Fluoride ion adsorption isotherms, kinetics, and thermodynamics on iron(III) oxyhydroxide powders containing cellulose nanofibrils
Masahiro Umehara, Yoshiaki Kumamoto, Kenta Mukai, Akira Isogai
Abstract
Abstract The adsorption isotherms, kinetics, and thermodynamics of fluoride ions (F − ) on FeOOH powders in water were investigated to obtain fundamental information on FeOOH powders, which are used as F − adsorbents in drinking and industrial water, and industrial wastewater. FeOOH powders were prepared as precipitates by mixing aqueous FeCl 3 and NaOH solutions (1:3 mol/mol) in the presence of 2,2,6,6,-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanofibrils (TOCNs), carboxymethylcellulose (CMC), or TEMPO-oxidized cellulose (TOC) fibers (without nanofibrillation), and subsequent drying and pulverizing. The FeOOH:TOCN, FeOOH:CMC, and FeOOH:TOC dry mass ratios were controlled at 87:13. The amount of F − adsorbed by the FeOOH/TOCN powder per FeOOH mass was higher than those adsorbed by FeOOH, FeOOH/CMC, or FeOOH/TOC. The F − adsorption isotherms on the FeOOH-containing powders showed higher correlation coefficients with the Langmuir model than with the Freundlich model. This indicates that F − adsorbed on FeOOH initially formed a monolayer, predominantly via physical adsorption. Pseudo-second-order kinetics fitted well to the time-dependent F − adsorption behaviors on the FeOOH-containing powders. Thermodynamic analysis of F − adsorption on the FeOOH-containing powders showed that the Δ G values were negative, which indicates that F − adsorption on the FeOOH-containing powders proceeded spontaneously in water. The negative Δ G value for FeOOH/TOCN was higher than those for FeOOH, FeOOH/CMC, and FeOOH/TOC at the same temperature. This shows that the FeOOH/TOCN powder can be used as an excellent and efficient F − adsorbent in water. Graphical abstract