Nanocrystalline ferrites Ni{sub x}Zn{sub 1-x}Fe{sub 2}O{sub 4}: Influence of cation distribution on acidic and gas sensing properties
This work is devoted to a detailed analysis of the interconnection between composition, cation distribution and acidic properties of the surface of nanocrystalline ferrites Ni{sub x}Zn{sub 1-x}Fe{sub 2}O{sub 4} obtained by aerosol pyrolysis. The detailed analysis of the Moessbauer spectra allows us to determine the distribution of cations between tetrahedral and octahedral positions in spinel structure. Depending on samples composition, the tetrahedral positions can be occupied by only Fe{sup 3+} cations (inverse spinel, x{>=}0.4) or by Fe{sup 3+} and Zn{sup 2+} cations (mixed spinel, x=0, 0.2). Increasing the nickel concentration in the ferrite leads to decrease in the number of strong acid centers on the surface. It was found that the decrease in the contribution of strong surface acid sites leads to an increase in sensory sensitivity of the ferrite towards ammonia. For ethanol detection an inverse relationship between sensor signal and surface acidity was observed. - Graphical abstract: (a) n- and p-types change in electrical resistance and (b) sensor signal of Ni{sub x}Zn{sub 1-x}Fe{sub 2}O{sub 4} towards NH{sub 3} and ethanol vapor vs. the part of strong acid sites. Highlights: > Relationship between composition, cation distribution, and acidity in nanocrystalline Ni{sub x}Zn{sub 1-x}Fe{sub 2}O{sub 4}. > Degree of inversion of spinel is determined by Moessbauer spectroscopy. > Increase of nickel content leads to decrease in the number of strong acid centers. > This results in an increase in sensory sensitivity of the ferrite towards ammonia. > Relationship between sensor signal to ethanol and surface acidity is opposite.