Modification of Porous Carbon Material with Polymeric Cobalt Complex with a Schiff Base of Salen-Type for Electrodes of Electrochemical Supercapacitors

Polozhentseva, Yu. A.; Novozhilova, M. V.; Быков, В. А.; Карушев, М. П.

doi:10.1134/s1063785020090278

Cited by 6 publications

(3 citation statements)

References 18 publications

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“…This contrasts with more well-studied Ni-and Cu-based Salen-type polymers that are converted from neutral to oxidized state via ligand-based redox reactions involving consecutive formation of cation radicals and di-cations in biphenyl fragments, while metal centers act as structuring and redox-mediating units [12][13][14]. Efficient metal-centered redox reactions in Cobalt Salen-type metallopolymers enhance their capacitive properties [9,15] and make them useful in electrocatalytic [11] and sensing applications [16]. Unfortunately, the Co(II)/Co(III) redox process is usually observed only in very thin films of polymerized [Co(Salen)]-type complexes and diminishes in thick films, which complicates the practical use of these materials.…”

Section: Introductionmentioning

confidence: 93%

A Novel Cobalt Metallopolymer with Redox-Matched Conjugated Organic Backbone via Electropolymerization of a Readily Available N4 Cobalt Complex

Карушев

2021

Polymers

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Fast and reversible cobalt-centered redox reactions in metallopolymers are the key to using these materials in energy storage, electrocatalytic, and sensing applications. Metal-centered electrochemical activity can be enhanced via redox matching of the conjugated organic backbone and cobalt centers. In this study, we present a novel approach to redox matching via modification of the cobalt coordination site: a conductive electrochemically active polymer was electro-synthesized from [Co(Amben)] complex (Amben = N,N′-bis(o-aminobenzylidene)ethylenediamine) for the first time. The poly-[Co(Amben)] films were investigated by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM), in situ UV-vis-NIR spectroelectrochemistry, and in situ conductance measurements between −0.9 and 1.3 V vs. Ag/Ag+. The polymer displayed multistep redox processes involving reversible transfer of the total of 1.25 electrons per repeat unit. The findings indicate consecutive formation of three redox states during reversible electrochemical oxidation of the polymer film, which were identified as benzidine radical cations, Co(III) ions, and benzidine di-cations. The Co(II)/Co(III) redox switching is retained in the thick polymer films because it occurs at potentials of high polymer conductivity due to the optimum redox matching of the Co(II)/Co(III) redox pair with the organic conjugated backbone. It makes poly-[Co(Amben)] suitable for various practical applications based on cobalt-mediated redox reactions.

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Section: Introductionmentioning

confidence: 93%

A Novel Cobalt Metallopolymer with Redox-Matched Conjugated Organic Backbone via Electropolymerization of a Readily Available N4 Cobalt Complex

Карушев

2021

Polymers

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“…With the ongoing miniaturization of electronic devices, the industry of portable chemical energy sources such as lithium-ion batteries and supercapacitors is developing rapidly [ 1 , 2 ]. The use of nanocomposite materials based on multi-walled carbon nanotubes (MWCNTs) and conductive polymers as supercapacitors’ electrode materials is considered a way to improve the energy characteristics of these devices.…”

Section: Introductionmentioning

confidence: 99%

Improving the Adhesion of Multi-Walled Carbon Nanotubes to Titanium by Irradiating the Interface with He+ Ions: Atomic Force Microscopy and X-ray Photoelectron Spectroscopy Study

Korusenko,

Knyazev,

Petrova

et al. 2024

Nanomaterials

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A complex study of the adhesion of multi-walled carbon nanotubes to a titanium surface, depending on the modes of irradiation with He+ ions of the “MWCNT/Ti” system, was conducted using atomic force microscopy and X-ray photoelectron spectroscopy. A quantitative assessment of the adhesion force at the interface, performed using atomic force microscopy, demonstrated its significant increase as a result of treatment of the “MWCNT/Ti” system with a beam of helium ions. The nature of the chemical bonding between multi-walled carbon nanotubes and the surface of the titanium substrate, which causes this increase in the adhesion of nanotubes to titanium as a result of ion irradiation, was investigated by X-ray photoelectron spectroscopy. It was established that this bonding is the result of the formation of chemical C–O–Ti bonds between titanium and carbon atoms with the participation of oxygen atoms of oxygen-containing functional groups, which are localized on defects in the nanotube walls formed during ion irradiation. It is significant that there are no signs of direct bonding between titanium and carbon atoms.

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“…The introduction of transition metal centers into the conjugated backbone could significantly expand the applications and functionality of such materials. Metal-containing polymers based on transition metal complexes with Salen-type Schiff base ligands are widely studied as promising materials for many different applications [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. The properties of these materials largely depend on substituents in the ligand environment and the metal center, special attention has been given to polymeric nickel(II) complexes with Salen-type ligands.…”

Section: Introductionmentioning

confidence: 99%

Reversible Redox Processes in Polymer of Unmetalated Salen-Type Ligand: Combined Electrochemical in Situ Studies and Direct Comparison with Corresponding Nickel Metallopolymer

Polozhentseva

Novozhilova

Карушев

2022

IJMS

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Most non-metalized Salen-type ligands form passivation thin films on electrode surfaces upon electrochemical oxidation. In contrast, the H2(3-MeOSalen) forms electroactive polymer films similarly to the corresponding nickel complex. There are no details of electrochemistry, doping mechanism and charge transfer pathways in the polymers of pristine Salen-type ligands. We studied a previously uncharacterized electrochemically active polymer of a Salen-type ligand H2(3-MeOSalen) by a combination of cyclic voltammetry, in situ ultraviolet–visible (UV–VIS) spectroelectrochemistry, in situ electrochemical quartz crystal microbalance and Fourier Transform infrared spectroscopy (FTIR) spectroscopy. By directly comparing it with the polymer of a Salen-type nickel complex poly-Ni(3-MeOSalen) we elucidate the effect of the central metal atom on the structure and charge transport properties of the electrochemically doped polymer films. We have shown that the mechanism of charge transfer in the polymeric ligand poly-H2(3-MeOSalen) are markedly different from the corresponding polymeric nickel complex. Due to deviation from planarity of N2O2 sphere for the ligand H2(3-MeOSalen), the main pathway of electron transfer in the polymer film poly-H2(3-MeOSalen) is between π-stacked structures (the π-electronic systems of phenyl rings are packed face-to-face) and C-C bonded phenyl rings. The main way of electron transfer in the polymer film poly-Ni(3-MeOSalen) is along the polymer chain, while redox processes are ligand-based.

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Modification of Porous Carbon Material with Polymeric Cobalt Complex with a Schiff Base of Salen-Type for Electrodes of Electrochemical Supercapacitors

Cited by 6 publications

References 18 publications

A Novel Cobalt Metallopolymer with Redox-Matched Conjugated Organic Backbone via Electropolymerization of a Readily Available N4 Cobalt Complex

A Novel Cobalt Metallopolymer with Redox-Matched Conjugated Organic Backbone via Electropolymerization of a Readily Available N4 Cobalt Complex

Improving the Adhesion of Multi-Walled Carbon Nanotubes to Titanium by Irradiating the Interface with He+ Ions: Atomic Force Microscopy and X-ray Photoelectron Spectroscopy Study

Reversible Redox Processes in Polymer of Unmetalated Salen-Type Ligand: Combined Electrochemical in Situ Studies and Direct Comparison with Corresponding Nickel Metallopolymer

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