A Versatile Self-Detoxifying Material Based on Immobilized Polyoxoniobate for Decontamination of Chemical Warfare Agent Simulants

Article abstract of DOI:10.1002/chem.201804523

A decontaminating composite, Mg₃Al-LDH-Nb₆, has been successfully prepared by immobilizing Lindqvist [H₃Nb₆O₁₉]^5? (Nb₆) into a Mg₃Al-based layered double hydroxide (Mg₃Al-LDH). To our knowledge, this represents the first successful approach to the immobilization of polyoxoniobate. As a versatile catalyst, Mg₃Al-LDH-Nb₆ can effectively catalyze the degradation of both vesicant and nerve agent simulants by multiple pathways under mild conditions. Specifically, the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), is converted into the corresponding nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) by selective oxidation, whereas the Tabun (G-type nerve agent) simulant, diethyl cyanophosphonate (DECP), and the VX (V-type nerve agent) simulant, O,S-diethyl methylphosphonothioate (OSDEMP), are detoxified through hydrolysis and perhydrolysis, respectively. A possible mechanism is proposed on the basis of control experiments and spectroscopic studies. The Mg₃Al-LDH-Nb₆ composite exhibits remarkable robustness and can be readily reused for up to ten cycles with negligible loss of its catalytic activity. More importantly, a protective “self-detoxifying” material has easily been constructed by integrating Mg₃Al-LDH-Nb₆ into textiles. In this way, the flexible and permeable properties of textiles have been combined with the catalytic activity of polyoxoniobate to remove 94 % of CEES in 1 h by using nearly stoichiometric dilute H₂O₂ (3 %) as oxidant with 96 % selectivity.

Full text of DOI:10.1002/chem.201804523

A Journal of
Accepted Article
Title: A Versatile Self-Detoxifying Material Based on Immobilized
Polyoxoniobate for Decontamination of Chemical Warfare Agent
Simulants
Authors: Jing Dong, Hongjin Lv, Xiangrong Sun, Yin Wang, Yuanman
Ni, Bo Zou, Nan Zhang, Anxiang Yin, Yingnan Chi, and
Changwen Hu
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To be cited as: Chem. Eur. J. 10.1002/chem.201804523
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FULL PAPER
A Versatile Self-Detoxifying Material Based on Immobilized
Polyoxoniobate for Decontamination of Chemical Warfare Agent
Simulants
Jing Dong, Hongjin Lv, Xiangrong Sun, Yin Wang, Yuanman Ni, Bo Zou, Nan Zhang, Anxiang Yin,
Yingnan Chi,* and Changwen Hu*
Abstract: A decontaminating composite, Mg
successfully prepared by immobilizing Lindqvist [H
into Mg Al-based layered double hydroxide (Mg Al-LDH). To our
knowledge, this represents the first successful approach to
immobilize polyoxoniobate. As a versatile catalyst, Mg Al-LDH-Nb
3
Al-LDH-Nb
6
, has been
accessible catalytic active sites, from the practical point of view,
the materials that can catalytically decompose CWAs with high
robustness and excellent recyclability are more desirable. For
example, a self-detoxifying material can be used to produce
personal protective equipment by integrating into suits, gloves
and boots.
5-
3
Nb
6
O
19
]
6
(Nb )
3
3
3
6
can effectively catalyze the degradation of both vesicant and nerve
agent simulants via multiple pathways under mild conditions.
Specifically, the sulfur mustard simulant, 2-chloroethyl ethyl sulfide
Recently, several kinds of decontamination materials
[4]
[5]
including metal-organic frameworks (MOFs), metal oxides,
(
CEES), converts to the corresponding nontoxic 2-chloroethyl ethyl
and supported polyoxometalates (POMs)[6] have been
developed and investigated. A series of MOFs containing Lewis
acidic Zr4 centers have been proven to be effective for the
hydrolysis of nerve agents and/or their simulants. Metal oxides
and supported POMs also exhibit satisfactory activities in the
oxidative decontamination of sulfur mustard simulants. However,
most previously reported catalytic materials can only
decontaminate CWAs via single detoxification pathway (e.g.
hydrolysis or oxidation), that causes limitations to the
complicated scenarios containing multiple types of CWAs.
Therefore, it is essential to develop a versatile and cost-effective
material for the effective decontamination of various CWAs
simultaneously.
sulfoxide (CEESO) by selective oxidation; while the tabun (G-type
nerve agent) simulant, diethyl cyanophosphonate (DECP), and the
+
VX
(V-type
nerve
agent)
simulant,
O,S-diethyl
methylphosphonothioate (OSDEMP), are detoxified through
hydrolysis and perhydrolysis, respectively. A possible mechanism
was proposed according to control experiments and spectroscopic
studies. The Mg
3
Al-LDH-Nb
6
composite exhibits remarkable
robustness and can be readily reused for up to ten cycles with
negligible loss of its catalytic activity. More importantly, a protective
“
self-detoxifying” material is easily constructed by integrating Mg
LDH-Nb onto textiles, which combines the flexible and permeable
properties of textiles with the catalytic activity of polyoxoniobate and
it removes 94% CEES in 1 h using nearly stoichiometric dilute H
3%) as oxidant with 96% selectivity.
3
Al-
6
O
2 2
As a special subclass of POMs, polyoxoniobates (PONbs)
are a kind of potential versatile catalysts to accelerate the
(
decontamination of CWAs. Hill and Nyman have reported that
(X=Si or Ge)[7] and [Nb
O
19]8-
[8]
can
K12[Ti
2
O
2
][XNb12
O
40
]
6
catalyze the basic hydrolysis of nerve agent and their simulant in
Introduction
liquid and gas phase. Recently, we first found that a double-
V
(VIV
anion complex,
H
13[(CH
3
)
4
N]12[PNb12
O
40(V O)
2
4
O
12
)
2
], are
Effective decontamination of chemical warfare agents
capable of activating H
2
2
O , which can simultaneously catalyze
(
CWAs) is a vital scientific and humankind issue due to their
the hydrolysis of nerve agent simulant and the selective
unanticipated use in past wars and recent terrorist attacks.[
Among all kinds of CWAs, nerve agents and vesicants are
considered as the most nefarious and dangerous ones. Nerve
agents, including Soman, Sarin, Tabun and VX, are
organophosphorous compounds, which can be destructed by
cleavage of the P-X bonds.[2] While vesicants such as sulfur
mustard (also known as “King of the Battle Gases”) is usually
detoxified via selective oxidation approach.[3] Although
homogeneous catalysts show excellent activities due to highly
1]
[9]
oxidation of sulfur mustard simulant in homogeneous system.
However, the poor reusability restricts its practical application.
Normally, immobilization is a preferred method to realize the
heterogeneity of POMs as it provides dispersed and accessible
[10]
active sites. To our knowledge, the immobilization of PONbs
is unexplored yet. The possible reasons include: (1) PONbs are
highly basic and the immobilization methods based on acidic
POMs are unsuitable for PONbs; (2) PONbs have higher
charge-density (e.g. [Nb
to balance the negative charge is a challenge;
precursors of PONbs (e.g. K HNb 19 or Nb ∙nH
limited solubility in water and organic solvents.
Herein we report novel approach to fabricate
decontaminating material, Mg Al-LDH-Nb , by integrating active
Lindqvist [H Nb ) into Mg Al-based layered double
hydroxide (Mg Al-LDH-NO ). The use of Mg Al-LDH as the host
6
O19]: 0.32, [SiNb12O40]: 0.30) and how
[
11]
(3) The
2
O) have
7
6
O
2
O
5
[
a]
J. Dong, Prof. H. J. Lv, X. R. Sun, Dr. Y. Wang, Dr. Y. M. Ni, Dr. B.
Zou, N. Zhang, Prof. A. X. Yin, Prof. Y. N. Chi, Prof. C. W. Hu
Key Laboratory of Cluster Science Ministry of Education, Beijing Key
Laboratory of Photoelectronic/Electrophotonic Conversion Materials,
School of Chemistry and Chemical Engineering
Beijing Institute of Technology
a
a
3
6
O
19]5- (Nb
6
3
3
6
3
3
3
Beijing, 100081 (P.R. China)
E-mail: chiyingnan7887@bit.edu.cn
are based on the following considerations: (1) LDHs usually
have good interlayer anion-exchange capability, (2) the charge
density and acid/base property of LDH can be easily tuned by
varying elemental compositions and molar ratios,[12] (3) the
special interlayer structure of LDH allows the high exposure of
cwhu@bit.edu.cn
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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3 6
Figure 1. The synthesis process of Mg Al-LDH-Nb by a hydrothermal ion-
exchange method.
catalytic active sites of Nb
not only is compatible with the working pH region of Nb
might provide additional catalytic activity. Interestingly, the
obtained Mg Al-LDH-Nb composite exhibits versatile catalytic
capability for detoxification of different CWA simulants: selective
oxidation for sulfur mustard (vesicant agent) simulant, basic
hydrolysis for Tabun (G-type nerve agent) simulant, and
perhydrolysis for VX (V-type nerve agent) simulant. More
importantly, such composite exhibits great potential for the
preparation of portable, permeable, and economical self-
detoxifying material by integrating them onto soft textiles.
6
, (4) the basicity of Mg
3
Al-LDH-NO
3
6
but also
3
6
Control experiments indicate that the loading amounts of
can be regulated by tuning the amount of TMA-Nb used in
the hydrothermal reactions (Table 1) and a maximum loading
Nb
6
6
amount of 28 wt% (corresponding to NO -
exchanging rate of
6
8%) can be reached. In addition, K HNb O19 was also used as
3
5
7
Nb source under otherwise identical conditions, but the PXRD
Figure S2) suggests that [HNb
19]7- could not be incorporated
into Mg Al-LDH. Such difference might be attributed to the
higher charge-density of [HNb
Nb
19]5- (0.20). Furthermore, we also found that the in situ
formed Mg Al-LDH-NO slurry and the hydrothermal treatment
are necessary to the synthesis of Mg Al-LDH-Nb . No target
product was obtained when using dried Mg Al-LDH-NO or
performing the ion-exchange at ambient temperature.
(
6
O
3
7
-
6
O
19
]
(0.28) compared to
[
H
3
6
O
Results and Discussion
3
3
3
6
3 6
Synthesis and Characterization of Mg Al-LDH-Nb
3
3
The preparation of Mg
in Figure 1. The Mg Al-LDH-NO
precipitation of Mg(NO and Al(NO
under N
atmosphere. After aging at 80 oC for 12 h, the
3
Al-LDH-Nb
was first prepared by the co-
solution with NaOH
6
composite is illustrated
3
3
3
)
2
3 3
)
2
precipitate was washed with deionized water and re-dispersed in
deionized water to form a slurry. Hydrothermal treatment of
o
TMA-Nb
6
and Mg
3
Al-LDH-NO
3
slurry at 100 C for 24 h produces
Mg Al-LDH-Nb
3
6
. PXRD pattern of the Mg
3
Al-LDH-Nb
6
(Figure 2a
and S1) reveals the characteristic diffraction peak of the (003)
lattice plane for LDH splits into two peaks with a new peak
emerging at lower angle region compared with that of Mg
LDH-NO , demonstrating that Nb is partially intercalated into
the host layers. According to the basal spacing of d(003) (11.1
Å), the calculated gallery height of 0.63 nm reveals that Nb
cluster is inserted with its C axis nearly parallel to the LDH
3
Al-
3
6
6
2
o
layers. Furthermore, the (110) diffraction peak (2θ = 60.9 ) is
unshifted, indicating that the structure of the LDH is retained
after the intercalation of Nb
6
.[13] Based on the inductively coupled
plasma atomic emission spectroscopy (ICP-AES) and CHN
elemental analyses (Table S1), we concluded that around 58%
-
of NO
Mg
vibrations of Nb=O
3
was exchanged by Nb
6
. The FT-IR absorption bands of
at 865, 720 and 541 cm-1 are attributed to the
3
Al-LDH-Nb
6
t
and Nb-O
b
(t, terminal; b, bridging),
-
respectively (Figure 2b). The characteristic peak of residual NO
is observed at 1383 cm , which is consistent with the result of
PXRD.
3
-1
Figure 2. (a) The XRD patterns of Mg
3 6 3 3
Al-LDH-Nb and Mg Al-LDH-NO ; (b)
FT-IR spectra of Mg Al-LDH-NO , Mg Al-LDH-Nb
3
3
3
6
, and TMA-Nb .
6
SEM and TEM images show that the as-prepared Mg
3
Al-
LDH-Nb (Figure 3a-3c) exhibits typical nanosheet morphology
6
of LDH with the sizes of 200 to 400 nm. Energy dispersive X-ray
spectroscopy (EDS) (Figure S5) and elemental mapping
measurements (Figure 3d) reveal that the composite contains
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Mg, Al, Nb, O and N elements, and Nb is evenly dispersed in the
LDH layers. Figure S6 shows the BET measurements on the
composite and the host. The N
of Mg Al-LDH-Nb exhibit the type IV isotherm pattern with a
clear hysteresis loop, indicating the presence of mesopores. It is
2
adsorption-desorption isotherms
3
6
worth mentioning that the surface area of Mg
3
Al-LDH-Nb
6
2
(
(
176.09 m /g) is three times higher than that of Mg
56.02 m /g) (Table S2) and such increased surface area could
3
Al-LDH-NO
3
2
facilitate the diffusion of substrates to the catalytic active centers
and thus improve the decontamination efficiency.
Figure 3. (a) and (b) SEM images of Mg
3 6
Al-LDH-Nb ; (c) TEM image of
Mg Al-LDH-Nb ; (d) EDS elemental mapping of Mg
3
6
3
Al-LDH-Nb
6
.
Figure 4. (a) Catalytic decontamination of CEES; (b) Concentration time-
course plots for CEES oxidative transformation using Mg
Recycle test for CEES decontamination using Mg Al-LDH-Nb
conditions: CEES (0.5 mmol), Mg Al-LDH-Nb (0.003 mmol) and 1,3-
3
Al-LDH-Nb
6
; (c)
3
6
.
Reaction
3
6
Oxidative Decontamination of CEES
dichlorobenzene (internal standard, 0.25 mmol), 3% aqueous H
mmol) and acetonitrile (4 mL) at room temperature.
2 2
O (0.525
6 2 2
Given the fact that Nb can activate H O in homogeneous
system[ and selective oxidation is the most promising pathway
6e]
for sulfur mustard degradation,[14] the catalytic activity of Mg
LDH-Nb was first evaluated in the oxidative decontamination of
CEES, a sulfur mustard simulant (Figure 4a). In a typical
reaction, CEES (0.5 mmol), 1,3-dichlorobenzene (internal
Al-
6 3
To evaluate the role of Nb and Mg Al-LDH to the
3
degradation reaction, a series of control experiments were
conducted. No appreciable conversion of CEES was observed in
the absence of catalyst (Table 1, entry 7). Under otherwise
6
standard, 0.25 mmol) and Mg
dispersed in acetonitrile (4 mL). After 2 min of stirring at room
temperature, 3 % aqueous H (0.525 mmol) was added to
initiate the reaction. Figure 4b shows that 95% of CEES is
converted in 2 h and the half-life (50% conversion of CEES) is
about 15 min. In the oxidative degradation of sulfur mustard, the
selectivity is a very important factor to consider as the nontoxic
sulfoxide is more preferred than the highly toxic sulfone. In our
experiment, the selectivity for CEESO exceeds 96%, which is
much higher than most of the reported catalytic materials, such
3
Al-LDH-Nb
6
(0.003 mmol) were
identical conditions, Mg
conversion of CEES (Table 1, entry 1), while the precursor TMA-
Nb in homogeneous system decontaminates 100% CEES
within 15 min (Table 1, entry 2). The activity of Mg Al-LDH-Nb
with different loading amounts was also investigated (Table 1,
entry 3-6). The conversion of CEES increases with the loading
3
Al-LDH-NO
3
only catalyzes 12%
2
O
2
6
3
6
amount of Nb
6
. Above analyses suggest that the intercalated
clusters work as main catalytic active sites. The Mg Al-LDH-
-28% was used in the following decontamination reactions.
Nb
Nb
6
3
6
as saponite[15] (Sele.: 73%, oxidant: 30% aq. H
metal oxidates[16] (Sele.: 71%, oxidant: 30% aq. H
porous (Sele. 82%, oxidant:
materials[5b]
hydroperoxide). In addition, our catalytic system is more
environmentally benign due to the use of nearly stoichiometric,
O
2
), nanosized
), and
tert-butyl
2
Table 1. Decontamination of CEES using different catalysts.[a]
2
O
2
Entry
Catalyst
Time (h)
Conv. (%)
Selec. (%)
1
2
Mg
3
Al-LDH-NO
3
2
12
99
98
2 2
diluted H O (3%) as oxidant.
TMA-Nb [
b]
0.25
100
6
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3 6
To verify the heterogeneity of Mg Al-LDH-Nb composite,
3
4
5
6
7
Mg
Mg
Mg
Mg
3
3
3
3
Al-LDH-Nb
Al-LDH-Nb
Al-LDH-Nb
Al-LDH-Nb
Blank
6
6
6
6
-13%
-20%
-25%
-28%
2
2
2
2
2
31
68
81
95
0
99
97
96
97
0
leaching test was performed. The catalyst was filtered off when
the conversion reached about 30%. The solution was kept
running under the same conditions for another 1.5 h, but
negligible conversion of CEES was observed (Figure S12).
Moreover, ICP-AES (detection limit ca. 1 ppm) reveals that no
detectable niobium exists in the filtrate. The above results
confirm that Mg
cluster. In addition, we also evaluated the recyclability and
stability of such Mg Al-LDH-Nb composite. The activity of
Mg Al-LDH-Nb shows negligible decrease after ten cycles
3 6
Al-LDH is an effective and stable host for Nb
[
a] Reaction conditions: CEES (0.5 mmol), catalyst (0.003 mmol) and 1,3-
dichlorobenzene (internal standard, 0.25 mmol), 3% aqueous H (0.525
catalyzes
3
6
2
O
2
mmol) and acetonitrile (4 mL) at room temperature; [b] TMA-Nb
6
3
6
CEES decontamination in homogeneous system.
(Figure 4c) and also no obvious change is observed from the
PXRD patterns and IR spectra before and after the recycle
According to previous investigations, radical process might
be involved in the oxidation reaction using H as oxidant. To
understand the mechanism, radical scavengers, such as p-
experiment (Figure S13 and S14). The stability of our Mg
LDH-Nb composite outperforms that of the reported organic-
inorganic hybrids.
selectivity maintains above 95%. The robustness and
recyclability of Mg Al-LDH-Nb composite makes it a promising
3
Al-
2
O
2
6
[19]
More importantly, during each recycle the
−
benzoquinone (for •O
2
/•O
2
H), tert-butyl alcohol and
[
17]
diphenylamine (for •OH), were chosen and used in the CEES
oxidation reaction. As shown in Figure 5a, after adding
scavengers the conversion of CEES remains unchanged and so
we can rule out any radical species responsible for the selective
oxidation of CEES. As POMs tend to form peroxo-metal species
3
6
catalytic material for effective decontamination of sulfur mustard.
Hydrolytic decontamination of DECP
2 2
O
,[18] we proposed a possible non-radical
in the presence of H
reaction mechanism. As shown in Figure 5c, the intercalated
hexaniobates may interact with H to form active peroxo
Given the catalytic performance of hexaniobate in basic
hydrolysis of nerve agents,[8] we examine the activity of the
2
O
2
Mg
Figure 6a). Using Mg
converted into the nontoxic product, diethyl hydrogen phosphate
DEHP), in 30 min with a half-life of ~5 min in the absence of
3
Al-LDH-Nb
6
towards hydrolysis of the tabun simulant, DECP
species (side-on peroxo or end-on hydroperoxo), which
subsequently oxidize the accessible CEES. Such speculation is
supported by Raman spectra of H O -treated TMA-Nb solution,
2 2 6
where a peak at 867 cm-1 attributed to the O-O stretch is
observed (Figure 5b), proving the existence of active peroxo
species.
(
3
Al-LDH-Nb as catalyst, 97% of DECP is
6
(
extra organic base such as N-ethylmorpholine that is commonly
used in MOF-catalyzed decontaminating system[4] (Figure 6b). In
contrast, the blank test shows only 20% DECP decontamination
in 30 min. Furthermore, the control experiments support that
both Nb
reaction: conversions are 100% and 40%, respectively and this
displays that Mg Al-LDH not only acts as a good supporter but
also provides additional catalytic activity (Figure 6c).
6 3
and Mg Al-LDH do catalyze the basic hydrolysis
3
3 6
Figure 5. (a) Decontamination of CEES catalyzed by Mg Al-LDH-Nb without
adding radical scavengers (red); with adding diphenylamine (blue), p-
benzoquinone (pink), and t-butanol (green) as radical scavengers; (b) Raman
6 2 2
spectra of TMA-Nb before and after adding 3% aqueous H O ; (c) Possible
reaction mechanism of CEES decontamination.
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react with VX.[21] As both the Mg
Nb
LDH-Nb
Al-LDH and the intercalated
3
6
are basic, one might speculate that the activity of Mg
3
Al-
6
comes from its alkalinity. To better understand the
catalytic process, a control experiment using 2 equivalents
NaOH as homogeneous catalyst was performed under
otherwise identical conditions. Surprisingly, only 33% of
OSDEMP was converted (Figure 7b and S15) which is much
lower than that of Mg Al-LDH-Nb -catalyzed system (90%),
3 6
indicating that alkalinity is not the main factor to accelerate the
perhydrolysis reaction. In other control experiments (Figure S16),
the host itself, Mg
in 5 h, while TMA-Nb
1
3
Al-LDH-NO
in homogeneous system decomposes
00% of OSDEMP in 30 min. Therefore, we speculate that the
3
, converts only 42% of OSDEMP
6
intercalated Nb
and the interactions between Nb
6
plays a key role in the perhydrolysis process
and H are responsible for
its catalytic performance. To our knowledge, the reported Mg Al-
LDH-Nb represents the first material that can simutaneously
6
2 2
O
3
6
decontaminate vesicant, G-type nerve agent, and V-type nerve
agent.
Figure 6. (a) Catalytic hydrolysis of DECP; (b) Concentration time-course
plots for DECP transformation with Mg
3 6
Al-LDH-Nb and without catalyst; (c)
DECP decontamination using different catalysts. Reaction conditions: DECP
-
2
(20 μL), catalyst (0.003 mmol), nitrobenzene (internal standard, 3.25×10
mmol), H O (100 μL), DMF (1200 μL) at room temperature for 30 min.
2
Perhydrolytic decontamination of OSDEMP
3 6
In addition, we also evaluated the activity of Mg Al-LDH-Nb
composite towards detoxifying V-type nerve agent, O-ethyl-S-[2-
(
diisopropylamino)ethyl]-methylphosphono-thioate (VX), that is
3
more potent than Sarin with lethal dose of 0.0096 mg/m .
Hydrolysis of VX under basic conditions leads to the cleavage of
both P-S and P-O bonds: the product of P-S cleavage is the
nontoxic EMPA (ethyl methylphosphonic acid) while P-O
cleavage yields the toxic EA-2192.[20] In contrast, the
2 2
perhydrolysis of VX in the presence of H O is a more attractive
route due to the exclusive cleavage of P-S bond and fast
reaction rate.[ The low toxic simulant, OSDEMP, was used to
21]
investigate the activity of Mg
extent of decontamination is monitored by 1P NMR. Under mild
conditions, the Mg Al-LDH-Nb composite removes 90% of
OSDEMP within 5 h while the blank control experiment only
yields a conversion of 15%. More importantly, only the product
of P-S cleavage, nontoxic EMPA (δ= 26.5 ppm), is detected
3
Al-LDH-Nb
6
(Figure 7a) and the
Figure 7. (a) Two pathways of OSDEMP degradation; (b) 31P spectra of
3
OSDEMP decontamination using Mg Al-LDH-Nb6 (red) and NaOH (blue), and
3
without catalyst (black) after 5 h. Reaction conditions: OSDEMP (5 μL), D
500 μL), acetonitrile (200 μL), catalyst (0.008 mmol for Mg Al-LDH-Nb and
.016 mmol for NaOH) and 30% aqueous H (700 μL) at room temperature.
2
O
3
6
(
3
6
0
2 2
O
(
Figure 7b). Generally, the perhydrolysis proceeds in strong
Decontaminaiton of CEES by the Mg
Material
3 6
Al-LDH-Nb -based
-
alkali solution, where the in situ generated peroxy anions (OOH )
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Furthermore, we have investigated the potential practical
application of such Mg Al-LDH-Nb composite in fabricating
3 6
protective materials. Recently, several MOF-based self-
detoxifying materials towards CWAs have been reported.[22]
Given the excellent activity, high robustness and recyclability of
our Mg
cleaning clothing by incorporating Mg
cloth (CC) substrate. Typically, a so-called “catalyst ink” was first
prepared by dispersing freshly-prepared Mg Al-LDH-Nb into the
3
Al-LDH-Nb
6
composite, we initiatively construct a self-
3
Al-LDH-Nb onto carbon
6
3
6
DMF solution of polyvinylidene fluoride. Then, a piece of carbon
cloth was soaked in the “catalyst ink” under ultrasonic conditions
to obtain the carbon cloth-supported Mg
LDH-Nb -CC) (Figure 8a). The SEM images and optical
photographs demonstrate that Mg Al-LDH-Nb is well-dispersed
on the carbon cloth (Figure 8b-c and S7): the integrated
composite maintains the typical plate-like morphology of Mg Al-
LDH-Nb without obvious aggregation and the flexibility of the
3 6 3
Al-LDH-Nb (Mg Al-
6
3
6
3
6
textile (Figure 8d). It is noted that such supporting substrate can
also be extended to other textiles; the purpose of using carbon
cloth is to
Figure 9. (a) Decontamination of CEES on Mg
Concentration time-course plots for the CEES oxidative transformation on
Mg Al-LDH-Nb -CC; (e) Recycle test for CEES decontamination on Mg Al-
LDH-Nb -CC.
3 6
Al-LDH-Nb -CC; (b)
3
6
3
Figure 8. (a) Procedure for preparing Mg
images of the carbon cloth fibers; (d) Optical photograph of Mg
CC under twisted state; (e) PXRD patterns of Mg Al-LDH-Nb -CC, Mg
Nb and CC.
3
Al-LDH-Nb
6
-CC; (b) and (c) SEM
Al-LDH-Nb
Al-LDH-
6
3
6
-
3
6
3
6
Conclusions
obtain high-quality SEM images. Furthermore, XRD patterns
confirm that the structure of Mg Al-LDH-Nb keeps unchanged
Figure 8e). When a solution containing CEES and H was
absorbed by such cloth (Figure 9a), without further treatment
4% CEES was decontaminated in 1 h and the selectivity for
CEESO reaches 96% (Figure 9b). After the first catalytic run, we
recycled the “self-cleaning clothing” by simply washing with H
and acetonitrile, and reused for the next run. Even after three
catalytic runs, the activity and selectivity is still comparable to
that of the first run (Figure 9c), indicating the high robustness of
In summary, the active hexaniobate cluster has been
successfully intercalated into Mg Al-LDH to form an immobilized
Mg Al-LDH-Nb . As a versatile catalyst, Mg Al-LDH-Nb can
effectively decontaminate three CWA simulants through the
optimal pathway of each: selectively oxidizing sulfur mustard
simulant (CEES), hydrolyzing a G-type nerve agent simulant
3
6
3
(
2 2
O
3
6
3
6
9
2
O
(
(
DECP), and perhydrolyzing a V-type nerve agent simulant
OSDEMP). As an all-inorganic material, such Mg Al-LDH-Nb
3
6
composite exhibits excellent stability and recyclability for
continuous catalytic runs. Importantly, a self-detoxifying cloth is
3 6
such Mg Al-LDH-Nb -CC composite.
fabricated by integrating Mg
remove 94% of CEES without stirring in 1 h in the presence of
nearly stoichiometric 3% H . The reported Mg Al-LDH-Nb
composite catalyst not only represents a novel and effective
3 6
Al-LDH-Nb onto textiles that can
2
O
2
3
6
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Chemistry - A European Journal
10.1002/chem.201804523
FULL PAPER
decontaminating material but also offers a new opportunity in
making portable, permeable, and economical protective self-
detoxifying clothing (e.g. protective suits, gloves, and boots, etc.)
against chemical warfare agents.
Synthesis of Mg
3
Al-LDH-Nb
6
-CC
60 mg wet Mg
3
Al-LDH-Nb
6
sample was dispersed in 2 mL DMF
under ultrasonic conditions for 10 min in a vial. 1 mL polyvinylidene
fluoride (PVDF) solution (20 mg) was then added to the suspension. The
combined Mg
3 6
Al-LDH-Nb /PVDF suspension was sonicated for additional
1
0 min, resulting in a catalyst “ink”. A piece of carbon cloth (CC) was
Experimental Section
immersed in the catalyst “ink” under ultrasonic conditions for 10 min and
then dried under vacuum at 70 C for 12 h.
o
Materials and Methods
Catalytic oxidation of 2-chloroethyl ethyl sulfide (CEES) with Mg
LDH-Nb
3
Al-
All reagents and other starting materials were obtained commercially
6
[23]
and used as received. K
Nb
)[24] were prepared using the literature methods. 2-chloroethyl ethyl
sulfide (CEES) was purchased from Aladdin Industrial Corporation.
Diethyl cyanophosphonate (DECP) and O, S-diethylmethyl
HNb O
7 6 19
3 4 5 3 6
and [(CH ) N] [H Nb O19] (TMA-
6
The selective oxidation (decontamination) of CEES using different
catalysts were performed as follows. Catalyst (0.003 mmol) was
dispersed in acetonitrile (4 mL) and to this solution CEES (0.5 mmol) and
phosphonothioate (OSDEMP) were purchased from Alfa Aesar (China)
Chemicals Co., Ltd.. Caution: the simulants of CWAs (CEES, DECP,
OSDEMP) are highly toxic and must be handled only by trained
personnel using applicable safety procedures in a closed system or in a
hood under good ventilation. Powder X-ray diffraction (PXRD) data on
samples were recorded on a Bruker instrument equipped with graphite-
1
,3-dichlorobenzene (internal standard, 0.25 mmol) were added. After
stirring for 2 minutes at room temperature, 3% aqueous H (0.525
2 2
O
mmol) was added dropwise. The reaction was monitored by gas
chromatography at various time intervals and the products were
qualitatively analyzed by GC-MS.
monochromatized Cu Kα radiation (λ = 0.154 nm; scan speed = 5° min−1
θ = 5−70°) at room temperature. IR spectra were collected (as KBr-
;
Catalytic hydrolysis of diethyl cyanophosphonate (DECP) with
Mg Al-LDH-Nb
3 6
2
pressed pellets) on a Nicolet 170SXFT-IR spectrophotometer in the
range 400−4000 cm−1. The X-ray photoelectron spectrum (XPS) analysis
was conducted on an ESCALAB 250 spectrometer using an Al Kα
radiation as the X-ray source (1486.7 eV) with a pass energy of 30 eV
and the pressure inside the analyzer was maintained at 10-9 Torr.
Elemental analyses (C, H and N) were conducted on an ElementarVario
EL cube Elmer CHN elemental analyzer; Mg, Al and Nb were determined
by a ThermoiCAP 6000 atomic emission spectrometer. TGA of the
sample was performed using a Shimadzu DTG-60AH thermal analyzer
under air with a heating rate of 10 °C min−1. The morphology and
microstructure of the samples were observed by scanning electron
microscopy (SEM, JEOLS-4800) and transmission electron microscopy
The hydrolysis of DECP with various catalysts were performed as
follows. Catalyst (0.003 mmol) was added to the mixture of H O (100 μL)
and DMF (1200 μL), followed by addition of DECP (0.12 mmol) and
nitrobenzene (internal standard, 3.25×10-2 mmol). The reaction was
monitored by gas chromatography at various time intervals.
2
Catalytic Perhydrolysis of O,S-diethyl methylphosphonothioate
(OSDEMP) with Mg Al-LDH-Nb
3 6
The perhydrolysis of OSDEMP using different catalysts were
conducted as follows. Catalyst (0.008 mmol) was dispersed in the
(TEM, JEOL JEM-2010). The Brunauer-Emmett-Teller (BET) specific
surface areas were performed at 77 K in a Belsorp-max surface area
detecting instrument. The GC analyses were performed on Shimadzu
mixture of D
2
O (500 μL) and acetonitrile (200 μL). After stirring for 2 min
at room temperature, OSDEMP (5 μL) and 30% aqueous H
was added to initiate the reaction. The mixture was monitored by 31P
NMR at various time intervals.
2 2
O
(700 μL)
GC-2014C with a FID detector equipped an HP-5 ms capillary column.
3
1P NMR spectra were determined on a Bruker 400 MHz instrument in
2 3 4
D O, and all the chemical shifts were referenced to aqueous H PO
solution (85%). Raman spectra were obtained on SNFT-SRLab1000
equipped with an excitation wavelength of 785 nm.
3 6
Catalytic Decontamination of CEES with Mg Al-LDH-Nb -CC
The degradation of CEES using Mg
as follows. CEES (0.1 mmol), 1,3-dichlorobenzene (internal standard,
.05 mmol) and 3% aqueous (0.105 mmol) were mixed in
3 6
Al-LDH-Nb -CC were conducted
3 6
Synthesis of Mg Al-LDH-Nb Composite
0
2 2
H O
A 10 mL solution containing 6 mmol of Mg(NO
Al(NO , and an aqueous solution of NaOH (0.2 M) were simultaneously
dropped into a 250 mL three-necked flask with vigorous stirring under N
3
)
2
and 2 mmol of
acetonitrile (400 μL) to produce a “toxic solution”. The above prepared
“toxic solution” was absorbed by the cloth (Figure 9a) and the
degradation experiment was performed under ambient conditions without
other treatment. To detect the products, at various time intervals, the
cloth was washed with acetonitrile (500 μL) and the extract was
monitored by gas chromatography. The catalytic data in Figure 9b are
from four parallel experiments.
3 3
)
2
at room temperature. The relatively adding rate of two solutions was
adjusted to keep the final pH value of the mixture to ~10. After aging at
o
8
0 C for 12 h, the precipitate was washed with water for 3 times and re-
dispersed in 8 mL water preparing Mg
Mg Al-LDH-NO slurry and 8 mL TMA-Nb
.1 g TMA-Nb for Mg Al-LDH-Nb -13%; 0.4 g TMA-Nb
-20%; 0.8 g TMA-Nb for Mg Al-LDH-Nb -25% and 1.0 g TMA-Nb
Al-LDH-Nb -28%) were mixed and stirred for 20 min under N
3
Al-LDH-NO
aqueous solution (containing
for Mg Al-LDH-
3
slurry. Then, 2 mL
3
3
6
0
Nb
6
3
6
6
3
6
6
3
6
6
for
at
Acknowledgements ((optional))
Mg
3
6
2
room temperature. Then the mixture was transferred to a Teflon-lined
o
stainless steel autoclave (23 mL), kept in an oven at 100 C for 24 h and
This work was financially supported by the National Natural
Science Foundation of China (21671019, 21871026, 21771020),
3 6
left to cool down to room temperature. A white solid of Mg Al-LDH-Nb
composite was obtained after washing with water for 3 times and drying
973 Program (2014CB932103) and the Thousand Young
o
at 80 C for 12 h under vacuum.
Talents Program of China.
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Chemistry - A European Journal
10.1002/chem.201804523
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A novel decontaminating material,
Mg Al-LDH-Nb , was prepared by
3 6
immobilizing hexaniobate into layered
double hydroxide. As a versatile
3 6
catalyst, Mg Al-LDH-Nb , effectively
Jing Dong, Hongjin Lv, Xiangrong Sun,
Yin Wang, Yuanman Ni, Bo Zou, Nan
Zhang, Anxiang Yin, Yingnan Chi,* and
Changwen Hu*Author(s), Corresponding
Author(s)*
degrades a sulfur mustard simulant by
selective oxidation, a G-type and a V-
type nerve agent simulants by
Page No. – Page No.
A Versatile Self-Detoxifying Material
Based on Immobilized
Polyoxoniobate for Decontamination
of Chemical Warfare Agent Simulants
hydrolysis and perhydrolysis,
respectively. Furthermore, such
catalyst can be integrated onto textiles
to construct a portable and permeable
self-detoxifying clothing.
Layout 2:
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Author(s), Corresponding Author(s)*
((Insert TOC Graphic here; max. width: 11.5 cm; max. height: 2.5 cm))
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Title
Text for Table of Contents
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