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Record W2088883329 · doi:10.1002/anie.201405232

Catalytic Consequences of the Thermodynamic Activities at Metal Cluster Surfaces and Their Periodic Reactivity Trend for Methanol Oxidation

2014· article· en· W2088883329 on OpenAlexaff
Weifeng Tu, Ya-Huei Cathy Chin

Bibliographic record

VenueAngewandte Chemie International Edition · 2014
Typearticle
Languageen
FieldMaterials Science
TopicCatalytic Processes in Materials Science
Canadian institutionsUniversity of Toronto
Fundersnot available
KeywordsChemistryEnthalpyOxygenReactivity (psychology)Reaction rate constantCatalysisMetalKineticsActivation energyEntropy of activationPhysical chemistryMethanolChemical kineticsThermodynamicsInorganic chemistryOrganic chemistry

Abstract

fetched live from OpenAlex

The periodic reactivity trend and the connection of kinetics to the thermodynamic activity of oxygen are established for the oxidation of methanol on metal clusters. First-order rate coefficients are a single-valued function of the O2 -to-CH3OH ratio, because this ratio, together with the rate constants for O2 and CH3OH activation, determine the oxygen chemical potential, thus the relative abundance of active sites and bulk chemical state of the clusters. CH3OH activation rate constants on oxygen-covered Ag, Pt, and Pd and on RuO2 clusters vary with the metal-oxygen binding strength in a classical volcano-type relation, because the oxygen-binding strength directly influences the reactivities of oxygen as H abstractors during the kinetically relevant CH3OH activation step. The differences in oxygen thermodynamic activity lead to five orders of magnitude variation in rates (Pt>Pd>RuO2>Ag, 373 K), because of its strong effects on the activation enthalpy and more prominently activation entropy in CH3OH activation.

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)0.001
metaresearch head score (Gemma)0.001
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 score0.007
Threshold uncertainty score0.395

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0010.001
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.001
Scholarly communication0.0000.001
Open science0.0000.000
Research integrity0.0000.000
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 head0.014
GPT teacher head0.252
Teacher spread0.238 · 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

Citations20
Published2014
Admission routes1
Has abstractyes

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