Electrocatalytic H<sub>2</sub> Generation from Water Relying on Cooperative Ligand Electron Transfer in “PN<sup>3</sup>P” Pincer‐Supported Ni<sup>II</sup> Complexes
Bibliographic record
Abstract
Abstract Water is the most sustainable source for H2 production, and the efficient electrocatalytic production of H2 from mixed water/acetonitrile solutions by using two new air‐stable nickel(II) pincer complexes, [Ni(κ3‐2,6‐{Ph2PNR}2(NC5H3)Br2] (R=H I, Me II) is reported. Hydrogen generation from H2O/CH3CN solutions is initiated at −2 V against Fc+/0, and bulk electrocatalysis studies showed that the catalyst functions with an excellent Faradaic efficiency and a turnover frequency of 160 s−1. A DFT computational investigation of the reduction behavior of I and II revealed a correlation of H2 formation with charge donation from electrons originating in a reduced ligand‐localized orbital. As a result, these catalysts are proposed to proceed by a novel mechanism involving electron/proton transfer between a Ni0I species bonded to an anionic PN3P ligand (“L−/Ni0I”) and a NiI‐hydride (“Ni−H”). Furthermore, these catalysts are able to reduce phenol and acetic acid, more active proton sources, at lower potentials that correlate with the substrate pKa.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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) | 0.001 | 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 source (direct Gemma or distilled Codex), 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".