Catalytic Fluorination in Heterogeneous Systems

Catalytic fluorination in heterogeneous systems has become a cornerstone of modern synthesis, enabling the efficient insertion or removal of fluorine atoms under controlled conditions. The exceptionally strong C–F bond imparts unique chemical and physical properties, such as enhanced metabolic stability in pharmaceuticals, improved thermal resistance in polymers and tailored electronic characteristics in advanced materials. Heterogeneous catalysts—typically metal fluorides or fluorinated oxides supported on high‐surface‐area substrates—offer practical advantages including facile recovery, minimised waste streams and robust operation under continuous flow. Mechanistically, these catalysts often exploit Lewis acidic sites to activate fluorinating reagents or substrates, while Brønsted acidity and tunable surface hydroxylation permit fine control over reactivity and selectivity. Recent advances have focused on nanoengineering of catalyst morphology, optimisation of acid‐base pairing and integration within microreactor technologies, opening new avenues for scalable, energy‐efficient fluorination processes with broad industrial and environmental relevance.

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Catalytic Fluorination in Heterogeneous Systems publication trend

The graph below shows the total number of articles in catalytic fluorination in heterogeneous systems across all publications each year (not limited to Nature Index journals).

Technical terms

Heterogeneous catalysis: A catalytic process in which the catalyst and reactants exist in different phases, commonly solid catalysts with liquid or gas‐phase substrates.

Lewis acid: An electron‐pair acceptor site, often a metal centre or metal fluoride, that activates substrates by coordinating electron donors.

Brønsted acid: A proton donor site on the catalyst surface that can facilitate proton‐transfer steps in fluorination or dehydrofluorination reactions.

Fluorolytic sol–gel synthesis: A non‐aqueous route to metal fluorides in which alkoxide precursors are progressively replaced by fluoride ions, yielding nanostructured catalysts.

Specific surface area: The available surface per unit mass of catalyst, typically expressed in m2 g–1, which influences the number of accessible active sites.

References

1. The non-aqueous fluorolytic sol–gel synthesis of nanoscaled metal fluorides. Dalton Transactions (2015).
2. The Effects of Various Parameters of the Microwave-Assisted Solvothermal Synthesis on the Specific Surface Area and Catalytic Performance of MgF2 Nanoparticles. Materials (2020).
3. Energy and Resource Efficient Production of Fluoroalkenes in High Temperature Microreactors. ChemEngineering (2019).
4. Theoretical Study on the Lewis Acidity of the Pristine AlF3 and Cl-Doped α-AlF3 Surfaces. Catalysts (2021).