Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation

Luna, María Eugenia; Moyano, Fernando; Sereno, Leonides; D’Eramo, Fabiana

doi:10.1016/j.electacta.2014.04.157

Cited by 17 publications

(12 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Synthetic manganese porphyrins have been widely studied, with respect to their potential applications in the fields of catalysis and functional materials, − and several meso - and/or β-substituted manganese porphyrins have also been electrochemically examined. − However, to the best of our knowledge, no electrochemical data on manganese(III) β,β′-butanoporphyrins has been reported in the literature and only a few manganese(III) β,β′-benzo-substituted tetraarylporphyrins have been characterized to date. − These earlier studies on benzoporphyrins were devoted mainly to oxidations and applications of the compounds in catalysis, and very little is known about their reductive behavior, which we wished to investigate in detail.…”

Section: Introductionmentioning

confidence: 99%

Spectral, Electrochemical, and ESR Characterization of Manganese Tetraarylporphyrins Containing Four β,β′-Pyrrole Fused Butano and Benzo Groups in Nonaqueous Media

Fang

Wang

et al. 2019

Inorg. Chem.

View full text Add to dashboard Cite

Two series of β,β′-pyrrole butano- and benzo-substituted mangenese(III) tetraarylporphyrins were synthesized and characterized with regard to their spectral and electrochemical properties. The investigated compounds have the general formula butano(Ar)4PorMnCl and benzo(Ar)4PorMnCl, where Por is the dianion of the porphyrin and Ar is a p-CH3Ph, Ph or p-ClPh group on each of the four meso-positions of the macrocycle. Each manganese(III) butano- or benzoporphyrin was examined in CH2Cl2 and/or pyridine containing 0.1 M tetra-n-butylammonium perchlorate and the data then were compared to that of the parent tetraarylporphyrins having the same meso-substituents. Up to four reductions are observed for each compound, the first being metal-centered to generate a Mn(II) porphyrin, and the second and third being porphyrin ring-centered to give a Mn(II) porphyrin π-anion radical and dianion, respectively. The one-electron reduced manganese porphyrins have an ESR spectrum with signals at g ⊥= 5.6–5.8 and g // = 2.0, indicating a mixture of the four- and five-coordinated Mn(II) complexes in a high-spin state (3d5, S = 5/2, I = 5/2). Data from cyclic voltammetry and spectroelectrochemistry both suggest that formation of the porphyrin dianion is followed by a chemical reaction at the electrode surface to give an electroactive phlorin anion. The effects of solvent and porphyrin substituents on ultraviolet–visible light (UV-vis) spectra, redox potentials, and electron transfer mechanisms are discussed.

show abstract

Section: Introductionmentioning

confidence: 99%

Spectral, Electrochemical, and ESR Characterization of Manganese Tetraarylporphyrins Containing Four β,β′-Pyrrole Fused Butano and Benzo Groups in Nonaqueous Media

Fang

Wang

et al. 2019

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…In the following two decades, homogeneous porphyrin-based catalysts have been greatly enriched. Many water-soluble non-noble metalloporphyrins, such as manganese porphyrin ([PMn(III)]Cl 5 ) [ 38 ], cobalt porphyrin (TDMImP, TM4PyP, TTMAP) [ 39 ], and nickel porphyrin [ 40 ] (structures are shown in Figure 2 ), have been well-investigated as key components for electrocatalytic OER. However, perhaps not limited to metalloporphyrins, there are still critical problems to be resolved, such as high overpotentials, which means paying more energy costs.…”

Section: Porphyrin-based Systems As Electrochemical Oer Catalysts For...mentioning

confidence: 99%

Recent Advances in Porphyrin-Based Systems for Electrochemical Oxygen Evolution Reaction

Yao

Wang

et al. 2022

IJMS

View full text Add to dashboard Cite

Oxygen evolution reaction (OER) plays a pivotal role in the development of renewable energy methods, such as water-splitting devices and the use of Zn–air batteries. First-row transition metal complexes are promising catalyst candidates due to their excellent electrocatalytic performance, rich abundance, and cheap price. Metalloporphyrins are a class of representative high-efficiency complex catalysts owing to their structural and functional characteristics. However, OER based on porphyrin systems previously have been paid little attention in comparison to the well-described oxygen reduction reaction (ORR), hydrogen evolution reaction, and CO2 reduction reaction. Recently, porphyrin-based systems, including both small molecules and porous polymers for electrochemical OER, are emerging. Accordingly, this review summarizes the recent advances of porphyrin-based systems for electrochemical OER. Firstly, the electrochemical OER for water oxidation is discussed, which shows various methodologies to achieve catalysis from homogeneous to heterogeneous processes. Subsequently, the porphyrin-based catalytic systems for bifunctional oxygen electrocatalysis including both OER and ORR are demonstrated. Finally, the future development of porphyrin-based catalytic systems for electrochemical OER is briefly prospected.

show abstract

“…In the first coordination sphere, corrole, porphyrin and pyridinophane containing pyrrole or pyridine rings are the most commonly used ligands. These ligands are directly attached to the high‐valent TM ions, forming stable four‐coordinated TMN 4 units ( Figure a) as water oxidation centers . Besides, additional oxygen‐containing groups (e.g., carbonate, acetate) may occupy partially the coordination sites in the equatorial or axial position of the ligands, so TM ions can bond with N and O atoms simultaneously, which are also the active sites for water oxidation by SMMCs .…”

Section: Smmcs For Water Oxidationmentioning

confidence: 99%

Catalysis of a Single Transition Metal Site for Water Oxidation: From Mononuclear Molecules to Single Atoms

et al. 2019

View full text Add to dashboard Cite

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.201904037.Low-cost, nonprecious transition metal (TM) catalysts toward efficient water oxidation are of critical importance to future sustainable energy technologies. The advances in structure engineering of water oxidation catalysts (WOCs) with single TM centers as active sites, for example, single metallic molecular complexes (SMMCs), supported SMMCs, and single-atom catalysts (SACs) in recent reports are examined. The efforts made on these configurations in terms of design principle, advanced characterization, performances and theoretical studies, are critically reviewed. A clear roadmap with the correlations between the single-TM-site-based structures (coordination and geometric structure, TM species, support), and the catalytic performances in water oxidation is provided. The insights bridging SMMCs with SACs are also given. Finally, the challenges and opportunities in the single-TM-site catalysis are proposed.

show abstract

Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation

Cited by 17 publications

References 41 publications

Spectral, Electrochemical, and ESR Characterization of Manganese Tetraarylporphyrins Containing Four β,β′-Pyrrole Fused Butano and Benzo Groups in Nonaqueous Media

Spectral, Electrochemical, and ESR Characterization of Manganese Tetraarylporphyrins Containing Four β,β′-Pyrrole Fused Butano and Benzo Groups in Nonaqueous Media

Recent Advances in Porphyrin-Based Systems for Electrochemical Oxygen Evolution Reaction

Catalysis of a Single Transition Metal Site for Water Oxidation: From Mononuclear Molecules to Single Atoms

Contact Info

Product

Resources

About