Scanning Electrochemical Microscopy Analyses of Surfaces Using Ferrocenated Gold Nanoparticle Mediators

Abstract

Small ferrocenated gold nanoparticles, meaning ferrocenyl-functionalized nanoparticles with an approximate radius of 2 nm, were evaluated as redox mediators for surface analysis in Scanning Electrochemical Microscopy (SECM) experiments in feedback mode. In the presence of a bulky anion electrolyte (BarF⁻), these nanoparticles are sufficiently soluble in dichloromethane (CH₂Cl₂) in both their reduced and oxidized states for such analyses in organic media. SECM approach curves were analyzed using the Cornut-Lefrou approximations on several types of substrates. When the nanoparticles are used to probe either a conducting substrate, such as carbon, or an insulating substrate, such as glass, the experimental results are in good agreement with the theoretical behavior expected for diffusion-controlled processes.

On a modified substrate coated with a COOH-terminated organic layer, interactions between the nanoparticles and the surface were detected. These interactions led to an enhancement of the positive feedback response of the approach curve, due to lateral charge transport at the interface, while electron transfer through the organic layer remained negligible. All curves were quantified using the Cornut-Lefrou's equations. This simple treatment of nanoparticle-surface interactions using SECM approach curves associated with analytical approximations appears as an effective way to probe the affinity of redox nanoparticles for a surface, as reflected by an increase in the positive feedback response. Since the method does not require an electrical connection of the sample, and considering the versatility of the nanoparticle preparation, this approach could be applied to a wide range of substrates, whether conducting or insulating.

Immersion-Controlled Nanoparticle Electrodeposition on a Patterned Pyrolyzed Photoresist Film Electrode for Single-Entity Electrochemistry Studies Using Scanning Electrochemical Cell Microscopy.
Takashi Ito, Kathleen O Bailey, Josselyn De Leon +3
Langmuir : the ACS journal of surfaces and colloids1 Oct 2026Peer-reviewedCC BYFull textElectrochemistry & energyEurope PMC
Aryldiazonium reduction mechanism deciphered by scanning electrochemical microscopy through an EC’ process
Nikolaos Kostopoulos, Viacheslav Shkirskiy, Catherine Combellas +3
Electrochimica Acta8 Oct 2026Peer-reviewedLicence not stated1 citedElectrochemistry & energyHAL
Array-addressed scanning electrochemical cell microscopy for single-cell dual-cadherin profiling during epithelial-mesenchymal transition
Yuanyuan Zhang, Meihong Peng, Pufeihong Xia +3
Chemical science23 Oct 2026Peer-reviewedCC BY-NCFull textElectrochemistry & energyEurope PMCPMC
Scanning Electrochemical Microscopy Study of Proton-Coupled Electron Transfer Processes in Aqueous and Concentrated Hydrogen-Bonded Electrolytes: Reorganization Energies and Kinetic Correlations with Medium Acidity
Peisen Qian, Saransh Gupta, Kristin Martin +6
ChemRxiv13 Oct 2026PreprintCC BYFull textElectrochemistry & energyChemRxiv
In situ reduction of CO2 forms surface redox mediators on nanoparticle catalysts
Sucharita Vijayaraghavan, Hung-Ling Yu, Adam J. Senko +3
Chemical science16 Oct 2026Peer-reviewedCC BYFull textOrganic chemistryEurope PMC

Cite

BibTeX RIS

BibTeX

@article{pignol2026scanning,
  title = {{Scanning Electrochemical Microscopy Analyses of Surfaces Using Ferrocenated Gold Nanoparticle Mediators}},
  author = {Guilhem Pignol and Shuai Liu and Yann R. Leroux and Bingwei Mao and Jiawei Yan and Philippe Hapiot},
  journal = {ACS Electrochemistry},
  year = {2026},
  month = jul,
  doi = {10.1021/acselectrochem.6c00145},
  url = {https://hal.science/hal-05742448v1},
  note = {CC BY-NC-ND 4.0},
}

RIS

TY  - JOUR
TI  - Scanning Electrochemical Microscopy Analyses of Surfaces Using Ferrocenated Gold Nanoparticle Mediators
AU  - Guilhem Pignol
AU  - Shuai Liu
AU  - Yann R. Leroux
AU  - Bingwei Mao
AU  - Jiawei Yan
AU  - Philippe Hapiot
PY  - 2026
DA  - 2026/07/14
JO  - ACS Electrochemistry
DO  - 10.1021/acselectrochem.6c00145
UR  - https://hal.science/hal-05742448v1
AB  - Small ferrocenated gold nanoparticles, meaning ferrocenyl-functionalized nanoparticles with an approximate radius of 2 nm, were evaluated as redox mediators for surface analysis in Scanning Electrochemical Microscopy (SECM) experiments in feedback mode. In the presence of a bulky anion electrolyte (BarF⁻), these nanoparticles are sufficiently soluble in dichloromethane (CH₂Cl₂) in both their reduced and oxidized states for such analyses in organic media. SECM approach curves were analyzed using the Cornut-Lefrou approximations on several types of substrates. When the nanoparticles are used to probe either a conducting substrate, such as carbon, or an insulating substrate, such as glass, the experimental results are in good agreement with the theoretical behavior expected for diffusion-controlled processes.  On a modified substrate coated with a COOH-terminated organic layer, interactions between the nanoparticles and the surface were detected. These interactions led to an enhancement of the positive feedback response of the approach curve, due to lateral charge transport at the interface, while electron transfer through the organic layer remained negligible. All curves were quantified using the Cornut-Lefrou's equations. This simple treatment of nanoparticle-surface interactions using SECM approach curves associated with analytical approximations appears as an effective way to probe the affinity of redox nanoparticles for a surface, as reflected by an increase in the positive feedback response. Since the method does not require an electrical connection of the sample, and considering the versatility of the nanoparticle preparation, this approach could be applied to a wide range of substrates, whether conducting or insulating.
SN  - 2997-0571
SN  - 2997-0571
ER  -

Abstract

Related

Cite