Elucidating the Time Scale and Geometry of Phosphate and Phosphonate Rotation in Solid Acid Electrolytes Using Multinuclear NMR
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Bibliographic record
Abstract
The dynamics of the anions in a series of solid acid electrolyte materials have been determined using solid-state 31 P CODEX NMR. The time scale and activation energy of the phosphate reorientation were quantified; however, the characterization proved to be nontrivial due to interactions with the quadrupolar 133 Cs nuclei. The series of compounds studied included other known proton conductors, where the alkali cation was replaced systematically with Rb +, Tl +, or K + . The nuclear properties of the cations, together with the relative proton conductivities of these electrolyte analogues, allowed for a complete analysis of the interactions (both structure reorientations and spin dynamics) giving rise to the observed CODEX buildup curves. The high-temperature super-protonic transition, and the narrow range of thermal stability, limits the usefulness of cesium dihydrogen phosphate (CDP) in fuel cell applications. With the goal of achieving a broader range of thermal stability and enhanced proton dynamics, the phosphate anion was substituted for methyl phosphonate. This altered the type of motion available to the anion and significantly reduced the energy barrier for anion rotation in this electrolyte.
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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 | 0.000 | 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) | 0.000 | 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