Electrocatalytic oxygen reduction reaction with metalloporphyrins

Comprehensive SummaryDeveloping electrocatalysts with high activity and selectivity for the oxygen reduction reaction (ORR) is vital to promote the performance of the next‐generation energy technologies, which depend on the efficiency of the catalytic reduction of dioxygen. In the structure of cytochrome c oxidases (CcOs), a histidine imidazole residue binding to the axial position of Fe plays a crucial role in facilitating the selective reduction of O2 to water. Inspired by nature, we herein report on the synthesis of CoIII corrole 1 tethered with an imidazole ligand as well as its electrocatalytic ORR and O2 binding features. As compared to the imidazolium‐free analogue, complex 1 displayed remarkably boosted activity for the selective four‐electron/four‐proton (4e‐/4H+) ORR with a half‐wave potential of E1/2 = 0.82 V versus reversible hydrogen electrode (RHE) in 0.1 mol/L KOH solutions. Importantly, we demonstrate that the tethered axial imidazole ligand improves the O2 binding ability of 1 thermodynamically and dynamically, which is crucial to boost electrocatalytic ORR performance. This work presents an example to improve electrocatalytic ORR activity and selectivity of Co corroles by introducing an axial imidazole ligand to enhance the O2 binding and activation.

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“…[ 36‐39 ] However, highly active and selective electrocatalysts for 4e ‐ /4H + ORR are still required. [ 40‐51 ]…”

Section: Background and Originality Contentmentioning

confidence: 99%

A Cobalt(III) Corrole with a Tethered Imidazole for Boosted Electrocatalytic Oxygen Reduction Reaction

Peng

Luo

2023

Chin. J. Chem.

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“…However, macrocyclic catalysts still present challenges in ORR activity, durability and electrical conductivity. [44] In light of the highperforming property, variety of applications and ease of synthesis, this retrospective effort focuses on the structural merits of meso-positioned porphyrins and the effects from the catalyst support materials for electrocatalytic ORRs, as illustrated in Figure 1. Meso-rather than β-positioned metalloporphyrins are arranged.…”

Section: Introductionmentioning

confidence: 99%

“…The in‐depth study of macrocyclic compounds is conducive to exploring their catalytic active sites, catalyst morphology and understanding the reaction mechanism, which provides an opportunity to adjust the molecular structure and support materials to further advance the catalytic activities. However, macrocyclic catalysts still present challenges in ORR activity, durability and electrical conductivity [44] . In light of the high‐performing property, variety of applications and ease of synthesis, this retrospective effort focuses on the structural merits of meso ‐positioned porphyrins and the effects from the catalyst support materials for electrocatalytic ORRs, as illustrated in Figure 1.…”

Section: Introductionmentioning

confidence: 99%

Meso‐substituted Metalloporphyrin‐based Composites for Electrocatalytic Oxygen Reduction Reactions

Yuan

George

et al. 2023

ChemNanoMat

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Metalloporphyrins have been regarded as one of the most promising electrocatalysts for oxygen reduction reactions (ORRs) due to their ease of structure modification and the robust coordinated M−N4 environment. However, the electrocatalytic activity, selectivity and stability of the metalloporphyrin‐based composite catalysts are often reported to be much poorer than those of the Pt‐based materials, arousing researchers to devote to exploring a thorough understanding of the relationship between the catalyst structures and ORR performance/mechanisms. Here we will review the design of meso‐positioned porphyrin structures from the aspects of selection of central metal ion species in both monometallic and bimetallic molecules, and modulation of peripheral functional substituents to introduce beneficial effects, including electron affinity, steric effects, interfacial charge states and proton management. Influences from different carbon materials as the support for composite catalysts as well as the electrolytes on oxygen reduction properties will be briefly illustrated before presenting the perspectives and insights for future works in conclusion remarks. We hope that this Review will serve as a roadmap for advancing the insights of the molecular structural and substrate morphological factors impacting ORR properties with the ultimate goal of developing and improving novel metalloporphyrins as efficient and durable electrocatalysts to champion the precious Pt/C.

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Recent progress of electrodes in rechargeable zinc–air batteries

Ran¹,

Wang²,

Gao³

2022

Sci. Sin.-Chim

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Electrocatalytic oxygen reduction reaction with metalloporphyrins

Cited by 3 publications

References 120 publications

A Cobalt(III) Corrole with a Tethered Imidazole for Boosted Electrocatalytic Oxygen Reduction Reaction

A Cobalt(III) Corrole with a Tethered Imidazole for Boosted Electrocatalytic Oxygen Reduction Reaction

Meso‐substituted Metalloporphyrin‐based Composites for Electrocatalytic Oxygen Reduction Reactions

Recent progress of electrodes in rechargeable zinc–air batteries

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Electrocatalytic oxygen reduction reaction with metalloporphyrins

Cited by 3 publications

References 120 publications

A Cobalt(III) Corrole with a Tethered Imidazole for Boosted Electrocatalytic Oxygen Reduction Reaction

A Cobalt(III) Corrole with a Tethered Imidazole for Boosted Electrocatalytic Oxygen Reduction Reaction

Meso‐substituted Metalloporphyrin‐based Composites for Electrocatalytic Oxygen Reduction Reactions

Recent progress of electrodes in rechargeable zinc&ndash;air batteries

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Recent progress of electrodes in rechargeable zinc–air batteries