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Does Coherence Affect the Multielectron Oxygen Reduction Reaction?

ABSTRACT: The oxygen reduction reaction (ORR) is the key for oxygen-based respiration and the operation of fuel cells. It involves the transmission of two pairs of electrons. We probed what type of interaction between the electrons is required to enable their efficient transfer into the oxygen. We show experimentally that the transfer of the electrons is controlled by the "hidden property" and present a theoretical model suggesting that it is related to coherent phase relations between the two electrons. Using spin polarization electrochemical measurements, with electrodes coated with different thicknesses of chiral coating, we confirm the special relation between the electrons. This relation is destroyed by multiple scattering events that result in the formation of hydrogen peroxide, which indicates a reduction in the ORR efficiency. Another indication for the possible role of coherence is the fluctuations in the reaction efficiency as a function of thickness of the chiral coated electrode.

SUBMITTER: Gupta A

PROVIDER: S-EPMC10614294 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature

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Does Coherence Affect the Multielectron Oxygen Reduction Reaction?

Gupta Anu A Kumar Anil A Bhowmick Deb Kumar DK Fontanesi Claudio C Paltiel Yossi Y Fransson Jonas J Naaman Ron R

The journal of physical chemistry letters 20231012 42

The oxygen reduction reaction (ORR) is the key for oxygen-based respiration and the operation of fuel cells. It involves the transmission of two pairs of electrons. We probed what type of interaction between the electrons is required to enable their efficient transfer into the oxygen. We show experimentally that the transfer of the electrons is controlled by the "hidden property" and present a theoretical model suggesting that it is related to coherent phase relations between the two electrons. ...[more]

PMID: 37824289

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Project description:High-spin trinuclear iron complex ((tbs)L)Fe3(thf) ([(tbs)L](6-) = [1,3,5-C6H9(NC6H4-o-NSi(t)BuMe2)3](6-)) (S = 6) facilitates 2 and 4e(-) reduction of NxHy type substrates to yield imido and nitrido products. Reaction of hydrazine or phenylhydrazine with ((tbs)L)Fe3(thf) yields triiron μ(3)-imido cluster ((tbs)L)Fe3(μ(3)-NH) and ammonia or aniline, respectively. ((tbs)L)Fe3(μ(3)-NH) has a similar zero-field (57)Fe Mössbauer spectrum compared to previously reported [((tbs)L)Fe3(μ(3)-N)]NBu4, and can be directly synthesized by protonation of the anionic triiron nitrido with lutidinium tetraphenylborate. Deprotonation of the triiron parent imido ((tbs)L)Fe3(μ(3)-NH) with lithium bis(trimethylsilyl)amide results in regeneration of the triiron nitrido complex capped with a thf-solvated Li cation [((tbs)L)Fe3(μ(3)-N)]Li(thf)3. The lithium capped nitrido, structurally similar to the pseudo C3-symmetric triiron nitride with a tetrabutylammonium countercation, is rigorously C3-symmetric featuring intracore distances of Fe-Fe 2.4802(5) Å, Fe-N(nitride) 1.877(2) Å, and N(nitride)-Li 1.990(6) Å. A similar 2e(-) reduction of 1,2-diphenylhydrazine by ((tbs)L)Fe3(thf) affords ((tbs)L)Fe3(μ(3)-NPh) and aniline. The solid state structure of ((tbs)L)Fe3(μ(3)-NPh) is similar to the series of μ(3)-nitrido and -imido triiron complexes synthesized in this work with average Fe-Nimido and Fe-Fe bond lengths of 1.941(6) and 2.530(1) Å, respectively. Reductive N═N bond cleavage of azobenzene is also achieved in the presence of ((tbs)L)Fe3(thf) to yield triiron bis-imido complex ((tbs)L)Fe3(μ(3)-NPh)(μ(2)-NPh), which has been structurally characterized. Ligand redox participation has been ruled out, and therefore, charge balance indicates that the bis-imido cluster has undergone a 4e(-) metal based oxidation resulting in an (Fe(IV))(Fe(III))2 formulation. Cyclic voltammograms of the series of triiron clusters presented herein demonstrate that oxidation states up to (Fe(IV))(Fe(III))2 (in the case of [((tbs)L)Fe3(μ(3)-N)]NBu4) are electrochemically accessible. These results highlight the efficacy of high-spin, polynuclear reaction sites to cooperatively mediate small molecule activation.

Dataset Information

Does Coherence Affect the Multielectron Oxygen Reduction Reaction?

Publications

Does Coherence Affect the Multielectron Oxygen Reduction Reaction?

Similar Datasets

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