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org Research Article

Ultrafast Degradation and High Adsorption Capability of a Sulfur

Mustard Simulant under Ambient Conditions Using Granular UiO-
66-NH2 Metal−Organic Gels
Chuan Zhou, Bo Yuan, Shouxin Zhang, Guang Yang, Lin Lu,* Heguo Li,* and Cheng-an Tao*
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ABSTRACT: Zirconium-based metal−organic frameworks (Zr-MOFs) have been

considered as prospective materials for the degradation of nerve chemical warfare agents
(CWAs) but show poor catalytic performance toward blister agents. Moreover, the
powder issues and the poor adsorption capability also remain as the major challenges for
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the application of Zr-MOFs in practical CWA detoxification. Herein, a series of defected

granular UiO-66-NH2 metal−organic gels are synthesized via adjusting the amount of
added concentrated hydrochloric acid for the decontamination of 2-chloroethyl ethyl
sulfide (2-CEES), a sulfur mustard simulant. The half-life of 2-CEES decontaminated by
defected granular UiO-66-NH2 metal−organic gels can be shortened to 7.6 min, which
is the highest reported value for MOFs under ambient conditions. The mechanism of
decontamination is that the amino group on the linkers in UiO-66-NH2 MOGs
undergoes a substitution reaction with 2-CEES to yield 2-(2-(ethylthio)ethylamino)-
terephthalic acid, which is less toxic and fixed in the frameworks. The recycling test corroborates that the granular UiO-66-NH2
xerogels possess good stability and reusability. Static adsorption and desorption tests show that UiO-66-NH2 xerogels possess a high
2-CEES vapor adsorption capacity of 802 mg/g after exposure for 1 d and only 28 wt % desorption capacity after air exposure for 7
d. The dual function of ultrafast degradation and high adsorption capability provide a firm foundation for using UiO-66-NH2
xerogels as a future protection media.
KEYWORDS: metal−organic gel, metal−organic framework, chemical warfare agent, 2-chloroethyl ethyl sulfide, detoxification, adsorption

1. INTRODUCTION MOFs are unsuitable for decontamination application because

Chemical warfare agents (CWAs) including nerve agents and
blistering agents continue to be a significant long-lasting threat
to both mankind and environment, although prohibited by an
international convention. Sulfur mustard (HD) is a canonical
vesicant that can cause severe erosion of epithelial tissue, injury
of the respiratory/digestive tract, and damage of visual systems
on contact.1−3 Due to the facile synthesis, high stability, and
low volatility, the production, storage, and distribution of HD
still exist to date.4,5 As a result, the development of advanced
materials for rapid detoxification of HD into less toxic products
remains to be a momentous concern.
Recently, metal−organic frameworks (MOFs) have gained
tremendous research attention as promising candidates for
CWA adsorption and decontamination owing to their
adjustable structures and functionalities, well-defined porous
structures, large surface area, and rich catalytic sites.6−8 These
isolated metal sites within nanoporosity endow MOFs with
strong reactivity toward CWAs. Although multifarious MOFs
have been proved to effectively detoxify HD in aqueous
solution,9,10 the poor aqueous solubility of HD and its normal
presence in the gaseous phase improve the difficulty of HD
decontamination in real-life scenarios.11,12 Moreover, most
of their low moisture stability and high cost.13
Zirconium-based metal−organic frameworks (Zr-MOFs) are
foreseen as promising materials for the degradation of CWAs
due to their ease and plentiful synthesis methods and
exceptional thermal, chemical, and mechanical stability.14−16
UiO-66-NH2 is a representative type of Zr-MOF that is
assembled by Zr6(μ3-O)4(μ3-OH)4 clusters with 2-amino-
terephthalic acid through coordination bonds. It exhibits
excellent activity on actual nerve agents and their simulants but
lower efficacy against the detoxification of blistering agents and
their simulants.17−20 Furthermore, the crystallization of UiO-
66-NH2 tends to form microcrystalline powders. The
practicability of powdered MOFs is greatly restricted due to
its particle aggregation, poor processability, mass-transfer
limitations, high air resistance, and difficult recycle.21−24 On
Received: February 8, 2022
Accepted: May 2, 2022
Published: May 12, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsami.2c02401

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Scheme 1. Schematic Illustration of the Formation of UiO-66-NH2 Xerogel and the Decontamination and Adsorption Process
of 2-CEES
the other hand, adsorption performance is another important
capability for defense against CWAs. However, due to the
small size of the internal pore size of the most MOFs, it is
difficult for many large-sized CWA molecules to enter MOFs’
interior, resulting in poor adsorption performance.
Metal−organic gels (MOGs), known as a class of extended
MOF architecture, have aroused extensive concern because of
their low density, large surface area, open metal sites, abundant
pore structure, gentle synthesis condition, and low cost of
production.25−29 MOGs can be manufactured as macroscopic
monoliths or granules by aggregating MOF particles into
tridimensional networks through metal−ligand coordination
associated with van der Waals interactions, hydrogen binding,
and π−π stacking.30,31 The critical point is to adjust synthetic
factors such as reactant concentration, temperature, time, and
solvent for the preparation of MOGs, which consisted of
nanoparticles.32−34 Compared to MOFs, MOGs can not only
surmount the limitations of MOF powders in practical
applications but also their hierarchically porous structure is
conducive to reducing diffusion barriers between substrates
and active sites, and accelerating the mass-transfer rate, which
endow MOGs with reinforced performance in adsorption and
catalysis; moreover, the hierarchically porous structure also
endows MOGs with special adsorption capacity, which makes
MOGs show good adsorption performance for CWAs. Very
recently, the macroscopic monolithic UiO-66-X xerogels for
decomposition of CWAs in solution have been reported by us
for the first time.35 However, to the best of our knowledge,
there have been investigations neither about the decontami-
nation of HD on MOGs in the pure phase nor the dual
function of decontamination and adsorption toward HD or its
simulants.
Herein, a series of defected granular UiO-66-NH2 MOGs
are prepared by using HCl as both modulator and activator
(Scheme 1). The effect of the modulator on structure,
degradation ability, and adsorption capability toward 2-
chloroethyl ethyl sulfide (2-CEES), a sulfur mustard simulant,
in the pure phase (without any solvents or additives) under
ambient conditions is investigated. The synthesized UiO-66-
NH2 xerogels are demonstrated to not only exhibit high
decontamination performance for 2-CEES and good reusability
but also show high adsorption capability toward 2-CEES. To
the best of our knowledge, this is the first demonstration of the
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use of MOGs to ultrafast decontaminate sulfur mustard
simulant in the pure phase and the first example of MOGs with
dual function of decontamination and adsorption.
2. EXPERIMENTAL SECTION
2.1. Materials. Zirconyl chloride octahydrate (ZrOCl2·8H2O,
99.9%), hydrofluoric acid (HF, 49%), dimethyl sulfoxide-d6 (DMSO-
d6, 99.9%), and deuterium oxide (D2O, 99.9%) are obtained from
Macklin Biochemical (Shanghai, China). 2-Aminoterephthalicacid
(NH2-BDC, 99%) is purchased from Alfa Aesar Chemical (Tianjin,
China). Anhydrous ethanol (99.8%) and N,N-dimethylformamide
(DMF, 99.9%) are obtained from Aladdin Chemical (Shanghai,
China). Potassium phosphate (K3PO4, 99%) and methanol (99.8%)
are purchased from J&K Chemical (Chongqing, China). Acetone and
concentrated hydrochloric acid (HCl, 37%) are obtained from
Sinopharm Chemical (China). 2-CEES (98%) and 2-hydroxydiethyl
sulfide (2-HEES, 98%) are purchased from Inno Chemical (Beijing,
China). All chemicals are used as received without further
purification.
2.2. Preparation of Defected Granular Zr-MOGs. The
defected granular Zr-MOGs are acquired with different amounts of
concentrated hydrochloric acid (HCl), which are labeled Zr-MOG-X
(where x = 0, 1, 4, 7, and 10), representing the volume of HCl added
to the reaction. Typically, ZrOCl2·8H2O (2.34 g, 7.25 mmol) and
NH2-BDC (0.92 g, 5 mmol) are weighed into a 100 ml Pyrex Schott
bottle and dissolved in DMF (30 mL) under sonication. Then, a
certain amount of HCl is added into the solution. Subsequently, the
bottle is placed in an oven after ultrasonic dispersion for 5 min. The
reaction temperature is held at 100 °C for 2 h. After cooling naturally,
the synthesized gels are washed three times with anhydrous ethanol
and dried in air at 30 °C. The obtained products are further washed
three times in acetone and methanol under sonication and then dried
at 30 °C overnight to produce a series of defected Zr-MOG-X, as
shown in Scheme 1. Zr-MOG-X is activated by heating to 110 °C
under vacuum for 12 h prior to use.
2.3. Degradation of 2-CEES. The “pure-phase” detoxification of
2-CEES in this paper indicates the direct destruction of 2-CEES by
Zr-MOG-X without any solvents or additives. 2-CEES (1 μL) is
spiked into 10 mg of desired Zr-MOG-X in a 4 mL vial and allows to
stand for various periods of time before extracting the residual 2-
CEES from the vial with acetonitrile. Specifically, 3 mL of acetonitrile
is added into the above vial and vigorously mixed with a shaker for 3
min. Subsequently, the extracted solution is passed through a 0.22 μm
filter using plastic syringes prior to GC analysis.
2.4. Adsorption and Desorption of 2-CEES. Closed vapor
adsorption. Three pieces of glass sheet with a diameter of 2 cm
containing about 30 mg of Zr-MOG-X were placed into a 200 mL
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Figure 1. SEM images and particle size distributions of (a) Zr-MOG-0, (b) Zr-MOG-1, (c) Zr-MOG-4, (d) Zr-MOG-7, and (e) Zr-MOG-10.
Insets: Photographs of the corresponding Zr-MOG-X.
Figure 2. (a) PXRD patterns, (b) TGA curves, (c) FT-IR spectra, and (d) N2 adsorption−desorption isotherms of the as-synthesized Zr-MOG-X.
reaction vessel. 2-CEES (250 μl) was placed in a 1 mL vial located
inside the reaction vessel. Then, the vessel was immediately sealed
using a ground glass stopper and kept at 25 °C for 1 day. Finally, the
vessel was opened, and the xerogels were weighed. The mass obtained
as a result of the interactions of 2-CEES vapors with the materials was
recorded and expressed as weight uptake (WU, mg/g).
Desorption. After the vessel was opened, the materials were left
inside a fume cupboard under ambient conditions, and after 2 and 7
days, they were weighed. A desorbed amount was calculated as a mass
difference of the materials before and after the desorption process.
2.5. Characterization. A Zeiss Sigma 300 (Germany) field-
emission scanning electron microscope was used for morphological
studies. PXRD patterns were collected on a diffractometer (Rigaku D/
MAX 2500V, Japan) with Cu Kα = 1.5406 Å. Thermogravimetric
analyses (TGA) were performed on a thermal analyzer (Q600 SDT,
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USA) under air flow at a heating rate of 5 °C/min up to 800 °C.
Nitrogen adsorption−desorption isotherms were measured at 77 K on
a Micrometer ASAP 2020 analyzer (USA). Nuclear magnetic
resonance (NMR) spectra were obtained from a Bruker 400M
spectrometer (Germany). Fourier transform infrared (FT-IR) spectra
were recorded on a spectrometer (PerkinElmer Frontier, USA). Gas
chromatography (GC) with a flame photometric detector (Agilent
Technologies) was used for quantitative analysis of residual 2-CEES
after the decomposition experiments (Agilent Technologies 6890,
USA). Gas chromatography−mass spectrometry (GC−MS, Agilent
Technologies 7890A, USA) with a 5975C detector (Agilent
Technologies) was used to analyze the degradation products.
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Figure 3. (a) Profiles of the removal efficiency. (b) Half-life of Zr-MOG-X. (c) Profiles of the removal efficiency after degradation of Zr-MOG-4
toward 2-CEES. (d) Proposed decontamination reaction of Zr-MOG-X and 2-CEES.
3. RESULTS AND DISCUSSION
3.1. Characterization of UiO-66-NH2 MOGs. Concen-
trated hydrochloric acid (HCl, 37%) possesses functions of
both modulation and activation.36,37 We adopt HCl as both a
modulator and an activator to synthesize a series of defected
granular Zr-MOG-X xerogels by adjusting the amount of HCl.
As shown in the insets of Figure 1, as HCl increases, the color
of macroscopic monolithic Zr-MOG-X (∼ a few millimeters)
changes from brown to light yellow. The surface morphology
and particle size of the as-synthesized Zr-MOG-X xerogels are
investigated by SEM observation (Figure 1). The SEM images
show the rough surface of all Zr-MOG-X samples, which are
primarily attributed to the densely packed nanoparticles. As
shown in Figure 1a, the Zr-MOG-0 xerogel synthesized
without a modulator has smallest particle size and exhibit an
aggregated and irregularly interconnected structure composed
of nanocrystals. As hydrochloric acid continues to increase, we
can clearly see that the borders of the nanoparticles that made
up the samples become clearer and the sizes of the
nanoparticles grow larger. Obviously, the particle sizes of the
Zr-MOG-X xerogels can be adjusted by the addition of a
modulator.
The crystalline characteristic of the synthesized Zr-MOG-X
products is demonstrated by PXRD measurements (Figure 2a).
It can be observed that there are obvious peaks at 7.3 and 8.5°
of the prepared Zr-MOG-X, broadly consistent with the
simulated theoretical PXRD patterns. The PXRD pattern of
Zr-MOG-0 shows the broadness and weakness of the
characteristic diffraction peaks, which indicate that Zr-MOG-
0 is of low crystallinity with the amorphous phase during the
gelation process of UiO-66-NH2 primary nanoparticles. The
diffraction peaks of the fabricated samples become sharper
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with the increase of the modulator, indicating that larger
crystallites are obtained. These results are also consistent with
the SEM data.
TGA analyses are performed to investigate the information
of missing linker defects of the as-synthesized Zr-MOG-X
samples, as shown in Figure 2b. The missing linker defects of
Zr-MOG-X can be calculated by Lillerud’s protocol.38 The
estimated numbers of the resulting missing linker of Zr-MOG-
0, Zr-MOG-1, Zr-MOG-4, Zr-MOG-7, and Zr-MOG-10 are
1.04, 1.87, 1.70, 1.50, and 1.00, respectively. The molar ratios
of HCOO− and NH2-BDC are obtained from 1H NMR spectra
(Table S1 and Figure S1-S7). Based on above both TGA and
1
H NMR data, the composition of Zr-MOG-X can be
calculated, and the results are listed in Table S2. On the
basis of crystal growth theory, Zr-MOG-0 is expected to
possess smaller particle size and higher defect density on
account of the faster rate of crystal nucleation. Contrary to
previous reports,39,40 we astonishingly find that with the
further increase of the modulator, fewer defects are generated
due to the enhancement of the crystallinity for the Zr-MOG-X
(X = 1, 4, 7, and 10), which correspond well with the PXRD
data.
The FT-IR spectrum is further performed to substantiate the
consequence of the prepared xerogels (Figure 2c). The FTIR
spectra of all the samples are consistent with one another. The
overall resultant Zr-MOG-X delivers the −NH2 asymmetric
and symmetric stretching characteristic peaks at 3468 and
3356 cm−1, the two distinctive peaks at 1567 and 1384 cm−1 of
carboxyl groups, and the Zr−O stretching vibration peaks in
the range of at 800−600 cm−1, in good agreement with
previous reports.41 By comparing these samples, it can be
found that the intensity of peaks at 1258 cm−1 corresponding
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Table 1. Comparison of Various Materials Used as Protection Media for the Detoxification of HD or Its Simulant 2-CEES
materials material weight, mg material amount, μmol agent volume, μL half-life refs
MgO 111 2754.3 HD, 5 17.8 h 50
CaO 115 2050.6 HD, 5 8.7 h 51
Al2O3 80 784.6 HD, 4 6.3 h 52
TiO2 200 2504.1 HD, 5 3.8 h 53
MnO2 50 575.1 2-CEES, 2 4.6 h 54
VOx 200 2007.2 HD, 5 6.3 h 55
NiO NpsAg-clinoptilolite zeolite 300 2-CEES, 8 7.3 h 56
POMs/Carbon 100 HD, 1 15 h 57
POMs/Al2O3 100 HD, 5 214 min 58
HKUST-1 50 75.9 2-CEES, 5 16.1 min 59
Ag NPs@HKUST-1 30 HD, 4 15 min 60
UiO-66 40 24.0 2-CEES, 6 1.3 h 61
UiO-66-NH2@PAN-2h 20 2-CEES, 5 <0.5 h 20
UiO-66-NH2@PAN-3h 20 2-CEES, 5 <0.5 h 20
Zr-MOG-0 10 5.7 2-CEES, 1 8.2 min this work
Zr-MOG-1 10 5.7 2-CEES, 1 7.6 min this work
Zr-MOG-4 10 5.7 2-CEES, 1 12.6 min this work
Zr-MOG-7 10 5.7 2-CEES, 1 25.4 min this work
Zr-MOG-10 10 5.7 2-CEES, 1 33.7 min this work

to the δ(OH)+ δ(CH) mode weakens gradually with the
increase of the modulator as fewer defects are introduced.
The N2 adsorption−desorption isotherms of Zr-MOG-X are
displayed in Figure 2d. Each of the samples manifests a
representative IV hysteresis loop, which reveals the existence of
micro-mesoporosity in the structure of gels. As shown in Table
S3, with the increasing amount of modulator, the Brunauer−
Emmett−Teller (BET) surface area of Zr-MOG-X is first
significantly increased to 1178 m2 g−1 and then slightly
decreased to 1117 m2 g−1. The same tendency as the BET
surface area is observed with the pore volume. Furthermore,
the NLDFT and BJH pore diameter distributions are displayed
in Figures S8 and S9, respectively. It can be obviously observed
that both the strength of peaks for NLDFT pore diameter
distributions and the pore diameter for BJH pore diameter
distributions are increased. Therefore, based on the above
results, it can be reconfirmed that the modulator (HCl)
influences the growth of the MOF during the progress of self-
assembly of the infrastructure architecture building blocks.
3.2. Detoxification Performance toward 2-CEES. The
decontamination performance of the defected granular Zr-
MOG-X is investigated by conducting the detoxification of the
sulfur mustard simulant 2-CEES in the pure phase at room
temperature. The conversion profiles of the as-synthesized Zr-
MOG-X MOGs are presented in Figure 3a as a function of
time. The results demonstrate that initial degradation reactions
are faster, followed by a steady-state reaction. The fast initial
reaction is due to the rapid adsorption and diffusion of 2-CEES
within the pores and its interaction with the accessible reactive
sites. The restricted surface reaction prevails over the initial fast
reaction when the reactive sites are depleted. The Zr-MOG-0
and Zr-MOG-1 samples show outstanding decontamination
performance toward 2-CEES with half-lives of about 8 min.
The decontamination performance of Zr-MOG-X gradually
deteriorates as the increase of the amount of HCl added during
synthesis. The values of half-life for all the Zr-MOG-X
materials are shown in Figure 3b. Specially, Zr-MOG-0 with
unsatisfactory porosity and missing linker defects exhibits
fastest 2-CEES degradation rate with a half-life of 8.2 min and
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nearly 80% conversion within 30 min, which may be attributed
to the smaller particle size of the samples.
The stability and reusability are important properties of
decontaminants. The stability of Zr-MOG-X (X = 4, 7, or 10)
after the decontamination of 2-CEES is valuated by PXRD and
N2 adsorption−desorption isotherms (Figure S10). Signifi-
cantly and impressively, the PXRD patterns of the collected Zr-
MOG-X show that the crystal structure of Zr-MOG-X can be
essentially maintained. Furthermore, the N2 adsorption−
desorption isotherms indicate that Zr-MOG-X exhibits the
same type IV behavior as the pristine Zr-MOG-X and show an
almost constant surface area. Therefore, Zr-MOG-X can be
considered as a renewable decontaminant suitable for 2-CEES
degradation. A reusability test is further carried out to
demonstrate. The recyclable Zr-MOG-4 displays a very similar
conversion profiles to fresh Zr-MOG-4 in the beginning and
further a little lower than that of fresh Zr-MOG-4, as presented
in Figure 3c, suggesting the preservation of most decontami-
nation performance. Both these excellent stability and
reusability further ensure defected granular UiO-66-NH2
metal−organic gels for CWA removal as a promising
candidate.
In order to investigate the mechanism of degradation of 2-
CEES by Zr-MOG-X, it is necessary to validate the
decomposition products extracted with acetonitrile by GC−
MS analysis. Take Zr-MOG-4 as an example (Figure S11), the
data illustrates that 2-hydroxyethyl ethyl sulfide (2-HEES)
(with m/z values at 106, 75, and 47) as the sole hydrolysis
product of 2-CEES, is monitored. This hydrolysis product with
relatively low toxicity is usually the goal of chemical
decontamination of 2-CEES. Similar results are also observed
by other researchers in several studies.20,42,43 Unfortunately,
the amount of the hydrolysis product is extremely low. In
addition to the hydrolysis product, the residual 2-CEES
amount (with m/z values at 124, 109, 89, 75, and 47) is more.
According to the GC analysis, about 83% of 2-CEES has been
degraded. To find out the degradation products, the residual
Zr-MOG-4 solid is digested with 750 μL of 1.8 M HF in
DMSO-d6. As shown in Figure S12, the unperturbed 2-amino
terephthalic acid linker and the 2-(2-(ethylthio)ethylamino)-
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Figure 4. 2-CEES adsorption capacity of Zr-MOG-X at 298 K (a) and the amounts desorbed expressed as weight change of the samples exposed to
air for 2 d and 7 d (b).
terephthalic acid reaction product were observed. The reaction
is shown in Figure 3d. The ratio of these two species is
determined by the ratio of H atoms at 7.79 and 7.86 ppm. As
listed in Table S4, the reacted linkers achieve 19% among all
linkers, that is, 1.14 per 6 linkers. Considering that the Zr-
MOG-4 MOG has the linker missing defects, there is nearly
one reacted 2-CEES molecule in each periodic pores.
Assuming that the Zr-MOG-4 MOG has the ideal formula of
UiO-66-NH2, the amount of reacted 2-CEES can be estimated
to be 6.5 μmol, which is about 76 mol % of original 2-CEES. It
can be concluded that most of the 2-CEES is decontaminated
by reaction with amino of linkers, and a very small part is
hydrolyzed to 2-HEES.
Previous reports44−49 have revealed that the two factors of
the size of MOFs and defect degree are often intertwined to
affect the decontamination performance of MOF powders in
solution. The smaller the size of MOF crystals is, the more
specific surface area/active sites are available. In addition, the
greater the degree of MOF defects (such as missing linkers or
nodes) is, the better the decontamination performance of
MOF is. The three-dimensional relationship diagram of the
half-life with the sizes of the MOF Zr-MOG-X MOGs and
their defect degrees are shown in Figure S13. For the other
MOGs (i.e., Zr-MOG-1, Zr-MOG-4, Zr-MOG-7, and Zr-
MOG-10), with the increase of the amount of HCl, the size of
the obtained MOGs increased, the defect density also
increased, and the half-life of the degradation reaction
decreased, which is consistent with the previous reports.
Besides, in the MOG case, the intergranular porosity is another
key factor for the catalysis performance. We further investigate
the properties and the 2-CEES degradation performance of
selected Zr-MOG-0 and Zr-MOG-4 xerogels and their
corresponding grinding powder. Compared with Zr-MOG-0
and Zr-MOG-4 xerogels, the porosity, crystallinity, and
degradation performance of milled Zr-MOG-0 and Zr-MOG-
4 powder decreased obviously (Figures S14−S16). This can be
explained by the fact that mechanical grinding destroys part of
the porous structure of xerogel, resulting in decreased porosity
and crystallinity and increased mass-transfer resistance.
In order to evaluate the degradation performance of the as-
synthesized Zr-MOG-X MOGs, a comparison is made between
their performance and that of some typical reference materials
(metal oxides, zeolites, POMs, and MOFs), as shown in Table
1. It should be noted that the amount of these reference
materials used for HD or 2-CEES decontamination in the
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literature is usually about 100 mg (∼2000 μmol vs 4−5 μL
agent) and the values of the half-life are generally in the range
of the tens of minutes to several hours. Notably, Zr-MOG-X
can be used directly for 2-CEES decontamination with less
amount (10 mg vs 1 μL 2-CEES) and lower half-life (about 8
min), highlighting the advanced degradation of our developed
Zr-MOG-X materials.
3.3. Adsorption Capability of Zr-MOG-X Xerogels.
The adsorption capabilities of all Zr-MOG-X xerogels against
the vapors of 2-CEES are evaluated based on the WUs after the
exposure. The results are presented in Figure 4a. The
adsorption capacity of Zr-MOG-X has been significantly
improved with the increasing amount of the modulator, but
a decrease is observed by further increasing the amount of
modulator after a 1 day exposure. This trend indicates the
trade-offs between adsorption capacity and material formula-
tions. Interestingly, Zr-MOG-0 shows outstanding degradation
activity toward 2-CEES benefiting from its small particle size
but lower adsorption capacity due to its smaller pore volume.
Zr-MOG-4 reveals the highest WU value of 802 mg/g after 1
day of exposure, which demonstrates a much higher value than
that of various active inorganic nanomaterials62−64 with WU
values in the range of 90−210 mg/g and porous carbon textiles
under the same condition with a WU value of 255 mg/g.65 To
investigate whether MOG would degrade 2-CEES after
physical adsorption of 2-CEES, they were extracted and
quantified with GC. As shown in Figure S17, there were
neither an obvious peak of the hydrolyzed product, 2-HEES,
and nor peaks of other substances, and 2-CEES was quantified
to be 23.4 mg in total, which is almost equal to the value
evaluated by weight. This indicates that the MOG hardly reacts
with 2-CEES after adsorption of 2-CEES vapor, which is not
consistent with the situation of UiO-66-NH2 powders66 or
fabrics.20
Another important feature of protection materials is their
ability to retain adsorbed CWA on their surface/in the porous
structure. Though there have been few reports on the
adsorption of CWA vapors by MOFs,42,67 the evaluation of
desorption process related to two critical factors for real
applications including the released absolute amount and the
percent of the desorbed amount of toxic vapors has not been
involved yet. The weight change of the Zr-MOG-X exposed to
2-CEES vapors for 1 day is monitored after the air desorption
tests for 2 d and 7 d, respectively. The absolute values of
weight losses are included in Figure 4a, and the weights of Zr-
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MOG-X themselves are stable (Figure S18). The weight
changes after air exposure are presented in Figure 4b. Among
the samples desorbed for 7 d, Zr-MOG-1, Zr-MOG-4, Zr-
MOG-7, and Zr-MOG-10 display a similar retained absolute
amount adsorbed. The removed percentage of the adsorbed
species in the case of Zr-MOG-10 is evidently lower than that
of Zr-MOG-1, Zr-MOG-4, and Zr-MOG-7. Thus, for the
protection against the CWA vapors, Zr-MOG-10 can be
considered as the most competitive protection media for real
applications.
4. CONCLUSIONS
A series of granular Zr-MOG-X xerogels with variable
nanoparticle size and defect density are synthesized with
dramatically enhanced surface area and pore volume by tuning
the amount of concentrated hydrochloric acid and investigated
for the destruction of the sulfur mustard simulant, 2-CEES. All
the Zr-MOG-X xerogels show outstanding performance for 2-
CEES degradation with the half-life less than 8.0 min. This is
the highest value reported to date for MOF under pure-phase
reaction conditions. The mechanism of decontamination is
that the amino group on the linkers in UiO-66-NH2 MOGs
undergoes a substitution reaction with 2-CEES. The granular
Zr-MOG-X xerogels also demonstrate good stability and
reusability. Static adsorption and desorption tests demonstrate
that Zr-MOG-X xerogels have both a high WU value of up to
802 mg/g and low desorption capacity with only 28 wt %.
Accordingly, we conclude that granular Zr-MOG-X xerogels
can effectively overcome the issues of Zr-MOF powders and
demonstrate a remarkable prospect in future CWA military
applications.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.2c02401.
1 Toxicity of Mustard Gas: A Concise Review. Toxicol. Lett. 2021, 343,
H NMR analysis of Zr-MOG-X; missing linker
evaluated from TGA curves; porosity data of the
defected Zr-MOG-X; pore size distributions; relation-
ship diagram of the half-life with the sizes of the MOF
catalysts and their defect degrees; characterization and
the 2-CEES removal efficiency of Zr-MOG-0/4 and
their milled powder; N2 adsorption−desorption iso-
therms and PXRD patterns of Zr-MOG-X after 2-CEES
degradation; and GC−MS analysis of acetonitrile
extraction of 2-CEES degraded by Zr-MOG-4 (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Lin Lu − State Key Laboratory of NBC Protection for Civilian,
Beijing 102205, PR China; Email: 18911066102@189.cn
Heguo Li − State Key Laboratory of NBC Protection for
Civilian, Beijing 102205, PR China; Email: liheguo1972@
126.com
Cheng-an Tao − College of Liberal Arts and Science, National
University of Defense Technology, Changsha 410073, China;
orcid.org/0000-0003-4720-1064; Email: taochengan@
nudt.edu.cn
Authors
Chuan Zhou − State Key Laboratory of NBC Protection for
Civilian, Beijing 102205, PR China
23389
www.acsami.org Research Article
Bo Yuan − State Key Laboratory of NBC Protection for
Civilian, Beijing 102205, PR China
Shouxin Zhang − State Key Laboratory of NBC Protection for
Civilian, Beijing 102205, PR China
Guang Yang − State Key Laboratory of NBC Protection for
Civilian, Beijing 102205, PR China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.2c02401
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We acknowledge the Scientific Compass (https://www.
shiyanjia.com/) and the Analytical Instrumentation Center of
Peking University for their technical support in character-
ization. This work was financially supported by the National
Natural Science Foundation of China (no. 22075319) and the
Huxiang Young Talent Project (2020RC3033).
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