Electrochemistry of Metalloporphyrins in Nonaqueous Media

Kadish, Karl M.; Caemelbecke, Eric Van

doi:10.1002/9783527610426.bard090006

Cited by 70 publications

(152 citation statements)

References 338 publications

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Section: Pyrolyzed Metal Macrocycle For Promoting Inner-sphere Electrmentioning

confidence: 99%

“…Figure 6 [30,31,74]. As seen in the SWV profile, the peaks at 1.260 V in 0.1 M HClO 4 and 1.508 V in 0.1 M NaOH correspond to the one-electron redox transition involving the delocalized π-electron system in the macrocycle ligand [74]. As observed in the literature [30], CV of the heat-treated catalysts does not yield useful information, since in most cases after heat treatment the double-layer charging current overwhelms the Faradaic currents.…”

Section: Pyrolyzed Metal Macrocycle For Promoting Inner-sphere Electrmentioning

confidence: 99%

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Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

Ramaswamy

Mukerjee

2012

Advances in Physical Chemistry

341

255

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Complex electrochemical reactions such as Oxygen Reduction Reaction (ORR) involving multi-electron transfer is an electrocatalytic inner-sphere electron transfer process that exhibit strong dependence on the nature of the electrode surface. This criterion (along with required stability in acidic electrolytes) has largely limited ORR catalysts to the platinum-based surfaces. New evidence in alkaline media, discussed here, throws light on the involvement of surface-independent outer-sphere electron transfer component in the overall electrocatalytic process. This surface non-specificity gives rise to the possibility of using a wide-range of non-noble metal surfaces as electrode materials for ORR in alkaline media. However, this outer-sphere process predominantly leads only to peroxide intermediate as the final product. The importance of promoting the electrocatalytic inner-sphere electron transfer by facilitation of direct adsorption of molecular oxygen on the active site is emphasized by using pyrolyzed metal porphyrins as electrocatalysts. A comparison of ORR reaction mechanisms between acidic and alkaline conditions is elucidated here. The primary advantage of performing ORR in alkaline media is found to be the enhanced activation of the peroxide intermediate on the active site that enables the complete four-electron transfer. ORR reaction schemes involving both outer-and inner-sphere electron transfer mechanisms are proposed.

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Section: Pyrolyzed Metal Macrocycle For Promoting Inner-sphere Electrmentioning

confidence: 99%

Section: Pyrolyzed Metal Macrocycle For Promoting Inner-sphere Electrmentioning

confidence: 99%

Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

Ramaswamy

Mukerjee

2012

Advances in Physical Chemistry

341

255

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“…The electrochemical behaviour of II to IV were clearly understood from the voltammogram, (see Fig. 2), it represents two step one electron reversible oxidation and two step one electron reduction 16,17 . The redox processes can be summarized as The cyclic voltammogram of metal precursor V in acetonitrile (Fig.…”

Section: Results and Discussion: Uv-visible Studiesmentioning

confidence: 98%

Untitled

2017

IJPSR

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Porphyrins are ever-present large class of naturally occurring macrocyclic compounds with many significant biological representatives comprising heme and chlorophyll. Novel bi-metallic porphyrins derived from [5-(4-hydroxyphenyl)-10,15,20-tri(4-methyl phenyl) porphyrin] and salicylideneamino-2-(N,N-dimethylamino) ethane copper (II) perchlorate was obtained in good yields. The results from various physico-chemical studies reveal a change in the geometry of the copper environment after coordination at the periphery of the porphyrin. The EPR of monocuperated metalloporphyrins have signals of copper with planar geometry and lacks the lines corresponding to peripheral metal due to dipolar broadening. Weak interaction between the metal centers is clear from nickel porphyrin.

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“…Early electrochemistry and spectral properties of Mn III and Mn II -porphyrins in non-aqueous media were reported in detail. [2][3][4][5][6][7][8][9][10][11] The high valent manganese porphyrins (Mn 4+ and Mn…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Characterization of β-Alkyl Substituted Porphyrins and Mn(III) Complexes in Alkaline Solution

Berezina¹,

Klueva²,

Базанов³

2017

MHC

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Electrochemistry of Metalloporphyrins in Nonaqueous Media

Abstract: The sections in this article are Introduction Porphyrin Electrochemistry in the Early 1960 s and the 1970 s Porphyrin Electrochemistry in the 1980s and the 1990s Selection of Appropriate Solvent and Supporting Electrolyte Selection of Appropriate Supporting Electro… Show more

Cited by 70 publications

References 338 publications

Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

Untitled

Electrochemical Characterization of β-Alkyl Substituted Porphyrins and Mn(III) Complexes in Alkaline Solution

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