Detoxification of Chemical Warfare Agents Using a Zr6-Based Metal–Organic Framework/Polymer Mixture

Article abstract of DOI:10.1002/chem.201603976

Owing to their high surface area, periodic distribution of metal sites, and water stability, zirconium-based metal–organic frameworks (Zr₆-MOFs) have shown promising activity for the hydrolysis of nerve agents GD and VX, as well as the simulant

Full text of DOI:10.1002/chem.201603976

DOI: 10.1002/chem.201603976
Communication
&
Metal–Organic Frameworks
Detoxification of Chemical Warfare Agents Using a Zr6-Based
Metal–Organic Framework/Polymer Mixture
Su-Young Moon,[a] Emmanuel Proussaloglou,[a] Gregory W. Peterson,[b] Jared B. DeCoste,[b]
Morgan G. Hall,[b] Ashlee J. Howarth,[a] Joseph T. Hupp,[a] and Omar K. Farha*[a, c]
Abstract: Owing to their high surface area, periodic distri-
bution of metal sites, and water stability, zirconium-based
metal–organic frameworks (Zr6-MOFs) have shown promis-
ing activity for the hydrolysis of nerve agents GD and VX,
as well as the simulant, dimethyl 4-nitrophenylphosphate
(DMNP), in buffered solutions. A hurdle to using MOFs for
this application is the current need for a buffer solution.
Here the destruction of the simulant DMNP, as well as the
chemical warfare agents (GD and VX) through hydrolysis
using a MOF catalyst mixed with a non-volatile, water-in-
soluble, heterogeneous buffer is reported. The hydrolysis
of the simulant and nerve agents in the presence of the
heterogeneous buffer was fast and effective.
Some organophosphates, such as DNA and RNA, are essential
biomolecules, whereas others such as pesticides (parathion
and paraoxon) and nerve agents (GD and VX) (Figure 1c) can
Figure 1. Chemical structures of a) NU-1000 and b) linear-polyethyleneimine
be extremely toxic. Although their toxicity (ex. LD50, VX>GD@
pesticides) and physical properties such as vapor pressure and
boiling point vary, their mechanism of action in the human
body is identical.[1] Toxic organophosphates bind irreversibly to
the enzyme acetylcholinesterase (AChE), preventing the break-
down of acetylcholine, which leads to sustained muscle con-
traction, and eventually oxygen deprivation and death.[1,2]
Though some organophosphates can be decomposed by hy-
drolysis in water, reaction rates in the absence of catalysts are
typically too slow to be effective. There have been many stud-
ies focusing on the detoxification or removal of simulants and
nerve agents using catalysts such as metal oxides (TiO2,
(PEI), and c) hydrolysis reaction of phosphonate-based nerve agents (O-pina-
colyl methylphosphonofluoridate, GD and O-ethyl S-(2-(diisopropylamino)-
ethyl)methylphosphonothioate, VX) and a simulant (dimethyl 4-nitrophenyl
phosphonate, DMNP).
Zr(OH)4, and Al2O3),[3] activated carbon,[4] mesoporous silica,[5]
zeolites,[6] and surfactants/metallosurfactants.[7] However, more
highly potent catalytically active materials are needed.
Towards the goal of nerve-agent detoxification, some re-
search groups including ours have studied various kinds of cat-
alysts including supramolecular assemblies,[8] porous organic
polymers (POPs),[9] and metal–organic frameworks (MOFs).[10] In
particular, MOFs have shown great potential as catalysts given
the high concentration of well-dispersed and periodic metal-
based nodes and organic linkers, combined with exceptionally
high surface areas and impressive water stability over a wide
pH range.[11] Recently, we have focused on the detoxification of
nerve agents and simulants through hydrolysis utilizing MOF
catalysts containing Zr6 clusters in basic aqueous buffer solu-
tion (0.45m N-ethylmorpholine solution).[10a–e,g,12] Remarkably,
Zr-MOFs show high catalytic activity for the hydrolysis of simu-
lants and real nerve agents in buffer solution. For example,
some Zr-MOFs are among the fastest synthetic catalysts report-
ed to date, including UiO-66-NH2,[10b] NU-1000-dehydrated,[10c]
and MOF-808,[10d] and show half-lives of <2 min for the de-
struction of the simulant (DMNP) and nerve agents (GD and
VX), in buffer solution.
[a] Dr. S.-Y. Moon, E. Proussaloglou, Dr. A. J. Howarth, Prof. J. T. Hupp,
Prof. O. K. Farha
Department of Chemistry, Northwestern University
2145 Sheridan Road, Evanston, IL 60208-3113 (USA)
E-mail: j-hupp@northwestern.edu
o-farha@northwestern.edu
[b] G. W. Peterson, Dr. J. B. DeCoste, M. G. Hall
Edgewood Chemical Biological Center
US Army Research, Development, and Engineering Command
5183 Blackhawk Road, Aberdeen Proving Ground, MD 21010 (USA)
[c] Prof. O. K. Farha
Department of Chemistry, Faculty of Science
King Abdulaziz University
Jeddah (Saudi Arabia)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201603976.
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Although Zr-MOFs show high catalytic activity for the hy-
drolysis of the organophosphorus simulant and nerve agents,
the reaction requires the presence of N-ethylmorpholine as
a buffer solution. The buffer acts to remove acidic byproducts
from the reaction such as HF as well as to deprotonate water
molecules and facilitate the reaction. The need for a buffering
solution makes it difficult to use these catalysts in applications
such as masks and protective suits.[13] To overcome the limita-
tions associated with the use of a homogeneous buffer, we
sought to heterogenize the buffer using a basic polymer.
Polyethyleneimine (PEI) is a polymer containing amine
groups and aliphatic carbons that can be linear or branched.
This polymer is used in detergents, adhesives, cosmetics, water
treatment agents, and in CO2-capture applications.[14] In partic-
ular, linear polyethyleneimine (Figure 1b) consists of a number
of secondary amines and is insoluble in water, making it
a great candidate for use as a basic heterogeneous buffer for
the MOF-catalyzed hydrolysis of nerve agents and simulants. In
this study, we demonstrate the hydrolysis of the simulant
(DMNP) and nerve agents (GD and VX) with a MOF catalyst/
heterogeneous buffer mixture.
To evaluate the heterogeneous buffering ability of the cat-
ionic polymer, the hydrolysis of DMNP utilizing the Zr-MOF,
NU-1000 (Figure 1a), and PEI was conducted under conditions
similar to those previously reported for NU-1000. Thus, PEI was
used in place of a 0.45m aqueous solution of N-ethylmorpho-
line. NU-1000 was chosen as a test catalyst due to its well-de-
fined pore structure, controllable particle size, and tunable cat-
alytically active sites.[10c] The hydrolysis of DMNP was moni-
tored in situ by 31P NMR spectroscopy, and hydrolysis profiles
were plotted as conversion versus time. As shown in Figure 2a,
NU-1000 with PEI buffer (NU-1000/PEI) hydrolyzes DMNP effec-
tively in water. In addition, the rate of hydrolysis is affected by
the amount of PEI used (Figure S1 in the Supporting Informa-
tion). It should be noted that the hydrolysis reaction with NU-
1000 or PEI alone in water is negligible (Figure S1). Under opti-
mized conditions, NU-1000/PEI [1.5 mmol of NU-1000 (3.3 mg),
0.003 mmol of PEI (7.5 mg, MW: 2,500), 0.16 mmol of amine]
showed an identical hydrolysis rate (8 min half-life) to NU-
1000/N-ethylmorpholine (0.39 mmol of amine; Figure 2a and
Table 1). That fewer amine groups were required to reach the
same reaction rate when using PEI as the buffer versus N-ethyl-
morpholine might indicate that the amines are more effective
as buffers in heterogeneous than homogeneous form. The re-
Figure 2. a) Hydrolysis profiles of DMNP using NU-1000 and PEI (MW: 2,500)
in water and NU-1000 under 0.45m N-ethylmorpholine buffer solution, b) hy-
drolysis profiles of DMNP using the NU-1000 previously dehydrated at
3008C with different molecular weight PEIs in water; the moles of amine for
the different molecular weight polymers were kept consistent at 0.31 mmol
to facilitate comparisons.
usability of NU-1000/PEI was also demonstrated after testing
the initial catalytic hydrolysis (see the Experimental Section in
the Supporting Information). A second cycle using NU-1000/
PEI showed 60% conversion of DMNP at 30 min under the
same conditions used previously. The decrease in catalytic ac-
tivity is attributed to residual hydrolysis products on the cata-
lyst causing inhibition and loss of catalyst and/or PEI after
washing.
Table 1. Comparison of the hydrolysis rate of a simulant (DMNP) and nerve agents (GD and VX) with MOFs under different buffers.
Substrate
MOF[a]/base
mmol
Molecular weight of base
Amine
[mmol]
Half life
[min][e]
[gmolÀ1
]
NU-1000/ethylmorpholine
NU-1000/PEI
NU-1000-dehydrated/PEI
0.39 (50 mL)
0.003 (7.5 mg)
0.006 (14.5 mg)
115
2,500
2,500
0.39
0.16
0.31
8.3Æ0.2
8.4Æ0.2
1.8Æ0.1
DMNP[b]
(simulant)
GD[c] (Soman)
VX[d]
NU-1000-dehydrated/PEI
NU-1000-dehydrated/PEI
0.006 (14.5 mg)
0.0006 (14.5 mg)
2,500
25,000
0.31
0.31
4.8Æ0.1
12.7Æ0.4
[a] 1.5 mmol of catalyst and [b] 25 mmol of DMNP, [c] 14.6 mmol of GD, [d] 14.7 mmol of VX were used for each reaction. [e] Initial half-lives were calculated
by plotting the natural log of conversion versus time; the slope (m=k) is related to the half-life by t1/2 =ln2/k (Figure S3 in the Supporting Information).
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In a previous study, the dehydrated form of NU-1000
showed remarkably enhanced catalytic activity for the hydroly-
sis of DMNP, yielding a half-life of 1.5 min in 0.45m N-ethylmor-
pholine buffer solution.[10c,15] As a result, we tested if NU-1000-
dehydrated/PEI could hydrolyze DMNP in water. Indeed, NU-
1000-dehydrated/PEI (MW: 2,500) showed a significantly en-
hanced reaction rate, half-life of ꢀ2 min, which is similar to
that of NU-1000-dehydrated in the presence of 0.45m N-ethyl-
morpholine buffer solution (Figure 2b and Table 1). It is also
worth noting that the rate of hydrolysis of the simulant signifi-
cantly decreases as the molecular weight of the polymer in-
creases (as shown in Figure 2b); we attribute this to the rela-
tively low pH of the polymer solution with high molecular
weight PEI in water (MW2,500: pH 9.2, MW25,000: pH 8.8, and
MW250,000: 7.7). It should be noted that bimodal kinetic be-
havior was observed for the hydrolysis of DMNP using NU-
1000-dehydrated and high-MW PEI. This is attributed to the ef-
fects of product inhibition on the catalyst after the fast initial
reaction rate.
NU-1000-dehydrated/PEI (MW: 2500) in water, which is compa-
rable to the half-life of 1.8 min for DMNP hydrolysis with the
same mixture. The detoxification of VX is considerably more
complicated than that of GD owing to the presence of multi-
ple potential hydrolysis sites. For example PÀO cleavage pro-
duces the toxic byproduct EA-2192, which is equally as toxic as
VX (Figure S2 in the Supporting Information).[10e,16] Importantly,
VX is selectively hydrolyzed to non-toxic products, ethylmethyl-
phosphonic acid (EMPA) and 2-(diisopropylamino)ethanethiol
(DESH) by cleavage of the PÀS bond with a half-life of 12.7 min
in the presence of NU-1000-dehydrated/PEI (Figure 3b). Intri-
guingly, the molecular weight of the polymer has a significant
effect on the half-lives of detoxification for GD and VX. For GD,
low molecular weight PEI (MW: 2,500) is more effective than
high-molecular-weight PEI (MW: 25,000), which is similar to the
behavior of the simulant DMNP. In contrast, VX is hydrolyzed
more quickly with high-MW PEI.[17] A tentative explanation cen-
ters on the observations that the pH of the reaction solution in
the presence of MW2,500 PEI is 9.2 compared to 8.8 for
MW25,000 PEI and that the first step in the hydrolysis of VX
entails protonation of the tertiary amine (pKa =8.6), a step that
is thermodynamically more favorable in the pH 8.8 environ-
ment engendered by high-MW PEI.[2c,18]
Inspired by these results, we decided to test the NU-1000-
dehydrated/PEI system for the hydrolysis of the chemical war-
fare agents GD and VX in water. We again used in situ 31P NMR
spectroscopy to investigate the decomposition of GD and VX
with NU-1000-dehydrated/PEI in water. As shown in Figure 3a,
GD is effectively hydrolyzed with a half-life of 3.8 min using
Given the success of the heterogeneous catalyst and buffer
system in water, we prepared a simple solid composite materi-
al consisting of a MOF catalyst, polymer buffer, and cellulose
as a substrate, which is portable and amenable for use in pro-
tective gear such as masks, suits, gloves, and cleaning mats. In
addition, cellulose has a highly porous structure that can
absorb liquid (water), making it a great candidate as a matrix
for the catalytic hydrolysis reaction with MOF/PEI. To prepare
the MOF/PEI/cellulose composite, NU-1000-dehydrated and PEI
were evenly dispersed in water using sonication, and then cel-
lulose was added to the mixture. The simulant was dropped
on a glass slide and then wiped using the cellulose composite
(Figure 4, see also the Experimental Section in the Supporting
Information). To evaluate the hydrolysis of DMNP, the reaction
solution was obtained after sitting in the composite for 30 min
by placing the composite inside a centrifuge tube equipped
with a filter and then centrifuging and collecting the filtrate.
An internal standard (7.5 mg, 0.091 mmol of phosphonic acid)
was then added to the solution to allow for quantification of
the hydrolysis reaction. The 31P NMR spectrum of the resulting
solution showed only a peak for dimethoxy phosphate anion
Figure 4. Detoxification of DMNP with MOF/PEI/cellulose composite. a) MOF
and PEI were dispersed in water. b) A cotton ball was place into the mixture
solution, which absorbed the solution mixture immediately. c) and d) 4 mL
DMNP on the glass was wiped using MOF/PEI/cellulose composite and then
the composite was squeezed and the solution was transferred to an NMR
tube after 30 min.
Figure 3. Hydrolysis profiles of a) GD and b) VX in the presence of catalyst
and/or different molecular weight PEI. Solid lines are used as a guide.
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(DMPA, product) without any evidence of DMNP (Figure S4a in
the Supporting Information). In addition, 78% of the maximum
expected DMPA product was observed in the initial filtrate col-
lected. To confirm the nature of the residual chemical left in
the composite, water (2ꢁ2 mL) was added to wash the com-
posite and the filtrate was obtained in the same way as de-
scribed previously. The 31P NMR spectrum of the wash solu-
tions show only a peak for dimethoxy phosphate anion and
nearly all of the product (97% total) was retrieved by the
washes (Figure S4b and S4c in the Supporting Information).
This proof-of-concept experiment implies that the heterogene-
ous MOF/polymer can also be easily impregnated/incorporated
into fabric, making it amenable for use in a variety of protec-
tive or remedial applications.
MRSEC program of the National Science Foundation (DMR-
1121262) at the Materials Research Center of Northwestern
University. G.W.P. and J.B.D. acknowledge funding by the De-
fense Threat Reduction Agency (project Nos. BA07PRO104 and
BA13PHM210).
Keywords: heterogeneous buffer · heterogeneous catalysis ·
hydrolysis · nerve agents · zirconium MOF
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In conclusion, a heterogeneous system consisting of a Zr-
MOF catalyst, NU-1000, and a cationic polymer (PEI) is capable
of hydrolyzing the simulant DMNP in water. In particular, NU-
1000-dehydrated not only hydrolyzes DMNP, but also the
nerve agents in water with remarkable efficiency (initial t1/2 of
1.8 min for DMNP, 3.8 min for GD, and 12.7 min for VX). Impor-
tantly, this heterogeneous mixture can also be prepared as
a composite with a cellulose fiber that is still effective at detox-
ifying the simulant. Our team is currently exploring the feasibil-
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Experimental Section
Monitoring the hydrolysis of DMNP
Hydrolysis profiles were recorded by in situ 31P NMR spectroscopy
at room temperature. NU-1000/NU-1000-dehydrated (3.3 mg,
1.5 mmol of Zr6-based nodes) and PEI (7.5 mg) were loaded into
a 1.5 dram vial and 1 mL of 10% D2O solution (0.9 mL DI water/
0.1 mL D2O) was added and then sonicated for 1 min to disperse
homogeneously. DMNP (4 mL, 25 mmol) was added to mixture solu-
tion and swirled for 20 s. The reaction mixture was then transferred
to an NMR tube and the spectrum was immediately measured.
Background reactivity was evaluated under identical conditions,
apart from the absence of catalyst or PEI, and monitored by in situ
31P NMR spectroscopy.
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Nguyen, J. Am. Chem. Soc. 2013, 135, 11720–11723; b) R. K. Totten,
M. H. Weston, J. K. Park, O. K. Farha, J. T. Hupp, S. T. Nguyen, ACS Catal.
2013, 3, 1454–1459.
[10] a) M. J. Katz, J. E. Mondloch, R. K. Totten, J. K. Park, S. T. Nguyen, O. K.
Farha, J. T. Hupp, Angew. Chem. Int. Ed. 2014, 53, 497–501; Angew.
Chem. 2014, 126, 507–511; b) M. J. Katz, S.-Y. Moon, J. E. Mondloch,
M. H. Beyzavi, C. J. Stephenson, J. T. Hupp, O. K. Farha, Chem. Sci. 2015,
6, 2286–2291; c) J. E. Mondloch, M. J. Katz, W. C. I. III, P. Ghosh, P. Liao,
W. Bury, G. W. Wagner, M. G. Hall, J. B. DeCoste, G. W. Peterson, R. Q.
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2015, 54, 6795–6799; Angew. Chem. 2015, 127, 6899–6903; e) S.-Y.
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1269–1278.
Monitoring the hydrolysis of nerve agents GD and VX
NU-1000/NU-1000-dehydrated (3.3 mg, 1.5 mmol of Zr6-based
nodes) and PEI (14.5 mg) were loaded into a 5 mm NMR tube fol-
lowed by 1 mL of 10% D2O solution. A nerve agent (GD 2.6 mL,
14.6 mmol or VX 3.9 mL, 14.6 mmol) was then added, the tube
capped, and vigorously shaken before placing into the NMR
magnet for monitoring by 31P NMR. Caution! Experiments utilizing
GD and VX should be run by trained personnel using appropriate
safety procedures.
Acknowledgements
O.K.F. and J.T.H. acknowledge funding by the Army Research
Office (project no. W911NF-13-1-0229). This work made use of
the J. B. Cohen X-ray Diffraction Facility supported by the
[11] S.-Y. Moon, A. J. Howarth, T. Wang, N. A. Vermeulen, J. T. Hupp, O. K.
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Received: August 21, 2016
Published online on && &&, 0000
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COMMUNICATION
A heterogeneous catalyst system con-
sisting of a Zr-MOF and cationic poly-
mer could effectively detoxify not only
a nerve agent simulant, dimethyl 4-ni-
trophenylphosphate, but also nerve
agents, GD and VX, in water. This heter-
ogeneous mixture was prepared as
a composite with cellulose fiber, which
can be used in protective gear such as
masks, suits, gloves, and cleaning mats.
&
Metal–Organic Frameworks
S.-Y. Moon, E. Proussaloglou,
G. W. Peterson, J. B. DeCoste, M. G. Hall,
A. J. Howarth, J. T. Hupp, O. K. Farha*
&& – &&
Detoxification of Chemical Warfare
Agents Using a Zr6-Based Metal–
Organic Framework/Polymer Mixture
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