Electrochemical functionalization of graphene rationalized by Hammett and Swain-Lupton parameters
Abstract
Graphene's sp^{2}-bonded carbon lattice makes it exceptionally resistant to covalent functionalization, with existing approaches relying on chemically specific and often harsh methods, fragmenting our understanding of its reactivity. Here we show that electric fields of approximately 1 V nm^{-1} in non-aqueous electrolytes enable the electrochemical functionalization of monolayer graphene with a broad range of substituents, leading to two-order-of-magnitude conductance modulation stable over 5,000 cycles and semi-reversible electronic conductor-insulator transitions. Analysis of the oxidation potentials across substituents reveals trends governed by classical descriptors. Species forming localised σ bonds display increasing oxidation potentials with the meta-Hammett constant (σ_m), whereas substituents interacting via delocalised π orbitals follow an inverse dependence on the modified Swain-Lupton resonance parameter (R). These relationships indicate that graphene's oxidation potential increases with the electron-withdrawing strength of the substituent. Our results provide new insights into the electrochemical activity of inert materials under strong electric fields.
Related
- Rapid Proton‐Transfer‐Induced Alkylamine Functionalization of MXene for High‐Force Electrochemical Actuators
- Electrochemical functionalization of allylic amines: a straightforward route to relevant aza-compounds
- The influence of surface functionalization and signal transduction on electrochemical aptamer-based sensors
- Epoxy and Vinyl Silane Functionalization of Graphene Nanoplatelets
- Introducing Chirality into Graphene Oxide Layers through a Facile Amino Acid-Based Covalent Functionalization
BibTeX
@misc{chen2026electrochemical,
title = {{Electrochemical functionalization of graphene rationalized by Hammett and Swain-Lupton parameters}},
author = {L. Chen and H. Li and C. Li and X. Zhang and Q. Dai and M. Alhashmi and J. Tong and E. Hoenig and Y. Li and A. Campbell and K. Hu and Y. -C. Soong and C. Sevik and L. F. Vega and F. M. Peeters and M. Lozada-Hidalgo},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.39997},
eprint = {2610.39997},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.39997},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Electrochemical functionalization of graphene rationalized by Hammett and Swain-Lupton parameters
AU - L. Chen
AU - H. Li
AU - C. Li
AU - X. Zhang
AU - Q. Dai
AU - M. Alhashmi
AU - J. Tong
AU - E. Hoenig
AU - Y. Li
AU - A. Campbell
AU - K. Hu
AU - Y. -C. Soong
AU - C. Sevik
AU - L. F. Vega
AU - F. M. Peeters
AU - M. Lozada-Hidalgo
PY - 2026
DA - 2026/10/29
PB - arXiv
DO - 10.48550/arxiv.2610.39997
UR - https://arxiv.org/abs/2610.39997
AB - Graphene's sp^{2}-bonded carbon lattice makes it exceptionally resistant to covalent functionalization, with existing approaches relying on chemically specific and often harsh methods, fragmenting our understanding of its reactivity. Here we show that electric fields of approximately 1 V nm^{-1} in non-aqueous electrolytes enable the electrochemical functionalization of monolayer graphene with a broad range of substituents, leading to two-order-of-magnitude conductance modulation stable over 5,000 cycles and semi-reversible electronic conductor-insulator transitions. Analysis of the oxidation potentials across substituents reveals trends governed by classical descriptors. Species forming localised σ bonds display increasing oxidation potentials with the meta-Hammett constant (σ_m), whereas substituents interacting via delocalised π orbitals follow an inverse dependence on the modified Swain-Lupton resonance parameter (R). These relationships indicate that graphene's oxidation potential increases with the electron-withdrawing strength of the substituent. Our results provide new insights into the electrochemical activity of inert materials under strong electric fields.
ER -