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Phougat, Neelam; Vasudevan, Padma; Jha, Ν. K.; Bandhopadhyay, Deb Kumar

doi:10.1023/a:1026095426207

Cited by 18 publications

(10 citation statements)

References 81 publications

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“…6 One problem to overcome is the large overpotential that hampers the use of, for example, glassy carbon electrodes. 9 Particular attention has been paid to electrocatalytic reduction of carbon dioxide by metal (e.g., Ag(II), Pd(II), Co(II), Fe(0)) porphyrin derivatives. 8 For some time transition metal porphyrins have been known for their applications in electrocatalysis including many industrially imperative reactions.…”

Section: Introductionmentioning

confidence: 99%

“…8 For some time transition metal porphyrins have been known for their applications in electrocatalysis including many industrially imperative reactions. 9 Particular attention has been paid to electrocatalytic reduction of carbon dioxide by metal (e.g., Ag(II), Pd(II), Co(II), Fe(0)) porphyrin derivatives. [10][11][12] Examples of electrochemical proton reduction catalysed by metal (e.g., Co(I), Fe(0)) porphyrin derivatives are also known, 13,14 however no examples are known for palladium(II) and copper(II) porphyrin complexes.…”

Section: Introductionmentioning

confidence: 99%

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The ferrocene effect: enhanced electrocatalytic hydrogen production using meso-tetraferrocenyl porphyrin palladium(ii) and copper(ii) complexes

et al. 2015

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Copper(ii) and palladium(ii) meso-tetraferrocenylporphyrins ( and ) were employed as catalysts for electrochemical proton reduction in DMF using trifluoroacetic acid (TFA) or triethylamine hydrochloride (TEAHCl) as acids. Gas analysis under electrocatalytic conditions at a glassy carbon working electrode confirmed the product as H2. showed catalytic behavior for both TFA and TEAHCl, whereas only TFA worked for . The performance of the two compounds for electrocatalytic hydrogen generation was compared to the analogous copper(ii) and palladium(ii) meso-tetraphenylporphyrins ( and ) under identical conditions. The presence of the ferrocence groups on the porphyrin favourably shift the overpotential to a less negative value by around 200 mV and increases the catalytic rate of hydrogen production in DMF/TFA by an order of magnitude to 6 × 10(3) s(-1). Moreover, while is fully inactive in a DMF/TEAHCl mixture, the ferrocene subunits activate the catalyst. Spectroelectrochemistry experiments and DFT calculations were consistent with a catalytic process proceeding via the phlorin anion.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The ferrocene effect: enhanced electrocatalytic hydrogen production using meso-tetraferrocenyl porphyrin palladium(ii) and copper(ii) complexes

et al. 2015

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“…Metalloporphyrins have been studied for a variety of applications including catalysis, chemical sensors, medicine, biotechnology, and water remediation to name a few. − Additionally, there is specific interest in understanding the interaction between porphyrins and surfaces for a variety of new technologies. − Interest in this class of compounds is generated by their stability, structural flexibility, and the ability to adjust the porphyrin properties for a particular application by altering either the central metal atom coordinated to the ring or the peripheral sustitutents. ,, The metal atom is particularly important in electrocatalytic processes because of its redox potential.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Atomic Force Microscopy and First-Principles Calculations of Ferriprotoporphyrin Adsorption and Polymerization

et al. 2018

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The adsorption and subsequent electrooxidative polymerization of ferriprotoporphyrin IX chloride (hemin; FePPCl) was investigated on highly ordered pyrolytic graphite, glassy carbon, and polycrystalline Pt electrodes using electrochemical atomic force microscopy, first-principles calculations, and cyclic voltammetry. Hemin was shown to readily adsorb to all three surfaces; however, it was more continuous over the carbon surfaces compared to the Pt surface. This disparity in adsorption appears to be a major contributing factor to differences observed between the electrodes following hemin electropolymerization. Despite differences in roughness and morphology, hemin polymerized as a continuous layer over each electrode surface. Periodic density functional theory calculations were used to model FePP (without Cl) on both the Pt(111) and graphite surfaces using the vdW-DF-optPBE functional to account for the dispersion interactions. Our calculations suggest that the FePP molecule chemisorbs to the Pt surface while at the same time exhibiting intramolecular hydrogen bonding between the carboxylic acid groups, which are extended away from the surface. In contrast to FePP-Pt chemisorption, FePP was found to physisorb to graphite. The preferred spin state upon adsorption was found to be S = 2 on Pt(111), whereas on graphite, the high and intermediate spin states were nearly isoenergetic. Additionally, gas-phase calculations suggest that much of the surface roughness observed microscopically for the polymerized porphyrin layer may originate from the nonparallel stacking of porphyrin molecules, which interact with each other by forming four intermolecular hydrogen bonds and through dispersion interactions between the stacked porphyrin rings. Regardless of polymer thickness, the underlying electrode appears to be able to participate in at least some redox processes. This was observed for the hemin-polymerized Pt electrode using the 2H/H redox couple and was suspected to be due to some Pt surface atoms not being specifically coordinated to the hemin molecules and therefore available to react with H that was small enough to diffuse through the polymer layer.

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“…Different electrodes were used for electrochemical reduction of chlorate ion: a hybrid material, for detection of halogenate ion species in aqueous solutions, modified with: electroactive silver nanoparticles [38], titanium [24,39], carbon [40], boron doped diamond [41], or dimensionally stable anodes for chlorate electrolysis [42]. An autocatalytic chlorate-triiodide reaction was investigated in acid and neutral media [43].…”

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confidence: 99%

Chlorate Electrochemical Removal from Aqueous Media Based on a Possible Autocatalytic Mechanism

Badea¹,

Aleya²,

Mustăţea³

et al. 2019

Rev. Chim.

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The electrochemical chlorate reduction at the Pt electrode in 0.5 M H2SO4 deaerated solutions has been studied using potentiostatic steady-state voltammetry. The kinetics parameters (Tafel slope, charge transfer coefficient, current density, and reaction order) were evaluated in function of chlorate concentration (1x10-4 � 0.2 M KClO3). The process of chlorate reduction is a complex one that implies two charge transfer controlled steps with formation of free radicals and an extent potential region controlled by the concentration polarization. The current density dependence of chlorate concentration tends to an exponential growth at concentration � 0.1 M KClO3 and becomes exponential in the conditions of the catalyst system presence. In the second charge transfer, a surface reaction between free radical �Cl-2 and platinum electrode with formation of complex anions PtCL42- and PtCL62- is responsible for the rapid increase of the reaction rate.

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Cited by 18 publications

References 81 publications

The ferrocene effect: enhanced electrocatalytic hydrogen production using meso-tetraferrocenyl porphyrin palladium(ii) and copper(ii) complexes

The ferrocene effect: enhanced electrocatalytic hydrogen production using meso-tetraferrocenyl porphyrin palladium(ii) and copper(ii) complexes

Electrochemical Atomic Force Microscopy and First-Principles Calculations of Ferriprotoporphyrin Adsorption and Polymerization

Chlorate Electrochemical Removal from Aqueous Media Based on a Possible Autocatalytic Mechanism

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