An integrated experimental-theoretical approach to understand the electron transfer mechanism of adsorbed ferrocene-terminated alkanethiol monolayers

Stragliotto, María Fernanda; Fernández, José Luis Fernández; Dassie, Sergio Alberto; Giacomelli, Carla E.

doi:10.1016/j.electacta.2017.12.091

Cited by 5 publications

(4 citation statements)

References 72 publications

(87 reference statements)

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“…It is clear that both switched and nonswitched peak current densities are proportional to scan rate v in Figure c. This is consistent with the theory of electrochemical response of an adsorbed layer, which is often observed in the voltammogram of modified electrodes attached with a monolayer . For an irreversible reaction with an electroactive adsorbed layer, the cathodic peak current density j p ad and peak potential V p are given by where n is the number of transferred electrons, α is the transfer coefficient, F is the Faraday constant, Γ* is the initial amount of adsorbed species, e is the mathematical constant, R is the gas constant, T is the temperature, E 0′ is the formal potential of reaction, and k 0 is the standard heterogeneous rate constant.…”

Section: Resultssupporting

confidence: 84%

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Negative Differential Resistance in Oxygen-ion Conductor Yttria-stabilized Zirconia for Extreme Environment Electronics

Yuan

Podpirka

et al. 2022

ACS Appl. Mater. Interfaces

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Oxygen-ion conductors have traditionally been studied in the context of high temperature (≈ 873 to 1773 K) energy conversion and sensor technologies. However, there is growing interest in exploring ion-based electronics for harsh environments (400 to 573 K) that represents an emerging field. Here, we utilize a blocking electrode to modify the interface properties of oxygen-ion conducting yttria-stabilized zirconia (YSZ) thin film electrochemical cells. The modified YSZ cell exhibits negative differential resistance (NDR) in the current–voltage curves at 543 K in the air. A double-sweep method and analysis of the scan-rate dependence of the j–V characteristics clearly suggest that the NDR behavior is formed by the reduction reaction of adsorbed oxygen or platinum oxide at the YSZ/Pt interface. A stable and switchable YSZ NDR device is realized with a high peak-to-valley current ratio of 5.8 at 543 K. Utilizing the NDR effect, we demonstrate a proof-of-concept switchable ternary inverter by interfacing with a silicon transistor. Oxygen-ion conductors and their interfaces offer new directions to design electronics for extreme environments.

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Section: Resultssupporting

confidence: 84%

“…This is consistent with the theory of electrochemical response of an adsorbed layer, 37 which is often observed in the voltammogram of modified electrodes attached with a monolayer. 38 For an irreversible reaction with an electroactive adsorbed layer, the cathodic peak current density j p ad and peak potential V p are given by 37…”

Section: ■ Introductionmentioning

confidence: 99%

Negative Differential Resistance in Oxygen-ion Conductor Yttria-stabilized Zirconia for Extreme Environment Electronics

Yuan

Podpirka

et al. 2022

ACS Appl. Mater. Interfaces

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“…Charge integration of the Fc redox wave is consistent with monolayer formation. Ferrocene-terminated thiol monolayers on Au have been estimated to be correlated with a charge integration of ∼43 μC cm –2 . ,− This theoretical value is determined by taking the radius of ferrocene and assuming a densely packed monolayer. The hypothetical charge integration for the C18-Fc monolayer is ∼24 μC cm –2 (see SI, Table S6 and Figure S12).…”

Section: Resultsmentioning

confidence: 99%

Non-Covalent Interactions Mimic the Covalent: An Electrode-Orthogonal Self-Assembled Layer

et al. 2023

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Charge-transfer events central to energy conversion and storage and molecular sensing occur at electrified interfaces. Synthetic control over the interface is traditionally accessed through electrode-specific covalent tethering of molecules. Covalent linkages inherently limit the scope and the potential stability window of molecularly tunable electrodes. Here, we report a synthetic strategy that is agnostic to the electrode’s surface chemistry to molecularly define electrified interfaces. We append ferrocene redox reporters to amphiphiles, utilizing non-covalent electrostatic and van der Waals interactions to prepare a self-assembled layer stable over a 2.9 V range. The layer’s voltammetric response and in situ infrared spectra mimic those reported for analogous covalently bound ferrocene. This design is electrode-orthogonal; layer self-assembly is reversible and independent of the underlying electrode material’s surface chemistry. We demonstrate that the design can be utilized across a wide range of electrode material classes (transition metal, carbon, carbon composites) and morphologies (nanostructured, planar). Merging atomically precise organic synthesis of amphiphiles with in situ non-covalent self-assembly at polarized electrodes, our work sets the stage for predictive and non-fouling synthetic control over electrified interfaces.

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“…This value signifies a total coverage of 3.2 %, referred to the maximum theoretical excess of 4:8 � 10 À 10 mol cm 2 . [39] This low coverage, together with the presence of ethanol, allows us to prevent the appearance of multiple redox responses due to different functional domains at the monolayer, [40][41][42] as well as steric hindrances in the formation of the inclusion complex [29] The rate constant and formal potential of the ferrocene/ferrocinimum redox couple are 415 s À 1 and 338 mV vs. SCE reference electrode, respectively. The high value of k 0 allows us to consider the electron transfer process as Nernstian for the range of scan rates used here.…”

Section: Resultsmentioning

confidence: 99%

Kinetic Influence of Surface Charge Transfer Reactions Preceded by Non‐Electrochemical Processes on the Response in Cyclic Voltammetry

et al. 2018

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A general analytical explicit expression for the response of a surface charge transfer preceded by a non‐electrochemical process has been deduced. This solution is applicable to any electrochemical technique independent of the rates of both reactions. Interesting simplified cases are obtained for very common experimental situations in which the rates of electrochemical and non‐electrochemical steps are similar. These expressions have been applied to cyclic voltammetry in order to analyze the kinetic influences on the current‐potential response and to propose procedures for determining the rate and equilibrium constants of the mechanism. Moreover, it has been obtained an “apparent” rate constant of the overall process that reduces to a pure non‐electrochemical rate‐limiting process or to a pure electrochemical rate limiting one, under the right conditions. Experimental verification of the theoretical framework has been done with the analysis of the host‐guest complexation between a surface confined electroactive ferrocene moiety and a solution soluble cyclodextrin in a water‐ethanol media. From the dynamic analysis of the influence of the scan rate on the cyclic voltammetry curves, values have been obtained for the binding constant (4.96×105M-1 ) and rate constants for the inclusion complex formation and dissociation showing the great stability of the electro‐inactive ferrocene‐cyclodextrin complex.

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An integrated experimental-theoretical approach to understand the electron transfer mechanism of adsorbed ferrocene-terminated alkanethiol monolayers

Cited by 5 publications

References 72 publications

Negative Differential Resistance in Oxygen-ion Conductor Yttria-stabilized Zirconia for Extreme Environment Electronics

Negative Differential Resistance in Oxygen-ion Conductor Yttria-stabilized Zirconia for Extreme Environment Electronics

Non-Covalent Interactions Mimic the Covalent: An Electrode-Orthogonal Self-Assembled Layer

Kinetic Influence of Surface Charge Transfer Reactions Preceded by Non‐Electrochemical Processes on the Response in Cyclic Voltammetry

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