Perspectives on Electron Transfer Kinetics Across Graphene-Family Nanomaterials and the Interplay of Electronic Structure with Defects and Quantum Capacitance

Sanju Gupta; Magdalena Narajczyk; Mirosław Sawczak; Robert Bogdanowicz

doi:10.1038/s41598-025-04357-x

Perspectives on Electron Transfer Kinetics Across Graphene-Family Nanomaterials and the Interplay of Electronic Structure with Defects and Quantum Capacitance

Abstrakt

This perspective presents a combined experimental-theory investigation of the mechanistic outer-sphere electron transfer (OS-ET) kinetics in an adiabatic regime for a cornerstone electrochemical reaction, fundamental to efficient energy interconversion as in electrochemical double layer supercapacitors, across graphene-family nanomaterials (GFNs) ranged from pristine graphene to nitrogen-doped graphene aerogel and the novel laser-induced graphene. Using scanning electrochemical microscopy (SECM) operating in feedback mode and co-located spectroscopy, the ET rate constant, k0 (or kET, cm/s) was quantified while imaging electroactivity of OS potassium hexacyanoferrate (III/IV) [Fe (CN)64-/3-] or ferrocene methanol [Fc0/Fc+] redox probe yielding unexpected trends. We examined factors affecting the kinetic rate constant rationalized through physical model and parameterized using density functional theory with incorporation of defects and dopant. We attributed the improved kinetic rates (0.010.1 via SECM) compared with ensemble-averaged method (0.0010.01 cm/s) to pointlike topological defects in basal plane (number density ~1012/cm2), oxygen functional groups (C/O ratio: 4:112:1) and nitrogen doping, edge plane hydrogen-bonding sites (density: 0.11.0 μm-1), altered electronic structure factored into available density of states near Fermi level (-0.2+0.2 eV), and quantum capacitance. We elucidated the ET kinetics tunability by engineering the electronic band structure, varying electrode potential, and morphological diversity.

Cytowania

0

CrossRef
0

Web of Science
0

Scopus

Autorzy (4)

Sanju Gupta dr
Magdalena Narajczyk dr
- Faculty of Biology, University of Gdansk, Gdansk
Mirosław Sawczak dr hab. inż.
- The Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Sciences
Robert Bogdanowicz dr hab. inż.

Cytuj jako

Pełna treść

pobierz publikację

pobrano 0 razy

Wersja publikacji: Submitted Version
DOI:: Cyfrowy identyfikator dokumentu elektronicznego (otwiera się w nowej karcie) 10.1038/s41598-025-04357-x
Licencja: otwiera się w nowej karcie

Słowa kluczowe

Informacje szczegółowe

Kategoria:

Publikacja w czasopiśmie

Typ:

artykuły w czasopismach

Opublikowano w:

Scientific Reports nr 15, strony 1 - 15,
ISSN: 2045-2322

Język:

angielski

Rok wydania:

2025

Opis bibliograficzny:

Gupta S., Narajczyk M., Sawczak M., Bogdanowicz R.: Perspectives on Electron Transfer Kinetics Across Graphene-Family Nanomaterials and the Interplay of Electronic Structure with Defects and Quantum Capacitance// Scientific Reports -, (2025), s.1-15

DOI: