Ultra-fast catalytic detoxification of organophosphates by nano-zeolitic imidazolate frameworks

Article abstract of DOI:10.1016/j.mcat.2020.110965

Detrimental and injurious impacts of Organophosphates that have had on environment, humans, organisms and the other animals or plants have not been surreptitious to anyone worldwide. Nevertheless, up to now, among many efforts that have been devoted to detoxification of Organophosphates (OPs), catalytic detoxification has been the most applicable, cost-effective, efficacious and safest way to break down these dangerous materials. Herein, the utilization of zeolitic imidazolate frameworks (ZIFs), for the first time, has been reported to deactivate Diazinon as an organophosphate agent demonstrated at room temperature. In the following research, the catalysts were analyzed by PXRD, FT-IR, FE-SEM, BET, CO₂ adsorption/desorption and TG. The decontamination processes were followed by ³¹P NMR, HPLC, and UV–vis to evaluate catalytic efficiency. Interestingly, supreme reusability, durability and potentially stunning catalytic activity represent them as alternate materials for their amazing elimination of OPs compared to the other MOFs.

Full text of DOI:10.1016/j.mcat.2020.110965

MolecularCatalysis490(2020)110965
Contents lists available at ScienceDirect
Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat
Ultra-fast catalytic detoxification of organophosphates by nano-zeolitic
imidazolate frameworks
Arash Ebrahimia, Ehsan Nassireslamia,*, Ramin Zibasereshtb,c, Maedeh Mohammadsalehid
a Department of Pharmacology & Toxicology, Faculty of Medicine, Aja University of Medical Sciences, Tehran, Iran
b Biomaterials and Medicinal Chemistry Research Center, Aja University of Medical Sciences, Tehran, Iran
c Department of Chemistry and Physics, Faculty of Sciences, Maritime University of Imam Khomeini, Nowshahr, Iran
d Department of Pharmaceutical Chemistry, Pharmaceutical Sciences Branch, Islamic Azad University, Tehran, Iran
A R T I C L E I N F O
A B S T R A C T
Keywords:
Detrimental and injurious impacts of Organophosphates that have had on environment, humans, organisms and
the other animals or plants have not been surreptitious to anyone worldwide. Nevertheless, up to now, among
many efforts that have been devoted to detoxification of Organophosphates (OPs), catalytic detoxification has
been the most applicable, cost-effective, efficacious and safest way to break down these dangerous materials.
Herein, the utilization of zeolitic imidazolate frameworks (ZIFs), for the first time, has been reported to deac-
tivate Diazinon as an organophosphate agent demonstrated at room temperature. In the following research, the
catalysts were analyzed by PXRD, FT-IR, FE-SEM, BET, CO2 adsorption/desorption and TG. The decontamination
processes were followed by 31P NMR, HPLC, and UV–vis to evaluate catalytic efficiency. Interestingly, supreme
reusability, durability and potentially stunning catalytic activity represent them as alternate materials for their
amazing elimination of OPs compared to the other MOFs.
Zeolitic imidazolate frameworks
Catalytic detoxification
Hydrolysis
Organophosphates simulant
Diazinon
1. Introduction
most extensively applicable and the most convenient procedure in
terms of practicability, efficiency and turnover as well as productivity
Demanding for detoxification of Organophosphates (OPs) such as
Diazinon and Malathion due to their high toxicity and their en-
vironmentally deleterious effects on natural surroundings and in-
dividuals have been growing of concerns in recent years [1–3]. Among
them, the case Organophosphorus pesticides (OPs) as highly venomous
compounds have broadly used for agriculture [4,5]. Owing to their
dangerous effects on organisms may cause paralysis and organ in-
abilities [6,7]. Moreover, Diazinon is also admitted as paronymous
organophosphate pesticide with the virtue of relatively high toxicity
should be examined to compare the analogous efficacy of the catalysts
[1]. Lately, much more concerns in expanding the methodologies for
catalytic detoxification of phosphate ester bond as a challenging issue
have been ongoing to investigate the removal of such OPs [1,8]. Even
though, it is mandatory to try developing the strategies that they have
been helpful to degrade the PeO bonds employing the hydrolytic
cleavage catalytically as the most advantageous method so far.
compared to others.
Of highly efficient and superior materials showing to degrade such
pesticides [12,14–21], metal-organic frameworks (MOFs), a novel
subdivision of crystalline porous materials, formed through bridging
metal ions or clusters to the ligands in diverse topologies [22–27].
Owing to their tunable porosity, versatile flexible structural frame-
works, remarkably high surface areas and post-synthesis of modified
architectures with functional groups proven to be promising as an at-
tractive material in diverse applications namely CO2 capture [28], gas
adsorption/storage [29], separation [30,31], photoluminescence [32],
catalysis [33,34], chemical sensing [35,36] and drug delivery [37]. As
subfamily of MOFs, zeolitic imidazolate frameworks (ZIFs), are hybrid
material possessing simultaneously characteristics of both zeolite and
MOFs such as chemical and thermal stability, crystallinity, chemical
versatility, hydrophobic surfaces [38,39] which are basically made up
of tetrahedral coordinated metal ions (Zn2+, Co2+, Cu2+) and imida-
zolate ligands in a 3D neutral open frameworks [40]. Existence of both
acidic and basic functionality on ZIFs at the same time which induces
by metal nodes and imidazolate groups, respectively, execute the het-
erogeneous catalytic activity, properly [41,42].
As regards, recently, various efforts have been utilized to overcome
these barriers which have been carried out by exploiting the hydrolysis
manner. Most of them have been manipulated by Farha et al. [9–13] are
illustrative of its significant importance insisting on its simplicity, the
⁎ Corresponding author.
E-mail address: nassireslami@gmail.com (E. Nassireslami).
https://doi.org/10.1016/j.mcat.2020.110965
Accepted 14 April 2020
2468-8231/©2020ElsevierB.V.Allrightsreserved.

A. Ebrahimi, et al.
MolecularCatalysis490(2020)110965
Highly active phosphotriesterase (PTE) enzyme, has been re-
Table 1
Summary of mainly recent experiments data obtained in hydrolysis degradation
by various MOFs toward diverse Organophosphates.
cognized to be an effective agent in the hydrolysis of the PeO bond
[43,44]. Considering the similarity of catalytic and structural aspects
between PTE and ZIFs, in the case of PTE, a pair of Zn (II) ions compose
the active site of PTE linked by OH ligand and enclosed by 2–3 ni-
trogen-based donor ligands (histidine imidazole). On the other hand,
the Zn(II) and imidazolate sites in ZIFs can function collaboratively to
accomplish the cleavage of PeO bonds; in both, Zn(II) center attaches
and gives rise to activate the PeO bond whereas others trigger to
transfer an OH− to inspire the breakage of an eOR moiety [9,10,45].
To date, most of catalytic detoxification and capture of OPs have
been operated prosperously by MOF materials especially by water-
stable mesoporous Zr-based MOFs and methyl paraoxon simulant and
less performed by the other MOFs like CuBTC-MOF and/or by the other
pesticides at room temperature in aqueous solution [12,14–21].
Avoiding long story but to name some recently outstanding of them in
order to make it clear, many of previously demonstration of such works
have been provided. Specifically, degradation of OPs performed by Ryu
et al. [46] which were utilized by MOF-808, UiO-66 and UiO-66-NH2
series in neat and aqueous solutions at room temperature showed half-
life time of optimized MOF-808 equaled to 0.7 min. Navarro research
group illustrated the synergistic properties of Zirconium-based MOFs
and some certain functional group employing nucleophilic basic func-
tionality linked to the organic linker and basic lithium alkoxides in-
corporated within their framework to boost their catalytic proficiency;
with UiO-66-0.25NH2@LiOtBu presenting the most great rate (t1/
2 = 0.4 min) displayed a favorable harmony between framework ap-
proachability and nucleophilicity of the materials [47]. The other ex-
ample of similar work has been operated by Koning et al. [48] using
UiO-66-NH2, NU-1000, MOF-808, and PCN-777 in buffer solutions were
assessed to decompose some chemically dangerous OPs. The observa-
tions there represented to reveal the main characteristics and me-
chanism that control these detoxification reactions resulted in tre-
mendously swift hydrolysis rates which terminated to complete
breakdown of pesticide during the reaction time only up to 5.5 min.
More obviously, the two prominent researches virtually resembled to
our work done by Farha et al. exceptionally encouraged us to execute
similar work. In both of their work, they studied the catalytic detox-
ification of methyl paraxon simulant agents where engaging NU-901
[49] and MOF-808 (6-connected) [10] as detoxifier to attack and finally
to assert their highly active catalytic performances. In the former case
(NU-901), also showed the comparison between the efficiency of less-
volatile branched polymers and dendrimers to the volatile N-ethyl-
morpholine solution as buffer additives to accelerate the reaction. The
examination displayed the decrease in reaction half-life time up to <
2 min declaring that amino-functionalized branched polymers and
dendrimers would assist as an efficacious alternative bases for hydro-
lysis which could be nearly the same as N-ethylmorpholine. On the
other hand, for the latter case (MOF-808 (6-connected)), the half-life
time and the situation of the reaction were more relatively identical to
our study which motivated us more to evaluate the application of a
series of ZIFs catalyst in OPs decontamination. In this case, the opti-
mized MOF-808 (6-connected) would successfully prosper to degrade
simulant with less than 6 min of rection time and half-life of < 0.5 min.
Besides, the turnover frequency (TOF) value was more than 1.4 s−1
which was meaningfully much higher compared to those MOFs in-
vestigated in this survey. As shown below, for more clarified compar-
ison the described data were gathered in Table 1.
MOF
Amount of catalyst
[mg]
t1/2 [min] TOF [s−1
]
Ref
MOF-808
UiO-66-0.25NH2@
LiOtBu
20
20
0.7
0.4
1.05
1.7
[46]
[47]
PCN-777
NU-901
MOF-808
ZIF-8
1−2
3.3
1.1
1
0.5
1.5
[48]
[49]
[10]
–
< 2
< 0.5
0.5
0.14
> 1.4
> 1.3
(Our work)
Diazinon to illustrate their exceptionally resembling performance
compared either with MOFs or with other pesticides. In fact, in follow-
up contribution, what we are trying to do is to examine the catalytic
activity of nanocrystals of ZIF-7 and ZIF-8 toward Diazinon as
Organophosphate, which has been confirmed by 31P NMR, HPLC, and
UV–vis spectra. Finally, all the consequences ascertain that these ma-
terials can be executed as ultra-highly efficacious materials comparable
to those which have been already reported.
2. Experimental
2.1. Materials
All the chemicals including Benzimidazole (C7H6N2, 98%), 2-
Methylimidazole (C4H6N2, 99%), Ammonia solution (NH3, 25%, 7 M),
Absolute ethanol (C2H5OH, 96%), Zinc nitrate tetrahydrate (Zn
(NO3)2·4H2O, 98.5%), Diazinon (C12H21N2O3PS, 96%), Acetonitrile
anhydrous (99.8%, HPLC grade) and N-ethylmorpholine (C6H13NO,
97%) were provided from Merck and Sigma-Aldrich and executed as
received without any excessive purification.
2.2. Fabrication of materials (ZIF-7 and ZIF-8)
All the fabrications were conducted based on our previous manner
with some modifications [50]. Briefly, in the case of ZIF-7, 0.118 g BIM
(Benzimidazole; 1 mmol) was dispersed in 10 mL ethanol. Then, 0.130 g
Zn(NO3)2·4H2O (0.5 mmol) was poured into the solution. The mixture
and the other 10 mL vial encompassing 5 mL of ammonia were placed
in tightly capped 250 mL Teflon-lined autoclave. After 5 min stirring,
the solution was kept under the ammonia atmosphere at room tem-
perature for 30 min. The precipitate was completely centrifuged and
rinsed with absolute ethanol two times and dried in the air for 24 h
(Sample 1 (S1)).
Concerning ZIF-8, 0.082 g 2-mIM (2-Methylimidazole; 1 mmol) was
dissolved in 10 mL ethanol. Afterward, 0.130 g Zn(NO3)2·4H2O
(0.5 mmol) was added into the solution. The mixture was tightly capped
in 250 mL Teflon-lined autoclave under 5 mL of ammonia atmosphere
at room temperature for 10 min stirring. Then, the residue was gathered
by centrifugation, two times washed with ethanol, dried and kept
overnight in the air (Sample 2 (S2)).
2.3. Instrumentation
With keeping these viewpoints in mind, we have postulated that ZIF
materials also could prove their potential ability as great alternatives in
detoxification of Organophosphates. Regarding to the best of our
knowledge, heretofore, no catalytic reaction has been applied using
ZIFs for decontamination of Diazinon and the other OPs.
Moreover, regarding the high toxicity of organophosphates and
possibility of their being high-risk in exploiting them, mainly in the
vapor state, we tended to assess the catalytic activity of ZIFs employing
X-ray diffraction patterns of the as-fabricated materials were con-
ducted on a Phillips X'Pert Pro X-ray diffractometer with Cu Kα
(λ = 1.5418 Å) radiation at a scan rate of 2 degrees per minute with a
step size of 0.028. Fourier transform infrared (FT-IR) spectra were ob-
tained on a Nicolet Magna 550 spectroscope with the KBr pellet tech-
nique in the range of 4000−400 cm−1. Field-emission scanning elec-
tron microscopy (FE-SEM) images were gained by a Zeiss model SIGMA
VP-500 (Germany). BET experiments were measured at liquid N2
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A. Ebrahimi, et al.
MolecularCatalysis490(2020)110965
temperature (77 K) operating
a volumetric adsorption analyzer
(BElSORP Mini from Microtrac Bel Corp. Co). CO2 ads-des examination
was carried out at 273 K (Microtrac BELSORP-HP analyzer) which the
samples were degassed in the high vacuum at 423 K for 3 h before the
measurements. Thermal gravimetric analysis (TGA) was performed on a
Netzsch STA 409 PC/PG thermal analyzer (Germany) in argon gas at-
mosphere from 27 up to 750 °C in a heating rate of 20 °C min−1
.
Hydrolysis progress illustrated by NMR spectra were collected on The
Bruker Avance III 400 MHz NMR spectrometer. HPLC evaluations were
recorded by an instrument (Agilent 1200 series) equipped with a
UV–vis detector fixed at λmax = 254 nm. UV–vis spectra were gathered
in the range of 200−800 nm by Shimadzu 2100 spectrophotometer at
room temperature.
2.4. Catalytic activity examinations
2.4.1. P NMR studies
31P NMR measurements were recorded at room temperature. The
reactions were operated based on Farha et al. methods with some rec-
tification [10]. In brief, 1 mg of catalysts (S1 (3.31 μmol) and S2
(4.36 μmol)) were separately poured into 1 mL H2O in a 10 mL vial.
Then, adding solution of N-ethylmorpholine 0.45 M (1 mL solution;
0.05 mL N-ethylmorpholine, 0.9 mL DI water/0.1 mL D2O) and stirring
for 5 min to disperse homogeneously. Next, Diazinon (5 μL; 18 μmol)
was added to the mixture solution. Then, after certain interval times
(1−6 min for S1 and 1−4 min for S2), the reaction mixtures were fil-
tered by a syringe filter (0.22 μm pores). Afterwards, the mixtures were
immediately transferred to an NMR tube each separately and the
spectra were collected instantaneously shortly after the start of the
reaction. The first spectrum was measured at 1 min after adding of
Diazinon and the remaining solutions were recorded at 4, 6, 20 min and
5 days for S2, S1, S2 post-filtration and Diazinon (in the absence of
catalysts) by in situ 31P NMR, respectively.
Fig. 1. PXRD patterns of (a) the as-obtained ZIF-7 lp-phase (S1) (b) of the as-
synthesized ZIF-8 (S2).
2 times and then dried in the air after centrifugation.
3. Results and discussion
2.4.2. HPLC measurements
3.1. Framework and textural characterization
Similar procedures were applied for HPLC and UV–vis experiments.
Instead, after filtrations, 30 μL of residue was injected into the HPLC
apparatus (mobile phase: water/acetonitrile (65/35); stable phase: re-
verse phase C18, column temperature 25 °C at a rate of 1 mL/min)
equipped with a UV–vis detector fixed at λmax = 254 nm especially for
detection of Diazinon and 2-isopropyl-6-methyl-4-pyrimidinol (IMP) at
ambient temperature. Besides, excess of 10 min were required to re-
instate the primary condition to gather the next sample spectra.
As shown in Fig. 1a, the sharp characteristics peaks at 2θ = 7.2° and
2θ = 7.7° and the other peaks in X-ray diffraction (XRD) patterns of the
as-obtained sample demonstrate efficacious incorporation with the
SOD-type of microporous ZIF-7 (lp-phase, S1) [50–52]. XRD patterns of
ZIF-8 (S2) which is depicted in Fig. 1b also confirming the formation of
SOD-type without any additional peaks indexed to (011), (002), (112),
(022), (013), (222), (114), (233), (134), (044), (244) and (235) dif-
fraction lines, respectively, which is in accordance with those reported
previously [51,53,54]. Fig. 2a and b depicts the FT-IR spectra of as-
obtained S1, bIM, and 2-mIM, as-produced S2, respectively. There are
broad peak ranges from 2200 to 3400 cm−1 with the maximum peak at
the center around 2800 cm−1 as well as the sharp band situated at
1408 cm−1 (NeH⋯N stretching and bending vibrations of bIM, re-
spectively) and sharp band at 3130 cm−1 and weak band near
1823 cm−1 due to C–H are ascribed to stretching and bending vibra-
tions of 2-mIM, respectively. After full deprotonation of nitrogen atoms,
all of those peaks disappear suggesting that ZIF-7 and ZIF-8 were fab-
ricated successfully [51,55–59].
2.4.3. UV–vis spectra tests
Furthermore, UV–vis investigations were run and evaluated under
similar environments at room temperature. Progress of the reactions
were analyzed by taking a 300 μL liquid from the mixtures and diluted
by adding an aqueous solution of N-ethylmorpholine (5 mL, 0.45 M)
before injection to UV/Vis instrument. Reactions’ profiles were ob-
tained by absorbance at several specified time with the increment of
each 25 s up to 4 min in the range of 200−800 nm.
2.4.4. Heterogeneous trait and recycling inspections
Additionally, the authentication of the heterogeneity property of
catalyst (S2) was corroborated by filtration via 0.22 μm syringe after
stopping the reaction at minute 1 which was calculated for 20 min.
To examine the reusability of ZIF (S2), Diazinon hydrolysis pro-
cesses were run in five times one after another. After the termination of
each cycle, the catalyst was gathered by centrifugation from container
vial and then the solvent was removed. To rinse any product such as
unwanted and un-reacted materials from the outermost surface and
structure of ZIF, the process was operated for 3 times where after
adding 2 mL of 0.15 M N-ethylmorpholine to the vial containing the
catalyst, the solution was then stirred for 20 min. Next, after stirring,
the solvent was eliminated. Finally, the solid was washed with ethanol
The morphology of S1 is composed of an average size of 1−2 μm
cubic and smaller spherical crystals. Also, S2 particles are made up of
500 nm to 1 μm average size such that indicating both S1 and S2 have
been formed from low-ordered crystals with the mean size of 500 nm to
1 μm and 200−500 nm for S1 and S2, respectively, illustrated by FE-
SEM in Fig. 3a-b representing integrated micrometer-scaled cubic,
spherical and to some extent rhombic-dodecahedron structures which
are relatively identical to those formerly prepared [53,54].
Taking into account, the hysteresis loop suggesting the dual meso/
microporous trait of ZIF-7 because of the interparticle mesopores in
which nitrogen molecules are not penetrable to small windows of ZIF-7
[54–56,60,61]. Besides, due to the larger kinetic diameter of N2
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A. Ebrahimi, et al.
MolecularCatalysis490(2020)110965
Fig. 2. FT-IR spectra of (a) bIM and S1 (b) 2-mIM and S2.
(∼0.36 nm) than the aperture size of ZIF-7 (∼0.3 nm) [60,63], N2
cannot enter into ZIF-7 pores [62,63]. In comparison with relatively
smaller CO2 (kinetic diameter of 0.33 nm) than that of N2 and con-
sidering the flexible structure of ZIF-7 [61,50,54], CO2 molecules are
much more achievable to the cavities. Type I isotherm CO2 ads/des of
the as-prepared ZIF-7 lp-phase presents in Fig. 4a demonstrating a gate-
opening phenomenon near at 20 kPa and also flexible property of the
framework is indicated by the hysteresis loop. The great CO2 adsorption
capacity of about 58.32 cm3 g−1 at 115 kPa represents that CO2 is not
degassed easily throughout the framework of S1 [50,52,61,64,65].
4

A. Ebrahimi, et al.
MolecularCatalysis490(2020)110965
Fig. 3. FE-SEM images of (a) S1 and (b) S2.
Fig. 5. TGA curves of S1 and S2.
showing its relatively high porosity and a high specific area in com-
parison to other counterparts synthesized in the severe situation
[53,54].
As depicted in Fig. 5, first gradual weight loss of 6.72% up to 200 °C
and 23% up to 250 °C which is displayed in thermogravimetry (TG)
curves of S1 and S2 attributed to the removal of all guests in the cavities
(especially ethanol) or the other species on the surface of the as-made
ZIF-7 and ZIF-8 throughout the synthesis reaction, respectively. Second
step weight loss of 14.46% and 54.58% of S1 and S2 from 200 to 700 °C
and 250 to 675 °C related to the framework decomposition to ZnO,
respectively [50,53,54,64–69].
3.2. Catalytic performance investigations
As above mentioned, intrigued by quite catalytic activity monitored
by those metal-organic frameworks (MOFs) concerning organopho-
sphates [9–13] and much better availability of Diazinon in our lab, the
efficiency of ZIF materials were weighed by the hydrolytic dissociation
of Diazinon.
The hydrolysis reaction of the Diazinon (LD50; Oral, rat 66 mg/kg)
to its comparatively much less toxic compounds [70–73]; 2-isopropyl-6-
methyl-4-pyrimidinol (IMP) (LD50; Oral, rat 2700 mg/kg) and O,O-
diethyl phosphorothioic acid (PA) (LD50; Oral, rat 4510 mg/kg), the
hydrolysis products, using ZIFs in aqueous buffer solution illustrates in
Scheme 1. Additionally, all the toxicity degrees related to Diazinon and
their hydrolysis products (PA and IMP) were provided in Table 2.
As shown in Fig. 6a and b, in situ 31P NMR spectra measurements
demonstrating the abrupt degradation of diazinon to O,O diethyl
Fig. 4. (a) CO2 ads/des isotherm of S1 at 273 K and (b) N2 ads/des diagram of
S2 (black squares and red circles) and S2 after 5 runs (blue and green triangles)
at 77 K. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
Inversely, the type I nitrogen isotherm of S2 (Fig. 4b, black squares, and
red circles) displays the presence of micropores and macropores proved
by high N2 uptake at relatively low and high pressures which is made
during packing of ZIF-8 crystals, respectively. Total pore volume and
micropore volume of as-obtained ZIF-8 are about 1.09 and
0.60 cm3 g−1, respectively. Furthermore, SBET was obtained 1156 m2/g
5

A. Ebrahimi, et al.
MolecularCatalysis490(2020)110965
Scheme 1. The hydrolysis reaction of Diazinon in the presence of ZIFs.
The conversion diagram for S1, S2, S2 post-filter, and Diazinon
(without the catalyst) is shown in Fig. 8a. In this case, surprisingly, the
hydrolysis of Diazinon in the proximity of a catalytic amount of ZIF is
nearly instantaneous. The quantitative alternation of Diazinon into the
IMP and PA is observed within 4 min (S2). The percentages of hydro-
lysis reaction were beheld to be measured 13.15 and 30.68% at 1 min,
29.34 and 58.21% at 2 min, 46.34 and 80.76% at 3 min and 60.6 and
99.6% at 4 min for S1 and S2, respectively. Comparison of their ob-
tained turnover frequency (TOF) between S1 (0.6 s−1) and S2 (more
than 1.3 s−1) was something nearly greater than two times for S2 (red
circles in Fig. 8a) compared to S1 (black squares in Fig. 8a) at each time
which would be analogous to those organophosphates simulant de-
composition followed recently [9,10].
Subsequently, the catalysis heterogeneous trait test was ascertained
by the filtration of the optimized S2 mixture using a 0.22 μm syringe
after 1 min. Blue triangles in Fig. 8a and chiefly the 31P NMR peaks in
Fig. 8b at 1, 5, 10 and 20 min, revealing the reaction did not promote
substantially and then determining negligibly less catalysis reactivity
up to less than 0.1% after 20 min in the absence of the catalyst. Hence,
it can be deduced that the reaction is certainly accelerated by ZIF cat-
alyst and not solely by the other soluble species such as solvent or
buffer.
Table 2
Relative toxicity degrees of Diazinon, PA and IMP in Oral, rat.
Toxicant
LD50 (mg/kg)
Ref
Diazinon
PA
IMP
66
4510
2700
[70]
[71]
[72,73]
phosphorothioic acid (PA) which were computed by estimating the 31P
NMR peaks for Dizinon (δ = 61.2 ppm) to that of PA (δ = 56.3 ppm)
[74] from 1 to 6 min and 1 to 4 min after the adding of Diazinon in
solution for S1 and S2, respectively. Initial rate estimations in Fig. 7a
and b, evidence incontrovertibly that S2 exceptionally further lower the
Diazinon half-life from 2.22 to 0.5 min. What’s more, it is worthwhile to
express that in addition to much more stabilization of ZIF-8 framework
than that of ZIF-7 in water, corresponding comparably lower particle
size and higher surface area of S2 than that of S1 in this research and
particularly, the spatial hindrance (induce by benzene ring at imida-
zolate moiety in S1 and Diazinon aromatic ring compared to S2); pre-
sumably would avoid effective contacting to approach catalytic centers
(metal and imidazolate) significantly which have had phenomenally
considerable role in higher hydrolysis rate of S2.
Additionally, the background reaction was also operated without
Fig. 6. 31P NMR spectra illustrating the hydrolysis track of Diaziinon (δ = 61.2 ppm) to PA (δ = 56.3 ppm) in the presence of (a) S1 and (b) S2.
6

A. Ebrahimi, et al.
MolecularCatalysis490(2020)110965
Fig. 7. Kinetic plots depicting the reaction of Diazinon with (a) S1 and (b) S2 in buffer solution, respectively. Initial half-life (t1/2) was simply measured by drawing
the obvious Ln of the conversion versus time; the slope (k) is correlated to the half-life by t1/2 = Ln 2/k.
Fig. 8. (a) Reaction conversion percent/time diagram of Diazinon
in the presence of S1 (black squares), S2 (red circles), post-fil-
tration of S2 solution after 1 min (blue triangles) and in the ab-
sence of catalyst (green triangles) and 31P NMR spectra of (b) S2
post-filter in the period of 1–20 min and of (c) Diazinon without
catalyst in different times from 1 min to 5 days at ambient tem-
perature, respectively. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web
version of this article.)
the catalyst. However, the 31P NMR peaks of Diazinon were collected
without the catalyst in aqueous solution at 1, 20, 60 min, 1 day, 3 and 5
days (Fig. 8c). Meanwhile, the conversion after 20 min and 5 days ac-
counted only up to less than 0.1% and 0.2% (green triangles in Fig. 8a)
altogether the 31P NMR of Diazinon in Fig. 8c affirming the reaction did
not proceed remarkably without catalyst even over 5 days.
All of these monitoring describe clearly the complete fracture of the
PeO bond in the presence of catalysts and much more comparably
excellent effectiveness of S2 than that of S1 after 4 min versus 6 min as
well. Given these, therefore, S2 was opted as an optimized sample for
more investigations not to perform much more excessive work to show
their potential competence in cleavage of organophosphates.
Fortunately, to a great extent of precision likewise 31P NMR in-
vestigations and encouraged by it, HPLC measurements that were
conducted on optimized S2 is again an indication of fast completion of
hydrolysis reaction by S2 over a period of 4 min. Fig. 9a presents the
swift growth of IMP peak intensity at the retention time of 1.8 min
versus that of Diazinon at 6.4 min, endorses the bond breakage. It ex-
plicitly would be occurred by ZIF in an exact optional attack of the PeO
moiety in Diazinon which would be applicable to the other
7

A. Ebrahimi, et al.
MolecularCatalysis490(2020)110965
Fig. 9. Hydrolysis progress of Diazinon (6.4 min) to IMP (1.8 min)
by (a) HPLC spectra and (b) UV–vis spectra (* displays the ab-
sorbance at which Diazinon observes and ** indicates the absor-
bance of IMP absorbs) demonstrating degradation has been hap-
pened at the times between 0–4 min using optimized S2,
respectively (c) Profile of conversion percentage versus 5 succes-
sive runs.
organophosphates [75,76]. Furthermore, the conversion percentage of
each time were 32.28, 61.53, 79.45 and 99.56% and also product yields
were 5.82, 11.08, 14.3 and 17.93 μmol according to the initial input
reactant (Diazinon; 18 μmol) for 1, 2, 3 and 4 min after addition of
Diazinon, respectively. The comparatively similar results earned by
HPLC data also indicating the great harmony with the spectra mon-
itored by 31P NMR instrument (Fig. 6b).
Fig. 9b represents the UV/Vis spectra of the hydrolysis reaction in
the presence of the optimized S2 with the interval time of each 25 s up
to 4 min where the one asterisk mark (*) in the range of 225−255 nm
and two asterisks ones (**) spanning over about 200–220 and
300−350 nm are ascribed to Diazinon and IMP, respectively. These
wavelengths at which simultaneously the absorbance of reagent (Dia-
zinon) are descending and those of product (IMP) are ascending;
thereby explaining the particularly selective dissociation of PeO bond
in Organophosphates by ZIF and subsequently illustrating that these
data are in line again with the identical afore-reported contributions
[9,10,77].
Subsequently, free pair electrons of nitrogen which serves as Lewis base
would efficaciously enhance the reaction directly by attachment attack
to the sufficiently high polarized P atom of the P]S bond and then
reaches a highly energetic transition state (TS; shown in bracket).
Further, R′OH moiety (IMP; observed by UV–vis-equipped HPLC ac-
companied by UV–vis spectroscopy), simultaneously is eliminated by
the second nucleophilic attack of OH− ions generated from H2O solvent
molecules (N-ethylmorpholine; buffer solution function as wiping out
agent of acidic byproduct (here including R′OH) and deprotonating
agent of water as well as to elevate the speed of the reaction [78,79])
again to phosphorus atom to terminate the reaction by forming the
other moiety PS(OR)2OH (PA; monitored by 31P NMR). In this stage the
process begins itself again by reverting of the catalyst to its initial form.
In our case, the synergistic catalytic activation of the OP imposed by
concomitantly Lewis acid-cum-Lewis base behavior of ZIF would be
practically beheld graphically here to boost the detoxification of such
deleterious compound [14,80–84].
3.4. Recycling and inviolability inspections
3.3. Hydrolysis reaction mechanism
Fascinatedly enough, the surface areas of S2 diminished from 1156
to 846 m2/g after 5 sequential reactions which have been depicted in
Fig. 4b (blue and green triangles) stating that the conversion percen-
tages were lessened from 98.35 in run 1 to 97.04 (run 2), 96.01 (run 3),
95.06 (run 4), and to 90.04% in run 5 is the delineation of the re-uti-
lization of S2 would be done after consecutive cycles with little de-
crease in its efficiency (Fig. 9c). With having this said, the assumption is
also reinforced by the color alternation of S2 from white to pale yellow.
As a consequence, ZIF retained its stability during process which was
confirmed by excellent durability of optimized S2 architecture and was
checked by X-ray diffraction (XRD), FT-IR spectra and FE-SEM images
depicted in Figs. 10, 11 and 12, respectively. Within the hydrolysis
process though the catalytic efficiency was not declined through the
blocking of the S2 windows and voids by diverse species in solution; in
Actually, the whole process would be comprehended better in a
meaningfully visual depiction by its suggested mechanism which is
hypothetically proposed as a main overall procedure for catalytic de-
gradation of OPs. As can be seen in Scheme 2, the process commences
with the first step which the imidazolate ligands on the surface of the
catalyst may detach partly instantly duo to the differences of charges
happened by solvent and the other components throughout the reac-
tion. Next, after the dissociation of linker, an electrophilic attack would
be taken placed by Zn (II) Lewis acid center to the sulfur atom of the
P]S bond of Diazinon to construct a complex resulting in making P]S
bond more polarized and triggered it to being more prone to activate
the acceleration of the nucleophilic attack performed by free non-
bonding nitrogen atom on another Zn atom in the further step.
8

A. Ebrahimi, et al.
MolecularCatalysis490(2020)110965
Scheme 2. Proposed overall hypothetical catalytic detoxification mechanism.
Fig. 10. PXRD patterns of pre- and post-catalysis of optimized S2 after 5 se-
quential cycles.
turn, representing that the catalyst maintains its post-catalysis crystal
structure inviolability after 5 incessant cycles. As can be observed, the
comparison of the pre- and post-catalysis patterns, spectra and images
vividly presents its approximately wonderful unspoiled framework ex-
posure to the simulant and solvent in the solution. Not having en-
visaged previously that the pore closure has no considerably high im-
pact on hydrolysis enhancement alongside even much more larger size
of Diazinon than the aperture size of ZIF (∼0.3 nm) [50,61–64], As a
result, it causes not to pass through the gate of ZIF to locate into the
innermost of ZIF structure; successively regarding that reaction would
take place uniquely on the outer sites of ZIF framework. Thereby, it can
be deduced that the reaction is happening extremely swift.
Fig. 11. FT-IR spectra of pre- and post-catalysis of optimized S2 after 5 in-
cessant successions.
4. Conclusions and outlooks
By and large, Successfully, we here have proved for the first time the
hydrolysis degradation of OP pesticide (Diazinon) was performed by a
series of ZIFs in aqueous solution demonstrating high capability of these
materials in catalytic detoxification of organophosphates simulant in
comparison to those have been studied ever which have proven their
catalytic efficiency too time-consuming. Unequivocally, such swift
catalytic detoxification of the organophosphate (Diazinon) was
9

A. Ebrahimi, et al.
MolecularCatalysis490(2020)110965
Fig. 12. FE-SEM images of (a) pre- and (b) post-catalysis of optimized S2 and after 5 consecutive runs, respectively.
confirmed by 31P NMR and HPLC within 4 min, favorably. As a con-
sequence, all the observations illustrated here also approve that ZIFs
materials, particularly wondrous optimized S2 (ZIF-8), have been pro-
minent for their chemical and thermal stabilities in harsh media defi-
nitely acknowledging its marvelous perseverance and relatively high
performance after several incessant catalysis reactions which can be led
that the usage of them would be as an exceptional competitor and
premium alternative material to those MOFs investigated, so far.
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CRediT authorship contribution statement
[17] C. Montoro, F. Linares, E.Q. Procopio, I. Senkovska, S. Kaskel, S. Galli,
N. Masciocchi, E. Barea, J.A.R. Navarro, J. Am. Chem. Soc. 133 (2011)
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2012.06.011.
Arash Ebrahimi: Conceptualization, Investigation, Writing - ori-
ginal draft. Ehsan Nassireslami: Supervision, Writing - review &
editing, Project administration. Ramin Zibaseresht: Supervision,
Methodology, Resources. Maedeh Mohammadsalehi: Software,
Formal analysis, Data curation.
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O.K. Farha, Inorg. Chem. 54 (2015) 10829–10833, https://doi.org/10.1021/acs.
inorgchem.5b01813.
Declaration of Competing Interest
[21] P. Nunes, A.C. Gomes, M. Pillinger, I.S. Gonçalves, M. Abrantes, M. Abrantes,
Microporous Mesoporous Mater. 208 (2015) 21–29, https://doi.org/10.1016/j.
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The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
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