A Peanut-Like Sb-Embedded Polyoxoniobate Cage for Hydrolytic Decomposition of Chemical Warfare Agent

Article abstract of DOI:10.1002/ejic.202100089

A Sb-embedded polyoxoniobate has been originally synthesized under hydrothermal conditions. Particularly, the peanut-like [Sb₂Nb₂₄O₇₂]^18? cluster cage in 1 with C_2h symmetry is composed of two 9-nuclear {SbNb₉O₃₃} motifs and one {Nb₆O₂₄} crown-shaped ring. The compound 1 present the novel structure of Sb-substituted sandwich-type polyoxoniobate with antimoniobate cluster cage. Decomposition catalytic studies indicate that compound 1 exhibits good hydrolytic activity and stability on the degradation of nerve agent simulant dimethylphosphonate (DMMP).

Full text of DOI:10.1002/ejic.202100089

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A Peanut-Like Sb-Embedded Polyoxoniobate Cage for
Hydrolytic Decomposition of Chemical Warfare Agent
Yan-Lan Wu,[a] Zhuo-Hao Zhong,[a] Ping-Xin Wu,[a] Yan-Qiong Sun,*[a] Xin-Xiong Li,[a] and
Shou-Tian Zheng*[a]
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A Sb-embedded polyoxoniobate has been originally synthe-
sized under hydrothermal conditions. Particularly, the peanut-
like [Sb2Nb24O72]18À cluster cage in 1 with C2h symmetry is
composed of two 9-nuclear {SbNb9O33} motifs and one {Nb6O24}
structure of Sb-substituted sandwich-type polyoxoniobate with
antimoniobate cluster cage. Decomposition catalytic studies
indicate that compound 1 exhibits good hydrolytic activity and
stability on the degradation of nerve agent simulant dimeth-
ylphosphonate (DMMP).
crown-shaped ring. The compound
1 present the novel
Introduction
mony (Sb) as a metal element adjacent to the Te amphoteric
element in the same period, has been found in many
polyoxotungstates as the substituted metal.[22] But the Sb-
embedded polyoxoniobates have not yet been reported until
now, which may be attributed to the harsh synthetic conditions.
Sb exhibits acidophilic, and it is inclined to hydrolyze very
quickly in water, which leads to a large amount of precipitate.
Thus, it is an enormous challenge to synthesize Sb-embedded
PONbs. Based on this consideration, we attempt to introduce
the Sb element to polyoxoniobates to construct novel hetero-
polyoxoniobates with fascinating architectures.
Chemical warfare agents (CWAs) have attracted great
attention of biological and chemical workers to explore the
effective materials with hydrolytic decomposition for CWAs in
the past decades. Since Nyman M[23a], Craig L. Hill and co-
workers[23b] reported that PONbs could be used as catalyst to
degrade these toxic CWAs, such as dimethylphosphonate
(DMMP) and diethyl cyanophonate (DECP), PONbs have been
regarded as effective catalysts to hydrolyze chemical warfare
agent simulants. However, there remains a continuous demand
for developing new materials and methods to rapidly, fully
degrade all the main CWAs under mild conditions.
Polyoxoniobates (PONbs) have attracted great interests due to
their potential applications in base-catalysis, photocatalysis,
virology and nuclear waste treatment.[1–4] Great progresses have
been made in the syntheses isopolyoxoniobates in the past few
years, such as {Nb10},[5a] {Nb16},[5b] {Nb20},[5b,c] {Nb24},[5d] {Nb27},[5e]
{Nb31},[5e] {Nb32},[5f] {Nb47},[5g] {Nb52},[5h,i] {Nb81},[5h] {Nb114},[5h] and
{Nb288}.[5g] Since Nyman and coworkers firstly reported the first
example of a heteropolyniobate in 2002,[6] the introduction of
metal cations, such as transition metal (TM) and lanthanide
cations, into PONbs has been an effective strategy to construct
hetero-polyoxoniobates with tunable compositions and rich
structures. TM-containing PONbs such as {Cu25.5Nb56},[7]
{Co14Nb56},[8] {Co8Nb24},[9] {Ti12Nb6},[10] {Fe3Nb25},[11] {Cr2.5Nb27.5},[12]
{Ni10Nb32}[13] and lanthanide-containing PONbs {Ln12W12Nb72}
(Ln=Y, La, Sm, Eu, Yb)[14] have been reported. However, in a
large number of TM-encapsulating polyoxoniobates with vari-
ous compositions, sizes, and shapes, most of the metal cations
are used as linkages in the structures, while very few of them
act as substitutes of Nb atoms in the polyoxoniobates
chemistry.[15–16] Thus, it is a challenge to synthesize the metal-
substituted polyoxoniobates in which some Nb atoms are
replaced by metal cations.
Herein, we have synthesized a peanut-like Sb-embedded
PONb cage, H4Na8K6[Sb2Nb24O72]·30H2O (1), which is a new Sb-
embedded PONb with sandwich structure. Base-catalysis studies
reveal that compound 1 is an effective catalyst to the
decomposition of DMMP.
The PONbs based on tetrahedral heteroanion templates
(e.g., SiO44À , PO43À , GeO44À , AsO43À ) have been reported with
2À
Keggin type structures.[17–20] The heteroanion TeO3
was
introduced to the PONbs for the first time by Niu and coworkers
in the structure of K4[{Cu(en)2(H2O)}4{Cu(en)2}(H2Te2Nb24O72)],[21]
which presents the first member of telluroniobate. The Result and Discussion
TeO32À adopts special trigonal pyramidal configuration. Anti-
Compound, H4Na8K6[Sb2Nb24O72]·30H2O (1) crystallizes in ortho-
rhombic space group Cmca with C2h symmetry. As shown in
Figure 1, The polyanion of [Sb2Nb24O72]18À in 1 can be described
as a peanut-like cage structure with C2h symmetry, which is
composed of two 9-nuclear {SbNb9O33} (SbNb9) motifs and one
{Nb6O24} crown-shaped ring (Figure S1). In {Nb6O24} cluster ring,
six Nb centers all adopt 6-coordinated distorted pentagonal
pyramidal geometry with NbÀ O bond lengths in the range of
1.672(2)–2.261(3) Å (Figure S2, Table S1). The adjacent Nb
[a] Dr. Y.-L. Wu, Z.-H. Zhong, P.-X. Wu, Prof. Y.-Q. Sun, Prof. X.-X. Li, S.-T. Zheng
State Key Laboratory of Photocatalysis on Energy and Environment
College of Chemistry
Fuzhou University
Fuzhou, Fujian, 350108, China
E-mail: sunyq@fzu.edu.cn
stzheng@fzu.edu.cn
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/ejic.202100089
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centers are bridged by two μ2-O atoms to generate a crown-
The {Nb6O24} cluster ring is sandwiched by the two SbNb9
units to form a peanut-shell-like cage cluster [Sb2Nb24O72]18À , in
which the Sb atoms are like peanut-kernels embedded in the
niobium cage (Figure 1b), which can be further verified by EDS,
EDS-mapping and ICP(Figure S4–S8). It is intersting that two
SbNb9 subunits in {Sb2Nb24O72} cage are related by two-fold axis
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shaped cluster ring with C2h point symmetry. The m plane
perpendicular to a axis passes through the two Nb(3) atoms
while a two-fold axis parallel to the a axis is perpendicular to
the m plane, so the remaining four Nb(6) atoms in {Nb6O24}
cluster ring are related by C2h symmetry (Figure 1a). If all of the
O atoms are omitted, {Nb6O24} cluster ring shows an interesting
chair configuration (Figure 1e). SbNb9 cluster is described as an
B-typed trivacant lacunary α-Keggin ion decorated with one
SbO3 triangle pyramid and is formed by removing the capping
{Nb3O13} triad of corner-sharing NbO6 octahedra from saturated
α-Keggin cluster. The incorporated Sb atoms are 3-coordinated
trigonal pyramidal geometry with SbÀ O bond lengths in the
range of 1.954–1.963(2) Å (Figure S3),[24] and the m plane
perpendicular to a axis passes through the Sb atoms with the
occupancy of 0.5. The SbO3 triangle pyramid shares three
corners with the NbO6 octahedra of SbNb9 cluster, in which all
the Nb centers exhibit distortion octahedral geometry, with
short terminal NbÀ O bonds and the long NbÀ O bonds. The
ranges of the observed bond distances for NbO6 octahedra are
NbÀ Ot =1.757(1)–1.769(4) Å (t=terminal oxygen, bonded to
one Nb), NbÀ Ob =1.898(4)–2.363(4) Å (b=bridging oxygen,
bonded to two or three Nb), which is little longer than those of
NbÀ O=1.672(2)–2.261(3) Å in the belt. It is noted that the
SbNb9 subunit is observed in polyoxoniobates for the first time
although the TeNb9 subunit is reported by Niu group in 2017.[21]
°
parallel to the a axis with rotating by 180 (Figure S1). So the
{Sb2Nb24O72} cluster cage possesses C2h symmetry and the Sb,
Nb(2), and Nb(3) atoms are located in the m plane. The linkages
among four Nb(6) and two Sb atoms generate an regular
octahedral cavity with Sb…Sb distance of 5.0926 Å (Figure S3).
Therefore, {Sb2Nb24O72} cluster cage is a novel Sb-embedded
sandwich-type polyoxoniobate, whose structure is different
from the dicapped {PSb2Nb12O40}.[25]
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The K+ and Na+ cations are directly bonded to each
{Sb2Nb24O72} polyanion in the lattice. Every {Sb2Nb24O72} frag-
ment links other four {Sb2Nb24O72} fragments via
NbÀ OÀ KÀ OÀ Nb and NbÀ OÀ NaÀ OÀ Nb bonds to generate a 2D
(4, 4) grid layer in the ab plane(Figure 2). These 2D grid layers
are packed in the À ABABÀ mode along c axis with interlayer
pores occupied by alkali metals cations and neutral guest water
molecules.
Bond-valences sum calculations show that the valence state
of Nb, Sb atoms are +5,+3, respectively. To balance the
charges, four protons should be added into compound 1. These
protons cannot be located and are assumed to be delocalized
on the overall structures, which are common in POMs.[26]
Figure 1. (a) Ball-and-stick representation of polyanion [Sb2Nb24O72]18À cage
in compound 1 with C2h symmetry. (b) Polyhedron view of peanut-like
{Sb2Nb24} cage in 1. (c) Polyhedron view of polyanion [Sb2Nb24O72]18À in 1.
(d) Top view of {Nb6O12} crown ring derived from motif {Nb6O24} ring omitted
the terminal oxygen atoms. (e) Side view {Nb6} chair configuration of
{Nb6O24} crown ring. Color code: Sb, yellow; O, red; Nb, cyan; NbO6 octa-
hedra, cyan.
Figure 2. (a) 1D chain in compound 1. (b) 2D (4, 4) inorganic grid layer in the
ab plane connected by K+ and Na+ in compound 1. Color code: NbO6 octa-
hedra, cyan; NbO6 distorted pentagonal pyramids, purple.
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Recently, we reported the antimoniobate cluster cage
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H4Na8K6[Sb2Nb24O72]·30H2O (1), in which the polyoxoanion
{Sb2Nb24O72} is isostructural with the {Te2Nb24O72} in K4[{Cu-
(en)2(H2O)}4{Cu(en)2}(H2Te2Nb24O72)][21] reported by Niu and co-
workers. But there are three differences in their structures: a)
The Sb3+ metal cations take the places of the amphoteric Te4+
,
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which diversifies the limit types of PONbs. b) The {Sb2Nb24O72}
cage possesses C2h symmetry, which is higher than that of
{Te2Nb24O72}. c) In K4[{Cu(en)2(H2O)}4{Cu(en)2}(H2Te2Nb24O72)], the
{Te2Nb24O72} cluster are grafted by copper-organic fragments to
form ribbon-like 1D zigzag chains, which are further sew to
generate a 2D inorganic-organic hybrid layer, while in com-
pound 1, the K+ and Na+ cations connect the {Sb2Nb24O72}
clusters into a 2D inorganic layer.
The phase purity of rhombus crystalline 1 has been
validated by comparing experimental and simulated powder X-
ray diffraction (PXRD) patterns (Figure S9). Morphology and
composition of compounds 1 can be verified by EDS, SEM and
EDS-mapping (Figure S5–S8).
It is stable in air and practically insoluble in water. Besides,
the PXRD patters of 1 obviously reveals that it can maintain its
skeleton in aqueous solutions with different pH values (pH=3,
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 adjusted by HCl and NaOH) for
24 h (Figure S10). However, when the crystals of compound 1
were soaked for 24 hours in acidic solution with low pH value,
the crystals of compound 1 collapsed slowly (Figure S10). The
XRD patterns of compound 1 in strongly alkaline solutions, such
as 6 M or 12 M NaOH solutions, actually showed some changes,
which may be a different phase (Figure S10–S13). So compound
1 can’t keep its skeleton for long time in strongly acidic or
strongly alkaline solutions.
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Figure 3. (a) The hydrolytic pathway from DMMP to MP. (b) Temporal course
of the degradation of DMMP without catalyst and in aqueous dispersions of
catalyst 1. (c) Three-cycle catalytic reaction of DMMP by compound 1.
Owing to high negative charges and basic surface oxygen
atoms, PONbs have always been considered as promising
candidates for hydrolyzing chemical warfare agents, such as
dimethyl methylphosphonate (DMMP). The U.S. Army nomi-
nated DMMP as an ideal model chemical for toxicology and
carcinogenesis studies. In this study, compound 1 can hydrolyze
DMMP to methyl phosphonic (MP) under mild conditions (with
only water at room temperature). Hydrolysis of the phosphate
ester bonds was observed and monitored by 31P NMR
spectroscopy. As a kind of chemical warfare agent, DMMP is
very difficult to be degraded completely due to the production
production methyl phosphonic acid (MP) of DMMP can be
detected, suggesting that 1 is an efficient DMMP catalyst, which
is more active than many MOFs and approximately with the
effective PONb Nb47 reported recently from our group (46%
conversion under the same conditions).[5g] The extent of
conversion was calculated as the ratio of the integrated 31P
NMR peak for MP (the only product) to that of DMMP. In
addition, there was no activity in the whole test for supernatant
liquid after we filtered the catalyst for degradation of DMMP.
To check stability of 1 during catalytical process, the
recyclability of it was also investigated. The results reveal that it
has good recyclability with almost the same conversions of
DMMP for three-run duplicate operations (Figure 3c). PXRD and
IR spectra were collected after three-cycle successive catalytic
reactions at room temperature. Both the IR spectra and powder
XRD patterns of it after successive catalytic reaction were
consistent with those of samples at room temperature (Fig-
ure S16–18), confirming that 1 could maintain physical and
structural integrity in the process of catalytic reactions.
of MP which inhibits the reaction[23b]
.
To examine the stability of compound 1 in water, com-
pound 1 was immersed in water, and It is insoluble and
collected for PXRD, The result showed it kept stable and no
other new phases were formed (Figure S14).
The experiments were performed in heterogeneous phase
verified by test later. The 50 mg sample 1 as catalyst, 15.5 mM
DMMP was added to 1 mL H2O and 0.6 mL D2O at room
temperature and 1 atm. The results showed that 35.9% of
DMMP was conversed to methyl phosphoric acid over the time
course of 264 h when compound 1 was used (Figure 3, Conclusion
Figure S15). The rates of DMMP hydrolysis by 1 slow down after
ca 150 h due to the production of MP which inhibits the
reaction. Compared with blank experiment without catalysts
under the same conditions, no obvious nontoxic degradation
In summary, a novel Sb-embedded PONb cage has been
synthesized under hydrothermal conditions. The compound 1
presents new member of very limited PONb cluster family.
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successive runs, and the activity of supernatant liquid was checked
again to determine its catalysis phase.
Table 1. Crystal data and structure refinement for 1.
1
2
1
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Empirical formula
M
T/K
Crystal system
Space group
a/Å
b/Å
c/Å
H64Na8K6Sb2Nb24O102
4523.86
175(2)
Orthorhombic
Cmca
21.5957(1)
28.2915(5)
16.0621(8)
90
90
90
9813.5(9)
4
3.062
3.640
8416
4439/24/327
0.0358
0.1036
1.060
General Methods
IR spectra were conducted on a Nicolet IS50 Fourier transform
infrared spectrometer in the range 400–4000 cmÀ 1. The Uv-vis
spectra were collected on PERSEE TU-1950 Spectrophotometer. XPS
analyses were conducted on a Thermo Scientific Nexsa. 31P NMR
spectra conducted on a Bruker AVANCE III 400 MHz, were applied
to monitor the reagents and products from the hydrolytic reactions.
Samples were collected in 5 mm O.D. NMR tubes and chemical
°
α/
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°
β/
°
γ/
°
shifts were based on H3PO4 (taken as 0 ppm at 25 C).
V/Å3
Z
1calcd(gcmÀ 3
μ/mmÀ 1
F(000)
)
Structure Refinement
X-ray data were collected at room temperature on a Bruker APEX
Due CCD area diffractometer with X-ray source (Mo Kα radiation,
λ=0.71073 Å). Lorentz and polarization corrections as well as
empirical absorption correction were carried out for the net
intensities. The structures were solved by direct methods and
refined by full-matrix least-squares techniques using SHELXTL-97.[24]
All non-hydrogen atoms were treated anisotropically. No attempt
was made to locate the hydrogen atoms of water. The SQUEEZE
method in PLATON was applied to solve the disordered solvent
molecules. The crystallographic data is summarized in Table 1.
Data/restraints/parameters
R1 (I>2σ(I))[a]
wR2 (all data)[a]
Goodness-of-fit on F2
[a] R1 =�j jF0 jÀ jFC j j/�jF0 j; wR2 =�[w(F0 À FC2)2]/�[w(F0 )2]1/2
.
2
2
Compound 1 exhibits good chemical stability in different pH.
The activity of compound 1 indicates that it can effectively
catalyze the hydrolytic degradation of nerve agent simulant
DMMP. In the future, the syntheses and catalytic activities of
more novel Sb-containing PONbs will be explored.
Deposition Number 2010822 (for 1) contains the supplementary
crystallographic data for this paper. These data are provided free of
charge by the joint Cambridge Crystallographic Data Centre and
Fachinformationszentrum Karlsruhe Access Structures service
www.ccdc.cam.ac.uk/structures.
Supporting information (see footnote on the first page of this
article): Experimental details, additional characterizations, tables
and figures available.
Experimental Section
Except for the precursor K7H[Nb6O19]·13H2O was prepared accord-
ing to literature,[27] all chemicals were commercially available
without further purification. And the detail discussion was given in
supporting materials.
Acknowledgements
This work was supported by the National Natural Science
Foundations of China (No. 21971040, 21971039 and No.
21773029), National 1000 Youth Talents Plan, and Ministry of
Education of China-111 project.
Synthesis of H4Na8K6[Sb2Nb24O72]·30H2O (1)
K7HNb6O19 ·13H2O (0.535 g, 0.390 mmol), NaHCO3 (0.122 g,
1.45 mmol), Sb2O3 (0.085 g, 0.292 mmol), KCl (0.1 g, 1.34 mmol) was
mixed in 1 mL trihydroxyaminomethane-HCl buffer solution
(0.208 M, pH=7.5) and 6 mL Na2CO3/NaHCO3 buffer solution
(0.035 M, pH=11.5), After stirred 1 hour, the resulting mixture was
°
Conflict of Interest
sealed in a Teflon-lined autoclave (23 mL) and heated at 160 C for
5 days. After cooling to room temperature, colorless crystals were
obtained. Yield: 70 mg (15.63%, based on Nb). The pH values
before and after reaction were ca. 10.0 and 9.5, respectively.
Elemental analysis (based on dried sample) calcd (found %) for
H64Na8K6Sb2Nb24O102: Na, 4.09 (4.13); K, 5.24 (5.29); Sb, 5.42 (5.48);
Nb, 50.13 (50.17). IR (KBr, cmÀ 1): 3174m, 1616s, 895w, 849s, 763w,
726w, 663s, 519s, 456w (Figure S6).
The authors declare no conflict of interest.
Keywords: Base catalysis
compound · Antimoniobate
·
Cage compound
·
Cluster
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Manuscript received: February 2, 2021
Revised manuscript received: February 23, 2021
Accepted manuscript online: February 23, 2021
Eur. J. Inorg. Chem. 2021, 1505–1509
www.eurjic.org
1509
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