Communication
ChemComm
[
4+4] condensation of TPPDA(NH
2
)
4
with tetraformyl linkers. The
resultant TPPDA-COFs had excellent crystallinities, extraordinary
thermal stabilities and high surface areas. In addition, the TPPDA-
COFs had excellent electrochemical capacitances because their
chemical structures contained redox-active triphenylamine units.
Moreover, the two TPPDA-TPTPE and TPPDA-TPPyr COFs displayed
À1
excellent cycling stability at 10 A g , with 86.2 and 85.6% retention,
respectively, of their original capacitances after 5000 cycles. We
surmise that the massive stabilities of TPPDA-COFs possessing
TPPDA redox-active moieties might be promising materials for
high-performance real supercapacitors in several fields, particularly
electrochemical energy storage devices.
Conflicts of interest
There are no conflicts to declare.
Notes and references
1
2
3
Z. Yu, L. Tetard, L. Zhai and J. Thomas, Energy Environ. Sci., 2015, 8, 702.
G. Wang, L. Zhang and J. Zhang, Chem. Soc. Rev., 2012, 41, 797S.
M. Sevilla and R. Mokaya, Energy Environ. Sci., 2014, 7, 1250.
Fig. 3 (a and b) CV and (c and d) GCD profiles, recorded in 1 M KOH, of the
4 D. Yang, Y. Song, Y. J. Ye, M. Zhang, X. Sun and X. X. Liu, J. Mater.
Chem. A, 2019, 7, 12086.
(a and c) TPPDA-TPPyr and (b and d) TPPDA-TPTPE COFs. (e) Corresponding
5
Z. P. Song, H. Zhan and Y. H. Zhou, Angew. Chem., Int. Ed., 2010, 49, 8444.
specific capacitances determined at various current densities. (f) Cycling
performance measured at a current density of 10 A g for 5000 cycles.
À1
6 X. Han, C. Chang, L. Yuan, T. Sun and J. Sun, Adv. Mater., 2007, 19, 1616.
7
(a) J. Wang, Y. Lee, K. Tee, S. N. Riduan and Y. Zhang, Chem.
Commun., 2018, 54, 7681; (b) Y. Sun, Y. Sun, Q. Pan, G. Li, B. Han,
D. Zeng, Y. Zhang and H. Cheng, Chem. Commun., 2016, 52, 3000.
J. M. Moon, N. Thapliyal, K. K. Hussain, R. N. Goyal and Y. B. Shim,
Biosens. Bioelectron., 2018, 102, 540.
curves of the TPPDA-TPPyr and TPPDA-TPTPE COFs measured at
8
À1
various current densities from 2 to 20 A g . These GCD curves had
triangular shapes featuring a slight bend, suggesting both pseudo-
capacity and EDLC characteristics. The discharging time of the
TPPDA-TPTPE COF was longer than that of the TPPDA-TPPyr COF
9 C. Su, H. He, L. Xu, K. Zhao, C. Zheng and C. Zhang, J. Mater. Chem. A,
2017, 5, 2701.
13
1
0 (a) A. F. M. El-Mahdy and S.-W. Kuo, RSC Adv., 2018, 8, 15266;
(
b) A. F. M. El-Mahdy and S.-W. Kuo, Polymer, 2018, 15, 10.
(
Fig. 3c and d), indicating that the capacitance of the former was 11 R. Kabe and C. Adachi, Nature, 2017, 550, 384.
1
1
2 A. Petr, C. Kvarnstrom, L. Dunsch and A. Ivaska, Synth. Met., 2000, 108, 245.
3 A. F. M. El-Mahdy, Y.-H. Hung, T. H. Mansoure, H.-H. Yu, T. Chen
and S.-W. Kuo, Chem. – Asian J., 2019, 14, 1429.
larger than that of the latter. We used eqn (S1) (ESI†) to determine
the specific capacitances from the GCD curves (Fig. 3e). The specific
capacitance of the TPPDA-TPTPE COF (237.1 F g ) was larger than 14 S. Lin, C. S. Diercks, Y. B. Zhang, N. Kornienko, E. M. Nichols,
that of the TPPDA-TPPyr COF (188.7 F g ) at a current density of
À1
À1
Y. B. Zhao, A. R. Paris, D. Kim, P. Yang, O. M. Yaghi and C. J. Chang,
Science, 2015, 349, 1208–1213.
5 A. F. M. El-Mahdy, C.-H. Kuo, A. A. Alshehri, J. Kim, C. Young,
Y. Yamauchi and S.-W. Kuo, J. Mater. Chem. A, 2018, 6, 19532.
16 A. F. M. EL-Mahdy, C. Young, J. Kim, J. You, Y. Yamauchi and
À1
2
A g . This excellent performance of the TPPDA-TPTPE COF was
1
2
À1
due to its higher surface area (1067 m g ) and pore volume
3
À1
(0.84 cm g ), along with its heteroatoms, all of which made it
S.-W. Kuo, ACS Appl. Mater. Interfaces, 2019, 11, 9343.
7 H. Wei, S. Z. Chai, N. T. Hu, Z. Yang, L. M. Wei and L. Wang, Chem.
Commun., 2015, 51, 12178.
8 L. Bai, S. Z. F. Phua, W. Q. Lim, A. Jana, Z. Luo, H. P. Tham, L. Zhao,
Q. Gao and Y. Zhao, Chem. Commun., 2016, 52, 4128.
9 C. R. DeBlase, K. E. Silberstein, T.-T. Truong, H. D. Abru n˜ a and
W. R. Dichtel, J. Am. Chem. Soc., 2013, 135, 16821.
0 (a) D. Chen, L. Li, Y. Xi, J. Li, M. Lu, J. Cao and W. Han, Electrochim.
Acta, 2018, 286, 264; (b) M. Lu, L. Li, S. Shen, D. Chen and W. Han,
New J. Chem., 2019, 43, 1032; (c) D. Chen, M. Lu, L. Li, D. Cai, J. Li,
J. Cao and W. Han, J. Mater. Chem. A, 2019, 7, 21759.
2
1
easier for the electrolytes to access the surface of the electrode.
Table S5 (ESI†) summarizes the corresponding surface areas
and specific capacitances. We examined the durability of our
TPPDA-COFs by cycling them over 5000 times at 10 A g
1
1
1
2
À1
(
Fig. 3f). These two TPPDA-TPTPE and TPPDA-TPPyr COFs
displayed excellent cycling stability, with 86.2 and 85.6% retention,
respectively, of their original capacitances after 5000 cycles. Com-
paring with reported stable electrode materials such as metal
oxides and MOF-derived metal oxides, our TPPDA-COFs are
among the highest stable electrodes. These high stabilities might
be originated from the extraordinary thermal stability and excellent
crystallinity of our COFs materials. The related Ragone plot
23
24
21 F. Hu, J. Wang, S. Hu, L. Li, W. Shao, J. Qiu, Z. Lei, W. Deng and
X. Jian, ACS Appl. Mater. Interfaces, 2017, 9, 31940.
2 A. M. Khattak, Z. A. Ghazi, B. Liang, N. A. Khan, A. Iqbal, L. Li and
Z. Tang, J. Mater. Chem. A, 2016, 4, 16312.
3 (a) X. Xia, S. Deng, D. Xie, Y. Wang, S. Feng, J. Wu and J. Tu, J. Mater.
Chem. A, 2018, 6, 15546–15552; (b) X. Xia, S. Deng, S. Feng, J. Wu and
J. Tu, J. Mater. Chem. A, 2017, 5, 21134.
2
2
(Fig. S19, ESI†) suggested that these two TPPDA-COFs electrodes
possessed good energy and power densities.
In summary, we have prepared a novel redox-active triphenyl-
2 4
amine derivative TPPDA(NH ) and then used it in the synthesis of
24 (a) R. R. Salunkhe, Y. V. Kaneti and Y. Yamauchi, ACS Nano, 2017,
1, 5293; (b) R. R. Salunkhe, J. Tang, N. Kobayashi, J. Kim, Y. Ide,
S. Tominaka, J. H. Kim and Y. Yamauchi, Chem. Sci., 2016, 7, 5704;
c) C. Young, J. Wang, J. Kim, Y. Sugahara, J. Henzie and
Y. Yamauchi, Chem. Mater., 2018, 30, 3379.
1
(
two TPPDA-COFs—TPPDA-TPPyr and TPPDA-TPTPE COFs---through
This journal is ©The Royal Society of Chemistry 2019
Chem. Commun., 2019, 55, 14890--14893 | 14893