Efficient Catalytic Oxidative Desulfurization toward Thioether and Sulfur Mustard Stimulant by Polyoxomolybdate-Resorcin[4]arene-Based Metal-Organic Materials

Article abstract of DOI:10.1021/acs.inorgchem.0c00225

The design and synthesis of effective and recyclable oxidative desulfurization catalysts is of great importance in view of environmental protection and human health. Herein, a family of polyoxomolybdate-based inorganic-organic hybrid materials, namely, [Mn(TMR4A)(H₂O)₄][Mo₆O₁₉]·0.5CH₃CH₂OH·H₂O (1), [Ni(TMR4A)(H₂O)₄][Mo₆O₁₉]·0.5CH₃CH₂OH·H₂O (2), [Zn(TMR4A)(H₂O)₄][Mo₆O₁₉]·0.5CH₃CH₂OH·H₂O (3), and [Co₂(TMR4A)₂(H₂O)₄(β-Mo₈O₂₆)]·CH₃CN·12H₂O (4), were assembled by the functionalized resorcin[4]arene ligand (TMR4A) with polyoxomolybdate and metal ions under solvothermal conditions. In isostructural 1-3, the [M(TMR4A)(H₂O)₄]²⁺ species (M = Mn^II, Ni^II, Zn^II) and [Mo₆O₁₉]^2- anions are held together via C-H···O hydrogen bonds to give a 3D supramolecular architecture. In 4, two [Co(TMR4A)(H₂O)₂]²⁺ cations were linked by one [β-Mo₈O₂₆]^4- anion to produce an attractive molecular dimer. Remarkably, 1-4, as recyclable heterogeneous catalysts, exhibit efficient catalytic oxidation desulfurization activities toward thioethers. Particularly, 1, as a representative example, features selective catalytic oxidation for sulfur mustard simulant. Moreover, their electrochemical properties were also studied.

Full text of DOI:10.1021/acs.inorgchem.0c00225

pubs.acs.org/IC
Article
Efficient Catalytic Oxidative Desulfurization toward Thioether and
Sulfur Mustard Stimulant by Polyoxomolybdate−Resorcin[4]arene-
Based Metal−Organic Materials
Ming-Yue Yu, Jin Yang,* Ting-Ting Guo, and Jian-Fang Ma*
Cite This: https://dx.doi.org/10.1021/acs.inorgchem.0c00225
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: The design and synthesis of effective and recyclable oxidative
desulfurization catalysts is of great importance in view of environmental
protection and human health. Herein, a family of polyoxomolybdate-based
inorganic−organic hybrid materials, namely, [Mn(TMR4A)(H2O)4]-
[Mo6O19]·0.5CH3CH2OH·H2O (1), [Ni(TMR4A)(H2O)4][Mo6O19]·
0.5CH3CH2OH·H2O (2), [Zn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·
H2O (3), and [Co2(TMR4A)2(H2O)4(β-Mo8O26)]·CH3CN·12H2O (4), were
assembled by the functionalized resorcin[4]arene ligand (TMR4A) with
polyoxomolybdate and metal ions under solvothermal conditions. In
isostructural 1−3, the [M(TMR4A)(H2O)4]2+ species (M = MnII, NiII,
ZnII) and [Mo6O19]2− anions are held together via C−H···O hydrogen bonds
to give a 3D supramolecular architecture. In 4, two [Co(TMR4A)(H2O)2]2+
cations were linked by one [β-Mo8O26]4− anion to produce an attractive
molecular dimer. Remarkably, 1−4, as recyclable heterogeneous catalysts, exhibit efficient catalytic oxidation desulfurization
activities toward thioethers. Particularly, 1, as a representative example, features selective catalytic oxidation for sulfur mustard
simulant. Moreover, their electrochemical properties were also studied.
activity.41−47 Nevertheless, POMs are easily soluble in solvents,
INTRODUCTION
■
which limits their application as recycled catalysts. POM-based
The effective removal of sulfur-based compounds from
metal−organic materials, assembled with POMs, organic
petroleum remains a serious environmental problem owing
ligands, and metal ions, feature structural diversity and
to the negative influence on the atmosphere and human health
stability.48 Thus, they were used as heterogeneous catalysts
arising from their combustions.1,2 As a result, it is an important
in various catalytic reactions.37,49,50 Moreover, the organic
process for desulfurization of transportation fuels in the case of
ligands play an important role in the assembly of the target
safeguarding the environments.3−6 In this regard, hydro-
POM-based metal−organic catalysts.
desulfurization (HDS) is considered to be the most commonly
Resorcin[4]arenes are excellent organic ligand candidates for
used industrial process for removing sulfur diesels,7−10 while
the construction of POM-based metal−organic materials
this technique is usually carried out under severe operating
because of their bowl-shaped aromatic cavities and easily
conditions with low desulfurization efficiencies.11−14 Recently,
modified structure features.51−53 Usually, the target structures
alternative desulfurization approaches have been developed
of the resorcin[4]arenes can be achieved by well modifying
including oxidative desulfurization (ODS),15−19 adsorp-
their upper rims with different functional groups.54−56 In this
tion,20−22 biodesulfurization, etc. Among them, ODS is
facet, the mercaptopyridine N-oxide groups possess strong and
regarded as the most promising technique for deep
flexible coordination ability with metal ions. In particular, the
desulfurization of fuel.23−25 In particular, the ODS method is
substituted 2-mercaptopyridine N-oxide groups on the
greatly efficient for the removal of refractory aromatic sulfur-
modified resorcin[4]arenes tend to chelate metal ions to
based species relative to HDS.25
On the other hand, sulfur mustard (mustard gas), used as
one of the most typical and toxic chemical warfare agents
produce stable structures.57 Thus, the 2-mercaptopyridine N-
Received: January 21, 2020
(CWAs) in World War I, is a major threat to human
health.26−32 The ODS technique is the most popular method
to selectively oxidize sulfur mustard to nontoxic sulfoxide
rather than sulfone in the presence of suitable catalysts.33−36
In this facet, polyoxometalates (POMs), one of the most
popular types of catalysts,37−40 demonstrate remarkable ODS
https://dx.doi.org/10.1021/acs.inorgchem.0c00225
© XXXX American Chemical Society
Inorg. Chem. XXXX, XXX, XXX−XXX
A

Inorganic Chemistry
pubs.acs.org/IC
Article
oxide group-functionalized resorcin[4]arenes are potential
organic ligand candidates for constructing POM-based
metal−organic catalysts.58−60
desulfurization activity toward thioethers as stable and
recyclable heterogeneous catalysts. More importantly, 1, as a
representative example, exhibits selective catalytic oxidation for
the sulfur mustard simulant 2-chloroethyl ethyl sulfide
(CEES). Moreover, their electrochemical properties were
also investigated.
Herein, we successfully synthesized four new inorganic−
organic hybrid materials, namely, [Mn(TMR4A)(H2O)4]-
[Mo6O19]·0.5CH3CH2OH·H2O (1), [Ni(TMR4A)(H2O)4]-
[Mo6O19]·0.5CH3CH2OH·H2O (2), [Zn(TMR4A)(H2O)4]-
[ M o 6 O 1 9 ] · 0 . 5 C H 3 C H 2 O H · H 2 O ( 3 ) , a n d
[Co2(TMR4A)2(H2O)4(β-Mo8O26)]·CH3CN·12H2O (4),
with a functionalized resorcin[4]arene ligand (TMR4A),
metal ions, and POMs. These hybrid materials exhibit
structural diversities adjusted by POMs and TMR4A (Scheme
1). Markedly, 1−4 feature efficient catalytic oxidation
EXPERIMENTAL SECTION
■
The materials and characterizations used in this work are given in the
Supporting Information. The organic ligand TMR4A was prepared by
following the literature.57 Quantities of catalysts 1−4 were achieved
by using a large number of Teflon reactors (15 mL) under
hydrothermal conditions.
Synthesis of [Mn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·
H2O (1). A mixture of MnCl2·4H2O (0.008 g, 0.04 mmol), TMR4A
(0.011 g, 0.01 mmol), [(n-C4H9)4N]4[Mo8O26] (0.023 g, 0.01
mmol), ethanol (5 mL), and deionized water (3 mL) was placed in
a Teflon reactor (15 mL) and heated at 100 °C for 6 days. After
cooling to room temperature, yellow-green rod crystals were achieved
Scheme 1. Structure of TMR4A
in 40% yield. Anal. Calcd for C61H65MnMo6N4O36.5S4 (Mr
=
2196.99): C, 33.35; H, 2.98; N, 2.55. Found: C, 32.57; H, 3.12; N,
2.52. IR data (KBr, cm−1): 3733 (w), 3419 (w), 3108 (m), 2970 (w),
1591 (w), 1557 (w), 1472 (s), 1426 (m), 1375 (w), 1280 (w), 1252
(m), 1220 (m), 1149 (m), 1096 (m), 1049 (w), 1018 (m), 960 (s),
800 (s), 756 (s), 708 (m), 688 (m), 646 (m), 578 (m), 501 (m), 438
(m).
Synthesis of [Ni(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O
(2). A mixture of NiCl2·6H2O (0.010 g, 0.04 mmol), TMR4A (0.011
g, 0.01 mmol), [(n-C4H9)4N]4[Mo8O26] (0.023 g, 0.01 mmol),
Figure 1. (a) Coordination sphere of MnII. (b) Hydrogen-bonding interactions formed by one [Mn(TMR4A)(H2O)4]2+ cation with six
[Mo6O19]2− anions. (c) Hydrogen-bonding interactions formed by one [Mo6O19]2− anion with six [Mn(TMR4A)(H2O)4]2+ cations. (d) 3D
architecture constructed by [Mo6O19]2− anions and [Mn(TMR4A)(H2O)4]2+ cations via hydrogen bonds. Symmetry codes: #1, x, −y, z; #2, −x +
1, y, −z.
B
https://dx.doi.org/10.1021/acs.inorgchem.0c00225
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
Figure 2. (a) Coordination sphere of CoII. (b) Dimeric structure of 4. (c−d) 3D supramolecular framework constructed by the [β-Mo8O26]4−
anions and [Co(TMR4A)(H2O)2]2+ cations through hydrogen-bonding interactions. Symmetry code: #1, −x + 1, −y, −z.
ethanol (6 mL), and deionized water (2 mL) was sealed in a Teflon
reactor (15 mL) and heated at 100 °C for 6 days. After cooling to
room temperature, green rod crystals were collected in 32% yield.
Anal. Calcd for C61H65Mo6N4NiO36.5S4 (Mr = 2200.76): C, 33.29; H,
2.98; N, 2.55. Found: C, 31.88; H, 3.09; N, 2.50. IR data (KBr, cm−1):
3733 (w), 3421 (w), 3112 (w), 2970 (w), 1592 (w), 1557 (w), 1473
(s), 1427 (m), 1281 (w), 1250 (w), 1218 (m), 1150 (w), 1096 (m),
1051 (w), 1019 (m), 961 (s), 801 (s), 757 (s), 709 (m), 688 (m),
579 (m), 502 (w), 441 (m).
Synthesis of [Zn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O
(3). 3 was prepared with a method similar to that of 2 except that
NiCl2·6H2O (0.010 g, 0.04 mmol) was replaced by Zn(NO3)2 (0.012
g, 0.04 mmol) and 1.2 M HCl (1 drop) was used. Green rod crystals
were obtained in 30% yield. Anal. Calcd for C61H65Mo6N4O36.5S4Zn
(Mr = 2207.42): C, 33.20; H, 2.97; N, 2.54. Found: C, 32.89; H, 3.00;
N, 2.38. IR data (KBr, cm−1): 3564 (w), 3110 (w), 2969 (w), 1591
(w), 1557 (w), 1473 (s), 1427 (m), 1281 (w), 1250 (m), 1219 (m),
1150 (m), 1096 (m), 1050 (w), 1019 (m), 961 (s), 801 (s), 756 (s),
708 (m), 688 (m), 578 (m), 501 (m), 437 (m).
Synthesis of [Co2(TMR4A)2(H2O)4][β-Mo8O26]·CH3CN·12H2O
(4). A mixture of TMR4A (0.011 g, 0.01 mmol), CoCl2·6H2O (0.010
g, 0.04 mmol), [(n-C4H9)4N]4[Mo8O26] (0.023 g, 0.01 mmol),
acetonitrile (3 mL), and deionized water (5 mL) was sealed in a 15
mL Teflon reactor at 100 °C for 3 days. After cooling to room
temperature, pink rod crystals were obtained in 25% yield. Anal. Calcd
for C122H139Co2Mo8N9O66S8 (Mr = 3929.27): C, 37.29; H, 3.57; N,
3.21. Found: C, 37.32; H, 3.29; N, 3.14. IR data (KBr, cm−1): 3733
(w), 3356 (m), 2972 (m), 1634 (w), 1594 (w), 1559 (w), 1472 (s),
1426 (m), 1339 (w), 1300 (w), 1250 (m), 1212 (m), 1151 (m), 1093
(m), 1054 (m), 1020 (m), 981 (s), 903 (s), 837 (m), 756 (m), 720
(s), 580 (m), 414 (m).
RESULTS AND DISCUSSION
■
Structures of 1−3. Compounds 1−3 were prepared in the
mixed solutions of ethanol and water. Noticeably, the
precursor [Mo8O26]4− was transformed to [Mo6O19]2− during
the hydrothermal syntheses.61 Isostructural 1−3 crystallize in
the monoclinic C2/m space group (Table S1). Thus, the
crystal structure of 1 will be described (Figures S1 and S2).
The asymmetric unit of 1 contains half of a TMR4A ligand,
half of a MnII cation, half of a [Mo6O19]2− anion, a quarter of a
free ethanol molecule, two coordination water molecules, and
half of a free water molecule. Each MnII cation exhibits an
octahedral coordination sphere, completed by two oxygen
atoms of one TMR4A ligand (O6 and O6#1) and four oxygen
atoms of four water molecules (O1W, O2W, O3W, and
O3W#1) with Mn−O distances of 2.079(7)−2.199(7) Å
(Figure 1a). Noticeably, the [Mo6O19]2− anion is free and
balances the positive charge of the [Mn(TMR4A)(H2O)4]2+
unit. Remarkably, each [Mn(TMR4A)(H2O)4]2+ cation
interacts with six [Mo6O19]2− anions (Figure 1b), and each
[Mo6O19]2− anion is interlinked by six [Mn(TMR4A)-
(H2O)4]2+ cations (Figure 1c) through C−H···O hydrogen
bonds (Table S2), yielding a 3D supramolecular architecture
(Figure 1d).
C
https://dx.doi.org/10.1021/acs.inorgchem.0c00225
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
Figure 3. PXRD patterns of 1 in different organic solvents (a) and different pH values (b).
Structure of 4. Compound 4 was synthesized in the mixed
solution of acetonitrile and water. In the refinement of 4, the
SQUEEZE routine was employed to remove the disordered
solvents.62 Elemental analysis, the electron diffraction density,
and thermogravimentric analysis (TGA) suggest that there
exist half of a free CH3CN and six free water molecules in each
unit cell (Figure S3). As illustrated in Figure 2a, each CoII is
six-coordinated by six oxygen atoms from one TMR4A ligand
(O9 and O10), two water molecules (O1W and O2W), and
two [β-Mo8O26]4− anions, with Co−O distances ranging from
2.028(7) to 2.123(6) Å (Table S3). Markedly, two [Co-
(TMR4A)(H2O)2]2+ cations are held together by one [β-
Mo8O26]4− anion to produce an elegant dimer (Figure 2b).
Adjacent dimers are further joined by weak C−H···O hydrogen
bonds to give a 3D supramolecular framework (Table S2 and
Figure 2c,d).
During the syntheses of 1−4, we find that their crystallinities
are highly dependent on the solvent systems used. Isostructural
1−3 always crystallize in the mixture of ethanol and water,
while the crystals of 4 are only obtained in the mixed solution
of acetonitrile and water. Clearly, the different solvent systems
influenced the complex crystal nucleation and growth.61
Besides, the [Mo8O26]4− anions were transformed to the free
[Mo6O19]2− anions in 1−3 and the large [β-Mo8O26]4− anions
in 4, which may also account for the different solvent systems
used under the hydrothermal conditions.63
Stability. Chemical stability is a key prerequisite for the
property study of the compounds.64 In this study, 1 as a
representative example was used to explore the stability. The
samples of 1 were soaked in different organic solvents or
aqueous solutions (pH = 0, 2, 4, 6, 8, 10, and 12) for 12 h. To
gain full interaction between the acid−base and compound, the
soaking time of the sample was prolonged to 12 h. Afterward,
the samples were filtered and washed with methanol. The dried
samples in air were then used for powder X-ray diffraction
(PXRD) measurements. As described in Figure 3, their PXRD
patterns correspond to the simulated one, indicating structural
integrity.
Catalytic Oxidation for CEES. CWAs have caused
extremely serious damage to humankind, and therefore it is
greatly necessary to find effective catalysts for the oxidation or
degradation of CWAs. In this regard, the POM-based metal−
organic materials are effective catalyst candidates.65,66 Here,
considering the high toxicity of CWAs, CEES, featuring
chemical properties and structures similar to those of CWAs,
was chosen as the simulant molecule (Scheme 2). The catalytic
Scheme 2. Catalytic Oxidation of CEES to CEESO and
CEESO2 Catalyzed by 1 Using 3% H2O2
oxidative reaction for CEES was conducted in methanol (4
mL) with 1 as the catalyst (1.25 μmol) and 3% H2O2 as the
oxidant (1 mmol). The catalytic oxidative reaction was
1
monitored by H NMR data (Figures 4 and S4). Noticeably,
in the absence of catalyst 1, only 12% of CEES was
transformed into the corresponding CEESO and CEESO2 at
40 °C within 25 min (entry 1, Table 1). When 1 was used as
the catalyst, the conversions of CEES reach 93% and 99% at 30
and 40 °C within 25 min, respectively (Table 1). Further, the
catalytic oxidative dynamics toward CEES were also studied.
The conversion of CEES was monitored every 5 min. As
shown in Figure 5, the conversion rapidly reached 73% within
10 min and gradually increased to 99% when the reaction time
was prolonged to 25 min.
Remarkably, the catalytic oxidation activity of 1 toward
CEES is comparable to those of the reported POM-based
metal−organic catalysts.67−70 For example, the conversion of
CEES catalyzed by 1 is up to 99% with a CEESO selectivity of
97% at 40 °C within 25 min (entry 2, Table 1). For the known
PW12@NU-1000 catalyst, a similar conversion (98%) of CEES
was achieved under the similar conditions, but the selectivity of
CEESO is only up to 57%.70 The result indicates that 1
features a superior catalytic performance and high selectivity
toward CEES.
Catalytic ODS. Catalytic ODS of 1 toward sulfur-based
compounds was also studied. Methyl phenyl sulfide (MBT)
was selected as a model substrate (Scheme 3).42 The catalytic
oxidative reaction was carried out in CH3OH (5 mL) by using
D
https://dx.doi.org/10.1021/acs.inorgchem.0c00225
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
within 1 h by using 1 as the catalyst and H2O2 as the oxidant
(entry 1, Table 2). When 3% H2O2 and methanol were
a
Table 2. Catalytic Desulfurization of MBT with 1
temperature
time
(h)
conversion
b
entry catalyst oxidant
(°C)
solvent
(%)
1
2
3
4
5
1
1
1
none
H2O2
40
40
40
40
30
CH3OH
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
1
0.5
1
1
1
68
91
>99
22
TBHP
TBHP
TBHP
TBHP
1
92
a
Reaction conditions: substrate, 0.4 mmol; TBHP, 1 mmol; 1, 2
b
μmol; solvent, 5 mL. GC was used to determine the conversion.
replaced by 70% tert-butyl hydroperoxide (TBHP) and
dichloromethane, respectively, a satisfactory conversion was
achieved, as illustrated in Table 2. The conversion of MBT
reaches 91% within 0.5 h in the presence of TBHP and
dichloromethane (entry 2). Under the same conditions, almost
all MBT was oxidized by extending the reaction time to 1 h
(entry 3). When the reaction temperature was reduced under
the same conditions, the conversion decreases as well (entry
5). Noticeably, only 22% conversion of MBT was obtained in
the absence of catalyst (entry 4). Thus, the catalytic ODS was
measured in the presence of 1 mmol of TBHP, 2 μmol of
catalyst, and 5 mL of CH2Cl2 at 40 °C for 1 h.
1
Figure 4. H NMR data for the catalytic products of CEES at 40 °C
and different reaction times using 1 as the catalyst and H2O2 as the
oxidant and without a catalyst at 25 min in CDCl3. Peaks used for
calculations were labeled (the signals between 1.5 and 2.5 ppm were
generated from water and methanol).
a
Table 1. Catalytic ODS of CEES Catalyzed by 1
Further, different sulfur-based compounds were employed as
substrates to explore the catalytic behavior of 1. As listed in
Table 3, the monophenyl thioether substrates with electron-
withdrawing or -donor groups could be completely converted
into sulfoxides and sulfones at 40 °C within 1 h (entries 1−6).
For the diphenyl sulfide substrate, the steric hindrance has no
obvious influence on the catalytic performance of 1 (entry 7).
However, for thiophene sulfides, it will take prolonged time to
be completely oxidized under the same conditions. For
example, almost all of dibenzothiophene (DBT) was oxidized
within 5 h (entry 8). Owing to the steric hindrance and
electron density around the sulfur atoms on the thiophene
sulfides, the conversions of benzothiophene and 4,6-
dimethyldibenzothiophene (4,6-DMDBT) reached to 92%
and 98%, respectively, within 10 h (entries 9 and 10).
Moreover, the catalytic behaviors of 2−4 toward DBT and 4,6-
DMDBT were also investigated under the same conditions
(entries 11−16). Compounds 2−4 exhibit similar catalytic
activities for the oxidation of different thioethers.
temperature
time
conversion selectivity
b c
entry catalyst
(°C)
oxidant (min)
(%)
(%)
1
2
3
none
1
1
40
40
30
H2O2
H2O2
H2O2
25
25
25
12
99
93
98
97
99
a
Reaction conditions: 1, 1.25 μmol; H2O2, 1 mmol; substrate, 0.25
b
1
mmol; CH3OH, 4 mL. Isolated conversion was determined by H
c
NMR. Selectivity for CEESO.
The catalytic dynamic behaviors of 4,6-DMDBT and DBT
were studied with 1 as the catalyst. As depicted in Figure 6, the
catalytic oxidation conversions of the substrates were
monitored at different time intervals. Only 42% of DBT was
transformed into the corresponding oxidation products within
1 h, and the catalytic reaction finished after 5 h. For the
catalytic oxidation of 4,6-DMDBT, the conversion was
significantly enhanced (56%) within 2 h (Figures 7 and S5).
Afterward, the conversions slowly reached 98% after 10 h.
Meanwhile, no obvious catalytic reaction activity for the
remaining filtrate was observed when the catalyst was removed
after 3 h (Figure 7). Moreover, the inductively coupled plasma
(ICP) analysis demonstrates that no MnII cations were leached
in the filtrate, suggesting the heterogeneity of the catalytic
reaction.
Figure 5. Catalytic oxidative dynamics of CEES catalyzed by 1.
Scheme 3. Catalytic Desulfurization of MBT to MBTO and
MBTO2 by 1 in CH2Cl2 at 40 °C
1 (2 μ mol) and 3% H2O2 (1 mmol) at 40 °C. Gas
chromatography (GC) was applied to determine conversion of
the substrate. The conversion of MBT was only up to 68%
To examine the reusability of catalyst 1, a series of recycling
experiments for the oxidation of MBT were performed. As
E
https://dx.doi.org/10.1021/acs.inorgchem.0c00225
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
a
Table 3. Catalytic Oxidation of Various Thioethers by 1−4 Using TBHP as the Oxidant
a
b
Reaction conditions: CH2Cl2, 5 mL; catalyst, 2 μmol; substrate, 0.4 mmol; TBHP, 1 mmol; 40 °C. High-performance liquid chromatography was
used to determine the conversion.
F
https://dx.doi.org/10.1021/acs.inorgchem.0c00225
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
Figure 6. Dynamic curve for the catalytic oxidation of DBT by 1.
Figure 9. PXRD patterns of 1 for simulated (black), experimental
(red), and recycled data after 4 runs of the catalytic oxidation of MBT
(blue).
Figure 7. Conversion curves of 4,6-DMDBT with the reaction time
catalyzed by 1 (red) and by filtrate after 3 h of catalytic reaction
(blue).
Figure 10. FT-IR spectra of 1 before (black) and after four cycles of
the catalytic oxidation reaction (red).
illustrated in Figure 8, the catalytic activity of 1 was well-
maintained after four runs of the catalytic reaction. In addition,
CuCl2 when the reaction time was prolonged to 4 h (entry 1,
Table S4). Moreover, in the presence of NiCl2·6H2O and
TMR4A, only 25% MBT was converted to the products at 50
°C for 1 h (entry 2, Table S4). In addition, the typical
polyoxomolybdate, [Mo8O26]4− anion, featured remarkable
catalytic activity (82.3% conversion) toward DBT at 30 °C
within 1.5 h (entry 3, Table S4). The result further indicates
that polyoxomolybdates in 1−4 are the main catalytic active
species for the catalytic oxidation reactions.40,49
On the other hand, the catalytic ODS performances of 1 are
comparable to those of the related POM-based catalysts
(Table S5). For instance, MBT was completely converted to
catalytic products, with 1 as the catalyst at 40 °C within 1 h.
When the POM-based [Co2L0.5V4O12]·3DMF·5H2O (L = 2-
(2-pyridyl)imidazole-functionalized resorcin[4]arene) and
(en)[Cu3(ptz)4(H2O)4][Co2Mo10H4O38]·24H2O [en = ethyl-
enediamine; ptz = 5-(4-pyridyl)-1H-tetrazole] were used as
catalysts, the overall conversions of MBT were accomplished
within 4 h under similar conditions (Table S5).42,49 In
addition, the catalytic oxidation of DBT by 1 finished within 5
h (entry 8, Table 3), while the similar conversions were
achieved by using [CoII(HBBTZ)(BBTZ)2.5][PMo12O40]
[BBTZ = 4,4′-bis(1,2,4-triazol-1-ylmethyl)benzene] and [Co-
(BBPTZ)3][HPMo12O40]·24H2O [BBPTZ = 4,4′-bis(1,2,4-
triazol-1-ylmethyl)biphenyl] within the prolonged reaction
Figure 8. Recycling experiments for the oxidation of MBT with 1.
the Fourier transform infrared (FT-IR) spectra and PXRD
patterns further indicate that catalyst 1 still retains structural
stability after four cycles of catalytic reactions (Figures 9 and
10).
It is well established that the POMs usually act as catalytic
active sites.36,41,42 For instance, the substrate MBT was
completely transformed to catalytic products with 1 as the
catalyst at 40 °C within 1 h (entry 3, Table 2). In contrast, the
conversion of MBT was only up to 28% in the presence of
G
https://dx.doi.org/10.1021/acs.inorgchem.0c00225
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
time (9 and 8 h).43 The result demonstrates that 1 is an
efficient potential heterogeneous catalyst for ODS.
REFERENCES
■
(1) Yang, C.; Ji, H.; Chen, C.; Ma, W.; Zhao, J. Desulfurization of
Thiophenes in Oils into H2SO4 Using Molecular Oxygen. Appl. Catal.,
B 2018, 235, 207−213.
(2) Zeng, X.; Xiao, X.; Chen, J.; Wang, H. Electron-Hole
Interactions in Choline-Phosphotungstic Acid Boosting Molecular
Oxygen Activation for Fuel Desulfurization. Appl. Catal., B 2019, 248,
573−586.
CONCLUSIONS
■
In summary, we have successfully synthesized a series of
POM−resorcin[4]arene-based metal−organic catalysts
through a solvothermal method. These hybrid materials exhibit
structural diversities tuned by POMs as well as TMR4A.
Markedly, they are very stable in different organic solvents as
well as different pH values. Importantly, 1 features an effective
oxidation degradation for toxic representative CEES. In
particular, they feature efficient catalytic activities for catalytic
ODS as recycled catalysts. These materials are also potentials
for the oxidation of ascorbic acid and the reduction of NaBrO3.
(3) Juliao
Goncalves, I. S.; Balula, S. S. Desulfurization of Liquid Fuels by
̃
, D.; Gomes, A. C.; Pillinger, M.; Valenca̧ , R.; Ribeiro, J. C.;
̧
Extraction and Sulfoxidation Using H2O2 and [CpMo(CO)3R] as
Catalysts. Appl. Catal., B 2018, 230, 177−183.
(4) Liu, L.; Guo, F.; Xu, J.; Hu, J.; Wang, H.; Liu, H.; Wang, M.
Adsorption-Enhanced Oxidative Desulfurization by a Task-Specific
Pyridinium-Based Porous Ionic Polymer. Fuel 2019, 244, 439−446.
(5) He, J.; Liu, H.; Xu, B.; Wang, X. Highly Flexible Sub-1 nm
Tungsten Oxide Nanobelts as Efficient Desulfurization Catalysts.
Small 2015, 11, 1144−1149.
(6) Wang, L.; Qi, T.; Wu, S.; Zhang, S.; Qi, D.; Xiao, H. A Green
and Robust Solid Catalyst Facilitating the Magnesium Sulfite
Oxidation in the Magnesia Desulfurization Process. J. Mater. Chem.
A 2017, 5, 8018−8028.
ASSOCIATED CONTENT
■
sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c00225.
(7) Zhou, W.; Wei, Q.; Zhou, Y.; Liu, M.; Ding, S.; Yang, Q.
Hydrodesulfurization of 4,6-Dimethyldibenzothiophene over NiMo
Sulfide Catalysts Supported on Meso-Microporous Y Zeolite with
Different Mesopore Sizes. Appl. Catal., B 2018, 238, 212−224.
(8) Rangarajan, S.; Mavrikakis, M. On the Preferred Active Sites of
Promoted MoS2 for Hydrodesulfurization with Minimal Organo-
nitrogen Inhibition. ACS Catal. 2017, 7, 501−509.
(9) Fu, W.; Zhang, L.; Tang, T.; Ke, Q.; Wang, S.; Hu, J.; Fang, G.;
Li, J.; Xiao, F. S. Extraordinarily High Activity in the Hydro-
desulfurization of 4, 6-Dimethyldibenzothiophene over Pd Supported
on Mesoporous Zeolite Y. J. Am. Chem. Soc. 2011, 133, 15346−
15349.
Experimental details, crystallographic data, structural
figures, TGA and cyclic voltammetry curves, H NMR,
FT-IR, GC, high-performance liquid chromatography,
PXRD patterns, and tables (PDF)
1
Accession Codes
CCDC 1909233−1909235 and 1909237 contain the supple-
mentary 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.
(10) Kulkarni, P. S.; Afonso, C. A. M. Deep Desulfurization of Diesel
Fuel Using Ionic Liquids: Current Status and Future Challenges.
Green Chem. 2010, 12, 1139−1149.
AUTHOR INFORMATION
(11) Pouladi, B.; Fanaei, M. A.; Baghmisheh, G. Optimization of
Oxidative Desulfurization of Gas Condensate via Response Surface
Methodology Approach. J. Cleaner Prod. 2019, 209, 965−977.
(12) Craven, M.; Xiao, D.; Kunstmann-Olsen, C.; Kozhevnikova, E.
F.; Blanc, F.; Steiner, A.; Kozhevnikov, I. V. Oxidative Desulfurization
of Diesel Fuel Catalyzed by Polyoxometalate Immobilized on
Phosphazene-Functionalized Silica. Appl. Catal., B 2018, 231, 82−91.
(13) Li, F.; Wu, B.; Liu, R.; Wang, X.; Chen, L.; Zhao, D. An
Inexpensive N-Methyl-2-Pyrrolidone-Based Ionic Liquid as Efficient
Extractant and Catalyst for Desulfurization of Dibenzothiophene.
Chem. Eng. J. 2015, 274, 192−199.
■
Corresponding Authors
Jin Yang − Key Laboratory for Polyoxometalate Science,
Department of Chemistry, Northeast Normal University,
Changchun 130024, China; Email: yangj808@nenu.edu.cn
Jian-Fang Ma − Key Laboratory for Polyoxometalate Science,
Department of Chemistry, Northeast Normal University,
Changchun 130024, China; orcid.org/0000-0002-4059-
8348; Email: majf247@nenu.edu.cn; Fax: +86-431-
85098620
(14) Toutov, A. A.; Salata, M.; Fedorov, A.; Yang, Y.-F.; Liang, Y.;
Cariou, R.; Betz, K. N.; Couzijn, E. P. A.; Shabaker, J. W.; Houk, K.
N.; Grubbs, R. H. A Potassium Tert-Butoxide and Hydrosilane
System for Ultra-Deep Desulfurization of Fuels. Nat. Energy 2017, 2,
17008.
(15) Bhutto, A. W.; Abro, R.; Gao, S.; Abbas, T.; Chen, X.; Yu, G.
Oxidative Desulfurization of Fuel Oils Using Ionic Liquids: A Review.
J. Taiwan Inst. Chem. Eng. 2016, 62, 84−97.
(16) Bokare, A. D.; Choi, W. Bicarbonate-Induced Activation of
H2O2 for Metal-Free Oxidative Desulfurization. J. Hazard. Mater.
2016, 304, 313−319.
Authors
Ming-Yue Yu − Key Laboratory for Polyoxometalate Science,
Department of Chemistry, Northeast Normal University,
Changchun 130024, China
Ting-Ting Guo − Key Laboratory for Polyoxometalate Science,
Department of Chemistry, Northeast Normal University,
Changchun 130024, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c00225
(17) Bhadra, B. N.; Song, J. Y.; Khan, N. A.; Jhung, S. H. TiO2-
Containing Carbon Derived from a Metal-Organic Framework
Composite: A Highly Active Catalyst for Oxidative Desulfurization.
ACS Appl. Mater. Interfaces 2017, 9, 31192−31202.
Notes
The authors declare no competing financial interest.
(18) Dou, J.; Zeng, H. C. Integrated Networks of Mesoporous Silica
Nanowires and Their Bifunctional Catalysis-Sorption Application for
Oxidative Desulfurization. ACS Catal. 2014, 4, 566−576.
(19) Bagheri, M.; Masoomi, M. Y.; Morsali, A. A MoO3-Metal-
Organic Framework Composite as a Simultaneous Photocatalyst and
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (Grants 21771034 and 21471029).
H
https://dx.doi.org/10.1021/acs.inorgchem.0c00225
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
Catalyst in the PODS Process of Light Oil. ACS Catal. 2017, 7,
6949−6956.
(40) Yang, H.; Jiang, B.; Sun, Y.; Zhang, L.; Huang, Z.; Sun, Z.;
Yang, N. Heterogeneous Oxidative Desulfurization of Diesel Fuel
Catalyzed by Mesoporous Polyoxometallate-Based Polymeric Hybrid.
J. Hazard. Mater. 2017, 333, 63−72.
(41) Cai, L.-X.; Li, S.-C.; Yan, D.-N.; Zhou, L.-P.; Guo, F.; Sun, Q.-
F. Water-Soluble Redox-Active Cage Hosting Polyoxometalates for
Selective Desulfurization Catalysis. J. Am. Chem. Soc. 2018, 140,
4869−4876.
(42) Lu, B.-B.; Yang, J.; Liu, Y.-Y.; Ma, J.-F. A Polyoxovanadate-
Resorcin[4]arene-Based Porous Metal-Organic Framework as an
Efficient Multifunctional Catalyst for the Cycloaddition of CO2 with
Epoxides and the Selective Oxidation of Sulfides. Inorg. Chem. 2017,
56, 11710−11720.
(43) Hao, X.-L.; Ma, Y.-Y.; Zang, H.-Y.; Wang, Y.-H.; Li, Y.-G.;
Wang, E.-B. A Polyoxometalate-Encapsulating Cationic Metal-
Organic Framework as a Heterogeneous Catalyst for Desulfurization.
Chem. - Eur. J. 2015, 21, 3778−3784.
(44) Huang, L.; Wang, S.-S.; Zhao, J.-W.; Cheng, L.; Yang, G.-Y.
Synergistic Combination of Multi-ZrIV Cations and Lacunary Keggin
Germanotungstates Leading to a Gigantic Zr24-Cluster-Substituted
Polyoxometalate. J. Am. Chem. Soc. 2014, 136, 7637−7642.
(45) Li, H.-L.; Lian, C.; Chen, L.-J.; Zhao, J.-W.; Yang, G.-Y. Two
Ce3+-Substituted Selenotungstates Regulated by N, N-Dimethyletha-
nolamine and Dimethylamine Hydrochloride. Inorg. Chem. 2019, 58,
8442−8450.
(46) Han, M.; Niu, Y.; Wan, R.; Xu, Q.; Lu, J.; Ma, P.; Zhang, C.;
Niu, J.; Wang, J. A Crown-Shaped Ru-Substituted Arsenotungstate for
Selective Oxidation of Sulfides with Hydrogen Peroxide. Chem. - Eur.
J. 2018, 24, 11059−11066.
(47) Wang, J.; Niu, Y.; Zhang, M.; Ma, P.; Zhang, C.; Niu, J.; Wang,
J. Organophosphonate-Functionalized Lanthanopolyoxomolybdate:
Synthesis, Characterization, Magnetism, Luminescence, and Catalysis
of H2O2-Based Thioether Oxidation. Inorg. Chem. 2018, 57, 1796−
1805.
(48) Du, D.-Y.; Qin, J.-S.; Li, S.-L.; Su, Z.-M.; Lan, Y.-Q. Recent
Advances in Porous Polyoxometalate Based Metal-Organic Frame-
work Materials. Chem. Soc. Rev. 2014, 43, 4615−4632.
(20) Ahmed, I.; Jhung, S. H. Adsorptive Desulfurization and
Denitrogenation Using Metal-Organic Frameworks. J. Hazard. Mater.
2016, 301, 259−276.
(21) Khan, N. A.; Jhung, S. H. Adsorptive Removal and Separation
of Chemicals with Metal-Organic Frameworks: Contribution of π-
Complexation. J. Hazard. Mater. 2017, 325, 198−213.
(22) Khan, N. A.; Bhadra, B. N.; Jhung, S. H. Heteropoly Acid-
Loaded Ionic Liquid@Metal-Organic Frameworks: Effective and
Reusable Adsorbents for the Desulfurization of a Liquid Model Fuel.
Chem. Eng. J. 2018, 334, 2215−2221.
(23) Campos-Martin, J. M.; Capel-Sanchez, M. C.; Perez-Presas, P.;
Fierro, J. L. G. Oxidative Processes of Desulfurization of Liquid Fuels.
J. Chem. Technol. Biotechnol. 2010, 85, 879−890.
(24) Yang, H.; Jiang, B.; Sun, Y.; Zhang, L.; Sun, Z.; Wang, J.;
Tantai, X. Polymeric Cation and Isopolyanion Ionic Self-Assembly:
Novel Thin-Layer Mesoporous Catalyst for Oxidative Desulfurization.
Chem. Eng. J. 2017, 317, 32−41.
(25) Wu, P.; Zhu, W.; Chao, Y.; Zhang, J.; Zhang, P.; Zhu, H.; Li,
C.; Chen, Z.; Li, H.; Dai, S. A Template-Free Solvent-Mediated
Synthesis of High Surface Area Boron Nitride Nanosheets for Aerobic
Oxidative Desulfurization. Chem. Commun. 2016, 52, 144−147.
(26) Yang, Y. C.; Baker, J. A.; Ward, J. R. Decontamination of
Chemical Warfare Agents. Chem. Rev. 1992, 92, 1729−1743.
(27) Liu, Y.; Moon, S.-Y.; Hupp, J. T.; Farha, O. K. Dual-Function
Metal-Organic Framework as a Versatile Catalyst for Detoxifying
Chemical Warfare Agent Simulants. ACS Nano 2015, 9, 12358−
12364.
(28) Atilgan, A.; Islamoglu, T.; Howarth, A. J.; Hupp, J. T.; Farha, O.
K. Detoxification of a Sulfur Mustard Simulant Using a BODIPY-
Functionalized Zirconium-Based Metal-Organic Framework. ACS
Appl. Mater. Interfaces 2017, 9, 24555−24560.
(29) Son, Y. R.; Kim, M.-K.; Ryu, S. G.; Kim, H. S. Rapid Capture
and Hydrolysis of a Sulfur Mustard Gas in Silver-Ion-Exchanged
Zeolite Y. ACS Appl. Mater. Interfaces 2018, 10, 40651−40660.
(30) Decoste, J. B.; Peterson, G. W. Metal-Organic Frameworks for
Air Purification of Toxic Chemicals. Chem. Rev. 2014, 114, 5695−
5727.
(49) An, H.; Hou, Y.; Wang, L.; Zhang, Y.; Yang, W.; Chang, S. Z.
Evans-Showell-Type Polyoxometalates Constructing High-Dimen-
sional Inorganic-Organic Hybrid Compounds with Copper-Organic
Coordination Complexes: Synthesis and Oxidation Catalysis. Inorg.
Chem. 2017, 56, 11619−11632.
(50) Bromberg, L.; Diao, Y.; Wu, H.; Speakman, S. A.; Hatton, T. A.
Chromium(III) Terephthalate Metal Organic Framework (MIL-101):
HF-Free Synthesis, Structure, Polyoxometalate Composites, and
Catalytic Properties. Chem. Mater. 2012, 24, 1664−1675.
(51) Lu, B.-B.; Yang, J.; Che, G.-B.; Pei, W.-Y.; Ma, J.-F. Highly
Stable Copper(I)-Based Metal-Organic Framework Assembled with
Resorcin[4]arene and Polyoxometalate for Efficient Heterogeneous
Catalysis of Azide-Alkyne “Click” Reaction. ACS Appl. Mater.
Interfaces 2018, 10, 2628−2636.
(31) Enserink, M. U.N. Taps Special Labs to Investigate Syrian
Attack. Science 2013, 341, 1050−1051.
(32) Raushel, F. M. Catalytic Detoxification. Nature 2011, 469,
310−311.
(33) Hou, Y.; An, H.; Zhang, Y.; Hu, T.; Yang, W.; Chang, S. Rapid
Destruction of Two Types of Chemical Warfare Agent Simulants by
Hybrid Polyoxomolybdates Modified by Carboxylic Acid Ligands.
ACS Catal. 2018, 8, 6062−6069.
(34) 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, 346, 101−111.
(35) Li, X.; Dong, J.; Liu, H.; Sun, X.; Chi, Y.; Hu, C. Recoverable
Amphiphilic Polyoxoniobates Catalyzing Oxidative and Hydrolytic
Decontamination of Chemical Warfare Agent Simulants in Emulsion.
J. Hazard. Mater. 2018, 344, 994−999.
(36) Dong, J.; Hu, J.; Chi, Y.; Lin, Z.; Zou, B.; Yang, S.; Hill, C. L.;
Hu, C. A Polyoxoniobate-Polyoxovanadate Double-Anion Catalyst for
Simultaneous Oxidative and Hydrolytic Decontamination of Chem-
ical Warfare Agent Simulants. Angew. Chem., Int. Ed. 2017, 56, 4473−
4477.
(37) Wang, S.-S.; Yang, G.-Y. Recent Advances in Polyoxometalate-
Catalyzed Reactions. Chem. Rev. 2015, 115, 4893−4962.
(38) Walsh, J. J.; Bond, A. M.; Forster, R. J.; Keyes, T. E. Hybrid
Polyoxometalate Materials for Photo(Electro-) Chemical Applica-
tions. Coord. Chem. Rev. 2016, 306, 217−234.
(39) Cai, G.; Jiang, H.-L. A Modulator-Induced Defect-Formation
Strategy to Hierarchically Porous Metal-Organic Frameworks with
High Stability. Angew. Chem., Int. Ed. 2017, 56, 563−567.
(52) Lu, B.-B.; Jiang, W.; Yang, J.; Liu, Y.-Y.; Ma, J.-F.
Resorcin[4]arene-Based Microporous Metal-Organic Framework as
an Efficient Catalyst for CO2 Cycloaddition with Epoxides and Highly
Selective Luminescent Sensing of Cr2O72‑. ACS Appl. Mater. Interfaces
2017, 9, 39441−39449.
(53) Zhao, S.-S.; Yang, J.; Liu, Y.-Y.; Ma, J.-F. Fluorescent Aromatic
Tag-Functionalized MOFs for Highly Selective Sensing of Metal Ions
and Small Organic Molecules. Inorg. Chem. 2016, 55, 2261−2273.
(54) Zhai, Q.-Y.; Su, J.; Guo, T.-T.; Yang, J.; Ma, J.-F.; Chen, J.-S.
Two Porous Polyoxometalate-Resorcin[4]arene-Based Supramolecu-
lar Complexes: Selective Adsorption of Organic Dyes and Electro-
chemical Properties. Cryst. Growth Des. 2018, 18, 6046−6053.
(55) Pei, W.-Y.; Xu, G. H.; Yang, J.; Wu, H.; Chen, B. L.; Zhou, W.;
Ma, J.-F. Versatile Assembly of Metal-Coordinated Calix[4]-
resorcinarene Cavitands and Cages through Ancillary Linker Tuning.
J. Am. Chem. Soc. 2017, 139, 7648−7656.
(56) Zhang, S.-T.; Yang, J.; Wu, H.; Liu, Y.-Y.; Ma, J.-F. Systematic
Investigation of High-Sensitivity Luminescent Sensing for Polyox-
I
https://dx.doi.org/10.1021/acs.inorgchem.0c00225
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
ometalates and Iron(III) by MOFs Assembled with a New
Resorcin[4]arene-Functionalized Tetracarboxylate. Chem. - Eur. J.
2015, 21, 15806−15819.
(57) Yu, M.-Y.; Yang, J.; Xu, X.; Ma, J.-F.; Wang, Z. Highly Stable
Polyoxometalate-Resorcin[4]arene-Based Inorganic-Organic Com-
plexes for Catalytic Oxidation Desulfurization. Appl. Organomet.
Chem. 2019, 33, No. e5169.
(58) Wang, X.-X.; Yang, J.; Xu, X.; Ma, J.-F. Highly Stable
Copper(I)-Thiacalix[4]arene-Based Frameworks for Highly Efficient
Catalysis of Click Reactions in Water. Chem. - Eur. J. 2019, 25,
16660−16667.
(59) Zhang, Q.; Catti, L.; Pleiss, J.; Tiefenbacher, K. Terpene
Cyclizations Inside a Supramolecular Catalyst: Leaving-Group-
Controlled Product Selectivity and Mechanistic Studies. J. Am.
Chem. Soc. 2017, 139, 11482−11492.
(60) Matthews, S. E.; Cecioni, S.; O’Brien, J. E.; MacDonald, C. J.;
Hughes, D. L.; Jones, G. A.; Ashworth, S. H.; Vidal, S. Fixing the
Conformation of Calix[4]arenes: When are Three Carbons Not
Enough? Chem. - Eur. J. 2018, 24, 4436−4444.
(61) Xu, G.; Bai, H.; Huang, X.; He, W.; Li, L.; Shen, G.; Han, G.
Self-Assembled 3D Flower-Like Perovskite PbTiO3 Nanostructures
and Their Application in the Catalytic Oxidation of CO. J. Mater.
Chem. A 2015, 3, 547−554.
(62) Spek, A. L. PLATONSQUEEZE: A Tool for the Calculation of
the Disordered Solvent Contribution to the Calculated Structure
Factors. Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 9−18.
(63) Klemperer, W. G.; Shum, W. Synthesis and Interconversion of
the Isomeric. Alpha.- and. Beta.-Molybdate (Mo8O264‑) Ions. J. Am.
Chem. Soc. 1976, 98, 8291−8293.
(64) Jiang, W.; Yang, J.; Liu, Y.-Y.; Song, S. Y.; Ma, J.-F. A Stable
Porphyrin-Based Porous Mog Metal-Organic Framework as an
Efficient Solvent-Free Catalyst for C-C Bond Formation. Inorg.
Chem. 2017, 56, 3036−3043.
(65) Okun, N. M.; Anderson, T. M.; Hill, C. L. [(FeIII(OH2)2)3(A-
α-PW9O34)2]9‑ on Cationic Silica Nanoparticles, a New Type of
Material and Efficient Heterogeneous Catalyst for Aerobic Oxida-
tions. J. Am. Chem. Soc. 2003, 125, 3194−3195.
(66) Guo, W. W.; Lv, H. J.; Sullivan, K. P.; Gordon, W. O.; Balboa,
A.; Wagner, G. W.; Musaev, D. G.; Bacsa, J.; Hill, C. L. Broad-
Spectrum Liquid- and Gas-Phase Decontamination of Chemical
Warfare Agents by One-Dimensional Heteropolyniobates. Angew.
Chem., Int. Ed. 2016, 55, 7403−7407.
(67) Li, J.-K.; Dong, J.; Wei, C.-P.; Yang, S.; Chi, Y.-N.; Xu, Y.-Q.;
Hu, C.-W. Controllable Synthesis of Lindqvist Alkoxopolyoxovana-
date Clusters as Heterogeneous Catalysts for Sulfoxidation of Sulfides.
Inorg. Chem. 2017, 56, 5748−5756.
(68) Sun, X.; Dong, J.; Li, Z.; Liu, H.; Jing, X.; Chi, Y.; Hu, C.
Mono-Transition-Metal-Substituted Polyoxometalate Intercalated
Layered Double Hydroxides for the Catalytic Decontamination of
Sulfur Mustard Simulant. Dalton Trans. 2019, 48, 5285−5291.
(69) Zhang, X.; Li, Y.; Li, Y.; Wang, S.; Wang, X. Polyoxometalate
Immobilized on Graphene via Click Reaction for Simultaneous
Dismutation of H2O2 and Oxidation of Sulfur Mustard Simulant. ACS
Appl. Nano Mater. 2019, 2, 6971−6981.
(70) Buru, C. T.; Li, P.; Mehdi, B. L.; Dohnalkova, A.; Platero-Prats,
A. E.; Browning, N. D.; Chapman, K. W.; Hupp, J. T.; Farha, O. K.
Adsorption of a Catalytically Accessible Polyoxometalate in a
Mesoporous Channel-Type Metal-Organic Framework. Chem.
Mater. 2017, 29, 5174−5181.
J
https://dx.doi.org/10.1021/acs.inorgchem.0c00225
Inorg. Chem. XXXX, XXX, XXX−XXX