New method for generating fluorochemicals without HF gas

Chemists have achieved a groundbreaking feat in the world of fluorochemicals, a group of chemicals with diverse applications in various industries. Published in the prestigious journal Science, their innovative method has the potential to revolutionize the production process, enhancing safety and reducing the industry’s carbon footprint.

Traditionally, fluorochemicals are generated using the hazardous and energy-intensive hydrogen fluoride (HF) gas. This gas is known for its toxicity and corrosiveness, leading to accidents and environmental damage. To tackle this issue, a team of brilliant minds from the University of Oxford, FluoRok, University College London, and Colorado State University looked to nature’s biomineralization process found in teeth and bones for inspiration.

Their ingenious approach involves working directly with the mineral fluorspar (CaF2) without producing HF as an intermediate. They achieved this by activating solid-state CaF2 through a process inspired by biomineralization. The team ground CaF2 with potassium phosphate salt in a ball-mill machine for several hours, utilizing a mechanochemical process similar to grinding spices with a pestle and mortar.

The outcome was a powdered product called Fluoromix, which astonishingly facilitated the synthesis of over 50 different fluorochemicals directly from CaF2 with impressively high yields of up to 98%. This breakthrough method not only makes the production process safer but also has the potential to optimize the supply chain and decrease energy requirements, aligning with sustainability goals and significantly reducing the industry’s carbon footprint.

With fluorochemicals playing a crucial role in polymers, agrochemicals, pharmaceuticals, and lithium-ion batteries for electronic devices and electric vehicles—a market valued at $21.4 billion in 2018—this new approach could have far-reaching implications and contribute to a safer, greener future for the industry.

Using high precision techniques, such as X-ray diffraction, the researchers unlocked key insights into the composition of Fluoromix and structures of the fluorinating species. The diagram shows structures of crystalline constituents of Fluoromix, which serve as fluorinating reagents. Credit: Prof. Michael Hayward.

In an exciting breakthrough, the newly developed solid-state process proved equally effective with acid grade fluorspar (> 97%, CaF2) as it was with synthetic reagent grade CaF2. This revolutionary method is poised to completely transform the global manufacturing of fluorochemicals and has given rise to the establishment of FluoRok, a dynamic spin‑out company dedicated to commercializing the technology and fostering the development of safe, sustainable, and cost-effective fluorinations. The researchers are optimistic that their study will inspire scientists worldwide to tackle challenging chemical problems and generate disruptive solutions for the betterment of society.

Calum Patel, one of the lead authors from the Department of Chemistry at the University of Oxford, expressed his excitement about the invention of the mechanochemical activation of CaF2 with a phosphate salt. He emphasized that this seemingly simple process provides an exceptionally effective solution to a complex problem. However, unraveling the intricacies of this novel reaction required collaborative efforts and expertise from various disciplines. Patel believes that solving significant challenges necessitates multidisciplinary approaches, and this work exemplifies the significance of such collaborations.

Lead author Professor Véronique Gouverneur FRS, also from the Department of Chemistry at the University of Oxford, conceived and led this groundbreaking study. She considers the direct use of CaF2 for fluorination as a long-sought-after holy grail in the field. With the urgent need to transition towards sustainable chemical manufacturing processes that minimize environmental impact, Gouverneur stresses the importance of ambitious programs and a comprehensive reevaluation of current practices.

This study represents a significant stride in that direction, as the method developed at Oxford can be easily adopted in both academia and industry. Its implementation has the potential to reduce carbon emissions by shortening supply chains and bolster the reliability of global supply networks, especially given their present fragility. By embracing this new approach, the industry can pave the way for a greener, more efficient future.

Source: University of Oxford

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