Catechol-Coordinated Framework Film-based Micro-Supercapacitors with AC Line Filtering Performance

Article abstract of DOI:10.1002/chem.202100171

Coordination polymer frameworks (CPFs) have broad applications due to their excellent features, including stable structure, intrinsic porosity, and others. However, preparation of thin-film CPFs for energy storage and conversion remains a challenge because of poor compatibility between conductive substrates and CPFs and crucial conditions for thin-film preparation. In this work, a CPF film was prepared by the coordination of the anisotropic four-armed ligand and Cu^II at the liquid–liquid interface. Such film-based micro-supercapacitors (MSCs) are fabricated through high-energy scribing and electrolytes soaking. As-fabricated MSCs displayed high volumetric specific capacitance of 121.45 F cm^?3. Besides, the volumetric energy density of MSCs reached 52.6 mWh cm^?3, which exceeds the electrochemical performance of most reported CPF-based MSCs. Especially, the device exhibited alternating current (AC) line filtering performance (?84.2° at 120 Hz) and a short resistance capacitance (RC) constant of 0.08 ms. This work not only provides a new CPF for MSCs with AC line filtering performance but also paves the way for thin-film CPFs preparation with versatile applications.

Full text of DOI:10.1002/chem.202100171

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&
Electrochemistry |Hot Paper|
Catechol-Coordinated Framework Film-based Micro-
Supercapacitors with AC Line Filtering Performance
Tianliang Yu,[a, b] Youfu Wang,[b] Kaiyue Jiang,[b, e] Guangqun Zhai,*[a] Changchun Ke,*[c]
Jichao Zhang,[f] Jiantong Li,[d] Diana Tranca,[b] Emmanuel Kymakis,[g] and
Xiaodong Zhuang*[b]
Abstract: Coordination polymer frameworks (CPFs) have
broad applications due to their excellent features, including
stable structure, intrinsic porosity, and others. However,
preparation of thin-film CPFs for energy storage and conver-
sion remains a challenge because of poor compatibility be-
tween conductive substrates and CPFs and crucial condi-
tions for thin-film preparation. In this work, a CPF film was
prepared by the coordination of the anisotropic four-armed
ligand and CuII at the liquid–liquid interface. Such film-based
micro-supercapacitors (MSCs) are fabricated through high-
energy scribing and electrolytes soaking. As-fabricated MSCs
displayed high volumetric specific capacitance of
121.45 FcmÀ3. Besides, the volumetric energy density of
MSCs reached 52.6 mWhcmÀ3, which exceeds the electro-
chemical performance of most reported CPF-based MSCs. Es-
pecially, the device exhibited alternating current (AC) line fil-
tering performance (À84.28 at 120 Hz) and a short resistance
capacitance (RC) constant of 0.08 ms. This work not only
provides a new CPF for MSCs with AC line filtering per-
formance but also paves the way for thin-film CPFs prepara-
tion with versatile applications.
(or supercapacitors)[3] possess obvious superiority, such as high
power density, long cycle lifetime, fast charge and discharge
rates, and compatibility of integration with various electronic
components.[4] Recent studies have found that thin-film-based
flat micro-supercapacitors (MSCs)[5] based on nanostructured
functional materials, such as graphene,[6] graphene-based
nanocomposites,[7] monolithic carbide-derived carbon,[4a] poly-
mer films,[8] and others, can provide new components for
modern on-chip integrated circuits. However, most of the devi-
ces based on these materials demand multiple processing
Introduction
With the rapid development of portable and wearable elec-
tronic devices, lightweight, miniaturized, and efficient energy
storage devices become more and more important.[1] Commer-
cially available micro-batteries have already shown great po-
tential in this field. However, batteries still have intrinsic prob-
lems of low power density and limited cycling performance,
hindering their application as reliable micro-power sources.[2]
As a novel energy storage device, electrochemical capacitors
[a] T. Yu, Prof. G. Zhai
[d] Dr. J. Li
meso-Entropy Matter Lab
School of Electrical Engineering and Computer Science
KTH Royal Institute of Technology
Electrum 229, 16440 Kista (Sweden)
Jiangsu Key Laboratory of Environmentally Friendly Polymeric Materials
School of Materials Science and Engineering
Changzhou University
Changzhou 213164 (China)
E-mail: zhai_gq@cczu.edu.cn
[e] K. Jiang
College of Chemistry and Molecular Engineering
Zhengzhou University
[b] T. Yu, Y. Wang, K. Jiang, Dr. D. Tranca, Prof. X. Zhuang
Themeso-Entropy Matter Lab
Zhengzhou 450001, Henan (China)
[f] Dr. J. Zhang
State Key Laboratory of Metal Matrix Composites
Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing
School of Chemistry and Chemical Engineering
Frontiers Science Center for Transformative Molecules
Shanghai Jiao Tong University
Shanghai Synchrotron Radiation Facility
Zhangjiang Laboratory
Shanghai Advanced Research Institute
Chinese Academy of Sciences, No. 239
Zhangheng Road, Shanghai 201204 (China)
800 Dongchuan Road, Shanghai 200240 (China)
E-mail: zhuang@sjtu.edu.cn
[g] Prof. E. Kymakis
Department of Electrical & Computer Engineering
Hellenic Mediterranean University
Estavromenos, 71410 Heraklion (Greece)
[c] Dr. C. Ke
Institute of Fuel Cells
School of Mechanical Engineering
Shanghai Jiao Tong University
Shanghai 200240 (China)
E-mail: kechangchun@sjtu.edu.cn
Supporting information and the ORCID identification number(s) for the au-
thor(s) of this article can be found under:
https://doi.org/10.1002/chem.202100171.
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steps, such as complicated photolithography processes or
high-temperature preparation of electrode materials. The de-
velopment of MSCs through a simple fabrication process is sig-
nificant for their practical applications.
cene-2,3,6,7-tetraol) (denoted as DTHAB, Scheme S1) and Cu2+
in solution. Both of the monomers, DTHAB and DM-THA (9,10-
dimethyl-2,3,6,7-tetrahydroxyanthracene, Scheme S2), possess
anisotropic topology. The synthesis and characterizations can
be found in the Experimental Section and Supporting Informa-
tion (Figures S1–S16).
Alternating current (AC) line filtering is one of the most im-
portant features of MSCs and can be used to filter AC ripple
on the line-powered devices.[9] As one of the paramount prop-
erties of renewable electronic power systems, AC line filtering
can be used for power generation. However, only commercially
available aluminum electrolytic capacitors (AECs) can be used
for such application and suffer from low energy density and
bulky volume dimensions. Therefore, AECs are not compatible
with fast-developing portable electronic devices. So far, porous
carbon-based supercapacitors have shown promising AC line
filtering performance. However, the slow response of the polar-
ization, limited signal propagation, and poor film formation
property of porous carbons hinder the practical application.
Development of new materials with AC line filtering per-
formance remains a great challenge.
X-ray absorption fine structure (XAFS) and extended X-ray
absorption fine structure (EXAFS) techniques were employed
to analyze the electronic structure and coordination geometry
of Cu-DTHAB in comparison with Cu foil, CuO, and Cu2O. As
shown in Figure 1a, the enlarged pre-edge of Cu-DTHAB lo-
cates between CuO and Cu2O, indicating that the average va-
lence state of Cu atoms is between +2 and +1.[10] Meanwhile,
the Fourier-transform (FT) EXAFS oscillation spectrum of Cu-
DTHAB (Figure 1b) presents a predominant peak at 1.57 Š,
which originates from the CuÀO bond,[11] suggesting the coor-
dination of Cu ions with DTHAB. Moreover, least-squares
EXAFS fitting is carried out to realize quantitative structural pa-
rameters of Cu in Cu-DTHAB (Figure S17a), indicating the coor-
dination number of Cu is 4 (Table S1). Wavelet transform (WT)
(WT-EXAFS) is also performed to analyze the atomic dispersion
Herein, a coordination polymer framework (CPF) film is syn-
thesized by a liquid–liquid interfacial method based on an ani-
sotropic four-armed ligand. Such framework film based on cat-
echol-Cu node shows uniform thickness, a large horizontal
area reaching several square centimeters, and a narrow band
gap of 0.84 eV. As electrode material for MSCs, such film can
achieve areal and volumetric specific capacitances of
2.89 mFcmÀ2 and 121.45 FcmÀ3, respectively. Moreover, the
MSC exhibits a high energy density of 52.6 mWhcmÀ3 and
power density of 13.1 WcmÀ3. Noteworthy, the device shows
promising AC line filtering performance (À84.28 at 120 Hz) and
a short resistance capacitance (RC) time constant (tRC) of
0.08 ms. This work provides a new material option for the fab-
rication of MSCs with AC line filtering performance.
À1
of Cu atoms (Figure S17b). The intensity maximum at 6.5 Š is
attributed to the CuÀO contribution for Cu-DTHAB.[12] To fur-
ther study the chemical structure of the Cu-DTHAB, X-ray pho-
toelectron spectroscopy (XPS) was employed. The survey XPS
spectrum (Figure S18) is dominated by C, O, Cu peaks. The
O1s core level spectrum (Figure 1c) reveals the OÀCu peak at
532.4 eV, and the residual O peak at 533.7 eV, demonstrating
the coordination between O and Cu atoms.[13] In addition,
Cu2p core level spectrum (Figure 1d) consists of the CuII 2p3/2
peak at 935.1 eV, CuI 2p3/2 peak at 935.1 eV, CuII 2p1/2 peak at
952.6 eV, CuI 2p1/2 peak at 954.2 eV, as well as the shake-up sat-
ellite peaks at 959.8–967.1 and 938.7–948.6 eV.[14] The XPS
spectrum of Cu-THA was also analyzed and shows similar phe-
nomena (Figure S19). To further verify the coordination of cate-
chol units and copper ions, the chemical structures of DTHAB
and Cu-DTHAB were studied through Fourier-transform infra-
red (FTIR) spectroscopy (Figure S20a) and Raman spectroscopy.
Compared to the FTIR spectrum of DTHAB, the reduced OÀH
stretching band at approximately 3228 cmÀ1 indicates the
prosperous coordination between the phenolic hydroxy and
copper ions. Moreover, the band centered at 1266 cmÀ1 for
Cu-DTHAB exhibits a distinct transformation to higher energy
compared with the CÀO stretching at 1234 cmÀ1 for DTHAB.[13]
Meanwhile, the phenolic hydroxyl peak at approximately
3169 cmÀ1 of the Cu-DTHAB (Figure S21a) disappeared by com-
paring with DTHAB. All these results indicate that the pro-
posed structure was successfully realized through coordination
between CuII and catechol.
Results and Discussion
The preparation of CPF and control linear coordination poly-
mer Cu-THA is illustrated in Scheme 1. CPF was prepared by
the coordination of the ligand 9,9’-(1,4-phenylene)bis(anthra-
Furthermore, the optoelectronic properties of Cu-DTHAB
were studied. The ultraviolet-visible absorption spectrum was
tested by UV/Vis-NIR spectroscopy (Figure S22). The optical
band gap could be calculated from the UV/Vis absorption
edge (Figure 2a). Cu-DTHAB reveals a band gap of 0.84 eV ac-
cording to the Kubelka–Munk (K–M) function.[15] The UV photo-
electron spectroscopy (UPS, Figure 2b) was further used to de-
termine the valence band (EVB). The EVB of À4.83 eV (vs.
Scheme 1. Synthesis of Cu-THA and Cu-DTHAB.
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Figure 1. (a) Normalized XANES spectra of Cu-DTHAB, Cu foil, CuO, and Cu2O. (b) Fourier transformation EXAFS spectra of Cu-DTHAB with Cu foil, CuO, and
Cu2O as control samples. (c) O1s XPS spectrum of Cu-DTHAB. (d) Cu2p XPS spectrum of Cu-DTHAB.
vacuum level) was calculated according to a well-established
method.[16] Then, the conduction band (ECB) can be calculated
as À3.99 eV (vs. vacuum level) based on optical band gap (Fig-
ure 2c). The cyclic voltammetry (CV) curves of Cu-DTHAB and
DTHAB were investigated in CH3CN at 20 mVsÀ1 (Figure 2d).
The highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO) levels of Cu-DTHAB are
significantly different from those of DTHAB. The calculated
band gap according to CV curves (Eg,CV) of Cu-DTHAB (1.14 eV)
is smaller than that of DTHAB (1.67 eV). Meanwhile, the CV
curves of Cu-THA and DM-TMA (Figure S23) were also em-
ployed through the same test method, the Eg,CV of Cu-THA
(1.22 eV) is also smaller than DM-THA (1.55 eV). These results
demonstrate the semiconducting properties of the Cu-DTHAB
and Cu-THA.
0.92, 0.68, and 0.58 eV, respectively. As is known, 3D structure
should be the preferred structure for Cu-DTHAB because of
the free rotated CÀC bonds between benzene and anthracene
of DTHAB. The calculated band gap of Cu-DTHAB-3D (0.92 eV)
is close to the optical band gap (0.84 eV) and CV-based band
gap (1.14 eV), indicating the preferred 3D structure for Cu-
DTHAB.
The porosity of Cu-DTHAB was studied by nitrogen physical
adsorption measurement (Figure S24). The Brunauer–Emmett–
Teller (BET) surface area of Cu-DTHAB is 127 m2 gÀ1. The pore
volume and pore diameter of Cu-DTHAB are 0.29 cm3 gÀ1 and
8.7 nm (Table S2), respectively. The thermogravimetric analysis
(TGA) curve of Cu-DTHAB (Figure S25a) shows mass loss by
6.6% at 2008C, indicating good thermal stability of the struc-
ture. The TGA curve of DTHAB was also recorded for better
comparison to Cu-DTHAB (Figure S25b). To investigate the
magnetic character of the Cu-DTHAB, magnetization measure-
ments were performed through a superconducting quantum
interference device-vibrating sample magnetometer (SQUID-
VSM, Figure S26). It embodies the variation of the magnetiza-
tion with the applied magnetic field (H) measured at 298 K, a
sigmoidal shape of M(H) signs the weak ferromagnetism be-
havior.[17] In addition, the solid-state electron paramagnetic res-
To better estimate the electronic structures of the Cu-DTHAB
framework, density functional theory (DFT) was used for calcu-
lation. Figure 3a,b shows the possible three-dimensional (3D)
and two-dimensional (2D) models of the Cu-DTHAB (denoted
as Cu-DTHAB-3D and Cu-DTHAB-2D, respectively). Figure 3c
shows the model of the control sample Cu-THA. The calculated
density of states (DOS) curves (Figure 3d) reveal narrower
band gaps of Cu-DTHAB-3D, Cu-DTHAB-2D, and Cu-THA of
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Figure 2. (a) (hva)2 against hv curve of Cu-DTHAB. (b) UPS spectrum of Cu-DTHAB. (c) ECB and EVB positions of Cu-DTHAB. (d) CV profiles of Cu-DTHAB and
DTHAB measured in CH3CN at a scan rate of 20 mVsÀ1. EHOMO =À(EOx +4.42 eV); ELUMO =À(ERed +4.42 eV); Eg,CV =EHOMOÀELUMO
.
Figure 3. Models of Cu-DTHAB in 3D (a) and 2D (b) configurations and the control linear polymer Cu-THA (c). Grey: C; red: O; orange: Cu. (d) Calculated densi-
ty of states of Cu-DTHAB-3D, Cu-DTHAB-2D and Cu-THA.
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onance (EPR) was also employed to analyze the distribution of
unpaired electrons in the Cu-DTHAB (Figure S27). A nearly sym-
metrical signal is displayed at g=2.10, which is the behavior of
the metal-centered radicals.[18]
A series of thin Cu-DTHAB films were performed by liquid–
liquid interfacial polymerization for the preparation of micro-
supercapacitors. The procedure is shown in Figure 4a. In short,
the Cu-DTHAB films (Figure 4b) were transferred to Au sub-
strate. Then Cu-DTHAB/Au films were laser-scribed to prepare
interdigitated electrodes.[8b] After appending electrolyte and
solidification overnight, Cu-DTHAB based MSCs (denoted as
MSC-Cu-DTHAB) can be obtained. Cu-DTHAB films with an
average thickness of approximately 240Æ5 nm were used to
perform flat MSCs (Figure 4c). As-prepared Cu-DTHAB films
have continuous and uniform characteristics (SEM, Figure S28).
Meanwhile, the elemental mapping images (Figure S29) sug-
gest the C, O and Cu are evenly distributed in Cu-DTHAB. The
SEM images (Figure 4d) of the as-fabricated MSC-Cu-DTHAB
show glossy edges along the interdigital finger electrodes. In
addition, the mechanical properties (elastic modulus and hard-
ness) of Cu-DTHAB film were characterized through Nano In-
dentor (Table S3), which show such film has a certain mechani-
cal strength.
The electrochemical performance of the MSC-Cu-DTHAB was
researched through CV from 10 mVsÀ1 to 1.0 VsÀ1 in different
electrolytes (PVA/LiCl, PVA/H2SO4 and [EMIM][BF4]). It can be
seen from Figures S30a, S31a, and S32a, MSC-Cu-DTHAB shows
an obvious pseudocapacitive effect with redox peaks. The
areal and volumetric specific capacitances of MSC-Cu-DTHAB
can be calculated through CV curves (Figure 5a). The MSC-Cu-
DTHAB exhibits the high volumetric specific capacitance of
Figure 5. MSCs performance in PVA/LiCl, PVA/H2SO4, and [EMIM][BF4].
(a) Rate-dependent specific volumetric capacitance. (b) Nyquist plots. (c) Im-
pedance phase angles on the frequency. (d) Plot of capacitance (Cv’and Cv”)
versus the frequency of MSC-Cu-DTHAB. (e) Cycling stability of MSC-Cu-
DTHAB at the scan rate of 50 mVsÀ1. (inset: the 1st and 2500th CV curves of
MSC-Cu-DTHAB at the scan rate of 50 mVsÀ1). (f) Ragone plots for MSC-Cu-
DTHAB.
121.45 FcmÀ3 in PVA/LiCl electrolyte at
a
scan rate of
based supercapacitors (Table S4). The volumetric specific ca-
pacitance maintains 7.98 FcmÀ3 at a high scan rate of 1 VsÀ1,
demonstrating a high capacitance and rate performance of
MSC-Cu-DTHAB.
10 mVsÀ1, which exceeds the value of most reported polymer-
Meanwhile, the electrochemical impedance spectroscopy
(EIS) was employed to research the frequency response of
MSC-Cu-DTHAB based on different electrolytes (Figure 5b). The
minimum values of equivalent series resistance (ESR) were
found to be 15.02, 30.2, and 39.53 W in different electrolytes
(PVA/LiCl, PVA/H2SO4, and [EMIM][BF4]), respectively.[19] The Ny-
quist plot of the MSC-Cu-DTHAB based on [EMIM][BF4] contains
a small arc in the initial position. The frequency-dependent
phase angle (Figure 5c) indicates capacitive and inductive be-
havior at frequencies.[9b] The phase angle of the device reaches
À84.78 at frequency of approximately 26 Hz, indicating that
the performance of the MSCs is 94.1% of an ideal capacitor
(defined by a phase angle of À908).[20] In addition, the charac-
teristic frequency (f0) of the system, corresponding to the maxi-
mum of the dispersed energy curve (obtained from the phase
angle of 458) is 16374 Hz in PVA/LiCl, 1312 Hz in PVA/H2SO4,
and 1281 Hz in [EMIM][BF4]. The f0 value for MSCs is a specific
balance point where the resistive value is equal to the value of
capacitive impedance. Therefore, the corresponding time con-
stant t0 (t0 =1/f0) can be calculated as 0.06, 0.76, and 0.78 ms
for the MSC-Cu-DTHAB in PVA/LiCl, PVA/H2SO4, and [EMIM]
[BF4], respectively.[8a] Moreover, MSC-Cu-DTHAB shows an im-
Figure 4. (a) Schematic illustration of fabricating Cu-DTHAB film-based MSC.
i) Synthesis of Cu-DTHAB films using liquid–liquid polymerization; ii) transfer-
ring Cu-DTHAB films onto Au current collector; iii) laser scraping Cu-DTHAB/
Au heterolayer to fabricate an interdigital pattern; iv) drop-casting and solid-
ification gel electrolytes onto interdigitated fingers to fabricate Cu-DTHAB
based MSCs. (b) Photograph of the formed Cu-DTHAB film. (c) Profile of Cu-
DTHAB film. (d) SEM image of interdigital finger electrodes on a glass.
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pedance phase angle of À84.28 at 120 Hz, indicating promising
AC line filtering performance (Table S5).[21] The calculated RC
time constant (tRC) based on the imaginary capacitance (Fig-
ure 5d) is 0.08 ms in MSC-Cu-DTHAB. The cycling test was in-
vestigated at a routine scan rate of 50 mVsÀ1 over 2500 cycles
(Figure 5e). The first circle and the 2500th circle CV shapes are
relatively close. The capacitance retention of 83.8% can be
achieved after 2500 cycles, indicating good stability for MSC-
Cu-DTHAB. MSC-Cu-DTHAB exhibits a high energy density of
52.6 mWhcmÀ3 at 0.05 mAcmÀ2 (Figure 5 f); the value is higher
than most recently reported functional materials-based super-
capacitors, such as CNTs-graphene carpets,[21] d-Ti3C2Tx,[4a] and
elastic carbon films and carbon onions.[22] These results suggest
that the prepared Cu-DTHAB film is a promising electrode ma-
terial for MSCs.
120 Hz) and a short resistance capacitance (RC) constant (tRC)
of 0.08 ms. This work offers new options for coordination poly-
mer framework film-based MSCs and paves the way for inte-
grated on-chip energy storage devices.
Experimental Section
Materials: Cupric acetate (Adamas, 98%+), ethyl acetate (Adamas
99.8%), LiCl (Adamas, 99%+), polyvinyl alcohol (Adamas, CPS: 4.6–
5.4), 1-ethyl-3-methylimidazolium tetrafluoroborate (Adamas, 99%),
poly (1,1-difluoroethylene) (Fluorochem), sulfuric acid (Adamas,
96%), N,N-dimethylformamide (Adamas, 99.8%), 1-ethyl-3-methyli-
midazolium tetrafluoroborate (Adamas, 99%), and acetone
(Adamas, ꢀ99.5%) were commercially purchased. In addition, the
monomers DM-THA and DTHAB were synthesized according to the
literature.
To further understand the energy storage mechanism of Cu-
DTHAB, electrochemical quartz crystal microbalance (EQCM)
measurement was used to reveal the mass changes and vis-
coelastic properties of the electrodes during charge-discharg-
ing in 1.0 molLÀ1 H2SO4.[23] Figure S34a shows the frequency,
potential and response resistance curves with time. The reso-
nance resistance does not show a particularly large response,
and it is stable in a small range (Æ7 W). Therefore, it satisfies
the conditions of the Sauerbrey equation. The CV curve and
mass changes of Cu-DTHAB at 10 mVsÀ1 were displayed in Fig-
ure S34b. During the potential increasing process from 0 to
1 V, the electrode mass increased. When the potential reaches
the maximum, the electrode mass also reaches the maximum
value, indicating the adsorbed ions reach the maximum. After
a cycle, the electrode mass becomes slightly smaller. Fig-
ure S34c shows the relationship between experimental and
theoretical ion population changes (DG) and charge density
(DQ) during the charging and discharging process. The adsorp-
tion of H3O+ ions was considered, and exactly Mi of 19 gmolÀ1
for DGtheor and DGexp was a good coincidence. In addition, the
capacitance of MSC-Cu-DTHAB has the behavior of double-
layer capacitance (Cdl) and pseudocapacitance (Cp). The respec-
tive capacitance contribution was researched using Trasatti
analysis. The plot of reciprocal of areal capacitance (CÀ1)
against the square root of scan rate (v0·5) and the plot of areal
capacitance (C) against reciprocal of the square root of scan
rate (vÀ0·5) was displayed in Figure S35. The total capacitance
contributions from Cdl and Cp were calculated through the Tra-
satti method are 74 and 26%, respectively,[24] which quantita-
tively analyzes the pseudocapacitance contribution value of
MSC-Cu-DTHAB.
Synthesis of 9-bromo-2,3,6,7-tetramethoxyanthracene (Br-
TMOA): In a 500 mL three-necked round bottom flask, 2,3,6,7-tetra-
methoxyanthracene (TMOA) (4 g, 13.4 mmol) was dissolved in
300 mL CHCl3. CuBr2 (6 g, 26.8 mmol) was added to the solution,
and the reaction was stirred overnight at 708C. Then, the mixture
was filtered, and the solution was concentrated under reduced
pressure. It was further purified by column chromatography (silica)
with ethyl acetate and petroleum ether as eluent; the final product
was obtained as
a
pale-yellow solid (64% yield).[25] 1H NMR
(500 MHz, CDCl3): d=8.05 (s, 1H), 7.66 (s, 2H), 7.16 (s, 2H), 4.13 (s,
6H), 4.07 ppm (s, 6H). 13C NMR (500 MHz, CDCl3): d=150.74,
149.52, 127.71, 126.43, 124.38, 122.59, 105.10, 105.04, 55.97 ppm.
MS (MALDI-TOF): calculated for C18H17BrO4: 376.03, found: 375.970.
Synthesis of 1,4-bis(2,3,6,7-tetramethoxyanthracen-9-yl) ben-
zene (DTMOAB): In a 250 mL three-necked round bottom flask, a
mixture of toluene (36 mL) and EtOH (36 mL) was sparged for 1 h
under N2, then Br-TMOA (1 g, 2.65 mmol), 1,4-phenylenediboronic
acid (200 mg, 1.2 mmol) and Pd(PPh3)4 (278 mg, 0.24 mmol,
5 mol%) were added while sparging for another 30 min. A solution
of K2CO3 (1.5 g, 10.8 mmol) in H2O (4 mL) was added to the flask,
and then the reaction mixture was refluxed overnight. After the re-
action was over, the mixture was first cooled to room temperature.
The resulting suspension was filtered and the solid washed succes-
sively with H2O and EtOH. It was further purified by column chro-
matography (silica) with dichloromethane and petroleum ether as
eluent; the final product was obtained as a white solid (42%
yield).[26] 1H NMR (500 MHz, CDCl3): d=8.20 (s, 2H), 7.72 (s, 4H),
7.27 (s, 4H), 7.03 (d, 4H), 4.10 (s, 12H), 3.81 ppm (s, 12H). 13C NMR
(500 MHz, CDCl3): d=149.26, 136.55, 133.07, 131.43, 127.51, 125.94,
122.41, 105.13, 103.68, 55.93, 54.89 ppm. MS (MALDI-TOF): calculat-
ed for C42H38O8: 670.26, found: 670.228.
Synthesis of 9,9’-(1,4-phenylene)bis(anthracene-2,3,6,7-tetraol)
(DTHAB): In a 250 mL three-necked round bottom flask, DTMOAB
(120 mg, 0.179 mmol) was suspended in 30 mL anhydrous di-
chloromethane under N2, and BBr3 (0.73 mL, 7.5 mmol) was careful-
ly added using a syringe. The mixture was stirred for 4 days at
room temperature, then injected slowly with 10 mL H2O after the
reaction was over. The precipitate was collected by centrifugation
and washed with dichloromethane for three times. The product
was dried under vacuum to give DTHAB as a dark green solid
(40% yield).[27] 1H NMR (500 MHz, [D6]DMSO): d=10.42 (s, 8H), 7.44
(d, 4H), 7.48 (s, 2H), 7.19 (s, 4H), 7.09 (s, 4H), 6.98 ppm (s, 4H). MS
(MALDI-TOF): calculated for C34H22O8: 558.13, found: 558.17.
Conclusions
A novel coordination polymer framework film based on CuO4
linkage is successfully prepared through the liquid–liquid inter-
face polymerization method. The sample is employed to fabri-
cate flat micro-supercapacitors by laser scribing and exhibits a
high volumetric specific capacitance of 121 F cmÀ3, and the
maximum volumetric energy density of 52.6 mWhcmÀ3. More
importantly, the micro-supercapacitors (MSCs) display typical
alternating current (AC) line filtering performance (À84.28 at
Synthesis of 9,10-dimethyl-2,3,6,7-tetrahydroxyanthracene (DM-
THA): In a 250 mL three-necked round bottom flask, DM-TMOA
(1 g, 3.06 mmol) was suspended in 30 mL anhydrous dichlorome-
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thane under N2, and BBr3 (6.07 mL, 64.19 mmol) was carefully
added using a syringe. The mixture was stirred for 2 days at room
temperature, then injected slowly with 10 mL H2O after the reac-
tion was over. The precipitate was collected by centrifugation and
washed with dichloromethane for three times. The product was
dried under vacuum to give DM-THA as a green solid (61%
yield).[27] 1H NMR (500 MHz, [D6]DMSO): d=9.41 (s, 4H), 7.34 (s,
4H), 2.70 ppm (s, 6H). 13C NMR (500 MHz, CDCl3): d=146.36,
125.71, 121.44, 106.04, 14.63 ppm. MS (MALDI-TOF): calculated for
C16H14O4: 270.09, found: 270.096.
Conflict of interest
The authors declare no conflict of interest.
Keywords: alternating current line filtering · catechol
coordination polymer framework · copper · micro-
supercapacitor
·
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Acknowledgements
T.Y. and Y.W. contributed equally to this work. This work was fi-
nancially supported by National Key Research and Develop-
ment Program of China (2017YFE9134000), NSFC (51973114,
21878188, 21720102002, 51811530013), and Science and Tech-
nology Commission of Shanghai Municipality (19JC412600),
Greece-China joint R&D project Calypso (T7DKI-00039), co-fi-
nanced by Greece, the EU Regional Development Fund. C.K.
thanks the financial support from the Key Science and Technol-
ogy Project in Henan Province (Innovation Leading Project:
191110210200). D.T. thanks the support from China Postdoctor-
al Science Fund (2020M671117). J.Z. thanks the support from
NSFC (11705270, 11975100). We thank the beamline BL14W1
and BL15U1 of the Shanghai Synchrotron Radiation Facility
(SSRF, China) for providing the beamtime.
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Manuscript received: January 16, 2021
Accepted manuscript online: February 10, 2021
Version of record online: March 5, 2021
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