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Structure–redox reactivity relationships in $Co_{1-x}Zn_{x}Fe_{2}O_{4}$ : the role of stoichiometry
Structure–redox reactivity relationships in $Co_{1-x}Zn_{x}Fe_{2}O_{4}$ : the role of stoichiometry
- Publication Year :
- 2019
-
Abstract
- Nanostructured Zn-doped cobalt ferrites (Co1−xZnxFe2O4, where x ranges from 0.0 to 1.0 with a step of 0.1) were studied in order to elucidate the relation between their cationic distribution within the spinel sublattices and catalytic properties. The thermal transformation of the precursors (metal hydroxides) obtained through the hydroxide co-precipitation method was studied by DTA, TGA and FTIR. The thermal behavior of the precursors showed that cobalt ferrite was formed at a lower temperature (376 °C) in comparison to zinc ferrite (478 °C). FTIR analysis revealed vibrational bands around 400 cm−1 and 600 cm−1 related to (MO4)6− and (MO6)9− groups, respectively. The cationic distribution was determined from Mossbauer spectra analysis and the results showed that Zn ions occupy the A-sites, while Co and Fe ions are located in the A- and B-sites. The spectra indicate spinel magnetic ordering in samples with x = 0.0…0.5. The increase in Zn content influences the difference in the Pauling electronegativities, distances between magnetic ions (hopping length) and polaron radius of Co1−xZnxFe2O4 ferrites, inducing changes in the ionic bond strength for the A- and B-sites. Photoelectrochemical measurements demonstrated that the introduction of Zn2+ into the spinel structure modifies the ability of the materials to reduce O2. Whereas photoinduced reduction of dioxygen at CoFe2O4 competes successfully with anodic photocurrent generation (observed as a decrease of photocurrent), for ZnFe2O4 this process is negligible. The relation between the cationic distribution (analyzed in terms of antistructure modeling) and the catalytic activity of spinel ferrites was demonstrated for the example of the soot combustion process. It was shown that the octahedral cobalt centers exhibit a higher catalytic activity than the tetrahedral ones.
- Subjects :
- Spinel
chemistry.chemical_element
Ionic bonding
02 engineering and technology
General Chemistry
engineering.material
010402 general chemistry
021001 nanoscience & nanotechnology
01 natural sciences
Catalysis
0104 chemical sciences
Metal
Electronegativity
Zinc ferrite
chemistry.chemical_compound
chemistry
visual_art
Materials Chemistry
visual_art.visual_art_medium
engineering
Physical chemistry
Hydroxide
0210 nano-technology
Cobalt
Stoichiometry
Subjects
Details
- Language :
- English
- Database :
- OpenAIRE
- Accession number :
- edsair.doi.dedup.....e1d41b9cdc573d2187062a734369dd68