Synthesis of a Zr-Based Metal-Organic Framework with Spirobifluorenetetrabenzoic Acid for the Effective Removal of Nerve Agent Simulants

Article abstract of DOI:10.1021/acs.inorgchem.7b02022

A new microporous Zr(IV)-based metal-organic framework (MOF) containing 4,4′,4″,4t″-(9,9′-spirobi[fluorene]-2,2′,7,7′-tetrayl)tetrabenzoic acid (Spirof-MOF) was synthesized, characterized, and size-controlled for the adsorption and decomposition of a nerve agent simulant, dimethyl 4-nitrophenylphosphate (DMNP). Spirof-MOF showed a hydrolysis half-life (t_1/2) of 7.5 min to DMNP, which was confirmed by using in situ ³¹P NMR spectroscopy. Additionally, size-controlled Spirof-MOFb (～1 μm) exhibited a half-life of 1.8 min and 99% removal within 18 min for DMNP. The results show that Spirof-MOF is a new active material in removing nerve agent simulants by adsorption and hydrolytic decomposition.

Full text of DOI:10.1021/acs.inorgchem.7b02022

Communication
pubs.acs.org/IC
Synthesis of a Zr-Based Metal−Organic Framework with
Spirobifluorenetetrabenzoic Acid for the Effective Removal of Nerve
Agent Simulants
†
†
‡
†
§
∥
Hea Jung Park, Jin Kyu Jang, Seo-Yul Kim, Jong-Woon Ha, Dohyun Moon, In-Nam Kang,
‡
†
,†
Youn-Sang Bae, Suhkmann Kim, and Do-Hoon Hwang*
†Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Busan 609-735, Republic of
Korea
‡
Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 03722, Republic of
Korea
§
Beamline Division, Pohang Accelerator Laboratory, Pohang, Kyungbuk 790-784, Republic of Korea
∥
Department of Chemistry, The Catholic University of Korea, Bucheon, Gyeonggi-do 420-743, Republic of Korea
*
S Supporting Information
necessary; however, the development of a new MOF is another
important effort in the further detoxification of nerve agents.
When a MOF is used as the catalyst, combination factors, such as
the crystal size, pore size, organic functionality, or metal activity,
ABSTRACT: A new microporous Zr(IV)-based metal−
organic framework (MOF) containing 4,4′,4″,4‴-(9,9′-
spirobi[fluorene]-2,2′,7,7′-tetrayl)tetrabenzoic acid (Spi-
rof-MOF) was synthesized, characterized, and size-
controlled for the adsorption and decomposition of a
nerve agent simulant, dimethyl 4-nitrophenylphosphate
12,13,19
affect the reaction rate.
The catalytic properties of MOFs
are usually affected by more than one factor, which make it
difficult to compare different MOFs as catalysts.
(
DMNP). Spirof-MOF showed a hydrolysis half-life (t )
1/2
Because of the high water stability and thermal stability of Zr-
of 7.5 min to DMNP, which was confirmed by using in situ
20−23
based MOFs,
we focused on a MOF involving the Zr(IV)
3
1
P NMR spectroscopy. Additionally, size-controlled
cluster metal node. In the ligand, a spirobifluorene derivative,
Spirof-MOFb (∼1 μm) exhibited a half-life of 1.8 min
and 99% removal within 18 min for DMNP. The results
show that Spirof-MOF is a new active material in removing
nerve agent simulants by adsorption and hydrolytic
decomposition.
which is thermally, chemically, and morphologically stable, was
24
selected to develop a new Zr-based MOF. There are a few
25−28
studies of spirobifluorene-based MOFs,
but a Zr-based
MOF with a spirobifluorene derivative is absent from the
literature. The pyrene unit of NU-1000 was replaced by
spirobifluorene, which has a reduced π conjugation but similar
molecular size to that of pyrene. Two fluorene units of
spirobifluorene are orthogonally connected by a spiro carbon
as the center, which induces separate π conjugation by two parts.
Herein, the new Zr-based MOF containing 4,4′,4′′,4′′′-(9,9′-
spirobi[fluorene]-2,2′,7,7′-tetrayl)tetrabenzoic acid (L), namely
Spirof-MOF, was designed and synthesized as a new catalyst for
the hydrolysis of DMNP. The metal node of Spirof-MOF is a
[Zr (μ -O) (COOH) (H O) ] cluster containing eight carbox-
erve agents [e.g., soman (GD), sarin (GB), and tabun
1
,2
N
(GA)] are lethal chemical weapons
that inhibit
acetylcholinesterase, resulting in asphyxiation at very low
3
exposure levels. The efficient detoxification of those volatile
phosphonate nerve agents has received great attention because of
4
the threat of terrorism. Steady efforts have been devoted to
5
−10
degrading or adsorbing toxic nerve agents.
The most
6
3
8
8
2
8
common method to detoxify G-type nerve agents is hydrolysis
ylate groups from a tetratopic linker (8-connected) and eight
water molecules. Spirof-MOF has the same 8-connected Zr6
cluster node as NU-1000, which is an active site for DMNP
hydrolysis. L as a tetratopic organic linker was prepared
according to a literature procedure, and all spectra matched the
of the P−X bond (X = F, CN). Metal−organic frameworks
(MOFs) are emerging as key catalysts for the hydrolysis of nerve
agents and their simulants. Hupp, Farha, and co-workers have
carefully studied and applied Zr(IV)-based MOFs to degrade
11−17
28
nerve agents and their simulants.
Lewis acidic Zr(IV) nodes
previously reported data (Scheme S1). Detailed synthetic
bridged by hydroxides are noteworthy for hydrolysis of
phosphate esters because the nodes of the MOF Zr cluster
resemble the natural enzyme active site (Zn−OH−Zn) of
procedures for L and Spirof-MOF are described in the
Supporting Information. The solvothermal reaction of L and
ZrOCl ·8H O in the presence of formic acid (as a modulator) at
2
2
1
1,18
1
30 °C in an oven gave a white crystal powder. The crystal
phosphotriesterase.
For hydrolysis of dimethyl 4-nitro-
structure was determined by single-crystal X-ray diffraction, and
the crystal data, structure refinement, and relevant bond lengths
phenylphosphate (DMNP, a nerve agent simulant), NU-1000
exhibited half-lives (t ) of 15 and 1.5 min for its hydrated and
1
/2
12
dehydrated Zr cluster nodes, respectively. Screening and
examination to find the best MOF among those already reported
for the hydrolysis of nerve agents and their simulants are
Received: August 9, 2017
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b02022
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
and angles are listed in Tables S1 and S2. The diffraction lines
were indexed with an orthorhombic unit cell with refined
parameters a = 17.842(4) Å, b = 37.867(8) Å, c = 33.693(7) Å, α
conventional method of evacuating at 130 °C for 18 h) exhibited
2
a BET surface area of 330 m /g, which is 6 times lower than that
of the ScD Spirof-MOF. The PXRD pattern of the convention-
=
90°, β = 90°, and γ = 90°.
ally dried Spirof-MOF sample at 130 °C indicated a collapsed
29,30
Spirof-MOF has a binodal 4,8-connected scu net topology
MOF architecture after drying under a vacuum at 130 °C
4
2
16 12
with the point symbol {4 ·6 }{4 ·6 }. More specifically, the
hexa-Zr(IV) node is connected to eight organic linkers (i.e., L),
and L is connected to four Zr clusters (Figure S1). The remnant
(FigureS4). However, the topology of Spirof-MOF was
unchanged after mild drying at 100 °C under evacuation for 16
2
h, showing a BET surface area of 1895 m /g (Figure S4). All of
6
of the Zr cluster metal node was occupied by eight water
the catalytic Spirof-MOF samples were activated by the same
conventional mild drying conditions (evacuating at 100 °C for 16
h).
6
molecules rather than formate anions used as modulators in the
reaction (formate-free form). The aperture sizes of the diamond-
shaped channels through the a and c axes in the microporous
Spirof-MOF were calculated using dummy-pillar diameters of 6
and 8 Å, respectively (Figure 1). Therefore, materials with the
The scanning electron microscopy (SEM) image shows a
particle size for the bulk Spirof-MOF of approximately 14−16
μm (maximum dimension; Figure S13a,b). Additionally, two
size-controlled Spirof-MOF samples (Spirof-MOFa and Spirof-
MOFb) were prepared by control of the reaction time and
showed similar maximum dimensions of 0.8−1 μm (Figure
S13c,d). However, Spirof-MOFb contained additional 400−700
nm small particles, which can be expected to have a faster DMNP
hydrolysis rate.
The particle-diameter distributions were measured for well-
dispersed samples in an ethanol solution using a laser diffraction
particle size analyzer. The particle diameter was obtained as an
equivalent sphere diameter (Dsurface), which is the diameter of a
sphere with an external surface area equal to that of the measured
particle. The particle diameter is less than the maximum
dimension of the sample because of the nonspherical shape of
Spirof-MOF. Bulk Spirof-MOF, which has a maximum
dimension of 14−16 μm (SEM images), showed maximum
particle-diameter distributions for D
= 3.2 μm. This
surface
indicates that bulk Spirof-MOF provided the same external
surface area in the catalytic reaction as that of an equivalent
sphere with a diameter of 3.2 μm (Figure S12a). Size-controlled
Spirof-MOFa showed a maximum particle-diameter distribution
at 258 nm, which is 12 times smaller than that of the bulk sample
(
Figure S12b). However, Spirof-MOFb had a maximum particle-
diameter distribution at 76 nm, which is the smallest diameter
among the Spirof-MOF samples, and a second distribution at 258
nm. On the basis of the particle-diameter distribution of the
synthesized Spirof-MOF samples, Spirof-MOFb (with the
smallest particle diameter) will have the largest external surface
area per unit weight among the prepared Spirof-MOF samples.
The effect of the external surface area per unit weight of the
prepared samples was explored in the hydrolysis test using size-
controlled Spirof-MOF samples as catalysts.
Figure 1. Structural features of Spirof-MOF [Zr (μ -
6
3
O) (C H O ) (H O) ]. Space-filled representation and 3D channel
8
53 28
8
2
2
8
diameters along the (a) a axis (6 Å) and (b) c axis (8 Å) of Spirof-MOF.
appropriate molecular sizes with respect to the window can freely
move in and out through the channels within Spirof-MOF.
Additionally, prolate spheroid cages of approximately 28.6 Å
We hydrolyzed DMNP using 1.5 μmol of the Spirof-MOF
catalyst loading with different particle sizes, which were
monitored by in situ 31P NMR spectra at room temperature.
The reaction conversion progress was calculated by comparing
(
(
maximum dimension) were observed inside Spirof-MOF
Figure S3). The synthesized bulk Spirof-MOF and simulated
31
powder X-ray diffraction (PXRD) patterns, which were obtained
from the single-crystal X-ray data, showed reasonable agreement
the integrated P NMR peak for DMNP (δ = −4.4 ppm) to that
of the dimethyl phosphate anion (δ = 2.8 ppm) hydrolysis
13,14
(Figure S4). The thermal stability of the as-synthesized Spirof-
product.
The results are summarized in Table 1.
MOF was assessed by thermal gravimetric analysis (TGA). The
mass decrease of approximately 66% (solvent loss) upon heating
to 250 °C suggests a substantial internal surface area (Figure S7).
Figure 2 shows the hydrolysis reaction of DMNP in an
aqueous buffer solution with Spirof-MOF as a catalyst with the
percent conversion of DMNP by Spirof-MOF as a function of
time at room temperature. The pore diameters of NU-1000 are
Both the as-synthesized and activated (supercritical CO drying,
2
21
ScD) Spirof-MOF samples were stable up to 511 °C.
12 and 30 Å, which are larger than those of Spirof-MOF (6 and
8 Å); therefore, DMNP (ca. 4.8 × 5.5 × 8.6 Å) is expected to
move in and out via the NU-1000 mesopores more easily than via
the Spirof-MOF micropores. However, bulk Spirof-MOF
showed t1/2 = 7.5 min, which is 1.7 times faster than that of
Spirof-MOF treated by ScD had a Brunauer−Emmett−Teller
2
(
BET) surface area of 2020 m /g and a total pore volume of 0.99
3
cm /g, estimated from the N sorption isotherm at 77 K (Figure
2
S8). The pore-size distribution was obtained from the N2
isotherm, indicating pore diameters in the expected range of
12,14
NU-1000 (15 min).
While NU-1000 showed 77% DMNP
8.8−10.5 Å (Figure S9). The degassed Spirof-MOF sample (a
conversion within 60 min, Spirof-MOF exhibited 97% DMNP
B
DOI: 10.1021/acs.inorgchem.7b02022
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
samples. Stacked in situ 31P NMR spectra showed that the
hydrolysis reaction was 99% complete within 18 min, and the
DMNP peak at −4.4 ppm disappeared (Figure S19). The other
Table 1. Summary of DMNP Degradation by Spirof-MOF and
NU-1000
particle size
amount of
t1/2
TOF
31
a
−1
c
in situ P NMR spectra for the hydrolysis of DMNP with the
sample
(μm)
catalyst (μmol) (min) (s
)
ref
Spirof-MOF samples are summarized in Figures S16−S18.
Additionally, Spirof-MOFb showed an 8.3 times shorter half-life
and a 9 times greater turnover frequency (TOF) than those of
NU-1000 under the same reaction conditions. Moreover, crystal
size control of Spirof-MOFb achieved a half-life similar to that of
dehydrated NU-1000 (t1/2 = 1.5 min), which possesses more
active metal sites than hydrated NU-1000.
In conclusion, we developed a new Zr(IV)-based Spirof-MOF
with a tetratopic organic linker L as an active material for the
effective removal of nerve agents and their simulants. Spirof-
MOF exhibited a shorter half-life and total DMNP conversion
NU-1000
NU-1000
NU-
15
0.37
1.5
80
15
0.007 19
0.009 12, 14
0.093 12, 14
1.5
1.5
48
7.5
1
000(dehyd)
b
Spirof-MOF
16
16
1
0.37
1.5
0.012 this
work
b
Spirof-MOF
0.018 this
work
b
b
Spirof-MOFa
1.5
3.5
1.8
0.040 this
work
Spirof-MOFb
1
1.5
0.077 this
work
a
b
Maximum dimension length determined by SEM. Activated at 100
time than NU-1000, which has the same 8-connected Zr cluster
6
c
°
C with evacuating for 16 h. TOF values were calculated at t [TOF
active site and a similar BET surface area but larger pores than
Spirof-MOF. The size-controlled Spirof-MOF, Spirof-MOFb,
showed the shortest half-life (1.8 min) among the three Spirof-
MOF samples and 99% DMNP conversion within 18 min.
Spirof-MOFb showed the fastest DMNP hydrolysis rate with a
1/2
1
=
( / mol of DMNP)/(mol of catalyst)(t1/2)]. Slightly larger values
2
are obtained if the initial rates are used to calculate TOF.
hydrated 8-connected Zr cluster metal node reported to date.
6
These results reveal that Spirof-MOF is clearly effective in
removing the nerve agent simulant DMNP. Spirof-MOF
provides a scaffold for achieving improved hydrolysis rates for
the nerve agent and its simulant through the development of a
new MOF.
ASSOCIATED CONTENT
■
*
S
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b02022.
1
Detailed compound synthesis and characterization, H
31
and P NMR, TGA, PXRD, N isotherms, SEM images,
2
and single-crystal X-ray crystallography data (PDF)
Figure 2. (a) Hydrolysis scheme of DMNP and (b) hydrolysis rates of
DMNP using the Spirof-MOF samples.
Accession Codes
CCDC 1478753 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_
request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336033.
conversion within only 35 min. This indicates that DMNP can
more easily access the active site of Spirof-MOF than that of NU-
1
000, even though Spirof-MOF has smaller pores than NU-1000.
It seemed that the closer distance between the neighbor Zr6
nodes of Spirof-MOF than that of NU-1000 helped DMNP
approach the active site. Additionally, DMNP hydrolysis was
performed with Spirof-MOF, having similar particle size to NU-
AUTHOR INFORMATION
■
1
000, because the hydrolysis performance of the MOF catalyst is
Corresponding Author
19
significantly affected by the MOF crystal size. To fairly
compare the hydrolysis rate between two MOFs, 0.37 μmol of
the bulk Spirof-MOF (16 μm) catalyst was used for the DMNP
hydrolysis test at the same conditions as those used for NU-1000
*
E-mail: dohoonhwang@pusan.ac.kr.
ORCID
Do-Hoon Hwang: 0000-0003-4183-0185
19
(15 μm) in the literature. In the similar particle size, Spirof-
Notes
MOF exhibited a 1.7 times shorter half-life (t1/2= 48 min) than
The authors declare no competing financial interest.
that of NU-1000 (t = 80 min) (Table 1). The size-controlled
1/2
Spirof-MOF samples, Spirof-MOFa and Spirof-MOFb, exhibited
.1−4.2 times faster hydrolysis rates for DMNP than the bulk
Spirof-MOF did (t1 = 7.5 min). Spirof-MOFa showed t = 3.5
min and 97% DMNP conversion after 32 min. As expected from
the Dsurface results and SEM images from the particle size analysis,
Spirof-MOFb, which showed the smallest particle size, provided
the shortest half-life (1.8 min) among the prepared Spirof-MOF
ACKNOWLEDGMENTS
2
■
This work was supported by a National Research Foundation of
Korea grant funded by the Korean Government (Grant NRF-
2017R1A2A2A05001345 and GCRC-SOP No. 2011-0030013).
The X-ray crystallography BL2D-SMC beamline at PLS-II was
supported, in part, by MSIP and POSTECH.
/2
1/2
C
DOI: 10.1021/acs.inorgchem.7b02022
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Inorganic Chemistry
Communication
(
19) Li, P.; Klet, R. C.; Moon, S.-Y.; Wang, T. C.; Deria, P.; Peters, A.
REFERENCES
■
W.; Klahr, B. M.; Park, H. J.; Al-Juaid, S. S.; Hupp, J. T.; Farha, O. K.
Synthesis of nanocrystals of Zr-based metal−organic frameworks with
csq-net: significant enhancement in the degradation of a nerve agent
simulant. Chem. Commun. 2015, 51, 10925−10928.
(
1) Bajgar, J. Organophosphates/nerve Agent Poisoning: Mechanism
of Action, Diagnosis, Prophylaxis, and Treatment. Adv. Clin. Chem.
004, 38, 151−216.
2) Yang, Y.-C. Chemical Detoxification of Nerve Agent VX. Acc.
Chem. Res. 1999, 32, 109−115.
3) Eubanks, L. M.; Dickerson, T. J.; Janda, K. D. Technological
Advancements for the Detection of and Protection Against Biological
and Chemical Warfare Agents. Chem. Soc. Rev. 2007, 36, 458−470.
4) Kim, K.; Tsay, O. G.; Atwood, D. A.; Churchill, D. G. Destruction
2
(
(
20) Guillerm, V.; Ragon, F.; Dan-Hardi, M.; Devic, T.; Vishnuvarthan,
M.; Campo, B.; Vimont, A.; Clet, G.; Yang, Q.; Maurin, G.; Ferey, G.;
́
(
Vittadini, A.; Gross, S.; Serre, C. A Series of Isoreticular, Highly Stable,
Porous Zirconium Oxide Based Metal-Organic Frameworks. Angew.
Chem., Int. Ed. 2012, 51, 9267−9271.
(
(
21) Mondloch, J. E.; Bury, W.; Fairen-Jimenez, D.; Kwon, S.;
and Detection of Chemical Warfare Agents. Chem. Rev. 2011, 111,
345−5403.
5) Zou, R.; Zhong, R.; Han, S.; Xu, H.; Burrell, A. K.; Henson, N.;
DeMarco, E. J.; Weston, M. H.; Sarjeant, A. A.; Nguyen, S. T.; Stair, P.
C.; Snurr, R. Q.; Farha, O. K.; Hupp, J. T. Vapor-Phase Metalation by
Atomic Layer Deposition in a Metal-Organic Framework. J. Am. Chem.
Soc. 2013, 135, 10294−10297.
5
(
Cape, J. L.; Hickmott, D. D.; Timofeeva, T. V.; Larson, T. E.; Zhao, Y. A
Porous Metal-Organic Replica of α-PbO2 for Capture of Nerve Agent
Surrogate. J. Am. Chem. Soc. 2010, 132, 17996−17999.
(
́
22) Furukawa, H.; Gandara, F.; Zhang, Y.-B.; Jiang, J.; Queen, W. L.;
Hudson, M. R.; Yaghi, O. M. Water Adsorption in Porous Metal-
(
6) Montoro, C.; Linares, F.; Quartapelle Procopio, E.; Senkovska, I.;
Organic Frameworks and Related Materials. J. Am. Chem. Soc. 2014, 136,
Kaskel, S.; Galli, S.; Masciocchi, N.; Barea, E.; Navarro, J. A. R. Capture
of Nerve Agents and Mustard Gas Analogues by Hydrophobic Robust
MOF-5 Type Metal-Organic Frameworks. J. Am. Chem. Soc. 2011, 133,
4
(
369−4381.
23) Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti, C.;
Bordiga, S.; Lillerud, K. P. A New Zirconium Inorganic Building Brick
Forming Metal Organic Frameworks with Exceptional Stability. J. Am.
Chem. Soc. 2008, 130, 13850−13851.
(24) Saragi, T. P. I.; Spehr, T.; Siebert, A.; Fuhrmann-Lieker, T.;
Salbeck, J. Spiro Compounds for Organic Optoelectronics. Chem. Rev.
2007, 107, 1011−1065.
(25) Wong, K.-T.; Liao, Y.-L.; Peng, Y.-C.; Wang, C.-C.; Lin, S.-Y.;
Yang, C.-H.; Tseng, S.-M.; Lee, G.-H.; Peng, S.-M. A Novel Right-
Angled Ligand that Forms Polymeric Metal-Organic Frameworks with
Nanometer-Sized Square Cavities. Cryst. Growth Des. 2005, 5, 667−671.
(26) Clews, P. K.; Douthwaite, R. E.; Kariuki, B. M.; Moore, T.;
Taboada, M. Layered Compounds Incorporating 9,9′-Spirobifluorene:
Hydrogen-Bonded and Metal-Organic Networks Derived from 9,9′-
Spirobifluorene-2,2′,7,7′-tetracarboxylic Acid. Cryst. Growth Des. 2006,
6, 1991−1994.
(27) Collins, C. S.; Sun, D.; Liu, W.; Zuo, J.-L.; Zhou, H.-C. Reaction-
Condition-Controlled Formation of Secondary-Building-Units in Three
Cadmium Metal-Organic Frameworks with an Orthogonal Tetrakis-
(tetrazolate) Ligand. J. Mol. Struct. 2008, 890, 163−169.
(28) Moreau, F.; Audebrand, N.; Poriel, C.; Moizan-Basle, V. J.; Ouvry,
A. 9,9′-Spirobifluorene Based Metal-Organic Framework: Synthesis,
Structure Analysis and Gas Sorption Properties. J. Mater. Chem. 2011,
1
(
1888−11891.
7) Bandosz, T. J.; Laskoski, M.; Mahle, J.; Mogilevsky, G.; Peterson, G.
W.; Rossin, J. A.; Wagner, G. W. Reactions of VX, GD, and HD with
Zr(OH)4: Near Instantaneous Decontamination of VX. J. Phys. Chem. C
012, 116, 11606−11614.
8) Wang, S.; Bromberg, L.; Schreuder-Gibson, H.; Hatton, T. A.
Organophophorous Ester Degradation by Chromium(III) Terephtha-
late Metal-Organic Framework (MIL-101) Chelated to N,N-Dimethy-
laminopyridine and Related Aminopyridines. ACS Appl. Mater. Interfaces
013, 5, 1269−1278.
9) Roy, A.; Srivastava, A. K.; Singh, B.; Shah, D.; Mahato, T. H.;
2
(
2
(
Gutch, P. K.; Halve, A. K. Degradation of Sarin, DEClP and DECNP
over Cu-BTC Metal Organic Framework. J. Porous Mater. 2013, 20,
1
(
103−1109.
10) DeCoste, J. B.; Peterson, G. W. Metal-Organic Frameworks for
Air Purification of Toxic Chemicals. Chem. Rev. 2014, 114, 5695−5727.
11) Katz, M. J.; Mondloch, J. E.; Totten, R. K.; Park, J. K.; Nguyen, S.
T.; Farha, O. K.; Hupp, J. T. Simple and compelling biomimetic metal-
organic framework catalyst for the degradation of nerve agent simulants.
Angew. Chem., Int. Ed. 2014, 53, 497.
(
(
12) Mondloch, J. E.; Katz, M. J.; Isley, W. C., III; Ghosh, P.; Liao, P.;
2
(
1, 18715−18722.
Bury, W.; Wagner, G. W.; Hall, M. G.; DeCoste, J. B.; Peterson, G. W.;
Snurr, R. Q.; Cramer, C. J.; Hupp, J. T.; Farha, O. K. Destruction of
Chemical Warfare Agents Using Metal-Organic Frameworks. Nat.
Mater. 2015, 14, 512−516.
29) Feldblyum, J. I.; Liu, M.; Gidley, D. W.; Matzger, A. J. Reconciling
the Discrepancies between Crystallographic Porosity and Guest Access
As Exemplified by Zn-HKUST-1. J. Am. Chem. Soc. 2011, 133, 18257−
1
8263.
(
13) Katz, M. J.; Moon, S.-Y.; Mondloch, J. E.; Beyzavi, M. H.;
(30) Nelson, A. P.; Farha, O. K.; Mulfort, K. L.; Hupp, J. T.
Stephenson, C. J.; Hupp, J. T.; Farha, O. K. Exploiting Parameter Space
in MOFs: A 20-Fold Enhancement of Phosphate-ester Hydrolysis with
UiO-66-NH2. Chem. Sci. 2015, 6, 2286−2291.
Supercritical Processing as a Route to High Internal Surface Areas and
Permanent Microporosity in Metal-Organic Framework Materials. J.
Am. Chem. Soc. 2009, 131, 458−460.
(
14) Moon, S.-Y.; Liu, Y.; Hupp, J. T.; Farha, O. K. Instantaneous
Hydrolysis of Nerve-Agent Simulants with a Six-Connected Zirconium-
Based Metal-Organic Framework. Angew. Chem., Int. Ed. 2015, 54,
6
(
795−6799.
15) Moon, S.-Y.; Wagner, G. W.; Mondloch, J. E.; Peterson, G. W.;
DeCoste, J. B.; Hupp, J. T.; Farha, O. K. Effective, facile, and selective
hydrolysis of the chemical warfare agent VX using Zr6-based metal-
organic frameworks. Inorg. Chem. 2015, 54, 10829−10833.
(
16) Moon, S.-Y.; Proussaloglou, E.; Peterson, G. W.; DeCoste, J. B.;
Hall, M. G.; Howarth, A. J.; Hupp, J. T.; Farha, O. K. Detoxification of
chemical warfare agents using a Zr6-based metal-organic framework/
polymer mixture. Chem. - Eur. J. 2016, 22, 14864−14868.
(
17) Liu, Y.; Howarth, A. J.; Vermeulen, N. A.; Moon, S.-Y.; Hupp, J.
T.; Farha, O. K. Catalytic degradation of chemical warfare agents and
their simulants by metal-organic frameworks. Coord. Chem. Rev. 2017,
3
(
46, 101−111.
18) Wong, K.-Y.; Gao, J. The Reaction Mechanism of Paraoxon
Hydrolysis by Phosphotriesterase from Combined QM/MM Simu-
lations. Biochemistry 2007, 46, 13352−13369.
D
DOI: 10.1021/acs.inorgchem.7b02022
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