F-doping of nanostructured ZnO: a way to modify structural, electronic, and surface properties

Polycrystalline ZnO is a material often used in heterogeneous catalysis. Its properties can be altered by the addition of dopants. We used gaseous fluorine (F_2(g)) as direct way to incorporate fluoride in ZnO as anionic dopants. Here, the consequences of this treatment on the structural and electronic properties, as well as on the acidic/basic sites of the surface, are investigated. It is shown that the amount of F incorporation into the structure can be controlled by the synthesis parameters (t, T, p). While the surface of ZnO was altered as shown by, e.g., IR spectroscopy, XPS, and STEM/EDX measurements, the F₂ treatment also influenced the electronic properties (optical band gap, conductivity) of ZnO. Furthermore, the Lewis acidity/basicity of the surface was affected which is evidenced by using, e.g., different probe molecules (CO₂, NH₃). In situ investigations of the fluorination process offer valuable insights on the fluorination process itself.