Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite
Bibliographic record
Abstract
Phosphorus removal and recovery technologies have been implemented to tackle the anthropogenic eutrophication caused by phosphate runoff into waterways. In pursuit of a better utilization of the phosphates recovered from waste water treatment, we herein report that condensed phosphates can be employed to phosphorylate hydride reagents under solvent-free mechanochemical conditions to furnish phosphite (HPO3)2−, a versatile chemical with phosphorus in the +3 oxidation state. Hydride phosphorylation, as a two-electron one-proton reduction of a main group element oxide, constitutes a direct parallel with CO2 reduction to formate. Using potassium hydride as the hydride source, sodium trimetaphosphate (Na3P3O9 ), triphosphate (Na5P3O10), and pyrophosphate (Na4P2O7) engendered phosphite in 44, 58, and 44% yields based on total P content, respectively, under their optimal conditions. Formation of overreduced products including hypophosphite (H2PO2−) was identified as a competing process, and mechanistic investigation revealed that hydride attack on in situ generated phosphorylated phosphite species is a potent pathway for overreduction. The phosphite generated from our method could be easily isolated in the form of barium phosphite, a useful intermediate for production of phosphorous acid. This method circumvents the need to pass through white phosphorus (P4) as a high energy intermediate and mitigates involvement of environmentally hazardous chemicals. A bioproduced polyphosphate from baker’s yeast was demonstrated to be a viable starting material for the production of phosphite. This example demonstrates the possibility of accessing reduced phosphorus compounds in a more sustainable manner, and more importantly, closing the modern phosphorus cycle.
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How this classification was reachedexpand
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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.003 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, 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".