Electropolymerized Conjugated Microporous Poly(zinc‐porphyrin) Films as Potential Electrode Materials in Supercapacitors

Abstract

polymerization (EP) between electroactive moieties such as carbazoles, [ 5 ] which can simultaneously accomplish the controlled polymerization and directed fi lm-forming process in one step. Moreover, this approach offers a powerful tool to precisely control the fi lm thickness by modulating the polymerization conditions, to conveniently manipulate diverse pore structures by designing proper monomers, and to widely tune the electronic conductivities by regulating the doping levels, [ 6 ] thus providing a new platform for functional exploration.Herein we report on the high-performance fi lm-state supercapacitors based on CMP fi lms. We intentionally synthesized a Zn (II) 5,10,15,20-tetrakis[(carbazol-9-yl)phenyl]porphyrin (ZnmTCPP) monomer based on a zinc-porphyrin core and four carbazole peripherals ( Figure 1 ). Zinc porphyrins participate in biological electronic exchange and energy conversion and play an important role in redox processes. They have been widely studied in biomimetics such as oxygen-carrying hemoglobin and electron transfer of cytochrome-c. [ 7 ] N -Substituted carbazole units upon electrooxidative reaction form cation radical species that are highly active in coupling with each other and yield dimer in near-unity effi ciency without the generation of other oligomers. [ 6d,e , 8 ] Both zinc porphyrins and polycarbazoles have been reported to exhibit reversible electrochemical properties which are essential for supercapacitor utilization. [ 9 ] The 3D network structure resulted from the tetrahedral confi guration of the Zn-mTCPP monomer would provide high surface areas and facilitate ion transportation. Through fast and reversible electrochemical reactions, i.e., doping and dedoping, CMP fi lms based on Zn-mTCPP would operate as a promising electrode material of pseudocapacitor to store and release energy.The CMP fi lms were fabricated by cyclic voltammetry (CV) between the potential range of 0-1.4 V in CH 2 Cl 2 with the ZnmTCPP concentration of 1.5 × 10 −5 M ( Figure 2 a,b). During the fi rst cycle of anodic sweep, a broad peak appears from 0.6 to 0.85 V, which is attributed to the oxidation of zinc-porphyrin cores. [ 9c,d ] Another peak at 1.14 V is assigned to the formation of carbazole radical cations, which couple with each other to form dimeric carbazole cations. During the cathodic sweep process, the dimeric carbazole dication is reduced to its neutral state through two one-electron steps, [ 10 ] which results in two peaks at 1.07 and 0.82 V, respectively, whereas the peak appeared at 0.61 V during the backward sweep corresponds to the reduction of oxidized zinc porphyrin. During the second anodic sweep, a new oxidative peak appears at 0.86 V, which is assigned to the oxidation of newly formed dicarbazole groups. A distinct feature is that the current increases with the cycle numbers, which demonstrates that the CMP fi lms gradually grow on Supercapacitors are energy-storage and power-supply devices that are developed to meet the increasing demand for applications in powering vehicle...

The microwave-assisted solvothermal synthesis of a novel β-ketoenamine-linked conjugated microporous polymer for supercapacitors

“…Two minor plateaus between À0.1-0.0 and 0.2-0.4 V redox couple can be observed. [14][15][16][17][18][19] Nyquist plots in Fig. The KECMP-1 electrodes can work well even at a current density above 200 A g À1 , revealing an excellent rate capability.…”

“…The galvanostatic charge-discharge tests are studied and shown in Fig. 18,19 In addition, cycling tests suggest that the KECMP-1 electrodes reect the outstanding stability in 1 M H 2 SO 4 electrolyte. Two minor plateaus between À0.1-0.0 and 0.2-0.4 V redox couple can be observed.…”

“…[18][19][20][21] The Bode plots of KECMP-1 (Fig. The charge transfer resistance of electrode (R ct ) was 0.085 U.…”

Electrochemically Generated Thin Films of Microporous Polymer Networks: Synthesis, Properties, and Applications

“…a) Cyclic voltammograms of P9 ‐films in monomer‐free solution at different scan rates, b) relationship between peak currents and scan rates, c) galvanostatic charge/discharge plots at different current densities, and d) capacitance values for different current densities. Reproduced with permission …”

“…Reproduced with permission. [38] place, [36] and (ii) the formation of charge-transfer complexes between the electron-poor nitroaromatic analytes and the electron-rich MPN films thus decreasing the interfacial charge-transfer resistance. [37] The use of microporous polymer films in electrochemical supercapacitors has been also explored by Ma and co-workers.…”