Greathouse, P. S. Crozier, H. Y. Zhao, P. J. Chupas and T.
M. Nenoff, Chem. Mater., 2013, 25, 2591-2596.
Y. Feng, H. Jiang, S. Li, J. Wang, X. Jing, Y. Wang and M.
Chen, Colloids Surf. A, 2013, 431, 87-92.
This work was part of the MiRE project (Mitigation of outside
releases in case of nuclear accident), which is funded by the French
National Research Agency (ANR) through the PIA (Programme
d'Investissement d'Avenir) under contract "ANR-11-RSNR-0013-01".
2
1.
The authors would like to thank Mrs Nora Djelal and Laurence 22.
Burylo for their technical assistance with SEM images and powder
S. S. Kaye, A. Dailly, O. M. Yaghi and J. R. Long, J. Am.
Chem. Soc., 2007, 129, 14176-14177.
2
3.
C. Volkringer, H. Leclerc, J. C. Lavalley, T. Loiseau, G.
Férey, M. Daturi and A. Vimont, J. Phys. Chem. C, 2012,
X-ray analysis. Chevreul Institute (FR 2638), CNRS, Ministère de
l’Enseignement Supérieur de la Recherche, Région Hauts-de-France
and FEDER are acknowledged for supporting and funding partially
this work. CV thanks L. Cantrel for helpful discussion.
1
16, 5710-5719.
2
4.
M. Haouas, C. Volkringer, T. Loiseau, G. Férey and F.
Tauelle, J. Phys. Chem. C, 2011, 115, 17934-17944.
IRSN, personal communication.
T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M.
Henry, T. Bataille and G. Ferey, Chem. Eur. J., 2004, 10,
2
2
5.
6.
Notes and references
1
373-1382.
2
7.
K. A. Cychosz and A. J. Matzger, Langmuir, 2010, 26,
17198-17202.
1.
2.
3.
J. R. See themed issue Metal-Organic Frameworks: Long
and Y. O.M., Chem. Soc. Rev., 2009, 38, 1201.
28.
M. J. Berger, J. H. Hubbell, S. M. Seltzer, J. Chang, J. S.
Coursey, R. Sukumar, D. S. Zucker and K. Olsen, NIST
Standard Reference Database 8, NIST, Gaitersburg, MD,
1998.
S. B. Dhiman, G. S. Goff, W. Runde and J. A. LaVerne, J.
Nucl. Mater., 2014, 453, 182-187.
B. J. Riley, J. D. Vienna, D. M. Strachan, J. S. McCloy and J.
L. Jerden, Jr., J. Nuc. Mater., 2016, 470, 307-326.
D. F. Sava, M. A. Rodriguez, K. W. Chapman, P. J. Chupas,
J. A. Greathouse, P. S. Crozier and T. M. Nenoff, J. Am.
Chem. Soc., 2011, 133, 12398-12401.
29.
4
.
.
D. Banerjee, A. J. Cairns, J. Liu, R. K. Motkuri, S. K. Nune, C. 30.
A. Fernandez, R. Krishna, D. M. Strachan and P. K.
Thallapally, Acc. Chem. Res., 2015, 48, 211-219.
C. Falaise, C. Volkringer, J. Facqueur, T. Bousquet, L.
Gasnot and T. Loiseau, Chem. Commun., 2013, 49, 10320-
L. Berthon, S. I. Nikitenko, I. Bisel, C. Berthon, M. Faucon,
B. Saucerotte, N. Zorz and P. Moisy, Dalton Trans., 2006,
2526-2534.
5
10322.
6
.
.
M. Carboni, C. W. Abney, S. B. Liu and W. B. Lin, Chem.
Sci., 2013, 4, 2396-2402.
W. Yang, Z.-Q. Bai, W.-Q. Shi, L.-Y. Yuan, T. Tian, Z.-F. Chai,
H. Wang and Z.-M. Sun, Chem. Commun., 2013, 49,
7
10415-10417.
4
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