화학공학소재연구정보센터
Inorganic Chemistry, Vol.48, No.16, 7962-7969, 2009
Electrochemical Fluorination of La2CuO4: A Mild "Chimie Douce" Route to Superconducting Oxyfluoride Materials
The fluorination of La2CuO4 was achieved for the first time under normal conditions of pressure and temperature (1 MPa and 298 K) via electrochemical insertion in organic fluorinated electrolytes and led to lanthanum oxyfluorides of general formula La2CuO4Fx. Analyses showed that, underneath a very thin layer of LaF3 (a few atomic layers), fluorine is effectively inserted in the material's structure. The fluorination strongly modifies the lanthanum environment, whereas very little modification is observed on copper, suggesting an insertion in the La2O2 blocks of the structure. In all cases, fluorine insertion breaks the translation symmetry and introduces a long-distance disorder, as shown by electron spin resonance. These results highlight the efficiency of electrochemistry as a new "chimie douce" type fluorination technique for solid-state materials. Performed at room temperature, it additionally does not require any specific experimental care. The choice of the electrolytic medium is crucial with regard to the fluorine insertion rate as well as the material deterioration. Successful application of this technique to the well-known La2CuO4 material provides a basis for further syntheses from other oxides.