Connection of thermodynamics and kinetics in oxidation reactions catalyzed by transition metals and oxides
Bibliographic record
Abstract
This chapter examines the oxidation reactions of alcohols and alkanes on transition metal or metal oxide surfaces. The diverse sets of reactions, including oxidative dehydrogenation, partial oxidation, reforming, and combustion, occur over temperature and oxygen chemical potential ranges spanned over many orders of magnitude, but they share similar active site requirements and mechanistic events—the oxygen chemical potentials dictate the thermodynamically stable states of the surfaces and type of reactive oxygen, on which catalytic turnovers occur via the general cycles of reductant and oxidant activation, kinetically coupled together. The chapter begins with an exploration on the thermodynamics of a bulk metal–O2 system and its application as a first approximation on the oxide phase and oxygen storage capacity, as well as the driving force in oxide redox reactions, the latter being graphically captured in an Ellingham diagram. Aside from bulk properties, the thermochemical properties of individual lattice oxygen atoms in dispersed metal oxides, such as their vacancy formation enthalpies, are expected to depend on their local coordination sphere. Through case studies, the chapter explores the general mechanistic trends, especially how the thermochemical properties of the reactive oxygen atoms, either as chemisorbed oxygen or lattice oxygen, mediate the catalytic conversion of alcohols and alkanes, through altering the active site structures and/or the character and activation free energy of the kinetically relevant C–H bond scission transition states.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.002 | 0.003 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.002 |
| Insufficient payload (model declined to judge) | 0.008 | 0.002 |
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".