Textile/metal-organic-framework composites as self-detoxifying filters for chemical-warfare agents

Article abstract of DOI:10.1002/anie.201502094

Abstract The current technology of air-filtration materials for protection against highly toxic chemicals, that is, chemical-warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self-cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal-organic framework (MOF) materials to develop advanced self-detoxifying adsorbents of chemical-warfare agents containing hydrolysable P-F, P-O, and C-Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air-permeation properties of the textiles with the self-detoxifying properties of the MOF material. The silk of human kindness: Insertion of lithium alkoxides in zirconium metal-organic frameworks (MOF) which are then deposited on silk fibers gives rise to protective fabrics capable of self-detoxifying chemical-warfare agents. The fabrics combine the air-permeation properties of the textiles with the highly active phosphotriesterase catalytic activity of the MOF for the hydrolysis of P-F, P-O, and C-Cl bonds.

Full text of DOI:10.1002/anie.201502094

Angewandte
Chemie
International Edition: DOI: 10.1002/anie.201502094
German Edition: DOI: 10.1002/ange.201502094
MOF Catalysts Very Important Paper
Textile/Metal–Organic-Framework Composites as Self-Detoxifying
Filters for Chemical-Warfare Agents**
Elena Lꢀpez-Maya, Carmen Montoro, L. Marleny Rodrꢁguez-Albelo,
Salvador D. Aznar Cervantes, A. Abel Lozano-Pꢂrez, Josꢂ Luis Cenꢁs, Elisa Barea,* and
Jorge A. R. Navarro*
[
4–7]
Abstract: The current technology of air-filtration materials for
protection against highly toxic chemicals, that is, chemical-
warfare agents, is mainly based on the broad and effective
adsorptive properties of hydrophobic activated carbons. How-
ever, adsorption does not prevent these materials from behav-
ing as secondary emitters once they are contaminated. Thus, the
development of efficient self-cleaning filters is of high interest.
Herein, we report how we can take advantage of the improved
phosphotriesterase catalytic activity of lithium alkoxide doped
zirconium(IV) metal–organic framework (MOF) materials to
develop advanced self-detoxifying adsorbents of chemical-
warfare agents containing hydrolysable PÀF, PÀO, and CÀCl
been studied in the capture and degradation of CWAs,
however, the results show a poor performance related to its
[8]
limited stability to hydrolysis. The more robust [Al (OH)F-
(bdc_NH ) ] (NH -MIL-101(Al)) and [AlOH(bdc_NH )]
(NH -MIL-53(Al)) systems, where bdc_NH = 2-aminoben-
zene-1,4-dicarboxylate, have been assayed for the hydrolysis
of the nerve-agent simulant diisopropylfluorophosphate
(DIFP) after the covalent attachment of 4-methylaminopyr-
idine nucleophile, to the bdc_NH linkers. In the search for
more efficient MOF materials for this application,
3
2
2
2
2
2
2
[9]
2
[Zr O (OH) (bdc) ]
(bdc = benzene-1,4-dicarboxylate)
system, named UiO-66 (Figure 1), is receiving attention
because of its robustness and the Lewis acidic nature of
6
4
4
6
[
10]
bonds. Moreover, we also show that it is possible to integrate
these materials onto textiles, thereby combining air-permeation
properties of the textiles with the self-detoxifying properties of
the MOF material.
T
he threat of terrorist attacks with chemical-warfare agents
CWAs) prompts the research on new materials capable of
removing toxic chemicals at ambient temperature and
(
[1,2]
humidity.
In this regard, activated carbons and their
modifications with impregnates (metal salts, acids, and
amines) are the most widespread materials in air-purification
systems. However, the development of self-cleaning materi-
[
3]
als should be the technology of choice to avoid the
contaminated adsorbents behaving as secondary emitters.
Metal–organic frameworks (MOFs) arise as an alternative
class of porous materials with a high potential for this
Figure 1. Structure of [Zr O (OH) (bdc) ] (UiO-66) and schematic
6
4
4
6
representation of the insertion of LiOR in the Zr O clusters of the fully
6
6
[
1,2]
activated framework to yield [UiO-66@LiOR] basic catalysts.
application.
Indeed, the suitability of the established
[
Cu (btc) ] (btc = benzene-1,3,5-tricarboxylate) system has
3
2
4
+
[11]
the Zr centers which combined with the basic hydroxide
residues gives rise to biomimetic phosphotriesterase activity
useful for the hydrolysis of simulants of nerve agents.
[
*] E. Lꢀpez-Maya, Dr. C. Montoro, Dr. L. M. Rodrꢁguez-Albelo,
Dr. E. Barea, Prof. J. A. R. Navarro
Departamento de Quꢁmica Inorgꢂnica
Universidad de Granada
Av. Fuentenueva S/N, 18071 Granada (Spain)
E-mail: jarn@ugr.es
[12]
Herein, we show different post-synthetic approaches
introduction of acidic and basic sites and/or missing linker
(
defects) to further improve the phosphotriesterase activity of
UiO-66 for the capture and hydrolytic degradation of CWA
simulants (Figure 1 and Scheme 1). Moreover, we compare
the performance of these UiO-66 modified materials with
representative “state-of-the-art” porous materials (i.e. acti-
vated carbons, hydrophobic MOFs, porous metal oxides)
towards the capture and eventual degradation of diisopropyl-
ebaream@ugr.es
Homepage: http://www.ugr.es/local/jarn
Dr. S. D. Aznar Cervantes, Dr. A. A. Lozano-Pꢃrez, Prof. J. L. Cenꢁs
Departamento de Biotecnologꢁa, IMIDA, Instituto Murciano de
Investigaciꢀn y Desarrollo Agrario y Alimentario
C/Mayor S/N, 30150 La Alberca, Murcia (Spain)
[
**] We thank the Spanish Ministries of Economy (CTQ2011-22787/
fluorophosphate
DMMP), 2-chloroethylethylsulfide (CEES), and diethylsul-
fide (DES), as respective models of nerve and vesicant CWAs
Scheme 2). Moreover, we also demonstrate that it is possible
to integrate these MOFs on the surface of silk fibroin fibers,
(DIFP),
dimethylmethylphosphonate
PPQ, CTQ2014-53486-R) and Defense (COINCIDENTE), MC-IIF
(
(
LMRA), Junta de Andalucia (P09-FQM-4981) and ERDF Operative
Program of the Region of Murcia 2007–2013 (AALP) for funding.
(
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201502094.
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Figure 2. Impact of missing-linker defects and introduction of acidic/
basic catalytically active sites on the porosity of UiO-66 framework, as
Scheme 1. Routes to improve the catalytic activity of [Zr O (OH) -
6
4
4
probed by N adsorption at 77 K. Solid symbols denote adsorption,
2
(
bdc) ] (UiO-66) by introduction of missing-linker defects and/or
6
open symbols denote desorption (P/P =partial pressure).
O
acidic and basic sites.
capacity in the defect systems or a decrease
À
of capacity after the insertion of HSO4
and LiOR functionalities (Figure 2 and
Figure S3 in the Supporting Information).
Once the modified materials were charac-
terized, we proceeded to evaluate the
effect of the post-synthetic functionaliza-
tion of UiO-66 framework on the eventual
catalytic degradation of CWAs analogues
DIFP, DMMP, and CEES. In this regard,
the hydrolytic pathway is one of the most
simple and effective ways of remedying
the contamination caused by CWAs mol-
ecules (Scheme 2). For this purpose, we
have studied the variation of concentra-
tion of CWAs models both in the aqueous
and adsorbate phases after its exposure to
the MOF catalyst at room temperature by
Scheme 2. a) Hydrolytic and oxidative degradation pathways of chemical warfare agents
CWAs): Sarin and VX nerve agents and sulfur mustard vesicant gas; b) CWAs model
3
1
(
GC and P-MAS-NMR.
compounds used in our studies.
The degradation profiles of DIFP on
the essayed materials are summarized in
Figure 3 and Figure S6. As it can be
giving rise to self-detoxifying protective fabrics, which
complement air permeation with adsorption and catalytic
degradation of the toxic compounds.
appreciated, all the [UiO-66@X] materials are active in the
hydrolytic degradation of DIFP whereas hydrophobic MOF
[
8,15]
materials
and activated carbon Blꢀcher-101408 which is
Taking into account all the above, we proceeded to
implemented in “state-of-the-art” Saratoga filtering sys-
[10]
[16]
modulate the catalytic activity of both defect-free UiO-66,
and missing-linker-defect [Zr O (AcO) (bdc) ] [UiO-
tems
are not (Figure S9 and Table S2). Remarkably,
LiOtBu insertion gives rise to the highly active and reusable
[UiO-66@LiOtBu] catalyst exhibiting a half-life for PÀF bond
6
4
6
5
[
13]
6
6@AcO] by means of the introduction of acidic Brønsted
sites in [Zr O (AcO) (bdc) (SO H) ] ([UiO-66@SO H]) and
hydrolysis of 5 min only (turnover frequency (TOF)
6
4
4
5
4
2
4
À1
the insertion of lithium alkoxides in [Zr O (bdc) (LiOtBu) ]
0.13 min ) and full hydrolysis of this bond after 30 min
6
6
6
0.3
(
6
6
[UiO-66@LiOtBu]),
[Zr O (bdc) (LiOtBu) ]
([UiO-
(Figure 3 and Figure S8). The heterogeneity of the catalytic
process can also be demonstrated by the loss of catalytic
activity after removal of the MOF by filtration (Figure 3b).
Analogous results are obtained with [UiO-66@LiOEt]
although, the kinetics are slowed, namely, half-life of 30 min
6
8
4
0.3
6@AcO_LiOtBu]) and [Zr O (bdc) (LiOEt)0.25] ([UiO-
6 6 6
[
14]
6@LiOEt]). Noteworthy, X-ray powder diffraction studies
are indicative that the original fcu topology of UiO-66
framework is maintained in the post-synthetically modified
materials (see Supporting Information). Likewise, N (77 K)
adsorption experiments are indicative that the post-synthetic
treatment does not prevent access to the porous network,
although, is responsible for either an increase of adsorption
À1
(TOF 0.017 min ) and full conversion after 250 min, which
2
À
might be attributed to the lower basicity of EtO compared to
À
31
tBuO . P-MAS-NMR studies further confirm the rapid
hydrolysis of the PÀF bonds (Figure S14). In contrast, both
2
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6
6@LiOtBu], clearly outperforms porous ZrO (Figure S6).
2
These results demonstrate the synergistic combination of
alkoxide basicity and Lewis acidity of metal centers for
improving UiO-66 phosphotriesterase activity.
3
1
P-MAS-NMR
spectroscopy
studies
for
[
8]
[
Zn O(dimethylcarboxypyrazolate) ] are indicative of both
4
3
a slow adsorption process (half-life of 1 h) and slow degra-
dation of DIFP (half-life of 24 h; Figure S15c). Likewise,
II
hydrophobic MOF materials based on Ni bis(pyrazolate)
[
15]
systems and activated carbon adsorb DIFP very rapidly
from the aqueous phase but once adsorbed DIFP remains
intact since the hydrophobic pore structure prevents its
hydrolysis, with a concomitant risk of this adsorbent becom-
ing a second emitter (see Figure S9 and Table S2).
To further demonstrate the suitability of the [UiO-66@X]
materials towards the degradation of CWAs we have studied
their catalytic activity towards the hydrolysis of DMMP
(Figure 4) and CEES (Figure 5) which have the characteristic
Figure 3. a) Hydrolytic degradation reaction of an aqueous solution of
DIFP nerve-gas simulant (0.028m) catalyzed by b) [UiO-66@LiOtBu]
(
0.014 mmol) at room temperature (295 K) and c) UiO-66 under the
same conditions. The poisoning effect of CWA degradation products
on the catalytic activity of UiO-66@X materials, namely, phosphoric
acid (0.028m) and methylphosphonic acid (0.028m) was also studied.
The dotted line in (b) indicates the effect of removal of [UiO-
6
6@LiOtBu] by filtration to demonstrate the heterogeneity of the
catalysis.
Figure 4. a) Hydrolytic degradation reaction of DMMP nerve-gas simu-
lant; b) degradation profiles of an aqueous solution of DMMP
(0.028m) catalyzed by [UiO-66@LiOtBu], [UiO-66], and porous ZrO2
at room temperature (295 K). The poisoning effect of methylphos-
phonic acid (0.028m) on the catalytic activity of UiO-66@X and ZrO
materials is also shown. Solid lines are a guide for the eye.
pristine UiO-66 and defect [UiO-66@AcO] exhibit a three-
fold slower kinetics (TOF 0.05 min ) than [UiO-66@LiOtBu]
2
À1
and their activity is lost after the degradation of approx-
imately 75% of the DIFP (Figure S6). The loss of activity was
indicative of catalyst poisoning, by the degradation products,
which was confirmed by the significant decrease in the
catalytic activity of UiO-66 after the addition of equimolec-
ular amounts of either methylphosphonic acid (0.014 mmol)
or phosphoric acid (0.014 mmol) to the reaction media
methylphosphonate and chlorine residues found in nerve
agents and vesicant mustard gas, respectively. Once again,
[UiO-66@LiOtBu] is the most active material in DMMP
À1
degradation, exhibiting a half-life of 25 min (TOF 0.02 min )
for the first hydrolysis step (Figure 4 and Figure S16). It
should also be noted that [UiO-66@LiOtBu] outperforms
both NaOH (0.1m) and LiOtBu (0.1m) in the homogeneous
phase (Figure S10). By contrast, pristine UiO-66 and porous
(
6
Figure 3c). In contrast, the catalytic performance of [UiO-
6@LiOtBu] is not affected by methylphosphonic acid or
phosphoric acid (Figure 3b). The significant lowering of the
catalytic activity of UiO-66 upon the addition of the
degradation products (1:6 ratio of degradation product to
Zr centers) points to a probable poisoning of the active basic
catalytic sites placed at the surface of the UiO-66 nano-
ZrO exhibit a much poorer performance with DMMP with
2
respective degradation values of 30 and 15% being achieved
after 500 min. Finally, while the addition of methylphosphonic
acid (0.028m) to the reaction media gives rise to some
poisoning effect of [UiO-66@LiOtBu] catalytic activity (deg-
radation half-life increases to 75 min and TOF decreases to
À
crystals. The introduction of acidic HSO4 active sites on
[
UiO-66@SO H] is responsible for a further loss of catalytic
4
À1
activity with only 30% of DIFP degradation being achieved
after 6 h (see Figure S6). It should also be noticed that [UiO-
0.007 min ), UiO-66 and ZrO2 become almost inactive
(Figure 4).
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a methanolic sonicated suspension of the desired
MOF onto electrospun silk fibroin which, after
appropriate curing, gave rise to hybrid silk@MOF
composites with to 1:1 silk to MOF ratios. The
images of scanning electron microscopy show the
successful deposition of both UiO-66 and [UiO-
6
6@LiOtBu] MOF nanocrystals (ca. 200 nm) on
silk fibers (ca. 1 mm wide) (Figure 6a and Fig-
ure S17). Moreover, X-ray powder diffraction
(XRPD) and N2 adsorption measurements are
diagnostic that both the MOF crystallinity and the
porosity of the MOF materials are maintained
while air permeability of the textile fabric is
preserved (Supporting Information). Note that
the silk@[UiO-66@LiOtBu] composite textile
exhibits the best performance towards the degra-
dation of the CWA analogues with respective
Figure 5. a) Hydrolytic degradation reaction of CEES vesicant gas simulant; b) deg-
radation profiles of an aqueous:ethanolic (1:1) solution of CEES (0.028m) without
catalyst (blank) and in the presence of [UiO-66@LiOtBu], [UiO-66], and porous
degradation
half-lives
of
20 min
(TOF
À1
À1
0
.025 min ), 50 min (TOF 0.01 min ), and 8 min
À1
(
(
TOF 0.06 min ) for DIFP, DMMP, and CEES
Figure 6b–d). Moreover, the removal of the silk@-
ZrO at room temperature (295 K). The poisoning effect of HCl (0.028m) on the
2
catalytic activity of UiO-66@X and ZrO materials is also shown. Solid lines are
2
MOF composites stops the reaction, an indication
a guide for the eye.
Similarly, [UiO-66@LiOtBu] is
also the most active material in the
degradation of CEES exhibiting
a half-life of 3 min only (TOF
À1
0
2
1
.17 min ) and full conversion to
-hydroxyethylethylsulfide
6 min (Figure 5). It should also be
after
noted that [UiO-66@LiOtBu] per-
formance is analogous to NaOH
(
0.1m) in the homogeneous phase
but outperforms LiOtBu (0.1m; Fig-
ure S12). Pristine UiO-66 as well as
ZrO exhibit a much poorer perfor-
2
mance with only partial degradation
values of CEES, namely 80% being
achieved after 500 min, indicative of
catalyst
poisoning
(Figure 5).
Indeed, while the addition of hydro-
chloric acid (0.028m) does not affect
significantly the catalytic activity of
[
UiO-66@LiOtBu]
(degradation
half-life increases to 3.4 min) in the
case of UiO-66 and porous ZrO the
2
catalytic activity is lost and their
behavior becomes analogous to the
control (Figure 5).
Taking all the above results into
consideration, we thought of the
possibility of integrating these mate-
rials into protective fabrics to com-
Figure 6. a) VP-SEM (VP=variable pressure) images of silk@[UiO-66@LiOtBu] composite. Hydro-
lytic degradation profiles of b) DIFP, c) DMMP, and d) CEES, all catalyzed by silk@[UiO-66@LiOtBu]
composite at room temperature. The dotted lines indicate the effect of removing the [UiO-
6
6@LiOtBu] by filtration to demonstrate the heterogeneity of the catalytic process.
bine the self-detoxifying properties of the catalysts with the
air permeation of the textiles. With this purpose, we chose silk
fibroin fabrics as a proof-of-concept textile owing to its
biocompatibility, resistance, and lightness. The procedure of
MOF deposition onto the fibers consisted of spraying
of the heterogeneous nature of the catalysis and that lack of
MOF leaching from the fabric.
It can be concluded that the insertion of lithium alkoxides
in the zirconium oxide clusters gives rise to a boosting of the
phosphotriesterase catalytic activity for the hydrolysis of PÀF,
4
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Chemie
PÀO, and CÀCl bonds typically found in CWAs. Furthermore,
these features can also be integrated into self-detoxifying
protective fabrics which combine air permeation and self-
detoxifying properties. Computational work is in progress to
fully understand the behavior of the UiO-66 modified
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Published online: && &&, &&&&
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Angewandte
Communications
Communications
MOF Catalysts
The silk of human kindness: Insertion of
lithium alkoxides in zirconium metal–
organic frameworks (MOF) which are
then deposited on silk fibers gives rise to
protective fabrics capable of self-detoxi-
fying chemical-warfare agents. The fab-
rics combine the air-permeation proper-
ties of the textiles with the highly active
phosphotriesterase catalytic activity of
the MOF for the hydrolysis of PÀF, PÀO,
and CÀCl bonds.
E. Lꢁpez-Maya, C. Montoro,
L. M. Rodrꢂguez-Albelo,
S. D. Aznar Cervantes,
A. A. Lozano-Pꢃrez, J. L. Cenꢂs, E. Barea,*
J. A. R. Navarro*
&&&& — &&&&
Textile/Metal–Organic-Framework
Composites as Self-Detoxifying Filters for
Chemical-Warfare Agents
6
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