Magnesium Exchanged Zirconium Metal-Organic Frameworks with Improved Detoxification Properties of Nerve Agents

Article abstract of DOI:10.1021/jacs.9b05571

UiO-66, MOF-808 and NU-1000 metal-organic frameworks exhibit a differentiated reactivity toward [Mg(OMe)₂(MeOH)₂]₄ related to their pore accessibility. Microporous UiO-66 remains unchanged while mesoporous MOF-808 and hierarchical micro/mesoporous NU-1000 materials yield doped systems containing exposed MgZr₅O₂(OH)₆ clusters in the mesoporous cavities. This modification is responsible for a remarkable enhancement of the catalytic activity toward the hydrolytic degradation of P-F and P-S bonds of toxic nerve agents, at room temperature, in unbuffered aqueous solutions.

Full text of DOI:10.1021/jacs.9b05571

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Communication
Magnesium exchanged zirconium metal-organic frameworks
with improved detoxification properties of nerve agents
Rodrigo Gil-San-Millan, Elena López-Maya, Ana E. Platero-Prats, Virginia Torres-Pérez, Pedro
Delgado, Adam Augustyniak, Min Kun Kim, Hae Wan Lee, Sam Gon Ryu, and Jorge A.R. Navarro
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b05571 • Publication Date (Web): 19 Jul 2019
Downloaded from pubs.acs.org on July 19, 2019
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Magnesium exchanged zirconium metal-organic frameworks
with improved detoxification properties of nerve agents
Rodrigo Gil-San-Millana, Elena López-Mayaa, Ana E. Platero-Pratsb, Virginia Torres-Péreza,
Pedro Delgadoa, Adam W. Augustyniaka,c, Min Kun Kimd, Hae Wan Leed, Sam Gon Ryud* and
Jorge A. R. Navarroa*
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aDepartamento de Química Inorgánica, Universidad de Granada, Av. Fuentenueva S/N, 18071, Granada, Spain.
bDepartamento de Química Inorgánica, Universidad Autónoma de Madrid, 28049 Madrid, Spain.
cDepartament of Chemistry, University of Wroclaw, Wroclaw, Poland.
dAgency for Defense Development, Yuseong P.O.Box35, Daejeon 34186, South Korea.
Supporting Information Placeholder
ABSTRACT: UiO-66, MOF-808 and NU-1000 metal-organic
frameworks exhibit
a differentiated reactivity towards
[Mg(OMe)2(MeOH)2]4 related to their pore accessibility.
Microporous UiO-66 remains unchanged while mesoporous
MOF-808 and hierarchical micro/mesoporous NU-1000
materials yield doped systems containing exposed
MgZr5O2(OH)6 clusters in the mesoporous cavities. This
modification is responsible for a remarkable enhancement of
the catalytic activity towards the hydrolytic degradation of P-
F and P-S bonds of toxic nerve agents, at room temperature,
in unbuffered aqueous solutions.
Organophosphonate based nerve agents are amongst the
most toxic compounds known to mankind. Their toxicity
arises from their easy penetration through human mucosa
and ulterior damage of the central nervous system by the
inhibition of acetylcholinesterase (AChE) enzyme1. Some
examples of nerve agents include soman (GD), tabun (GA)
and VX. Although declared illegal by international
agreements2, recent attacks with chemical weapons (CWA)
against civil and military populations have been reported3,4.
Consequently, protection and decontamination of these toxic
chemicals is a very important societal challenge. Their
hydrolytic degradation under environmental conditions
(room temperature and ambient moisture) is one of the most
convenient detoxification pathways, however, it will only
take place in the presence of a suitable catalyst.
Figure 1. Schematic representation of the postsynthetic
modification of the MOF mesopores with
[Mg(OMe)2(MeOH)2]4 to yield MgZr5O2(OH)6 clusters (Mg is
highlighted in green) and the ulterior detoxification of nerve
agents taking place in the pore structure of MOF-
808@Mg(OMe)2 and NU-1000@Mg(OMe)2.
The accessibility of the organophosphonates to the active
metal clusters is determined by the pore size and
connectivity of the MOFs. In this regard, MOF-80818 based
on the tritopic benzene-1,3,5-tricarboxylate (btc) linker and 6
connectivity with 1.8 nm and 2.2 nm pore sizes and NU-
100019 based on the tetratopic 4,4′,4″,4″′-(pyrene-1,3,6,8-
tetrayl)tetrabenzoate linker and 8 connectivity exhibiting a
hierarchical micro-mesoporous structure with 1.3 nm and 3.4
nm pore sizes, are ideally suited for the detoxification of
these chemicals. The high accessibility to the active catalytic
sites of these systems leads to almost instantaneous
degradation of nerve agents (i.e. GD and VX), under N-
ethylmorpholine basic buffer15,17. Nevertheless, the absence of
the buffer leads to diminished activity20, as a probable
consequence of nerve agent degradation products anchoring
Metal-organic frameworks (MOFs) are being thoroughly
studied for CWA detoxification as a consequence of their
high porosity and functional tailorability5-8. Among them,
zirconium MOFs based on Zr6O4(OH)4 clusters have shown
to be highly active in the hydrolysis of simulant9-14 and real
nerve agents15-17 as
a
consequence of the suitable
combination of highly Lewis acidic zirconium metal centers
and basic hydroxide/oxide groups.
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to the oxohydroxometal cluster14. This problem can be
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overcome by buffer heterogenization by formation of
polymeric organic amine/MOF composites21,22 and/or doping
with lithium alkoxides23,24 leading to highly efficient
detoxification catalysts, in unbuffered aqueous solutions.
Organic amines toxicity or lithium alkoxides air
sensitivityprompt the search of alternative catalysts able to
work under real environmental conditions.
In this report, we show that the pore size and distribution in
UiO-66 (microporous), MOF-808 (mesoporous) and NU-
1000 (hierarchical micro/mesoporous) materials determine
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the
reactivity
towards
the
bulky
reagent
[Mg(OMe)2(MeOH)2]4 and their detoxification performance
(Figure 1).
UiO-66, MOF-808 and NU-1000 were prepared according to
reported synthetic methods18,
25. The activated MOF
19,
materials were treated at room temperature with magnesium
methoxide methanolic solutions at 1:1, 1:2 and 1:4 Zr6:Mg
molar ratios to give rise to MOF@Mg(OMe)2 1:n materials
(Figure 1, SI). Characterization ofMg(OMe)2 doped MOFs
shows that crystallinity and porosity of UiO-66 remain
unaltered (Figures S2-3). By contrast,N2 isotherms of MOF-
808 and NU-1000 systems show a decrease of the second
step (mesopore region) upon increasing loadings of
Mg(OMe)2 (Figures 2a,b, S3). Density functional theory
(DFT) analysis ofpore size distribution agrees with a
diminution of accessible mesopore volume for MOF-
808@Mg(OMe)2 and NU-1000@Mg(OMe)2 systems (Figure
2c, d). MOF-808 exhibits adual pore distribution of 1.8 nm
(pore windows) and 2.2 nm (pore voids). For MOF-
808@Mg(OMe)2 1:1 and 1:2 systems we observe a decrease in
accessibility of the 2.2 nm pore voids with MOF-
808@Mg(OMe)2 1:4 system exhibiting a mainlymonotonic
1.8 nm pore size distribution (Figure 2c, S3b).
Figure 2. Modification of N2 adsorption isotherms at 77 K and
DFT pore size distribution (using a model of cylindrical pores
of
a metal oxide as implemented in Micrommeritics
software) for MOF-808 (black), MOF-808@Mg(OMe)2 1:1
(green), MOF-808@Mg(OMe)2 1:4 (purple) (a,c) and for
NU-1000 (gray), NU-1000@Mg(OMe)2 1:1 (blue) and NU-
1000@Mg(OMe)2 1:4 (orange) (b,d). SEM-EDX Zr and Mg
distribution for MOF-808@Mg(OMe)2 1:4.(e,g) and NU-
1000@Mg(OMe)2 1:4 (f,h). Open symbols denote the
desorption branch of the isotherms.
For NU-1000 we also observe the maintenance of the
micropore volume along with a diminution of mesopore
accessibility for NU-1000@Mg(OMe)2 1:1 and 1:2 with total
loss of mesoporosity for NU-1000@Mg(OMe)2 1:4 (Figure 2b,
d). Monte Carlo molecular modelling calculations26 were
carried out to assess the accessibility and most probable
adsorption configurations of [Mg(OMe)2(MeOH)2]4 (1.3 nm x
1.3 nm)27 into the pore structure of UiO-66, MOF-808 and
NU-1000. The results show that this reagent is unable to
enter the micropore structure of UiO-66 while it is
selectively incorporated into the mesopores of MOF-808 and
NU-1000 (Figure S20). SEM-EDX analyses of MOF-
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808@Mg(OMe)2 and NU-1000@Mg(OMe)2 are indicative of
Å, respectively. Moreover, the decrease in the signal centered
at ~1.6 Å, which is associated with Zr-O(formates) bond
distances at 2.28± 0.08 Å, can be attributed to partial loss
(50%) of formate groups upon Mg(OMe)2 doping (see
above).
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a highly homogeneous distribution of magnesium in the
MOF particles (Fig. 2e-h). XPS analyses (Figure S6) agree
with increasing amounts of magnesium upon Mg(OMe)2
loading into the MOF-808@Mg(OMe)2 and NU-
1000@Mg(OMe)2 systems up to 0.64 atoms of Mg per
The effect of the formation of MgZr5O2(OH)6 heterometallic
clusters on the SBUs of MOF-808@Mg(OMe)2 and NU-
1000@Mg(OMe)2 on the catalytic activity was evaluated
against the hydrolytic degradation of the nerve agent model
diisopropylfluorophosphate (DIFP) using a MOF:simulant 1:2
ratio, at room temperature, in unbuffered aqueous media
(Figure 4). The results show a significant enhancement of
catalytic activity of MOF-808 upon doping with Mg(OMe)2.
Indeed, the material MOF-808@Mg(OMe)2 formed with the
addition of 4 equivalents of Mg(OMe)2, exhibits a fast
degradation of the DIFP (t1/2 6.8 min, TOF 0.1 min-1) with ca.
10 folds enhancement of activity compared to pristine MOF-
808 (t1/2 43 min, TOF 0.01 min-1) (Figures 4a, S16 and Table
S3). For pristine NU-1000 (Figure 4b and Table S3) we
observe an initial fast detoxification which is followed by
reaction halting at ca. 90 % of DIFP degradation, indicative
of catalyst poisoning as a consequence of a probable
anchoring of DIFP degradation products to Zr-SBUs. By
contrast, NU-1000@Mg(OMe)2 gives rise to a steady and fast
degradation of DIFP (t1/2 2.7 min, TOF 0.26 min-1) with 100 %
detoxification after 35 min (Figure 4b and Table S3). As
expected, treatment of microporous UiO-66 with Mg(OMe)2
does not increase of the reaction rate (Figure S12, Table S3).
Filtration tests are indicative of the heterogenous nature of
the catalytic process (Figure S14). Moreover, the catalytic
activity of MOF-808@Mg(OMe)2 remains unaltered during
long storage periods while UiO-66@LiOtBu23 catalytic
activity notably decreases in a 30-days timeframe (Figure
S12), which agrees with the benefit of Mg incorporation into
the MOF SBUs in comparison with LiOtBu doping taking
place on its periphery.29 pH measurements for the MOF
catalysts suspensions before the DIFP degradation process
(Table S5) are indicative that the doped materials possess a
moderate basicity: pH 4.1 for pristine NU-1000 vs pH 7.7 for
NU-1000@Mg(OMe)2. However, the buffering effect of the
Mg(OMe)2 doping is limited with the pH values after the
degradation process lying close to the values of pristine
material under unbuffered conditions (3.6-5.3) (Table S5).
Moreover, plain Mg(OMe)2 solution (initial pH = 10) gives
rise to a limited hydrolysis of DIFP (Figure S12 and Table S3).
1
Zr6O4(OH)4 metal cluster. H NMR analyses of the digested
doped systems show 50% loss of formate residues for MOF-
808@Mg(OMe)2 as well as the absence of methoxide groups
for both MOF-808@Mg(OMe)2 and NU-1000@Mg(OMe)2
(Figure S4). The latter fact is indicative of the actual
conversion of Mg(OMe)2 into Mg(OH)2 on the pore surface
of the materials.
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Figure 3. k2-weighted χ(r) Zr K-edge EXAFS data collected
on pristine MOF-808 (black) and after modification with
Mg(MeO)2 on MOF-808@Mg(MeO)2 (green). The inset
shows the MgZr5O2(OH)6 SBU model in the doped system.
In order to better understand the precise location of the
magnesium centers within the Zr-MOF systems, Zr K-edge
EXAFS were collected at 77K on UiO-66 and MOF-808
before and after the treatment with the magnesium alkoxide.
The results show that UiO-66 remains unaltered while for
MOF-808 significant changes are noticed (Figures 3, S7-S11).
EXAFS data collected on MOF-808@Mg(OMe)2 evidence a
significant decrease in the intensity of the χ(r)-signal at ~3.1
Å which corresponds to the 3.54 Å Zr···Zr distances within
octahedral Zr-clusters, after application of appropriate
structural model and phase correction (Figure 3). The
intensity of this EXAFS signal is associated with the
coordination number (N) of Zr within the node – that is,
number of neighboring Zr atoms at a distance ~3.54 Å per
each Zr. For a regular octahedral Zr6-node within pristine
MOF-808, N = 4. For a structural model in which Mg is
attached to the Zr6-node on the second-shell via
hydroxyl/aqua groups, N would remain unaltered. Fitting of
N values are indicative of a decrease from 3.7 ± 0.6 for
pristine MOF-808 to 2.6 ± 0.4 for MOF-808@Mg(OMe)2.
These results are closely related to recently reported Zr6-xCex
heterometallic clusters in UiO-6628 and point to the actual
formation of MgxZr6-x heterometallic clusters. EXAFS data
can be fitted using an octahedral MgZr5 heterometallic
cluster (Figures S10-11), demonstrating the simultaneous
occurrence of Mg···Zr and Zr···Zr distances at 3.34 Å and 3.56
We have also essayed the catalytic performance of the
materials in N-ethylmorpholine buffered solutions (pH value
0f 9.2). The results show that pristine MOF-808 and MOF-
808@Mg(OMe)2 1:1 and 1:2 materials are very active under
these conditions, outperforming the results in unbuffered
aqueous media (Table S4, Figure S17). This behavior is
attributed to the large excess of N-ethylmorpholine which
acts both as sacrificial base and nucleophile. The observed
diminished activity for MOF808@Mg(OMe)2 1:4 system can
be related to the lower pore accessibility of this material.
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O
P
O
P
OH
OH
H2O
1
2
+
2x
+
HF
O
O
HO
OH
F
3
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t (min)
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(b)
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t (min)
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Figure 4. Disopropylfluorophosphate (DIFP) hydrolytic
degradation reaction. Profiles of catalytic hydrolytic
degradation of DIFP by MOF-808 (black) and MOF-
808@Mg(OMe)2 materials (1:1 green, 1:4 brown) (a) and NU-
1000 (gray) and NU-1000@Mg(OMe)2 materials (1:1 blue, 1:4
orange) (b) in unbuffered aqueous. 0.007 mmol of the
activated MOF were suspended in 0.5 mL of unbuffered
aqueous solution and subsequently DIFP (0.014 mmol) was
added.
Figure 5. Degradation reaction and reaction profiles of nerve
agents GD in 1:1 water:ACN mixture solution (a) and VX in 1:1
water:ethanol mixtures (b) upon exposure to MOF-808
(black),MOF-808@Mg(OMe)2 materials (1:1 green, 1:4
brown) and blank (white dots). 0.007 mmol of activated
MOF suspended in 0.5 mL of unbuffered solution with GD
(0.014 mmol) or VX (0.028 mmol) at room temperature.
Computational modelling of the VX nerve agent
accommodated in the mesopores of MOF-808@Mg(OMe)2
(c).
The results with DIFP simulant prompted us to study the
degradation of real nerve agents GD and VX in unbuffered
aqueous solutions. The experiments are indicative of a clear
improvement on P-F and P-S bonds cleavage upon MOF
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doping with Mg(OMe)2 (Figures 5, S18 and Table S3). Doped
ACKNOWLEDGMENT
MOF-808@Mg(OMe)2 (t1/2 11.6 min, TOF 0.06 min-1) exhibits
a better performance towards P-F hydrolysis in the GD
degradation (MOF:GD 1:2 ratio) compared to MOF-808 (t1/2
34.7 min, TOF 0.02 min-1) (Figure 5a). Noteworthy, MOF-
808@Mg(OMe)2 materials gives rise to instantaneous
hydrolysis of the P-S bond of VX (MOF:VX ratio 1:4) in 1:1
water ethanol mixture whereas pristine MOF-808 (t1/2 5.0
min, TOF 0.14 min-1) possesses a moderate activity in
unbuffered solutions (Figure 5b).
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The authors thanks Spanish MINECO (CTQ2017-84692-R),
EU Feder Funding, ADD’s research project (#912412201).
Comunidad de Madrid TALENTO grant (2017-T1/IND5148),
SOLEIL ROCK synchrotron radiation beamline (20180480)
and Dr. Valerie Briois for assistance.
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(10) Li, P.; Klet, R. C.; Moon, S.; Wang, T. C.; Deria, P.; Peters, A.
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9
For NU-1000 the detoxication results are similar although
somewhat more moderate. Indeed, GD degradation by NU-
1000@Mg(OMe)2 1:4 (t1/2 15.7 min, TOF 0.044 min-1)
outperforms NU-1000 (t1/2 53 min, TOF 0.013 min-1). In the
case of VX the results show a closely related behavior of all
materials with NU-1000@Mg(OMe)2 1:2 (t1/2 10.1 min, TOF
0.068 min-1) slightly outperforming pristine NU-1000 (t1/2 19
min, TOF 0.0363 min-1) (Figure S18). These results are
indicative that the improvement of NU-1000 activity upon
Mg(OMe)2 doping seems to be more limited compared to
MOF-808 material. The different behavior of MOF-
808@Mg(OMe)2 and NU-1000@Mg(OMe)2 can be
explained on the basis of the extent of Mg(OMe)2 doping on
both systems. As above mentioned, Monte Carlo
computational modelling for the incorporation of both the
doping agent and the toxic molecules on the pore structure
of MOF-808 shows that both reagent and toxic molecules are
located in the mesopore cavities (Figures S20-S22). By
contrast, NU-1000 doping agent is incorporated exclusively
onto the mesopore channels while toxic molecules can
diffuse through both micropores and mesopores (Figures
S20-S22). Consequently, for MOF-808@Mg(OMe)2 the toxic
molecules are fully exposed to MgZr5O2(OH)6 SBUs of
mesoporous cavities while for NU-1000@Mg(OMe)2 the
lower extent of magnesium doping gives rise to a lower
exposition to MgZr5O2(OH)6 SBUs with a concomitant lower
benefit of Mg(OMe)2 functionalization. We believe that the
increased basicity (increased nucleophilicity of OH-/O2-
residues) and charge gradients in the MgZr5O2(OH)6
heteronuclear cluster gives rise to a synergistic effect
affording polar P-X bonds (X= F, OR, SR) hydrolitic cleavage.
Summarizing, the different accessibility of the UiO-66,
MOF-808 and NU-1000 pore structures determine both their
reactivity towards [Mg(OMe)2(MeOH)2]4 and their
detoxification properties.
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ASSOCIATED CONTENT
Supporting Information
(11) Moon, S.; Liu, Y.; Hupp, J. T.; Farha, O. K. Instantaneous
Hydrolysis of Nerve-Agent Simulants with
Zirconium-Based Metal–Organic Framework. Angewandte Chemie
International Edition 2015, 54, 6795-6799, DOI:
10.1002/anie.201502155.
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Y.; Kim, S.; Hwang, D. Synthesis of a Zr-Based Metal-Organic
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a Six-Connected
Synthetic protocols, full characterization of materials and
details of catalytic studies. The Supporting Information is
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AUTHOR INFORMATION
Correspondings Authors
SGR sgryu@add.re.kr and JARN jarn@ugr.es
Notes
The authors have filled the patent: Korean patent application
number 10-2017-0107281 (2017, 24th Aug.).
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