Water-stable [Ni(salen)]-type electrode material based on phenylazosubstituted salicylic aldehyde imine ligand

Vereschagin, Anatoly A.; Sizov, V. V.; Vlasov, Petr S.; Alekseeva, Elena V.; Konev, Alexander S.; Levin, Oleg V.

doi:10.1039/c7nj03526h

Cited by 17 publications

(17 citation statements)

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“…39,40 As already proposed in the literature, these features are consistent with a film growth mechanism in which the formation of the polymer film begins with the adsorption of the [Ni(salen)] monomer on the surface of the electrode in the positive scan; next the monomers present in the solution react with the adsorbed monomers, resulting in the electropolymerization via stacking of monomers. 41 Figure S2 shows the typical electrochemical CV profile of poly[Ni(salen)] film in monomer-free 0.1 M TBAP/CH 3 CN electrolyte, showing the features related to the Ni oxi-reduction process in the polymeric film. 21 After the electropolymerization step, the poly[Ni(salen)] electrode was electrochemically activated in 1.0 M NaOH solution (in the absence of monomer) at 50 mV s −1 (Figure 1B), leading to the formation of a new electroactive material (poly[Ni(salen)] ATV ).…”

Section: Resultsmentioning

confidence: 99%

Electrocatalytic Oxidation of Methanol, Ethanol, and Glycerol on Ni(OH)₂Nanoparticles Encapsulated with Poly[Ni(salen)] Film

Bott‐Neto

Martins

Machado

et al. 2019

ACS Appl. Mater. Interfaces

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This study describes a systematic investigation of the electrocatalytic activity of poly [Ni(salen)] films, as catalysts for the electrooxidation of Cn alcohols (Cn = methanol, ethanol, and glycerol) in alkaline medium. The [Ni(salen)] complex was electropolymerized on a glassy carbon surface and electrochemically activated in NaOH solution by cyclic voltammetry. X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy results indicate that during the activation step the polymeric film hydrolyzes, leading to the formation of β-Ni(OH) 2 spherical nanoparticles, with an average size of 2.4 ± 0.5 nm, encapsulated with the poly[Ni(salen)] film. Electrochemical results obtained together with the in situ Fourier transform infrared spectroscopy confirm that the electrooxidation of methanol, ethanol, and glycerol occurs by involving a cycling oxidation of β-Ni(OH) 2 with the formation of β-NiOOH species, followed by the charge transfer to the alcohols, which regenerates β-Ni(OH) 2 . Analyses of the oxidation products at low potentials indicate that the major product obtained during the oxidation of methanol and glycerol is the formate, while the oxidation of ethanol leads to the formation of acetate. On the other hand, at high potentials (E = 0.6 V), there is evidence that the oxidation of Cn alcohols leads to carbonate ions as an important product.

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Section: Resultsmentioning

confidence: 99%

Electrocatalytic Oxidation of Methanol, Ethanol, and Glycerol on Ni(OH)₂Nanoparticles Encapsulated with Poly[Ni(salen)] Film

Bott‐Neto

Martins

Machado

et al. 2019

ACS Appl. Mater. Interfaces

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“…This significantly simplifies acquiring detailed information about the electronic structure of this complex. Various techniques, such as optical, near infrared, and infrared absorption spectroscopy; near edge X-ray absorption fine structure (NEXAFS); and X-ray photoelectron spectroscopy (XPS) and their combinations thereof are used to obtain this information [ 15 , 16 , 17 , 18 ].…”

Section: Introductionmentioning

confidence: 99%

The Valence Band Structure of the [Ni(Salen)] Complex: An Ultraviolet, Soft X-ray and Resonant Photoemission Spectroscopy Study

Корусенко

Королева

Vereshchagin

et al. 2022

IJMS

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The valence band photoemission (VB PE) spectra of the [Ni(Salen)] molecular complex were measured by ultraviolet, soft X-ray and resonant photoemission (ResPE) using photons with energies ranging from 21.2 eV to 860 eV. It was found that the Ni 3d atomic orbitals’ (AOs) contributions are most significant for molecular orbitals (MOs), which are responsible for the low-energy PE band at a binding energy of 3.8 eV in the VB PE spectra. In turn, the PE bands in the binding energies range of 8–16 eV are due to the photoionization of the MOs of the [Ni(Salen)] complex with dominant contributions from C 2p AOs. A detailed consideration was made for the ResPE spectra obtained using photons with absorption resonance energies in the Ni 2p3/2, N 1s, and O 1s Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectra. A strong increase in the intensity of the PE band ab was found when using photons with an energy 854.4 eV in the Ni 2p3/2 NEXAFS spectrum. This finding is due to the high probability of the participator-Auger decay of the Ni 2p3/2−13d9 excitation and confirms the relationship between the PE band ab with the Ni 3d-derived MOs.

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“…Moreover, noncovalent π−π interactions between π-electronic systems of neighboring molecules are possible. In this case, π-stacks formed within the polymer film can be part of the charge transfer pathway [30][31][32]. The structure and properties of the formed films are vastly dependent on the structure of initial monomers [24].…”

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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Water-stable [Ni(salen)]-type electrode material based on phenylazosubstituted salicylic aldehyde imine ligand

Abstract: We have synthesized a new water-stable [Ni(salen)]-type electrode material, which was found to be a stacked polymer due to the presence of substituents, preventing oxidative coupling of the phenyl rings.

Cited by 17 publications

References 50 publications

Electrocatalytic Oxidation of Methanol, Ethanol, and Glycerol on Ni(OH)₂Nanoparticles Encapsulated with Poly[Ni(salen)] Film

Electrocatalytic Oxidation of Methanol, Ethanol, and Glycerol on Ni(OH)₂Nanoparticles Encapsulated with Poly[Ni(salen)] Film

The Valence Band Structure of the [Ni(Salen)] Complex: An Ultraviolet, Soft X-ray and Resonant Photoemission 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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Water-stable [Ni(salen)]-type electrode material based on phenylazosubstituted salicylic aldehyde imine ligand

Abstract: We have synthesized a new water-stable [Ni(salen)]-type electrode material, which was found to be a stacked polymer due to the presence of substituents, preventing oxidative coupling of the phenyl rings.

Cited by 17 publications

References 50 publications

Electrocatalytic Oxidation of Methanol, Ethanol, and Glycerol on Ni(OH)2Nanoparticles Encapsulated with Poly[Ni(salen)] Film

Electrocatalytic Oxidation of Methanol, Ethanol, and Glycerol on Ni(OH)2Nanoparticles Encapsulated with Poly[Ni(salen)] Film

The Valence Band Structure of the [Ni(Salen)] Complex: An Ultraviolet, Soft X-ray and Resonant Photoemission 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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Electrocatalytic Oxidation of Methanol, Ethanol, and Glycerol on Ni(OH)₂Nanoparticles Encapsulated with Poly[Ni(salen)] Film

Electrocatalytic Oxidation of Methanol, Ethanol, and Glycerol on Ni(OH)₂Nanoparticles Encapsulated with Poly[Ni(salen)] Film