A Surface Grafting of Carbon Allotropes with <i>in‐situ</i> Generated 3‐aryl Diazonium Chlorides: Electrochemical Kinetic Studies
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Bibliographic record
Abstract
Abstract In this work three different carbon allotropes: multi‐walled carbon nanotubes (MWCNT), graphene and carbon nanohorns (CNH) were covalently bound with in‐situ generated 3‐diazonium aryl chlorides. These species were attached to the carbon surface using an electrochemically‐initiated radical coupling, similar to the Gomberg‐Bachman type reaction. An electrochemical grafting of the extended π‐systems at the carbon surface was performed in aqueous media in a simple 3‐electrode system and its kinetics was investigated by a modified Butler‐Volmer approach. The analysis of Hammett constants demonstrated a strong influence of the type of electron donating‐/withdrawing substituents on the reduction potential peak position and the peak current. Moderately or strong electron withdrawing groups like ‐carboxy or ‐nitro tend to shift reduction potential towards more positive values, which facilitates an electron uptake. The deposition time varies for different carbon allotropes and depends on the carbon graphitization and the surface area. The best surface coverage was obtained at 90–150 sec of the deposition. Although, the surface functionalities are less conductive than the carbon, the electrodes showed a low internal resistance and thus a high rate of electron transfer (high exchange current density and the electron transfer rate constant), with the most promising observed for carbon nanohorns. The best performing carbon revealed also superior mass transport of the redox active species toward the electrode surface, owing to their unique particle shapes and its very porous structure. The Tafel analysis complemented by an impedance spectroscopy allowed selecting the best carbon substrate for the functionalization with a 3‐aminobenzoic acid.
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it