Preparative Electrosynthesis of Strong Oxidizers at Boron‐Doped Diamond Electrode in Anhydrous HF

The first successful electrosynthesis of polycrystalline Ag(II)FBF4 and single crystalline Ag(II)F2 in both galvanostatic and potentiostatic conditions was achieved at the Boron-Doped Diamond electrode in anhydrous hydrogen fluoride. Silver(I) oxidation and the F2 evolution reactions are well separated in the potential scale. Temperature of performing electrosynthesis as well as BF3 overpressure were found to be key variables of the process. Impedance spectroscopy measurements provided insight into the mechanism of formation of silver(II) fluorides pointing out to the presence of HF-soluble Ag(BF4)2 intermediate. The phase purity of the products was determined by X-ray diffraction