Investigation of Structural Dynamics in KF-ZrF Molten Salt Systems via High-Temperature Raman Spectroscopy and Quantum Electrochemical Methods.

The KF-ZrF molten salt system has emerged as a promising candidate solvent for fourth-generation reactor designs, where its physicochemical characteristics are fundamentally governed by the ionic structure within the molten fluoride matrix. A variety of complex Zr-F ions, including ZrF, ZrF, ZrF, and ZrF, were identified in KF-ZrF molten salts with different molar ratios through Raman spectroscopy and quantum chemical calculations. Furthermore, the ZrF ion with a bridging F structure was discovered in KF-ZrF molten salts with molar ratios of 1 and 0.65, and the experimental Raman spectrum of this ion was obtained. At higher KF to ZrF molar ratios of 5.7 and 2.3, ZrF and ZrF dominated, while ZrF and ZrF were predominant at molar ratios of 1 and 1.5. At a lower ratio of 0.67, ZrF emerged as the primary species. As the KF to ZrF molar ratio decreased, the system favored the formation of less-coordinated Zr-F ions. Moreover, a dynamic mutual transformation equilibrium existed among these complex ions, and this equilibrium was influenced by the zirconium fluoride content in the molten salt. Quantum electrochemical analysis revealed that ZrF was mainly involved in the cathode reaction. Zr was first released from ZrF, gaining three electrons to form Zr. Subsequently, Zr gained one electron, transforming into metallic zirconium at the cathode interface. These findings deepen our understanding of the physicochemical properties of molten salt reactors and have significant implications for advanced applications in metal purification, spent nuclear fuel recovery, and zirconium alloy production, thereby contributing to improved nuclear materials management and energy sustainability.