Accepted Article

Title: Electrochemistry of polyoxometalates: From fundamental aspects

to applications

Authors: Tadaharu Ueda

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To be cited as: ChemElectroChem 10.1002/celc.201701170

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A Journal of

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ChemElectroChem 10.1002/celc.201701170

REVIEW

Electrochemistry of
polyoxometalates: From
fundamental aspects to
applications
Tadaharu Ueda*[a,b]

Dedicated to 70th birthday of Prof. Alan M. Bond

Accepted Manuscript

This article is protected by copyright. All rights reserved.

ChemElectroChem
REVIEW
Abstract: Electrochemistry of polyoxometalates is very rich
since many of them can accommodate many electrons without
their structure change. Recently, extensive attentions have been
paid to the development of new generation battery such as fuel
cell, redox flow battery, with polyoxometalates as catalysts. On
the other hand, the detailed voltammetric behavior of
polyoxometalates still remains unclear although a huge number
of polyoxometalates have been prepared and characterized for a
long time. This review addresses electrochemical properties of
various polyoxometalates from fundamental and practical points
of view.
Introduction
Polyoxometalates (POMs), which are a class of metal oxide
cluster anions, consist of addenda atoms such as tungsten and
molybdenum, heteroatoms such as phosphorus and silicon, and
oxygen, which are bonded to the addenda atoms and
heteroatoms.[1] The structure of POMs is a three-dimensional
molecular architecture and is similar to the surface of metal oxides.
Recently, many researchers have focused on the synthesis of
structure-controlled hybrid materials of POMs with organic
molecules. The typical POM structures are the Keggin-type
structure, [XM12O40]n-, and the Wells-Dawson-type structure,
[X2M18O62]n- (Fig. 1). The structures of many other POMs are
based on these two types of structure. Some parts of the
framework of POMs can be substituted with other metal ions to
form metal-substituted POMs. POMs possessing defects in the
framework can behave as ligands. Such POMs can be combined
with several metal ions to form complicated POMs, such as those
with sandwich-type structures, [Z4(X2W 15O56)2]n- (X=P, As;
Z=transition metals) and [Z4(X’W 9O34)2]n- (X’=Si, P) (Fig. 2). POMs
have been applied to a wide range of scientific fields: catalysis,
analytical chemistry, biochemistry and materials chemistry. Most
POMs based on the Keggin-type and the Wells-Dawson-type
structures are redox active. Multi-electron transfer occurs
reversibly in multiple steps, which creates unique chemical
properties unlike those of general metal complexes with various
ligands. In addition, reduced and mixed-valence species of POMs
exhibit an intense blue colour, which is called ‘heteropolyblue’ or
‘molybdenum blue’. Based on the redox properties and the
corresponding colour change, POMs have been applied to the
sensitive spectrophotochemical determination of phosphorus
(molybdenum blue method) [2] and the evaluation of the
[a] Prof. T. Ueda
Department of Marine Resources Science, Faculty of Agriculture
and Marine Science
Kochi University
Monobe-Otsu 200, Nankoku 783-8502, Japan
E-mail: chuji@kochi-u.ac.jp
[b] Center for Advanced Marine Core Research
Kochi University
Monobe-Otsu 200, Nankoku 783-8502, Japan
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.
10.1002/celc.201701170
antioxidant capacities of food and beverages (Fouline-Ciolato
method).[3] In addition, protonated POMs are more acidic and less
corrosive than the mineral acids H2SO4 and HCl. [4] POMs have
been used as acids and oxidation catalysts in a variety of green
and sustainable chemistry-based organic syntheses. POMs have
been fundamentally and practically studied for a long time.
Recently, POMs have been tested as catalysts and materials for
future energy sources, including fuel cells, redox flow batteries
and supercapacitors. Although the electrochemical behaviour of
POMs has also been extensively investigated, unclear aspects
remain, e.g., the precise reduced positions in the POMs and the
detailed redox mechanism coupled with protons.
This review article describes the recent achievements of the
Accepted Manuscript
solution-phase electrochemical studies of POMs, especially
metal-substituted POMs, which were mostly reported after the
previous reviews were published.[5,6] In addition, applications
based on and related to the electrochemistry of POMs will be
described in this review.
Prof. Tadaharu Ueda was born in Osaka in
1970, and received his BS. in 1993 and
MS. in 1995 from Kobe University. He was
appointed as Assistant Professor at Kochi
University in 1997, and was promoted to
Associate Professor in 2004 and Full
Professor in 2016. He obtained his PhD:
in .1999 under the supervision of Prof. S
Himeno. His research interests are the
synthesis, electroanalytical
characterization, and catalytic and analytical applications of novel
polyoxometalates.
General electrochemical properties of POMs
The electrochemistry of POMs has been extensively investigated
in various solutions containing different electrolytes and
electrodes by using electrochemical techniques, which involve
cyclic voltammetry in most cases. The typical voltammetric
behaviour of POMs has already been described in several books
and review articles. [1,6] Here, only the important aspects of the
voltammetric behaviour of the Keggin-type ([XM12O40]n- (M=Mo,
W)) and Wells-Dawson type ([X2M18O62]n- (M=Mo, W)) POMs will
be briefly described again. The electrochemical behaviour of
Keggin-type POMs has been investigated in aqueous and non-
aqueous media. Because the redox potentials of POMs are very
sensitive to the concentration of acid (pH) in solution and the
protons that act as a counter cation and because proton-coupling
constants strongly depend on the anionic charge (reduced level)
and structure of POMs, it is better to compare the redox potentials
in aqueous solution under pH regions where no proton coupling
occurs and in non-aqueous media and ionic liquids under neutral
ChemElectroChem
REVIEW
conditions. Generally, the redox potentials of molybdenum POMs
(heteropolymolybdates) under neutral conditions are more
positive than those of the corresponding tungsten POMs
(heteropolytungstates) e.g., [PMo12O40]3- > [PW 12O40]3-,
[SiMo12 O40]4- > [SiW 12O40]4-. In addition, the 1st redox potentials of
POMs with the same framework are linearly related to the anionic
charge of the POMs in any solvent, e.g., [SM 12O40]2-> [PM12O40]3-
> [SiM12O40]4- (M=Mo, W). The redox potentials of the Keggin-type
POMs [SiW 12O40]4-, [PW 12O40]3-, [PMo12O40]3- and [GeMo12 O40]4-
and the Wells-Dawson-type POM [P2W 18O62]6- are related to the
acidity and basicity of the organic solvent. Keggin-type POMs
have several isomers that are generated from the π/3 rotation of
each M3 O13 unit. Redox waves of the β-form appear at more
positive potentials than those of the corresponding -form, e.g.,
β-[PM12O40]3- > -[PM12O40]3- (M=Mo, W).
Electrochemistry of POMs in the solution
phase
Some portion of the tungsten and molybdenum in the framework
of POMs can be substituted with other metals while retaining the
original Keggin- and Wells-Dawson-type structures. In addition,
lacunary POMs, which are prepared by treating the parent POMs
with a weak base and contain defects in their frameworks,
function as ligands and coordinate to several metal ions to form
sandwich-type POMs. Both types of POMs are well-known as so-
called metal-substituted POMs. They exhibit different
voltammetric behaviours from their corresponding parent POMs
that depend on the substituted metals. The electrochemistry of
metal-substituted POMs will be discussed in the following section.
Tungsten-framework POMs with Keggin- and Wells-Dawson-type
structures can be partially decomposed by the addition of a weak
base, such as KHCO3, or through sophisticated control of the pH
to form lacunary species, such as [XW 11O39]n- and [X2W 17O61]n-.[7]
Other metal ions can be incorporated into the defect sites of
lacunary POMs to form metal-substituted POMs, which exhibit
fascinating chemical properties that depend on the incorporated
metal ions. The electrochemical properties of metal-substituted
POMs are also different from those of the corresponding parent
POMs. Table 1 shows the redox potentials of Keggin-type metal-
substituted POMs. It is difficult to compare the two types of POMs
because there are fewer papers on the voltammetric behaviour of
Keggin-type metal-substituted POMs across the entire potential
range under the same conditions. However, a general trend was
found in the electrochemical behaviour of Keggin-type metal-
substituted POMs: In manganese- and cobalt-substituted POMs,
MnII and CoII can be oxidized to MnV and CoIII, respectively. MnV
is irreversibly electrochemically reduced to Mn II via MnIII, while
CoIII is quasi-reversibly reduced to CoII. In iron-substituted POMs,
the reduction of FeIII to FeII occurs at a more positive potential
than the reduction of tungsten in the framework of the POMs.
However, the corresponding re-oxidation wave of FeII to FeIII is
not observed in most cases, although (quasi)reversible tungsten
redox waves are obtained. These voltammetric behaviour would
depend on interaction between substituted metals and oxygen in
H2O or OH-. Manganese(V) and Iron(III) can be attracted to
oxygen while manganese(II) and (III) and iron (II) released oxygen
although the analysis of the detailed redox mechanism with
chemical reactions would be desirable. In the case of zinc- and
cobalt-substituted POMs, the reduction potential of the tungsten
This article is protected by copyright. All rights reserved.
10.1002/celc.201701170
framework shifts to more negative potentials than that of the
corresponding lacunary POMs, indicating that these metal-
substituted POMs are more stable than the lacunary POMs,
although no wave was observed due to the redox of the
substituted metals. The electrochemistry of many types of
vanadium-substituted POMs has been extensively investigated in
various solutions. The reduction wave due to reduction of VV to
VIV appears at a more positive potential than that of the tungsten
and molybdenum framework of POMs (Table 2). [9] Vanadium-
substituted POMs have been applied as catalysts in the oxidation
reactions of organic syntheses. The electrochemistry of
vanadium-substituted POMs was described in detail in ref. [10].
The detailed voltammetric behaviour corresponding to
[SVW 11O40]3-/4- (VV/IV) and [SVW 11O40]4-/5- (W VI/V) processes was
investigated with different electrodes (glassy carbon, platinum,
Accepted Manuscript
gold and boron-doped diamond) in dimethylformamide containing
[n-Bu4N][PF6] as the supporting electrolyte by using large-
amplitude Fourier-transformed alternating current (FTAC)
voltammetry.[11] The electrode material greatly affected the W VI/V
processes, and an irreversible reduction wave was observed due
to slow electron transfer kinetics in all cases except for the glassy
carbon electrode. The electron transfer kinetics significantly
increased with increasing concentration of [n-Bu4N][PF6]. In
addition, the electron transfer kinetics were drastically changed
by the addition of 1-butyl-3-methylimidazolium
hexafluorophosphate as a supporting electrolyte instead of [n-
Bu4 N][PF6], with an increase of a factor of 2 to 4 for the VV/IV
process and 10- to 100-fold for the W VI/V process. Moreover, the
electron transfer kinetics, especially for the W VI/V processes, were
highly dependent on the size of the electrolyte cations: Larger
cations gave slower electron transfer kinetics in the order of
(C2H5)4N+> (n-C3 H7)4N+ > (n-C4H9)4N+ > (n-C6H13)4N+. All copper-
substituted POMs exhibit interesting voltammetric behaviours. A
sharp anodic desorption peak is observed after re-oxidation of the
tungsten framework in reduced copper-substituted POMs.
However, the current of the corresponding reduction wave due to
reduction of CuII to Cu0 via CuI is always quite small in magnitude
and appears as a pre-wave or tiny bump. In addition, no
adsorption wave is observed under any conditions even though
the POMs were adhered to the electrode by electrochemical
quartz crystal microbalance (EQCM) analysis during reduction. [12]
Detailed theoretical analysis would be needed to elucidate the
reduction/oxidation and adsorption/desorption processes of
cupper in POMs.
Many ruthenium complexes exhibit fascinating chemical
properties because they are very stable, even in different valence
states. [13] Ru-substituted POMs also exhibit excellent
electrochemical and photochemical properties. [14] In the case of
mono-Ru-substituted POMs, [XRu(H2O)W 11O39], the ruthenium is
oxidized from +III to +IV and +V and reduced from +III to II, while
it is reversibly re-reduced and re-oxidized to +III (Table 3).[14]
Interestingly, the oxidation and reduction processes of ruthenium
occur at more positive potentials than the reduction of tungsten.
In addition, the ligand water on ruthenium can be substituted with
other organic molecules (L), including DMSO, pyridine, bipyridine,
NO and CO. The redox waves of the Ru component in Ru-
substituted POMs with (organic) molecules attached,
[XRu(L)W 11O39], are always observed at more positive potentials
than those of the corresponding [XRu(H2O)W 11O39].
In the case of Wells-Dawson-type POMs, two types of isomers
exist depending on whether the polar or belt position metals are
substituted, and these two isomers are described as 2 (or 1)-
ChemElectroChem
REVIEW
[X2MW 17O61]n- and 1 (or 4)-[X2 MW 17O61]n- (X=S, P, As;
M=substituted metals), respectively. In addition, Wells-Dawson-
type parent POMs ([X2W 18O62]n-) can be partially decomposed
with a weak base to form [X2W 15O56]m-, which has large defective
sites on the polar side. Several metal ions (four in most cases)
can be accommodated in the vacant sites between two
[X2W 15O56]m- units to form sandwich-type metal-substituted POMs
(Fig. 2). Generally, 1 (or 4)-[X2 MW 17O61]n- is reduced at more
positive potentials than 2 (or 1)-[X2MW 17O61]n- under the same
neutral conditions. The potential corresponding to the redox
reaction of the vanadium component in the 1 isomer of
[X2VW 17O40] is more positive than that in the 2 isomer (Table 2).
Interestingly, regardless of the structure type, the voltammetric
behaviours of the Wells-Dawson-type and sandwich metal-
substituted POMs are similar to those of the Keggin-type metal-
substituted POMs, although the redox potentials differ as follows
(Tables 4 and 5): Manganese is oxidized from +II to +IV. Copper
is adsorbed to the surface of the electrode without any adsorption
waves, although a sharp desorption wave appears. Iron is
reduced at a more positive potential than tungsten. Ni- and Zn-
substituted POMs do not exhibit any specific reduction waves
except for the reduction waves of tungsten in the framework.
Titanium oxide has expanded through the research of its
photocatalysis since it was found to function as a photocatalyst
for oxygen evolution in water. Titanium can also be incorporated
into the tungsten framework to form titanium-substituted Wells-
Dawson- and Keggin-type POMs (Table 6). The titanium-
substituted POMs were treated with H2O2 to transform the oxygen
attached to titanium to a peroxo group. The titanium was reduced
from +IV to +III at a more positive potential than the reduction of
the tungsten framework. In addition, the peroxo group was
reduced at a more positive potential than titanium.
Recently, inorganic-organic hybrid materials have been
extensively prepared to elicit excellent synergetic chemical
properties by combining functional inorganic molecules with rigid
structures and functional organic molecules with flexible
structures. Many POMs themselves exhibit excellent chemical
properties, especially in acid and oxidation catalysis. However,
their separation from the reaction mixture and reuse is always a
problem. Insoluble POM-organic hybrid materials provide one
solution to this problem. In addition, some functional organic
molecules and/or metal complexes have been bound to POMs to
generate synergetic effects, e.g., the combination of organic
molecules as light absorbers with POMs as electron mediators.
Moreover, the voltammograms of a variety of hybrid-type POMs
have been measured by incorporating them in a carbon paste
electrode due to their insolubility in solution. Unfortunately, in
many cases, defined reversible waves were not obtained due to
the decreased mass transport. Voltammograms have been used
only to determine if POMs are present in hybrid materials. In
addition, poor or no assignment of the waves was performed in
many papers. Systematic and easy electrochemical
measurement methods for inorganic-organic hybrid POM
materials would be desirable for determining the detailed
relationship between their electrochemistry and other chemical
properties.
Photoelectrochemistry of POMs
POMs have an LMCT band from the UV region to visible region,
indicating that many POMs could change the active species to
react with some organic molecules. In addition, photocurrent was
This article is protected by copyright. All rights reserved.
10.1002/celc.201701170
produced in solution in the presence of POMs with a
photosensitizer and mediator on an ITO electrode under visible
light irradiation.
Wells-Dawson-type [S2M18O62]4- (M=Mo,W) in CH3CN and
Keggin-type [SMo12O40]2- in acetone promoted the photooxidation
of benzyl alcohol, ethanol, and (-)-menthol to the corresponding
aldehydes under irradiation by white light.[18a] All three POMs were
re-oxidized when a +0.2 V potential vs. Ag/AgCl was applied, and
these reactions were monitored by the oxidative current. Only
[S2M18O62]4- was regenerated from the reduced species through
oxidation by H+ or O2. The photo-oxidation mechanism of alcohols
with POMs is summarized in Scheme 1.
Accepted Manuscript
Wells-Dawson-like -[(SO3)2W 18O54]4– gave five reversible waves
in neutral CH3CN and exhibited photoactivity. -[(SO3)2W 18O54]4–
oxidized benzyl alcohol to benzaldehyde under irradiation by
white light. In addition, a similar photocurrent was obtained in
DMF, which functioned as both the solvent and the electron donor
when a +400 mV vs. Fc/Fc+ potential was applied to oxidize the
reduced POM species. [18b] The β-form of -[(SO3)2W 18O54]4– also
exhibited photoactivity. An adduct of [Ru(bpy)3]2+ and - or β-
[(SO3)2W 18O54]4– was drop-casted on an ITO electrode, and its
photoactivity in contact with benzyl alcohol was investigated
under white-light irradiation. Unfortunately, the maximum
photocurrent decreased by approximately 60% and 30% for the 
and β forms, respectively, relative to the tetrapentylammonium
salt of [(SO3)2W 18O54]4–.[18c] In a similar manner, the
photoelectrochemistry of the adduct of [Ru(bpy) 3]2+ and
[S2M18O62]4- (M=Mo,W) was investigated in CH3CN in the
presence of DMF. The detailed redox mechanism as well as the
photochemistry were extensively explored by utilizing various Ru
complexes as counter cations. The Ru complex cations of
[S2M18O62]4- decreased the magnitude of the photocurrent relative
to that of the tetraalkylammonium salt. This is because the excited
state of the cation Ru* complex would take part in a quencher-
fluorophore electron transfer reaction and/or act as a filter of the
light irradiation.[18d] However, under irradiation by white light in
CH3CN, a thin film of [Ru(bpy)3]2+ and γ*-[S2M18O62]4- exhibited a
significantly higher photocurrent (59 Acm-2) corresponding to the
photooxidation of benzyl alcohol than the other POM films: [18e]
copper phthalocyanine and [SiMo12O40]4- (~4 Acm-2, λ> 400 nm);
porphyrin and 2-[FeIIIP2W 17O61]7- (~2 Acm-2, λ> 385 nm);
[Ru(bpy)2(dpbpy)]2+, TiO2 and [{Ru4O4(OH)2(H2O)4}(γ-
SiW 10O36)2]10- (~15Acm-2, λ= 420–470 nm); hemicyanine and
[Cu4(H2 O)2(PW 9O34)2]10- (~3.3 Acm-2, λ = 325–730 nm).
Many polyoxometalates exhibit photocatalysis and photoactivity,
although they have not been used practically. However,
polyoxometalates have been promising compounds for
photoelectric devices. POM-porphyrin hybrid compounds
deposited on an ITO electrode generated photocurrent under
irradiation by visible light with I3- as a redox mediator in aqueous
solution. Hybrid compounds were prepared by
electropolymerisation of porphyrin with organo-Wells-Dawson-
type [P2V3W 15O62]9-, of which two pyridine rings were connected
to three vanadium units through a 1,3,5-trisubstituted benzene
ring with an organic backbone by diolamide grafting. [19] An ITO
electrode fabricated with the n-Bu4N salt of
[P2V3W 15O62{(OCH2)3CNHCO(ZnTPP)]6- (ZnTPP=zinc(II)-
tetraphenylporphyrin) by the inverted transfer method also
exhibited photoactivity under visible light. The photocurrent
mechanisms of these two POM-porphyrin-modified ITO
ChemElectroChem
REVIEW
electrodes were basically same. Electrons flowed from the ITO
electrode to the porphyrin. The visible-light-excited porphyrin
accepted electrons and then passed them to the Pt counter
electrode via the POM and the I3- redox mediator.
An electrostatic thin film of POM and hemicyanine dyes or
ruthenium complexes fabricated through the layer-by-layer
method on a cationic surface prepared by treating an ITO
electrode with (3-aminopropyl)trimethoxysilane exhibited a large
cathodic photocurrent under irradiation by visible light. [20a-c]]
Several hemicyanine dyes were used, as shown in Fig. 3. The
sandwich-type POMs [Ni4(H2O)2(PW 9O34)2]10-,
[Cu4(H2 O)2(PW 9O34)2]10-, [Zn4(H2O)2(PW 9O34)2]10- and
[Cd4(H2 O)2(PW 9O34)2]10- were used, and methyl viologen diiodide
acted as the electron acceptor. Electrons were transferred from
ITO to the hemicyanine dyes via the POM. The hemicyanine dyes
as photosensitizers were excited under irradiation by visible light,
and then electrons were transferred from the excited hemicyanine
dyes to the electron acceptor, which was I3-, oxygen or methyl
viologen (Scheme 2). Cadmium sulfide is one of the
semiconductor materials that exhibit photoactivity. An ITO glass
substrate coated with a thin film of [P2W 18O62]6- deposited on
poly(allylamine hydrochloride)-modified CdS by the layer-by-layer
self-assembly method generated photocurrent in a 1 M Na 2S
solution at a constant bias of 0 V under irradiation by visible
light.[20d]] The CdS absorbed visible light and generated electron-
hole pairs. The photogenerated electrons were transferred from
the conduction band of CdS to the ITO substrate via [P 2W 18O62]6-.
The [α-SiCo3W 9O37(H2O)3]10-/reduced graphene oxide
nanocomposite exhibits Jsc of 17.5 mA cm −2, Voc of 0.705 V and
FF of 0.558 for the photoanode in the pure inorganic donor-
acceptor type dye-sensitized solar cells. [21a)] Many of POMs,
[PW 12O40]3-, [PMo12O40]3-, [SiW 12O40]4- and [P2W 18O40]3-
immobilized on the surface of ITO, FTO and TiO 2 with
photosensitizer organic materials improved their photovoltaic
performances. [21b)-k)]
Next-generation energy with POMs: Fuel cells,
water splitting, batteries and supercapacitors
Recently, extensive attention has been focused on the
development of effective energy generation from natural
resources, such as in solar power and biomass systems.
Unfortunately, such energy generation systems are difficult to
control in most cases because they strongly depend on the
natural conditions. Energy storage is a crucial key requirement for
using such natural resource energy without any loss. A promising
method for storing energy is electrocatalytic hydrogen evolution
from water. Energy has always been an important issue for
human life. Hydrogen is also a promising source of energy in the
future because it produces water, which does not damage nature,
unlike coal, oil, natural gas and nuclear-based energy. Some
POMs have been reported to exhibit high potentials of effective
catalysis for water splitting to evolve hydrogen and oxygen. In this
section, the electrochemistry of such POMs will be reviewed.
Water oxidation
This article is protected by copyright. All rights reserved.
10.1002/celc.201701170
Sandwich-type [{Ru4 O4(OH)2(H2 O)4}(γ-SiW 10O36)2]10- with
[Ru(bpy)3]3+ catalysed water oxidation to generate O2 (18 moles
O2/mol POM).[22a)] The detailed voltammetric behaviour of
[{Ru4O4(OH)2(H2O)4}(γ-SiW 10O36)2]10- was investigated in an
aqueous medium over pH 2 −12 (Britton-Robinson buffer) in the
presence of various supporting electrolytes by using
hydrodynamic voltammetry, FT-AC voltammetry and simulations.
The voltammetric analysis elucidated the reduction processes of
the tungsten framework and a series of RuIII/IV and RuIV/V redox
processes. Potassium cations strongly interacted with
[{Ru4O4(OH)2(H2O)4}(γ-SiW 10O36)2]10- to alter its voltammetric
behaviour. The RuIV/V redox processes in the {Ru4O4(OH)2(H2O)4}
core related to water oxidation catalysis were highly affected by
protons.[22b,c)] In addition, a graphene-supported
[{Ru4O4(OH)2(H2O)4}(γ-SiW 10O36)2]10- electrode exhibited
Accepted Manuscript
excellent catalytic activity and high stability in the water oxidation
reaction at neutral pH in the presence of 1 M Ca(NO 3)2. The
activity of the electrode was comparable to that of IrO 2.[22d)]
The cyclic and differential pulse voltammograms of
[RuIV4O5(OH)(H2O)4(γ-PW 10O36)2]9- were measured in a buffer
solution at pH 0-7. Several waves were obtained due to the
electron transfer processes of the ruthenium cores from to
{RuIV2RuV2} to {RuIIRuIII3}.[22e)] The {RuIV4} species exhibited a
positive enough redox potential to be oxidized to the {RuV4}
species by [Ru(bpy)3]3+. [RuIV4O5(OH)(H2O)4(γ-PW 10O36)2]9-
produced O2 with a turnover number up to 120 in an Ns2SiF6
buffer solution at pH 5.8 in the presence of [Ru(bpy) 3]3+ and S2O82-
under visible light.
For [RuIII2Zn2(H2O)2(ZnW 9O34)2]14–, a three-step redox process
occurred at -0.15, +0.28 and +0.76 vs. SHE, and these peaks
were assigned to the RuII/III, RuIII/IV, and RuIV/V couples,
respectively. O2 was generated at a Au anode by applying a
positive potential in a phosphate buffer solution in the presence
of [RuIII2Zn2(H2O)2(ZnW 9O34)2]14–, while the Keggin-type
[PW 11O39RuIII(H2O)]4– exhibited no catalysis in O2 generation
under the same conditions. [22f)]
Sandwich-type [Co4(H2O)2(PW 9O34)2]10- was initially reported to
perform electrocatalytic water oxidation at 1.1 V vs. Ag/AgCl in a
phosphate buffer solution at pH 8.0. However, it was found that
the CoOx produced from partial decomposition was the main
catalyst in water oxidation. Careful attention needs to be paid to
experiments on POMs in solution over a wide range of pH values,
especially in the basic region, because POMs are stable in a
limited pH range (mostly acidic range). [22g)]
Unlike [Co4(H2O)2(PW 9O34)2]10-, [Co2Bi2(-B-CoW 9O34)2]14- and
[Co2Bi2(β-B-CoW 9O34)2]14- are stable at a neutral pH and exhibited
catalytic activity in electrochemical water oxidation to O 2 in a
phosphate buffer solution at pH 7.4 in the presence of [Ru(bpy) 3]2+.
In addition, both of the POMs produced O2 (5.3 and 16.8 mol,
respectively, after 40 min) in the presence of [Ru(bpy) 3]2+ as a
photosensitiser and S2 O82- as a sacrificial electron acceptor under
irradiation by visible light. [22h)]
Ionic liquids exhibit specific chemical properties, such as
nonvolatility, high conductivity, and chemical interactions, which
lead to high yields and/or high selectivities for many chemical
reactions. Wells-Dawson-type [P2W 18O62]6−, [S2Mo18O62]4−, and
[S2W 18O62]4− did not produce O2 in water or water-organic mixed
ChemElectroChem
REVIEW
media but did generate O2 at water-ionic liquid and water-
diethylether interfaces under irradiation by white light (275–750
nm) or sunlight.[22i,j)] The ionic liquids (ILs) employed were aprotic
([Bmim]X; Bmim 1-butyl-3-methylimidazolium, X=BF4, PF6) and
protic (DEAS =diethanolaminehydrogen sulphate;
DEAP=diethanolamine hydrogen phosphate). The
photogenerated POM species oxidized water, which acted as the
electron donor to generate O2 with H+:
4 POM + 2 H2O + hv → 4 one-electron-reduced POM + 4 H+ + O2
The specific structure of water at the interface was different from
that of bulk water, and the interfacial structure broke the hydrogen
bonds to activate the water molecules, which reacted easily with
the photogenerated POM species. Similar reactions occurred
upon light irradiation of the solid POM salts in the presence of
water vapor.
Hydrogen storage
When POMs are reduced in acidic solution, they couple with
protons due to the increase in their anionic charge. On the other
hand, POMs release protons when the reduced proton-coupled
POMs are oxidized. This implies that POMs can function as a
proton storage and proton carrier medium. H4SiW 12O40 was
reduced to the two-electron, two-proton coupled H6 SiW V2W VI10O40
POM on carbon in an H3PO4-containing aqueous solution at pH 1.
H6SiW V2W VI10O40 released protons to effectively generate highly
pure H2 (only 0.08% O2) on a Pt/C surface.[23a)] A WO3-FTO
photoanode in 1 M CH3SO3 H (pH 1) under visible light generated
electricity as well as oxygen, whereas H3PMo12 O40 was reduced
in conjunction with proton coupling to H5 PMo12O40 on carbon felt
as a cathode in water at pH 0.1. [23b)] When H5 PMo12O40 was
reoxidized to H3PMo12O40, H2 was evolved in a 100% Faradaic
yield, implying that this system should be an excellent H2 storage
method.
Redox flow batteries
Considerable attention has been paid to the development of redox
flow batteries as the next-generation battery. POMs are one of the
promising compounds for electricity carriers in redox flow
batteries because of their highly stable redox cycles.[24a-c)]
Combinations include [SiVV3W VI9O40]7-/[SiVIV3W VI9O40]10- at the
positive electrode and [SiVIV3W VI9O40]10-/[SiVIV3W V3W VI6O40]13- at
the negative electrode, [PVIV3W VI9O40]9−/[PVV3W VI9O40]6− at the
positive electrode and [PVIV3W VI9O40]9−/[PVIV3W V3W VI6O40]12− at
the negative electrode, and
[(SiFe3W 9(OH)3O34)2(OH)3]11−/[(SiFe3W 9(OH)3O34)2(OH)3]14− at
the positive electrode and
[(SiFe3W 9(OH)3O34)2(OH)3]17−/[(SiFe3W 9(OH)3O34)2(OH)3]14− at
the negative electrode. Wells–Dawson-type [P2V3W 15O62]9− has
been tested as an electricity carrier in redox flow batteries.
However, this POM was not suitable for a redox flow battery due
to the poor stability and inaccessibility of the highly reduced
materials. An [SiV3W 9O40] redox flow battery system exhibited
coulombic efficiencies greater than 95% with relatively low
capacity fading over 100 cycles. The coulombic efficiencies of
[PV3W 9O40] and [(SiFe3W 9(OH)3O34)2(OH)3] redox flow battery
systems were > 80% and 83%, respectively, but these systems
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10.1002/celc.201701170
were noticeably less efficient than the [SiV3W 9O40] redox flow
battery system.
Based on the similar concept of redox-flow battery, Pt-free
systems have been developed for oxygen reduction reaction in
the fuel cell. [24d-f)] The vanadium components of Keggin-type
[PVxMo12-xO40](3+x)-(x=2-4) at cathode in polymer electrolyte fuel
cell were reduced with proton which came through membrane
from anode. The reduced vanadium-substituted POMs were
transported by pump into “regenerator unit”. Then, the reduced
vanadium-substituted POMs were oxidized by oxygen in air to
transport into cathode in polymer electrolyte fuel cell. The best
performance was recorded with a peak power density of 1.078
Wcm-2 in the case of [PV4 Mo8 O40]7-.
Accepted Manuscript
Lithium-ion batteries
Lithium-ion batteries have been widely used as compact
rechargeable batteries with high voltages and high current
densities for many electrical items, such as mobile phones and
laptop computers. Some POMs have been tested as electrode
materials.
Standard Keggin-type saturated POMs, [XM12O40] n- (X=Si, P;
M=Mo,W), were combined with organic molecules to form the
organized nano-structure materials, which have been
investigated in lithium-ion battery performance. Some examples
are mentioned as follows: The [PMo12O40]3--polyaniline hybrid
nanofibers exhibit electrochemical performance with lithium
storage capacity of 183.4 mAhg-1 at 0.1 C rate, cycling stability of
80.7% capacity retention after 50 cycles, and rate capability of
94.2 mAhg-1 at 2 C rate. [25a)]
The
[Ag(trz)][Ag12(trz)9][HSiW 12O40]2H2O,
[Ag(trz)][Ag12(trz)9][PMo12 O40]2H2 O,
[Ag5(pyttz)3 Cl(H2O)][H3SiMo12 O40]3H2O and
[Ag5(trz)6][H5SiMo12O40], which were prepared by reaction of
POMs with 1,2,4-triazole (trz) or 3-(pyrid-4-yl)-5-(1H-1,2,4-triazol-
3-yl)-1,2,4-triazolyl (pyttz) and AgNO3 under hydrothermal
conditions, exhibit electrochemical performance with the first
discharge capacities of 1182, 1355, 1344 and 1452 mAhg -1, and
stabilized discharge capacity of 330, 520, 520 and 570 mAhg -1,
respectively, after 100 cycles at the current density of 0.5 or 0.1
Ag-1. [25b),c)] The vanadium-substituted Keggin type POM,
[PV2Mo10O40]5-, and polydopamine sphere composite material
prepared in situ polymerization method under hydrothermal
conditions exhibit a high and stable specific capacity of 915.3
mAhg-1 at a current density of 100 mAg-1, remarkable rate
capability, and good cycling stability of 93% capacity retention
after 300 cycles at a high current density of 1000 mAg-1. [25d)]
Structurally organized carbon materials, carbon nanotube and
graphene, and POMs nanocomposites exhibit excellent
electrochemical performances for electrode materials as a lithium
ion battery. The [SiW 11O39[O(Si(CH2)3NH-COOCH2C16H9)2]4-
covalently bounded with pyrene moiety, were immobilized by -
interaction with single walled carbon nano tube (SWCNT) to form
a hybrid material. This hybrid material exhibits the initial discharge
capacity of 1569.8 mAhg-1 , and a high discharge capacity of 580
mAhg-1 with high capacity retention (37%) for up to 100 cycles at
a current density of 0.5 mA cm-2. [25e)] The nanocomposite material
prepared by covalent bound of
[SiW 11O39{O(SiCH2CH2CH2NH2HCl)2}]4- directly to SWCNT
ChemElectroChem
REVIEW
exhibits the first discharge capacity of 1189 mA h g -1 and stable
charge capacity of 650 mAhg-1 with high capacity retention
(54.6%) for up to 100 cycles at a current density of 0.5 mA cm-2.
The electrochemical performance of this composite was improved
than that of the above sample because the SiW 11O39 unit was
tightly bound to SWCNT. [25f)] The [PVMo11O40]4- wiring
nanocrystals periodically deposited on SWCNT with tunable size
and shape performed stable discharge capacities of 850 mA h g-
1
for up to 100 cycles at a current density of 0.5 mA cm-2, although
the first discharge capacity is 3014.1 mAhg-1 and the discharge
capacity decreases to 1052.6 mA h g-1 in the second cycle. [25g)]
The nano composite material of [P2Mo18O62]6- with imidazolium-
based ionic liquids grafted covalently on the surface of graphene
oxides exhibit a high reversible capacity of 903.9 mAhg-1 with a
high retention ratio(63%) even after over 1000 cycles. [25h)]
In most cases, redox active POMs have been used as electrode
materials for lithium-ion battery. Although the POMs with
Andersson structure themselves show no reversible redox waves,
single-walled carbon nanotubes (SWNTs) covalently bound to
[MnMo6 O24]9- were functionalized with tris(NH2C(CH2 OH)3)
moieties, and the resulting redox-active, organo-modified
polyoxometalate (POM) clusters were employed as the anode
material in a lithium-ion battery. This battery showed a high
discharge capacity of up to 932 mA h g-1 at a current density of
0.5 mA cm-2 with good long-term cycling stability and decreased
electrochemical impedance.[25i)]
Li7[V15O36(CO3)] exhibited rapid lithium ion diffusion and good
electron conductivity, leading to rapid charging and discharging of
the corresponding Li-ion battery. The Li7[V15O36(CO3)] active
material showed excellent rates and cycling performance at a high
current density and generated a high power density output of 25.7
kWkg-1 with an energy density output of 370 Wh kg-1.[25j)] Then,
Li7[V15O36(CO3)] based symmetric devices achieved an ultrahigh
specific power of 51.5 kW kg-1 at 100 A g-1 and a specific energy
of 125 W h kg-1 with a long cycling life (>500 cycles) by using
different VIV/V redox potentials of vanadium in this POM. [25k)] The
Li7[V15O36(CO3)] also indicated promising potentials to apply to
sodium ion battery. Moreover, the other vanadium-based
polyoxometalates, Na6[V10O28] and Na2 H8[MnV13O38], were
reported to show electrochemical performances as electrode
materials for sodium-ion battery. [25l),m)]
Supercapacitors
The development of energy storage materials and devices is quite
important research area for sustainable chemistry as well as that
of energy generation. POMs are one class of promising
compounds work as electrochemical supercapacitors. A variety of
cationic substances, conducting polymers and polymeric ionic
liquids, have been investigated with anionic POMs to fabricate
POMs-modified electrodes because POMs are needed to
immobilize on the surface of electrode to check their capacitance
(Table 7).[26] At the moment, the combination of Keggin-type
[PW 12O40]3- and activated carbon or reduced graphene oxide
exhibit the best performance of supercapacitor in terms of
maximum capacitance and stability for charge-discharge
cycles. [26n,o)] Wells-Dawson type [P2 Mo18O62]6- and vanadium-
substituted POMs, [VV2W 10O40]5- and [PVxMo12-xO40](3+x)-(x=1-3),
performed the similar level of capacitance to the other POMs, but
exhibit poorer stability than [PMo12O40]3- and [PW 12O40]3-.[26p-r)]
However, the stability of [PV2Mo10 O40]5- was improved by using
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10.1002/celc.201701170
SWCNT as a deposit material. [26s)] It is of great interest and
importance for sustainable chemistry that high amounts of
[PMo12 O40]3- loaded pine cone exhibit an excellent supercapacitor
property.[26m] The supercapacitor performance was greatly
improved in the aqueous solution in the presence of ionic liquid,
[Bmim]HSO4, as supporting electrolyte, instead of a mineral acid,
e.g. H2 SO4.[26i)] The nano structure of POM/binder
molecules/electrode composite should affect greatly on the
supercapacitor performance and stability. [26f)]
Simulation
Currently, cyclic voltammograms are measured whenever novel
Accepted Manuscript
redox-active POMs are synthesized. Unfortunately, the procedure
for displaying voltammograms is not accurate, and the
assignments of the obtained peaks are poor in some cases.
POMs undergo ion paring with small cations, especially protons,
to change their voltammetric behaviour in complicated ways.
Protons greatly affect the voltammetric behaviour and the
formation of POMs. Generally, one-electron transfer occurs in a
stepwise fashion under neutral conditions, whereas two-electron
transfer occurs under highly acidic conditions. However, only
qualitative analysis, even for defined voltammograms, is carried
out in most cases. The digital simulation software Digisim
(Bioanalytical Systems Inc.) and DigiElch (GAMRY) for
voltammograms connected with ion-association and
disproportionation reactions provide various equilibrium constants
and kinetic constants as well as redox potentials that cannot be
measured directly, although it is still difficult to obtain definite
constants based on only experimental electrochemical data. As
many electrochemists know, simulation software provides
parameters for fitting the observed voltammograms, regardless of
the chemically correct answer. If the redox mechanism is
proposed from the experimental results of various
electrochemical measurements as well as other measurements,
e.g., spectroscopy, and simulation is conducted based on this
redox mechanism, the parameters obtained from the simulation
may be nearly chemically correct. Such equilibrium constants are
very important and useful for electrochemical-based applications
of POMs. In this section, the simulation of the cyclic
voltammograms of POMs will be reviewed.
The electrochemistry of the Keggin-type POMs [XM12O40]n- has
long been extensively investigated in aqueous solution and
organic solvents. In most cases, only the redox potential changes
that depend on the concentration of acid (pH) were examined,
although the redox reactions were anticipated to lead to
disproportionation reactions. [27a)] Recently, the detailed
voltammetric behaviour of the α and β forms of [PW 12O40]3- was
investigated in CH3CN containing n-Bu4 NPF6 in the presence of
designated concentrations of acid (CF3 SO3 H).[27b)] The diffusion
coefficients of the unprotonated POMs were calculated from
cyclic voltammograms obtained in the absence of acid over the
scan rate range of 20 to 500 mV s -1 and the Randles-Sevcik
equation. The diffusion coefficients of the protonated species
were similarly estimated from the scan rate dependence found in
the presence of a significant excess of acid when only a single
reduction process was found. The reported diffusion coefficient
for H+ in acetonitrile was 3.1×10-5cm2s-1 for the simulation.
In the presence of excess acid, in principle, the electrochemistry
can be described by the reaction given in equation 1.
ChemElectroChem
REVIEW
[HxPW 12VIO40](3-x)- + yH+ + 2e- → V
← [Hx+yPW 2 W 10O40]
(3+2-(x+y))+
(1)
Furthermore, an estimate of the difference (y) in the number of
protons can be gained from the slope of a plot of the reversible
potential versus the logarithm of the concentration of acid when
the acid concentration is in a large excess. The slope of ca. 60 in
the mid-point potentials(Emid) versus -log[H+] plot for both the α
and β forms of [PW 12O40]3- is indicative of a maximum value of y
= 2.
The 183W NMR spectra of the α and β forms of [PW 12O40]3- in the
absence and presence of excess CF3SO3H suggested that the α
form was protonated equally at the oxygens of nearly any W
position, whereas the β form was protonated at the oxygens
between W I and W II regions (Fig. 1). Analysis of the EPR spectra
of the α and β forms of the one-electron-reduced [PW VW VI11O40]4-
in the absence of CF3SO3H indicated that one electron was
delocalized at any W position in the α form due to its high
symmetry (Td), whereas one electron was localized at the W I or
W III regions in the β form. From the results of the voltammetry,
NMR and EPR measurements, a redox mechanism with the
protonation reactions could be proposed, as shown in Scheme 3.
Simulations of the voltammetry were undertaken as a function of
the acid concentration according to Scheme 3. A comparison of
the simulated and experimental cyclic voltammograms for two
isomers of [PW VI12O40]3-, [PW VW VI11O40]4- and [PW V2W VI10O40]5-, is
shown in Fig. 4. The simulated cyclic voltammograms are
generally in good agreement with the observed ones over all
concentrations of CF3 SO3 H studied. The detailed parameters
used for the simulation can be seen in ref. [27b)].
The vanadium-substituted POMs, [XV xM12-xO40] n- and [X2VxM18-
n-
xO62] , have been widely used as oxidation catalysts because the
redox potentials of the V(V) POMs are more positive than those
of the corresponding parent POMs, [XM12O40]n- and [X2M18O62]n-,
indicating that the V(V) POMs should be stronger oxidants. Taking
the reaction stage of the catalytic oxidation reaction with
vanadium-substituted POMs and the stability of the reduced
vanadium-substituted POMs into consideration, the voltammetric
behaviour of the vanadium component of the Keggin-type
vanadium-substituted POMs [XVM11O40]n- (X=P, As, S; M=Mo, W)
in CH3CN was extensively investigated in the presence of
designated concentrations of acid in a similar manner as the
analysis of the voltammetric behaviour of the two isomers of
[PW 12O40]3-.[9] Moreover, voltammograms of the Keggin-type
XVM11 (X=Si, Ge, P, As, S; M=Mo, W) were measured in CH3CN
under neutral conditions (Table 2). Similar to the case of the non-
substituted Keggin-type POMs, the potential due to the redox
reaction of the VV/IV components was linearly related to the anionic
charge, implying that the mean bond valence estimated from the
structural information of the vanadium-substituted POMs could be
related to the redox potential.
Quantitative analysis of the complicated coupled electron and
proton transfer steps during reduction of the Wells-Dawson-type
-[P2W 18O62]6- and Keggin-type -[H2W 12O40]6- POMs in a 0.5 M
NaCl aqueous solution has been achieved by simulation of the
cyclic voltammograms over a wide range of anion concentrations,
pH values (1-6), and scan rates.[27c)] The cyclic voltammograms of
both complexes were simulated by estimating the three
protonation constants combined with the experimentally
determined reversible redox potentials for the two one-electron
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10.1002/celc.201701170
transfer processes under the assumption of fast electron transfer
and protonation kinetics. Finally, the detailed redox scheme with
protonation reactions was obtained, as shown in Scheme S1.
The detailed voltammetric behaviour of the FeIII/FeII component of
2-[Fe(OH2)P2W 17O61]7- in buffered and unbuffered aqueous
solutions over the pH range 3.45-7.50 with a maintained ionic
strength of approximately 0.6 M was studied (Scheme S2). [27d)]
The voltammetric behaviour of Keggin-type [SiW 12O40]4- was
investigated with a rotating disk electrode and cyclic voltammetry
over pH 2.1–6.8 to obtain a significant number of parameters
experimentally (Scheme S3). [27e)].
The four-electron reduction processes of γ*-[S2W 18O62]4-, which is
Accepted Manuscript
derived from 60° rotation of one-half of the  form and then 60°
rotations of both trinuclear caps, were examined in CH3CN (0.1 M
with n-Bu4NClO4 as a supporting electrolyte) in the presence of
designated concentrations of acid (HClO4) with the help of
hydrodynamic voltammetry.[27f)] The detailed redox mechanism of
γ*-[S2W 18O62]4- with its protonation reactions was obtained, as
shown in Scheme S4.
The detailed voltammetric behaviour of the two-electron-reduced
species of the Wells-Dawson-like [(SO3)2Mo18O54]4- was
investigated in an aqueous solution at pH 4-9.4.[27g)] Simulation of
the CVs was conducted for the two one-electron oxidation
processes decoupled from H+ at pH 4-6, as shown in Scheme S5.
Surprisingly, four reversible waves due to one-electron transfer
processes were observed for the oxidized [(SO3)2Mo18 O54]4-
species, even at pH 9.4, which is parallel to the result in CH3CN.
Generally, molybdenum-based POMs are less stable than
tungsten-based POMs at pH>6. It is noted that [(SO3)2Mo18 O54]4-
is stable in a basic aqueous solution, although there are no data
on its long-term stability at pH 9.4.
Small cations can also affect the voltammetric behaviour of POMs
in organic solvents in addition to protons. The effects of Li + and
Na+ on the voltammetric behaviour of Keggin-type POMs were
investigated in various solvents with the help of 7 Li NMR, leading
to the selective solvation of Li+ in binary solvents. The Li-coupled
reduction processes of PMo12 was investigated in acetone to
obtain protonation constants and Li association constants
(Scheme S6). [27 h-j)]
Voltammetry measurements of [S2Mo18 O62]4- gave five reduction
waves in CH3CN in the presence of 0.1 M LiClO4. Each of the
waves is attributed to one-electron transfer processes except for
the third wave, which is two-electron transfer process. [27k)] Upon
the addition of 5% (v/v) H2O, five- and six-electron-reduced
species precipitated as Li+ salts. Simulation of the cyclic
voltammograms for the first four processes of [S 2Mo18 O62]4- was
carried out in 95% (v/v) CH3CN+5% (v/v) H2O in the presence of
designated concentrations of Li+(ClO4-) (0-10 mM). The reaction
mechanism and parameters were obtained, as shown in Scheme
S7. The oxidized [S2Mo18O62]4- and one-electron-reduced species,
[S2Mo18O62]5-, did not interact with Li+. Li+ ions solvated by water
are difficult to couple with these two species, especially in this
case.
Theoretical considerations: DFT calculations
ChemElectroChem
REVIEW
It is difficult to define which part was reduced or oxidized from only
the voltammetric behaviour. This is weakest point of
electrochemistry. In addition, it is quite difficult to find the precise
positions in the POMs adopted by each electron, especially after
one-electron transfer processes. Density functional theory (DFT)
calculations could provide clues into the redox positions of the
POMs. In addition, the degree of negativity at each position in the
POMs could be obtained from DFT calculations. The ion paring
position could be indicated at various redox levels of the POMs.
The DFT calculation of POMs will be discussed in this section.
As X-ray crystallographic techniques have progressed, detailed
structural information is available for many POMs. DFT
calculations based on this structural information may give us
reasonable explanations for the stability, position of reduction,
and protonation sites of POMs. Because the  form of the Keggin-
type saturated POM [XM12O40] n- has high symmetry and each of
the twelve addenda atoms (M) is equivalent, the first electron can
be accommodated by the addenda atoms with the same
probability, except in the case of certain POMs, e.g., [CoW 12O40].
However, the second electron can be accommodated by six
different addenda sites in the one-electron-reduced Keggin-type
saturated -POM, implying that it is not possible to define which
site is reduced by the second electron. On the other hand, two
types of addenda atoms exist in the polar and belt sites, even in
the case of the  form of Wells-Dawson-type POMs, indicating
that the reduced probability should be different.
DFT calculations were carried out for several types of POMs:
Keggin-type [SiW 9M3O40]n- (M=W, Mo, V and Nb) and Wells-
Dawson-type [P2M18O62]6- (M= W and Mo) and [P2M15M’3O62] m-
(M=W and Mo, M’=W, Mo, and V).[28a)] The HOMO levels in
[SiW 9M3O40]n- (M=W, Mo, V and Nb) were estimated after full
geometry optimization in C3v symmetry to obtain a trend in the
increase in their energy levels in the order of M=V<Mo<W<Nb).
This result is similar to the order of their redox potentials,
indicating that [SiW 9V3O40] exhibits the strongest oxidizing power
among these POMs. Interestingly, P2Mo18O62 was estimated to
have a lower HOMO-LUMO gap in D3h symmetry than in D3
symmetry. Wells-Dawson-type POMs generally favour the
accommodation of the first electron at a belt site. However, the
first electron in [P2W 15V3O62], whose three vanadium atoms were
substituted at cap sites, was accommodated at a cap vanadium
site, although the HOMO-LUMO level of cap-[P2W 15V3O62] was
higher than that of belt-[P2W 15V3O62]. It is important to know which
part of the POM will be protonated. The basicity of POMs with
several types of structures was calculated by DFT. The basicity of
external oxygens in [SiW 9V3O40]n- and [SiW 9Mo3 O40]n- was
estimated, and the following order was obtained: O bridgeV2 >
Obridge Mo2 > Obridge VW > Obridge MoW > ObridgeW 2 > OterminalV >
OterminalW > OterminalMo. In a similar manner, the basicity of the
external oxygens in [XW 9M3O40]n- (X=Al, Si, P; M=V, Nb, Ti) was
estimated through DFT calculations. [28b)] In any POM, corner-
shared oxygens bound to two metals are the most basic among
all external oxygens.
The stability was calculated by DFT for different reduced levels of
the two isomers (α and β forms) of Keggin-type [XM12O40]n- (M=W,
Mo; X=P, As, Si, Ge, Al, Ga). [28c)] In the case of the fully oxidized
POMs, the α form is more stable than the β form except in the
case of [AlW 12O40]5- and [GaM12O40]5-, while the opposite trend is
observed in the case of the four-electron-reduced species.
Generally, the β form is reduced at a more positive potential than
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10.1002/celc.201701170
the α form. The four-electron-reduced species of α-[XMo12O40]
spontaneously transformed to the β form, while the oxidized β
form transformed to the oxidized α form.
Wells-Dawson-type POMs have six types of isomers (α, β, γ, α*,
β*, and γ*), which are generated by π/3 rotation of the polar unit
(M3O13) and/or the half unit (XM9 O31) of α-[X2M18O62]n-.[28d)] DFT
calculations were conducted to define the optimized distances,
HOMO-LUMO energies, stabilities and reduction potentials of the
six isomers of [P2W 18O62]6-. The six isomers exhibited stabilities
that followed the order of α > β > γ > γ* > β* > α*. The DFT
calculation results indicated a direct relationship between the
overall stability and distortion in the belt parts of [P 2W 18O62]6-. The
reduction potentials were calculated and followed the order of γ >
Accepted Manuscript
β > α both for the first and second one-electron transfer processes,
while the order of γ* > β* > α* was observed for the first process
and the order of β* > γ* > α* was observed for the second process.
Although the observed reduction potentials were different from
the calculated ones for the α isomer, unfortunately, the order in
the first reduction potential of β > α was indeed found for the real
sample.
Recently, it was reported that the first redox potential obtained
under neutral conditions was related to the mean bond valence of
W-μ4O, in which the oxygen is linked to heteroatoms, as well as
the anionic charge of Keggin-type POMs. [28e,f)] Moreover, based
on the relationship between the redox potential and the mean
bond valence, the introduction of energy from Coulomb
interactions can theoretically lead to the redox potentials of four
one-electron processes. In addition, the redox potentials of two
two-electron processes coupled with protons can be calculated by
taking the Gibbs energy of protonation into consideration.
Concluding remarks
The quantitative and theoretical analysis of the electrochemical
properties of saturated POMs, [XM12O40]n- and [X2M18O62]n-, have
been conducted through simulations and DFT calculations with
the help of NMR, EPR, and UV-Vis spectroscopies and other
measurements to clarify their complicated chemical properties
step by step. On the other hand, metal-substituted POMs,
[XZM11O39]n-, [X2ZM17O61]n-, [Z4(X2 ZM15O56)]n-, etc., exhibit
fascinating chemical properties different from those of the
saturated POMs. Some of the metal-substituted POMs exhibit
excellent water oxidation catalysis to generate O2 and function as
redox flow battery carriers. The detailed quantitative and
theoretical analyses of the voltammetric behaviour of such metal-
substituted POMs have not investigated yet, although a trend in
their electrochemical properties that depends on the substituted
metals was obtained. If the detailed voltammetric behaviour linked
with other chemical properties of most POMs was elucidated for
metal-substituted POMs, various electrochemical properties
could be controlled and tuned by the appropriate conditions,
leading to an expansion in the applicable range of metal-
substituted POMs.
Keywords: Polyoxometalate; electrochemistry; application;
simulation; DFT
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and practical points of view
Electrochemistry of
polyoxometalates: From fundamental
aspects to applications

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(a)

II

III
(b)

(c)

Figure 1 Polyhedral representation of structure of (a) α-Keggin type, (b) β-Keggin type and (c) Wells-
Dawson type polyoxometalates.

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(b)

Figure 2 Structure of sandwich type polyoxometalates: (a) [Z4(X2W15O54)2]n- and (b) [Z4(XW9O34)2]n-.

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Figure 3 Structure of hemicyanine dyes.

(a)

(b)

(c)
5μA

-1500 -1000 -500

+
E/mV vs Fc/Fc

Figure 4 Comparison of simulated (○○○) and experimental (─) cyclic voltammograms for reduction of
α-[PW12O40]3- (black) and β-[PW12O40]3- (red)in CH3CN (0.1 M [n-Bu4N][PF6]) in the presence of
designated concentrations of CF3SO3H. [CF3SO3H]/mM= (a) 0.0; (b) 1.0; (c) 5.0. Scan rate: 100 mV s-1.

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Scheme 1 Schematic representation for reaction mechanism of polyoxometalates in the presence of
organic substances under irradiation of visible light.

Scheme 2 Schematic representation for mechanism which photocurrent was generated from a system of
polyoxometalates in the presence of photosensitizer and I 3- mediator organic substances under
irradiation of visible light.

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ChemElectroChem 10.1002/celc.201701170

REVIEW

Accepted Manuscript
Scheme 3 Coupled electron transfer and proton reaction scheme and parameters used for simulations of
the cyclic voltammetry associated with the first two reduction steps for α-[PW12O40]3- (black) and β-
[PW12O40]3- (red) in acidic solutions of CH3CN (0.1 M [n-Bu4N][PF6]).

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ChemElectroChem 10.1002/celc.201701170

REVIEW
Table 1 Redox Potentials(V) of Keggin-type metal-substituted POMs.
POMs Potential(V) Solution Ref.
[PW11CrIII(H2O)O39]4- -0.570, -0.780 (WVI/V) A 8a
III 4- III/II VI/V
[PW11Mn (H2O)O39] -0.778 (Mn ), -2.115 (W ) B 8b
[PW11MnO39]6- +0.65 (MnII/III)a C 8c
[PW11FeIII(H2O)O39]4- -0.550, -0.678 (WVI/V) A 8a
III 4- III/II VI/V
[PW11Fe (H2O)O39] -0.818 (Fe ), -2.038 (W ) B 8b
[PW11CoIIO39]5- +0.88 (CoII/III) B 8d
II 5- VI/V
[PW11Co (H2O)O39] -0.65, -0.85(W ) D 8e
[PW11CoII(H2O)O39]5- -0.548, -0.686 (WVI/V) A 8a

Accepted Manuscript
II 5- VI/V
[PW11Co (H2O)O39] -1.440, -2.098, -2.257(W ) B 8b
[PW11NiII(H2O)O39]5- -0.542, -0.672 (WVI/V) A 8a
II 5- VI/V
[PW11Ni (H2O)O39] -1.411, -2.116, -2.261 (W ) B 8b
[PW11CuII(H2O)O39]5-, b -0.35 (CuII/I/0)a, -0.62(WVI/V)a E 8f
III 5- VI/V
[SiW11Cr (H2O)O39] -0.591, -0.754 (W ) A 8a
[SiW11MnIII(H2O)O39]5- -0.646 (MnIII/II), -1.828, -2.052 (WVI/V) B 8b
[SiW11FeIII(H2O)O39]5- -0.585, -0.706 (WVI/V) A 8a
III 5- III/II VI/V
[SiW11Fe (H2O)O39] -0.693 (Fe ), -1.548, -1.964, -2.199 (W ) B 8b
[SiW11CoII(H2O)O39]6- -0.589, -0.705 (WVI/V) A 8a
II 6- VI/V
[SiW11Co (H2O)O39] -1.328, -1.446, -1.921, -2.166 (W ) B 8b
[SiW11NiII(H2O)O39]6- -0.580, -0.690 (WVI/V) A 8a
II 6- VI/V
[SiW11Ni (H2O)O39] -1.358, -1.452, -1.959, -2.148 (W ) B 8b
[SiW11CuII(H2O)O39]6-, b -0.42 (CuII/I/0)a, -0.62(WVI/V)a E 8f
III 6- VI/V
[BW11Cr (H2O)O39] -0.565, -0.764 (W ) A 8a
[BW11FeIII(H2O)O39]6- -0.562, -0.733 (WVI/V) A 8a
[BW11CoII(H2O)O39]7- -0.571, -0.751 (WVI/V) A 8a
II 7- VI/V
[BW11Ni (H2O)O39] -0.571 (W ) A 8a
a)
Working electrode: Glassy carbon; Reference electrode: Ag/AgCl electrode or SCE
b) POMs form in the solution
A: NaClO4-HClO4 buffer solution(pH 2.2); B: CH3CN(n-Bu4NClO4); C: pH 4.3; D: pH 3.3; E:
Na2SO4/H2SO4 buffer solution (pH 3)

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ChemElectroChem 10.1002/celc.201701170

REVIEW
Table 2 Potentials(E1, mV) due to the redox of VV/IV component in Keggin-type and Wells-Dawson-
type vanadium-substituted POMs.[9]
POMs E1 POMs E1
Keggin type
SVMo12a +55d SVW12a +160d
a d a
PVMo12 -415 PVW12 -300d
AsVMo12a -360d AsVW12a -230d
a d a
VVMo12 -360 VVW12 -230d
SiVMo12a,c -690d SiVW12a,c -590d
a,c d a,c
GeVMo12 -625 GeVW12 -590d

Accepted Manuscript
Wells-Dawson type
1-S2VW17a -130d 4-S2VW17a 0d
b e b
1-P2VW17 -415 4-P2VW17 -300e
1-As2VW17b -360e 4-As2VW17b -230e
a Measured in CH3CN containing 0.1 M n-Bu4NPF6.
b Measured in an aqueous solution pH 7.0 (0.4 M NaH2PO4+NaOH).
c Measured after addition of n-Bu4NOH to neutralize proton present as a counter cation.
d vs. Fc/Fc+
e vs. SDE

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ChemElectroChem 10.1002/celc.201701170

REVIEW
Table 3 Redox Potentials(V) of ruthenium-substituted POMs.
Solu
POMs Potential(V) Ref.
tion
[PW11Ru(dmso)O39]6- +0.376 (RuII/III), -0.688, -0.873 (WVI/V) A4 14a
[PW11Ru(NO)O39]4- 1.29 (RuII/III), -1.00 (WVI/V) B 14b
[SiW11RuIII(H2O)O39]5- 0.773(RuIV/V), +0.499(RuIII/IV), -0.199(RuIII/II) C 14c
IV/V III/IV III/II VI/V
III
[SiW11Ru (H2O)O39] 5-
+0.762(Ru ), +0.487(Ru ), -0.202(Ru ), -0.8(W ) D 14d
[SiW11RuIII(dmso)O39]5- +0.181(RuIII/II), -0.74(WVI/V) D 14e
IV/V a III/IV a III/II a
III
[SiW11Ru (bipy)O39] 5-
+0.884(Ru ) , -0.122(Ru ) , -1.22(Ru ) , B 14f
[GeW11RuIII(H2O)O39]5- 0.793(RuIV/V), +0.488(RuIII/IV), -0.153(RuIII/II) A 14c

Accepted Manuscript
III/IV III/II VI/V
III
[GeW11Ru (dmso)O39] 5-
+1.228(Ru ), +0.238 (Ru ), -0.71, -0.89(W ) A 14g
Working electrode: Glassy carbon; Reference electrode: Ag/AgCl electrode or Fc/Fc+ scalea)
A: KH2PO4 buffer solution (pH 2.0); B: CH3CN(n-Bu4NClO4); C KH2PO4 buffer solution(pH 4.3); D:
KH2PO4 buffer solution(pH 4.5)

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ChemElectroChem 10.1002/celc.201701170

REVIEW
Table 4 Redox Potentials(V) of Wells-Dawson-type metal-substituted POMs.
POMs Potential(V) Solution Ref.
α1-[P2VW17O61] -0.446(WVI/V) A 15a
VI/V
α2-[P2VW17O61] (-0.280),-0.372(W ) A 15a
α1-[P2MnW17O61] (-0.330), -0.468(WVI/V) A 15a
α2-[P2MnW17O61] (-0.358), -0.394 (WVI/V) A 15a
8- II/III
α2-[P2W17MnO61] +0.470 (Mn ) B 8c
α1-[P2FeW17O61] -0.500(WVI/V) A 15a
α2-[P2FeW17O61] (-0.340), -0.402 (WVI/V) A 15a
α1-[P2CoW17O61] -0.462(WVI/V) A 15a

Accepted Manuscript
VI/V
α2-[P2CoW17O61] (-0.330), -0.392 (W ) A 15a
α1-[P2NiW17O61] -0.460(WVI/V) A 15a
VI/V
α2-[P2NiW17O61] (-0.325), -0.406 (W ) A 15a
α1-[P2CuW17O61] (-0.254), -0.350 (WVI/V) A 15a
VI/V
α2-[P2CuW17O61] -0.306 (W ) A 15a
α1-[P2ZnW17O61] -0.450(WVI/V) A 15a
α2-[P2ZnW17O61] (-0.300), -0.386 (WVI/V) A 15a
VI/V
α1-[P2MoW17O61] -0.088(W ) A 15a
α2-[P2MoW17O61] -0.236 (WVI/V) A 15a
8- V/IV
[P2V2W16O62] 0.298 (V ) C 15b
[P2V3W15O62]9- 0.122 (VV/IV) C 15b
7- V/IV
α1-[As2VW17O62] 0.569 (V ) C 15b
α2-[As2VW17O62]7- 0.446 (VV/IV) C 15b
II 9- II/IV
α2-[H4AsMn (H2O)W17O61] +0.892(Mn ) D 15c
α2-[H4AsFeIII(H2O)W17O61]8- -0.230(FeIII/II) D 15c
α2-[H4AsCoII(H2O)W17O61]9- +1.406(CoII/III) D 15c
II 9- II/I
α2-[H4AsCu (H2O)W17O61] -0.348(Cu ) D 15c
Working electrode: Glassy carbon; Reference electrode: SCE
A: Na2SO4-H2SO4 buffer solution (pH 3); B: pH 4.5; C: NaH2PO4-NaOH buffer solution (pH 7); D:
AcONa-AcOH buffer solution (pH 5)

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ChemElectroChem 10.1002/celc.201701170

REVIEW
Table 5 Redox Potentials(V) of sandwich-type metal-substituted POMs.
POMs Potential(V) Solution Ref.
[Mn4(H2O)2(P2W15O56)2]16- +1.000 (MnII/IV) A 16a
-0.404, -0.533, -0.733 (WVI/V)
[Fe4(H2O)2(P2W15O56)2]16- +0.187, +0.110, -0.028 (FeIII/II) A 16a
-0.352, -0.403, -0.517, -0.735 (WVI/V)
[Co4(H2O)2(P2W15O56)2]16- -0.354, -0.416, -0.534, -0.788, -0.837 A 16a
(WVI/V)
[Ni4(H2O)2(P2W15O56)2]16- -0.366, -0.472, -0.755 (WVI/V) A 16a
[Cu4(H2O)2(P2W15O56)2] 16-
-0.150 (CuII/I/0), -0.295, -0.353, A 16a

Accepted Manuscript
VI/V
(W )
[Zn4(H2O)2(P2W15O56)2]16- -0.358, -0.583, -0.748 (WVI/V) A 16a
VI/V
[Cd4(H2O)2(P2W15O56)2] 16-
-0.400, -0.703, -0.779 (W ) A 16a
[Mn4(H2O)2(As2W15O56)2]16- -0.346a,-0.517a, -0.644 (WVI/V)a B 16b
a a VI/V a
[Co4(H2O)2(As2 W15O56)2] 16-
-0.349 , -0.533 , -0.740 (W ) B 16b
[Cu4(H2O)2(As2 W15O56)2]16- -0.324a, -0.383a, -0.610 (WVI/V)a B 16b
[Zn4(H2O)2(As2W15O56)2]16- -0.415a, -0.671a, -0.837 (WVI/V)a B 16b
a a VI/V a
[Cd4(H2O)2(As2 W15O56)2] 16-
-0.364 , -0.550 , -0.685 (W ) B 16b
[Fe2(OH2)2Ni2(As2 W15O56)2]14– +0.004 (FeIII/II), -0.398, -0.604, - C 16c
VI/V
0.834(W )
[Fe(OH2)Ni(OH2)Ni2(As2W15O56)2]15- +0.018 (FeIII/II), -0.396, -0.606, - C 16c
VI/V
0.832(W )
[Ni3Na(H2O)2(PW9O34)2]11- -0.738, -0.882 (WVI/V) D 16d
III 6- 1 III/II
[Fe4(H2O)10(β-As W9O33)2] -0.126 (Fe ) D 16e
[Ni3Na(H2O)2(AsW9O34)2]11- -0.710, -0.854 (WVI/V) D 16d
K10[Mn(H2O)2(γ-SiW10O35)2] +0.910 (MnII/IV), -0.800, -0.928 E 16f
VI/V
(W )
K10[Co(H2O)2(γ-SiW10O35)2] +0.990 (CoII/III), -0.760, -0.906 E 16f
VI/V
(W )
K10[Ni(H2O)2(γ-SiW10O35)2] -0.936 (WVI/V) E 16f
a)
Working electrode: Glassy carbon; Reference electrode: Ag/AgCl electrode or SCE
A: Na2SO4-H2SO4 buffer solution (pH 2.52); B: AcONa-AcOH buffer solution(pH 4.0); C Li2SO4-
H2SO4 buffer solution (pH 3); D: Na2SO4-H2SO4 buffer solution (pH 3); E: AcONa-AcOH buffer
solution (pH 5.0)

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ChemElectroChem 10.1002/celc.201701170

REVIEW
Table 6 Redox Potentials(V) of titanium -substituted POMs.
Solu
POMs Potential(V) Ref.
tion
[PW11TiO40]5- -1.23a, -2.12a A
17a
2-[P2W17TiO62]8- -0.19(TiIV/III), -0.42, -0.69, -0.92 (WVI/V) B
17b
2-[P2W17(TiO2)O61]8- -0.11 (O22-), - 0.20 (TiIV/III), -0.44, -0.71, 17b
VI/V B
-0.94 (W )
2-[P2W15Ti3O62]12- -0.17(TiIV/III), -0.52, -0.69, -0.94 (WVI/V) B 17b
2- IV/III
2-[P2W15(TiO2)3O59] 12- -0.08 (O2 ), - 0.18 (Ti ), -0.56, -0.71, 17b
B

Accepted Manuscript
-0.94 (WVI/V)
[(TiIVO)2(α-AsIIIW9O33)2]14− -0.850 (Ti), -0.972 (WVI/V) C 17c
[C6H5SbIII(TiIVO)2(α-AsIIIW9O33)2]12− -0.760 (Ti), -0.920 (WVI/V) D 17c
II IV III 12- VI/V
[Co (H2O)(Ti O)2(α-As W9O33)2] -0.875 (Ti), -0.968 (W ) C 17d
[NiII(H2O)(TiIVO)2(α-AsIIIW9O33)2]12- -0.867 (Ti), -0.960 (WVI/V) C 17d
[ZnII(H2O)(TiIVO)2(α-AsIIIW9O33)2]12- -0.890 (Ti), -0.950(WVI/V) C 17d
+ a)
Working electrode: Glassy carbon; Reference electrode: Ag/Ag electrode or SCE
b) POMs form in the solution
A: CH3CN(n-Bu4NClO4); B: AcONa-AcOH buffer solution (pH 4.7); C: AcOLi-AcOH buffer solution
(pH 6); D: AcOLi-AcOH buffer solution (pH 4)

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ChemElectroChem 10.1002/celc.201701170

REVIEW
Table 7 Supercapacitor performances of POMs with various binders and electrodes
decrease(%) in
binder specific capacitance (after
POMs electrode Ref.
substance capacitance multi charge-
discharge cycles)
[PMo12O40]3- PAni carbon foil 195 mFcm-2 10-15 (2000) 26a
3- -1
[PMo12O40] AC 183 Fg 9 (8000) 26b
[PMo12O40]3- PDDA MWCNT 106.9 Fcm-3 - 26c
3-
[PMo12O40]
PDDA MWCNT 92.7 Fcm-3 8 (2000) 26c
+[PW12O40]3-

Accepted Manuscript
[PMo12O40]3- Poly[Vbim][Br] AC 85.4 Fg-1 1.5 (500) 26e
3-
[PMo12O40] PPy RGO 2.61 mFcm-2 - 26e
Ti/Au coated
[PMo12O40]3- PPy 77.0 mFcm-2 ~0 (3500) 26f
film
[PMo12O40]3- Poly[Veim][Br] RGO 408 Fg-1 2 (2000) 26g
(hydrothermal RGO
[PMo12O40]3- 123 Fg-1 4 (10000) 26h
treatment)
[PMo12O40]3- AC 223 Fg-1 ~0 (10000) 26i
3-
[PMo12O40] PPy graphene 587 Fg-1 ~20 (1000) 26j
3- -1
[PMo12O40] PEDOT carbon 130 Fg ca. 40 (200) 26k
[PMo12O40]3- PAni carbon 168 Fg-1 ca. 47 (200) 26k
3- -1
[PMo12O40] RGO 299 Fg 26l
pine cone
[PMo12O40]3- 1.19 F cm−2 26m
biomass
[PW12O40]3- RGO 337.5 Fg-1 1.7 (8000) 26n
3-
[PW12O40] AC 254 Fg-1 2 (30000) 26o
3- -1
[PW12O40] RGO 370 Fg 26k
[P2Mo18O62]6- [Ru(bpy)3]2+ GC 125 Fg-1 11 (400) 26p
6- -1
[P2Mo18O62] AC 275 Fg 30 (2000) 26q
5+
[Ag 5 (brtmb) 4 ] GCE
[VV2W10O40]5- 206 Fg-1 18.3 (1000) 26r
nafion coating
[PV2Mo10O40]5- SWCNT 185 Fg-1 5 (6500) 26s
PDDA: poly(diallyldimethylammonium chloride); PAni: polyaniline; [Vbim][Br]: 1-vinyl-3-
butylimidazolium bromide; PPy: polypyrrole; [Veim][Br]: 1-vinyl-3-ethylimidazolium bromide,
Polymeric IL; brtmb: 1-bromo-4-(1,2,4-triazol-1-ylmethyl)benzene
MWCNT: multi walled carbon nano tube; AC: activated carbon; RGO: reduced graphene oxide;
PEDOT: poly(3,4-ethylenedioxythiophene); SWCNT single walled carbon nano tube

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