Applied Surface Science, Vol.307, 665-676, 2014
Agglomerated nanoparticles of hydrous Ce(IV) plus Zr(IV) mixed oxide: Preparation, characterization and physicochemical aspects on fluoride adsorption
Hydrous Ce(IV)-Zr(IV) oxide (Ce/Zr 1:1, mol/mol) (HCZMO) prepared by simple chemical precipitation was nanoparticles (60-70 nm) agglomerate with irregular surface morphology. The BET surface area, pore volume and p1-1,pc were estimated to be 185.04m2 g-1, 0.1219 cm3 g-1 and 5.8 (+0.2), respectively. Investigation of fluoride adsorption over HCZMO from its aqueous phase at an optimized pH 6.0 showed that the adsorption kinetics and equilibrium data described, respectively, the pseudo-second order equation (R2 =0.98-0.99) and the Langmuir isotherm (R2 >0.99) very well. Values of the computed Arrhenius activation energy, Ea (1.16 kJ mol-1), Langmuir monolayer capacity, 0(19.5 mg g-1), D-R adsorption energy, ED _R (15.05 kJ mol-1) and isosteric heat of reaction, AH, (0.518 kJ mol-1) suggested that the fluoride has high affinity for homogeneous HCZMO surface for adsorption. Evidences appeared from the equal distribution co-efficient values and too well Langmuir isotherm fit. The fluoride adsorption reactions at 298-313 K with HCZMO were spontaneous ( AG = negative) despite endothermic nature (AH, kJ mol-1= +3.53, +4.04), owing to the increase of entropy( AS J mol-1 K-1 = +12.4,13.8). More than 95% fluoride was released from F--HCZMO (24.8 mg F- g-1) by 1.0 M Na OH, confirming the ion-exchange adsorption mechanism inclining to chemisorption. 1 g HCZMO per liter of a groundwater (F-: 4.40 mg L-1) can reduce fluoride level below 1.5 mg L-1 in batch treatment. 2014 Elsevier B.V. All rights reserved.