Ultrastable conductive microporous covalent triazine frameworks based on pyrene moieties provide high-performance CO2 uptake and supercapacitance

Article abstract of DOI:10.1039/d0nj01292k

Covalent organic triazine frameworks (CTFs) are a subclass of covalent organic frameworks and conjugated microporous polymers that exhibit heteroatom effects and possess high surface areas and excellent chemical and thermal stabilities; they have applications in energy storage and gas adsorption. In this study, we prepared two microporous polymers the pyrene-functionalized CTFs Pyrene-CTF-10 and Pyrene-CTF-20 - through ionothermal treatment of 1,3,6,8-cyanopyrene (TCNPy) in the presence of molten zinc chloride (ZnCl₂) at 500 °C (at ZnCl₂-to-TCNPy molar ratios of 10?:?1 and 20?:?1, respectively). Pyrene-CTF-10 and Pyrene-CTF-20 had specific BET surface areas of 819 and 1019 m² g^-1, respectively, with pore size distributions of 1.10 and 1.35 nm, respectively, and high char yields (up to 70%). Furthermore, these Pyrene-CTF polymeric frameworks exhibited excellent specific capacitances at a current density of 0.5 A g^-1: 380 F g^-1 for Pyrene-CTF-10 and 500 F g^-1 for Pyrene-CTF-20. In addition, both Pyrene-CTFs had excellent cycling stability, retaining 97% of their capacitances after cycling 2000 times at a current density of 10 A g^-1. Moreover, Pyrene-CTF-10 displayed good CO₂ uptake capacity (2.82 and 5.10 mmol g^-1 at 298 and 273 K, respectively).

Full text of DOI:10.1039/d0nj01292k

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Ultrastable Conductive Microporous Covalent Triazine Frameworks
View Article Online
Based on Pyrene Moieties Provide High-Performance CO2 Uptake
DOI: 10.1039/D0NJ01292K
and Supercapacitance
Received 00th January 20xx,
Accepted 00th January 20xx
Mohamed Gamal Mohamed, a,bAhmed F. M. EL-Mahdy,a,b Yasuno Takashi,a
and Shiao-Wei Kuoa,c*
DOI: 10.1039/x0xx00000x
8
9
Covalent organic triazine frameworks (CTFs) are a subclass of covalent organic frameworks and conjugated
microporous polymers that exhibit heteroatom effects and possess high surface areas and excellent chemical
and thermal stabilities; they have applications in energy storage and gas adsorption. In this study, we
prepared two microporous polymers the pyrene-functionalized CTFs Pyrene-CTF-10 and Pyrene-CTF-20—
through ionothermal treatment of 1,3,6,8-cyanopyrene (TCNPy) in the presence of molten zinc chloride
(ZnCl2) at 500 °C (at ZnCl2-to-TCNPy molar ratios of 10:1 and 20:1, respectively). Pyrene-CTF-10 and Pyrene-
CTF-20 had specific BET surface areas of 819 and 1019 m2 g–1, respectively, with pore size distributions of
1.10 and 1.35 nm, respectively, and high char yields (up to 70%). Furthermore, these pyrene-CTF polymeric
frameworks exhibited excellent specific capacitances at a current density of 0.5 A g–1: 380 F g–1 for Pyrene-
CTF-10 and 500 F g–1 for Pyrene-CTF-20. In addition, both Pyrene-CTFs had excellent cycling stability,
retaining 97% of their capacitances after cycling 2000 times at a current density of 10 A g–1. Moreover,
Pyrene-CTF-10 displayed good CO2 uptake capacity (2.82 and 5.10 mmol g–1 at 298 and 273 K, respectively).
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solvent loss, and high cost.10–15 As a result, we need new and
effective methods for decreasing the emission and increasing the
Introduction
Supercapacitors, also known as electrochemical capacitors or
electric double-layer capacitors (EDLCs), are being used more
widely as replacements for fuel cells and batteries in energy storage
applications, military devices, electric vehicles, and electrochemical
devices because of their long lifetimes, rapid rates of charging and
discharging, and high power densities.1,2 The electrochemical
mechanisms behind the operation of supercapacitors can be
divided into two categories: nonfaradaic processes (e.g., in EDLCs)
depending on the accumulation of electrostatic charge at the
electrode–electrolyte interface and faradaic processes (e.g., in
pseudocapacitors) occurring at the surfaces of conjugated polymers,
heteroatom-doped carbon materials, and metal oxide/hydroxide
systems that feature fast redox reactions.2,3 Thus, the construction
of materials for use as electrodes in energy storage applications
requires that they have large specific surface areas, high nitrogen
contents, large surface areas available to the electrolyte, and
hierarchical porous structures.3–5 Anthropogenic carbon dioxide
(CO2) emissions will likely have many serious negative effects on
human life and the environment because of increasing global
temperatures and changes to weather events.6–9 Therefore,
lowering emissions and the levels of CO2 through sequestration and
capture has become a challenge for both academia and industry.
The wet cleaning method has been the most commonly used
chemical process for capturing and separating CO2 with aqueous
alkanolamine solutions (amine scrubbing), but this method has the
disadvantages of high energy consumption, low efficiency,
difficulties of renewal, amine-mediated corrosion of equipment,
capture of CO2 during industrial processes. Covalent organic
polymers (COPs) are attractive porous materials for many
applications, including sensors; the removal of pollutants; CO2
capture, storage, and separation; drug delivery; catalysis; SO2
adsorption; gene therapy; Li-S batteries; energy conversion; and
light-harvesting. They have many interesting properties:
outstanding thermal stability, high BET surface areas, accessible
porosity, large pore volumes, chemical resistance, biocompatibility,
and excellent electrical conductivity when compared with metal–
organic frameworks.16–26 The many types of COP materials include
covalent organic frameworks (COFs), covalent triazine frameworks
(CTFs), porous aromatic frameworks, benzimidazole-linked
polymers, carbazole-based microporous polymers, and porous
imine-linked networks.27–34 Amine scrubbing adsorbs CO2 through
chemisorption, as opposed to the physisorption mechanism of
COPs.10,12,34 Post-synthesis or bottom-up approaches can be used to
incorporate CO2-philic functional groups [e.g., carboxyl (COOH),
hydroxyl (OH), imine (-N=CH), benzimidazole, carbazole, and
triazine units] into covalent organic porous materials to improve
their CO2 capture.34–38 CTFs are both COFs and conjugated
microporous polymers that display large heteroatom effects,
possess permanent nanopores with high Brunauer–Emmett–Teller
(BET) surface areas, have excellent chemical and thermal stabilities,
and feature tunable electronic structures.39–43 Most CTF framework
materials have been prepared through ionothermal trimerization of
nitrile groups, superacid catalysis, and phosphorous pentoxide
(P2O5) catalysis.28,43–45 Many recent reviews have highlighted the
great potential of CTF materials in gas separation and storage,
heterogeneous catalysis, energy storage, and photocatalysis.46–
48Porous polymeric materials containing pyrene units have been
tested recently in many different fields—including chemical sensing,
photoelectric devices, gas storage and separation, and photo-
catalysis—because of their high propensity for forming excimers,
distinct solvatochromic phenomena, ready functionalization,
delayed fluorescence, and tunable photophysical properties.49–51
a. Department of Materials and Optoelectronic Science, Center of Crystal Research,
National Sun Yat-Sen University, Kaohsiung, Taiwan.
b. Chemistry Department, Faculty of Science, Assiut University, Assiut, 71516, Egypt
c. Department of Medicinal and Applied Chemistry, Kaohsiung Medical University,
Kaohsiung, 807, Taiwan
Email: kuosw@faculty.nsysu.edu.tw
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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Br
Br
Br
Br2, 110 oC
NaCN, DMF
nitrobenzene
Ethylenediamine, 150
oC
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Br
N
(c)
(d)
N
N
N
NC
CN
CN
N
N
N
N
ZnCl2
500 oC
NC
N
N
N
N
Pyrene-CTF
Scheme 1. Synthesis of (d) Pyrene-CTF from (a) Pyrene, (b) TBrPy, and (c) TCNPy.
In a previous study, we prepared a series of conductive bicarbazole- (crystallinity BET surface areas, porosities, chemical surface
based CTFs (Car-CTFs) through the trimerization of [9,9´- compositions, thermal stability, and chemical structures). We
bicarbazole]-3,3´,6,6´-tetracarbonitrile (Car-4CN) with molten zinc performed electrochemical measurements and CO2 uptake analyses
chloride (ZnCl2); these materials exhibited outstanding thermal to examine their potential applications as high-performance
stability, excellent energy storage, and CO2 uptake.28 Janiak et al. electrode materials and for gas adsorption.
prepared the CTFs PCTF-1 and PCTF-2 through reactions of tetra(4-
cyanophenyl)ethylene with ZnCl2 at 400 °C; these two materials
Experimental Section
Materials
captured CO2 at levels of 3.30 and 1.87 mmol g–1, respectively, at
273 K.52 Voort et al. prepared CTF materials from 4,4´,4´´,4´´´-(1,4-
phenylenebis(pyridine-4,2,6-triyl))tetrabenzonitrile in anhydrous
ZnCl2 under ionothermal conditions at 400 and 500 °C, with the
former material (CTF-20-400) providing a CO2 uptake of 3.48 mmol
g–1 at 273 K.8 Han et al. prepared the CTF TPC-1 through
defluorination carbonization and trimerization of the nitrile groups
of tetrafluoroterephthalonitrile in molten ZnCl2; this polymeric
framework had a high specific surface area (1940 m2 g–1) and
displayed excellent CO2 adsorption (4.9 mmol g–1 at 273 K). In this
study, we prepared pyrene-based CTFs (Pyrene-CTFs) through
trimerization of the nitrile groups of 1,3,6,8-cyanopyrene (TCNPy) in
the presence of molten ZnCl2 at 500 °C (Scheme 1). We used wide-
angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR)
spectroscopy, X-ray photoelectron spectroscopy (XPS), Raman
Pyrene, nitrobenzene, HCl solution (37%), ethanol (EtOH), and
methanol (MeOH) were purchased from Acros. Ethylenediamine
(99%), tetrahydrofuran (THF), N,N-dimethylformamide (DMF),
dichloromethane (DCM), acetone, and copper(I) cyanide (CuCN)
was purchased from Sigma–Aldrich.
1,3,6,8-Tetrabromopyrene (TBrPy)54,55
A solution of bromine (1.15 mL, 22 mmol) in nitrobenzene (5 mL)
was added dropwise to a solution of pyrene (1 g) in nitrobenzene
(15 mL) and then the mixture was heated at 120 °C for 4 h. Cooling
to room temperature provided a pale-green solid, which was
filtered off, washed three times with EtOH, and dried under vacuum
at 100 °C to provide a pale-green solid (2.21 g, 91%). M.p.: >300 °C.
spectroscopy,
transmission
electron
microscopy
(TEM),
thermogravimetric analysis (TGA), and the Brunauer–Emmett–
Teller (BET) method to examine the properties of these Pyrene-CTFs
1,3,6,8-Cyanopyrene (TCNPy)
A mixture of TBrPy (3.00 g, 4.65 mmol) and CuCN (9.69, 108 mmol)
in dry DMF (100 mL) was heated under reflux under a N2
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(a) TBrPy
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CN
(b) TCNPy
-1
-1
1382 cm
1540 cm
(c) Pyrene-CTF-10
2500
2000
1500
1000
-1
Wavenumber (cm )
Figure 1. FTIR spectra of (a) TBrPy, (b) TCNPy, and (c) Pyrene-CTF-10.
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CN
atmosphere at 140 °C for 3 days. The mixture was opened to the air
and cooled to room temperature, at which point it was then
filtrated to remove unreacted CuCN. The solution was poured into a
mixture of cold water (75 mL) and ethylenediamine (4 mL); this
mixture was heated at 50 °C for 2 h. The yellow powder was filtered
off and washed with water and MeOH to afford a yellow powder
(1.24 g). M.p.: >400 °C; FTIR (KBr, cm–1): 3070 (C–H stretching), 2220
(CN stretching).
(a) 25 oC
(b) 150 oC
(c) 210 oC
(d) 300 oC
Pyrene-CTFs
In an ampoule, TCNPy (200 mg, 0.46 mmol) was mixed with
anhydrous ZnCl2 [63 mg (4.63 mmol) or 126 mg (9.26 mmol)]
(Scheme 1). The temperature was raised to 500 °C at a heating rate
of 5 °C/min and then the samples were maintained at that
temperature for 48 h under the N2 atmosphere. After cooling, each
obtained black solid was washed with 1 M HCl and water (each for
24 h). The resultant black solids (Py-CTF-10, Py-CTF-20) were
washed several times with THF, DCM, and MeOH. Finally, the black
powders were dried for 24 h at 100 °C.
N
N
N
(e) 500 oC
2200 2000 1800 1600 1400 1200 1000 800
600
-1
Wavenumber (cm )
Figure 2. FTIR spectral profile of Pyrene-CTF-10, recorded at
temperatures from room temperature to 500 °C.
Results and Discussion
Synthesis of TBrPy, TCNPy, and Pyrene-CTFs
to give Pyrene-CTF-20 and Pyrene-CTF-20, respectively (Scheme 1,
Table 1). Figure 1 displays the FTIR spectra of TBrPy, TCNPy, and the
Pyrene-CTFs. The spectrum of TBrPy [Figure 1(a)] featured
characteristic absorption bands centered at 3050 and 804 cm–1,
assigned to the stretching of aromatic C–H56-59 and C–Br bonds,
respectively. The FTIR spectrum of TCNPy [Figure 1(b)] contained an
absorption band at 2220 cm–1 representing the stretching of CN
triple bonds, confirming its synthesis. As displayed in Figures 1(c),
the spectra of the Pyrene-CTFs featured absorption bands
The monomer 1,3,6,8-cyanopyrene (TCNPy) was synthesized in two
steps (Scheme 1). First, pyrene was reacted with bromine (Br2) in
nitrobenzene at 120 °C for 5 h to afford TBrPy as a pale-green solid,
which was reacted with CuCN in DMF at 140 °C for 48 h to give
TCNPy as a yellow powder. We then used an ionothermal method
for trimerization of the nitrile groups of TCNPy in the presence of
molten anhydrous ZnCl2 (at weight ratios of 1:10 and 1:20) at 500 °C
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Table 1. Thermal stabilities, porosity parameters, Raman spectral data, and electrochemical data of the Pyrene-CTFs.
Sample
TCNPy/
ZnCl2
Td10%
Char
yield
(%)
72
SBET
Pore
size
(nm)
1.10
1.35
Pore
volume
(cm3 g–1)
0.88
ID/IG
CV
View Article Online
(oC)
(m2 g–1)
(RamDaOI: 10.1039/D0NJ01292K
n)
1.07
1.47
(F g–1)
Pyrene CTF-10
Pyrene-CTF-20
1:10
1:20
500
474
819
380
500
72
1019
1.12
8
9
at 1565 and 1365 cm–1 representing the triazine rings, but no
signals for CN groups, confirming the successful
(a) Pyrene-CTF-10
(b) Pyrene-CTF-20
trimerization/cyclization reactions of the cyano groups.8,28,60 In
addition, the intensities of the characteristics absorption bands of
the triazine ring in Pyrene-CTF-20 gradually decreased at 500 °C,
due to the occurrence partial carbonization [Figure S1].61,62 We
performed FTIR spectral analyses to monitor the trimerization of
the nitrile groups in the preparation of Pyrene-CTF-10 from room
temperature to 500 °C (Figure 2). For temperatures between 25 and
300 °C, the FTIR spectrum of Pyrene-CTF-10 featured the
characteristic absorption band at 2220 cm–1 for stretching of the CN
triple bonds. When the temperature reached 500 °C, however, this
characteristic band disappeared completely and two new
absorption signals appeared at 1565 and 1360 cm–1, confirming the
complete trimerization of the nitrile groups and the formation of
triazine rings.28
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2 Theta
Figure 4. XRD patterns of Pyrene-CTF-10 and Pyrene-CTF-20.
We used solid state 13C CP/MAS NMR spectroscopy (Figure S2)
to confirm the chemical structures of TBrPy and TCNPy and the
formation of triazine rings in the Pyrene-CTFs materials. The solid
state 13C NMR spectrum of TBrPy [Figure S2(a)] displays signals at
127, 116 and 110 ppm at for the aromatic carbon atoms. Figure
S2(b) reveals that the spectrum of TCNPy features signals at 132
and 108 ppm for the aromatic carbon nuclei and signal at 116 ppm
for CN group. The solid state 13C NMR spectra [Figures S2(c) and (d)]
of Pyrene-CTF-10 and Pyrene-CTF-20 exhibited signals at 168, 136,
123 and 116 ppm which we assign to the carbon nuclei of the
triazine [–C(Ar)=N–] and the pyrene units.8,28,63 We determined the
thermal stabilities of TCNPy, Pyrene-CTF-10, and Pyrene-CTF-20
through TGA under a N2 atmosphere (Figure 3). Although Pyrene-
CTF-10 and Pyrene-CTF-20 were synthesized in molten ZnCl2 at 500
°C, the decomposition temperature (Td10) of Pyrene-CTF-10 (500 °C)
was higher than that of Pyrene-CTF-20 (474 °C); they had the same
char yield of 71 wt.%. These values for the TCNPy monomer were
346 °C and 4 wt.%, respectively. Thus, these Pyrene-CTFs displayed
outstanding thermal stability.8,28
Figure 4 provides the XRD patterns of Pyrene-CTF-10 and Pyrene-
CTF-20, revealing that they had partially crystalline structures with
two broad peaks at 13 and 25° that we assign to the vertical spacing
between stacked sheets (001) and the in-plane reflection (100),
respectively.15,64 Figure 5 presents the Raman spectra of Pyrene-
CTF-10 and Pyrene-CTF-20 in the range from 1000 to 1900 cm–1.
The spectra of both Pyrene-CTFs materials featured two strong
signals characteristic of D and G bands, suggesting the existence of
graphitic carbonized structures. In general, the D and G bands
represent the graphitic carbon atoms: second-order Raman
scattering with sp3 hybridization and first-order Raman scattering
with sp2 hybridization, respectively.15,28,64,65 From the Raman
spectra of Pyrene-CTF-10 and Pyrene-CTF-20, the D bands were
centered at 1342 and 1335 cm–1, respectively, while the G bands
appeared at 1584 and 1586 cm–1, respectively. The ID/IG ratios for
Pyrene-CTF-10 and Pyrene-CTF-20 were 1.07 and 1.47, respectively.
Thus, Pyrene-CTF-10 possessed a lower degree of graphitization and
featured less defects in its structure when compared with Pyrene-
CTF-20.
100
(a) Pyrene-CTF-10
(b) Pyrene-CTF-20
80
60
ID/IG = 1.07
(a)
40
20
Pyrene-4CN
ID/IG = 1.47
Pyrene-CTF-10
(b)
Pyrene-CTF-20
0
100
200
300
400
500
600
700
1000
1200
1400
Raman Shift (cm )
1600
1800
Temperature (oC)
-1
Figure 5. Raman spectra of Pyrene-CTF-10, and Pyrene-CTF-20.
Figure 3. TGA analyses of TCNPy, Pyrene-CTF-10, and Pyrene-CTF-20,
recorded under N2.
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C1s
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Figure 6. XPS survey spectra of (a) Pyrene-CTF-10and (b) Pyrene-CTF-20.
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N
1S
(b)
N
1S
396
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404 396
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404
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1S
(d)
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1S
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Binding Energy (ev)
Figure 7. XPS fitting curves of N 1s and O 1s orbitals: (a, c) Pyrene-CTF-10; (b, d) Pyrene-CTF-20.
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Table 2. Curve-fitting data and area fractions of the signals in the N1s and O1s plots in Figure 7.
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Sample
N species
N-5
21.44
23.97
O species
C–OH
15.61
15.58
N-6
68.24
59.92
N-Q
10.32
16.12
C–O
45.29
69.16
H2O
39.10
30.84
Pyrene-CTF-10
Pyrene-CTF-20
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Pyrene-CTF-10
Pyrene-CTF-20
Pyrene-CTF-10
Pyrene-CTF-20
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0 0.2 0.4 0.6 0.8 1.0
0 2 4 6 8 10 12 14 16 18 20
Relative Pressure (P/P0)
Pore Width (nm)
Figure 8. (a) N2 adsorption/desorption measurements and (b) pore size distributions of Pyrene-CTF-10and Pyrene-CTF-20, recorded at 77 K.
Figure 6 displays the XPS spectra of the Pyrene-CTFs. Three peaks We measured N2 adsorption/desorption isotherms (Figure 8,
appeared in each spectrum: at 284 eV (for carbon atoms in the Table 1) at 77 K to examine the porosities of our Pyrene-CTFs.
polymeric CTF framework), 400 eV (C–N bonds for the N 1s orbitals Figure 8(a) reveals that Pyrene-CTF-10 had microporous
in the triazine units), and 530 eV (O 1s orbitals for absorbed water characteristics, with a specific surface area of 819 m2 g–1 and a pore
and oxygen), respectively.28,53,66,67
volume of 0.88 cm3 g–1. The BET curve of Pyrene-CTF-20 featured a
We fitted the XPS curves for the N 1S and O 1S orbitals to type IV isotherm, with a high specific surface area of 1019 m2 g–1
investigate the chemical compositions on the surfaces of these and a pore volume of 1.12 cm3 g–1. Thus, the specific BET surface
Pyrene-CTFs (Figure 7, Table 2). The fitting results for the N 1s area of Pyrene-CTF-20 was higher than that of Pyrene-CTF-10,
orbitals [Figures 7(a) and 7(b)] revealed the presence of three N suggesting the presence of closely packed nanoparticles and a
species, including quaternary-N species (401 eV), pyrrolic species larger number of defects in the Pyrene-CTF-20 structure.8,28
(400 eV), and hexagonal pyridinic N atoms from the triazine ring Furthermore, we used NL-DFT theory to calculate the pore
(398.7 eV). According to quantitative analysis, the pyrrolic N and diameters in Pyrene-CTF-10 and Pyrene-CTF-20 [Figure 8(b), Table 1]
pyridinic species were the most abundant in the Pyrene-CTF to be 1.10 and 1.35 nm, respectively. TEM images (Figure 9)
frameworks. Furthermore, the surfaces of the Pyrene-CTF materials revealed that Pyrene-CTF-10 and Pyrene-CTF-20 both possessed
contained three O species [Figures 7(c) and 7(d)], with signals at irregular microporous structures.
531, 532, and 533 eV corresponding to polarized C–O bonds, water,
and absorbed oxygen.28,53,66,67
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Figure 9. TEM images of (a) Pyrene-CTF-10 and (b) Pyrene-CTF-20.
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-1
(a)
(b)
(c)
0.5 Ag
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
20
10
-1
1 Ag
-1
2 Ag
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7 Ag
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0
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15 Ag
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-20
-40
-60
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-100
20 Ag
-10
-20
-30
-1
-1
5 mVs
5 mVs
-1
-1
10 mVs
10 mVs
-1
-1
30 mVs
30 mVs
-1
-1
50 mVs
50 mVs
-1
-1
70 mVs
70 mVs
-1
-1
100 mVs
200 mVs
100 mVs
200 mVs
-1
-1
-1.0 -0.8 -0.6 -0.4 -0.2 0.0
-1.0 -0.8 -0.6 -0.4 -0.2 0.0
0
200 400 600 800 1000
Time (s)
Potential (V vs. Hg/HgO)
-1
(d)
(e)
(f)
0.5 Ag
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-0.4
-0.6
-0.8
-1.0
100
80
60
40
20
0
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500
1 Ag
-1
2 Ag
Pyrene-CTF-10
Pyrene-CTF-20
Pyrene-CTF-10
Pyrene-CTF-20
-1
3 Ag
-1
400
5 Ag
-1
7 Ag
-1
10 Ag
-1
300
15 Ag
-1
20 Ag
200
100
0
500
1000
1500
0
5
10
15
20
0
500 1000 1500 2000
-1
Ag
Time (s)
Current density
(
)
Cycle number
Figure 10. (a, b) CV curves of Pyrene-CTF-10 and Pyrene-CTF-20. (c, d) GCD profiles of Pyrene-CTF-10 and Pyrene-CTF-20, recorded at
various currents. (e) Specific capacitances of Pyrene-CTF-10 and Pyrene-CTF-20 recorded at current densities from 0.5 to 20 A g–1. (f)
Cycling stabilities of Pyrene-CTF-10 and Pyrene-CTF-20 electrodes, recorded at a current density of 10 A g–1 over 2000 cycles.
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Pyrene-CTF-20
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Relative Pressure (P/P0)
Figure 11. CO2 uptake of (a) Pyrene-CTF-10 and (b) Pyrene-CTF-20, measured at 298 and 273 K.
[Figure 10(f)]. Pyrene-CTF-10 and Pyrene-CTF-20 both retained 97%
of their initial capacitance after 2000 cycles, indicating their
excellent cycling stability in 1 M KOH as the electrolyte. Deng et al.
prepared conductive CTFs through ionothermal reactions of
tetracyanoquinodimethane (TCNQ) in the presence of molten ZnCl2
at various temperatures. They found that the specific capacitances
of TCNQ-CTF-600, TCNQ-CTF-700, TCNQ-CTF-800, and TCNQ-CTF-
900 at a current density of 0.2 A g–1 were 284, 350, 380, and 356 F
g–1, respectively. The highest specific capacitance (380 F g–1) was
that of TCNQ-CTF-800, presumably because of its high N-atom
content (8.13%) and large surface area (3663 m2 g–1).2 In addition,
Zhi et al. derived amorphous CTFs from terephthalonitrile that
displayed a specific capacitance of 298 F g–1 at 0.2 A g–1.70 In
addition, we have previously reported a series of Car-CTFs formed
through trimerization of Car-4CN with molten ZnCl2; among them,
Car-CFT-5-500 provided a specific capacitance of 545 F g–1 at 5 mV
s–1.28 In comparison with these other CTF materials, Pyrene-CTF-20
displays excellent supercapacitor performance (Table S1),
presumably because of its graphitic structure, microporosity, and N
and O atom contents. Figure S3 shows that the calculated
coulombic efficiency (CE) with the current density. It shows that the
CE is very high at current density of 0.5 and 1 A g-1, this is due to the
very small applied charging and discharging currents. While at
current density >1 A g-1, the CE is almost ~100%.]. We recorded CO2
adsorption isotherms for both Pyrene-CTFs at 25 and 0 °C [Figures
11(a) and 11(b)]. The CO2 uptake of Pyrene-CTF-10 was 2.82 and
5.10 mmol g–1 at 25 and 0 °C, respectively; for Pyrene-CTF-20, these
values were lower at 2.54 and 3.43 mmol g–1, respectively. Thus,
Pyrene-CTF-10 captured more CO2 at 25 °C (2.82 mmol g–1) than
other previously reported CTF materials at the same temperature,
including Car-CTF-10-500 (2.25 mmol g–1),28 CTF-1 (2.77 mmol g–1),71
PCTF-1–3 (2.02–3.00 mmol g–1),72 CTF-20-400 (3.48 mmol g–1),3 CTF-
0 (1.54–2.34 mmol g–1),73 and CTF-DCN-500 (2.70 mmol g–1),62 due
to Pyrene-CTF-10 having a specific surface area of 819 m2 g-1 and a
high N-atom content (9.85 wt%) arose from the presences of
triazine units, which leads to increase the binding affinity
interaction between CO2 molecules and Pyrene-CTF-10. Table S2
Energy Storage and CO2 Uptake of Pyrene-CTFs
From the BET and XPS data, we knew that our Pyrene-CTF materials
had high specific surface areas, N-heteroatom frameworks
(primarily pyridinic and pyrrolic N species), and mesoporous and
microporous properties. Therefore, we expected these materials to
have great potential applications in energy storage and gas
uptake.21 We measured the electrochemical properties of the
Pyrene-CTFs through cyclic voltammetry (CV) at various scan rates
(5–200 mV s–1) in 1 M aqueous KOH [Figures 10(a) and 10(b)]. The
CV profiles for the Pyrene-CTFs had rectangular (“rice-like”)
shapes.2,4,28 The appearance of rectangular CV curves for these CTF
materials based on pyrene units suggested a combination of electric
double-layer capacitance and pseudocapacitance, arising from the
presence of various types of nitrogen and oxygen species
(heteroatom effects, based on XPS data) in both of these polymeric
CTF materials.2,4,28 In addition, the galvanostatic charge/discharge
(GCD) profiles of Pyrene-CTF-10 and Pyrene-CTF-20 recorded at
various current densities [Figures 10(c) and 10(d)] had triangular
shapes, again suggesting the presence of both EDLC and
pseudocapacitance arising from the graphitic carbon structures
presenting various types of functionalized units (e.g., pyrrolic
species; hexagonal pyridinic N atoms in triazine rings; C=O and
phenolic OH groups).2,21 As displayed in Figure 10(e), at a current
density of 0.5 A g–1, Pyrene-CTF-10 and Pyrene-CTF-20 displayed
excellent specific capacitances of 380 and 500 F g–1, respectively.
The higher specific capacitance of Pyrene- CTF-20 compared with
that of Pyrene-CTF-10 presumably arose from its graphitic structure,
microporosity, and high N (7.19 wt%) and O atom (9.62 wt%)
contents. In addition, the specific capacitances of the Pyrene-CTFs
decreased upon increasing the scan rate, due to the adsorption of
electrolyte ions on the electrode surfaces.8,68,69 In addition, we
investigated the cyclic stabilities of Pyrene-CTF-10 and Pyrene-CTF-
20 through GCD measurements over 2000 cycles at a current
density of 10 A g–1
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provides
a
performance comparison Pyrene-CTFs and other range with different current densities from 0.5 to 20 Ag-1. The
reported CTFS for CO2 uptake. Thus, our CV and CO2 uptake capacitances (Cs) were calculated using th
D
e
OI
r
:
e
1
p
0
o
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3
e
9
d
Vie/wDeArticle Online
ions
0
q
N
u
J0
a
1
t
2
92K
measurements suggest that Pyrene-CTFs have great potential for for CV and GCD respectively.74,75
use in energy storage and gas storage.
Conflicts of interest
Conclusions
There are no conflicts to declare.
We have synthesized two pyrene-containing conductive CTFs,
Pyrene-CTF-10 and Pyrene-CTF-20, through reactions of TCNPy
with molten ZnCl2 (as catalyst) at 500 °C. These Pyrene-CTFs
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Acknowledgements
This study was supported financially by the Ministry of Science
and Technology, Taiwan, under contracts under contracts
MOST 106-2221-E-110- 067-MY3, 108-2638-E-002-003-MY2,
and 108-2221-E-110-014-MY3. We also thank Mr. Hsien-Tsan
Lin of the Regional Instruments Center at National Sun Yat-Sen
University for help with the TEM measurement.
exhibited outstanding thermal stabilities (high char yields),
partial crystallinity, and high specific surface areas, based on
BET, XRD, and TGA analyses. In addition, Pyrene-CTF-10
displayed gas uptake capacities for CO2 of 2.82 mmol g–1 at 25
°C and 5.10 mmol g–1 at 0 °C. More interestingly, the
electrochemical performances of our two Pyrene-CTFs were
highly stable and efficient, with highest capacitances at 0.5 mV
s–1 of 380 F g–1 for Pyrene-CTF-10 and 500 F g–1 for Pyrene-CTF-
20.
Notes and references
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DOI: 10.1039/D0NJ01292K
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Two pyrene-functionalized CTFs through ionothermal treatment
TCNPy in the presence of molten zinc chloride at 500 °C, which
displayed high-performance CO2 uptake and supercapacitance
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