Comparative Studies of Photoelectron Spectroscopy and Voltammetry of Ferrocene-Terminated Self-Assembled Monolayers Possessing Different Electron-Donating Abilities

Yokota, Yasuyuki; Mino, Yoshitada; Kanai, Yuta; Utsunomiya, Toru; Imanishi, Akihito; Wolak, Matthaeus; Schlaf, R.; Fukui, Ken–ichi

doi:10.1021/jp5023899

Cited by 25 publications

(42 citation statements)

References 73 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…5 and Supplementary Fig. 10 ) confirms that the pristine Fc SAM are indeed un-oxidised (neutral) Fc 50 . The sharp symmetry of the Fe 2p 3/2 peak at 707.9 eV (Fig.…”

Section: Resultssupporting

confidence: 53%

See 1 more Smart Citation

Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties

et al. 2020

Self Cite

View full text Add to dashboard Cite

Altering electrochemical interfaces by using electrolyte effects or so-called “electrolyte engineering” provides a versatile means to modulate the electrochemical response. However, the long-standing challenge is going “beyond cyclic voltammetry” where electrolyte effects are interrogated from the standpoint of the interfacial properties of the electrode/electrolyte interface. Here, we employ ferrocene-terminated self-assembled monolayers as a molecular probe and investigate how the anion-dictated electrochemical responses are translated in terms of the electronic and structural properties of the electrode/monolayer/electrolyte interface. We utilise a photoelectron-based spectroelectrochemical approach that is capable of capturing “snapshots” into (1) anion dependencies of the ferrocene/ferrocenium (Fc/Fc + ) redox process including ion-pairing with counter anions (Fc + –anion) caused by differences in Fc + –anion interactions and steric constraints, and (2) interfacial energetics concerning the electrostatic potential across the electrode/monolayer/electrolyte interface. Our work can be extended to provide electrolyte-related structure-property relationships in redox-active polymers and functionalised electrodes for pseudocapacitive energy storage.

show abstract

“…5 and Supplementary Fig. 10 ) confirms that the pristine Fc SAM are indeed un-oxidised (neutral) Fc 50 . The sharp symmetry of the Fe 2p 3/2 peak at 707.9 eV (Fig.…”

Section: Resultssupporting

confidence: 53%

“…The sharp symmetry of the Fe 2p 3/2 peak at 707.9 eV (Fig. 5a, b ) reflects the (low spin) diamagnetic character of Fe(II) 50 , 51 . Meanwhile, the UPS spectra shows a peak at 1.6 eV (Fig.…”

Section: Resultsmentioning

confidence: 94%

Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…21.2 eV. 85,88 Features observed in a binding energy range between 4.5 and 9.0 eV likely originate from s (C-C) orbitals from both Fc moieties and the alkyl chains. It should be noted that for shorter SAMs (n < 7), the contribution of the substrate valence band features (i.e., Au 5d ranging from 3 to 8 eV or Ag 4d ranging from 4 to 8 eV) are visible and they overlap with valence band features of the molecules above the HOMO peak.…”

Section: A (Ref 82-84)) Fe-vacuum Distances (D Estmentioning

confidence: 99%

The supramolecular structure and van der Waals interactions affect the electronic structure of ferrocenyl-alkanethiolate SAMs on gold and silver electrodes

Cao

Yang

et al. 2019

Nanoscale Adv.

View full text Add to dashboard Cite

show abstract

“…250mV with respect to the Fc-C 11 -SH [33][34][35][36]. The Fc-C 11 -SH exhibits an oxidation peak at E p =0.34V (versus Ag/AgCl), whereas the Fc-CO-C 11 -SH exhibits the redox peak at E p =0.59V (versus Ag/AgCl).…”

Section: Potential-assisted Modification Protocolmentioning

confidence: 99%

Selectivein situpotential-assisted SAM formation on multi electrode arrays

et al. 2016

View full text Add to dashboard Cite

The selective modification of individual components in a biosensor array is challenging. To address this challenge, we present a generalizable approach to selectively modify and characterize individual gold surfaces in an array, in an in situ manner. This is achieved by taking advantage of the potential dependent adsorption/desorption of surface-modified organic molecules. Control of the applied potential of the individual sensors in an array where each acts as a working electrode provides differential derivatization of the sensor surfaces. To demonstrate this concept, two different self-assembled monolayer (SAM)-forming electrochemically addressable ω-ferrocenyl alkanethiols (C) are chemisorbed onto independent but spatially adjacent gold electrodes. The ferrocene alkanethiol does not chemisorb onto the surface when the applied potential is cathodic relative to the adsorption potential and the electrode remains underivatized. However, applying potentials that are modestly positive relative to the adsorption potential leads to extensive coverage within 10 min. The resulting SAM remains in a stable state while held at potentials <200 mV above the adsorption potential. In this state, the chemisorbed SAM does not significantly desorb nor do new ferrocenylalkythiols adsorb. Using three set applied potentials provides for controlled submonolayer alkylthiol marker coverage of each independent gold electrode. These three applied potentials are dependent upon the specifics of the respective adsorbate. Characterization of the ferrocene-modified electrodes via cyclic voltammetry demonstrates that each specific ferrocene marker is exclusively adsorbed to the desired target electrode.

show abstract

Comparative Studies of Photoelectron Spectroscopy and Voltammetry of Ferrocene-Terminated Self-Assembled Monolayers Possessing Different Electron-Donating Abilities

Cited by 25 publications

References 73 publications

Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties

Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties

The supramolecular structure and van der Waals interactions affect the electronic structure of ferrocenyl-alkanethiolate SAMs on gold and silver electrodes

Selectivein situpotential-assisted SAM formation on multi electrode arrays

Contact Info

Product

Resources

About