Electrocatalysis via Intrinsic Surface Quinones Mediating Electron Transfer to and from Carbon Electrodes

Li, Danlei; Batchelor‐McAuley, Christopher; Chen, Lifu; Compton, Richard G.

doi:10.1021/acs.jpclett.9b03638

Cited by 7 publications

(10 citation statements)

References 35 publications

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“…The diffusion coefficient for Fe 2+ under these conditions has been determined to be 6.68 (±0.14) ⋅ 10 −10 m 2 s −1 . The used electrode has been previously calibrated and found to have a radius of 3.64 μm . We consider that this radius is accurate within 2 % and that the uncertainty in the bulk solution phase concentration of Fe 2+ is essentially negligible.…”

Section: Resultsmentioning

confidence: 98%

“…Second, at low over potentials a significant pre‐wave is observable. The origin of this pre‐wave has been investigated and shown to be due to a surface specific catalytic mechanism . Hence, two parallel oxidative mechanisms occur during the course of the voltammetric experiment.…”

Section: Resultsmentioning

confidence: 99%

“…There are two notable features regarding this voltammetric response, first as the formal potential for this redox couple is 0.4785 (� 0.0006) V vs. SCE then the main oxidation process occurs at a high overpotential. [21] Second, at low over potentials a significant pre-wave is observable. The origin of this pre-wave has been investigated and shown to be due to a surface specific catalytic mechanism.…”

Section: Experimental Example Of Using the Extraction Methodsmentioning

confidence: 99%

“…The origin of this pre-wave has been investigated and shown to be due to a surface specific catalytic mechanism. [21] Hence, two parallel oxidative mechanisms occur during the course of the voltammetric experiment. At low potentials the iron is oxidised by a surface (quinone) catalysed reaction and the turn-over rate of this surface process is limited leading to the occurrence of a pre-wave at low over potentials (~0.6 V).…”

Section: Experimental Example Of Using the Extraction Methodsmentioning

confidence: 99%

“…The used electrode has been previously calibrated and found to have a radius of 3.64 μm. [21] We consider that this radius is accurate within 2 % and that the uncertainty in the bulk solution phase concentration of Fe 2 + is essentially negligible. The voltammogram was analysed by solving the mass-transport problem, as outlined in the theory section of this work, so that the surface concen-tration of the Fe 2 + was determined at each time step.…”

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confidence: 99%

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Mass‐Transport‐Corrected Transfer Coefficients: A Fully General Approach

Batchelor‐McAuley

Compton

2020

ChemElectroChem

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The transfer coefficient (or, equivalently, the Tafel slope) is an experimentally measurable parameter defined as the change in the logarithm of the current density as a function of the applied potential, where the current density has been corrected (j corr) for changes in the concentration of the reagent at the interface. For some electrode geometries (such as the rotating disc or a micro hemispherical electrode) where the electroactive interface is uniformly accessible and the mass-transport is at steadystate, these changes in concentration can be corrected for analytically. Correcting for the depletion of the reagent significantly increases the range over which Tafel analysis can be used to accurately yield information regarding the electrontransfer process. The important question arises, therefore, for non-uniformly accessible electrodes or for a system not at steady state, such as often encountered with disc electrodes, how can the experimentally measured electrochemical flux be rigorously corrected for to account for the changes in the surface concentration of the reagent? This work presents a simple simulation technique that allows the voltammetry of a disc to be "mass-transport"-corrected without recourse to the use of analytical approximations.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Section: Experimental Example Of Using the Extraction Methodsmentioning

confidence: 99%

Section: Experimental Example Of Using the Extraction Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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Mass‐Transport‐Corrected Transfer Coefficients: A Fully General Approach

Batchelor‐McAuley

Compton

2020

ChemElectroChem

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Discovering Electrochemistry with an Electrochemistry‐Informed Neural Network (ECINN)

Chen,

Yang,

Smetana

et al. 2024

Angewandte Chemie

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Machine learning is increasingly integrated into chemistry research by guiding experimental procedures, correlating structure, and function, interpreting large experimental datasets, to distill scientific insights that might be challenging with traditional methods. Such applications, however, largely focus on gaining insights via big data and/or big computation, while neglecting the valuable chemical prior knowledge dwelling in chemists’ minds. In this paper, we introduce an Electrochemistry‐Informed Neural Network (ECINN) by explicitly embedding electrochemistry priors including the Butler‐Volmer (BV), Nernst and diffusion equations on the backbone of neural networks for multi‐task discovery of electrochemistry parameters. We applied the ECINN to voltammetry experiments of and redox couples to discover electrode kinetics and mass transport parameters. Notably, ECINN seamlessly integrated mass transport with BV to analyze the entire voltammogram to infer transfer coefficients directly, so offering a new approach to Tafel analysis by outdating various mass transport correction methods. In addition, ECINN can help discover the nature of electron transfer and is shown to refute incorrect physics if imposed. This work encourages chemists to embed their domain knowledge into machine learning models to start a new paradigm of chemistry‐informed machine learning for better accountability, interpretability, and generalization.

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Discovering Electrochemistry with an Electrochemistry‐Informed Neural Network (ECINN)

Chen,

Yang,

Smetana

et al. 2024

Angew Chem Int Ed

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Electrocatalysis via Intrinsic Surface Quinones Mediating Electron Transfer to and from Carbon Electrodes

Abstract: The electrochemistry of the Fe 2+ /Fe 3+ redox couple in aqueous solution at carbon electrodes is shown to be catalysed by surface quinone groups intrinsically present in the carbon surface. Such mediation is long speculated but hitherto unproven.

Cited by 7 publications

References 35 publications

Mass‐Transport‐Corrected Transfer Coefficients: A Fully General Approach

Mass‐Transport‐Corrected Transfer Coefficients: A Fully General Approach

Discovering Electrochemistry with an Electrochemistry‐Informed Neural Network (ECINN)

Discovering Electrochemistry with an Electrochemistry‐Informed Neural Network (ECINN)

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