Microwave-assisted activation and modulator removal in zirconium MOFs for buffer-free CWA hydrolysis

Article abstract of DOI:10.1039/c7dt03616g

A novel, facile and efficient method was developed for the activation of acetic acid modulated zirconium MOFs. The protocol involves briefly heating the material in water using microwave irradiation. MOF-808, DUT-84 and UiO-66 were all activated in this manner to remove the modulator and organic solvent from the framework post synthesis, with retention of MOF integrity post activation. The degree of activation was characterised by the use of TGA and NMR. The catalytic activity of the activated MOFs and their non-activated counterparts was investigated for chemical warfare agent (CWA) hydrolysis. Upon activation, an increase in the rate of hydrolysis was observed in the degradation of CWA simulant dimethyl 4-nitrophenyl phosphate (DMNP). MOF-808 and DUT-84 were also screened as catalysts for the hydrolysis of the V-series agent VM, with remarkable half-lives obtained for MOF-808 in the absence of any buffers. Currently employed MOF activation procedures involve the use of additional organic solvents post synthesis; we believe this method to be ideally efficacious for the organic desolvation of zirconium MOFs and removing modulator additives.

Full text of DOI:10.1039/c7dt03616g

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
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Microwave-Assisted Activation and Modulator Removal in
†
Zirconium MOFs for Buffer-Free CWA Hydrolysis
a
b
b
a
*ac
Received 00th January 20xx,
Accepted 00th January 20xx
Y. Kalinovskyy , N. J. Cooper , M. J. Main , S. J. Holder and B. A. Blight
A novel, facile and efficient method was developed for the activation of acetic acid modulated zirconium MOFs. The
protocol involves briefly heating the material in water with using microwave irradation. MOF-808, DUT-84 and UiO-66
were all activated in this manner to remove the modulator and organic solvent from the framework post synthesis, with
retention of MOF integrity post activation. The degree of activation was characterised by the use of TGA and NMR. The
catalytic activity of the activated MOFs and their non-activated counterparts was investigated for chemical warfare agent
DOI: 10.1039/x0xx00000x
www.rsc.org/
(CWA) hydrolysis. Upon activation, an increase in the rate of hydrolysis was observed in the degradation of CWA simulant
dimethyl 4-nitrophenyl phosphate (DMNP). MOF-808 and DUT-84 were also screened as catalysts for the hydrolysis of the
V-series agent VM, with remarkable half-lives obtained for MOF-808 in the absence of any buffers. Currently employed
MOF activation procedures involve the use of additional organic solvents post synthesis, we believe this method to be
ideally efficaceous for the organic desolvation of zirconium MOFs and removing modulator additives.
these. Zirconium MOFs are typically desolvated by the use of
solvent exchange techniques where the MOF is soaked in a low
boiling point organic solvent, this solvent is then exchanged a
Introduction
Zirconium Metal-organic frameworks (MOFs) are highly
1
,2
3,4
modular and robust structures which exhibit a high degree
number of times before subjecting the material to a high
dynamic vacuum. Modulators can be removed either by high
temperatures, which can compromise the structural
5
of porosity. These properties have allowed zirconium MOFs
,6
7
to find uses in applications such as gas sorption, drug
,8
2
3,24
9
,10
11,12
integrity,
alternative moiety.
the activation of three known zirconium MOFs; DUT-84 (6-
or by post-synthetic exchange (PSE) for an
delivery
and fluorescence sensing.
4
Additionally, the
2
2,25
+
Herein, we present a facile method for
abundance of Lewis acidic Zr sites on the Zr6 secondary
building unit (SBU) has made these frameworks an attractive
2
6
27
1
3,14
connected), MOF-808 (6-connected), and defective UiO-
2
66. The protocol utilises microwave irradiation and water to
facilitate the removal of the acetic acid modulator from the Zr
material for organic catalysis.
A number of solvent free and
routes have been reported for zirconium
MOF assembly, however, the vast majority of methods rely on
1
1
5,16
mechanochemical
6
1
7,18
SBU. Employing these MOFs with hydrated vacancies, we
further demonstrate enhanced catalytic activity in the
hydrolysis of selected organophosphorus compounds.
hydrothermal synthesis.
These hydrothermal techniques
often employ high boiling point solvents such as DMF and a
1
monodentate acid modulator.
9,20
The modulator is essential
Zirconium MOFs with missing linker defects/coordination
31
vacancies, such as MOF-808,
for controlling the assembly of the structure and can readily
influence the pore size, dimensionality and even the
2
8,29
30
Nu-1000 and UiO-67-NH
2
1
9,21
have been shown to effectively catalyse the degradation of
organophosphorus chemical warfare agents (CWAs). In the
presence of N-ethylmorpholine buffer, dimethyl 4-nitrophenyl
concentration of defects in the framework.
Post synthesis,
additional steps are required to ‘activate’ the MOF. Activation
can simply refer to the desolvation of the MOF pores (i.e.
removal of organic reaction solvent), it can also be used to
describe the extraction of any free or bound modulator used
3
2,33
phosphate (DMNP; a well-established hydrolysis simulant)
closely mimics the hydrolytic breakdown of V-agents such as
3
1
2
1,22
VX and VM. We used this system to probe the degradation
rates of the activated catalysts and compared them to the
degradation rates of their as-synthesised counterparts. As
hypothesised, a modest increase in the rate of hydrolysis was
observed using the activated material. We then subsequently
tested MOF-808 and DUT-84 on the V-series agent VM
during synthesis to create vacancies.
For clarity, in this
paper we will take the meaning of activation to be both of
(diethylaminoethyl O-ethyl methylphosphono-thioate). Unlike
DMNP, the screening of VM was conducted in the absence of
buffer as the minimisation of additional reagents is essential
for enhancing the practical application of these catalysts. Both
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the as-synthesised and activated variants of MOF-808 were same ratios were used, the only difference was that the testing
highly successful at hydrolysing VM. The activated variant of was conducted in the absence of any buffer.
DUT-84 was also successful at hydrolysing VM, albeit at a
slower rate than the MOF-808 variants.
Results and Discussion
Table 1. A comparison of the degree of activation achieved for each MOF based on the
Experimental
1
ratio of acetate to ligand, as observed by H NMR
Material
nMOF-
808
aMOF-
808
nDUT-
84
aDUT-
84
nUiO-
66
aUiO-
66
All reagents and solvents were used without further
purification. DMNP was prepared and purified using a Acetate:Ligand ratio
2
previously reported procedure. MOF-808, DUT-84, and
1.62
0.26
0.5
0.6
0.33
1.0
0.22
1.4
0.07
0.6
8
26
Acetate per unit
Exchange Efficiency
Acetate removed
3.25
1.9
2
1
84.6%
2.75
5.5
47.3%
0.9
57.1%
0.8
defective UiO-66 (Fig. 1) were all synthesised using slightly
modified procedures using acetic acid to modulate each of
a
Acetate-free sites
5
1.4
their syntheses. (S2–S3, ESI†)
a
The amount of coordination sites per formula unit cell that are free of modulator, this
only applies to the activated counterpart of each MOF.
General procedure for Microwave assisted activation
The degree of activation was initially investigated by digesting
each of the as-synthesised MOFs (henceforth termed non-
activated (n); ie. nMOF-808) and their activated (a; ie. aMOF-
A CEM Explorer Microwave Reactor with dynamic power
cycling was used for all MOF activation steps. 200 mg of as
synthesised MOF (nUiO-66, nDUT-84 or nMOF-808) was
suspended in 7 ml of distilled water in an 11 ml microwave
vessel. The vessel was sealed and placed in a microwave
8
2 4
08) counterparts in a mixture of DMSO/D SO . Proton NMR
spectra were then acquired and the ratio of ligand/acetic acid
was determined for each MOF, as shown in Table 1.
o
reactor where it was activated at 150 C for 20 minutes with
heavy stirring using a automated power program to regulate
o
the temperature at 150 C. After cooling to room temperature,
2
the MOF was vacuum filtered, washed with H O 3 x 10 ml and
acetone 3 x 10 ml to yield the activated material, aUiO-66,
aDUT-84 or aMOF-808.
nMOF-808
aMOF-808
1
Figure 2. A H NMR (in DMSO/D
2
SO
4
) overlay showing acetic acid (green), digested
nMOF-808 (black), free BTC ligand (red) and the digested aMOF-808 (blue).
Figure 1. Formula units and graphical representations of the activated zirconium MOFs.
Partial removal of the acetate modulator was achieved for all
activated MOFs. The complete extraction of residual DMF used
in synthesis was also observed for all activated samples. Each
DMNP and VM hydrolysis procedure
Zr
6
SBU can coordinate 12 carboxylate moieties in total.
2
8
The following procedure was used to probe the hydrolysis
rates of the as-synthesised MOFs and their activated
counterparts. An NMR tube was charged with DMNP, 20 µL
The most efficient exchange was achieved for MOF-808
(Fig. 2) which has a strut connectivity of 6, with 2.75 acetate
ligands removed per unit, leaving 5.5 free coordination sites.
2
6
(0.09 mmol). The MOF catalyst (0.11 µmol, 1.25 mol%) was
DUT-84 also has a strut connectivity of 6, but only 0.9
acetates per formula unit were removed resulting in 5
unmodulated sites. This is because the non-activated material
possesses just 2 acetate modulated sites. aUiO-66 had the
lowest quantity of acetate removed per unit owing to its
then added to the tube. 0.1 ml of D O along with 0.5 ml of 0.1
2
M N-ethyl morpholine aqueous buffer (0.1M) was then added
to the tube. The tube was inverted 3 times and immediately
loaded into an NMR auto-sampler and the first spectrum was
obtained within 3 minutes of the reaction commencing. The
sample was then cycled on the auto-sampler to collect
subsequent data points. For VM, the same procedure and the
2
1
higher strut connectivity requiring 10 sites, this meant that
there were fewer available coordination vacancies for the
modulator to occupy.
2
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-
1
o
Figure 3. TGA trace for the non-activated and activated counterparts of each MOF. Heating rate: 5 °C min in N
2
, 30 min isotherm at 150°C followed by a ramp to 500 C. A value
for the % weight loss post isotherm until end of the final ramp is shown on the TGA trace for each material.
The optimum microwave temperature for the activation to mass % difference. This value can be ascribed to the activation
o
occur was found to be 150 C, and reinforced by the process removing approximately 2.75 equivalents of acetate
observation of PXRD data showed that there was no loss of from each formula unit of the MOF (Table 1), and the largest
crystallinity after the activation procedure (Fig. S10–S12, ESI†). quantity of the three MOFs. This was followed by DUT-84 and
The activation of DUT-84 resulted in a transition to a then UiO-66, respectively. The thermal mass % difference for
‘
desolvated’ phase which was observed by the original authors each of the analysed MOFs was in agreement with the
26
upon utilising their own activation procedure. At higher quantity of acetate removed, as determined by NMR.
o
temperatures (160-200 C), the MOFs were converted to an
o
amorphous product, while at lower temperatures (120-140 C),
Table 2. A comparison of the weight loss observed during TGA analysis for the non-
activated and activated MOFs.
a significantly reduced exchange efficiency was observed. The
same was also true for increasing/ decreasing the duration of
nMOF-
08
aMOF-
808
nDUT-
84
aDUT-
84
nUiO-
66
aUiO-
66
8
the activation in the microwave reactor, where 20 minutes at
o
50 C was found to offer the best exchange without
a
Mass % Remaining
88.3%
25.0%
28.3%
89.3%
16.2%
18.1%
10.2%
93.0%
18.9%
20.3%
93.5%
12.3%
13.2%
7.1%
92.9%
14.8%
15.9%
92.1%
9.3%
10.1%
5.8%
1
b
Mass % Loss
degradation of crystallinity.
c
Rel. mass % Loss
Thermal data was also obtained for each of the activated mass % Difference
d
and non-activated samples (Figure 3). After the initial ramp,
o
each sample was subjected to a 30-minute isotherm at 150 C
a
o
b
Mass % Remaining after maintaining a 150 C isotherm. Mass % Loss after second
c
ꢀ
d
ramp. Relative mass % loss observed ( ꢂ ∗ 100. Difference in relative mass % Loss
ꢁ
to observe and ensure the complete removal of any adsorbed
moisture and residual solvent, thus leaving only the SBU, the
between the activated and non-activated materials.
struts and any coordinated modulator. The post-isotherm After determining the degree of activation using NMR, and
mass loss was then noted for each sample (Table 2). nMOF- confirming the loss of modulator using TGA, we decided to
8
08 and aMOF-808 showed the greatest mass % loss after the investigate the hydrolytic capabilities of the activated MOFs
second ramp. The large mass % loss for nMOF-808 can be and compare them to their non-activated counterparts.
attributed to the framework having the largest amount of
Zirconium MOFs, particularly those with coordination
bound acetate (Table 1). The second largest mass loss was defects, have been shown as highly effective hydrolysis
observed for the DUT-84 variants. The UiO-66 variants showed catalysts for the degradation of V- and G-series nerve
3
0,33
the smallest reduction mass % after the second ramp, this is agents.
DMNP, buffered with an aqueous solution of N-
likely due to the framework having the smallest number of ethyl morpholine, has been established as good simulant
bound acetate per unit cell. Particularly interesting was the system for mimicking the hydrolysis of VX (diisopropyl-
greater thermal stability of all activated MOFs after the second aminoethyl O-ethyl methylphosphonothioate) in solution, with
ramp (Figure 3). Unsurprisingly, MOF-808 showed the greatest good
agreement
in
the
degradation
rates.
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Figure 4. a) Reaction scheme for the hydrolysis of DMNP and a plot showing the hydrolysis of DMNP over time in the presence of the various MOF catalysts. Each set of data was
obtained in triplicate and is shown with standard deviation error bars. b) Reaction scheme showing the selective hydrolysis of the agent VM along with a degradation plot showing
the hydrolysis of VX over. Inset: highlights the slight difference between nMOF-808 and aMOF-808.
The buffered degradation of DMNP was found to best follow a pre-and post-microwave activation, and further demonstrates
first order rate model (Fig. S13 ESI†).
the utility of this modulator removal procedure.
3
4
Figure 4a shows the results obtained for the hydrolysis
The average pore limiting diameter in UiO-66 is ca. 5 Å,
study which was conducted with the activated and non- which is smaller than the molecular size of DMNP. The
activated MOFs. aMOF-808 was the most effective catalytic activity is therefore restricted to just the surface of
-3
-1
degradation catalyst (k = 9.5 x 10 s ), closely followed by the framework, significantly reducing the number of accessible
-3
-1
35
nMOF-808 (k = 8.8 x 10 s ). This can be explained by the 6- active sites. Among the 3 MOFs tested, a general trend was
connected nature of aMOF-808 along with the 5.5 acetate-free observed where a higher pore limiting diameter correlated
coordination sites (Table 1). These catalytic sites are Lewis with a higher rate constant k for DMNP hydrolysis (Fig. S14–
acidic and are able to facilitate the hydrolysis of the substrate S15, ESI†). This correlation, comprising of only three data
in the presence of H O. nMOF-808 performed slower in the points, is tempered by the fact that the particle size for MOF-
2
initial stage of the reaction but still performed relatively well 808 is much smaller than for DUT-84 resulting in much more
compared to the other tested materials. This performance can accessible surface area for reactivity on the surface of MOF-
be attributed to nMOF-808 framework possessing, on average, 808 (Fig. S16, ESI†).
2.75 vacancies per Zr SBU. Both MOF-808 variants have a pore
6
After screening the three MOF catalysts with simulant
limiting diameter of ca. 10 Å which is the largest of all the DMNP, we chose to test MOF-808 and DUT-84 on the V-series
MOFs investigated here, and large enough to facilitate the agent VM, a diethyl analogue of VX, which was readily
access of DMNP.
available at the time of testing. To further showcase the true
DUT-84 is a 6-connected framework and so we expected applicability of the zirconium MOF-808 as a degradation
the hydrolysis rate to be somewhat similar to that of MOF-808. catalyst, it was decided that the studies would be conducted in
The degradation was however significantly slower, an the absence of buffer. Excellent results were obtained for both
explanation for this could be the 2D morphology of DUT-84. nMOF-808 and aMOF-808 (Figure 4b). There was little
The two dimensionality results in less specificity for substrate discernible difference between the two catalysts because the
access to hydrated nodes. Despite the degradation being first measurement could only be acquired 12 minutes after the
rather slow, the degradation rate for aDUT-84 was significantly reaction had commenced, at which point most of the VM had
-3
-1
-4 -
enhanced (k = 1.8 x 10 s ) over that of nDUT-84 (k = 3 x 10 s been hydrolysed. This was an unfortunate safety limitation of
1
), simply through the activation protocol. UiO-66 was the the experimental procedure. The first DUT-84 was also
worst performer of the group. This was expected as aUiO-66 (k successful at hydrolysing VM, albeit, at a slower rate. As
-
3
-1
1.2 x 10 s ) has the smallest amount of acetate free sites postulated, aDUT-84 significantly outperformed nDUT-84, and
=
compared to the other MOFs. As a control, we also parallels with the simulant hydrolysis study. It should be noted
1
4
synthesised UiO-66 using a modulator free procedure and that when the zirconium MOFs were used, only P-S bond
observed no discernible difference in reaction rate between cleavage of the VM occurred. This is highly desirable as the
4
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hydrolysis product formed from P-O bond cleavage of a V-
series agent results in a product which maintains its toxicity.
For instance, hydrolysis with a strong base such as NaOH which
results in the competitive cleavage of both P-O and P-S bonds.
The above experiment further highlights the utility of these
Zirconium MOFs for rapid and selective hydrolysis of V-series
agents in the presence of only water (i.e. no buffer).
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Three acetic acid modulated MOFs were activated using a
highly facile method which relied on the use of microwave
irradiation. Microwave irradiation enables instant, evenly
distributed heating above boiling temperature, something
which is difficult to achieve with an autoclave vessel. The
extent of their activation was determined using NMR with
MOF-808 showing the greatest degree of activation, while the
enhanced thermal stability of each activated MOF, after
removal of acetate modulator, was demonstrated using TGA.
The activated MOFs, with hydrated nodes, were then
employed in the catalytic hydrolysis of a CWA simulant and
showed enhanced hydrolysis rates over that of their non-
activated counterparts, and further shown to degrade VM
without the necessity of a buffering reagent.
1
5
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Hupp, O. K. Farha and T. Friščić, Chem. Commun.
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Acknowledgements
BAB and SJH are grateful to the Defence Science and
Technology Laboratories for funding and Dr James T.A. Jones
for facilitating the NMR analysis of the active V-agent. We
would also like to thank the University of Kent for financial and
in-kind support. The authors would also like to further
1
2847
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L. T. Hoang, L. H. Ngo, H. L. Nguyen, H. T. Nguyen, C. K.
Nguyen, B. T. Nguyen, Q. T. Ton, H. K. Nguyen, K. E.
Cordova and T. Truong, Chem. Commun. 2015, 51
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,
acknowledge that YK is
researcher.
a
DSTL-funded post-graduate
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U. Olsbye, C. Lamberti, S. Bordiga and K. P.
Lillerud, Chem. Mater. 2014, 26, 4068-4071
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Graphical Abstract:
2.
No buffer
1.
VM – Highly toxic
Microwave
modulator
removal
Harmless degradation products
3.
No toxic by-products
6
| Dalton Trans., 2017, 00, 1-3
This journal is © The Royal Society of Chemistry 2017
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