A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water

Schöfberger, Wolfgang; Faschinger, Felix; Chattopadhyay, S; Bhakta, Snehadri; Mondal, Biswajit; Elemans, Johannes A. A. W.; Müllegger, Stefan; Tebi, Stefano; Koch, R.; Klappenberger, Florian; Paszkiewicz, Mateusz; Barth, Johannes V.; Rauls, E.; Aldahhak, Hazem; Schmidt, Wolf Gero; Dey, Abhishek

doi:10.1002/ange.201508404

Cited by 47 publications

(24 citation statements)

References 45 publications

(7 reference statements)

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“…Herein, we report a strategy by covalently grafting Co corrole 1 on conductive Fe 3 O 4 nanoarrays grown on Ti mesh ( 1 @Fe 3 O 4 NR/TM). Co corrole 1 is active and robust to catalyze OER and ORR . The 3D self‐supported Fe 3 O 4 NR/TM has advantages to offer large electrochemical surface area and to ensure rapid charge transfer and mass diffusion .…”

Section: Methodsmentioning

confidence: 99%

Molecular Engineering of a 3D Self‐Supported Electrode for Oxygen Electrocatalysis in Neutral Media

et al. 2019

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Electrodes for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are required in energy conversion and storage technologies. An assembly strategy involves covalently grafting Co corrole 1 onto Fe3O4 nanoarrays grown on Ti mesh. The resulted electrode shows significantly improved activity and durability for OER and ORR in neutral media as compared to Fe3O4 alone and with directly adsorbed 1. It also displays higher atom efficiency (at least two magnitudes larger turnover frequency) than reported electrodes. Using this electrode in a neutral Zn‐air battery, a small charge–discharge voltage gap of 1.19 V, large peak power density of 90.4 mW cm−2, and high rechargeable stability for >100 h are achieved, opening a promising avenue of molecular electrocatalysis in a metal–air battery. This work shows a molecule‐engineered electrode for electrocatalysis and demonstrates their potential applications in energy conversion and storage.

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Section: Methodsmentioning

confidence: 99%

Molecular Engineering of a 3D Self‐Supported Electrode for Oxygen Electrocatalysis in Neutral Media

et al. 2019

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“…The rate constant of the two‐electron/two‐proton reduction of O 2 was determined to be 3.81×10 3 m −1 s −1 at −0.64 V vs. Ag/AgCl (=−0.03 V vs. RHE) with a large overpotential of 1.8 V . The (tpfc)Mn III complex was reported to act as a water oxidation catalyst as well, exhibiting bifunctional catalytic activity …”

Section: Manganese and Nickel Complex Catalystsmentioning

confidence: 98%

“…The (tpfc)Mn III complex can also act as an electrocatalyst for ORR at pH 7, for which the number of electrons ( n value) involved in the reduction of O 2 was determined to be n =2.3, in accordance with the RRDE data, which showed a yield of approximately 90 % of H 2 O 2 . The rate constant of the two‐electron/two‐proton reduction of O 2 was determined to be 3.81×10 3 m −1 s −1 at −0.64 V vs. Ag/AgCl (=−0.03 V vs. RHE) with a large overpotential of 1.8 V .…”

Section: Manganese and Nickel Complex Catalystsmentioning

confidence: 99%

Mechanisms of Two‐Electron versus Four‐Electron Reduction of Dioxygen Catalyzed by Earth‐Abundant Metal Complexes

2017

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The two‐electron reduction of dioxygen with two protons produces hydrogen peroxide, which is directly used as a liquid fuel in hydrogen peroxide fuel cells, whereas the four‐electron reduction of dioxygen is combined with the two‐electron oxidation of hydrogen in hydrogen fuel cells. Platinum (Pt)‐based nanocomposites are the most efficient commercial electrocatalysts for the oxygen reduction reaction (ORR). However, the poor stability, scarcity and high cost of these Pt‐based oxygen electrocatalysts are major barriers for the large‐scale implementation of fuel cell technologies. Replacing noble metal‐based electrocatalysts with highly efficient and inexpensive earth‐abundant metal‐based oxygen electrocatalysts has been of critical importance for practical applications. To develop efficient catalysts for the two‐electron and four‐electron reduction of dioxygen, it is crucially important to clarify the catalytic mechanisms of two‐electron/two‐proton versus four‐electron/four‐proton reduction of dioxygen with earth‐abundant metal complexes. This review focused on the factors that control the two‐electron/two‐proton versus four‐electron/four‐proton reduction of dioxygen by electron donors (one electron reductants) such as ferrocene, catalyzed by earth‐abundant metal complexes such as iron, cobalt, copper, manganese and nickel complexes in the homogeneous phase, by detecting catalytic intermediates, which determine the catalytic pathways of the two‐electron versus four‐electron reduction of dioxygen. The electrocatalytic two‐electron or/and four‐electron reduction of dioxygen with earth‐abundant metal complexes and metal oxides has also been discussed in relation with the homogeneous catalysis.

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“…Corroles are tetrapyrrole macrocycles with a broad range of applications in various fields of science from physics and chemistry to bioscience and medicine . After the first synthesis of corroles more than 50 years ago, rich chemistry related to their peculiarity, namely the stabilization of high‐valent metal states promoting oxidation reactions, has been investigated with steadily increasing effort . There are also investigations that consider well‐defined interfaces formed by corroles adsorbed on clean substrates under ultra‐high vacuum (UHV) conditions .…”

Section: Introductionmentioning

confidence: 99%

Identifying On‐Surface Site‐Selective Chemical Conversions by Theory‐Aided NEXAFS Spectroscopy: The Case of Free‐Base Corroles on Ag(111)

Aldahhak

Paszkiewicz

Rauls

et al. 2018

Chemistry A European J

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We demonstrate here that theory-assisted near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy enables the site-sensitive monitoring of on-surface chemical reactions, thus, providing information not accessible by other techniques. As a prototype example, we have used free-base 5,10,15-tris(pentafluorophenyl)corroles (3H-TpFPC) adsorbed on Ag(111) and present a detailed investigation of the angle-dependent NEXAFS of this molecular species as well as of their thermally induced derivatives. For this, we have recorded experimental C and N K-edge NEXAFS spectra and interpret them based on XAS cross-section calculations by using a continuous fraction approach and core-hole including multiprojector PAW pseudopotentials within DFT. We have characterized the as-deposited low temperature (200 K) phase and unraveled the subsequent changes induced by dehydrogenation (at 330 K) and ring-closure reactions (at 430 K). By exemplarily obtaining profound insight into the on-surface chemistry of free-base corrolic species adsorbed on a noble metal this work highlights how angle-dependent XAS combined with accurate theoretical modeling can serve for the investigation of on-surface reactions, whereby even highly similar molecular structures, such as tautomers and isomers, can be distinguished.

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A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water

Cited by 47 publications

References 45 publications

Molecular Engineering of a 3D Self‐Supported Electrode for Oxygen Electrocatalysis in Neutral Media

Molecular Engineering of a 3D Self‐Supported Electrode for Oxygen Electrocatalysis in Neutral Media

Mechanisms of Two‐Electron versus Four‐Electron Reduction of Dioxygen Catalyzed by Earth‐Abundant Metal Complexes

Identifying On‐Surface Site‐Selective Chemical Conversions by Theory‐Aided NEXAFS Spectroscopy: The Case of Free‐Base Corroles on Ag(111)

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