Asymmetric Marcus theory: Application to electrode kinetics

Laborda, Eduardo; Henstridge, Martin C.; Compton, Richard G.

doi:10.1016/j.jelechem.2011.12.011

Cited by 48 publications

(69 citation statements)

References 36 publications

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“…This AMH formula has already demonstrated good agreement with experimental data in numerous studies [9,15,26] and is becoming increasingly important in understanding electrochemical systems, whenever symmetric MHC kinetics fails. Mathematically, however, the model is not well posed.…”

Section: Clarification Of the Amh Modelmentioning

confidence: 52%

“…2 is restricted in applicability based on the truncation of the approximating series by which it was derived [15]. Although the restrictions in relevant parameter ranges vary system to system, conservative estimates require | | < 0.35, 1, and |⌘| .…”

Section: B Asymmetric Marcus-hush Kineticsmentioning

confidence: 99%

“…Drawing from early work of Marcus [18], Compton and co-workers implemented and popularized the asymmetric Marcus-Hush (AMH) model, which has a single reorganization energy but introduces an asymmetry parameter to describe di↵erent inner-sphere force constants [7,14,15]. The BV, MHC, and AMH models are compared in Fig.…”

Section: Introductionmentioning

confidence: 99%

“…In the case of the AMH model, this leads to restrictions on the allowable overpotentials and truncation of the range of electron energy levels [15], in order to avoid the divergence of the improper integral over the Fermi distribution.…”

Section: Introductionmentioning

confidence: 99%

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Simple formula for asymmetric Marcus–Hush kinetics

Zeng

Bai

Smith

et al. 2015

Journal of Electroanalytical Chemistry

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The Marcus-Hush theory of electron transfer has seen increasing use as predictive alternative to the phenomenological Butler-Volmer (BV) equation for Faradaic reactions kinetics. Here, we analyze and simplify the asymmetric Marcus-Hush (AMH) model, first proposed by Marcus and recently used by Compton's group to fit experimental data that exhibit two di↵erent reorganization energies, depending on the sign of the overpotential. The AMH model has a single reorganization energy and an asymmetry parameter to account for di↵erent inner sphere force constants, but its practical use is hindered by the need to numerically evaluate the improper integral over electronic Fermi distribution. Moreover, the domain of integration must be arbitrarily truncated to avoid divergence, due to some ambiguities in the derivation, which also limit the validity of the AMH model to weakly curved Tafel plots. Nevertheless, by defining a region over which the formula applies, we derive a simple formula to replace the Fermi integral by exploiting similarities with our recent approximation of the symmetric limit of the Marcus-Hush-Chidsey (MHC) model. These results enable the AMH model to approach the same ease of use as both the MHC and BV models and highlight the need to develop a more comprehensive theory of asymmetric charge transfer.⇤ Corresponding

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Section: Clarification Of the Amh Modelmentioning

confidence: 52%

Section: B Asymmetric Marcus-hush Kineticsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Simple formula for asymmetric Marcus–Hush kinetics

Zeng

Bai

Smith

et al. 2015

Journal of Electroanalytical Chemistry

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“…Charge transfer coefficients for the cathodic (a c ) and anodic (a a ) reactions were calculated to be 0.108 and 0.908. The large deviation of a from 0.5 implies the force constants for the reactant and the product are unequal (according to the asymmetric Marcus theory), [16] which is in agreement with substantial structural changes upon reduction of 1 to 1 2À . [14] The apparent heterogeneous electron transfer rate constant (k s ) was calculated to be 1.33 AE 0.15 s À1 (see Supporting Information).…”

mentioning

confidence: 66%

Bilayer Vesicles as a Noncovalent Immobilization Platform of Electrocatalysts for Energy Conversion in Neutral Aqueous Media

et al. 2017

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We show that synthetic [FeFe]-hydrogenase mimics embedded within liposomes can be immobilized on high-surface-area carbon blacks for the construction of a three-dimensional (3D) electrode for H 2 production in neutral aqueous media. In this design, the bilayer vesicles (liposomes) serve as a waterinsoluble electrocatalyst carrier, facilitating access of the embedded catalysts to aqueous solution. Fast electron-transfer rates and low overpotentials are achieved compared to watersoluble catalysts. The electron-transfer rate constant between the embedded [(m-bdt)Fe 2 (CO) 6 ] (bdt = 1,2-benzenedithiolate; 1) and the electrode is estimated to be 1.33 AE 0.15 s À1 . Immobilized [(m,k 2 -bdt-Me)(m-PPh 2 )Fe 2 (CO) 5 ] (Me = methyl; 3) is able to catalyze H 2 production in Na 2 SO 4(aq) solution (pH = 7) at À1.06 V (vs. SHE) with an overpotential of approximately 400 mV. The reported general method for the construction of 3D electrodes paves the way to potential applications of molecular catalysts in energy devices.Green fuel production is a central issue nowadays because of the limited availability of fossil fuels and general consensus about climate change caused by greenhouse gases. In this regard, development of cheap catalysts for efficient generation of H 2 in aqueous media under mild conditions is of great interest. Substantial efforts have been made to design molecular electrocatalysts analogous to the active site of [FeFe]-hydrogenases in past decades [1] but their water insolubility hinders further applications. Immobilization of synthetic catalysts on solid supports is a strategy to overcome this intrinsic problem for investigation of their reactivity towards H 2 production in aqueous media, and evaluation of their potential for incorporation into energy devices. Anchoring organometallic molecules onto electrode surfaces is generally achieved by two methods: via covalent bonding [2] or intermolecular interactions between the solid support and molecules of interest with designed anchoring groups, such as through p-p interactions, hydrophobic interactions, self-assembly and chelation with metal oxide material. [3] However, these methods require the organometallic complexes bearing specific functional groups. It is not straightforward to all cases and sometimes presents synthetic challenges. Stability of the grafted catalyst film via covalent amide bonds during sustained electrolysis is the other concern. [4] Herein, we report a general method for construction of liposome-modified nanoparticles loaded with molecular catalysts, exhibiting high current densities in neutral aqueous solution for potential applications in energy devices. In the design (Figure 1), bilayer vesicles (or called liposomes) formed by a double chain cationic surfactant, didodecyldimethylammonium bromide (DDAB), [5] serve as cages to entrap synthetic water-insoluble hydrogen evolution reaction (HER) catalysts (1 and 3, respectively; 1 = [(m-bdt)Fe 2 (CO) 6 ], bdt = 1,2-benzenedithiolate; 3 = [(m,k 2 -bdt-Me)(m-PPh 2 )Fe 2 (CO) 5 ], Me = ...

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Recent Advances in Voltammetry

et al. 2015

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Recent progress in the theory and practice of voltammetry is surveyed and evaluated. The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity. This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler–Volmer and Marcus–Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry. The review of the latter field encompasses both the study of nanoparticle-modified electrodes, including stripping voltammetry and the new technique of ‘nano-impacts’.

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Asymmetric Marcus theory: Application to electrode kinetics

Cited by 48 publications

References 36 publications

Simple formula for asymmetric Marcus–Hush kinetics

Simple formula for asymmetric Marcus–Hush kinetics

Bilayer Vesicles as a Noncovalent Immobilization Platform of Electrocatalysts for Energy Conversion in Neutral Aqueous Media

Recent Advances in Voltammetry

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