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Record W2327819282 · doi:10.1021/ja408787k

Two-Electron HCl to H<sub>2</sub> Photocycle Promoted by Ni(II) Polypyridyl Halide Complexes

2013· article· en· W2327819282 on OpenAlexfundno aff
David C. Powers, Bryce L. Anderson, Daniel G. Nocera

Bibliographic record

VenueJournal of the American Chemical Society · 2013
Typearticle
Languageen
FieldEnergy
TopicCO2 Reduction Techniques and Catalysts
Canadian institutionsnot available
FundersNational Institute of General Medical SciencesRyerson UniversityHarvard University
KeywordsChemistryPhotochemistryHalideExcited stateDisproportionationHalogenUltrafast laser spectroscopySolvated electronSpectroscopyCatalysisInorganic chemistryPhysical chemistryRadiolysisAtomic physics

Abstract

fetched live from OpenAlex

Photochemical HX splitting requires the management of two protons and the execution of multielectron photoreactions. Herein, we report a photoinduced two-electron reduction of a polypyridyl Ni(II) chloride complex that provides a route to H2 evolution from HCl. The excited states of Ni complexes are too short to participate directly in HX activation, and hence, the excited state of a photoredox mediator is exploited for the activation of HX at the Ni(II) center. Nanosecond transient absorption (TA) spectroscopy has revealed that the excited state of the polypyridine results in a photoreduced radical that is capable of mediating HX activation by producing a Ni(I) center by halogen-atom abstraction. Disproportionation of the photogenerated Ni(I) intermediate affords Ni(II) and Ni(0) complexes. The Ni(0) center is capable of reacting with HX to produce H2 and the polypyridyl Ni(II) dichloride, closing the photocycle for H2 generation from HCl.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame distilled prediction

Teacher imitation

Not 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.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.163
Threshold uncertainty score0.611

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.001
Bibliometrics0.0000.001
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0010.000
Research integrity0.0000.001
Insufficient payload (model declined to judge)0.0000.000

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.

Opus teacher head0.006
GPT teacher head0.241
Teacher spread0.235 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

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".

Quick stats

Citations73
Published2013
Admission routes1
Has abstractyes

Explore more

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