Perspectives on electron transfer kinetics across graphene-family nanomaterials and interplay of electronic structure with defects and quantum capacitance
Abstract 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 sup...
Saved in:
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-06-01
|
| Series: | Scientific Reports |
| Subjects: | |
| Online Access: | https://doi.org/10.1038/s41598-025-04357-x |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1849725018667220992 |
|---|---|
| author | Sanju Gupta Magdalena Narajczyk Mirosław Sawczak Robert Bogdanowicz |
| author_facet | Sanju Gupta Magdalena Narajczyk Mirosław Sawczak Robert Bogdanowicz |
| author_sort | Sanju Gupta |
| collection | DOAJ |
| description | Abstract 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) ranging 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, k 0 (or k ET, cm/s) was quantified while imaging electroactivity of potassium hexacyanoferrate (III/IV) [Fe (CN) 6 4−/3−] or ferrocene methanol [Fc 0 /Fc +] redox probe yielding unexpected trends. We examined factors affecting the kinetic rate constant, rationalized through a physical model and parameterized using density functional theory by incorporating defects and dopants. 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), nitrogen doping, and edge plane hydrogen-bonding sites (density: 0.1–1.0 μm−1), altering the electronic structure factored into available density of states near Fermi level (− 0.2 to + 0.2 eV), and quantum capacitance. We elucidated the ET kinetics tunability by engineering the electronic band structure, varying electrode potential, and morphological diversity. |
| format | Article |
| id | doaj-art-d6e3a2e92bf040cf9ff1a061cb87e3e9 |
| institution | DOAJ |
| issn | 2045-2322 |
| language | English |
| publishDate | 2025-06-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj-art-d6e3a2e92bf040cf9ff1a061cb87e3e92025-08-20T03:10:35ZengNature PortfolioScientific Reports2045-23222025-06-0115112710.1038/s41598-025-04357-xPerspectives on electron transfer kinetics across graphene-family nanomaterials and interplay of electronic structure with defects and quantum capacitanceSanju Gupta0Magdalena Narajczyk1Mirosław Sawczak2Robert Bogdanowicz3Department of Metrology and Optoelectronics, Faculty of Electronics, Telecommunication and Informatics, Gdansk University of TechnologyFaculty of Biology, Bioimaging Laboratory, University of GdanskThe Szewalski Institute of Fluid-Flow Machinery, Polish Academy of SciencesDepartment of Metrology and Optoelectronics, Faculty of Electronics, Telecommunication and Informatics, Gdansk University of TechnologyAbstract 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) ranging 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, k 0 (or k ET, cm/s) was quantified while imaging electroactivity of potassium hexacyanoferrate (III/IV) [Fe (CN) 6 4−/3−] or ferrocene methanol [Fc 0 /Fc +] redox probe yielding unexpected trends. We examined factors affecting the kinetic rate constant, rationalized through a physical model and parameterized using density functional theory by incorporating defects and dopants. 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), nitrogen doping, and edge plane hydrogen-bonding sites (density: 0.1–1.0 μm−1), altering the electronic structure factored into available density of states near Fermi level (− 0.2 to + 0.2 eV), and quantum capacitance. We elucidated the ET kinetics tunability by engineering the electronic band structure, varying electrode potential, and morphological diversity.https://doi.org/10.1038/s41598-025-04357-xGFNsLaser-induced grapheneSECMElectron transferElectroactivityQuantum capacitance |
| spellingShingle | Sanju Gupta Magdalena Narajczyk Mirosław Sawczak Robert Bogdanowicz Perspectives on electron transfer kinetics across graphene-family nanomaterials and interplay of electronic structure with defects and quantum capacitance Scientific Reports GFNs Laser-induced graphene SECM Electron transfer Electroactivity Quantum capacitance |
| title | Perspectives on electron transfer kinetics across graphene-family nanomaterials and interplay of electronic structure with defects and quantum capacitance |
| title_full | Perspectives on electron transfer kinetics across graphene-family nanomaterials and interplay of electronic structure with defects and quantum capacitance |
| title_fullStr | Perspectives on electron transfer kinetics across graphene-family nanomaterials and interplay of electronic structure with defects and quantum capacitance |
| title_full_unstemmed | Perspectives on electron transfer kinetics across graphene-family nanomaterials and interplay of electronic structure with defects and quantum capacitance |
| title_short | Perspectives on electron transfer kinetics across graphene-family nanomaterials and interplay of electronic structure with defects and quantum capacitance |
| title_sort | perspectives on electron transfer kinetics across graphene family nanomaterials and interplay of electronic structure with defects and quantum capacitance |
| topic | GFNs Laser-induced graphene SECM Electron transfer Electroactivity Quantum capacitance |
| url | https://doi.org/10.1038/s41598-025-04357-x |
| work_keys_str_mv | AT sanjugupta perspectivesonelectrontransferkineticsacrossgraphenefamilynanomaterialsandinterplayofelectronicstructurewithdefectsandquantumcapacitance AT magdalenanarajczyk perspectivesonelectrontransferkineticsacrossgraphenefamilynanomaterialsandinterplayofelectronicstructurewithdefectsandquantumcapacitance AT mirosławsawczak perspectivesonelectrontransferkineticsacrossgraphenefamilynanomaterialsandinterplayofelectronicstructurewithdefectsandquantumcapacitance AT robertbogdanowicz perspectivesonelectrontransferkineticsacrossgraphenefamilynanomaterialsandinterplayofelectronicstructurewithdefectsandquantumcapacitance |