Spectroscopy takes electrochemistry beyond the interface: A compact analytical solution for the reversible first-order catalytic mechanism

Laborda, Eduardo; Gómez-Gil, José María; Molina, Á.; Compton, Richard G.

doi:10.1016/j.electacta.2018.07.070

Cited by 7 publications

(2 citation statements)

References 24 publications

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“…[12] Even considering only CPE, the outcome of a SEC experience is sensitive to the experimental conditions for molecular catalysis in solution due to inherent inhomogeneous concentrations in an electrolysis cell. Despite several formal descriptions of SEC experiments for molecular catalytic systems considering various configurations (light beam normal or parallel to the electrode surface; thinlayer or larger cells) being available, [13] reports on experimental SEC do not always pay attention to it in the data analysis and interpretation. Herein, we propose a simple modelling of CPE for a homogeneous catalytic reaction in a three electrode electrochemical cell configuration corresponding to typical laboratory-scale experiments as sketched in scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Controlled Potential Electrolysis: Transition from Fast to Slow Regimes in Homogeneous Molecular Catalysis. Application to the Electroreduction of CO₂ Catalyzed by Iron Porphyrin

Deeba,

Collard,

Rollin

et al. 2023

ChemElectroChem

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Molecular catalysis of electrochemical reactions is a field of intense activity because of the current interest in electrifying chemical transformations, including both electrosynthesis of organic molecules and production of fuels via small molecule activation. Controlled potential electrolysis (CPE) is often coupled with in situ in operando spectroscopic methods with the aim to gather mechanistic information regarding the catalytic species involved. Herein, considering a simple mechanism for a homogeneous molecular catalysis of an electrochemical reaction, we establish the concentration profile of the catalyst in the electrolysis cell enabling to envision the information that can be obtained from the coupling of this CPE with a spectroscopic probe in the cell compartment. We show how the characteristic parameters of the system (catalytic rate constant, cell dimensions and stirring rate) affect the response with particular emphasis on the transition between two limiting cases, namely a ‘fast’ catalysis regime where catalysis only takes place in a small layer adjacent to the electrode surface and a ‘slow’ catalysis regime where catalysis takes place in the bulk of the solution. These formal concepts are then illustrated with an experimental example, the electroreduction of CO2 in dimethylformamide homogeneously catalyzed by iron tetraphenylporphyrin and followed by UV‐vis spectroscopy.

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Section: Introductionmentioning

confidence: 99%

Controlled Potential Electrolysis: Transition from Fast to Slow Regimes in Homogeneous Molecular Catalysis. Application to the Electroreduction of CO₂ Catalyzed by Iron Porphyrin

Deeba,

Collard,

Rollin

et al. 2023

ChemElectroChem

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“…38 Moreover, recent work by Molina et al has focused on the theoretical study of electrochemically driven solution phase reactions. 39,40 In this paper we provide new physical insights to the two heavily industrialised generic electrochemical mechanismsdirect and mediated oxidation via proof-of-concept for mechanistic visualization using spectrofluorometric electrochemistry to probe the contrasting spatial distributions associated with the two mechanisms. We first report simulation results considering a thin-layer cell consisting of a cylindrical electrode, as commonly deployed experimentally.…”

Section: Introductionmentioning

confidence: 99%

Visualising electrochemical reaction layers: mediated vs. direct oxidation

Yang

Batchelor‐McAuley

et al. 2020

Phys. Chem. Chem. Phys.

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A reasoned general explanation about the concepts of diffusion and reaction layers

Laborda,

González,

Molina

2023

J Solid State Electrochem

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The understanding of the implication of the transport of matter is fundamental in the teaching of heterogeneous charge transfers, which are the central element of the electrochemical science and technologies. Thus, even in the absence of intrinsic kinetic complications, the overall rate of such events is frequently conditioned by the mass transport and also by the occurrence of homogeneous coupled chemical reactions. Upon comprehending and accounting for these two effects, the emergent and widely used concepts of the diffusion and reaction layers will be discussed and disentangled under potential-controlled conditions. First, some basic concepts about the transport of charged species in solution are recalled, in order to establish the experimental conditions under which diffusion-only transport can be considered. Under these premises, a fast electron transfer will be considered to introduce the concept of “diffusion layer”, discussing its relationship with the time of the experiment and with the characteristics of the diffusive field that is strongly influenced by the geometry and size of the electrode considered. Next, fast electron transfer reactions “conditioned” by homogeneous chemical reactions undergone by the reactant and/or the product of the redox couple will be analysed. A historical introduction to the concept of “reaction layer” is carried out, pointing out its value in processes with chemical regeneration of the electroactive species and its non-negligible interplay with the mode of diffusion.

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Spectroscopy takes electrochemistry beyond the interface: A compact analytical solution for the reversible first-order catalytic mechanism

Cited by 7 publications

References 24 publications

Controlled Potential Electrolysis: Transition from Fast to Slow Regimes in Homogeneous Molecular Catalysis. Application to the Electroreduction of CO₂ Catalyzed by Iron Porphyrin

Controlled Potential Electrolysis: Transition from Fast to Slow Regimes in Homogeneous Molecular Catalysis. Application to the Electroreduction of CO₂ Catalyzed by Iron Porphyrin

Visualising electrochemical reaction layers: mediated vs. direct oxidation

A reasoned general explanation about the concepts of diffusion and reaction layers

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Spectroscopy takes electrochemistry beyond the interface: A compact analytical solution for the reversible first-order catalytic mechanism

Cited by 7 publications

References 24 publications

Controlled Potential Electrolysis: Transition from Fast to Slow Regimes in Homogeneous Molecular Catalysis. Application to the Electroreduction of CO2 Catalyzed by Iron Porphyrin

Controlled Potential Electrolysis: Transition from Fast to Slow Regimes in Homogeneous Molecular Catalysis. Application to the Electroreduction of CO2 Catalyzed by Iron Porphyrin

Visualising electrochemical reaction layers: mediated vs. direct oxidation

A reasoned general explanation about the concepts of diffusion and reaction layers

Contact Info

Product

Resources

About

Controlled Potential Electrolysis: Transition from Fast to Slow Regimes in Homogeneous Molecular Catalysis. Application to the Electroreduction of CO₂ Catalyzed by Iron Porphyrin

Controlled Potential Electrolysis: Transition from Fast to Slow Regimes in Homogeneous Molecular Catalysis. Application to the Electroreduction of CO₂ Catalyzed by Iron Porphyrin