Patel, Calum;
André-Joyaux, Emy;
Leitch, Jamie A;
de Irujo-Labalde, Xabier Martínez;
Ibba, Francesco;
Struijs, Job;
Ellwanger, Mathias A;
... Gouverneur, Véronique; + view all
(2023)
Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF.
Science
, 381
(6655)
pp. 302-306.
10.1126/science.adi1557.
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Abstract
All fluorochemicals-including elemental fluorine and nucleophilic, electrophilic, and radical fluorinating reagents-are prepared from hydrogen fluoride (HF). This highly toxic and corrosive gas is produced by the reaction of acid-grade fluorspar (>97% CaF2) with sulfuric acid under harsh conditions. The use of fluorspar to produce fluorochemicals via a process that bypasses HF is highly desirable but remains an unsolved problem because of the prohibitive insolubility of CaF2. Inspired by calcium phosphate biomineralization, we herein disclose a protocol of treating acid-grade fluorspar with dipotassium hydrogen phosphate (K2HPO4) under mechanochemical conditions. The process affords a solid composed of crystalline K3(HPO4)F and K2-xCay(PO3F)a(PO4)b, which is found suitable for forging sulfur-fluorine and carbon-fluorine bonds.
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