molecules

Review
Polyoxometalate-Based Catalysts for CO2 Conversion
Yanwei Cao 1,2 , Qiongyao Chen 1,2 , Chaoren Shen 1, * and Lin He 1, *
1 State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP,
Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, China;
cyw929@licp.cas.cn (Y.C.); chenqiongyao17@mails.ucas.edu.cn (Q.C.)
2 University of Chinese Academy of Sciences, Beijing 100049, China
* Correspondence: shenchaoren@licp.cas.cn (C.S.); helin@licp.cas.cn (L.H.);
Tel.: +86-512-8188-0906 (C.S.); +86-931-496-8126 (L.H.)

Academic Editor: Santiago Reinoso




Received: 5 May 2019; Accepted: 23 May 2019; Published: 30 May 2019

Abstract: Polyoxometalates (POMs) are a diverse class of anionic metal-oxo clusters with intriguing
chemical and physical properties. Owing to unrivaled versatility and structural variation, POMs
have been extensively utilized for catalysis for a plethora of reactions. In this focused review,
the applications of POMs as promising catalysts or co-catalysts for CO2 conversion, including CO2
photo/electro reduction and CO2 as a carbonyl source for the carbonylation process are summarized.
A brief perspective on the potentiality in this field is proposed.

Keywords: polyoxometalates; catalysis; carbon dioxide; photo/eletroreduction; carbonyl source

1. Introduction
As the main greenhouse gas produced by human activity, about 10 ± 0.5 gigatons CO2 were
released in 2018, bringing the atmospheric CO2 concentration level over the threshold of 400 ppm [1].
The large increase of global CO2 levels has led to serious environment problem. Meanwhile, it is also
the most abundant and nontoxic carbon resource for preparing useful compounds [2]. From a practical
point of view, its catalytic conversion is of significance to the supply of renewable energy, chemicals,
and mitigation of global warming.
Polyoxometalates with {MOx } (x = 5, 6) as basic construction units have derived an enormous
fraternity of inorganic molecular complexes [3–6]. To obtain various composite materials with specific
function, the modification and decoration of POM can be attained by partially substituting {MOx } units
with different transition metal moieties or attaching organometallic complexes onto POM. Based on
geometrical morphology, most of POMs can be classified as Keggin, Wells-Dawson, Anderson-Evans,
Silverton, Waugh, Strandberg, Lindqvist, and Peacock-Weakley type structures, which are named
after their corresponding discoverers [7]. Among these types, Keggin-type POMs ([XM12 O40 ]n− ) are
comparatively well-studied. POMs discussed in the following sections are mostly Keggin type [8].
The original Keggin structure is designated α-, which consists of a tetrahedron central ion, [XO4 ]n − 8 ,
caged by twelve MO6 octahedron. The Keggin structure includes four additional isomers (β-, γ-, δ-, and
ε-), each resulting from 60◦ rotations of the four {M3 O13 } units [9]. The lacunary species of Keggin-type
POMs stem from removing a variable number of {MO6 } octahedra from the plenary polyanion, resulting
in metal-oxide clusters with vacant addenda metal sites. Such vacant sites can be treated as inorganic
multidentate ligands (Figure 1) [10], For example, sandwich-type POMs are usually synthesized by the
reaction of transition metal ions with appropriate lacunary POM precursors [5,8]. The extraordinary
diversity and synthetic accessibility of POMs have led to a wide spectrum of applications, ranging
from catalysis, biochemistry/medicinal chemistry, to materials science [11–14]. In the field of catalysis,
the development of POMs as oxidation and acid catalysts was flourish in the past few decades, with

Molecules 2019, 24, 2069; doi:10.3390/molecules24112069 www.mdpi.com/journal/molecules

Molecules 2019, 24, 2069 2 of 26

Molecules 2019,
molybdic and24,vanadomolybdic
x FOR PEER REVIEW
clusters being more employed in the former case and tungstic 2ones
of 26in

the latter [12,15]. The explorations of POMs as catalysts (or co-catalysts) for many other industrially
more employed in the former case and tungstic ones in the latter [12,15]. The explorations of POMs
important transformations were sought-after.
as catalysts (or co-catalysts) for many other industrially important transformations were sought-after.

Figure 1.1. Isomers

Figure Isomers andand mono-
mono- toto trilacunary derivatives of
trilacunary derivatives of the
the Keggin
Keggin structure;
structure; color
color code:
code: MO
MO6 6
octahedron,
octahedron,light
light blue;
blue; XO tetrahedron, red
XO44 tetrahedron, (X ==central
red (X centralatom).
atom).

As early as 1988, Kozik and co-workers first reported the coordination of CO2 with several POM
As early as 1988, Kozik and co-workers first reported the coordination of CO2 with several POM
derivatives
derivatives[16]. [16].Afterwards
Afterwardsmore moreresearches
researchesabout aboutthe theinteraction
interactionofof POMs
POMs with
with CO 2 emerged
CO 2 emerged [17–
[17–22].
Since the interaction
22]. Since the interaction betweenbetween CO 2 and POM is one of the crucial steps
CO2 and POM is one of the crucial steps for catalytic for catalytic transformations
of CO 2 , it is necessary to clarify
transformations of CO2, it is necessary to clarify the mode of such the interaction.
mode of suchHowever, interaction. considering
However, the facts that
considering
2− − 2–
CO can be
the2 facts thattransformed to CO3 or HCO
CO2 can be transformed to CO 3 3 with
or HCOwater – and this transformation is both reversible
3 with water and this transformation is both
and temperature-dependent, the explicit
reversible and temperature-dependent, the explicit “real” form of “real” form of dissolved COdissolved
2 to interact COwith POM catalyst,
2 to interact with
was challenging to challenging
be justified.toPOMs displayed variable interacting 13
POM catalyst, was be justified. POMs displayed variable modes.
interactingCmodes.
NMR, 13 UV/vis,
C NMR,IR
with isotope-labelled CO ( 13 CO and C18 O ), and X-ray crystallography are useful tools to solve
UV/vis, IR with isotope-labelled CO2 ( CO2 and C O2), and X-ray crystallography are useful tools to
2 2 13 2 18

this
solveissue. As pointed
this issue. As pointed in the seminal
in the seminal report
report of ofKozik
Kozik etetal.al.[16],
[16],thetheIR
IR spectra
spectra and andthermochromic
thermochromic
6− 2– 2− – −
behavior
behavior of of POM
POM α-[SiW α-[SiW11 11OO39 Co]6− ininthe
39Co] thepresence
presenceofofeither eitherCO CO or HCO was in contrast to the
3 3 or HCO3 3was in contrast to the
13 C NMR spectra, the 13 C chemical shifts of aqueous CO , HCO − 2−
scenario with CO . On
scenario with CO2. On C NMR spectra, the C chemical shifts of aqueous CO2, HCO
13 13 –
2 3 , and 3 , CO
and2–3 COare3
are respectively
respectively at 125,
at 125, 160,160,andand 162162 ppm. ppm. After After bubbling
bubbling CO2CO into2 into hydrous
hydrous toluenetoluene
solution solutionof α-of
OCo] 6−
α-[SiW
[SiW11O 1139 39 Co]
6–, the, appearance
the appearance of two of two signals
signals at 792 atand
792 596 andppm 596 ppm demonstrated
demonstrated the presence
the presence of twoof
two different kinds of paramagnetic
different kinds of paramagnetic CO2 species. CO species. In their report, two patterns
2 In their report, two patterns were suggested on the basis were suggested on
the basisCof 13
all IR C NMR, IR observations: (i) the complexation between 6−
of all 13 NMR, observations: (i) the complexation between α-[SiW 11Oα-[SiW
39Co] and
6–
11 O39CO Co] 2 was and CO2
either
was either
via CO via CO2 complexes
2 complexes with a direct with a direct η1 metal-carbon
η1 metal-carbon bond or bicarbonatebond or complexes;
bicarbonate(ii) complexes;
the existence (ii) of
the
2– 2−
existence
H-bonding of H-bonding in the CO2was
in the CO2 complexes complexes
plausible. wasOtherplausible.
modesOther modes 2oforPOM-CO
of POM-CO POM-CO 23 or POM-CO
interaction 3
interaction were also discovered.
were also discovered. Hill et al. Hill et al. the
reported reported the sandwich-type
sandwich-type encapsulation encapsulation
of CO 3 via
2–
CO2−
of forming3 via
[(YOH2)3[(YOH(CO3)(A-α-PW 9O34)2]11– [20].
11− [20].
forming 2 )3 (CO3 )(A-α-PW 9 O34 )[SiMo
2] 11CoO 38(CO11
[SiMo 2)] n polymeric
CoO 38 (CO2 )]nchains
polymericreported
chains byreported
Xu et al.by
displayed
Xu the μ-η1the
et al. displayed µ-η1 ,η1linear
,η1-OCO -OCOcoordination
linear coordination mode modeof POM-CO of POM-CO 2 interaction [21]. [21].
2 interaction Two Two kinds of
kinds
POM-CO
of POM-CO 2 interaction
2 interactionmodes modes were observed on
were observed on[(n-C
[(n-C 8H8H1717))44N]
N]88[α22-P
-P22W OO
W1717 61Zn-(CO
61 Zn-(CO 2)] 2 )]
[21].
[21].TheThe
stronger“side-on”
stronger “side-on”binding bindingofof CO CO
2 by
2 by
is is predominant
predominant at at
higherhigher temperatures
temperatures (room (room temperature
temperature down
down
to ca. 250to K)ca.and250the K) moreand theweakly more weakly coordinated
coordinated “end-on” POM-Zn-O-C-O
“end-on” POM-Zn-O-C-O structures were structures
observable wereat
observable
lower at lower(Figure
temperatures temperatures2). One(Figure 2). One
particular caseparticular
was uptaking case was 30 CO uptaking
2 molecules30 CO by2 molecules
one capsule byof
VI V
one capsule of [{(MoVI)Mo5 O21(H2O)6}12{Mo2 O4(CH3COO)}30]42–. In this case, CO2 reacted directly with
V 2–
the H2O ligands in {Mo2 O4(H2O)2}2+ linkers to generate CO3 at pH 7. Then the uptake of 30 CO2
 Molecules 2019, 24, 2069 3 of 26

[{(MoVI )MoVI O (H O) } {MoV

Molecules 2019, 24, 5x FOR21PEER 2 O4 (CH3 COO)}30 ]
2 REVIEW
6 12
42− . In this case, CO reacted directly with the H O
2 3 of 26 2
ligands in {Mo2 O4 (H2 O)2 } linkers to generate CO2−
V 2+
3 at pH 7. Then the uptake of 30 CO 2 molecules
was realized
molecules via the fast
was realized via exchange of acetateofbyacetate
the fast exchange carbonate ligands [22].
by carbonate Above
ligands cases
[22]. indicated
Above cases the
abundance of POM-CO interaction mode.
indicated the abundance of2POM-CO2 interaction mode.

Figure 2. Suggested modes of coordination of CO2 . Color code: W, black ball; P, green ball; O, red ball;
Figure 2. Suggested modes of coordination of CO2. Color code: W, black ball; P, green ball; O, red ball;
Zn, purple ball. Reprinted with permission from [21]. Copyright © 2018 Wiley-VCH Verlag GmbH
Zn, purple ball. Reprinted with permission from [21]. Copyright © 2018 Wiley-VCH Verlag GmbH
and Co. KGaA.
and Co. KGaA.
In this context, we have witnessed the leap in developing POMs-based catalysts for the photo-
In this context, we have witnessed the leap in developing POMs-based catalysts for the photo-
or electrocatalytic CO2 reduction and CO2 as C1 synthon in organic synthesis. Herein, in this
or electrocatalytic CO2 reduction and CO2 as C1 synthon in organic synthesis. Herein, in this review,
review, we focused on the recent experimental and theoretical advances in CO2 transformation with
we focused on the recent experimental and theoretical advances in CO2 transformation with POMs-
POMs-based catalyst or co-catalyst. The key factors for high-efficiency POMs-catalyzed CO2 conversion
based catalyst or co-catalyst. The key factors for high-efficiency POMs-catalyzed CO2 conversion are
are highlighted.
highlighted.
2. Photocatalytic CO2 Reduction
2. Photocatalytic CO2 Reduction
Only high-energy vacuum ultraviolet laser (<200 nm) is able to directly excite and split CO2 into
CO andhigh-energy
Only O fragments vacuum ultraviolet
[23], therefore laserefficient
highly (<200 nm) is able to directly
photocatalyst is vitalexcite and split
to motivate andCO 2 into
accelerate
COphotocatalytic
and O fragments [23], therefore highly efficient photocatalyst is vital to
CO2 reductions with low-energy common visible light (>380 nm). This reduction motivate and accelerate
photocatalytic CO2 involves
process usually reductions with low-energy
multi-electron transfercommon
and thevisible light (>380
final products are nm). This
carbon reduction
monoxide (CO),
process usually involves multi-electron transfer and the final products
formic acid (HCOOH), formaldehyde (HCHO), methanol (CH3 OH), and methane (CH4 ) [24,25]. are carbon monoxide (CO),
formic
Theacid (HCOOH),redox formaldehyde
potentials(HCHO), methanol CO(CH 3OH), and methane (CH4) [24,25]. The
corresponding for the possible 2 reduction at pH = 7 are listed in Table 1.
corresponding redox potentials for the possible CO2 reduction at pH = 7 are listed in Table 1.
Since the pioneering application Table 1. Redoxof potentials
Honda–Fujishima effect in TiO2-catalyzed CO2
for CO2 reduction.
photoreduction was reported [26], multitudinous different type of photocatalysts, including simple
Products Products Reaction E0 (V) E0 (V) pH = 7
metal oxides [25], perovskite oxides [27,28], C3N4 [29], MOFs [30], conjugated polymers [31,32], and
-
POMs [33,34] have been developed. HOthe
Since h+ → 1/2O
+ 2 seminal study
+
2 + 2Hon the photochemistry+0.82 of molybdates
- CO2 + e− → CO− −1.9
and tungstates for analytical purposes over half century ago [35,36], the photoredox chemistry of
2
HCOOH CO2 + 2 H+ + 2 e− → HCOOH −0.61
POMs has been verifiedCO for a long time. The +metals
CO2 + 2 H + 2 e− → in CO
POMs+ H2are
O fully oxidized
−0.53 with d electron
0

configuration. Light absorption

HCHO is mainly 2 H+ + 4 e−to
CO2 + attributed →O→M
HCHOligand+ H2 Oto-metal charge
−0.48 transfer (LMCT)
CO2 +spectra. +
6 H + 6Consequently,
e → CH3 OH +an
−
bands in the wide range CHof the electronic
3 OH H2electron
O is−0.38
promoted from a spin-
paired, doubly occupiedCH bonding
4 CO2 +
orbital 8 H+ + 8 to
(HOMO) e− an CH4 + 2H
→ empty, 2O
antibonding −0.24 (LUMO), thus an
orbital
- 2 H + + 2 e− → H –0.41
oxo-centered radical is generated. This photo-excited POMs2 are more reactive both in oxidation and
reduction than the non-excited species [37]. In the photocatalysis by POM with LMCT mode, forming
Since the
lower-energy O→M pioneering application is
LMCT transitions of vital
Honda–Fujishima effect inabsorb
to more efficiently TiO2 -catalyzed CO2 Substituting
visible light. photoreduction
was reported [26], multitudinous different type of photocatalysts, including
addenda centers with different metals has been well demonstrated as one of the effectual tactics simple metal oxidesto[25],
tuneperovskite oxides [27,28],
the photochemical C3 N4 of
properties [29],
POMs MOFs and[30], conjugated
optimize polymers
their visible [31,32],
light and POMs
absorption [33,34] have
via narrowing
the been
banddeveloped.
gap between Since the seminal
valence band and study on the photochemistry
conduction band. For instance, of molybdates and tungstates
Streb et al. discovered that for
analytical purposes over half century ago [35,36], the photoredox chemistry
the vanadium substitution effectively improved the visible light absorption and photocatalytic of POMs has been verified
for a of
activity long time. The[Mo
molybdate metals
6O19]in
2– POMs are fullycalculations
[38]. TD-DFT oxidized with d0 electron
disclosed configuration. Light
the corresponding absorption
contribution
of O→V LMCT on absorption profile in the visible range. The progress of such strategy on POM-
catalyzed selective photooxidation driven by visible light has been included in the recent review [15].
Besides altering the addenda centers on POMs, various other strategies have also been established in
order to foster POMs as effective photocatalyst and most of their utilization were focused on
Molecules 2019, 24, 2069 4 of 26

is mainly attributed to O→M ligand to-metal charge transfer (LMCT) bands in the wide range of the
electronic spectra. Consequently, an electron is promoted from a spin-paired, doubly occupied bonding
orbital (HOMO)
Molecules 2019, 24, to an empty,
x FOR antibonding orbital (LUMO), thus an oxo-centered radical is generated.
PEER REVIEW 4 of 26
This photo-excited POMs are more reactive both in oxidation and reduction than the non-excited
species [37]. In theofphotocatalysis
photooxidation by POM with
water, photodegradation LMCT dyes,
of organic mode,asforming
well as lower-energy O→M Here
H2 evolution [37,39]. LMCT the
transitions
progress is ofvital to more efficiently
photoreduction of CO2 absorb visible light.catalyst
with POMs-based Substituting addenda centers with different
was summarized.
metals has been well demonstrated as one of the effectual tactics to tune the photochemical properties
of POMs and optimize their visible Table 1. absorption
light Redox potentials for CO2 reduction.
via narrowing the band gap between valence band
and conduction band. For instance, Streb et al. discovered 0that the vanadium substitution effectively
Products Products Reaction E (V) E0 (V) pH = 7
improved the visible light absorption and photocatalytic activity of molybdate [Mo6 O19 ]2− [38].
- HO + 2 h+ → 1/2O2 + 2H+ +0.82
TD-DFT calculations disclosed the corresponding contribution – of O→V LMCT on absorption profile in
- CO2 + e– → CO2 –1.9
the visible range. The progress of such strategy on POM-catalyzed selective photooxidation driven by
HCOOH CO2 + 2 H + 2 e → HCOOH
+ – –0.61
visible light has been included in the recent review [15]. Besides altering the addenda centers on POMs,
CO CO2 + 2 H+ + 2 e– → CO + H2O –0.53
various other strategies have also been established in order to foster POMs as effective photocatalyst
HCHO CO2 + 2 H+ + 4 e– → HCHO + H2O –0.48
and most of their utilization were focused +on photooxidation of water, photodegradation of organic
CH3OH CO2 + 6 H + 6 e → CH3OH + H2O
– –0.38
dyes, as well as H2 evolution [37,39]. Here the progress of photoreduction of CO2 with POMs-based
CH4 CO2 + 8 H+ + 8 e– → CH4 + 2H2O –0.24
catalyst was summarized.
- 2 H + 2 e → H2
+ – –0.41
2.1. CO2 to CO
2.1. CO2 to CO
2.1.1. Homogeneous Catalysts
2.1.1. Homogeneous Catalysts
Neumann and co-workers reported that Ru-substituted POM ([RuIII (H2 O)SiW11 O39 ]5− ) in
Neumann
combination with and co-workers
tertiary reportedphotoactivity
amines exhibited that Ru-substituted POM ([Ru
for CO2 reduction III(H2O)SiW11O39]5–) in
Figure 3 [40]. Triethyl
combination
amine acted aswith tertiary amines
the sacrificial agent.exhibited
CO was photoactivity
the major product for CO(~50
2 reduction Figure
µmol after 20 h 3 [40]. Triethyl
irradiation
with ca. 2% quantum yield). None of HCOOH, MeOH, and CH4 was detected. UV/Vis, EPR, 13with
amine acted as the sacrificial agent. CO was the major product (~50 μmol after 20 h irradiation C
ca. 2%
NMR, andquantum
isotope yield). None
labelling of HCOOH,that
demonstrated MeOH, and CHCO
coordinated 4 was([Ru
2 detected.
III (COUV/Vis,
2 )SiW11 O EPR,
39 ] ) C NMR,
5−13 was and
easily
isotope
formed bylabelling demonstrated
substituting that
H2 O in [RuIII (H2coordinated
O)SiW11 O39 ]CO ([Ruresults
5− . 2DFT III(CO2)SiW11O39]5–) was easily formed by
demonstrated that CO2 tended to
substituting H O
III in [Ru III(H2O)SiW11O39]5–. DFT results demonstrated that CO2 tended to coordinate
coordinate to Ru by forming a Ru-O bond in an “end-on” manner. Based on these experimental and
2

to RuIII by forming
computational results, thea authors
Ru-O bond in anthat
concluded “end-on”
the RuIIImanner.
site was Based on these
responsible experimental
for activating CO2 viaand
computational
the results,
coordination and the the authors
lacunary concluded
[SiW O
11 39 ] 8− that
site the
acted Ru III site was responsible for activating CO2 via
as photocatalyst in this process.
the coordination and the lacunary [SiW11O39]8– site acted as photocatalyst in this process.

Figure
Figure 3. 3.
TheThe substitutionofofHH
substitution 2O2Owith
withCO
CO22in [RuIII
in [Ru III(H2O)SiW11O39]5–.5−
2 O)SiW11 O39 ] Reprinted with
. Reprinted permission
with from
permission
[40].
from Copyright
[40]. Copyright © 2010
© 2010 Wiley-VCH
Wiley-VCHVerlag GmbH
Verlag GmbH andand
Co.Co.
KGaA.
KGaA.

ByByemploying
employingH2Hinstead
2 instead ofoftertiary
tertiaryamines
aminesasasthethe sacrificial agent,
sacrificial agent,a viable
a viableCO 2 reduction
CO 2 reduction
VI VI
approach with Pt/C and Re I (L)(CO)
approach with Pt/C and Re (L)(CO) I -MHPW
3 3-MHPW O =
O40 (L = 5,6-(15-crown-5)-1,10-phenanthroline)asas
12 12 40 (L 5,6-(15-crown-5)-1,10-phenanthroline)
synergistic catalysts was developed. The grafting of of I (L)(CO)
ReRe
synergistic catalysts was developed. The grafting 3 complexes
I(L)(CO) 3 complexes onto
ontoPOMs
POMs was
wasachieved
achieved
viavia
thethe
complexation of crown ether moiety on L with the sodium
complexation of crown ether moiety on L with the sodium cation bindingcation binding two PW O
12 two
40 moieties
PW12O40
(Figure 4) [41].
moieties H2 was
(Figure oxidized
4) [41]. H2 was with the facilitation
oxidized with theoffacilitation
Pt(0) on theofPt/C
Pt(0)surface
on thetoPt/C
afford two protons.
surface to afford
Intwo
the following
protons. Instep,the protons
following andstep,
electrons
protonsretained by Pt were
and electrons simultaneously
retained by Pt weretransferred onto
simultaneously
VI VI V VI
transferred onto ReI(L)(CO)3(CH3CN)-MHPW12 O40 (MHPW12 O40 + 2H+ + 2e– → MH3PW2 W10 O40)
V VI
(Scheme 1). ReI(L)(CO)3-MH3PW2 W10 O40 possessed the photoreductive activity for converting CO2 to
CO, because its transition to excited CO2-reduction active state was allowed by absorbing visible
light. CO were almost exclusively produced with turnover of 22.6% and 1.1% quantum yield. Besides
CO, only trace CH4 but no further CO reduction products (e.g., CH3OH, HCHO, and HCOOH) was
Molecules 2019, 24, x FOR PEER REVIEW 5 of 26

Pt/C
H3 [PW VI12O 40 ] + H2
Molecules 2019, 24, 2069 H5 [PW VI10W V2O 40 ] 5 of 26

Re I( L)(CO)3(CH 3 CN) VI
H 5[PWVI10 WVVI
CO2 +CN)-MHPW
ReI (L)(CO)3 (CH 2 O40] VI
O40 + 2H+ + CO
2e−+→
H2MH
O + HPW
3[PW
V 12 O
VI40]
3 12 O40 (MHPW12light 3 2 W10 O40 ) (Scheme 1).
I V VI
Re (L)(CO)3 -MH3 PW2 W10 O40 possessed the photoreductive activity for converting CO2 to CO,
I VI
because its transition to excitedPt/C-Re (L)(CO)3 (CH
CO2 -reduction 3 CN)-MHPW
active state was O40
12allowed by absorbing visible light. CO
CO2 + H2 CO + H2 O
were almost exclusively produced with turnover of
light 22.6% and 1.1% quantum yield. Besides CO, only
trace CH4 but no further CO reduction products (e.g., CH3 OH, HCHO, and HCOOH) was detected on
GC-MS after 14 h irradiation.Scheme 1. Proposed photoreduction of CO2 with H2.

Figure 4.4. ReII(L)(CO)

(L)(CO)33-NaHPW
-NaHPW1212 OO presenting
4040 presentingthe
thecomplexation
complexationofoftwo two[PW[PW12O O]40
1240
3− units
3– ]units to Na. H
to Na.
H atoms
atoms andand solvent
solvent molecules
molecules areare omitted.
omitted. C, black
C, black ball;ball; N, blue
N, blue ball;ball; O, ball;
O, red red ball; P, purple
P, purple ball;ball;
Na,
Na, yellow
yellow
Molecules 2019, 24, xball;
ball; Re, Re,
FOR green
green
PEER ball;
ball;
REVIEW W,W,gray
grayball.
ball.Reprinted
Reprintedwith
withpermission
permission from
from [41]. Copyright©
Copyright© 2011 5 of 26
American
American Chemical
Chemical Society.
Society.

Pt/C
The TD-DFTHcalculations
VI disclosed a more detailed mechanism for the photoreduction of CO2
H5 [PW VI10W V2O 40 ]
3 [PW 12O 40 ] + H2
to CO with this POM-Re complex catalyst [42]. Simulated absorption spectrum of ReI-POM complex
I

was calculated at different functionalRe level

I L (i.e. X3LYP, M06X, B3LYP, and CAMB3LYP) and the
( )(CO)3(CH 3 CN)
CO2 + were
computed results
VI
H 5[PWfound V
10 W 2toO40] basically consistent withCO
be H2 O + H 3[PWVI12
the+ experimental O40]
absorption spectrum
light
(two major bands with maxima at 500 and 656 nm). In the ground state without any light irradiation,
–
bonding CO2 with ReI center Pt/C-Re I
to afford the reactive POM-ReVII-CO complex had to overcome a high
(L)(CO) 3 (CH3 CN)-MHPW 12 O402
CO2 + H2 −1 CO I + H2 O
energy barrier (≥38 kcal mol ), therefore, the direct light CO2 reduction with Re -POM occurred less likely
(Figure 5). In the conditions with photoexcitation, the excited ReI-POM was allowed to interact with
CO2 to form POM-ReI-COScheme
– 1. Proposed photoreduction
protonationof CO2further
with H .
2 . The subsequently
Scheme 1. Proposed photoreduction ofand
CO2 with H22.electron reduction process
were exothermic by more than 78 kcal mol−1. These energy profiles revealed that the role of POM as
The TD-DFT calculations disclosed a more detailed mechanism for the photoreduction of CO2 to
photosensitizer in the reduced state, electron “shuttles” as well as electron/proton reservoirs in this
CO with this POM-ReI complex catalyst [42]. Simulated absorption spectrum of ReI -POM complex
process. Plausible CO2 photoreduction mechanism consists of five steps: (1) photoexcitation and
was calculated at different functional level (i.e., X3LYP, M06X, B3LYP, and CAMB3LYP) and the
charge transfer; (2) disassociation of solvent molecule; (3) CO2 coordination; (4) proton and electron
computed results were found to be basically consistent with the experimental absorption spectrum
transfer; and (5) release of CO and recoordination of solvent.
(two major bands with maxima at 500 and 656 nm). In the ground state without any light irradiation,
bonding CO2 with ReI center to afford the reactive POM-ReI -CO− 2 complex had to overcome a high
energy barrier (≥38 kcal mol−1 ), therefore, the direct CO2 reduction with ReI -POM occurred less likely
(Figure 5). In the conditions with photoexcitation, the excited ReI -POM was allowed to interact with
CO2 to form POM-ReI -CO− 2 . The subsequently protonation and further electron reduction process
were exothermicI by more than 78 kcal mol−1 . These energy profiles revealed that the role of POM
Figure 4. Re (L)(CO)3-NaHPW12O40 presenting the complexation of two [PW12O40]3– units to Na. H
as photosensitizer in the reduced state, electron “shuttles” as well as electron/proton reservoirs in
atoms and solvent molecules are omitted. C, black ball; N, blue ball; O, red ball; P, purple ball; Na,
this process. Plausible CO2 photoreduction mechanism consists of five steps: (1) photoexcitation and
yellow ball; Re, green ball; W, gray ball. Reprinted with permission from [41]. Copyright© 2011
charge transfer; (2) disassociation of solvent molecule; (3) CO2 coordination; (4) proton and electron
American Chemical Society.
transfer; and (5) release of CO and recoordination of solvent.
The TD-DFT calculations disclosed a more detailed mechanism for the photoreduction of CO2
to CO with this POM-ReI complex catalyst [42]. Simulated absorption spectrum of ReI-POM complex
was calculated at different functional level (i.e. X3LYP, M06X, B3LYP, and CAMB3LYP) and the
computed results were found to be basically consistent with the experimental absorption spectrum
(two major bands with maxima at 500 and 656 nm). In the ground state without any light irradiation,
–
bonding CO2 with ReI center to afford the reactive POM-ReI-CO2 complex had to overcome a high
energy barrier (≥38 kcal mol−1), therefore, the direct CO2 reduction with ReI-POM occurred less likely
(Figure 5). In the conditions with photoexcitation, the excited ReI-POM was allowed to interact with
–
CO2 to form POM-ReI-CO2 . The subsequently protonation and further electron reduction process
were exothermic by more than 78 kcal mol−1. These energy profiles revealed that the role of POM as
photosensitizer in the reduced state, electron “shuttles” as well as electron/proton reservoirs in this
Molecules 2019, 24, 2069 6 of 26
Molecules 2019, 24, x FOR PEER REVIEW 6 of 26

−1 surface for the reduction of CO to CO catalyzed by

Figure 5. Potential
Figure 5. Potential energy
energy (units
(units in
in kcal
kcal mol
mol−1)) surface for the reduction of CO22 to CO catalyzed by
POM-Re I
POM-ReI complex.
complex.Reprinted
Reprintedwith
withpermission fromfrom
permission [42]. [42].
Copyright © 2016
Copyright ©American Chemical
2016 American Society.
Chemical
Society.
Recently, by replacing crown ether-affiliated 1,10-phenanthroline with 6-hydrazinyl-2,20 -bipyridine
on the Re complex,
Recently, by the Re2 (CO)crown
replacing 6 Cl2 L2 -H 3 PW12 O40 (L =1,10-phenanthroline
ether-affiliated 6-hydrazinyl-2,20 -bipyridine) hybrid pair and
with 6-hydrazinyl-2,2’-
related relay process
bipyridine onVIthe Re3− for CO reduction
complex,2 the Re2(CO)6Cl by photocatalysis and electrocatalysis was developed [43].
2L2-H3PW12O40 (L = 6-hydrazinyl-2,2’-bipyridine) hybrid
Initially, [PW O ] was reduced to [PW V
W VI
O ]5− by two electrons at −1.302 V (versus Fc/Fc+ ,
pair and related 40
12 relay process for CO2 reduction 2 40
by photocatalysis
10 and electrocatalysis was developed
Fc=
[43]. Initially, [PW12 O40] was reduced to [PW2 W10 O40functions
ferrocene). Then
VI the reduced POM undertook
3- V the
VI
]5– by Itwoofelectrons
photoreductant andVelectron/proton
at –1.302 (versus Fc/Fc+,
acceptors. Photo irradiation promoted the generation of Re (L − )(CO) via the electron transfer from
Fc= Vferrocene). Then the reduced POM undertook the functions 3 of photoreductant and
VI 5− to ReI (L)(CO) . This reductive ReI intermediate possessed reactivity for the selective
[PW 2 W 10 O 40 ] 3
electron/proton acceptors. Photo irradiation promoted the generation of Re (L–)(CO)3 via the electron
I
CO 2 reduction.
transfer from [PW Only
V VICO was observed in this catalytic electro-photochemical reduction process.
2 W10 O40]
5– to ReI(L)(CO)3. This reductive ReI intermediate possessed reactivity for
The result in the dark conditions
the selective CO2 reduction. Only CO indicated that light
was observed in facilitated
this catalytictheelectro-photochemical
CO2 reduction. The formation
reduction
of dirhenium
process. complex-H
The result in the3 PW 12 Oconditions
dark 40 hybrid pair via acid-base
indicated that lightinteraction
facilitatedwastheindispensable
CO2 reduction.to this
The
catalytic electro/photochemical transformation.
formation of dirhenium complex-H3PW12O40 hybrid pair via acid-base interaction was indispensable
to thisHeterogeneous
2.1.2. catalytic electro/photochemical
Catalysts transformation.

2.1.2.Photocatalytic
HeterogeneousCO 2 reduction by POMs-based heterogeneous catalyst has received intensive
Catalysts
research interests. As a POM-stabilized multi–Co-oxide clusters, [Co4 (PW9 O34 )2 ]10− is comprising
Photocatalytic CO2 reduction by POMs-based heterogeneous catalyst has received intensive
a Co4 O4 core stabilized by two oxidatively resistant polytungstate ligands10–(Figure 6a). The
research interests. As a POM-stabilized multi–Co-oxide clusters, [Co4(PW9O34)2] is comprising a
Na10 [Co4 (H2 O)2 (PW9 O34 )2 @graphitic carbon nitride hybrid material (Co4 @g-C3 N4 ) was reported
Co4O4 core stabilized by two oxidatively resistant polytungstate ligands (Figure 6a). The
for the efficient photocatalytic CO2 reduction [44]. It manifested the advantages of convenient
Na10[Co4(H2O)2(PW9O34)2 @graphitic carbon nitride hybrid material (Co4@g-C3N4) was reported for
recovery, steady reuse, simple preparation and flexible composition. The Co4 @g-C3 N4 photocatalyst
the efficient photocatalytic CO2 reduction [44]. It manifested the advantages of convenient recovery,
with 43 wt% Co4 content showed high CO yield (107 µmol g−1 h−1 ) and excellent selectivity (94%)
steady reuse, simple preparation and flexible composition. The Co4@g-C−13N4 photocatalyst with 43
(Figure 6b). After 10 h reaction, the production of CO–1 reached 896 µmol g (Figure 6c). After 5 runs,
wt% Co4 content showed high CO yield (107 μmol g h–1) and excellent selectivity (94%) (Figure 6b).
the activity still remained (Figure 6d). Experimental and characterization results revealed that the Co4
After 10 h reaction, the production of CO reached 896 μmol g–1 (Figure 6c). After 5 runs, the activity
unit both facilitated the charge transfer of g-C3 N4 and significantly enhanced the surface catalytic
still remained (Figure 6d). Experimental and characterization results revealed that the Co4 unit both
oxidative activity.
facilitated the charge transfer of g-C3N4 and significantly enhanced the surface catalytic oxidative
activity.
Molecules 2019, 24, 2069
x FOR PEER REVIEW 77 of
of 26

Figure 6. The photoreduction of CO2 by the Co4 @g-C3 N4 hybrid material. The structure of
Figure 6. The photoreduction of CO2 by the Co4@g-C3N4 hybrid material. The structure of
Na10 [Co4 (H2 O)2 (PW9 O34 )2 ]; color code: WO6 octahedron, light blue; PO4 tetrahedron, red; Co,
Na10[Co4(H2O)2(PW9O34)2]; color code: WO6 octahedron, light blue; PO4 tetrahedron, red; Co, purple
purple ball; O, red ball. (a). The photocatalytic activity of different photocatalysts (b). Time course of
ball;
the COO, and
red H
ball.(c).
(a).Recycling
The photocatalytic activity
experiments of different
(d). Reprinted photocatalysts
with (b). [44].
permission from TimeCopyright
course of ©
the2017
CO
2
and H2 (c). Recycling experiments (d). Reprinted with permission from [44]. Copyright © 2017
American Chemical Society.
American Chemical Society.
NENU-10 and NENU-3 are respectively Ti-substituted Keggin-type POM [PTi2 W10 O40 ]7− (This
NENU-10 and
Ti-disubstituted NENU-3 are
Keggin-type POM respectively
contains the Ti-substituted
Ti centers inKeggin-type POM [PTi
relative 1,5 positions 2W10O40]7–to
according (This
the
IUPAC nomenclature. This anion is one of the few cases in the literature in which a salt ofthe
Ti-disubstituted Keggin-type POM contains the Ti centers in relative 1,5 positions according to a
IUPAC nomenclature.
disubstituted This anion
Keggin species displays is one of the few cases
a predominant isomerin(ca. the 75%
literature
of the in which
α (1,5) a salt of
isomer)) anda
disubstitutedPOM
Keggin-type Keggin [PW species
12 O40 ]
displays
3− encaged a predominant
into MOF Cuisomer (ca. 75% of the α (1,5) isomer)) and
3 (BTC)2 (BTC: benzene-1,3,5-tricarboxylate;
Keggin-type POM [PW O ] 3− encaged into MOF Cu3(BTC)2 (BTC: benzene-1,3,5-tricarboxylate;
Cu3 (BTC)2 = HKUST-1) developed by Liu et al. Efficient photoreduction of CO2 catalyzed by hybrid
12 40

Cu3(BTC)Au@NENU-10
material 2 = HKUST-1) developed
(Both Au@NENU-10 by Liu et al.and Efficient
Au@NENU-3photoreduction of CO2 catalyzed
were prepared by one-pot bymethod.
hybrid
material Au@NENU-10 (Both Au@NENU-10 and Au@NENU-3
The Au NPs were in-situ deposited during the assembly of NENU-10 and NENU-3 as shown in were prepared by one-pot method.
The Au7.)NPs
Figure waswere in-situ
recently deposited
achieved [45].during
Table the assemblythe
2 illustrated of catalytic
NENU-10performance
and NENU-3 of as shown in
as-prepared
Figure in
hybrid 7.)the
was recentlyCO
reductive achieved [45]. Table 2 illustrated the catalytic performance of as-prepared
2 transformation to CO and CH4 under visible-light irradiation. Compared
hybrid in the reductive CO 2 transformation to CO and CH4 under visible-light irradiation. Compared
to Ti-free Au@NENU-3, Au@NENU-10 presented both higher activity and selectivity in the CO2
to Ti-free Au@NENU-3,
photoreduction. Similarly,Au@NENU-10
Au/K7 (PTi2 W10 presented
O40 ) also both higherperformance
had better activity andthan selectivity
Au/Na3in (PWthe CO2
12 O40 ).
photoreduction.
Results of controlSimilarly,
experiments Au/K 7(PTi2W10O40) also had better performance than Au/Na3(PW12O40).
implied the indispensability of Au nanoparticles to the CO reduction
Results of control experiments
activity and precursors was inactive. Combingimplied the indispensability
these patterns,ofauthors
Au nanoparticles
deduced thetofollowing the CO reduction
steps for
activity
the andprocess:
overall precursors wasAu
Firstly, inactive. Combing
nanoparticles these patterns,
produced electronsauthors
and holes deduced
wherethe thefollowing steps
holes oxidized
for the overall process: Firstly, Au nanoparticles produced electrons
H2 O to generate two electrons and two protons. Then the electrons and protons directly transferred and holes where the holes
oxidized
to [PTi2 WH 2O to7−generate two electrons
10 O40 ] to form [P(TiIII -H)2 WVI and two 7− protons. Then III the electronsVI and protonsreduced
7− species directly
10 O40 ] VI . Some of [P(Ti -H)2 W10 O VI
40 ]
transferred
CO to [PTi2W10O40] to form [P(Ti -H)2W10 O40] . Some
7–
2 to CO and H2 , and others further obtained electrons
III 7–
and of [P(Ti -H)
protons
III 2W10 O40] III
to form [P(Ti species
7−
-H2 )2 Wreduced
V VI
V 2 W8
VI
CO2]7−
O to intermediates.
CO and H2, andFinally,others further
[P(TiIII -H obtained V electrons
VI and
7− protonsCO to form [P(Ti -H2)2W2 W8 O40]7−
III
40 V
2VI)2 W2 W8 O40 ] reduced 2 to CH4 and simultaneously
intermediates.
returned Finally,
to initial state.[P(Ti
Ti-O-W
III-H2)2W W O40]7− reduced
in [PTi CO2 to CH4 and
7− may responsible simultaneously returned to
2
28W10 O40 ] to absorb CO2 . Compared with
initialWstate.
[PTi Ti-O-W
7− and [PWin [PTiO2W]103− O,40[PTi
] may
7– responsible
7− had to absorbelectron-coupling
CO2. Compared with [PTiability.
2W10O40]7–
2 10 O40 ] 12 40 2 W10 O40 ] stronger protons
and [PW12O40]3−, [PTi2W10O40]7– had stronger electron-coupling protons ability.
Molecules 2019, 24, 2069 8 of 26
Molecules 2019, 24, x FOR PEER REVIEW 8 of 26

Figure 7. Proposed crystal growth mechanism of Au@NENU-3 and Au@NENU-10. The intermediate
Figure 7. Proposed crystal growth mechanism of Au@NENU-3 and Au@NENU-10. The intermediate
of Cu2+ around polyoxometalate (POM) (a). The proposed the basic growing unit consisting of 1 POM,
of Cu2+ around polyoxometalate (POM) (a). The proposed the basic growing unit consisting of 1 POM,
24 Cu2+ , and 8 BTC ligands in which each Cu2 unit coordinates with 2 BTC ligands (b). Eight BTC
24 Cu2+, and 8 BTC ligands in which each Cu2 unit coordinates with 2 BTC ligands (b). Eight BTC
ligands are needed to coordinate with four Cu2 units when crystal grows along the h100i direction (c).
ligands are needed to coordinate with four Cu2 units when crystal grows along the 〈100〉 direction (c).
While only six BTC ligands are needed for three Cu2 units along the h111i direction (d). The enlarged
While only six BTC ligands are needed for three Cu2 units along the 〈111〉 direction (d). The enlarged
diagram of the dashed red circle (e). The exposed surface of the octahedron shape for Au@NENU-3
diagram of the
({111} plane dashed
where [PWred circle (e).
3− is The exposed surface of the octahedron shape forcube
Au@NENU-3
12 O40 ] sheltered by BTC (f). The exposed surface of the shape for
({111} plane where [PW 12O40]3− is sheltered 7− by BTC (f). The exposed surface of the
NENU-10 ({100} plane where [PTi2 W10 O40 ] is exposed wholly) (g). The SEM images for Au@NENU-3 cube shape for
NENU-10
and ({100} plane
Au@NENU-10, where [PTi2(h,
respectively W10i).
O40Reprinted
]7– is exposed wholly)
with (g). The
permission SEM[45].
from images for Au@NENU-
Copyright © 2018
3 and Au@NENU-10,
Wiley-VCH Verlag GmbH respectively
and Co. KGaA.(h, i). Reprinted with permission from [45]. Copyright © 2018
Wiley-VCH Verlag GmbH and Co. KGaA.
Table 2. Catalytic performance of CO, H2 , and CH4 from CO2 photoreduction a.
Table 2. Catalytic performance of CO, H2, and CH4 from CO2 photoreduction a.
Products (µmol g−1 h−1 )
Entry Catalysts
Products
CO CH4g h ) H2
(μmol –1 –1
Entry Catalysts
CO CH4 H2
1 Au@NENU-10 12.8 2.1 2.6
2 1 Au@NENU-10
Au@NENU-3 12.8
0.5 2.1 - 2.6 0.15
3 2 Au/Na Au@NENU-3
3 PW12 O40 ) 0.5
- - - 0.15 0.45
4 3 Au/K
Au/Na
7 (PTi W
PW10
32 O
12 O40
40) 2.1
- - 0.35 0.45 0.29
5 4 NENU-10
Au/K7(PTi2W10O40) -
2.1 0.35 - 0.29 -
6 NENU-3 - - -
5 NENU-10 - - -
7 HKUST-1 - - -
6 NENU-3 - - -
a. Reaction conditions: 100 mL quartz reactor, 15 mL H O, 100 mg catalyst, 40 ◦ C, 5 h, 300 W Xe lamp (λ > 420 nm).
2
7 HKUST-1 - - -
Solid catalyst was in the atmosphere of water vapor and CO instead of being immersed in water.
2
a.Reaction conditions: 100 mL quartz reactor, 15 mL H2O, 100 mg catalyst, 40 °C, 5 h, 300 W Xe lamp
2.2. CO>2 420
(λ nm). Solid catalyst was in the atmosphere of water vapor and CO2 instead of being immersed
to HCOOH
in water.
HCOOH is one of the promising hydrogen carriers and the important C1 source for organic
synthesis.
2.2. CO2 to The generation of HCOOH in CO2 photoreduction consumes the same amount of protons
HCOOH
and electrons as that for CO formation, but it requires slightly higher reduction potential.
HCOOH is one of the promising hydrogen carriers and the important C1 source for organic
The POM microions are the molecules denoted as {POM} in dilute solutions, they tend to afford
synthesis. The generation of HCOOH in CO2 photoreduction consumes the same amount of protons
suprestructural macroions denoted as {POM}n (POM macroions). Three POM macroions catalysts,
and electrons as
V that for CO formation,VI butVit requires slightly higher reduction potential.
Na15[MoVI126 Mo28 O462H14(H2O)70]0.5[Mo124 Mo28 O457H14(H2O)68]0.5 ({Mo154}1156), Na17[Mn6P3W24O94(H2O)2]
The POM microions are the molecules denoted as {POM} in dilute solutions, they tend to afford
suprestructural macroions denoted as {POM}n (POM macroions). Three POM macroions catalysts,
{Mo132}1064@RGO displayed better performance than {Mn6P3W24}931 (Table 3). This phenomenon can be
rationally explained by that the simultaneous excitation of multitudinous photoactive clusters on the
surface of {Mo154} and {Mo132} vesicles under light irradiation. For {Mo132}1064@RGO, good conductivity
of RGO may help the facile electrons transfer.
Molecules 2019, 24, 2069 9 of 26
Table 3. The photocatalytic performance of the different catalysts a.

Catalyst HCOOH Yield (μmol) TON TOF (s−1)

({Mn6 P3 W24 }931 ) and (NH4 )42 [MoVI Mo V
O 372 (CH 3 COO) 30 (H 2 O) 72 ]@RGO hybrid ({Mo } @RGO;
{Mo154}1165 72 60 116.7 778 377 132 1064
RGO = reduced graphene oxide) featured with peculiar structures, were respectively employed in the
{Mn6P3W24}931 40.6 270 56
photocatalytic CO2 reduction coupling with water oxidation [46]. The enormous spherical
{Mo132}1064@RGO 205 1366 610
superstructures in these three catalysts in dilute dispersion ({Mo154 }1156 , {Mn6 P3 W24 }931 ,
a. Catalyst containing 0.15 μmol of {Mo154}, {Mn6P3W24} or {Mo132} units. The reaction mixtures were
{Mo132 }1064 @RGO) are respectively made up by wheel-shaped {Mo154 } rings, bent rod−2{Mn6 P3 W24 }
kept in a photo-reactor under UV-light lamp with 373 nm wavelength and 19 mW cm energy
unitsdensity.
and “Keplerate” {Mo132 } spheres (Figure 8). The numbers of metal oxide cluster units in these
superstructures were calculated by following equation: n = (4πR2 )/(72.006σ2 ) × 60. (R, representing
Afterwards, POM
the hydrodynamic radiusmacroions
of POMfor the water
vesicles formed oxidization-coupled
in the dispersion,CO was 2 photoreduction
obtained by dynamic to HCOOH light
was extend to {Cu-PW 12} n=1348−2024 ({Cu-PW 12 } n = [(K 6.5 Cu(OH) 8.5
scattering analysis. σ, representing the diameter of isolated single cluster, was determined (H 2 O) 7.5 ) 0.5 @(K 3 PW 12 O40 )] n) [47]
by and
the
gigantic
van oxo-molybdate
der Waals radii of the catalyst Na48[Hatoms.)
constituent xMo368O1032 (H2results
The O)240(SO 4)48] ({Mo
showed that368})although
[48]. In theHCOOHformeriscase,
the
the max TON per mole was 613. Both FT-IR and Raman spectroscopies
main product of CO2 reduction with these three catalysts, a considerable amount of HCHO was also showed that the structure
remainedwhen
obtained integral
{Moafter reaction and the activity was kept after ten cycles. In the latter one, {Mo368},
154 }1156 and {Mo132 }1064 @RGO catalysts were applied. In the case of {Mn6 P3 W24 }931 ,
which
CO consisted of a central ball shaped unit {Mo288} and two {Mo40} capping units, showed excellent
2 was exclusively reduced to HCOOH. In terms of formic acid production, {Mo154 }1156 and
selectivity for HCOOH
{Mo132 }1064 @RGO displayed (95.73%) with impressive
better performance than TON
{Mn6 P(27666) and TOF (4419 h−1). Its external
3 W24 }931 (Table 3). This phenomenon can
quantum
be efficiency
rationally explainedreachedby that0.6%.theIt simultaneous
is worth noting that in all
excitation of above cases external
multitudinous photosensitizer
photoactive clusters
was unessential. Because intervalence charge transfers (IVCT) of Mo
on the surface of {Mo154 } and {Mo132 } vesicles under light irradiation. For {Mo132 }1064 @RGO, good
V to MoVI and WV to WVI have

appropriate gap
conductivity of RGObetween
may help conduction
the facileband and valence
electrons transfer.band, which can give rise to absorbance
maxima in the region of visible light.

Figure 8. The structures of {Mo154 }, {Mn6 P3 W24 }, and {Mo132 } POM macroions catalysts. Color code:
Mo, red ball; O, blue ball; Mn, yellow ball; P, pink ball; WO6 octahedron, grey. Reprinted with
permission from [46]. © 2016 Attribution-Non Commercial 3.0 Unported Licence (CC BY-NC 3.0).

Table 3. The photocatalytic performance of the different catalysts a.

Catalyst HCOOH Yield (µmol) TON TOF (s−1 )

{Mo154 }1165 116.7 778 377
{Mn6 P3 W24 }931 40.6 270 56
{Mo132 }1064 @RGO 205 1366 610
a. Catalyst containing 0.15 µmol of {Mo
154 }, {Mn6 P3 W24 } or {Mo132 } units. The reaction mixtures were kept in a
photo-reactor under UV-light lamp with 373 nm wavelength and 19 mW cm−2 energy density.

Afterwards, POM macroions for the water oxidization-coupled CO2 photoreduction to HCOOH
was extend to {Cu-PW12 }n=1348−2024 ({Cu-PW12 }n = [(K6.5 Cu(OH)8.5 (H2 O)7.5 )0.5 @(K3 PW12 O40 )]n ) [47]
and gigantic oxo-molybdate catalyst Na48 [Hx Mo368 O1032 (H2 O)240 (SO4 )48 ] ({Mo368 }) [48]. In the former
case, the max TON per mole was 613. Both FT-IR and Raman spectroscopies showed that the structure
remained integral after reaction and the activity was kept after ten cycles. In the latter one, {Mo368 },
which consisted of a central ball shaped unit {Mo288 } and two {Mo40 } capping units, showed excellent
selectivity for HCOOH (95.73%) with impressive TON (27666) and TOF (4419 h−1 ). Its external
quantum efficiency reached 0.6%. It is worth noting that in all above cases external photosensitizer
was unessential. Because intervalence charge transfers (IVCT) of MoV to MoVI and WV to WVI have
Molecules 2019, 24, x FOR PEER REVIEW 10 of 26

Molecules 2019, 24, 2069 10 of 26

Figure 8. The structures of {Mo154}, {Mn6P3W24}, and {Mo132} POM macroions catalysts. Color code: Mo,
red ball; O, blue ball; Mn, yellow ball; P, pink ball; WO6 octahedron, grey. Reprinted with permission
from [46]. gap
appropriate © 2016 Attribution-Non
between conductionCommercial
band and 3.0 Unported Licencewhich
valence band, (CC BY-NC 3.0). rise to absorbance
can give
maxima in the region of visible light.
2.3. CO2 to CH4
2.3. CO2 to CH4
Compared to the photoreductive conversion of CO2 to CO or HCOOH, photocatalytic
Compared
methanation of to
CO the photoreductive
2 involving conversion of CO
an eight-electron 2 to CO
transfer or HCOOH,
process was photocatalytic
much more challenging. methanation
7− was
[PTi2W210O40] was reported as the first POM-based photocatalyst for reducing CO22 to10 O
of CO involving
7– an eight-electron transfer process was much more challenging. [PTi W CH 40 ]4 with
reported
CH 3OH asas the first
electron POM-based
donator [49]. Althoughphotocatalyst [PTi2W for
10O reducing
40]7– had poor CO2 activity
to CH4 and withlimited CH3 OH as electron
efficiency in
donator [49]. Although 7−
photoreduction of CO2, [PTi this2 W result O
10 40 ] had
suggested poor activity
that POM and
could limited
be an efficiency
active in photoreduction
catalyst in the CO of
2

CO2 , this result suggested that POM could be an active catalyst in the CO2 photoreduction.
photoreduction.
Sincethis
Since thistime,
time,few fewworks
worksfocusingfocusingon onphotocatalytic
photocatalyticCO CO2 2reduction
reductiontotoCH CH 4 during
4 during pastdecades.
past decades.
Recently,aaremarkable
Recently, remarkableachievement
achievementin inphotocatalytic
photocatalyticCO CO2 2reduction
reductiontotoCH CH4 4with withtwo twohydrothermal-
hydrothermal-
synthesized POM catalysts
synthesized catalystsH[[Na H[[Na 2 K24K Mn4Mn 4 (PO
4(PO 4 )4)(H(H2 O)
2O)4 ]34][[Mo
3[[Mo 6O6O1212(OH)
(OH)33(HPO (HPO44))33(PO44)]44[Mn [Mn66(H (H22O) O)4]]
4 ]]
(NENU-605) and H[[Na
(NENU-605) H[[Na66CoMnCoMn33(PO (PO44)(H )(H22O)44]33[[Mo [[Mo66O O1212(OH)
(OH)33(HPO (HPO44)3)(PO 3 (PO 4 )]
4)] 4 [Co
4[Co Mn
1.51.5 Mn ]] ]](NENU-606)
4.54.5 (NENU-606)
wasreported
was reported[50]. [50].These
Thesetwo twowater-insoluble
water-insolublePOMs POMsshowed showedgood goodstructural
structuralstability stabilityand andextended
extended
solarspectrum
solar spectrumabsorption
absorptionrange rangeininaqueous aqueoussolutions.solutions.
UnderCO
Under CO2 2atmosphere
atmospherewith withtriethanolamine
triethanolamine(TEOA) (TEOA)asassacrificial sacrificialagent agentand and[Ru(bpy)
[Ru(bpy)3]Cl 3 ]Clas as
photosensitizer, CH
photosensitizer, CH44and and COCO were were the main gaseous gaseous photoreduction
photoreductionproducts, products,only onlyaatrace traceamount
amountof
ofHCOOH
HCOOHwas was detected
detected ininthe theaqueous
aqueous phase.
phase. The Theproductivity
productivity of of
CH CH 4 for4 for NENU-605
NENU-605 and andNENU-606
NENU-
reached
606 reached up upto 170
to 170nmolnmol (894.7
(894.7 nmol nmol g−1g–1 h−1 h–1) )andand402 402nmolnmol(1747.8 (1747.8nmol nmolgg−1 –1 h–1 −1 ) respectively. Good
) respectively. Good
CH4 4selectivity
CH selectivityofof 76.6%
76.6% (NENU-605)
(NENU-605) and and 85.5%
85.5% (NENU-606)
(NENU-606) waswas achieved
achieved (Table (Table 4, entry
4, entry 1 and 1 and
2).
2). Moreover,
Moreover, H2 evolution
H2 evolution as the side as the side reaction
reaction was not was not detected.
detected. RegardingRegarding to the higher to the CH4higher
selectivity CH4
II /CoII ions in NENU-606 might be
ofselectivity
NENU-606 of NENU-606
than NENU-605, than NENU-605, the heterometallic the heterometallic MnII/CoII Mn ions in NENU-606 might be more
more favorable II ions in NENU-605.
favorable to the to the adsorption
adsorption and activation
and activation of COof CO2 the
2 than thanhomometallic
the homometallic MnII Mn ions in NENU-605. In
In contrast,
contrast, Mn[MoMn[Mo 6O12 O
(OH) (OH)
3 (HPO (HPO
4 ) 3(PO ) 4(PO
)]2 )] (NENU-607),
(NENU-607), the the
dimerdimer containing
containing onlyonly oneoneMn Mn II IIatom
atom
6 12 3 4 3 4 2
sandwichedbetween
sandwiched betweentwo twoPP4Mo 4 Mo 6 6unitunitand anddisplaying
displayinga asimilar similarconnection
connectionmode modetotoNENU-605 NENU-605and and
NENU-606(Figure
NENU-606 (Figure9), 9),had
hadmuchmuchlower loweractivityactivity(Table (Table4,4,entry entry3). 3).Outcomes
Outcomesfrom fromcontrol controlexperiments
experiments
demonstratedthe
demonstrated thenecessities
necessitiesofofboth bothphotosensitizer
photosensitizerand andlight lightirradiation
irradiationasaswell wellasasthe thecontribution
contribution
fromsolvent
solventeffect effect (Table 4, entries 4–6). 13 C-isotope labelling verified that COthe
from (Table 4, entries 4–6). C-isotope labelling verified that CO 2 was 2 was carbon the source
carbon
13

ofsource
CO and ofCH CO4. and
DeducedCH4 .from Deduced from these
these patterns, patterns,
a plausible a plausible
multi-step multi-step
mechanism formechanism
the photocatalytic for the
photocatalytic
CO2 methanation was CO 2 methanation was proposed (Figure 10). Initially,
proposed (Figure 10). Initially, the photosensitizer absorbs light to produce the photosensitizer absorbs light
VI VI
to produce photo-excited
photo-excited electrons from electrons
its HOMO fromand its then
HOMO and then
transfers transfers
electrons to the electrons
P4Mo6 tounit thethrough
P4 Mo6 the unit
VI V − → P MoV ). Simultaneously, the electron holes
+
VI
through LUMO
matched the matchedpositionsLUMO (P4Mo positions
6 + 6e →
– (P
4 Mo
P 4 Mo
6 6 6e
). Simultaneously,
4 6 the electron holes produced in
+ + ).
produced
the valencein band the valence band of ruthenium
of ruthenium complex complex was consumed was consumed by TEOA by TEOA (TEOA (TEOA + h+ h→ →TEOA
+ TEOA). +
V
(MII+
II
V
Subsequently, strongly
Subsequently, strongly reductive PP44Mo66 unit unitfurther
further transfer
transfer electrons to the the active
active metal metalcenter center(M
− I I I I
+ee– → →MM).I).Then Thenthe theadsorbed
adsorbedCO CO 2 2(M(MI→→MM-CO I-CO)2obtains
2 ) obtains electrons
electrons fromfrom active
active metalmetal sites
sites (M(M -COI-CO→
2 2
II − – II −II
+ H2 →+
– II II
→MM -COII -CO 2 ) with
2 ) with thethe
helphelpof Hof 2 OH as2Oa proton
as a proton sourcesource (M -CO (M2 -CO +H M →+ M -COOH).
-COOH). II M -COMwas II-CO was
formed
formed
via the via the proton-
proton- and electron-assisted
and electron-assisted dehydroxylation
dehydroxylation (MII -CO (M H +
II-CO H 2
++
H + eH−+ → + e – →
M II -COM II+
-COH +O).H O).4
2CH
2 2
CH4 is eventually produced with further six-electron transfer process (M -CO + 6H + 6e → MII +4
is eventually produced with further six-electron transfer process (M II -CO II+ 6H + + 6e+ − → –M II + CH
+ H4 2+O).
CH H2O).

Figure 9. The asymmetric units of NENU-605 (a), NENU-606 (b) and NENU-607 (c). Reprinted with
Figure 9. Thefrom
permission [50]. © 2019
asymmetric unitsAttribution-Non
of NENU-605 (a), NENU-6063.0
Commercial (b)Unported
and NENU-607
Licence(c).
(CC Reprinted with
BY-NC 3.0).
permission from [50]. © 2019 Attribution-Non Commercial 3.0 Unported Licence (CC BY-NC 3.0).
Molecules 2019, 24,
Molecules 2019, 24, 2069
x FOR PEER REVIEW 11 of
11 of 26
26

Table 4. The photocatalytic reduction of CO2 to CH4 using different catalysts a.

Table 4. The photocatalytic reduction of CO2 to CH4 using different catalysts a.
CO CH4 CH4-TON CH4-TOF All-TON All-TOF
Entry Catalyst CO CH4 CH4 -TON CH 4 -TOF All-TON All-TOF
Entry Catalyst (nmol/g) (nmol/g)
(nmol/g) (10–3−3) (10 –3 h –1) (10–3) −3 (10–3 h(10
–1)
(nmol/g) (10 ) (10−3 h−1 ) (10 ) −3 h−1 )
1 NENU-605 52 170 104.1 5.5 135.9 7.2
1 NENU-605 52 170 104.1 5.5 135.9 7.2
2 NENU-606 68 402 241.4 10.5 282.2 12.3
2 NENU-606 68 402 241.4 10.5 282.2 12.3
3 3 NENU-607
NENU-607 47 47 70
70 15.2
15.2 0.75
0.75 25.425.4 1.3 1.3
4b
b NENU-606 n.d.n.d.
4 NENU-606 n.d.
n.d. -- - - - - - -
5c 5 c NENU-606
NENU-606 n.d.n.d. n.d.
n.d. -- - - - - - -
6d 6 d NENU-606
NENU-606 n.d.n.d. n.d.
n.d. -- - - - - - -
7 7 blank
blank n.d.n.d. n.d.
n.d. -- - - - - - -
a.
a.Reaction
Reactionconditions:
conditions:PSPS = =[Ru(bpy)
[Ru(bpy) 3 ]Cl2 .6H
3]Cl 2 O2(0.01
2.6H mmol,
O (0.01 ) H2)OH(28
mmol, 2O mL), SD =SD
(28 mL), TEOA (2 mL),
= TEOA CO2 (1
(2 mL), COatm),
2 (1
λ ≥ 420 nm, 20 ◦ C; b . without PS; c . In dark; d . Altering H O with dry MeCN. n.d. = not detected.
2
atm), λ ≥420 nm, 20 C; . without PS; . In dark; . Altering H2O with dry MeCN. n.d. = not detected.
o b c d

Figure 10. The proposed

Figure 10. proposed mechanism
mechanism forfor photocatalytic
photocatalytic reduction
reductionofofCO
CO22 to
to CH
CH44 using NENU-605 or
or
NENU-606.
NENU-606. Color code: P, yellow ball; Mo, blue ball; O, red ball. Reprinted with permission from [50].
Reprinted with permission
©
© 2019
2019 Attribution-Non
Attribution-Non Commercial
Commercial3.0 3.0Unported
UnportedLicence
Licence(CC
(CCBY-NC
BY-NC3.0).
3.0).

3. Electrocatalytic CO2 Reduction

3. Electrocatalytic CO2 Reduction
Electrocatalytic CO2 reduction to produce various C1 and C2 molecules, for instance, CO, HCOOH,
Electrocatalytic CO2 reduction to produce various C1 and C2 molecules, for instance, CO,
HCHO, CH3 OH, CH4 , oxalic acid, ethylene, and ethanol, is regarded as a promising proctol for the
HCOOH, HCHO, CH3OH, CH4, oxalic acid, ethylene, and ethanol, is regarded as a promising proctol
production of liquid fuels or bulk chemicals. The corresponding reactions and standard potentials
for the production of liquid fuels or bulk chemicals. The corresponding reactions and standard
were list in Table 5 [51].
potentials were list in Table 5 [51].
Molecules 2019, 24, 2069 12 of 26
Molecules 2019, 24, x FOR PEER REVIEW 12 of 26

Table
Table 5.2CO
5. CO 2 reduction
reduction potentials
potentials vs. SHE
vs. SHE a . a.

ProductsProductsHalf-Electrochemical
Half-Electrochemical Thermodynamic
Thermodynamic Reactions VVvs.vs.SHE
Reactions SHE
C CO2(g)++ 4 H+ −+ 4 e– = C(s) + 2 H2O(l) –0.210
C CO2 (g) + 4 H + 4 e = C(s)–+ 2 H2 O(l) −0.210
C CO2(g) + 2 H2O(l) + 4 e = C(s) + 4 OH– –0.627
C CO2 (g) + 2 H2 O(l) + 4+e− = –C(s) + 4 OH− −0.627
HCOOH CO2(g) ++ 2 H −+ 2e = HCOOH(l) –0.250
HCOOH CO2 (g) + 2 H + 2e =– HCOOH(l) −0.250
HCOO - CO 2 (g) + 2 H 2O(l) + 2 e = HCOO - (aq) + OH– –1.078
HCOO− CO2 (g) + 2 H2 O(l) + 2 e− = HCOO− (aq) + OH− −1.078
CO CO CO2 (g)CO + 22(g)H++ +2 2He−+ = 2 eCO(g)
+ – = CO(g) + H2O(l) –0.106
+ H2 O(l) −0.106
CO CO CO (g) + 2 H O(l)
CO2 (g) + 2 H2 O(l) + 2 e = CO(g) + 2 OH
2 2 −+ 2 e – = CO(g) + 2 − OH – –0.934
−0.934
HCHO HCHO CO 2 (g) +
CO2 (g) + 4 H + 4e = HCHO(l) + H2 O(l)
+ 4 H +−+ 4e– = HCHO(l) + H2O(l) –0.070
−0.070
HCHOHCHO CO2 (g)CO + 32(g)H2+O(l) 3 H+ 4 e−+=4 HCHO(l)
2O(l) e– = HCHO(l) + 4 OH+ 4 −OH– –0.898
−0.898
CH3 OH CH3OH CO2 (g)CO + 62(g) H+++6 6He+−+ = 6 eCH– = CH
3 OH(l)
3 +
OH(l) H +
2 O(l)
H 2 O(l) 0.016
0.016
CH3 OH CH3OH CO2 (g)CO + 52(g)H2+O(l) 5 H+2O(l)6 e−+=6 CH e– =3CH OH(l) + 6 OH
3OH(l) + 6 −OH– −0.812
–0.812
CH4 CH4 CO2 (g)CO + 82(g) H+++8 8He+−+ = 8 eCH – =4CH(g) 4+(g)2 +H2 O H(l)
2O (l) 0.169
0.169
CH4 CH4 CO2 (g)CO + 62(g)H2+O(l) + 8 e − = CH (g) + 8 OH−
6 H2O(l) + 8 e = CH4(g) + 8 OH
– 4 – −0.659
–0.659
oxalic acid 2 CO2 (g)2 CO H++ +
+ 22(g) 2H 2 e+ −+ =2 e(COOH)
– = (COOH) 2 (aq)2(aq)
−0.500
–0.500
oxalic acid
oxalate 2 CO2 (g) + 2 e− = C2– O2− 4C2(aq)
2− −0.590
oxalate 2 CO (g) + 2 e = O (aq) –0.590
2 CO2 (g) + 12 H+ + 12+e− = CH
2
2 CH2 (g) + 4 H2 O(l)
4
ethylene 0.064
ethylene 2 CO2(g) + 12 H + 12 e– = CH2CH2(g) + 4 H2O(l) 0.064
ethylene 2 CO2 (g) + 8 H2 O(l) + 12 e = CH2 CH2 (g) + 12 OH
− − −0.764
ethanolethylene 2 CO 2(g) + + 8 H 2O(l) + 12
2 CO2 (g) + 12 H + 12 e = CH3 CH2 OH(l) + 3 H2 O(l)
− e – = CH2CH2(g) + 12 OH− –0.764
0.084
ethanolethanol 2 CO (g)O(l)
+ 12+H12 + + 12
e− =e CH
– = CH3CH2OH(l) + 3 H2O(l) 0.084
2 CO2 (g) + 9 2H 2 3 CH2 OH(l) + 12 OH
− −0.744
ethanol 2 CO 2 (g) + 9 H 2O(l) + 12 e – = CH3CH2OH(l) + 12 OH– –0.744
a. Reprinted with permission from [51]. Copyright © 2014 Royal Society of Chemistry.
a. Reprinted with permission from [51]. Copyright © 2014 Royal Society of Chemistry.

Electrocatalytic
Electrocatalytic reduction
reduction of COof CO2 with2 with POM POM waswas firstfirst
reported
reported by Kozik
by Kozik et al.et [52]. Cyclic
al. [52]. Cyclic
voltammograms
voltammograms (CV)(CV)of several
of several POMs POMs with withor without
or without the thepresence
presence of CO 2 in2 various
of CO in various nonpolar
nonpolar
solvents were compared. For For 6− , 6–
solvents were compared. α-[SiW 11 O39
α-[SiW 11O Co]39Co] a, large
a largechange
change onon its its
CVCV was recorded
was recorded after COCO
after 2 was
2 was

bubbled. Meanwhile for forα-[Pα-[P W O ]6− ,6–almost no change was observed before and after bubbling
bubbled. Meanwhile 2 18 62
2 W 18 O 62] , almost no change was observed before and after bubbling
COCO 6− 6–
2 . The evidence
2. The evidence fromfrom CV CV hinted thatthat
hinted α-[SiW 11 O39
α-[SiW 11OCo]
39Co]might might be be
active to CO
active 2 reduction.
to CO 2 reduction. Further
Further
investigations on reduced 6− 6− showed
investigations on reduced α-[SiW 11 O39
α-[SiW 11Co]
O39Co]with CVCV
6– with indeed
indeed confirmed
confirmed that that
α-[SiW 11 O39
α-[SiW 11Co]
O39Co] 6– showed

thethe
electrocatalytic
electrocatalytic for for
COCO 2 reduction.
2 reduction. However,
However, thethefinal COCO
final 2 reduction
2 reduction product
product waswas unstated.
unstated.
MoreMore than decade
than decade later, Proust
later, Proust et etal.al.reinvestigated
reinvestigated this this reaction
reaction in more detail detail by by using
using [α-
[α-SiW
SiW11 11O Co]6–6−
O3939Co] ininthethe electro-assisted
electro-assisted reduction
reduction of COof CO
2 (Figure
2 (Figure11) 11)
[53]. [53].
The The
[α-SiW [α-SiW
11 O 39 Co]O Co] 6−
6– contained
11 39
contained
a CoII ina placeCoII inofplace
a WVIof VI . The square-pyramidal CoO with a vacant site was generated
a Wsquare-pyramidal
. The CoO5 with a 5vacant site was generated by losing a
by coordinated
losing a coordinatedwater molecule water molecule
from CoOfrom 5(H2O) CoO 5 (H2 O) octahedral
octahedral when the POM whenwas the extracted
POM wasfrom extracted
aqueous
from
to aqueous to organic
organic media. Except media.CO andExceptHCHO, CO and HCHO,
neither neither
H2 nor otherHCO 2 nor
2 other
reduction CO reduction
products
2 products
were detected.
were detected. This 6−
This indicated thatindicated
the unique that the unique
selectivity selectivity
of [α-SiW 11O39ofCo] [α-SiW
6– POM O
39 Co] inPOM
11 catalyst catalyst in the of
the electroreduction
electroreduction
CO2. The turnover of COof 2 . The
CO 2turnover
to CO of
reachedCO 2 to
to CO
3.7 reached
with the to 3.7
faradic with the faradic
efficiency of efficiency
13%. HCHO of was
13%.the
HCHO was the other detectable product. Its amount varied from 2.1 × 10 −7 –6
to 2.2 × 10 −6 mol with the
other detectable product. Its amount varied from 2.1 × 10 to 2.2 × 10 mol with the faradic yield –7

faradic
varyingyieldfromvarying
25%from (high 25%HCHO(high content
HCHO content with low with low electrolysis
electrolysis charge)charge)
to 0.8% to (low
0.8% HCHO(low HCHO content
content
with withhigh high electrolysis
electrolysis charge).charge).

Figure 11. Electroreduction of CO2 by [SiW11 O39 Co]6− catalyst. Color code: WO octahedron, light
Figure 11. Electroreduction of CO2 by [SiW11O39Co]6– catalyst. Color code: WO6 6octahedron, light blue;
blue; SiO4 tetrahedron, red; Co, purple ball; O, red ball. The notation of (_) in the above figure represents
SiO4 tetrahedron, red; Co, purple ball; O, red ball. The notation of (_) in the above figure represents a
a vacant coordination site.
vacant coordination site.
Inspired by organometallic CO2 reduction catalyst [Cp*RhIII (bpy)Cl]+ (Cp* = pentamethyl-
Inspired by
cyclopentadienyl organometallic
anion; CO2 reduction
bpy = 2,20 -bipyridine), [α-Hcatalyst [Cp*RhIII (bpy)Cl] 3−
III + (Cp* = pentamethyl-
2 PW11 O39 {Rh Cp*(OH2 )}] with analogous
cyclopentadienyl
coordination structureanion; bpy a= {Cp*Rh
via grafting 2,2’-bipyridine), [α-H
III }2+ fragment on2PW O39{Rh Cp*(OH
the11monovacant
III )}]O3– ]with
[PW211 analogous
7− anion was
39
coordination structure via grafting a {Cp*RhIII}2+ fragment on the monovacant [PW11O39]7– anion was
prepared (Figure 12) and tested as the electrocatalyst for CO2 reduction [54]. Compared to previously
prepared (Figure 12) and tested as the electrocatalyst for CO2 reduction [54]. Compared to previously
 Molecules 2019, 24, 2069 13 of 26
Molecules 2019, 24, x FOR PEER REVIEW 13 of 26

reported[CoSiW
[CoSiW1111OO3939 6− catalyst, its electrochemical behavior in the presence of CO exhibited a clear
reported ]6–] catalyst, its electrochemical behavior in the presence of CO2 2exhibited a clear
improvement, strongly suggesting
improvement, strongly suggesting some some interaction
interaction with
with the
the POM
POM derivative
derivative despite
despitethe
thepresence
presenceof
ofa
−
acoordinating
coordinatingsolvent.
solvent. But But HH22 was
was still
still as
as major product (68%
major product (68% faradic
faradic yield)
yield) with
with HCOO
HCOO− as asminor
minor
reduction product (4.5% faradic
reduction product (4.5% faradic yield).yield).

Figure 12. Synthesis of the organometallic derivative [α-H2 PW11 O39 (RhIII Cp*(OH2 ))]3− . Color code:
Figure 12. Synthesis
WO6 octahedron, of blue;
navy the organometallic derivative
PO4 tetrahedron, green; O,[α-H 2PW11O39(RhIIICp*(OH2))]3–. Color code:
red ball. Reprinted with permission from [54].
WO 6 octahedron, navy blue; PO4 tetrahedron, green; O, red ball. Reprinted with permission from [54].
Copyright © 2019 Wiley-VCH Verlag GmbH and Co. KGaA.
Copyright © 2019 Wiley-VCH Verlag GmbH and Co. KGaA.
The remarkable capability of storing and donating electrons endows POMs the feature of reversibly
The
transferringremarkable capability
multi-electrons. Hence,of selecting
storing and properdonating
co-catalystelectrons endows
to establish POMs catalytic
synergistic the feature of
systems
reversibly transferring multi-electrons. Hence, selecting proper co-catalyst
containing POM catalyst is reasonable to achieve the efficient CO2 reduction. On one side, by taking to establish synergistic
catalytic systems
the advantage of containing POM catalyst
POMs on reversible is reasonable
transfer to achieve
of multi-electrons the efficient
or protons, CO2 reduction.
co-catalysts On
can efficiently
one side, by taking the advantage of POMs on reversible transfer of multi-electrons
overcome the barrier of CO2 activation. On the other side, co-catalysts with good conductivity and or protons, co-
catalysts can efficiently overcome the barrier of CO activation. On the other
adsorbing CO2 capability can facilitate the electroreduction and improve the activity of catalytic system.
2 side, co-catalysts with
good
Poor conductivity and adsorbing
electrical conductivity CO2 capability can
and electron-donating facilitateare
capability the electroreduction
the major drawbacks andforimprove the
MOFs being
activity
as efficient electrocatalysts. Therefore, the integrated use of POM and MOF would combinethe
of catalytic system. Poor electrical conductivity and electron-donating capability are the
major drawbacks
strengths of each for
otherMOFs
and being
generateas efficient electrocatalysts.
electrocatalysts Therefore,
with excellent activitythe[55–57].
integrated use of POM
and MOF wouldthe
Following combine the strengths
above intention, Lan of each
et al. other and
prepared generate
various electrocatalysts with excellent
Polyoxometalate-Metalloporphyrin
activity [55–57].
Organic Frameworks (PMOFs) by assembling Zn-ε-Keggin cluster ε-PMoV VI
8 Mo4 O40 Zn4 with M-TCPP
Following
(M-TCPP the above intention, Lan et al. preparedM
= tetrakis[4-carboxyphenyl]-porphyrinato-M; various
= Co, Fe,Polyoxometalate-Metalloporphyrin
Ni, Zn) via the links between Zn2+
V VI
Organic Frameworks
ions of POM （PMOFs）
and carboxylates ofby assembling
porphyrin Zn-ε-Keggin cluster
in hydrothermal ε-PMo
conditions 8 Mo4 13)
(Figure O40and
Zn4 measured
with M-TCPP their
(M-TCPP = tetrakis[4-carboxyphenyl]-porphyrinato-M;
catalytic performances (Table 6) [58]. In the skeleton ofM = Co,
these Fe, Ni, Zn)the
M-PMOFs, viamoieties
the linksofbetween Zn2+
Zn-ε-Keggin
ions of POM
cluster, and carboxylates
as electron of porphyrin
reservoirs, potently helpedinthe hydrothermal
electron transfer conditions
to CO2 (Figure
reduction13)catalyst
and measured
M-TCPP
their
and improve its performance of CO2 reduction. The best results were obtained on Co-PMOFZn-ε-
catalytic performances (Table 6) [58]. In the skeleton of these M-PMOFs, the moieties of with
Keggin cluster,
lower onset as electron
potential, tafelreservoirs,
slope, andpotently helped the
electrochemical electronas
impedance transfer
well asto CO2 reduction
higher partial COcatalyst
current
M-TCPP
density (jand
CO ),improve its performance
electrochemical of COarea
active surface 2 reduction.
(ECSA),The bestefficiency
faradic results were obtained
for CO (FECOon Co-PMOF
) and turnover
with lower (TOF)
frequency onset. potential,
Co-PMOFtafel slope, CO
converted and2 electrochemical
to CO with a superior impedance
faradicasefficiency
well as higher
of 99%.partial CO
The value
current
of TOF density
was elevated to 1656 h−1 at −0.8
(jCO), electrochemical active surface
V. No evidentarea (ECSA),
activity faradic efficiency
attenuation for CO
was observed (FECO)the
during and36
turnover frequency (TOF) Co-PMOF converted
h stability test, which indicated the robustness of Co-PMOF.
. CO 2 to CO with a superior faradic efficiency of 99%.
The value of TOF was elevated to 1656 h−1 at –0.8 V. No evident activity attenuation was observed
a.
during the 36 h stability test, which Table 6.indicated the robustness
CO2 electroreduction of Co-PMOF.
performances

E Onset Potential jCO Tafel Slope ECSA EIS FEco TOF

Catalysts
V vs. SHE V mA cm−2 (mV dec−1 ) mF cm−2 Ω % H−1
Co-PMOF −0.8 −0.35 18.08 98 12.17 9.83 98.7 1656
Fe-PMOF −0.7 −0.53 0.47 211 10.26 10.26 28.8 17.45
Ni-PMOF −0.8 −0.58 0.27 675 10.16 10.70 18.5 8.11
Zn-PMOF −0.9 −0.60 0.02 206 9.83 12.17 0.95 0.005
Co-TMCP −0.9 −0.53 NA b 151 NA NA 40 NA
TMCP −0.6 −0.67 NA 552 NA NA 0.77 NA
NNU-12 −0.6 −0.6 NA 413 NA NA 1.8 NA
a. Electrolyte and pH 0.5 M KHCO3 , pH = 7.2; b . NA means not mentioned in the [58].
Molecules 2019, 24,
Molecules 2019, 24, 2069
x FOR PEER REVIEW 14 of
14 of 26
26

Figure 13. Schematic illustration of the structures of M-PMOFs (Polyoxometalate-Metalloporphyrin

Figure 13.
Organic Schematic illustration
Frameworks). Color code:ofMoO
the structures of M-PMOFs (Polyoxometalate-Metalloporphyrin
6 octahedra, bottle green; Zn, light blue ball; Ni, green ball; Fe,
Organicball;
orange Frameworks).
Co, magentaColor
ball,code: MoO
N, blue 6 octahedra, bottle green; Zn, light blue ball; Ni, green ball;
ball; C, grey ball; O, red ball; H was omitted. Reprinted with
Fe, orange ball; Co, magenta ball, N, blue ball;
permission from [58]. Copyright © 2015 AttributionC, grey4.0
ball; O, red ball; (CC
International H was
BYomitted.
4.0). Reprinted with
permission from [58]. Copyright © 2015 Attribution 4.0 International (CC BY 4.0).
DFT calculations was employed to explicitly understand the excellent performance of Co-MPOF
and synergism between Zn-ε-Keggin CO2 electroreduction
Table 6.cluster and Co-TCPP.performances
Owing to rather a.
high Gibbs free energies of
0.96 eV (∆G1 in Figure 14a), the formation of adsorbed intermediates * COOH was regarded as the
Onset jCO Tafel
rate-determining
Catalysts
step (RDS)
E for CO2 reduction on Zn-ε-Keggin ECSA cluster. OnEIS the contrary,
FEco the
TOFformation
Potential mA Slope
of adsorbed intermediatesV vs. SHE * CO onVCo-TCPPcmwas RDS with high mFGibbs
cm –2
freeΩenergies % of 0.53H–1eV (∆G2 in
–2 (mV dec−1)
Figure 14a). In accordance with expectation, remarkable drops of both ∆G1 and ∆G2 , particularly the
Co-PMOF –0.8 –0.35 18.08 98 12.17 9.83 98.7 1656
much lower ∆G1 = 0.34 eV, were revealed. For Co-PMOF, the more favorable CO2 reduction active
Fe-PMOF –0.7 –0.53 0.47 211 10.26 10.26 28.8 17.45
site is Co on Co-TCPP instead of Zn on POM. In fact, this Zn POM was inactive in CO2 reduction,
Ni-PMOF –0.8 –0.58 0.27 675 10.16 10.70 18.5 8.11
and the synergistic effect was derived from the intramolecular electron transfer between the electron
Zn-PMOF –0.9 –0.60 0.02 206 9.83 12.17 0.95 0.005
mediator of POM and Co-TCPP. The effect of different metal center in porphyrin was also computed
Co-TMCP –0.9 –0.53 NA b 151 NA NA 40 NA
(Figure 14b). The energy profile of reaction on different metal centers was well consistent with the
552 NA NA
outcomes of experiments. Based on the experimental results and theoretical calculations,NA
TMCP –0.6 –0.67 NA 0.77
the possible
NNU-12 –0.6 413 NA NA
mechanism about reducing CO2 –0.6 NA
to CO on Co-PMOF was suggested. Firstly, the1.8 NA
POM captures and
a. Electrolyte and pH 0.5 M KHCO3, pH = 7.2; b. NA means not mentioned in the [58].
transfers electrons from the electrode to the CoII center. Subsequently, CoII centers was reduced to
CoI . DFT CoI interacts
Thencalculations waswith CO2 to afford
employed to explicitly COO− , which
CoII -*understand the was converted
excellent to CoII -*ofCO
performance via the
Co-MPOF
proton-coupled electron transfer. Finally, CO is desorbed and released
and synergism between Zn-ε-Keggin cluster and Co-TCPP. Owing to rather high Gibbs free energies(Figure 14c,d).
The
of 0.96 eVdesign
(ΔG1 inand application
Figure 14a), theof [α-SiW12of
formation O40 ]4− -modified
adsorbed AgNC@BSA
intermediates * COOH catalyst
was (AgNC@BSA
regarded as the =
silver nanoclustersstep
rate-determining capped
(RDS) with
for bovine serum albumin;
CO2 reduction BSA is both
on Zn-ε-Keggin the stabilizer
cluster. and reducing
On the contrary, reagent
the formation
for the synthesis
of adsorbed of AgNC)*in
intermediates COtheonelectroreduction
Co-TCPP was RDS of CO 2 tohigh
with CO Gibbs
also exhibited the same
free energies of 0.53concept
eV (ΔG of2
synergism [59].InSimilar to thewith
caseexpectation,
of Co-PMOF, although [α-SiW 4−
in Figure 14a). accordance remarkable drops of 12 O 40 ] ΔG
both had little
1 and ΔG CO 2 reduction
2, particularly

activity,
the muchitlower
played ΔGthe
1 = role of electron
0.34 eV, transferFor
were revealed. mediator
Co-PMOF, and the
assisted
more the CO2 reduction
favorable CO2 reduction through its
active
strong interaction with
site is Co on Co-TCPP instead CO 2 on the surface of AgNC. It had excellent faradic efficiency
of Zn on POM. In fact, this Zn POM was inactive in CO2 reduction, (>75%) in DMF
containing 1% (v/v)effect
H2 O. wasThe derived
overpotential of [α-SiW 4−
and the synergistic from the 12 O40 ] -modified
intramolecular AgNC@BSA
electron transfer between electrode was
the electron
about 0.7 V. The onset potential for this POM-decorated AgNC electrocatalyst
mediator of POM and Co-TCPP. The effect of different metal center in porphyrin was also computed was about 400 mV more
positive than that
(Figure 14b). The on bulk profile
energy Ag. of reaction on different metal centers was well consistent with the
outcomes of experiments. Based on the experimental results and theoretical calculations, the possible
mechanism about reducing CO2 to CO on Co-PMOF was suggested. Firstly, the POM captures and
transfers electrons from the electrode to the CoII center. Subsequently, CoII centers was reduced to
CoI. Then CoI interacts with CO2 to afford CoII-* COO–, which was converted to CoII-* CO via the
proton-coupled electron transfer. Finally, CO is desorbed and released (Figure 14c,d).
Molecules 2019, 24, 2069 15 of 26
Molecules 2019, 24, x FOR PEER REVIEW 15 of 26

Figure 14. The DFT calculation and proposed reaction mechanism. The free energy diagrams
Figure 14. The DFT calculation and proposed reaction mechanism. The free energy diagrams CO2
CO2 reduction reaction (CO2 RR) for the Zn-ε-Keggin POM, the Co-TCPP metalloporphyrin and the
reduction reaction (CO2RR) for the Zn-ε-Keggin POM, the Co-TCPP metalloporphyrin and the Co-
Co-PMOF (a); comparison of the free energy of each elementary reaction (∆G1 , ∆G2 , and ∆G3 represent
PMOF (a); comparison of the free energy of each elementary reaction (ΔG1, ΔG2, and ΔG3 represent
the free energy of * COOH formation, * CO formation, and CO desorption process, respectively) in
the free energy of * COOH formation, * CO formation, and CO desorption process, respectively) in
CO2 RR for Co-PMOF, Fe-PMOF, Ni-PMOF, and Zn-PMOF (b); proposed mechanistic scheme for the
CO2RR for Co-PMOF, Fe-PMOF, Ni-PMOF, and Zn-PMOF (b); proposed mechanistic scheme for the
CO2 RR on Co-PMOF (c,d); color code: MoO6 octahedra, bottle green; Zn, light blue ball; Co, magenta
CO2RR on Co-PMOF (c, d); color code: MoO6 octahedra, bottle green; Zn, light blue ball; Co, magenta
ball, N, blue ball; C, grey ball; O, red ball. Reprinted with permission from [58]. Copyright © 2015
ball, N, blue4.0
Attribution ball; C, grey ball;
International (CCO,BY
red4.0).
ball . Reprinted with permission from [58]. Copyright © 2015
Attribution 4.0 International (CC BY 4.0).
Metal nanoparticles stabilized by POMs was extensively researched [60,61]. By replacing BSA
with The
POM design
as theand application
stabilizer of [α-SiW
of AgNC, O40]4–-modified
three12Ag-POM AgNC@BSA
nanocomposites catalyst (AgNC@BSA
respectively with [PMo12=Osilver3−
40 ] ,
nanoclusters
[α-SiW12 O40 ]capped
4− and [PWwith12bovine
O40 ]3−serum albumin; BSA
were synthesized byiselectrodeposition
both the stabilizermethod
and reducing reagent
[62]. POM for
is the
the synthesis of AgNC) in the electroreduction of CO 2 to CO also exhibited the same concept of
promoter for the CO2 reduction. Due to the higher charge density and stronger basicity associated
synergism
with [PMo12 [59].
O40 ]Similar to the case
3− , the activity of Co-PMOF,
of Ag-[PMo 12 O40 ]
3−although [α-SiW12
nanocomposite O40]better
was
4– had little CO2 reduction
than Ag-[PW12 O40 ]3−
activity, it played
and Ag-[α-SiW the 4−
role of electron transfer mediator and assisted the CO2 reduction through its
12 O40 ] . This nanocomposite exhibited efficient and sustained CO2 reduction at
strong
a wide potential rangeCO
interaction with 2 on the surface of AgNC. It had excellent faradic efficiency (>75%) in DMF
with faradic efficiency of 90 ± 5%. The Tafel slope, an inherent property
containing 1% (v/v)
of electrocatalyst H2O. The by
determined overpotential of [α-SiW
the rate-limiting O40]4–-modified
step12(formation of CO AgNC@BSA
− electrode was −
2 or protonation of CO2 ),
about 0.7 V.
calculated forThe onset 12
Ag-[PMo potential
O40 ]3− (60formV
thisdec
POM-decorated
−1 ) was very close AgNC electrocatalyst
to the was about
theoretical value (59 mV400
decmV−1 ),
more positive than that on bulk Ag. − 3−
which indicated the faster formation of CO2 on the Ag-[PMo12 O40 ] nanocomposite-modified electrode
Metal nanoparticles stabilized by POMs was extensively researched [60,61]. By replacing BSA
with POM as the stabilizer
4. Electromicrobial of AgNC,
Conversion of CO three
2 Ag-POM nanocomposites respectively with [PMo12O40]3–,
[α-SiW12O40]4– and [PW12O40]3– were synthesized by electrodeposition method [62]. POM is the
Since the introduction of lithoautotrophic bacterium Ralstonia eutropha H16 as the production host
promoter for the CO2 reduction. Due to the higher charge density and stronger basicity associated
for biological formate conversion as well as the coupling between this biological formate conversion
with [PMo12O40]3–, the activity of Ag-[PMo12O40]3– nanocomposite was better than Ag-[PW12O40]3– and
method and the electroreductive conversion of CO2 to formate on indium cathode was employed to
Ag-[α-SiW12O40]4–. This nanocomposite exhibited efficient and sustained CO2 reduction at a wide
produce fuels for internal combustion engines from CO2 [63], the integration of electrocatalytic reduction
potential range with faradic efficiency of 90 ± 5%. The Tafel slope, an inherent property of
with microbial conversion represents an edge-cutting strategy for the direct – but non-photosynthetic –
electrocatalyst determined by the rate-limiting step (formation of CO 2 or protonation of CO 2 ),
CO2 conversion to important3–molecules. -1
calculated for Ag-[PMo12O40] (60 mV dec ) was very close to the theoretical value (59 mV dec−1),
Microorganisms, represented by R. eutropha – and Clostridium spp, have been well harnessed to
which indicated the faster formation of CO 2 on the Ag-[PMo12O40]3– nanocomposite-modified
transform CO2 and H2 to energy-dense liquid fuels [64]. As potent hydrogen-oxidizing bacterium,
electrode
R. eutropha has exhibited its versatility in synthesize poly[R-(−)-3-hydroxybutyrate], which is one of
the ingredients to manufacture biodegradable plastics [65]. On the other aspect, many POMs-based
4. Electromicrobial Conversion of CO2
catalysts have presented excellent activity for hydrogen evolution reaction (HER) [12,66]. Searching
Since the introduction of lithoautotrophic bacterium Ralstonia eutropha H16 as the production
host for biological formate conversion as well as the coupling between this biological formate
 employed to produce fuels for internal combustion engines from CO2 [63], the integration of
electrocatalytic reduction with microbial conversion represents an edge-cutting strategy for the direct
but non-photosynthetic CO2 conversion to important molecules.
Microorganisms, represented by R. eutropha and Clostridium spp, have been well harnessed to
transform CO2 and H2 to energy-dense liquid fuels [64]. As potent hydrogen-oxidizing bacterium, R.
Molecules 2019, 24, 2069 16 of 26
eutropha has exhibited its versatility in synthesize poly[R-(−)-3-hydroxybutyrate], which is one of the
ingredients to manufacture biodegradable plastics [65]. On the other aspect, many POMs-based
catalysts havePOM-based
biocompatible presented excellent activity
HER catalysts and forutilizing
hydrogen evolution
suitable reaction (HER)
microorganism [12,66]. Searching
to catalytically reduce
CObiocompatible
2 by consuming POM-based
H 2
HER
generated catalysts
from HER and
can utilizing
effectuallysuitable microorganism
accomplish the to catalytically
electromicrobial reduce
conversion
CO
of CO2 .
2 by consuming H 2 generated from HER can effectually accomplish the electromicrobial
conversion
Recently,ofZhang
CO2. and co-workers demonstrated the feasibility of such reckoning. The combination
Recently, Zhang
of a heterometallic and co-workers
Co/Cu-containing demonstrated thecloth
polyoxometalate/carbon feasibility of such
(Cu6 Co7 /CC; Cu6 Co reckoning.
7 = [Cu(en)2 ]6
The
combination of a heterometallic Co/Cu-containing polyoxometalate/carbon
[((PW9 O34 )Co3 (OH)(H2 O)2 (O3 PC(O)(C3 H6 NH3 )PO3 ))2 Co] , en = ethanediamine; see the structure
2− cloth (Cu 6Co 7 /CC;
ofCuCu6Co 7 = [Cu(en)2]6[((PW9O34)Co3(OH)(H2O)2(O3PC(O)(C3H6NH3)PO3))2Co]2–, en = ethanediamine;
6 Co7 POM in Figure 15; CC = carbon cloth) precatalyst with bacterium R. eutropha H16 was
see the structure
developed of Cu
to achieved 6Co
the 7 POM in Figurebioconversion
electricity-driven 15; CC = carbon of COcloth) precatalyst with bacterium R.
2 to biomass in neutral water [67].
eutropha H16 was developed to achieved the electricity-driven
Cu6 Co7 /CC hybrid material possessed good biocompatibility in this CO2 conversion bioconversion of COsystem.
2 to biomassIt wasin
neutral water
evidenced [67].of Cu
that most the6Co
H27/CC hybrid
produced material
on the Cu6 Copossessed good biocompatibility in this CO2
7 /CC cathode was consumed by the bacteria for
conversion system. It was evidenced that most of the
living and growth. In excess of half input electrical energy was transportedH 2 produced on the Cubiomass.
into 6Co7/CC The cathode
authors was
consumed
assumed thatby
thethe bacteriawould
electricity for living and growth.
be supplied In excess device
by a photovoltaic of halfwith
inputan electrical
efficiency energy
of 18%, the was
transported
expected into
overall biomass. The efficiency
solar-to-biomass authors assumed
could reach that
10%,thewhich
electricity
would would
be nearlybe 10supplied
times higher by a
photovoltaic
than the natural device with an efficiency
photosynthesis. This Cuof 18%, the expected overall solar-to-biomass efficiency could
6 Co7 /CC-R. eutropha hybrid system exemplified the potential
toreach
explore10%, which would be nearly
non-photosynthetic 10 times
but highly higher
efficient CO2than the natural
-fixation methods photosynthesis. This Cucatalysts
by using POMs-based 6Co7/CC-

R. eutropha hybrid
and solar electricity. system exemplified the potential to explore non-photosynthetic but highly efficient
CO2-fixation methods by using POMs-based catalysts and solar electricity.

Figure
Figure15.15.Schematic
Schematicillustrations
illustrationsofofthe
thebioelectrochemical
bioelectrochemical system
systemforfor
CO 2 fixation.
CO Color code: WO6 6
2 fixation. Color code: WO
octahedra,
octahedra, light blue; Co, pink ball; P, orange ball; Cu spheres, green; C, black ball; dark
light blue; Co, pink ball; P, orange ball; Cu spheres, green; C, black ball; N, blueblue
N, dark ball;ball;
O,
O, red ball; H atoms have been omitted for clarity. Reprinted with permission from [67]. Copyright©©
red ball; H atoms have been omitted for clarity. Reprinted with permission from [67]. Copyright
2018
2018The
TheRoyal
RoyalSociety
SocietyofofChemistry.
Chemistry.
5. Non-Reductive CO2 Conversion to Carbonyl-Contained Organic Chemicals
5. Non-Reductive CO2 Conversion to Carbonyl-Contained Organic Chemicals
Non-reductive chemical CO2 conversion provides diverse alternatives to achieve both the synthesis
Non-reductive chemical CO2 conversion provides diverse alternatives to achieve both the
of practical chemicals and CO2 fixation at the same time [68]. Currently, the industrial manufacture of
synthesis of practical chemicals and CO2 fixation at the same time [68]. Currently, the industrial
several chemicals demands CO2 as starting material [69]. Predominantly, due to the basic properties
manufacture of several chemicals demands CO2 as starting material [69]. Predominantly, due to the
of POM-based materials, the capture and transformation of CO2 with these materials has been
basic properties of POM-based materials, the capture and transformation of CO2 with these materials
widely explored. Therefore, the versatility of POMs-based materials in non-reductive chemical
has been widely explored. Therefore, the versatility of POMs-based materials in non-reductive
CO2 fixation has been fully presented. Various useful chemicals, including cyclic carbonate [19],
chemical CO2 fixation has been fully presented. Various useful chemicals, including cyclic carbonate
dimethyl carbonate [70–74], urea [74], quinazoline-2,4-(1H,3H)-diones [74,75], 2-benzimidazolone [74],
[19], dimethyl carbonate [70–74], urea [74], quinazoline-2,4-(1H,3H)-diones [74,75], 2-
2-oxazolidinones [18], α-methylene cyclic carbonate [74], and methacrylic acid [76,77] were able
benzimidazolone [74], 2-oxazolidinones [18], α-methylene cyclic carbonate [74], and methacrylic acid
to be synthesized with POM-based catalyst (Scheme 2). Considering that several reviews have
[76,77] were able to be synthesized with POM-based catalyst (Scheme 2). Considering that several
already given comprehensive summaries of representative progress on non-reductive CO2 fixation
reviews have already given comprehensive summaries of representative progress on non-reductive
by POM catalysts [69,78,79], herein we briefly introduced the recent advances about non-reductive
CO2 conversion to organic chemicals, which were not collected in the very recent review published in
2018 [79].
Molecules 2019,
Molecules 2019, 24,
24, xx FOR
FOR PEER
PEER REVIEW
REVIEW 17 of
17 of 26
26

CO22 fixation
CO fixation byby POM
POM catalysts
catalysts [69,78,79],
[69,78,79], herein
herein we
we briefly
briefly introduced
introduced the
the recent
recent advances
advances about
about non-
non-
Molecules 2019, 24, 2069 17 of 26
reductive CO
reductive CO22 conversion
conversion toto organic
organic chemicals,
chemicals, which
which were
were not
not collected
collected in
in the
the very
very recent
recent review
review
published in 2018
published in 2018 [79]. [79].

Scheme 2.
Scheme 2. Non-reductive chemical fixation
Non-reductive chemical fixation of
of CO
CO222 by
by POM
POM catalysts.
catalysts.

Various
Various importantapplications
Various important
important applications
applications of
of of cyclic
cyclic carbonates
carbonates
cyclic carbonates make
makemake the research
the research
the research
on POM onorPOM
on POM
other or or other
material-
other
material-catalyzed
catalyzed synthesissynthesis
material-catalyzed synthesis of
of cyclic carbonatescyclic carbonates
always receive
of cyclic carbonates always
always receive
long-lasting long-lasting
interests [80].
receive long-lasting interests [80].
By integrating
interests [80]. By By
integrating
POM components,
integrating POM components,
POM components,
chiral organic chiral organic
catalysts
chiral organic andcatalysts and CO
CO2 activator
catalysts and activator
CO22inactivator
the skeletonin the
in theofskeleton
skeleton
a singleof ofMOF,
aa single
singlethe
MOF, the polyoxometallate-organocatalyst-metal
polyoxometallate-organocatalyst-metal organic organic
framework framework
(POMOF)
MOF, the polyoxometallate-organocatalyst-metal organic framework (POMOF) was designed by was (POMOF)
designed by was
Duan designed
group by
[81].
Duan
Duan group
Chiralgroup [81].
cyclic [81]. Chiral were
carbonates
Chiral cyclicproduced
cyclic carbonates
carbonates were produced
efficiently
were produced efficiently
from olefins and CO
efficiently from
2 on
from olefins
the POMOFs
olefins and CO
and CO22tandem
on the
on the
POMOFs
catalyst. tandem
By catalyst.
ingeniously By ingeniously
connecting connecting
Keggin-type POM Keggin-type
anions α-[ZnW POM anions
O ] 6− , α-[ZnW 12 O 40] 6–, L-
POMOFs tandem catalyst. By ingeniously connecting Keggin-type POM 12 anions
40 α-[ZnW12O40] , L-
l-proline-derived 6–

proline-derived
asymmetric organocatalysts
proline-derived asymmetric
asymmetric organocatalysts pyrrolidine-2-yl-imidazole
pyrrolidine-2-yl-imidazole
organocatalysts pyrrolidine-2-yl-imidazole
(PYI) and NH2 -functionalized (PYI) bridging
(PYI) and NH
and NH
links -
22-
functionalized 0 bridging via
2-amino-4,4 -bipyridine links 2-amino-4,4’-bipyridine
the2-amino-4,4’-bipyridine
six-coordinated Zn nodes II viainthe
the six-coordinated
these POMOFs (α-[ZnW ZnII nodes
II nodes 6−
in-PYIs),
these
functionalized bridging links via six-coordinated Zn 12 O40 ] in these
POMOFs
a clear (α-[ZnW
division of 12 O 40 ] 6–-PYIs), a clear division of catalytic working for oxidation-coupled CO2
catalytic working for oxidation-coupled
POMOFs (α-[ZnW12O40] -PYIs), a clear division of catalytic working
6– CO 2 conversion was established
for oxidation-coupled CO that2
conversion was
POM as an oxidation established that
catalyst,that POM
pyrrolidine as an oxidation catalyst, pyrrolidine II
moiety as a chiral
conversion was established POM asmoiety as a chiral
an oxidation organocatalyst,
catalyst, pyrrolidine Zn moiety
ions as as Lewis acid
a chiral
organocatalyst,
catalyst to activateZn II ions as Lewis acid catalyst to activate the epoxide intermediate
the epoxide intermediate and amino groups on 4,4 0 -bipyridines and as amino
renewable groups
CO
organocatalyst, Zn ions as Lewis acid catalyst to activate the epoxide intermediate and amino groups2
II

on 4,4’-bipyridines
absorption
on reagent inas
4,4’-bipyridines asthis
renewable CO22 absorption
tandem process
renewable CO absorption reagent
(Figure 16).reagent in this
this tandem
The multi-catalytic
in tandem process
sitesprocess
were orderly (Figure
(Figure 16). The
distributed
16). The
multi-catalytic
and spatially matched
multi-catalytic sites were
sites werein theorderly distributed
framework.
orderly distributed and
Theand spatially
captured matched
COmatched
spatially 2 molecules in the
in the framework.
areframework.
synergistically Thefixed
The captured
captured and
CO 2 molecules
activated by are synergistically
well-positioned fixed
pyrrolidine and
and activated
amine by
groups, well-positioned
providing
CO2 molecules are synergistically fixed and activated by well-positioned pyrrolidine and amine further pyrrolidine
compatibility and withamine the
groups,
terminal providing
W=O further
activated compatibility
epoxidation with
intermediate the terminal
and W=O
driving theactivated
tandem
groups, providing further compatibility with the terminal W=O activated epoxidation intermediate epoxidation
catalytic process intermediate
in a single
and driving
workup
and driving
stage the
the tandem
and catalytic process
an asymmetric
tandem catalytic process
fashion.inin aa single
single workup
workup stage
stage and
and an an asymmetric
asymmetric fashion. fashion.

Figure 16. Synthetic procedure of the polyoxometallate-organocatalyst-metal organic frameworks

Figure
(POMOFs)16. Synthetic
Figure 16. Synthetic
and procedure
the schematic
procedure of the
the polyoxometallate-organocatalyst-metal
polyoxometallate-organocatalyst-metal
representation
of of tandem catalysis for the asymmetric organic frameworks
cyclic
organic carbonate
frameworks
(POMOFs) and from
transformation the schematic
schematic representation
olefins and of tandem
tandem
CO2 . Color code: catalysis 6−
for, yellow
the asymmetric
asymmetric cyclic carbonate
(POMOFs) and the representation of α-[ZnW 12 O40 ] for
catalysis the polyhedral; Zn,carbonate
cyclic cyan ball;
transformation
transformation from
N, blue ball; C, from olefins
orange and
ball;and
olefins O, red
CO 2. Color
COball; code:was
H atom
2. Color code: α-[ZnW 12O40]6–
omitted.
α-[ZnW ,, yellow
yellow polyhedral;
Reprinted
12O40]6–
polyhedral; Zn, cyan
cyan
with permission
Zn, ball;[81].
from
ball; N,
N,
Copyright © 2015 Attribution 4.0 International (CC BY 4.0).
Molecules 2019, 24, x FOR PEER REVIEW 18 of 26

blue ball; C, orange ball; O, red ball; H atom was omitted. Reprinted with permission from [81].
Molecules 2019, 24, 2069 18 of 26
Copyright © 2015 Attribution 4.0 International (CC BY 4.0).

In conjunction
In conjunction with with ionic
ionic liquid
liquid co-catalyst,
co-catalyst, two two kinds
kinds of of POMs
POMs attached
attached with with metal
metal carbonyl
carbonyl
{P22W
{P W1515O
O5656Co
Co3(H
3 (H2O) 3(OH)
2 O) 3 (OH) 3Mn(CO)
3 Mn(CO) 3} } [82]
8–
3
8− and
[82] and{(Se 2WW
{(Se 2 11O )(Mn(CO)
1143O 43 )(Mn(CO)3)4} ) [83]
8–
3 4}
8− were
[83] reported
were reportedas
efficient catalysts for the cycloaddition of CO with epoxides under
as efficient catalysts for the cycloaddition of CO2 with epoxides under mild conditions. A rare
2 mild conditions. A rare three-
dimensional CO2-linked
three-dimensional CO2 -linkedPOMPOM polymer {PMo{PMo
polymer 12O40Zn 4(CO2)}2– exhibited
12 O40 Zn4 (CO2 )}
superior
2− exhibited performance
superior in the
performance
cycloaddition
in of CO2ofwith
the cycloaddition CO2epoxides
with epoxides[19]. The[19].structural featurefeature
The structural of catalyst is that is
of catalyst thethat
COthe
2 ligand
CO2
connects with two Zn-ε-Keggin cores in a linear and symmetrical
ligand connects with two Zn-ε-Keggin cores in a linear and symmetrical µ2 -η o,o coordination μ 2 -η 22o,o coordination

pattern(Figure 17).
pattern(Figure 17). Polyoxoniobates
Polyoxoniobates(DBUH) (DBUH) 3(NbO5), (TBA)6[Nb10O28] and Na16[SiNb12O40] were
3 (NbO5 ), (TBA)6 [Nb10 O28 ] and Na16 [SiNb12 O40 ] were
applied as Lewis base-type catalysts for the
applied as Lewis base-type catalysts for the cycloaddition of cycloaddition of CO
CO22 with
with epoxides
epoxides under under halide-free
halide-free
conditions [84–86]. Carbon nanotubes-supported Fe
conditions [84–86]. Carbon nanotubes-supported Fe1.5 PMo12 O40 (theoretical formulas) obtained 57.7%
1.5PMo 12 O 40 (theoretical formulas) obtained 57.7%
propylene oxide
propylene oxide conversion
conversion and and 99.0%
99.0% propylene
propylene carbonate
carbonate selectivity,
selectivity, both
both activity
activity andand selectivity
selectivity
were higher
were higherthan than FePMo
Fe1.5 1.5PMoO 12O40, Co1.5PMo12O40, Cu1.5PMo12O40, and Zn1.5PMo12O40 (theoretical
12 40 , Co1.5 PMo12 O40 , Cu1.5 PMo12 O40 , and Zn1.5 PMo12 O40 (theoretical
formulas). The
formulas). Thegood
goodactivity
activitycan canbebeattributed
attributed to to
thethewell
welldispersion
dispersionof the Fe1.5Fe
of the PMo 12O40 on the CNTs
1.5 PMo12 O40 on the
[87]. [87].
CNTs

Figure 17. The basic building blocks (a) and coordination model of CO2 (b) in [PMo12 O40 Zn4 (CO2 )]2− .
Figurecode:
Color 17. The
Zn,basic building
yellow blocks
ball; O, red (a) and
ball; C, coordination model
white ball; MoO of CO2 (b) in [PMo12O40Zn4(CO2)]2–.
6 octahedra, green; PO4 tetrahedron,
Color code:
magenta. Zn, yellow
Reprinted with ball; O, red from
permission ball; [19].
C, white ball;
© 2018 TheMoO 6 octahedra,
Royal green; PO4 tetrahedron,
Society of Chemistry.
magenta. Reprinted with permission from [19]. © 2018 The Royal Society of Chemistry.
6. Outlook
6. Outlook
POMs are regarded as discrete metal oxide clusters with much smaller nanometric size than
bulk metal
POMsoxides, therefore
are regarded most of metal
as discrete the distinctions
oxide clusters on chemical
with much properties, especially CO
smaller nanometric 2 reductive
size than bulk
conversion-related redox property, between bulk metal oxides and
metal oxides, therefore most of the distinctions on chemical properties, especially CO2 reductive POMs were originated from
quantum size effect.redox
conversion-related Quantum size effect
property, betweenleads to the
bulk metalchanges
oxidesofand
electronic
POMs configurations.
were originatedThese from
changes
quantumarise sizethrough
effect. systematic
Quantum size transformations
effect leadsintothe thedensity
changes of electronic energy
of electronic levels as a function
configurations. These
of the size.
changes arise Bythrough
plottingsystematic
the correlation between redox
transformations in thepotential
densityand electron density
of electronic energyper volume
levels as a
(Figure
function18a) as well
of the size.asBy the diagram
plotting theofcorrelation
band structurebetween(Figure 18b),
redox the quantum
potential size effect-resulted
and electron density per
distinction on redox property 4− has been clearly
volume (Figure 18a) as well as among
the diagrambulk of
WO 3 , colloid
band structureWO(Figure
3 and [SiW O40 ]quantum
18b),12the size effect-
illustrated [88]. Despite the prevalence of both POMs and bulk oxides
resulted distinction on redox property among bulk WO3, colloid WO3 and [SiW12O40] has been as photocatalysts of harvesting
4–

light
clearly in illustrated
recent years, theDespite
[88]. smaller the
sizeprevalence
endows POMs of bothwithPOMs widerand
gapbulk
and oxides
lower reduction potentials.
as photocatalysts of
The case given 10−
harvesting lightbyinHill
recentandyears,
Geletiithe
et smaller
al. involving water oxidation
size endows POMs with catalyst
wider[Cogap4 (H
and
2 O) (PW
lower
2 O ) ]
reduction
9 34 2
(Co 4 POM) also
potentials. Themanifested
case given thebydistinction
Hill and between
GeletiiPOM et al. andinvolving
bulk metalwateroxide on redox property.
oxidation catalyst
In their report, 9−
[Co 4(H2O) 2(PW(PW9O34)9 2]O10– )
34 (Co-sandwiched Co4 unit in Co
4POM) also manifested the4 POM was unambiguously
distinction between POM identified
and bulk as the
metal
dominant active center for water splitting and not CoO . [89]
oxide on redox property. In their report, (PW9O34x) -sandwiched Co4 unit in Co4POM was
9–

unambiguously identified as the dominant active center for water splitting and not CoOx. [89]
Molecules 2019, 24, 2069 19 of 26
Molecules 2019, 24, x FOR PEER REVIEW 19 of 26

Figure 18. The effect of particle size on the flat band redox potentials (a) and schematic band structure
Figure 18. The effect of particle size on the flat band redox potentials (a) and schematic band structure
diagram of POMs and WO3 (b). Reprinted with permission from [88]. © 1997 2018 Elsevier BV.
diagram of POMs and WO3 (b). Reprinted with permission from [88]. © 1997 2018 Elsevier BV.
The prospering arising of new POM structures provides vast opportunities to excavate latent
The for
catalysts prospering
chemical arising of new POM
CO2 conversion. structures
Titanium provides
oxo-clusters [90]vast
andopportunities to excavate[91]
polyoxo-noble-metalates latent
are
catalysts for chemical CO 2 conversion. Titanium oxo-clusters [90] and polyoxo-noble-metalates [91]
exemplified as two promising representatives among these new POM structures. Regarding titanium
are exemplified
oxo-clusters (alsoas namedtwo promising
polyoxotitanates),representatives among variants
there are diverse these new POM structures.
including Regarding
titanium oxoalkoxides
titanium oxo-clusters (also named polyoxotitanates), there are
clusters Tin Om (OR)4n–2m , titanium oxo-carboxo-alkoxides clusters Tin O2n–x/2–y/2 (OR)x (OOCR’) diverse variants including titanium
y , and
oxoalkoxides clusters Ti nOm(OR)4n–2m, titanium oxo-carboxo-alkoxides
titanium oxocarboxo clusters [Tin Om (OOCR)p ] (2m + p = 4n) [90]. The tunable wide polynuclearity clusters Ti nO2n–x/2–

y/2(OR)x(OOCR’)y, and titanium oxocarboxo clusters [TinOm(OOCR)p] (2m + p = 4n) [90]. The tunable
(the number of titanium atoms n varies from 2 to 28) and facile fabrication of hybrid architectures with
wide
organic polynuclearity
components by (thecovalent
numberbonding of titanium are theatoms
twonmajorvariesfeatures
from 2of tothese
28) and facile MOF
clusters. fabrication
MIL-125 of
hybrid
(MIL standsarchitectures
for Material with from
organic components
Insitut Lavoisier)byconsisting
covalent of bonding are the two major features of
1,4-benzenedicarboxylate-connected
these clusters. MOF MIL-125 (MIL stands for Material
titanium-oxo-hydroxo clusters has been reported to possess possible photocatalytic from Insitut Lavoisier) consisting
propertyofwhen 1,4-
benzenedicarboxylate-connected
alcohols are adsorbed inside its framework titanium-oxo-hydroxo
[92]. Basedclusterson this has been reported
indication and as thetoextensive
possess
possible photocatalytic property when alcohols are adsorbed inside
applications of titanium oxide in CO2 photocatalytic reduction [93–95], there are likely to be extensive its framework [92]. Based on this
indication and as the extensive applications of titanium oxide
catalytic application of hybrid materials containing titanium oxo-cluster cores in CO2 reductive in CO 2 photocatalytic reduction [93–

95], there areThe

conversion. likely to be extensive
emergance of variouscatalytic
novel application of hybrid materials
polyoxo-noble-metalates containing
including titanium oxo-
polyoxopalladates,
cluster cores in CO 2 reductive conversion. The emergance of various novel polyoxo-noble-metalates
-platinates, and -aurates [91] also provides different prospects for catalytic CO2 reductive conversion.
including polyoxopalladates, -platinates,
On these polyoxo-noble-metalates, the noble andmetal
-auratesatoms[91]Pd,alsoPt, provides
and Au act different prospects
as “addenda” atomsfor
catalytic
rather than CO2as reductive
heteroatoms conversion. On thesethat
[91]. Despite polyoxo-noble-metalates,
there are no direct accessible the nobleactive
metalsites
atoms onPd,
noblePt,
and Au act as “addenda” atoms rather than as heteroatoms
metal centers with saturated coordination environments, the very recent report about the catalytic[91]. Despite that there are no direct
accessible
Suzuki-Miyaura active cross-coupling
sites on noble metal centersofwith
application saturated coordination
polyoxopalladate-based MOFenvironments,
materials hasthe very
implied
recent report about the catalytic Suzuki-Miyaura cross-coupling
that these polyoxo-noble-metalates may acquire catalytic activity via in situ partial reduction [96]. For application of polyoxopalladate-
based MOF materials
polyoxoplatinate [Pt12 O has(SOimplied 4− that
[97],these polyoxo-noble-metalates may acquire catalytic activity
8 4 )12 ] although it is insoluble in any media, its six dumbbell-shaped
via
[Pt2in]6+situ partial
anionic reduction
units perhaps[96].willFor polyoxoplatinate
attract electrocatalytic[Pt 12O8(SO4)12] [97], although it is insoluble in
research
4–
interests, because they may be in-situ
any media, its six dumbbell-shaped [Pt 2]6+ anionic units perhaps will attract electrocatalytic research
partially reduced to molecular mixed-valent metal clusters or platinum black-type “suboxides” [98].
interests,
Then these because
plausible theyin-situ
may be in-situ partially
generated species may reduced to molecular
be applied as HER mixed-valent
catalysts formetal clusters or
electromicrobial
platinum
conversion black-type
of CO2 . “suboxides” [98]. Then these plausible in-situ generated species may be applied
as HER catalysts
More than the for mode
electromicrobial
of LMCT, developingconversion of CO2.
POM-based catalysts with the intrinsic function of
More than the mode of LMCT, developing
metal-to-metal charge transfer (MMCT) will also be beneficial to look for POM-based catalysts with the efficient
more intrinsic POM-based
function of
metal-to-metal charge transfer (MMCT) will also be beneficial
approach to harvest visible-near infrared emission of sunlight with higher quantum yield. The to look for more efficient POM-based
approach
MMCT transition to harvest occurs visible-near
when two infrared
metal centers emissionwith of sunlight
different withstates
valence higher
arequantum
coupled by yield. The
bridging
MMCT
ligands transition
(Ma+ -O-M’occurs b+ ). The when two metal
two metal centers centers with different
are respectively reduced valenceand states
oxidized are(M coupled
a+ -O-M’by b+
bridging
→M (a−1)+ligands
-O-M’ (M
(b+1)+ a+-O-M’b+). The two metal centers are respectively reduced and oxidized (Ma+-O-
) during this transition. The MMCT transition often takes place in polynuclear
M’ b+ → M (a-1)+-O-M’(b+1)+) during this transition. The MMCT transition often takes place in
complexes [99]. The oxo-bridged and all-inorganic heterobinuclear units such as ZrIV -O-CoII [100–103],
polynuclear
ZrIV -O-CuI [104], complexes [99]. II
TiIV -O-Co The oxo-bridged
[100], and TiIV -O-Mnand all-inorganic heterobinuclear
II [105] supported units such
on silica material thatas display
ZrIV-O-
Co
MMCT
II [100–103], ZrIV-O-CuI [104], TiIV-O-CoII [100], and TiIV-O-MnII [105] supported on silica material
transitions can extend the optical absorption from UV to visible regions. Some of these
that display
materials have MMCT transitions
been applied can extend
as catalyst the optical
or cocatalyst for absorption from UV [101–104].
CO2 photoreduction to visible regions. Some of
Several reported
these materials have been applied as catalyst or cocatalyst for CO
POM-based systems, such as the anchored polynuclear charge-transfer complexes consisting of CeIII ions2 photoreduction [101–104]. Several

reported POM-based
and CuII -substituted systems, Cu
Keggin-type suchII PW as Othe[106],anchored polynuclear
the metal-oxide charge-transfer
nanoclusters consistingcomplexes
of CeIII or
11 39
consisting of Ce ions and Cu -substituted Keggin-type Cu PW11O39 [106], the metal-oxide
III II II

nanoclusters consisting of CeIII or CoII ions and Keggin-type PW12O403– [107], [CoIIW12O40]6– [108], and
Molecules 2019, 24, 2069 20 of 26

CoII ions and Keggin-type PW12 O40 3− [107], [CoII W12 O40 ]6− [108], and [CoII (Mx OHy )W11 O39 ](12-x-y)−
(Mx OHy = VIV O, CrIII (OH2 ), MnII (OH2 ), FeIII (OH2 ), CoII (OH2 ), NiII (OH2 ), CuII (OH2 ), ZnII (OH2 )) [109]
have sufficiently demonstrated the feasibility that such molecular inorganic MMCT (or MPCT,
metal-to-polyoxometalate charge transfer) [108,109] transition enable POM-based catalyst to function
as efficient visible-light-driven multielectron-transfer catalysts. Regarding the metal-oxide nanoclusters
consisting of CeIII or CoII ions and Keggin-type PW12 O40 3− , even the straightforward video guide of
preparing catalytic material has been given [110]. These will further encourage to utilize MMCT of
POM-based catalytic materials in CO2 reduction. It is noteworthy that prolonging the picosecond-scale
lifetimes of photogenerated states during MMCT transition is still an important issue to be tackled [111].
The works from Lan and Hill et al. has validated the effects of heterometal location [108] and different
addenda substitution [109] on the lifetime of photo-excited state.
On the other hand, the tools of advanced operando spectral characterization techniques [112],
electrochemical measuring methods [113] and theoretical calculations [114], imbibing more
understandings and attaining insights on catalytic mechanisms and structure–reactivity relationships
of those reported POM-based catalysts will be helpful to design better POM catalysts for CO2
conversion with explicit destination. On CO2 photo/electroreduction, the hybridation of POM with
various novel materials can provide chances to fabricate catalysts with broader visible-light absorption
spectrum region or better selectivity but lower overpotential. In those systems with hybrid electro- or
photocaytalytic CO2 catalysts, once the light-harvesting/electron-storage centers and catalytically active
sites are designated in an integrated system, the key issue is the bridging of the two components—charge
kinetics. Exploiting time-resolved spectroscopic techniques to characterize charge kinetics is useful to
understand these hybrid catalysts and thus helps to improve their catalytic efficiencies [99].
In catalytic oxidation, POMs were looked upon as inorganic analogs of porphyrin [115–117]. The
thriving development of transition metal porphyrin or phthalocyanine derivatives as heterogeneous
molecular catalysts for electrochemical CO2 reduction [118] makes us have such confidence that
this analogy can be still established in electrochemical CO2 reduction. Therefore, the accumulated
understandings about electrochemical CO2 reduction by transition metal porphyrin or phthalocyanine
may help the development of POM-based catalysts for the electroreductive CO2 conversion. By sunlight
or solar electricity, producing fuels and chemicals via CO2 conversion is a promising and reliable option
for largely reducing fossil fuel consumption in the future [119]. Thus POM-catalyzed transformation
of CO2 with photo- or electrochemical methods will retain long-lasting interest of both academic and
industrial research.
To the non-reductive CO2 conversion, searching for POMs with stronger Lewis basicity will
benefit the elevation of turnover efficiency and the mitigation of harsh conditions under halogen-free
condition. To enhance Lewis basicity, high negative charge density on the terminal oxygen atoms on
POMs is required. Calculating and comparing natural bond orbital (NBO) charges of oxygen atoms
in POMs has been demonstrated as a useful access to gain more insights into the Lewis basicity on
POMs [84,120]. Making full use of both structural traits and diversity of POMs would help to break
through some ceilings of practical CO2 chemical conversion.

Author Contributions: Writing—original draft preparation, Y.C., Q.C., C.S.; writing—review and editing, Y.C.,
C.S., L.H.; conceptualization and project administration, L.H. The manuscript was written through contributions
of all authors. All authors have given approval to the final version of the manuscript.
Funding: This work was supported by NSFC (91645118) and NSF of Jiangsu Province (BK20180249).
Conflicts of Interest: The authors declare no conflicts of interest.

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