Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF

IF 47.3 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES

Science Pub Date : 2023-07-20 DOI:10.1126/science.adi1557

Calum Patel, Emy André-Joyaux, Jamie A. Leitch, Xabier Martínez de Irujo-Labalde, Francesco Ibba, Job Struijs, Mathias A. Ellwanger, Robert Paton, Duncan L. Browne, Gabriele Pupo, Simon Aldridge, Michael A. Hayward, Véronique Gouverneur

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引用次数: 2

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₋_xCa_y(PO₃F)_a(PO₄)_b, which is found suitable for forging sulfur-fluorine and carbon-fluorine bonds.

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通过磷酸盐机械化学工艺从萤石中提取氟化学品，绕过氢氟酸

所有氟化合物，包括元素氟、亲核、亲电和自由基氟化试剂，都是由氟化氢（HF）制备而成。这种剧毒和腐蚀性气体是由酸级萤石（97% CaF2）在苛刻条件下与硫酸反应生成的。通过绕过 HF 的工艺使用萤石来生产氟化合物是非常理想的，但由于 CaF2 的不溶性令人望而却步，因此仍是一个未解决的问题。受磷酸钙生物矿化的启发，我们在此公开了一种在机械化学条件下用磷酸氢二钾（K2HPO4）处理酸级萤石的方案。该工艺可获得由结晶 K3(HPO4)F 和 K2-xCay(PO3F)a(PO4)b 组成的固体，适合锻造硫-氟和碳-氟键。

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来源期刊

Science 综合性期刊-综合性期刊

CiteScore

61.10

自引率

0.90%

发文量

审稿时长

2.1 months

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