Assembly of polyoxometalate-thiacalix[4]arene-based inorganic-organic hybrids as efficient catalytic oxidation desulfurization catalysts

Article abstract of DOI:10.1039/d0dt04097e

Self-assembly of polyoxometalates, Ni(ii)/Ag(i) cations and tetra-[5-(mercapto)-1-methyltetrazole]-thiacalix[4]arene (L) yielded three inorganic-organic hybrids, namely, [Ni₃L₂(CH₃OH)₆(H₂O)₄][PMo₁₂O₄₀]₂·3CH₃OH·2H₂O (1), [Ni₃L₂(CH₃OH)₆(H₂O)₄][PW₁₂O₄₀]₂·3CH₃OH·2H₂O (2) and [Ag₃L(PMo₁₂O₄₀)] (3). In hybrids (1) and (2), Ni(ii) cations are linked by L ligands to produce layered frameworks, and H bonds among the [PMo₁₂O₄₀]^3?/[PW₁₂O₄₀]^3?anions and L ligands lengthen the structures to form 3D supramolecular architectures. Hybrid (3) exhibits a 3D architecture, of which Ag(i) cations not only coordinated with the N and O atoms of L ligands and [PMo₁₂O₄₀]^3?anions simultaneously, but also connected each other by Ag-Ag interactions. It is worth mentioning that1and3as recyclable catalysts show excellent heterogeneous catalytic activity in oxidation desulfurization reactions.

Full text of DOI:10.1039/d0dt04097e

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Assembly of polyoxometalate-thiacalix[4]arene-based DOI: 10.1039/D0DT04097E
inorganic-organic hybrids as efficient catalytic oxidation
desulfurization catalysts
Jie Li,a Peng Du,b Ying-Ying Liu*a and Jian-Fang Ma*a
aKey Lab of Polyoxometalate Science, Department of Chemistry, Northeast Normal
University, Changchun 130024, China
bCollege of Chemistry and Chemical Engineering, Dezhou University, Dezhou
253023, China
* Correspondence authors
E-mail: liuyy147@nenu.edu.cn
E-mail: majf247@nenu.edu.cn
Self-assembly
tetra-[5-(mercapto)-1-methyltetrazole]-thiacalix[4]arene
inorganic-organic hybrids,
[Ni3L2(CH3OH)6(H2O)4][PMo12O40]2·3CH3OH·2H2O
of
polyoxometalates,
Ni(II)/Ag(I)
cations
and
three
(L)
obtained
namely,
(1),
[Ni3L2(CH3OH)6(H2O)4][PW12O40]2·3CH3OH·2H2O (2) and [Ag3L(PMo12O40)] (3).
In the hybrids of 1 and 2, Ni(II) cations are attached by L ligands to produce layered
frameworks, and H bonds among the [PMo12O40]3-/[PW12O40]3- anions and L ligands
lengthen the structures to form 3D supramolecular architectures. Hybrid 3 exhibits a
3D architecture, of which Ag(I) cations not only coordinated with the N and O atoms
of L ligands and [PMo12O40]3- anions simultaneously, but also connected each other
by Ag-Ag interactions. It is worth mentioning that 1 and 3 as recycled catalysts show
excellent heterogeneous catalytic activity in oxidation desulfurization reactions.
1

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1. Introduction
At present, with the increase of sulfur-containing fossil fuels, environmental problems
become more and more serious, and sulfur removal has received great significance.1,2
Hydrodesulfurization, as a traditional technique, is the main sulfur removal method in
the business.3,4 Nonetheless, the method needs harsh conditions, such as high
temperature, catalysts and high pressure.5,6 Also, it is not efficient enough for those
heteroaromatic sulfur-compounds.7 So far, other methods have been developed, which
involve extractive desulfurization,8,9 adsorption desulfurization,10,11 oxidation
desulfurization (ODS),12-15 and biological desulfurization,16 etc. Among the above
methods, ODS is an efficient and mild deep desulfurization method.17,18 In ODS
reactions, the help of active oxidants are needed, such as hydrogen peroxide,19
molecular oxygen20,21 and tert-butylhydroperoxide (TBHP).22 Sulfur-containing
species could be oxidized rapidly by catalysts into corresponding sulfones and
sulfoxides.23 In this regard, the synthesis of efficient catalysts is essential and highly
necessary.
Polyoxometalates (POMs), defined as inorganic metal oxide clusters,24,25 are a kind
of metal oxides with unique physical and chemical properties.26-28 It is found that
POMs display promising properties in the field of oxidation catalysis,29,30 such as
ODS.24,31-33 The reason is attributed to the advantages of mild reaction conditions,
high efficiency, oxidation resistance and low price.34-37 But one of the most
worrisome drawbacks of POMs is their excellent water-solublility, which impedes
their application as recycled catalysts.38-41 Recently, POM-based inorganic-organic
hybrids were discovered application in the field of heterogeneous catalysts.42 Several
organic ligands, such as carboxylic acid,43 ionic liquids44 and calix[4]arene38,45 have
been used in the construction of POM-based inorganic-organic hybrid catalysts.46-48 In
this regard, functional calix[4]arenes have been diffusely applied as excellent
multidentate ligands, which can present great structural diversity of the hybrids.49-51
Inspired by this,
a
characteristic thiacalix[4]arene ligand with four
5-mercapto-1-methyltetrazole groups (L, Scheme 1) was ingenious designed. By
2

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assembling POM anions, L ligands and metal ions, three new hybrids
[Ni3L2(CH3OH)6(H2O)4][PMo12O40]2·3CH3OH·2H2O
(1),
[Ni3L2(CH3OH)6(H2O)4][Pw12O40]2·3CH3OH·2H2O (2) and [Ag3L(PMo12O40)] (3)
were synthesized. Noticeably, 1 and 3 could be employed as efficient heterogeneous
catalysts for ODS reactions.
Scheme 1 View of L ligand.
2. Experimental section
2.1. Preparation of [Ni3L2(CH3OH)6(H2O)4][PMo12O40]2·3CH3OH·2H2O (1)
The mixture of H3PMo12O40 (18 mg, 0.01 mmol), NiCl2·6H2O (10 mg, 0.04 mmol), L
(12 mg, 0.01 mmol), CH2Cl2 (3 mL) and ethanol (1 mL) were added into a Teflon
reactor (15 mL) and heated at 130 °C for 72 hours. Dark yellow crystals 1 were got
(yield of 28%). Anal. Calcd for C121H192N32O103S16P2Mo24Ni3 (Mr = 6796.64): C,
21.38; H, 2.85; N, 6.59. Found: C, 20.85; H, 2.53; N, 6.77. IR (KBr, cm−1): 3308 (w),
2966 (m), 2863 (w), 1612 (w), 1579 (w), 1547 (w), 1467 (m), 1429 (m), 1402 (w),
1380 (w), 1261 (m), 1245 (w), 1191 (m), 1067 (s), 965 (s), 873 (s), 804 (s), 703 (m),
593 (m), 507 (m) (Fig. S1†).
2.2. Preparation of [Ni3L2(CH3OH)6(H2O)4][PW12O40]2·3CH3OH·2H2O (2)
The synthesis of 2 was similar to 1 except the H3PW12O40 (29 mg, 0.01 mmol) was
3

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used. Pale green crystals 2 were got (yield of 27%). Anal. Calcd for
C121H192N32O103S16P2W24Ni3 (Mr = 8906.48): C, 16.32; H, 2.17; N, 5.03. Found: C,
15.88; H, 1.94; N, 5.15. IR (KBr, cm−1): 3369 (w), 2960 (m), 2868 (w), 1617 (w),
1584 (w), 1542 (w), 1472 (m), 1439 (m), 1407 (w), 1375 (w), 1299 (w), 1266 (m),
1234 (w), 1191 (w), 1080 (s), 979 (s), 896 (s), 819 (s), 739 (m), 706 (m), 593 (m), 521
(m).
2.3. Preparation of [Ag3L(PMo12O40)] (3)
The mixture of H3PMo12O40 (18 mg, 0.01 mmol), AgNO3 (7 mg, 0.04 mmol), L (12
mg, 0.01 mmol), acetonitrile (2 mL), ethanol (6 mL) and 4 drops of 2.3 M nitric acid
were put in a Teflon reactor and heated at 130 °C for 72 hours. Dark yellow brown
crystals 3 were got (yield of 18%). Anal. Calcd for C56H72N16O44S8PMo12Ag3 (Mr =
3435.63): C, 19.58; H, 2.11; N, 6.52. Found: C, 19.60; H, 1.95; N, 6.86. IR (KBr,
cm−1): 3430 (w), 2960 (w), 2868 (w), 1629 (w), 1472 (w), 1440 (w), 1412 (w), 1386
(w), 1283 (w), 1267 (w), 1240 (w), 1213 (w), 1186 (w), 1061 (s), 992 (m), 954 (s),
877 (s), 807 (s), 706 (m), 599 (m), 550 (m), 502 (m), 458 (m).
The crystallographic data of 1-3 are contained in Table 1.
Table 1 Crystallographic Data and Structural Refinements for 1-3
complex
formula
Mr
1
2
3
C121H192N32O103S16P2Mo24Ni3
C121H192N32O103S16P2W24Ni3
8906.48
C56H72N16O44S8PMo12Ag3
3435.63
Monoclinic
C2/c
6796.64
crystal system Triclinic
Triclinic
space group
a (Å)
P-1
P-1
13.4965(6)
14.0075(7)
32.2487(11)
91.811(3)
99.556(3)
106.631(4)
13.5204(5)
14.1184(5)
32.4331(12)
92.065(3)
99.761(3)
106.404(3)
30.4234(11)
12.8113(5)
25.0925(9)
90
b (Å)
c (Å)
α (°)
β (°)
90.597(3)
90
γ (°)
4

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V (Å3)
5740.4(4)
1
5829.9(4)
1
9779.6(6)
4
Z
Dcalc (g cm-3)
F (000)
Rint
1.966
3344
2.537
4112
2.333
6640
0.0465
1.030
0.0434
1.016
0.0630
0.0391
1.124
0.0879
0.1729
GOF on F2
R1a [I>2σ(I)] 0.0749
b
wR2 (all data) 0.2224
0.1549
2
2 2
aR1 = Σ||Fo| - |Fc||/Σ|Fo|. bwR2 = {Σ[w(Fo -Fc2)2]/Σw(Fo ) ]}1/2.
2.4. Procedure of ODS reaction
TBHP (0.50 mmol), substrate (0.25 mmol), CH2Cl2 (5 mL), biphenyl (0.25 mmol) and
catalyst (1: 1.47 μmol, 3: 2.91 μmol) were put into a 38 mL pressure-proof pipe. The
above mixture was stirred at 25 °C (for 1) or 50 °C (for 3). The conversion rate was
determined by GC or HPLC. The product was further proved by 1H NMR.
3. Results and discussion
For hybrids 1 and 2, SQUEEZE instruction of PLATON was used. Their formula
were affirmed by TGA, electron cloud density and elemental analysis (Fig. S2†).
3.1. Crystal structures of [Ni3(L)2(CH3OH)6(H2O)4][PMo12O40]2·3CH3OH·2H2O
(1) and [Ni3(L)2(CH3OH)6(H2O)4][PW12O40]2·3CH3OH·2H2O (2)
The framework of 2 is isomorphic with that of 1 (Fig. S3†). Therefore, the framework
of 1 will be described. The fundamental unit of 1 contains two halves of [PMo12O40]3-
anions, one and a half of Ni(II) cations, one L ligand, two water molecules, three
methanol molecules, a free water molecule, and one and a half of free methanol
molecules. The [PMo12O40]3- anions serve as counter ions to balance the positive
charge of the framework. The coordination environments of two Ni(II) cations are
extraordinary different (Fig. 1a). Ni1 lies at an inversion center, and has a
six-coordinated [N2O4] octahedral geometry defined by two L ligands and four
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methanol molecules. Ni2 is six-surrounded by three L ligands, two water molecules
and one methanol molecule. L ligands connect Ni(II) atoms to yield a layered
structure (Fig. 1b). As shown in Fig. 1c, the circumstances of two types of
independent [PMo12O40]3- anions are different, one type lies in the channel and
another scatters among the layers. There are C-H···O hydrogen-bond interactions
between the [PMo12O40]3- anions and
L
ligands (C18-H18B···O45,
C31-H31B···O32#3, and C57-H57C···O36), which connect the whole structure to
produce a 3D supramolecular structure (Table S1†).
(a)
(b)
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(c)
Fig. 1 (a) Coordination spheres of Ni(II) cations in 1. (b) 2D layered architecture. (c)
3D supramolecular structure.
3.2. Crystal structure of [Ag3(PMo12O40)(L)] (3)
The fundamental unit of 3 contains half of a [PMo12O40]3- anion, one and a half of
Ag(I) cations and half of a L ligand. Ag1 is four-coordinated with one S atom, two N
atoms from two disparate L ligands and one terminal-O atom of [PMo12O40]3- anion.
Ag2 is coordinated with one N atom from L ligand and one bridge-O atom from
[PMo12O40]3- anion.52 It is worth mentioning that Ag2 and its symmetry-related Ag2#1
atom form a metallic bond (Fig. 2a). The length of Ag2-Ag2#1 is 2.679(8) Å (Table
S2†).53 Ag(I) is linked by L ligands to form a planar structure (Fig. 2b). To be
specific, Ag(I) ions are connected by L ligands, [PMo12O40]3- anions and its
symmetry-related ions to yield a 3D architecture (Fig. 2c).
(a)
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(b)
(c)
Fig. 2 (a) Coordination environments of Ag(I) cations in 3. (b) 2D layered
architecture. (c) 3D architecture.
3.3. Catalytic performance of 1 and 3 for ODS reaction
To study the optimal condition, a series of explorations were carried out by using
TBHP as oxidant, biphenyl as internal standard and methyl phenyl sulfide (MBT) as
typical substrate separately (Table 2). The conversion rate of MBT was calculated by
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GC (Fig. S4 and S5†). Based on reported literature, Keggin-type POMs possess
excellent activities to ODS reactions.54 So firstly, the reactions were conducted by
using pure H3PMo12O40 and H3PW12O40 as catalysts (2.94 μmol), and the conversion
of 97% and 73% was obtained, respectively (entries 1 and 2). Hence, the reaction for
defining optimal conditions were conducted by using hybrid 1 as catalyst. With the
reaction time from 1 to 3 h at 25 °C, the conversion rates of MBT were 80%, 90% and
99%, respectively (entries 3-5). When NiCl2·6H2O and L ligand were used as
catalysts, the conversions were 36% and 38% separately (entries 6 and 7). When no
catalyst was added to the reaction, only 32% of MBT was converted to products
(entry 8). Subsequently, to explore the effect of other solvents, CH2Cl2 was displaced
by methanol and ethanol, and the conversions were 74% and 66% separately (entries
9 and 10). In order to further explore the influence of other oxidants on the catalytic
ODS reaction, 30% hydrogen peroxide was added and only 26% conversion was
achieved (entry 11). Hence, the optimal condition for catalyst 1 is TBHP as oxidant
and CH2Cl2 as solvent under the reaction time of 3 h at 25 °C.
Table 2 Catalytic ODS results under various conditions
Temp.
Entry
Catalyst
Oxidant
Solvent
Time (h)
Conversion (%)
(°C)
25
25
25
25
25
25
25
1
2
3
4
5
6
7
H3PMo12O40
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
3
3
1
2
3
3
3
97
73
80
90
99
36
38
H3PW12O40
1
1
1
NiCl2·6H2O
L
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8
9
None
TBHP
TBHP
TBHP
H2O2
CH2Cl2
methanol
ethanol
25
3
3
3
3
32
1
1
1
25
25
25
74
66
26
10
11
CH2Cl2
Simultaneously, we also studied the catalytic ODS reaction of hybrid 3 since it also
contains [PMo12O40]3- anions (Table 3, Fig. S6 and S7†). Firstly, catalyst 3 was
explored under the optimal condition of 1 by using MBT as the substrate, and the
conversion was only 56% (entry 1). Therefore, the optimal condition of catalyst 3 was
re-explored. At 40 °C, the conversions were 69% and 85% after 2 and 3 hours,
respectively (entries 2 and 3). Consequently, the temperature was raised to 50 °C, the
conversions of 92% and >99% at 1 and 2 h were achieved, respectively (entries 4 and
5). To confirm the effect of catalyst 3, blank experiment of pure TBHP was carried
out, and achieved a low conversion of 41% (entry 6). Subsequently, the reactions
were done in methanol and ethanol, respectively. The conversions of 62% and 74%
were obtained (entries 7 and 8). Hence, the optimal reaction time of catalyst 3 is 2 h
under the temperature of 50 °C.
Table 3 Catalytic oxidative desulfurization results under various conditions
Conversion
Entry Catalyst Oxidant Solvent
Temp. (°C) Time (h)
(%)
56
1
2
3
4
5
6
7
8
3
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
25
40
40
50
50
50
50
50
3
2
3
1
2
2
2
2
3
69
3
85
3
92
3
None
3
>99
41
TBHP methanol
TBHP ethanol
62
3
74
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To address the universality of catalysts 1 and 3, some other sulfur-containing
compounds were used as the substrates (Table 4, Figs. S8 and S9†). The
1
characterization of the catalyzed ODS products were performed by H NMR (Figs.
S10b and S10c†). Under the respective optimal conditions of 1 and 3, the reactions
were carried out with biphenyl as the internal standard and analyzed by HPLC. When
ethylthiobenzene, 4-chlorothioanisole, 4-bromothioanisole, 4-methoxythioanisole and
allylphenylsulfide were used as substrates, all of the conversion rates of 1 and 3 could
achieve high values of >99%, 99% or 98% (entries 1-6). The conversion rates of
4-nitrothioanisole with electron withdrawing group were only 81% for 1 and 68% for
3，which is lower than other monophenyl thioethers in the consistent condition. When
the reaction time was extended to 4 h for 1 and 7 h for 3, the conversions could reach
98% and 91%, respectively (entry 7). As to the diphenylsulfide substrate, the
conversion rates were 82% and 99% after 3 and 4 h for 1. For 3, after elongating the
reaction time from 2 to 3 h, the conversion of 84% increased to 91% (entry 8). As
showed in entries 9 and 10, the conversion rates of dibenzothiophene (DBT) and
benzothiophene (BT) were 73% and 19% for 1 and 98% and 55% for 3, respectively,
even after 12-h-long reactions. The results of entries 8-10 show that steric hindrance
has a major impact on the conversions.55 Both of DBT and BT have large steric
hindrance, but the S electron density of DBT is higher than BT. Hence, the conversion
of DBT is higher than BT for both 1 and 3, which indicates that electron density also
has a significant impact on the ODS reactions.56
Table 4 The ODS results of thioethers catalyzed by 1a and 3 b
Entry
1
Substrates
Time (h)a
Conversion (%)a Time (h)b Conversion (%)b
S
3
99
2
2
>99
>99
S
2
3
>99
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S
S
3
3
3
3
>99
99
2
2
2
2
99
3
4
Cl
99
>99
99
Br
S
98
5
6
H3CO
S
98
S
3
4
81
98
2
7
68
91
7
8
O2N
S
3
4
82
99
2
3
84
91
S
9
12
12
73
19
12
12
98
55
S
10
The catalytic kinetic experiments and filtration experiments were studied for 1 and
3, respectively. For 1, the conversion rate of 4-bromothioanisole elevated speedily to
79% at 1 h, and then a slow growth was observed in the next two hours (Fig. 3a).
When 1 was separated after 1 h, no noticeable catalytic conversion was observed (Fig.
S11†). For 3, 74% of MBT was converted to the corresponding products after 0.5 h,
then the conversion increased slowly to >99% in the following 1.5 h (Fig. 3b). After 3
was hot-filtered and stirred for another 1.5 h, the conversion rate of MBT was barely
increased (Fig. S12†). ICP analysis indicates that there is no Ni(II) or Ag(I) ions
leakage in the filtrates of 1 and 3, respectively. All of these proved that the ODS
reaction was heterogeneous.
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Fig. 3 (a) Catalytic kinetic experiment (orange) and filtration experiment (green) of 1
by using 4-bromothioanisole as substrate. (b) Catalytic kinetic experiment (purple)
and filtration experiment (pink) of 3 by using MBT as substrate.
The stability and circularity of 1 and 3 were further verified under their optimal
conditions. At the end of each cycle, 1 and 3 were collected by centrifugation, washed
with CH2Cl2, dried and then used for the next cycle. As shown in Fig. 4a and 4b, it
was found that after the isolated catalysts were reused for four times, the catalytic
performances of 1 and 3 could still reach high values of 99% and 98%, respectively
(Fig. S13 and S14†). The PXRD pattern of the newly collected 1 was consistent with
the simulation data. But the curve changed a bit when 1 was placed in air for a period
of time. After each recycles, the PXRD curve of reused 1 corresponded to that of
placed for a period of time (Fig. 4c). This fact reveals that although the framework of
1 has a minor change, it still remains high conversion for the ODS reaction. All of the
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PXRD curves of 3 completely consistent with the simulation data after each rounds
(Fig. 4d).
Fig. 4 Recycling experiments of 1 (a) and 3 (b). Experimental and catalysis PXRD
patterns of 1 (c) and 3 (d).
4. Conclusions
In conclusion, three polyoxometalate-thiacalix[4]arene-based inorganic-organic
hybrids 1-3 were synthesized by using a functional thiacalix[4]arene ligand with
metal ions and POM anions. In the isostructures of 1 and 2, the layered structures
formed by Ni(II) cations and L ligands are linked by [PMo12O40]3-/[PW12O40]3- anions
via hydrogen bonds to generate 3D supramolecular architectures. In 3, Ag(I) cations
are coordinated with L ligands, [PMo12O40]3- anions and its symmetry-related atoms
to form a 3D framework. Notably, 1 and 3 can be used in ODS catalytic reaction. The
ODS catalytic experiments verified that both hybrids have excellent heterogeneous
catalytic abilities.
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Author Contributions
Jie Li: Investigation, software, and writing original draft. Peng Du: Visualization.
Ying-Ying Liu: Data curation, validation, and writing-review & editing. Jian-Fang
Ma: Conceptualization, funding acquisition, and resources.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the NSFC (Grant No. 21761003).
†Electronic supplementary information (ESI) available: CCDC 2046939-2046941.
For ESI and crystallographic data in CIF or other electronic format see DOI: ?
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Three POM-thiacalix[4]arene-based organic-inorganic hybrids have been achieved by
applying a tetrazole-functionalized thiacalix[4]arene ligand. Hybrids 1 and 3 exhibit
efficient catalytic abilities for oxidation desulfurization reactions.
1