Ultra-Fast Degradation of Chemical Warfare Agents Using MOF–Nanofiber Kebabs

Article abstract of DOI:10.1002/anie.201606656

The threat associated with chemical warfare agents (CWAs) motivates the development of new materials to provide enhanced protection with a reduced burden. Metal–organic frame-works (MOFs) have recently been shown as highly effective catalysts for detoxifying CWAs, but challenges still remain for integrating MOFs into functional filter media and/or protective garments. Herein, we report a series of MOF–nanofiber kebab structures for fast degradation of CWAs. We found TiO₂coatings deposited via atomic layer deposition (ALD) onto polyamide-6 nanofibers enable the formation of conformal Zr-based MOF thin films including UiO-66, UiO-66-NH₂, and UiO-67. Cross-sectional TEM images show that these MOF crystals nucleate and grow directly on and around the nanofibers, with strong attachment to the substrates. These MOF-functionalized nanofibers exhibit excellent reactivity for detoxifying CWAs. The half-lives of a CWA simulant compound and nerve agent soman (GD) are as short as 7.3 min and 2.3 min, respectively. These results therefore provide the earliest report of MOF–nanofiber textile composites capable of ultra-fast degradation of CWAs.

Full text of DOI:10.1002/anie.201606656

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201606656
German Edition: DOI: 10.1002/ange.201606656
Metal–Organic Frameworks Hot Paper
Ultra-Fast Degradation of Chemical Warfare Agents Using MOF–
Nanofiber Kebabs
Junjie Zhao, Dennis T. Lee, Robert W. Yaga, Morgan G. Hall, Heather F. Barton,
Ian R. Woodward, Christopher J. Oldham, Howard J. Walls, Gregory W. Peterson,* and
Gregory N. Parsons*
Abstract: The threat associated with chemical warfare agents
CWAs) motivates the development of new materials to
highly effective adsorbents and catalysts for removing
[
8–16]
(
CWAs.
The ultra-high surface area and large porosity
[
8,9]
provide enhanced protection with a reduced burden. Metal–
organic frame-works (MOFs) have recently been shown as
highly effective catalysts for detoxifying CWAs, but challenges
still remain for integrating MOFs into functional filter media
and/or protective garments. Herein, we report a series of MOF–
nanofiber kebab structures for fast degradation of CWAs. We
make MOFs promising candidates for sorption of CWAs,
while the metal-containing secondary building units present
in MOFs can also function as Lewis-acidic catalytic sites for
[
10–16]
CWA destruction.
Among the reported MOF catalysts,
MOFs containing Zr-based clusters, including UiO-type
MOFs, NU-1000, MOF-808, and PCN-222/MOF-545, have
exhibited exceptional catalytic activity for degrading CWAs
found TiO coatings deposited via atomic layer deposition
2
[
10–16]
(
ALD) onto polyamide-6 nanofibers enable the formation of
conformal Zr-based MOF thin films including UiO-66, UiO-
6-NH , and UiO-67. Cross-sectional TEM images show that
and simulants with half-lives as short as 0.5 min.
While bulk MOF crystals exhibit excellent properties for
CWA destruction, many practical issues still need to be
addressed before these materials can be widely used for this
application. For example, the powder form of MOFs is not the
ideal configuration for gas filters, protective suits and cloth-
ing. Meanwhile, particle aggregation may lead to reduced
accessible catalytic sites and consequently decreased activity.
It is also important to minimize the volume and weight of the
active materials to reduce the burden for end users while
maintaining substantial long-term protection. In contrast,
MOF thin films immobilized on functional substrates can
6
2
these MOF crystals nucleate and grow directly on and around
the nanofibers, with strong attachment to the substrates. These
MOF-functionalized nanofibers exhibit excellent reactivity for
detoxifying CWAs. The half-lives of a CWA simulant com-
pound and nerve agent soman (GD) are as short as 7.3 min and
2
.3 min, respectively. These results therefore provide the ear-
liest report of MOF–nanofiber textile composites capable of
ultra-fast degradation of CWAs.
[
17,18]
C
hemical warfare agents (CWAs) are highly toxic com-
simplify the handling and deployment,
and are likely to
pounds that can injure, incapacitate, or even kill human
beings. Detoxification of CWAs is of great social significance
owing to the past accidental or deliberate emissions and
promote MOF applications in CWA detoxification.
In this paper, we report a series of MOF–nanofiber kebab
structures for CWA degradation. Electrospun polymeric
nanofibers were chosen as the scaffolds because nanofibers
can exhibit very high external surface area, excellent water
vapor transport properties, and good mechanical
[
1,2]
remaining threat posed to civilian and military personnel.
Materials that can efficiently capture and degrade these lethal
chemicals are therefore highly desired to protect soldiers,
first-responders, and the general public.
[
19,20]
strength.
As far as we know, only one report about
Recently, a wide variety of materials have been reported
MOF–textile composites for catalytic destruction of CWA
simulants has appeared in literature, where UiO-66 particles
[3–7]
with catalytic activity for degrading CWAs.
Among them,
[16]
metal–organic frameworks (MOFs) have been shown as
were physically sprayed onto silk microfibers. Conformal,
high-quality MOF thin-films grown on nanofibers are yet to
be explored for catalytic destruction of CWAs. Herein, we
show that the half-lives of the nerve agent soman (O-pinacolyl
methylphosphonofluoridate, also known as GD) are as short
as 2.3 min using our MOF–nanofiber composite catalysts. This
is also the first demonstration of effective destruction of a real
CWA compound using MOF–fabric composites, as previous
[
*] J. Zhao, D. T. Lee, H. F. Barton, I. R. Woodward, C. J. Oldham,
Prof. G. N. Parsons
Department of Chemical and Biomolecular Engineering
North Carolina State University
911 Partners Way, Raleigh, NC 27695 (USA)
E-mail: gnp@ncsu.edu
[
16]
R. W. Yaga, H. J. Walls
RTI International
work has only investigated simulants.
Figure 1 describes the procedure to synthesize our MOF–
nanofiber kebab structures. Free-standing polyamide-6 (PA-
3040 East Cornwallis Road
Research Triangle Park, NC 27709 (USA)
6
) nanofiber mats obtained from electrospinning were coated
M. G. Hall, G. W. Peterson
Edgewood Chemical Biological Center
with a conformal thin-layer ( ꢀ 5 nm thick) of TiO using
2
atomic layer deposition (ALD). This TiO2 ALD layer is
expected to promote MOF heterogeneous nucleation on
5183 Blackhawk Road, Aberdeen Proving Ground, MD 21010 (USA)
E-mail: gregory.w.peterson.civ@mail.mil
[
17]
fibers, and provides some contribution to catalytic CWA
Supporting information for this article can be found under:
http://dx.doi.org/10.1002/anie.201606656.
[
21,22]
detoxification.
Although our previous work has shown
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Figure 1. Synthetic procedure for Zr-based MOF–nanofiber kebab
structures on polyamide-6 nanofibers. The MOF crystal structures are
illustrated in the dashed box.
that Al O and ZnO ALD can also promote MOF growth on
2
3
[
17,23,24]
fibers,
these ALD films were not used as nucleation
layers in this case due to substrate incompatibility with the
Al O ALD process and instability of ZnO in the highly acidic
solvothermal solution we used.
Figure 2. a) Photo of a free-standing PA-6@TiO @UiO-66-NH nano-
2
2
2
3
fiber mat. b–d) SEM images of PA-6@TiO @UiO-66-NH . e–i) Energy
2
2
dispersive X-ray mapping images of PA-6@TiO @UiO-66-NH .
2
2
Three Zr-based MOFs, including UiO-66, UiO-66-NH2,
and UiO-67, were chosen because previous reports have
demonstrated excellent stability and good catalytic properties
67, respectively). Figures 3a–f are SEM and cross-sectional
TEM images of the MOF-nanofiber kebabs. Tubular features
observed in the TEM images represent the core@shell
[
10,12,13,25]
of these MOFs.
modulator for the solvothermal synthesis, which is similar to
We used concentrated HCl as the
[
26]
reported recipes for these MOFs, but developed our own
conditions to achieve optimized growth of MOF thin-films
onto nanofiber substrates. Specifically, 0.343 mmol of ZrCl4
and 0.343 mmol of dicarboxylic acid linkers (1:1 molar ratio)
were dissolved in 20 mL of DMF. Deionized water (25 mL)
and concentrated HCl (1.33 mL for UiO-66 and UiO-66-NH2,
structures of PA-6@TiO nanofibers sliced along the axial
2
direction. The diameters of PA-6 nanofibers measured from
TEM images (15–55 nm) are consistent with that measured
from SEM images (Figure S2). The average thickness of the
ALD TiO coatings is 5.7 Æ 1.3 nm, corresponding to an ALD
2
growth rate of ꢀ 0.6 ꢀ per cycle. The spherical MOF crystals
0
.67 mL for UiO-67) were added to the solution. Subse-
are found to nucleate and grow directly on and around the
quently, the TiO -coated PA-6 nanofiber (PA-6@TiO ) mat
PA-6@TiO nanofibers, indicating strong attachment to the
2
2
2
was transferred into the mixed solution, which was then
heated to 858C for 24 h. After the solvothermal synthesis, the
MOF–nanofiber kebabs were collected, washed, activated,
and investigated for CWA degradation.
substrates. There was no noticeable particle shedding during
the handling after synthesis, confirming good adhesion of our
MOF coatings to the nanofibers.
The quality of the Zr-based MOF thin-films grown on
nanofibers was characterized using XRD and BET. The sharp
XRD peaks in the patterns for the MOF–nanofiber kebabs
agree well with the corresponding MOF powders (Fig-
ures S3a–c), confirming the formation of targeted MOF
structures. N2 physisorption measurements (Figures S3d–f)
Figure 2a is a photo of a free-standing PA-6@TiO2
nanofiber mat coated with UiO-66-NH MOF kebabs (re-
2
ferred to as PA-6@TiO @UiO-66-NH ). The structural integ-
2
2
rity and flexibility were fully maintained after the solvother-
mal synthesis (Video S1). SEM images (Figures 2b–d) show
2
À1
2
À1
that UiO-66-NH crystals (average size = 126 Æ 25 nm) were
reveal that the BET surface area is 143.9 m g , 205.9 m g ,
2
2
À1
grown conformally on the PA-6@TiO nanofibers. While we
and 356.2 m g for the MOF–nanofiber kebabs with UiO-66,
2
and other groups have attempted various methods to deposit
UiO-66-type MOFs onto polymeric fibers in the past,
only the method reported here enables the formation of these
unique MOF–nanofiber kebab structures. In contrast, the
growth of UiO-66-NH2 on PA-6 nanofibers without TiO2
nucleation layers is patchy and does not result in a conformal
UiO-66-NH and UiO-67, respectively (Table S1). The sur-
2
[
16,17,27–29]
face area for the MOF–nanofiber kebabs is in excess of 10-
times larger than the nanofiber scaffolds alone, demonstrating
the high porosity of the MOF coatings. We also measured the
surface area of the UiO-type MOF powders collected from
the synthesis of MOF–nanofiber kebabs (Table S1) and found
the values consistent with previous reports for all three of the
thin-film on the nanofiber surface as that on TiO -coated PA-
2
[26]
6
nanofibers using the same synthesis conditions (Figure S1).
MOFs.
Energy dispersive X-ray analysis (Figures 2e–i) also con-
firmed uniform MOF growth on the nanofibers.
We find that it is difficult to analyze the MOF mass
fraction in the composites directly by weighing methods. The
net mass increase due to MOF loading is at mg scale and often
comparable to the expected mass change due to water uptake
by the hygroscopic nylon nanofibers. Using the BET surface
In addition to UiO-66-NH , kebab structures of UiO-66
2
and UiO-67 were also obtained on PA-6@TiO nanofibers
2
(
referred to as PA-6@TiO @UiO-66 and PA-6@TiO @UiO-
2 2
2
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Figure 4. a) Catalytic degradation of DMNP using MOF powder and
MOF–nanofiber kebab structures. b) UV/Visible absorption spectra for
monitoring DMNP hydrolysis. c–e) Conversion of DMNP to p-nitro-
phenoxide versus reaction time using MOF powder and MOF–nano-
fibers kebabs.
Figure 3. a,b) SEM and TEM images of PA-6@TiO @UiO-66,
2
c,d) SEM and TEM images of PA-6@TiO @UiO-66-NH , and e,f) SEM
2
2
and TEM images of PA-6@TiO @UiO-67.
2
nanofiber kebabs catalyst was dispersed in an aqueous buffer
solution of N-ethylmorpholine (0.45m, pH 10), and the
degradation kinetics of DMNP were characterized using
area of the MOF–nanofiber kebab composites and the
corresponding bulk MOF powders, we were able to estimate
the MOF mass fraction in the MOF–nanofiber kebab
structures (calculation details shown in the Supporting
Information). The calculated MOF mass fraction is 8.8%,
[
10,11]
a procedure similar to previous reports.
We monitored
the reaction progress by tracking the increased absorbance at
407 nm, which corresponds to p-nitrophenoxide (Figure 4b),
and calculated the concentration based on Lambert–Beer
Law. The percent conversion of DMNP is plotted as a function
of time in Figures 4c–e. For MOF powders, we observed 95,
98, and 96% DMNP conversion in 60 min of reaction when
1
4.7%, and 15.4% for PA-6@TiO @UiO-66, PA-
2
6
@TiO @UiO-66-NH , and PA-6@TiO @UiO-67, respec-
2
2
2
tively. These results were further confirmed by elemental
analysis using inductively coupled plasma optical emission
spectroscopy (ICP-OES; Table S2).
UiO-66, UiO-66-NH , and UiO-67 were used, respectively.
2
The half-lives (t ) of DMNP with MOF powder catalysts
1
/2
The mechanism for forming these MOF–nanofiber kebab
structures was also investigated. Using a similar solvothermal
(Table S1) showed similar trends to the reported data. UiO-
66-NH exhibits the fastest degradation rate (t = 2.8 min)
2
1/2
recipe and procedure, we synthesized UiO-66-NH thin-films
among the three MOF powders, while UiO-67 also signifi-
cantly reduces the half-life of DMNP compared to UiO-66.
2
on Si wafers. Cross-sectional TEM images, high-resolution
EDX mapping (Figure S4), and time-of-flight secondary ion
mass spectroscopy (TOF-SIMS; Figure S5) all confirmed that
The amine moiety in UiO-66-NH is thought to function as
2
a Brønsted base to synergistically enhance the catalytic
[
30]
the ALD TiO layer remains in between the MOF thin-film
activity,
while the large pore size of UiO-67 may allow
2
and the Si substrate. The unchanged thickness of the TiO2
faster diffusion and/or more access of DMNP molecules into
the active sites of the MOF.
[13,14]
layer also indicates no etching of TiO during the solvother-
2
mal reaction. Therefore, heterogeneous nucleation followed
with rapid crystal growth and film coalescence is likely to be
the mechanism for forming such kebab nanostructures (Fig-
ure S6).
To evaluate the catalytic property of our MOF–nanofiber
kebab composites for CWA destruction, we first analyzed the
hydrolysis of simulant 4-nitrophenyl phosphate (DMNP;
Figure 4a). 2.5 mg of MOF powders or 14 mg of MOF–
For untreated PA-6 nanofibers, DMNP shows negligible
rate of hydrolysis with an estimated t1/2 value over 65 h
(Figure S7). With TiO ALD coatings, PA-6@TiO reduces
2
2
the half-life to ꢀ 20 h, consistent with the reported reactivity
[21,22]
of TiO for CWAs. Compared with PA-6 and PA-6@TiO ,
2
2
MOF-nanofiber kebab structures exhibit significantly
enhanced catalytic performance. Both PA-6@TiO @UiO-66-
2
NH2 and PA-6@TiO @UiO-67 enable short half-life of
2
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DMNP (7.3 min and 7.4 min, respectively) and high conver-
phonic acid (PMPA) peak (approximately 27 ppm) began
growing at the same time, indicating detoxification of the
CWA to a non-toxic product. The half-lives of GD were
sion (> 90%) in 60 min. PA-6@TiO @UiO-66 shows a slower
2
DMNP hydrolysis rate, owing to the smaller MOF mass-
loading in the composite structure and the lower catalytic
activity of UiO-66. Detailed analyses of the reaction kinetics
are shown in Figures S8,S9 and Table S3. We noticed that the
extent of reaction stops immediately once the MOF–nano-
fiber catalyst is removed from the solution (Figure S10),
confirming this catalytic reaction is heterogeneous.
3.0 min (with PA-6@TiO @UiO-66), 3.7 min (with PA-
2
6@TiO @UiO-66-NH ),
and
2.3 min
(with
PA-
2
2
6@TiO @UiO-67), respectively. All three of the MOF–nano-
2
fiber composites showed fast GD destruction (t1/2 ꢁ 4 min)
and high conversion (ꢂ 80%) within 10 min. The fastest
reaction rate with PA-6@TiO @UiO-67 is possibly because
2
SEM images and EDX spectra taken for the MOF–
nanofiber kebabs after DMNP degradation (Figure S11) show
that significant amounts of Zr-based MOF coatings remain in
the composites even after strong agitation during the experi-
ments. XRD and BET data confirm these MOF coatings are
still crystalline and porous (Figure S12). These results all
demonstrate the good adhesion of our MOF thin-films to the
nanofiber substrates. Although these MOF-coated nanofibers
were not designed for recyclable protection from CWAs due
to potential secondary contamination during regeneration,
the MOF–nanofiber kebab catalysts still show high reactivity
the large pore size of UiO-67 allows diffusion of reactants into
the pores while the catalytic reactions occur mainly on the
[13]
external surface of UiO-66 and UiO-66-NH2.
To our
knowledge, this is the first demonstration of MOF–fiber
composites for detoxifying real CWA compounds. These
results clearly reveal that conformal MOF thin-films grown
onto nanofiber substrates can achieve excellent catalytic
activity even with small MOF loadings (< 20%). This
advantage will eventually benefit the end users by providing
substantial catalytic efficacy at a reduced burden.
In conclusion, we have shown a series of MOF–nanofiber
kebab structures capable of decomposing the CWA simulant
nd
during the 2 cycle of DMNP testing, and noticeable catalytic
rd
effect in the 3 cycle (Figure S13). Further investigation and
DMNP and nerve agent GD. ALD TiO nucleation layers
2
optimization may be needed for these materials to be applied
and reused for other catalysis systems.
enhance the heterogeneous nucleation of UiO-type MOF
crystals and enable the formation of kebab structures with
strong attachment to the substrates. Using these MOF–
nanofiber composites, the half-lives of DMNP and GD are as
short as 7.3 min and 2.3 min, respectively, indicating great
promise of our MOF–nanofibers for CWA protection. The
synthesis method and the MOF–nanofiber composite struc-
tures we have presented here will also offer new opportunities
to advance the development of gas filters, chemical sensors,
and potentially smart textile materials to protect against
harmful air pollutants.
In addition to simulant DMNP, we further tested our
MOF–nanofiber kebab composites for the destruction of
nerve agent GD (Figure 5a). For this test, 2.6 mL of GD was
added to approximately 14 mg of MOF–nanofiber catalyst in
an NMR tube, followed with vigorous shaking. GD concen-
3
1
tration was determined using P NMR (Figure 5b). The
doublet peaks at approximately 40 and 33 ppm associated
with GD immediately decreased upon exposure to the MOF–
nanofibers (Figures S14–S16). The pinacolyl methylphos-
Acknowledgements
The authors acknowledge funding from ECBC (grant no.
W911SR-07-C-0075) and the Joint Science and Technology
Office (Army Research Office grant no. W911NF-13-1-0173).
We acknowledge the use of the Analytical Instrumentation
Facility (AIF) at North Carolina State University, supported
by the State of North Carolina and the National Science
Foundation. We thank Roberto Garcia for TEM sample
preparation, Yiliang Lin and Xiahan Sang for TEM imaging,
Chuanzhen Zhou for TOF-SIMS analysis, Kim Hutchison for
ICP-MS measurement. We also appreciate the helpful
discussion with Prof. Omar Farha and Dr. Su-Young Moon
about DMNP test procedures.
Keywords: atomic layer deposition · chemical warfare agents ·
metal–organic frameworks · nanofibers · thin films
Figure 5. a) Catalytic reaction of GD hydrolysis using MOF–nanofiber
catalysts. b) Conversion of GD versus reaction time during catalysis.
Dashed lines are fitted results assuming first order reaction kinetics.
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[
17] J. Zhao, M. D. Losego, P. C. Lemaire, P. S. Williams, B. Gong,
S. E. Atanasov, T. M. Blevins, C. J. Oldham, H. J. Walls, S. D.
Revised: August 16, 2016
Published online: && &&, &&&&
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Metal–Organic Frameworks
J. Zhao, D. T. Lee, R. W. Yaga, M. G. Hall,
H. F. Barton, I. R. Woodward,
C. J. Oldham, H. J. Walls,
G. W. Peterson,*
G. N. Parsons*
&&&& — &&&&
Skewering nerve agents: Conformal
metal–organic framework (MOF) kebab
structures decorated on nanofibers that
can degrade chemical warfare agents
within minutes are described. These
MOF–nanofiber composites show excel-
lent reactivity towards both simulant and
nerve agent soman (GD).
Ultra-Fast Degradation of Chemical
Warfare Agents Using MOF–Nanofiber
Kebabs
6
www.angewandte.org
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
These are not the final page numbers!