Electrocatalytic Nitrite Reduction in Neutral Water with Ni(II) and Co(II) Macrocycle Complexes: Catalytic Evaluation and Mechanistic Elucidation
Bibliographic record
Abstract
Abstract Nitrite anions, of anthropogenic origin, in the environment disrupt the nitrogen cycle making the electrocatalytic reduction of nitrite a significant objective. Homogeneous Ni(II) and Co(II) complexes bearing a macrocyclic supporting ligand consisting of a tridentate redox active bis(imino)pyridine moiety coupled with a tertiary amine donor site are effective and selective for the electrocatalytic reduction of nitrite to ammonium ion and hydroxylamine in buffered (pH 7) aqueous solutions. Controlled potential coulometry at potentials from −0.98 to −1.05 V vs Ag/AgCl in 4‐morpholinepropanesulfonic acid (MOPS) buffer yielded ammonium as the major product with Faradaic efficiencies ranging from 76–90 %. A foot‐of‐the‐wave analysis yielded calculated turn‐over frequencies of 61 s −1 and 28 s −1 for the Ni and Co complexes, respectively. The Ni complex displayed a higher selectivity for NH 4 + /NH 2 OH than the Co analog. A computational examination of the catalytic mechanism of the Ni complex was used to support and elucidate the proposed chemical steps, provide some energetic details of the electron and proton transfers, and present a rationale for the selectivity of this reduction.
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How this classification was reachedexpand
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 | 0.000 |
| 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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".