Catalytic Consequences of Protons in Methanol Oxidative Dehydrogenation on Molybdenum-Based Polyoxometalate Clusters
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Bibliographic record
Abstract
This study unravels the catalytic effects of adjacent protons in redox catalysis of bifunctional Keggin-type phosphomolybdic acid clusters (H 3 PMo 12 O 40 ). Isolated redox sites (O*) and Brønsted acid-redox site pairs (OH/O*) catalyze methanol oxidative dehydrogenation (ODH), a redox reaction, via the identical elementary steps and the formation of the kinetically relevant [HOCH 2 ···H···O*] ‡ and [OH···HOCH 2 ···H···O*] ‡ transition states, but with different kinetic requirements, established from selective site inactivation, product tracking, dynamic pyridine/2,6-di- tert -butylpyridine titrations, and kinetic assessments. The presence of adjacent protons interacts with and stabilizes the methanol precursor in the OH···HOCH 2 –H···O* adsorbed state through additional H-bonding interactions by 57 kJ mol –1 in adsorption enthalpy and by 144 J mol –1 K –1 in adsorption entropy. These additional interactions, stabilizing the [OH···HOCH 2 ···H···O*] ‡ transition state, lead to a decrease in apparent methanol activation enthalpy of 50 kJ mol –1 and in activation entropy of 97 J mol –1 K –1, resulting in an overall increase in methanol ODH turnovers. The kinetic consequences of protons established here enable the rationalization of the redox reactivity on bifunctional POM clusters and display a nontraditional confinement effect to stabilize transition state energies.
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.001 | 0.002 |
| 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 it