Covalent conductive polymer chain and organic ligand ethylenediamine modified MXene-like-{AlW12O40} compounds for fully symmetric supercapacitors, electrochemical sensors and photocatalysis mechanisms

Article abstract of DOI:10.1039/c9ta14103k

We successfully synthesized two kinetically stable covalent polymer chains and ethylenediamine modified MXene-like-{AlW₁₂O₄₀} compounds. According to the energy storage research results, these materials showed high capacitance performance and cycle stability. The capacitance values of the 1-CC (carbon cloth) and 2-CC materials are 478.41 and 625.99 F g^-1 (1.0 A g^-1), and the capacitance retention is 95.71% and 97.62% after 5000 cycles, respectively. The symmetric water system supercapacitor device was assembled with two 2-CC and achieved an energy density of 6.32 W h kg^-1 at 237 W kg^-1. Compounds 1 and 2 were used to test the new sensitive current hydrogen peroxide sensor, displaying linear ranges of 1.20-3.20 mM (1-GCE: glassy carbon electrode) and 19.95 μM to 0.90 mM (2-GCE) with a detection limit of 0.93 μM and 0.86 μM, respectively. In addition, the photocatalysis mechanisms of compounds 1 and 2 were studied to provide a powerful basis for the photocatalytic mechanism of this series of compounds.

Full text of DOI:10.1039/c9ta14103k

View Article Online
View Journal
Journal of
Materials Chemistry A
Materials for energy and sustainability
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: L. G. Gong, X. Qi,
K. Yu, J. Gao, B. Zhou and G. Yang, J. Mater. Chem. A, 2020, DOI: 10.1039/C9TA14103K.
Volume
Number 12
March 2018
Pages 4883-5230
6
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
28
Journal of
Materials Chemistry A
Materials for energy and sustainability
rsc.li/materials-a
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 2050-7488
COMMUNICATION
Zhenhai Wen et al.
An electrochemically neutralized energy-assisted low-cost
acid-alkaline electrolyzer for energy-saving electrolysis
hydrogen generation
rsc.li/materials-a

Page 1 of 13
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
View Article Online
DOI: 10.1039/C9TA14103K
Journal Name
ARTICLE
Covalent conductive polymer chain and organic ligand
ethylenediamine modified MXene-like-{AlW O } compounds for
fully symmetric supercapacitors, electrochemical sensors and
photocatalysis mechanisms
1
2
40
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
a
a
a*
a
a*
b*
Li-Ge Gong , Xian-Xian Qi , Kai Yu , Jia-Qian Gao , Bai-Bin Zhou , Guo-Yu Yang
www.rsc.org/
We successfully synthesized two kinetically stable the covalent polymer chains and ethylenediamine acting MXene-like-
40} compounds. According to the results of energy storage research, these materials show high capacitance
{AlW12O
-1
-1
performance and cycle stability. The capacitors of 1-CC(carbon cloth) and 2-CC are 478.41 and 625.99F g (1.0 A g ), and
the capacitance retention is 95.71% and 97.62% after 5000 cycles. The symmetrical water system supercapacitor device is
assembled with two 2-CC and the energy density of 6.32Wh kg-1 at 237W kg . Meanwhile, compounds 1-2 were used to
test the new sensitive current hydrogen peroxide sensor, display that the linear ranges are 1.20-3.20mM(1-GCE:glassy
carbon electrode) and 19.95µM-0.90mM(2-GCE) with the detection limit of 0.93µM, 0.86µM. In addition, the
photocatalysis mechanisms of compounds 1-2 were studied to provide a powerful basis for the photocatalytic mechanism
of this series of compounds.
-1
2
7
can be exploited in many fields, such as electrochemistry , energy
storage/conversion , magnetism , catalysis30-31, photochemistry32,
2
8
29
Introduction
3
3
34-39
and sensors40-45. In particular,
ionic conductors , medicine
POMs have discrete ionic structures, including heteropoly anions
and movable countercations, such as H+,
With the rapid growth of the world's population, the deterioration
of the ecological environment and the shortage of fossil resources
left people urgently to pursue sustainable and renewable energy,
which in turn promotes the vigorous development of various clean,
efficient energy conversion and storage equipment, such as,
lithium-ion batteries1-6 supercapacitors (SCs)7-15 and fuel cells16-20
Among them, SCs have emerged from the numerous energy storage
devices because of their fast charging ability, long cycles stability,
high power density and environmental friendliness21-22. However,
electrode materials are one of the important factors that affect the
capacitance of SCs. The research on electrode materials which
improve the specific capacitance and cycles stability has grown up
to be a hot topic in the research of high performance SCs.
Polyoxometalates (POMs), an outstanding class of metal-oxygen
clusters, possess unparalleled versatile physical and chemical
properties, including attractive well-defined structures, regular
sizes, superior redox properties and can be used as electron
reservoirs23-26. In view of the generality mentioned above, POMs
+
H
3
O . This unique
structural feature enables POMs to perform fast and reversible
stepwise numerous electrons transfer reactions without changing
their structures, which makes POMs an excellent candidate for
supercapacitor electrode materials. However, POMs have some
shortcomings, such as the high solubility, poor cycling ability and
conductivity. To overcome these problems, many researchers have
proposed some solutions. On the one hand, since Gomez-Romero
et al.46 first reported that hybrid nanocomposites formed by
.
3
Polyaniline and H PMO12O40 as electrodes for supercapacitor, there
have been some reports47-48 of composites based on POMs and
conductive polymers materials. Conductive polymers can improve
the conductivity of POMs and facilitate electron transfer. However,
immobilization of POMs into a polymer matrix limits the redox
active sites of POMs and thus constrains their supercapacitor
performance.49 On the other hand, some researchers50-53 have
proposed the synthesis of hybrid coordination polymers by covalent
bonding of transition metals, organic ligands and POMs to solve the
problem of high solubility and low conductivity,but the low cycle
stability has not been alleviated.
a. Key Laboratory for Photonic and Electronic Band gap Materials, Ministry of
Education, Harbin Normal University, Harbin 150025, People's Republic of China.E-
mail: hlyukai188@163.com, zhou_bai_bin@163.com
Therefore, we propose a new approach based on the above-
mentioned researchers' approach: (1) Among central atoms of the
most Keggin type POMs are mainly group 14 and 15 elements and
some transition metals, which group 13 as central atoms have been
rarely extensively exploration54-55. It is noted that aluminium atoms
b. MOE Key Laboratory of Cluster Science, School of Chemistry, Beijing Institute of
Technology,Beijing, 100081 (China).Email:ygy@bit.edu.cn
†
Electronic Supplementary Information (ESI) available. CCDC : 1943851 and 1943852.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Page 2 of 13
ARTICLE
Journal Name
can not only as coordination atom56-59, but also be used as the 2.14(3)Å] and one {AlW12} [Ag-O:2.64(3)Å]. each Ag2 ion links 4,4’-
View Article Online
central atom, which the introducing of Al3+ into the center of Keggin bipy ligands into a one-dimensional polymeriDcOcIh: a10in.10[n3a9m/Ce9lTyA,1{4-410,43’K-
structure makes it easier to coordinate to transition metals and bipy-Ag2-4,4’-bipy-}
gives a wider kind of coordination types, owing to the [AlW12
40]5- In the structure, each Ag2 ions from two {-4,4’-bipy-Ag2-4,4’-bipy-}
anion possesses higher surface charge density . At the same time, chains link {AlW12} units through O atoms to form a 1D ladder
n
.
O
n
6
0
t
the aluminum atom is a boron group element which is electron- chain(Fig.S2). The most intriguing feature of 1 is the novel 2D sheet
deficient and has a strong tendency to make full use of valence structure(Fig.S3a) constructed by the strong polymerization
6
1
orbitals in order to enhance the stability of the system . (2) between that of the adjacent 1D ladder chain and {AlW12
40]5- anion connects with the chain of transition metal polyoxoanion. In this 2D structure, the {-4,4’-bipy-Ag1-4,4’-bipy-
complexes similar to conductive polymers through covalent bonds, Ag1-} chains are linked not only to [AlW12
40]5- units through
which not only solves the problems of high solubility and poor supramolecular interaction, but also to {-4,4’-bipy-Ag2-4,4’-bipy-}
}
[
AlW12O
n
O
n
circulation, but also increases the conductive energy and specific through π-π stacking interaction to form a new 2,4,6-connected
capacitance of the composites. As d10 transition-metal, the Ag(I) topology structure(Fig.S3b) with the aperture of 19.12×16.28 Å . In
and Cu(I) possesses high affinity for O and N donors,various this topology structure, Ag1 ions were assigned as four-connected
coordination numbers and versatile geometries62-69. 4, 4-bipyridine nodes, Ag2 ions as two-connected nodes and {AlW12} as six-
2
4
is an organic ligands similar to pyrrole, which contains many N connected nodes, then the topology symbol is {4.6 .8}
6
4
4
2
donors to facilitate coordination with metal ions. These features {4 .6.8 .10 }{4} . Besides, 2D layers formed 3D network via π-π
make Ag(I) and Cu(I) to use as a metallic linker to construct stacking interactions of {-4,4’-bipy-Ag1-4,4’-bipy-Ag1-}
n
chains of
transition metal complexes with 4,4-bipyridine ligands. (3) The small adjacent layers(Fig. S4).
ligand ethylenediamine was introduced to increase the interaction In the overall structure of compound 1, {-4,4’-bipy-Ag1-4,4’-bipy-
between POMs and transition metal complexes to reduce the Ag1-} polymer chain form a 1D pipe structure(Fig.1a) by connecting
resistance of the whole compound. oxygen from {AlW12}(Fig.1b), and{-4,4’-bipy-Ag2-4,4’-bipy-}
In this work, we prepared two new organic-inorganic hybrid polymer chain(Fig.1c) is located in the 1D pipe through hydrogen
compounds, [Ag(bpy)][{Ag(Hbpy)} O (1), [H en][{Cu- bonding and supramolecular interaction. The 1D pipe connected
bpy)} 40)] · 3H
O (2). The compounds 1-2 as electrode with {AlW12} to form a MXene-like layer structure70-71. Each MXene-
n
n
2
(AlW12
O
40)] ·H
2
2
(
3
(AlW12
O
2
materials have high capacitance and excellent cycling ability and like layer forms a 3D stacking structure(Fig.1d-e) through hydrogen
have been assembled into symmetrical SCs. In addition, the bonding and supramolecular interaction, and the distance between
electrochemical sensors and photocatalytic mechanisms of the layers is 11.36Å. The structure similar to MXene with metal
compounds 1-2 were studied in detail.
polymer chains is beneficial to increase the migration speed and
conductivity of ions and electron for SCs.
Results and discussion
Crystal structure
The structures of compounds 1 and 2 are all built on [α-AlW12O
40]5-
(
{
abbreviated as {AlW12}) and the transition metal complexes. The
AlW12} consists of a central AlO tetrahedron surrounded by four
13 groups. Each W 13 group is composed of
octahedra linked in a triangular arrangement by sharing
edges, and these four W 13 groups are linked together by sharing
4
vertex-sharing W
three WO
3
O
3
O
6
Fig 1. The 3D structure of compound 1: (a) 1D pipe structure (b)
3
O
{
n
AlW12} (c){-4,4’-bipy-Ag2-4,4’-bipy-} polymer chain is located in
corners. The central Al-O distances vary from 1.72(7)-1.75(8)Å in 1
and 1.74(9)-1.76(11)Å in 2, respectively. All bond distances are
equal to the reported range. {AlW12} possesses four kinds of oxygen
the 1D pipe (d) The front view (e)The side view
Crystal structure analysis reveals that compound 2 consists of one
atoms, the terminal oxygen atoms(O
oxygen atoms(O ), corner-sharing bridging oxygen atoms(O
central oxygen atoms(O ). Therefore, for compounds 1-2, W-O
t
), edge-sharing bridging
+
2+
2
{AlW12}, three [Cu(4,4’-bipy)] fragments and [H en] . As shown in
b
c
), and
Fig.S5, there are three crystallographically independent Cu ions in 2:
Cu1, Cu2 and Cu3 ions adopt T-shaped geometry, which link with
two
polyoxoanion through a bridging oxygen atom(for Cu3) or a
terminal oxygen atom (for Cu1 and Cu2). The bond lengths of Cu-N
are in the range of 1.89(7)-1.91(8)Å and Cu-O is 2.32(6)Å.
Moreover, Cu1,Cu2 and Cu3 formed two p olymer chains with 4,4’-
bipy ligands, (namely, {-4,4’-bipy-Cu1-4,4’-bipy-Cu3-}
bipy-Cu2-4,4’-bipy-Cu2-} ). {-4,4’-bipy-Cu1-4,4’-bipy-Cu3-}
a
distances are 1.64(3)-2.41(4) Å and 1.69(6)-2.28(5) Å, respectively.
N atoms from two 4,4’-bipy ligands and one {AlW12}
Crystal structure analysis reveals that compound 1 consists of
+
{
AlW12}, [{Ag(Hbpy)}
2
]4+ and [Ag(bpy)] . As shown in Fig.S1, there is
two crystallographically independent Ag ions(Ag1, Ag2) in 1: Ag1 ion
exhibits a linear geometry coordinated by two nitrogen atoms from
two 4,4’-bipy ligands [Ag-N:2.10(3)]. Each Ag1 ion links 4,4’-bipy
ligands into a one-dimensional polymeric chain [namely,{-4,4’-bipy-
n
and {-4,4’-
and {-
n
n
n
Ag1-4,4’-bipy-Ag1-} ]. Ag2 ion adopts T-shaped geometry, which
links with two N atoms from two 4,4’-bipy ligands [Ag-N:2.11(3)-
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 13
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Journal Name
ARTICLE
4
,4’-bipy-Cu2-4,4’-bipy-Cu2-}
n
) are parallel to each other to form an 962, 882, 812, and 761 cm-1 for 2, respectively, which can be
View Article Online
DOI: 10.10 37 39 /C9TA14103K
ABAB polymer plane.
t a b c
assigned to ν(W-O ), ν(Al-O ), ν(W-O ), and ν(W-O ) . In addition,
In the structure of compound 2, {AlW12} units link Cu3 ions from the characteristic absorption bands in the range of 1208-1612cm-1
two {-4,4’-bipy-Cu2-4,4’-bipy-} chains through terminal oxygen for compounds 1 and 2 are attributed to the en and 4,4 ’ -bipy
atoms to form a 1D chain(Fig.S6). The adjacent 1D ladder chains are ligands. The peaks at 3496 and 3442cm-1 are assigned to the
connected by two {-4,4’-bipy- Cu1-4,4’-bipy-Cu3-} chains and {-4,4’- vibration of water molecules for compounds 1 and 2.
fascinating sheet To investigate the thermal stabilities of compounds 1 and 2, TG
new topology. In this topology analyses were carried out, as shown in Fig.S10. From the TG curves,
n
n
bipy-Cu2-4,4’-bipy-Cu2-}
structure(Fig.S7a) with
n
chain form
a
a
structure(Fig.S7b), Cu1 ions were assigned as three-connected the weight loss processes both have two weight loss steps. In
nodes, Cu2 ions as three-connected nodes, Cu3 ions as four- compound 1 (Fig.S10a), the first weight loss of 0.55% between 50-
connected nodes and {AlW12} polyoxoanion as four-connected 265 ℃ could be attributed to the loss of water molecules(calc.
2
4
2
nodes, then the topology symbol is {6 .8}{6 .8 } with the different 0.48%). The second weight loss of 12.72% in the range of 500-700℃
2
2
sizes of holes (ABAB arrange), 19.41×15.36Å and 17.90×17.10Å , assigned to the loss of 4,4 ’ -bipy molecules (calc.12.60%). In
respectively. Furthermore, 2D layer interacts with ethylenediamine Fig.S10b, the TG curve for 2 shows a first weight loss of 0.74%
molecules through hydrogen bond to form 3D network (see Fig. S8). between 30-200 ℃ suggesting the loss of water molecules
From the whole structure, compound 2 is more characteristic than (calcd.1.48%). When the temperatures increases from 500 to 750℃,
compound 1. On the one hand, compound 2 has a 1D ions the weight loses 13.00% indicating the loss of 4,4 ’ -bipy and en
pipeline(Fig. 2a) formed by the connection between the same molecules (calcd. 14.54%).The weight losses from the TG curves are
polymer chain with {-4,4’-bipy-Cu1-4,4’-bipy-Cu3-}
terminal oxygen from {AlW12}(Fig. 2b), and {-4,4’-bipy-Cu2-4,4’- XRD patterns for compounds 1 and 2 are presented in the Fig. S11.
bipy-Cu2-} is occupied in the 1D pipe through the covalent bond The diffraction peaks of both simulated and experimental patterns
n
and the consistent with the molecular formula of compound 1 and 2. The
n
intereaction. On the other hand, the addition of are matched, thus indicating that the phase purity of the
ethylenediamine(Fig. 2c) increases the interaction between the a compounds 1 and 2 are good. The differences of intensity may be
MXene-like layers to form a 3D structure (Fig. 2d-e)with the wider due to the preferred orientation of the crystal samples.The UV
layer spacing of 13.71 Å, which makes compound 2 had better ion spectra are measured in the solid state as shown in Fig.S12 in the
and electron transport ability than compound 1.
range of 200-800nm. Two absorption bands appear at 215-217 nm
and 290-320 nm for 1-2 in the UV spectras, which are attributed to
*
pπ(Oterminal)→dπ (M) electronic transitions in the W=O bonds and
dπ-pπ-dπ electronic transitions between the energetic levels of the
7
4
W-O-W bonds , respectively.
The surveys of diffuse reflectivity for powder samples of 1-2 were
used to gain their band gaps (Eg), which were determined as the
intersection point between the energy axis and the line
extrapolated from the linear portion of the adsorption edge in a
plot of Kubelka-Munk (K-M) function (F) versus energy (E). As
shown in Fig.S13, the Eg values assessed from the steep absorption
edge of 1 and 2 were 2.90eV for 1 and 2.95eV for 2. The reflectance
spectra suggested that compounds 1-2 would be potential
photocatalysts, because of the presence of an optical band gap and
the semiconducting properties.
Fig 2. The 3D structure of compound 2: (a) {AlW12} (b){-4,4’[-bipy-
n
Cu2-4,4’-bipy-Cu2-} is occupied in the 1D pipe (c) ethylenediamine
(d) The front view (e) The side view
Structural and morphology characteristics of compounds 1-2
The Barrett-Emmett-Teller (BET) specific surface area of the
samples are measured by the t-plot method. The values of the BET
The valence bond calculation(BVS)72 shows that the average values
of the W centers of compounds 1 and 2 are 5.87 and 5.92,
respectively, which are equal to almost all W atoms in the +6
oxidation state. At the same time, BVS calculation shows that all Ag
and Cu centers are in the oxidation state of +1 for compounds 1-2.
In addition, one extra proton is added to the bipyridine ligand in
compound 1 and two extra protons should be added to the
ethylenediamine ligand in compound 2 to achieve charge balance,
which is consistent with the acid reaction environment.
2
surface area and langmuir surface area are 65.73 and 115.49 m /g
2
for compound 1, 87.74 and 158.25 m /g for compound 2(Fig S14).
The average desorption pore sizes(Fig. S15) from DFT method are
3
.41nm for compound 1 and 2.13 nm for compound 2. As shown in
Fig.S16a-b, the XPS of the compound 1(or compound 2) has Ag(or
Cu), W, O, Al, N and C elements, and the slight difference between
the atomic ratio and the molecular formula is due to the fact that
the XPS test does not contain H atoms. Two peaks75 at 37.68,
The IR spectra of compounds are shown in Fig.S9, which exhibits
characteristic vibration patterns derived from the Keggin
3
5.48eV for compound 1 and 37.33, 35.13eV for compound 2 may
6+
attribute to the W4f7/2 and W4f5/2 core levels of W , respectively
-1
polyoxoanions in 700-1000 cm . There are four characteristic bands
(Fig. S17a and Fig. S18a). The Al2p spectrum has a main peaks of
in the IR spectra appearing at 953, 887, 802, and 766cm-1 for 1, and
7
3.17eV for compound
1
and 73.30eV for compound 2,
J. Name., 2013, 00, 1-3 | 3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Page 4 of 13
ARTICLE
Journal Name
respectively(Fig. S17b and Fig. S18b), showing that the existence of
Al . The C spectra has a main peaks of 284.9eV for compound 1
and 284.59eV for compound 2, respectively(Fig. S17c and Fig. S18c),
which belongs to the C1s. The N1s spectrum48 is divided into two
i = avb
(1)
View Article Online
DOI: 10.1039/C9TA14103K
3
+
where a and b are the coefficients, i is the peak current density(A),
-1
and v is the scan rate (mV s ). The calculated value of b can be
distributed into capacitive and diffusion controlled charge
contributions for the charge storage mechanism in the electrode
peaks(Fig. S17d and Fig. S18d), which can be attributed to the -N=
+
and-NH -/-NH-fragments (399.38 and 401.68eV for compound 1
material. If b=0.5 (i∞v1/2) for the diffusion-controlled charges (Q
and b=1 (i∞v) for the surface capacitive (Q ). As shown in Fig. S24
and Fig.3c, good linear relationship is observed between
log(current density) and log(scan rate) for Na 40-, 1- and 2-
CC electrodes and and the b values are observed to be 0.93, 0.92,
and 0.90, respectively. The larger b value of these electrodes
indicated the kinetics behaviors are mainly quite attributed to the
d
)
and 399.2 and 401.6eV for compound 2). The O1s spectra reveal the
co-existence of C-O and C=O (532.08 and 531eV for compound 1
and 532.1 and 531eV for compound 2). Furthermore, the Ag3d
spectrum has two main peaks of 368.08 and 374.08eV for
compound 1, and they can clearly demonstrate the existence of Ag+
s
a
5
AlW12O
(
9
Figure S17e). In addition, the Cu2p spectrum has a main peak at the
32.9eV, and the existence of Cu (Fig. S18e) for compound 2.
+
40
surface layer capacitance due to the redox reaction of {AlW12O }
and the pseudocapacitances from the transformation of W (W to
As shown in Fig.S19a, S21a, the SEM of compounds 1 and 2 show
the morphology of block shape and the length and width of 400µm
6
+
5
+
W ).
×
297µm for compound 1 and 314µm × 107µm for compound 2,
respectively. EDS microanalysis of compounds 1 and 2 were shown
in Fig.S19b, S21b, which can be clearly seen in that the elements O,
C, Al, Cu(or Ag), N, and W were existenced. At the same time,
mapping diagram(Fig.S20 and S22) further confirmed that the
composition of compounds 1-2 were equably distributed.
At the same time, we further studied and separated the
contributions of capacitive and diffusion controlled charge from the
total charge storage(Q), using an approach reported elsewhere :
7
6
Q=Q +Q (2)
c
d
The contribution of Q
surface adsorption, which is the combination of a false capacitance
and a double-layer capacitor, and the contribution of Q is the
redox reaction ascribed to the electrode materials. Supposing the
semi-infinite linear diffusion processes at a fixed potential, Q is
obtained by plotting the stored charge(Q) vs. the reciprocal of the
square root of the scan rate and Q vary according to the scan rates.
c
is related to the scan rate, mainly due to
Electrochemical measurements
Cyclic voltammetry studies
d
The unique polymer chains, the small molecule ligands of
ethylenediamine, and multi-electron transfer process of
c
Na
potential applications in SCs. Three-electrode cyclic voltammetry
CV) curves at the 20 mV s-1 scan rate in 0.5M H
SO are presented
5
AlW12O40-, 1- and 2-CC provoke us to further investigate their
d
Hence, the total charge stored can be represented by the following
equation:
(
2
4
in Fig. 3a. The specific capacitances of these compounds are
correlated to the average areas of the CV curves which follow the
Q= Q
c
+ kv1/2
(3)
order of 2-CC> 1-CC> Na
polyanions, the specific capacitances of 2-CC with {-4,4’-bipy-Cu-4,4’
bipy} polymer chains and small-molecule ethylenediamine ligands
are much higher than 1-CC with {-4,4’-bipy-Ag-4,4’-bipy} , and the
capacitance of the Na 40 is the smallest of the three
compounds. These results clearly demonstrate that the specific
capacitances of {AlW12} materials are related to the polymer chains
and small-molecule ligands as well as their structural features. Fig.
S23 and Fig. 3b show the CV curves of 1-CC and 2-CC with a
potential window from -0.2 to 0.9 V at different scanning rates.
Clearly, 1-CC and 2-CC show the quadrilateral shape with a pair of
redox peaks, indicating the coexistence of both the electrical
double-layer capacitance and pseudocapacitance. With the increase
of scan rates, the current response is likewise gradually increased,
exhibiting good capacitive behaviour and charge storage
characteristics.
5
AlW12O40-CC. With the same {AlW12}
Where k is a constant. Fig. S25(a-c) are the linear diagram of Q and
the square root reciprocal of the scan rate(v-1/2) for Na
- and 2-CC electrodes, shown that the storage charge ability of 2-
CC is the strongest and consistent with the CVs. Q and Q are
5
AlW12O40-,
-
n
1
n
c
d
5
AlW12O
estimated and plotted in Fig.S26 and Fig.3(d), demonstrated the
normalized contribution ratio of capacitive and diffusion controlled
-1
charge storage capacities at 5-100 mV s . There are clearly seen
that the diffusion-controlled process contribution decreases
-1
gradually with increasing the scan rate (from 5 to 100 mV s ), while
the contribution of Q increases. Obviously, Q is more prominent in
c
c
these electrode materials and it shows the pseudocapacitive nature
of the electrodes.
In our view, 1- and 2-CC all show similar CV curves due to their
40]5-. Since the open
similar structures on the base of same [AlW12
O
metal sites of {AlW12} polyanions all are occupied by {-4,4’-bipy-M-
,4 ’ -bipy} (M= Ag, Cu) polymer chains or small-molecule
4
n
To further analyze the total charge storage (capacitive and diffusion
controlled charge contributions) of Na AlW12O40-, 1- and 2-CC
5
electrodes were achieved by estimating the current response of CV
curves. It is known that the peak current usually follows the power
law relationship with the scan rates. As showed in equation (1):
ethylenediamine ligands. H+ ions of electrolytes can continuously
attack polyoxoanion, and its auxiliary redox process at the open
metal center is suitable. Under this experimental condition, {AlW12
}
clusters may provide an effective electron transfer with inner-
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 13
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Journal Name
ARTICLE
cluster. The reversible processes with inner-cluster may better diffusion capacity of electrode materials. As showed ViniewFiAgr.tiSc3le1Onalninde
explain the above redox reactions. These redox reactions do not Fig.4d, the R values of 1-CC(2.63 Ω) and 2-DCOC(I3: 1.401.103Ω9/)Ca9fTteAr14510003K0
require the dissociation of metal ions from {AlW12} electrode cycles have little change opposed to those before circulation,
materials, which will effectively preserve the {AlW12} structure indicating that the two compounds have excellent stability and
conductivity. The equivalent circuit diagram of EIS for 2-CC is
showed in Fig.S32. The ion diffusion coefficient (D) of these
compounds can be calculated according to the linear relationship of
Z' and the reciprocal square root of the frequency in the low
effectively in the electrochemical process.
7
7
frequency region ,
2
2
R T
D 
( 4)
2
2
4
4
2
2
A n F C 
Where R, T, A, n, F, C and σ are the gas constant, absolute
temperature, the surface area of the electrode, the number of
electrons per molecule in the oxidation process, the Faraday
constant, the concentration of ions and the Warburg factor,
respectively.
Fig.3 (a) The CVs at the 20 mV s-1 scan rate for the different
compounds (b) The CVs of 2-CC at the different scan rates (c) The b
value of 2-CC (d) Q and Q are estimated for 2-CC
c d
Galvanostatic charge/discharge
The capacitance performance of these compounds electrodes were
studied using the galvanostatic charge-discharge curves (GCD) in
0
.5M H
2 4
SO solution with a potential window from -0.2 to 0.9 V. At
-1
the current density of 1 A g , the specific capacitances of
Na
4
-1
5
AlW12
O
40-, 1- and 2-CC electrodes(Fig.4a) are 130.27F g ,
78.41F g-1 and 625.99F g (according to equation (S1)),
-1
respectively, which are consistent with the results of CV curves. Fig.
S27 and Fig.4b show the GCD curves of 1-CC and 2-CC at 1, 2 , 3 , 5
Fig.4 (a) The GCD curves at the 1 A g-1 for the different compounds
(b) The GCD curves of 2-CC at the different current densities (c)
-
1
-1
and 10 A g . When the current density of 10 A g , the specific
Cycling stability of 2-CC after 5000 cycles (d) Impedance analysis of
the 2-CC
-1
capacitances (Fig.S28) of two compounds are 85.53 F g (1-CC) and
15 F g (2-CC) respectively, demonstrating two compounds have
-1
1
the good rate capability. Meanwhile, the cyclic stability tests of
these compounds were carried out at the current density of 10 A g
In particular, σ is related to Z' by the following equation:
Z' = B+σω-1/2(5)
-
1
,
showed that the initial specific volume of 1- and 2-CC remained
5.71%(Fig. S29), and 97.62% (Fig. 4c) after 5000 cycles, which are
better stability and cycle life of POMs as electrode materials(Table Where B is a constant and ω is the frequency. Therefore, σ is the
9
-1/2
S4).
slope of the linear relationship between Z' and ω (Fig. S33). The
σ of 1-CC and 2-CC are 19.49, 5.55, respectively, and the d value of
The electrochemical
performances of these compounds were 2-CC is 12 times of 1-CC. The results show that the small molecule
compared by electrochemical impedance spectroscopy (EIS). All the ligands of ethylenediamine and polymer layer can inhibit the charge
electrodes were produced in the same way and EIS were tested transfer resistance of the compound and improve the ion transfer
before and after 5000 cycles. Each Nyquist plot consists of a ability, which would results in excellent electrochemical
depressed semicircle and a sloping line. The depressed semicircle performance for these compounds.
and the sloping line can belong to the charge transfer process and
the solid-state diffusion of ions, respectively. So the internal We also tested EIS curves for compounds 1-2 in the temperature
resistance(R) can be calculated by the depressed semicircle at the range 20-80 ℃ (Fig.S34). The electrochemical transfer resistances
high frequency. As showed in Fig.S30, R of 2-CC(2.62 Ω ) is much was obtained from the Nyquist plot by taking the diameter of the
smaller than that of 1-CC(3.38Ω), and the slope of 2-CC is greater semicircle. It suggests that the charge transfer resistance decreases
than that of 1-CC in the low frequency region, indicates that the with higher temperature in the range of measured temperature,
addition of ethylenediamine reduces R and enhances the ion- indicating that the conductivity of compounds 1-2 are strong, which
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Page 6 of 13
ARTICLE
Journal Name
is beneficial to the improvement of capacitance performance. paper is used as a separator, and the same two pieces of 2-CC
View Article Online
D2 OI: 10.1039/C9TA14103K
Fig.S35 indicates the Arrhenius plots of above two compounds. The electrodes (Fig. 6a) with an area of 1 ×1 cm are parallelly to each
-
1
activation energies derived from the plot, which are 39.21kJ ·mol
2 4
other in the 0.5M H SO . In Fig. S36, the CV curves with 0.1-0.9 V
-1
and 44.86kJ · mol , respectively. There are two predominant working window at different scan rates, indicated an excellent
mechanisms of proton conduction: Grotthuss mechanism and
Vehicle mechanism . In the Vehicle mechanism, water assists
7
8
capacitive behavior and good charge transmission in the electrode
7
9
-1
even at an extremely high scan rate of 100mV s . At the same time,
+
proton movement by facilitating transport as a H
3
O species. It is
these curves are not strictly linear, which again prove the charge
storage mechanism of compound 2 which is the combination of
Faraday quasi-capacitance reaction at the anode and cathode.
different to Grotthuss mechanism, in which a large amount of water
can assist proton transport through a hydrogen-bonded network.
Moreover, the activation energy of the Vehicle mechanism is higher
more than 20.00kJ · mol ) than that of the Grotthuss mechanism
less than 15.00kJ·mol ). So, the proton conduction of compounds
and 2 occur via Vehicle mechanism. As far as we know, this is the
2
-
During the charge process, SO
4
ions migrate to the surface of the
-
1
(
(
electrode and form an electrochemical double layer between the
-
1 80
+
cathode and the electrolyte interface. Meanwhile, H ions diffuse to
1
the anode and inserts into the 3D stacked ion transport system of
compound 2. In the process of discharge, the anodized active
first time to be studied for {AlW12}.
+
+
material removes H ions and returns H ions back to the electrolyte.
In order to further evaluate its electrochemical performance, GCD
Compared with the performances of other POMs, the higher
performance of the 2-CC can belong to the following reasons(Fig.5):
I) The {AlW12} in the 3D stacking structure is involved in the redox measurements(Fig. 6b) were performed at 1-10 A g . At the current
reaction and provides pseudo-capacitance due to the mutual density of 1 A g , the supercapacitor shows a high specific
transformation of W and W (12 electron transfer). (II) On one capacitance of 71.12 F g (according to equation (S2)). With the
hand, ethylenediamine ligands can increase the conductivity of increase of current densities, the specific capacitance of the device
-1
(
-1
6
+
5+
-1
compounds and promote electron transfer. On the other hand,the
supramolecular interaction of ethylenediamine molecules increased
decreases and the retention ratio is considered to be
-1
1
4.76%(Fig.S37) as the current density increases to 10 A g . Energy
the interaction between the MXene-like layers. (III) The wide layer
density(E) and power density(P) are two crucial factors for practical
2
distance(13.71Å) and the large hole(19.41×15.36Å
1
and
application of supercapacitors and can be calculated as follows:
2
+
7.90×17.10Å ) not only promotes the contact area with H ion, but
2
E= CU /2V (6)
also increase the specific surface area of the compounds. (IV) the
covalent bond from the polymers chains inhibit the volume change
of AlW12 and improve the stability of the structure during charge-
discharge process. The polymers chains are rich in channels, which
not only act as the pseudocapacitance to facilitate ion diffusion and
P= E/t (7)
Where C is the total capacitance of the solid state device, U is the
operating voltage, V is the device volume, t is the discharge time.
The Ragone plot of the supercapacitor based on the compound 2 is
-1
shown in (Fig. 6c). The maximum energy density of 6.32 Wh kg can
be achieved at a power density of 237 W kg-1 from the symmetrical
water system supercapacitor device, which is clearly superior to
those of many previously reported supercapacitors81-85. Moreover,
the cycling stability is important considerations for the practical
applications of fiexible SCs. Fig. 6d illustrates that the capacitance
retention is 92.32% after applying 5000 operational cycles at a
storage /transport of electrons, but also evenly disperse {AlW12
}
uniformly and prevent {AlW12} from being dissolved in the
electrolyte.
-1
current density of 10 A g . All the electrochemical studies revealed
that compound 2 can be used as the electrode of high stability
supercapacitor with increased capacitance and energy density.
Fig.5 The relationship between the structure and the performance
of the super capacitor.
Electrochemical properties of aqueous symmetric supercapacitor
device
The symmetrical water system supercapacitor device is assembled
with compound 2 as both positive and negative electrodes. Filter
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 13
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Journal Name
ARTICLE
Fig.6 The symmetrical water system SCs device: (a)Working Fig. 8 The photocatalysis decomposition rates of the (aVi)ewRhABrti,cl(ebO)nMlinBe,
Mechanism of Devices (b) The GCD curves at the different current (c) MO solution in the use of the compound 1DaOnI:d10c.o1m03p9o/Cu9nTdA214f1o0r3K5
densities (c)The Ragone plot of the SCs (d) Cycling stability after recycles.
5
000 cycles
In order to study the main active components in photocatalytic
reaction and the possible mechanism of degradation process,
benzoquinone (BQ), EDTA and isopropanol (IPA) as scavengers were
added to the photocatalytic system(different dyes) to remove the
Photocatalytic
With the rapid development of human society, the problem of
environmental pollution is becoming ever more serious, especially
water pollution endangers human life and health. Photocatalytic
degradation of organic pollutants is part of the effective ways to
purify water. As the photocatalyst, POMs have the advantages of
green, safe, thorough purification and so on. Based on the above
considerations, the performances of complexes 1 and 2 against
photocatalytic degradation of RhB, MB and MO have been
investigated under UV irradiation. During 140min of irradiation, the
-
+
2
superoxide radical(•O ), hole (h ) and hydroxyl radical (•OH). As
shown in Fig.9a，it can be seen that the degradation efficiency of
MB, MO and RhB by compound 2 decreased slightly after adding BQ
and EDTA. However, after the addition of IPA, the degradation
efficiency were significantly reduced to 65.35%(MB), 30.42%(MO)
and 54.46%(RhB), respectively, suggesting that •OH is the principal
active substance in the degradation of three kinds of dyes and the
degradation reaction is advanced oxidation processes (AOPs). We
take RhB as an example and the possible mechanisms of
photocatalysis could be deduced as described below(Fig.9b): during
photocatalytic reaction, catalysts {AlW12} form the excited-state
species ({AlW12}*) by absorbing light energy higher than the band
gap of the {AlW12} (reactions (1)). {AlW12}* captures electrons of
degradation rate (1-C/C
compounds 1 and 2 (Fig.S38), and the degradation rate of MB is
1.87% and 90.25% for compounds 1 and 2 (Fig.S39). The
degradation rate of MO is 97.38% and 95.43% for compounds 1 and
(Fig.S40) after 180min of irradiation, respectively. A contrast
0
) of RhB is 98.21% and 90.83% for
9
2
experiment was also carried out under the same conditions without
any catalyst. Few degradations of RhB, MB and MO were observed
in
2
H O molecules to form •OH (reactions(2)). The reduced {AlW12} is
rapidly oxidized by with the generation of superoxides
O
2
the
experiment,
as
shown
in
Fig.7.
8
6
simultaneously (reactions(3)) . These reactions occur circularly
when the mixture is radiated in UV light87-88. Moreover, the RhB dye
is triggered into RhB* molecules in reaction (4). Then, the RhB dye
2 2
is degraded by the • OH radicals into H O and CO after several
8
9
circular reactions (reaction (5)) .
Fig. 7 The photocatalysis decomposition rates of the (a) RhB, (b) MB,
c) MO solution under UV irradiation in the use of the compound 1
(
and compound 2.
It can be observed that the degradation process was completed,
compounds 1-2 are photocatalysts with high degradation efficiency.
Furthermore, the reuse of the catalyst can reduce the cost of the
photocatalytic process. The catalyst was centrifuged and filtered
and then immersed in another aqueous solution of the same
amount of organic dye under the same conditions. As shown in
Fig.8, the residual concentration (C/C
0
) of the three dyes remained Fig.9 (a) The degradation efficiency of MB, MO and RhB were
almost unchanged after five catalysts cycles for componds 1-2. The treated with different scavengers. (b) The possible mechanisms of
XRD of compounds 1-2 before and after five cycles photocatalytic RhB of photocatalysis for compound 2
reaction are shown in Fig.S11. Comparing the XRD of the two
In order to prove that the products of dye degradation are H
2
O and
compounds before and after five cycles photocatalytic procedure,
the position and intensity of the peaks were nearly identical. These
results suggest that compounds 1 and 2 may be a potential
photocatalyst in reduction of some organic dyes, which have
excellent stability.
CO , the samples before and after dye degradation were analyzed
2
by liquid chromatography(LC). As showed in the Fig.S41, there is no
peak after degradation, indicating that the final products are
mineralized to
2 2
H O and CO . In addition, according to the
experimental results and related theories90-93, we propose the
possible degradation mechanisms of three kinds of dyes (Fig. 10 and
Fig.S42-43). The main results are as follows: Three dyes react with
•
OH to break the bonds(1-5) to form phenols, aldehydes, quinones,
carboxylic acids and alcohols, which are finally mineralized into H
and CO . (1) the C-S bond between the linked benzene ring and the
2
O
2
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Page 8 of 13
ARTICLE
Journal Name
sulfonic group (2) the azo group (3) the C-N bond of the benzene electrochemical behaviors of 1-2-GCEs have been invVeieswtiAgratitceledOinnlinae
ring (4) the ring opening cracking of the benzene ring (5) C-C and C- 0.1M H SO + 0.5M Na SO
aqueous solutionDaOtI:d1i0ff.1e0r3e9n/tCs9cTaAn14r1a0t3eKs
2
4
2
4
N bond.
in the potential range from -0.8 to 0.5 V(Fig. S44). In the cyclic
voltammetric (CV) curves of 1 and 2(Fig.S45), there are three
reversible redox peaks, which are attributed to three continuous
tungsten redox processes, observed that there are an additional
irreversible anodic peak (IV) for 1 and for 2, which should be ascribe
to the oxidation of Ag(I) and Cu(I), respectively . Moreover, it is
different from the CV curve of supercapacitor because of its
electrolyte and voltage window. As Fig.11a and Fig.S46 shown,
9
6
cyclic voltammograms for the electrocatalytic reduction of H
-GCE and 2-GCE in 0.1M H SO + 0.5M Na SO aqueous solution. It
can be seen that, with the addition of H , the first redox peak
2 2
O by
1
2
4
2
4
Fig.10 The possible degradation mechanism of MB
2 2
O
remains almost unchanged, nevertheless other reduction peak
currents gradually increase, which indicates that the reduction of
It’s noteworthy that compounds 1 and 2 have different degradation
effects on RhB, MB and MO, which could ascribe to different
structures of dyes. Chromophores anilino-, carboxyl and unstable N+
2
H O
2
is mediated by the reduced species of polyanions in
compounds 1 and 2. According to the equation (8):
of RhB are easily damaged by external factors to form some
unstable colorless organic intermediates or other isomers of RhB,
which causes the solution to fade quickly in photocatalytic process.
2 2
CAT = 100% ×[Ip{AlW12}H O -Ip{AlW12}]/Ip{AlW12}
+
Anilino- and =S - of chromophores in MB are destroyed to fade by
where Ip{AlW12}H
current of 1-GCE (or 2-GCE) with or without H
GCE and 2-GCE have the catalytic efficiency of 96.69% and 165.65%
for 40 mM H . Depending on the above investigations, we can get
2
O
2
and Ip{AlW12} represent the oxidation peak
the external factors. Meanwhile, MB may be removed methyl and
decompose smaller organic molecules in UV irradiation. Acid azo
structure and alkaline medium of MO are relatively stable, which
requires more energy to be removed from methyl and azo
2 2
O , respectively. 1-
2 2
O
some information about the 1-GCE and 2-GCE for their potential
application in the electrochemistry and electrocatalysis fields. From
the above measurement results, it can be seen that 1-GCE and 2-
9
4
reduction in reaction . Nevertheless, RhB and MB need less energy
to achieve the structural changes leading to fading of the solution.
Besides, the photocatalytic reaction occurs in the adsorbed
phase(on the surface of a catalyst), and the model of activation of
catalysts is photonic activation by {AlW12}* with light energy higher
than the band gap of the {AlW12}, which leads to intramolecular
charge transfer and the formation of an excited-state species
GCE have good electrocatalytic activity for the oxidation of H
and there are possible to become H sensor materials. Therefore,
we will test a series of sensing performance of 1-GCE and 2-GCE to
verify whether they can become H sensor materials in practical
2 2
O ,
2 2
O
2 2
O
applications. In electrochemical sensors, sensitivity and selectivity
depend on the choice of application potential, so we detected
*
95
(
{AlW12} ) . It ’ s inferred that identical {AlW12} may be the main
reason why compounds 1 and 2 exhibit very similar conversions to
the same dye. There are several reasons for speculation as follows:
seven kinds of interfering substances (CaCl
ZnSO , KIO and NaNO ) at different application potentials. As
shown in the Fig.S47 and Fig.11b, as the applied potential moves
forward, the catalytic current for H also increases gradually.
2 4
, MgSO , NaCl, glucoes,
4
3
2
{AlW12} units possess higher surface charge density, which could
adsorb cationic dyes during the reaction process; the second reason
may be attributed to the different packing structures of them. The
preferential orientations of crystal planes of them should be
different, thus the number of POMs on crystal planes perhaps
should be different. Furthermore, the introduction of different
transition metal complexes and small molecule organic
ethylenediamine perhaps has a bearing on the catalytic activity.
2 2
O
These results show that the more sensitive the applied potential is
shifted in the forward direction, and the response current is
maximum at -0.5V. For 1-GCE, the current responses of MgSO
.40%(-0.6V), 3.87%(-0.7V) and 16.06%(-0.8V) of H at the
different potentials, and the current responses of CaCl are 4.61%(-
.6V) 13.32%(-0.7V) and 7.89%(-0.8V) of H at the different
4
are
2
2 2
O
2
0
2 2
O
potentials. The other five substances have little current response in
the range of-0.4--0.8V. For compound 2, the current responses of
Electrochemical sensor
POMs can be redox by multi-step electron transfer without very
strict experimental conditions. In addition, the process can not only
react quickly and one step at a time, but also do not decompose in
the process. Meanwhile, POMs can be used as a good sensor
material due to its excellent electrochemical and electrocatalytic
performance, and may set off a research upsurge in the field of
CaCl
2
are 4.70% (- 0.4V)and 4.13%(-0.6V) of H
2 2
O , and the current
response of NaNO
2
is 3.58%(-0.4V) of H . The other substances
2 2
O
have little current response at different voltages of -0.4--0.8V.
These above data show that 1-GCE and 2-GCE electrochemical
sensors have excellent selectivity and anti-interference ability, and -
0
2 2
.5 V is chosen as the best application potential to detect H O .
2 2
sensors. Hydrogen peroxide (H O ) is a very important small
molecular substance, and its content is closely related to human
health and quality of life. Therefore, it is the focus of research in the
world to detect hydrogen peroxide conveniently at any time. The
The sensitivity and detection range of the sensor are two important
evaluation indexes for the sensor materials. Therefore, we use
amperometric current-time (i-t) measurements to study the senor
8
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 13
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Journal Name
ARTICLE
performance of 1-GCE and 2-GCE. As shown in Fig. S48 and Fig. 11c, continuous cyclic voltammetry scanning. The reprodVuiecwibAirltiitcyle Oonflin1e-
the measurements are performed by adding different GCE and 2-GCE are carried out by imDmOeIr:s1i0n.g103t9e/nC9TidAe14n1t0ic3aKl
concentrations of H
solution at the potential of -0.5V. With the addition of H
2
O
2
in 0.1M H
2
SO
4
+ 0.5M Na
2
SO
4
aqueous electrodes under the same condition in the above-described
, the analyte solution. As shown in Fig.S51, standard deviation(RSD) of 1-
2 2
O
response current of 1-GCE and 2-GCE are gradually enhanced. GCE and 2-GCE are 2.27% and 2.04%, show that the sensors have
However, the response current of 2-GCE is more than 1-GCE, excellent reproducibility.
indicating that the addition of ethylenediamine molecule is
The mechanism of the sensor is explained according to the previous
literature97-98, and the equation is as follows:
2 2
beneficial to enhance the catalytic performance of H O , which is
consistent with the conclusion obtained by CVs. A calibration
curve(Fig. S49 and Fig. 11d) is drawn to reflect the relationship
−
−
2 2
H O + e → OHad + OH (a)
between the response current(I) and the different concentrations of
2
H
9
2
O
2
(C): I= -0.073185C-39.71112 R =0.971(1-GCE), I= -0.07052C-
−
−
OHad + e → OH (b)
2
8.9396 R =0.993(2-GCE). The broad detection range of the sensors
to H
(
2
O
2
are 1.20 mM to 3.20mM (1-GCE) and 19.95 µM to 0.90 mM
2-GCE)(signal-to-noise ratio:S/N=3) with the detection limit of
−
+
2
2
OH + 2H → 2H O (c)
0
.93µM, 0.86µM and the response time is 4s, 2s, respectively. In During the reaction, the key step of controlling the reaction rate is
order to reflect the properties of compounds 1 and 2 sensor the formation of OHad. However, compound 2 has better sensor
materials more intuitively, we compare their properties with some performance than compound 1 and other studies are as following
reported studies in Table S5, shown that the two sensors have a reasons: (1) On the one hand, polymer chains and ethylenediamine
wider linear range and a lower detection limit. These properties are ligands are beneficial to the uniform dispersion of {AlW12} and
due to the rapid and progressive electronic transfer performance promote electron transfer. On the other hand, the covalent bond of
and excellent catalytic properties between {AlW12}, the polymer the polymer chains and the supramolecular interaction of
chains(Cu or Ag) can accelerate the transfer rate between electrons, ethylenediamine molecules inhibit the volume change of {AlW12
}
while the small ethylenediamine molecule provides more active and improve the stability and optimal contact property of the
sites.
material. (2) The {AlW12} in the stacking 3D structure is involved in
the redox reaction and provides electrons due to the mutual
transformation of W6+ and W , which is beneficial to the forward
movement of the reaction. (3) Polymers chains are rich in channels,
which not only promote the diffusion and storage/transmission of
electrons, but also evenly disperse {AlW12} uniformly to prevent
5+
{AlW12} from being dissolved in the electrolyte. (4) π - π binding
between different conductive polymer chains not only promotes
the polymerization of polymer chains on the surface of {AlW12}, but
also shortens the diffusion time, improves the efficiency of proton
transfer and the reaction kinetics on the surface of electrode
material. Therefore, the research of compounds 1-2 provides a new
idea for novel sensor materials.
Experimental
Synthesis of compound 1: A mixture of Na
2
WO
O(0.038 g, 0.1mmol), AgNO (0.05 g, 0.3mmol),
,4'-bipy(0.028 g, 0.2mmol), and H O (10mL) was stirred for half an
4 2
· 2H O (0.33 g,
1
4
mmol), Al(NO
3
)
3
·9H
2
3
-1
2 2
Fig. 11 (a) Reduction of H O at 2-GCE (Scan rate: 50mVs ) (b)The
2
selectivity profile of compound 2 at -0.4~-0.8V (c)The i-t curve of
compound 2 with successive additions of H (d)The linear
relationship between the current response of compound 2 and the
concentration of H
hour in air. Then the pH was adjusted to 4.0 by diluting
ethylenediamine solution and 4 M HNO . The mixture was then
transferred to a Teflon-lined autoclave (23mL) and kept at 160 ℃
for days. After the sample was slowly cooled to room
2 2
O
3
2 2
O
4
temperature, the light yellow crystals were filtered off, washed with
distilled water, and dried in a desiccator at room temperature to
The stability and repeatability are important in practice of the
excellent electrochemical sensors. The stability of 1-GCE and 2-GCE
are the CVs of 1000 cycles at a 50 m V s-1 with -0.8-0.5 V in the 0.1M
give
a
yield of 58.6% based on W. Anal. Calc. for
C30H24Ag3AlN6O44W12: C, 9.65; H, 0.64; Ag, 8.68; N, 2.25; Al, 0.72;
W, 59.18(%). Found: C, 9.41; H, 0.71; Ag, 8.63; N, 2.31; Al, 0.71; W,
2 4 2 4
H SO + 0.5M Na SO . As shown in Fig.S50, the peak current and
peak potential did not change significantly after 1000 cycles, and
the retention rates were 83.89%(1-GCE) and 93.32% (2-GCE),
indicating that compounds 1 and 2 had good stability after
-1
5
8
9(%). Selected IR (KBr pellet, cm ): 3496(m), 1608(s), 953(s),
87(s), 802(m), 766(s).
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins

J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Page 10 of 13
ARTICLE
Journal Name
Synthesis of compound 2: The synthesis of compound 2 is the same
as that of compound 1 except AgNO were replaced by CuCl ·6H
0.05g, 0.3mmol), the orange crystals were filtered off, washed with
distilled water, and dried in a desiccator at room temperature to
give a yield of 55.2% based on W. Anal. Calc.C30H24Cu3AlN6
O41W12 for: C, 10.14; H, 0.68; Cu,5.41; N, 2.37; Al, 0.76; W,
5
6
Z. Y. Wang, L. Zhou, X. W. Lou, Adv. Mater., 20V1ie2w, A2r4tic,le1O9n0li3ne-
911. DOI:10.1002/adma.201200469
1
DOI: 10.1039/C9TA14103K
3
2
2
O
H. Huang, S. Gao, A. m. Wu, K. Cheng, X. n. Li, X. x. Gao, J. j.
Zhao, X. L. Dong, G. Z. Cao, Nano Energy, 2017, 31, 74-83.
DOI:10.1016/j.nanoen.2016.10.059
(
7
8
9
1
1
S. L. Zhai, H. E. Karahan, C. J. Wang, Z. X. Pei, L. Wei, and Y.
Chen,
Adv.
Mater.,
2019,
1902387.
DOI:
1
0.1002/adma.201902387
6
6
8
2.18(%). Found: C, 10.24; H, 0.64; Cu, 5.35; N, 2.34; Al, 0.73; W,
2.24(%). Selected IR (KBr pellet, cm ): 3442(m), 1612(s), 962(s),
82(s), 812(m), 761(s).
L. B. Wang, H. L. Yang, X. X. Liu, R. Zeng, M. Li, Y. H.
Huang, X. L. Hu, Angew. Chem. Int. Ed., 2018, 56, 1105-1110.
DOI: 10.1002/anie.201609527
-1
Y. Z. Zhang, Y. Wang, T.Cheng, L. Q. Yao, X. C. Li, W. Y. Lai and
W. Huang, Chem. Soc. Rev., 2019, 48, 3229-3264. DOI:
1
0.1039/c7cs00819h
Conclusions
0 R. R. Salunkhe, Y. H. Lee, K. H. Chang, J. M. Li, P. Simon,
J.Tang, N. L. Torad, C. C. Hu, and Y. Yamauchi, Chem. Eur. J.,
In summary, using {AlW12} polyoxianions, metal ions, 4,4-bipy and
ethylenediamine as raw materials, two kinds of MXene-like single
crystals were successfully synthesized and directly used as
2
014, 20, 1-16. DOI: 10.1002/chem.201403649
1 H. Chen, S. Zhou, L. Wu, ACS Appl. Mater. Interfaces, 2014, 6,
621-8630. DOI:10.1021/am5014375
8
supercapacitors, sensor electrode materials and photocatalysts. The 12 R. R. Salunkhe, S. H. Hsu, K. C. W. Wu, Y. Yamauch,
ChemSusChem, 2014, 7, 1551-1556. DOI:
0.1002/cssc.201400147
capacitors of 1-CC and 2-CC electrodes are 478.41 and 625.99 F g-1
1
-1
(at 1.0 A g ), and the cyclic stability of two electrodes are above
1
3 Q. Zhang, A. A Zhou, J. J. Wang , J. F. Wu, H. Bai, Energy
Environ. Sci., 2017, 10, 2372-2382. DOI:10.1039/C7EE02018J
9
5% retention after 5000 cycles. A fully symmetrical water system
supercapacitor was prepared with compound 2, and the maximum 14 A. Borenstein, O. Hanna, R. Attias, S. Luski, T.
Brousse and D. Aurbach, J. Mater. Chem. A, 2017, 5, 12653-
2672. DOI:10.1039/C7TA00863E
5 A. González, E. Goikolea, J. A. Barrena, R. Mysyk, Renew Sust
Energ Rev., 2016, 58, 1189-1206. DOI:
0.1016/j.rser.2015.12.249
6 F. Yu, L. Wang, Y. Wang, X. J. Shen, Y. J. Cheng and J. Ma, J.
Mater. Chem. A, 2019, 7, 15999-16027.
DOI:10.1039/c9ta01264h
detection limit of 0.93µM, 0.86µM (response time: 4s, 2s). In 17 M.Volokh, G. Peng, B. Jesús, Angew. Chem. Int. Ed., 2019, 58,
-1
energy density of 6.32 Wh kg can be achieved at a power density
1
-1
of 237 W kg , which is clearly superior to those of many previously
reported supercapacitors. Meanwhile, compounds 1-2 were used as
electrode materials to test the new sensitive current hydrogen
peroxide sensor, display that the linear ranges are 1.20 mM to
1
1
1
3
.20mM (1-GCE) and 19.95 µM to 0.90 mM (2-GCE)with the
6
138-6151. DOI:10.1002/anie.201806514
addition, compounds exhibits excellent photocatalytic degradation
ability for typical dyes.•OH is the principal active substance and the
degradation reaction is AOPs. Three dyes react with •OH to break
1
8 V. Piradi, X. P. Xu, Z. Y. Wang, J. Ali, Q. Peng, F. Liu, X. J. Zhu,
ACS Appl. Mater. Interfaces, 2019, 11, 6283-6291.
DOI:10.1021/acsami.8b19240
the bonds to form phenols, aldehydes, quinones, carboxylic acids 19 L. L. Ye, Y. P. Xie, Y. Q. Xiao, J. L. Song, C. Li, H. T. Fu,
K. K. Weng, X. H. Lu, S. T. Tan and Y. M. Sun, J. Mater.
2 2
and alcohols, which are finally mineralized into H O and CO .
Chem. A, 2019, 7, 8055-8060. DOI: 10.1039/C9TA01285K
2
2
2
0 M. Marandi, P. Talebi, S. Bayat, J Mater Sci-Mater. El., 2019,
3
0, 3820-3832. DOI:10.1007/s10854-019-00666-w
Conflicts of interest
There are no conficts of interest to declare.
1 Q. F. Meng, K. F. Cai, Y. X. Chen, L. D. Chen, Nano Energy,
017, 36, 268-285. DOI: 10.1016/j.nanoen.2017.04.040
2 Y. X. Chen, W. J. Ma, K. F. Cai, X. W. Yang, C. J. Huang,
Electrochim. Acta, 2017, 246, 615-624.
DOI:10.1016/j.electacta.2017.06.102
2
Acknowledgements
23 A. Dolbecq, E. Dumas, C. R. Mayer and P. Mialane, Chem
Rev., 2010, 110, 6009-6048. DOI:10.1021/cr1000578
This work was supported the National Natural Science Foundation
of China (Grants 21571044 and 21771046 to B.Z.) and the Natural
Science Foundation of Heilongjiang Province (Grants JJ2016JQ0037
and B2017007 to B.Z.)
2
4 S. T. Zheng, J. Zhang, X. X. Li, W. H. Fang and G. Y. Yang, J.
Am. Chem. Soc., 2010, 132, 15102-15103.
DOI:10.1021/ja105986b
5 A. K. C. Gallegos, M. L. Cantu, N. C. Pastor and P. G. Romero,
Adv. Funct. Mater., 2005, 15, 1125-1133.
DOI:10.1002/adfm.200400326
2
2
2
2
2
6 H. N. Miras, J. Yan, D. L. Long and L. Cronin, Chem. Soc. Rev.,
2012,41, 7403-7430. DOI:10.1039/C2CS35190K
Notes and references
7 T.
Ueda,
Chemelectrochem,
2018,
5,
823-838.
1
L. Wang, X. Xie, K. N. Dinh, Q. Y. Yan, J. M. Ma, Coord. Chem.
Rev., 2019, 397, 138-167. DOI:
org/10.1016/j.ccr.2019.06.015
DOI:10.1002/celc.201701170
8 Y. C. Ji, L. J. Huang, J. Hu, C. Streb and Y. F. Song, Energy
Environ. Sci., 2015, 8, 776-789. DOI:10.1039/C4EE03749A
9 U. Kortz, A. Müller, J.V Slageren, J. Schnack, N. S. Dalal, M.
Dressel, Coord. Chem. Rev., 2009, 253, 2315-2327.
DOI:org/10.1016/j.ccr.2009.01.014
2
Y. R. Qi, Y. X. Lu, F. X. Ding, Q. Q. Zhang, H. Li, X. J. Huang, L.
Q. Chen, Y. S. Hu, Angew. Chem. Int. Ed., 2019, 58, 4361-
4
365. DOI: 10.1002/anie.201900005
3
4
L. Croguennec, M R Palacin, J. Am. Chem. Soc., 2015, 137,
140-3156. DOI:10.1021/ja507828x
X. Y. Yu, L. Yu , X. W. Lou, Adv. Energy Mater., 2016, 6,
501333-1501346. DOI:10.1002/aenm.201501333
3
0 Y. W. Liu, S. M. Liu, D. F. He, N. Li, Y. J. Ji, Z. P. Zheng, F. Luo,
S. X. Liu, Z. Shi, and C.W. Hu, J. Am. Chem. Soc., 2015,
3
1
37,12697-12703. DOI:10.1021/jacs.5b08273
1
1
0 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 11 of 13
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Journal Name
ARTICLE
3
3
1 S. S. Wang, G. Y. Yang, Chem. Rev., 2015, 115, 4893-4962. 55 Y. Chen, B. B. Zhou, J. X. Zhao, Y. G. Li, Z. H. SVuie,wZA.rtFic.leZOhnalinoe,
DOI:10.1021/cr500390v
Inorg.
Chim.
Acta,
2010,
363,
3897-3903.
DOI: 10.1039/C9TA14103K
2 Y. Zhang, Y. F. Wang, X. Y. Meng, L. Yu, Y. Ding, M. D. Chen, J
DOI:10.1016/j.ica.2010.07.060
Photoch
Photobio
A,
2018,
355,371-376. 56 M. M. Heravi, M. Mirzaei, S. Y. S. Beheshtiha, V. Zadsirjan, F.
M. Ameli, Appl Organometal Chem., 2018, 32, e4479.
DOI:10.1016/j.jphotochem.2017.08.016
3
3
3 M. L. Wei, X. X. Wang, J. J. Sun, X. Y. Duan, J Solid State
Chem., 2013, 202, 200-206. DOI:10.1016/j.jssc.2013.03.041
4 L. Wang, B.B. Zhou, K. Yu, Z.H. Su, S. Gao, L.L. Chu, J.R. Liu,
and G.Y. Yang, Inorg. Chem., 2013, 52, 5119-
DOI:10.1002/aoc.4479
57 S. Matsunaga, Y. Inoue, T. Otaki, H. Osada, and K. Nomiya,
Z. Anorg. Allg. Chem., 2016, 642, 539-545. DOI:
10.1002/zaac.201500794
5
127.DOI:10.1021/ic400019r
58 C. N. Kato, T. Kashiwagi, W. Unno, M. Nakagawa and H. Uno,
3
3
5 Z. Zhou, D. Zhang, L. Yang, P. Ma, Y. Si, U. Kortz, J. Niu, J.
Inorg
Chem.,
2014,
53,
4824-4832.
Wang, Chem. Commun., 2013, 49, 5189-5191. DOI:
DOI:10.1002/chin.201430020
1
0.1039/C3CC41628C
59 C. N. Kato, Y. Makino, W. Unno and H. Uno, Dalton Trans.,
2013, 42, 1129-1135. DOI:10.1039/C2DT32107F
6 L. Wang, K. Yu, B.B. Zhou, Z.H. Su, S. Gao, L.L. Chu and J. R.
Liu,
Dalton
Trans.,
2014,
43,
6070-6078. 60 Q. Lan, Y. Lu, Y. G. Li, H. Q. Tan, D. Liu, E. B. Wang, Transition
Met. Chem., 2012, 37, 445-451. DOI:10.1007/s11243-012-
DOI:10.1039/c3dt53030b
3
3
7 L. Wang, K. Yu, J. Zhu, B. B. Zhou, J. R. Liu and G. Y. Yang,
9608-1
Dalton Trans., 2017, 46,2874-2883,DOI: 10.1039/c6dt02420c 61 Y. Q. Huang, Train. Res. J.Hubei Univ.Edu., 2004, 21, 20-21.
8 L. Wang, S.B. Li, K. Yu, J. Zhu, H.J. Shi, B.B. Zhou, and J.R. Liu, 62 H. I. S. Nogueira, F. A. AlmeidaPaz, P. A. F. Teixeira, and J.
Adv. Healthcare Mater., 2019, 8, 1900471. DOI:
0.1002/adhm.201900471
Klinowski, Chem. Commun., 2006, 28, 2953-2955,
DOI:10.1039/b605973b
1
3
4
4
4
4
4
9 H. X. Zhao, L. Tao, F.M. Zhang, Y. Zhang, Y.Q. Liu, H.J. Xu, 63 S. R. Bajpe, S. Henke, J.H. Lee, P. D. Bristowea and A. K.
G.W. Diao, L.B. Ni, Chem. Commun., 2019, 55, 1096-1099,
DOI: 10.1039/C8CC07884J
Cheetham, CrystEngComm, 2016, 18, 5327-5332. DOI:
10.1039/c5ce02088c
0 L. Zhang, L. Ning, Z. F. Zhang, S. B. Li, H. Yan, H. J. Pang, H. Y. 64 Y.W. Li, L.Y. Guo, H.F. Su, M. Jagodič, M. Luo, X.Q. Zhou, S.Y.
Ma, Sensors Actuat B-Chem, 2015, 221, 28-36.
DOI:10.1016/j.snb.2015.06.070
Zeng, C.H. Tung, D. Sun, and L.S. Zheng, Inorg. Chem., 2017,
56, 52481-2489. DOI:10.1021/acs.inorgchem.6b02601
1 J. W. Zuo, Z. F Zhang, J. Jiao, H. J. Pang, D. Zhang, H. Y. Ma, 65 S.B. Li, L. Zhang,Y.Q. Lan, K. P. O’Halloran,H.Y. Ma and H.J.
Sensors Actuat B-Chem, 2016, 236, 418-424. DOI:
0.1016/j.snb.2016.05.159
Pang, Chem. Commun., 2018, 54, 1964-1967. DOI:
10.1039/c7cc09223g
1
2 N. S. Lopa, M. M. Rahman, F. Ahmed, S. Chandra Sutradhar, 66 M. T. Li,X. Y. Yang, J. S. Li, N. Sheng, G. D. Liu, J. Q. Sha, and Y.
T. Ryu and W. Kim,Electrochim. Acta, 2018, 274, 49-56.
DOI:10.1016/j.electacta.2018.03.148
Q. Lan, Inorg. Chem., 2018, 57, 3865-3872.
DOI:10.1021/acs.inorgchem.7b03228
3 Z. Y. Bai, C. L. Zhou, H. B. Xu, G. N. Wang, H. J. Pang, H. Y. Ma, 67 X. Li, X. Y. Yang, J. Q. Sha, T. Han, C. J. Du, Y. J. Sun, and Y. Q.
Sensors
Actuat
B-Chem,
2017,
243,
361-371.
Lan, ACS Appl. Mater. Interfaces, 2019, 11, 16896-16904.
DOI:10.1021/acsami.9b00872
DOI:10.1016/j.snb.2016.11.159
4 L. Zhang, S. B. Li, Z. F. Zhang, L. C. Tan, H. J. Pang, H. Y. Ma, J 68 Y. Hou, D. F. Chai, B. N. Li, H. J Pang, H. Y Ma, X. M. Wang and
Electroanalytical
Chem.,
2017,
807,
97-103.
L. C. Tan, ACS Appl. Mater. Interfaces, 2019, 11, 20845-
20853. DOI:10.1021/acsa mi.9b04649
DOI:10.1016/j.jelechem.2017.11.030
4
4
4
4
4
5 D. Zhu, J. W. Zuo, L. C. Tan, H. J. Pang and H. Y. Ma, New J 69 D. Chai, C. J. Gómez-García, B. Li, H. Pang, H. Ma, X. Wang, L.
Chem., 2019, 43, 1053-1062. DOI:10.1039/C8NJ04570D
6 A. Yamada and J. B. Goodenough, J Electrochem. Soc.,
Tan, Chem. Eng. J., 2019, 373, 587-597. DOI:
10.1016/j.cej.2019.05.084
70 M. Naguib, J. Come , B. Dyatkin, V. Presser, P. L. Taberna, P.
Simon, M. W. Barsoum, Y. Gogotsi, Electrochem Commun.,
2012, 16, 61-64. DOI:10.1016/j.elecom.2012.01.002
1
998, 145, 737-743. DOI: 10.1149/1.1838339
7 Y. G. Wang, X.G. Zhang, Solid State Ionics, 2004, 166, 61-67.
DOI: 10.1016/j.ssi.2003.11.001
8 G. N. Wang, T. T. Chen, S. B. Li, H. J. Pang, H. Y. Ma, Dalton 71 X. Zhang, Z. H. Zhang, Z. Zhou, J Energy Chem., 2018, 27, 73-
Trans, 2017, 46, 13897-13902. DOI:10.1039/C7DT02230A
85. DOI:10.1016/j.jechem.2017.08.004
9 H. J. Pang, J. Chen, J.Peng, J. Q. Sha, Z. Y. Shi, A. X. Tian, P. P. 72 W. Liu, H. H. Thorp, Inorg. Chem., 1993, 32, 4102-4105.
Zhang, Solid State Sci. 2009, 11, 824-828.DOI:
DOI:10.1021/ic00035a012
1
0.1016/j.solidstatesciences.2008.11.008
73 C. Rocchiccioli-Deltcheff, M. Fournier, R. Franck, and R.
Thouvenot, Inorg. Chem., 1983, 22, 207-216. DOI: 0020-
1669/83/1322-0207
5
0 H. Y. Chen, G. Wee, R. A. Oweini, J. Friedl, ꢀ K. S. Tan,Y. X.
Wang, C. L. Wong, U. Kortz, U, Stimming, M. Srinivasan,
ChemPhysChem.,2014,
0.1002/cphc.201400091
1 H. N. Wang, M. Zhang, A. M. Zhang, F. C. Shen, X. K. Wang, S.
15,
2162-2169.
DOI: 74 H. Zhang, K. Yu, S. Gao, C. M. Wang, C. X Wang, H. Y. Wang
1
and B. B. Zhou, CrystEngComm., 2014, 16, 8449-8456.
DOI:10.1039/C4CE01029A
5
5
5
5
N. Sun, Y. J. Chen, and Y. Q. Lan, ACS Appl. Mater. Interfaces, 75 D. P. Dubal, N. R. Chodankar, A. Vinu, D. H. Kim, P. Gomez-
2
018, 10, 32265-32270. DOI: 10.1021/acsami.8b12194
Romero, Chemsuschem, 2017, 10, 2742-2750. DOI:
10.1002/cssc.201700792
2 K. B. Wang, Z. K. Wang, S. Wang, Y. Chu, R. Xia, X. Y. Zhang,
H. Wu, Chem. Eng. J., 2019, 367, 239-248. 76 N. R. Chodankar, D. P. Dubal, Y. Kwon, D. H. Kim, NPG Asia
DOI:10.1016/j.cej.2019.02.145
Mater., 2017, 9, e419. DOI:10.1038/am.2017.145
3 K. P. Wang, K. Yu, J. H. Lv, M. L. Zhang, F. X. Meng, and B. B. 77 S. G. Mohamed, I. Hussain, J. J. Shim, Nanoscale, 2018, 10,
Zhou, Inorg. Chem., 2019, 58, 7947-7957. DOI:
0.1021/acs.inorgchem.9b00692
4 N. N. Du, L. G. Gong, L. Y. Fan, K. Yu, H. Luo, S. J. Pang, J. Q.
6620-6628. DOI:10.1039/C 7NR07338K
78 N. Agmon, The Grotthuss Mechanism, Chem Phys Lett., 1995,
244, 456-462. DOI:10.1016/0009-2614(95)00905-J
1
Gao, Z. W. Zheng, J. H. Lv, and B. B. Zhou, ACS Appl. Nano 79 K. D. Kreuer, W. Weppner, A. Rabenau. Angew. Chem. Int.
Mater., 2019, 2, 3039-3049. DOI:10.1021/acsanm.9b00409
Ed., 1982, 21, 9-208. DOI:10.1002/anie.198202082
0 K. Cheückiewicz, G. Zúukowska, W. Wieczorek, Chem.
Mater., 2001, 13, 379-384. DOI:10.1021/cm0011155
8
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 11
Please do not adjust margins

J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Page 12 of 13
ARTICLE
Journal Name
8
8
8
8
8
8
8
8
1 P. G. Romero, M. Chojak,K. C. Gallegos, J. A. Asensio, P. J.
Kulesza, N. C. Pastor, M. L. Cantú, Electrochem. Commun.,
003, 5, 149-153. DOI:10.1016/s1388-2481(03)00010-9
2 Z. L. Guo, L. Yang, W. Wang, L. X. Cao and B. H. Dong, J.
Mater. Chem. A, 2018, 6, 14681-14688.
DOI:10.1039/C8TA03812K
View Article Online
DOI: 10.1039/C9TA14103K
2
3 D.Y. Fu, H. W. Li, X. M. Zhang, G. Y. Han, H. H. Zhou, Y. Z.
Chang, Mater. Chem. Phys., 2016, 179, 166-173. DOI:
1
0.1016/j.matchemphys.2016.05.024
4 K. Qi, R. Z. Hou, S. Zaman, Y. B.Qiu, B.Y. Xia, and H. W. Duan,
ACS Appl. Mater. Inter, 2018, 10, 18021-18028.
DOI:10.1021/acsami.8b05802
5 L. Wang, X. Feng, L. T. Ren, Q. H. Piao, J. Q. Zhong, Y. B.
Wang, H. W. Li, Y. F. Chen, and B. Wang, J. Am. Chem. Soc.,
2
015,137, 4920-4923.DOI:10.1021/jacs.5b01613
6 L. Li, J. W. Sun, J. Q. Sha, G. M. Li, P. F. Yan and C. Wang,
CrystEngComm., 2015, 17, 633-641. DOI:10.1039/C
4
CE01725K
7 L.S. Cavalcante, J.C. Sczancoski, N.C. Batista, E. Longo, J.A.
Varela, M.O. Orlandi, Adv Powder Tech., 2013, 24, 344-353.
DOI: 10.1016/j.apt.2012.08.007
8 L. S. Cavalcante, F. M. C. Batista, M. A. P. Almeida, A. C.
Rabelo, I. C. Nogueira, N. C. Batista, J. A. Varela, M. R. M. C.
Santos, E. Longo and M.S. Li, RSC Adv., 2012, 2, 6438-6454.
DOI: 10.1039/c2ra20266b
8
9
9
9
9
9
9
9
9
9
9 Y. Q. Jiao, C.Qin, H.Y. Zang, W.C. Chen, C.G, Wang, T. T.
Zheng, K. Z. Shao and Z. M. Su, CrystEngComm, 2015, 17,
2
176-2189. DOI:10.1039/C4CE02007C
0 T. S. Natarajan, M. Thomas, K. Natarajan, H. C. Bajaj, R. J.
Tayade, Chem. Eng. J., 2011, 169, 126-134.
DOI:10.1016/j.cej.2011.02.066
1 A. Houas, H. Lachheb, M. Ksibi, E. Elaloui, C. Guillard, J. M.
Herrmann, Appl Catal B: Envir., 2011, 31, 145-157.
DOI:10.1016/S0926-3373(00)00276-9
2 J. J. Ma, L. C. Zhou, W. F. Dan, H. Zhang, Y. M. Shao, C. Bao, L.
Y. Jing, J Colloid and Inter Sci., 2015, 446, 298-306. DOI:
1
0.1016/j.jcis.2015.01.036
3 L. Gomathi Devi, S. Girish Kumar, K. Mohan Reddy, C.
Munikrishnappa, J Hazardous Mater., 2009, 164, 459-467.
DOI:10.1016/j.jhazmat.2008.08.017
4 R. B. Huang, S. Li, J. S. Hu, G.W. Qin, J. Mater. Metallurgy.,
2
6
012,
11,
303-307.
DOI:
10.14186/j.cnki.1671-
620.2012.04.015
5 H. Fu, Y. G. Li, Y. Lu, W. L. Chen, Q. Wu, J. X. Meng, X. L.
Wang, Z. M. Zhang and E. B. Wang, Cryst. Growth Des., 2011,
1
1, 458-465. DOI:10.1021/cg101224r
6 J. Q. Sha, J. Peng, Y. Q. Lan, Z. M. Su, H. J. Pang, A. X. Tian, P.
P. Zhang, and M. Zhu, Inorg. Chem., 2008, 47, 5145-5153.
DOI:10.1021/ic702407y
7 F. H. Meng, X. L. Yan, J. G. Liu, J. Gu, Z. G. Zou, Electrochim.
Acta,
0.1016/j.electacta.2011.02.105
8 B. Li, H. Y. Song, Z. P. Deng, L. H. Huo, S. Gao,Sensors Actuat
B-Chem, 2019, 288, 641-648. DOI:
0.1016/j.snb.2019.03.054
2011,
56,
4657-4662.
DOI:
1
1
1
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 13 of 13
Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/C9TA14103K
The covalent conductive polymer chain and organic ligand ethylenediamine modified
MXene-like-{AlW O } compounds are proposed to discover promising photo-electrically active
1
2 40
materials