Ferrihydrite Formation: The Role of Fe13 Keggin Clusters.
Environ Sci Technol
; 50(17): 9333-42, 2016 09 06.
Article
em En
| MEDLINE
| ID: mdl-27480123
ABSTRACT
Ferrihydrite is the most common iron oxyhydroxide found in soil and is a key sequester of contaminants in the environment. Ferrihydrite formation is also a common component of many treatment processes for cleanup of industrial effluents. Here we characterize ferrihydrite formation during the titration of an acidic ferric nitrate solution with NaOH. In situ SAXS measurements supported by ex situ TEM indicate that initially Fe13 Keggin clusters (radius â¼ 0.45 nm) form in solution at pH 0.12-1.5 and are persistent for at least 18 days. The Fe13 clusters begin to aggregate above â¼ pH 1, initially forming highly linear structures. Above pH â¼ 2 densification of the aggregates occurs in conjunction with precipitation of low molecular weight Fe(III) species (e.g., monomers, dimers) to form mass fractal aggregates of ferrihydrite nanoparticles (â¼3 nm) in which the Fe13 Keggin motif is preserved. SAXS analysis indicates the ferrihydrite particles have a core-shell structure consisting of a Keggin center surrounded by a Fe-depleted shell, supporting the surface depleted model of ferrihydrite. Overall, we present the first direct evidence for the role of Fe13 clusters in the pathway of ferrihydrite formation during base hydrolysis, showing clear structural continuity from isolated Fe13 Keggins to the ferrihydrite particle structure. The results have direct relevance to the fundamental understanding of ferrihydrite formation in environmental, engineered, and industrial processes.
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1
Base de dados:
MEDLINE
Assunto principal:
Compostos Férricos
/
Espalhamento a Baixo Ângulo
Idioma:
En
Ano de publicação:
2016
Tipo de documento:
Article