1. Department of Chemical Sciences, IISER Kolkata, Mohanpur, West Bengal, Pincode 741246, India 2. Environmental Nanoscience Laboratory, Department of Earth Sciences, IISER Kolkata, Mohanpur, West Bengal, Pincode 741246, India 3. Center for Climate & Environmental Studies, IISER Kolkata, Mohanpur, West Bengal, Pincode 741246, India
• Eco-friendly IONPs were synthesized through solvothermal method.
• IONPs show very high removal efficiency for CeO2 NPs i.e. 688 mg/g.
• Removal was >90% in all synthetic and real water samples.
• >80% recovery of CeO2 NPs through sonication confirms reusability of IONPs.
Increasing applications of metal oxide nanoparticles and their release in the natural environment is a serious concern due to their toxic nature. Therefore, it is essential to have eco-friendly solutions for the remediation of toxic metal oxides in an aqueous environment. In the present study, eco-friendly Iron Oxide Nanoparticles (IONPs) are synthesized using solvothermal technique and successfully characterized using scanning and transmission electron microscopy (SEM and TEM respectively) and powder X-Ray diffraction (PXRD). These IONPs were further utilized for the remediation of toxic metal oxide nanoparticle, i.e., CeO2. Sorption experiments were also performed in complex aqueous solutions and real water samples to check its applicability in the natural environment. Reusability study was performed to show cost-effectiveness. Results show that these 200 nm-sized spherical IONPs, as revealed by SEM and TEM analysis, were magnetite (Fe3O4) and contained short-range crystallinity as confirmed from XRD spectra. Sorption experiments show that the composite follows the pseudo-second-order kinetic model. Further R2>0.99 for Langmuir sorption isotherm suggests chemisorption as probable removal mechanism with monolayer sorption of CeO2 NPs on IONP. More than 80% recovery of adsorbed CeO2 NPs through ultrasonication and magnetic separation of reaction precipitate confirms reusability of IONPs. Obtained removal % of CeO2 in various synthetic and real water samples was>90% signifying that IONPs are candidate adsorbent for the removal and recovery of toxic metal oxide nanoparticles from contaminated environmental water samples.
Fig.1 (a) SEM image of IONPs and inside TEM image of IONPs (b) TEM image of CeO2 (c) Line-Scan of IONPs (d) change in hydrodynamic diameter of blank CeO2 suspension with time.
Fig.2 (a) XRD pattern of IONPs (b) Zeta potentials and pHPZC of IONPs and CeO2.
Model
K
Q (mg/g)
R2
? α (mg/(g·min))
Pseudo first order
9.79?10?3 min?1
171
0.75
?
Pseudo second order
1.41?10?3 g/(mg·min)
671
0.99
?
Elovich
0.0199 mg/g
?
0.93
120201
Intraparticle
8.8539 mg/(g·min1/2)
?
Tab.1 Obtained parameters for various kinetic models
Fig.3 Fitting of different kinetic models to CeO2 adsorption by IONPs: (a) pseudo-first-order, (b) pseudo-second-order, (c) Elovich, and (d) Intraparticle diffusion model.
Tab.2 Obtained parameters for various sorption isotherms
Fig.4 (a) Langmuir and (b) Freundlich adsorption isotherms.
Fig.5 (a) Effect of bicarbonate ions (HCO3?) concentration on CeO2 sorption and (b) adsorption capacity with varying pH.
Fig.6 Removal percentage of CeO2 NPs from complex matrix.
Fig.7 CeO2 adsorption and recovery methodology for IONPs.
Fig.8 (a, b) TEM and STEM image of CeO2-IONPs reaction precipitate respectively (c) elemental distribution along spherical IONPs in reaction mixture (d) DLS analysis of CeO2 and IONPs mixture suspension with time (e) FT-IR spectra of IONP, CeO2 and IONP-CeO2 reaction precipitate and (f) experimental images showing blank CeO2 suspension, magnetic separation after sorption, redispersion using sonication and recovered CeO2.
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