Differentiating Nanomaghemite and Nanomagnetite and Discussing Their Importance in Arsenic and Lead Removal from Contaminated Effluents: A Critical Review
Abstract
:1. Introduction
2. Synthesis Methods of Magnetic NPs
2.1. Co-Precipitation Method
2.2. Thermal Decomposition Method
2.3. Bulk Effects in Fe3O4 and γ-Fe2O3
3. Discussion about Main Differences Based on Physical Techniques
3.1. Can the XRD Technique Allow to Differentiate a Nanomagnetite or Nanomaghemite?
3.2. Mössbauer Technique as the Main Tool of Differentiation
3.3. High Resolution XPS and Synchrotron Radiation Techniques
4. In-Detail Discussion of the Adsorbent Properties
4.1. As Adsorption Experiments
4.1.1. Individual As Adsorptive Properties
4.1.2. Effect of pH in the Independent Removal of As(III) and As(V)
4.1.3. As Adsorption Mechanism and Adsorption Isotherm Models
4.1.4. Effect of Organic Pollutants on the As Simultaneous Uptake
4.1.5. Effect of the Coexisting Anions Cl−, NO3−, and SO42− on the As Adsorption
4.1.6. Influence of PO43− on the As Adsorption
4.1.7. Effect of the Coexisting of Metal Ions on the As Removal
4.2. Pb(II) Adsorption Experiments
4.2.1. pH and Adsorption Mechanism of Pb(II)
4.2.2. Effect of Initial Concentration on the Uptake of Pb(II)
4.2.3. Effect of Dosage on Pb(II) Removal
4.2.4. Temperature Dependence of the Pb(II) Removal
4.2.5. Simultaneous Removal of Divalent Metal Ions
4.2.6. Simultaneous Pb(II) and Organic Pollutants Adsorption
4.2.7. Removal of Pb(II) and Organic Compounds
4.2.8. Pb(II) Isotherm Models
4.2.9. Simultaneous Adsorption in Real Waters with Transition Metal-like Ions
4.3. Physicochemical Properties of Nano-Fe3O4 and Nano-γ-Fe2O3 Influencing As and Pb(II) Adsorption
4.4. Regeneration and Reuse of Magnetic Nanoadsorbents
4.5. Cost Evaluation
5. Conclusions
6. Future Perspectives
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Sample | Site | ± 0.02 | ± 0.02 | <Beff> (T) ± 0.5 | (°) ± 5 | <Bhf> (T) ± 0.5 | F (%) ± 1 | e (nm) ± 0.05 |
---|---|---|---|---|---|---|---|---|
NPEDTA1 | A | 0.18 | −0.01 | 58.8 | 26 | 51.8 | 28 | 0.38 |
B | 0.29 | 0.01 | 46.2 | 42 | 52.4 | 57 | 0.89 | |
C | 0.27 | −0.00 | 54.2 | 56 | 50.2 | 15 | 1.37 | |
NPEDTA2 | A | 0.36 | −0.00 | 59.6 | 21 | 52.2 | 43 | 0.24 |
B | 0.52 | 0.02 | 46.2 | 28 | 53.3 | 57 | 0.42 | |
NPEDTA3 | A | 0.37 | −0.04 | 60.2 | 14 | 52.7 | 40 | 0.10 |
B | 0.52 | 0.00 | 46.0 | 22 | 53.5 | 60 | 0.24 |
Bulk γ-Fe2O3 | Nano-γ-Fe2O3 | Bulk Fe3O4, nano-Fe3O4 |
---|---|---|
At 14 K, it has perfect asymmetric sextets. | At RT, the sextets collapse to a doublet or singlet-superparamagnetic-like regime (size < 10 nm). At 14 K, the in-field Mössbauer measurements reveal two or three magnetic components depending on particle size. Broadenings can still be significant due to overbarrier fluctuations of smaller particles. | Bulk stoichiometric Fe3O4 depicts two characteristic sextets at RT, while the nano-Fe3O4 presents a collapse spectrum to a doublet or singlet. At 6 K, the spectrum is fitted with three components of tetrahedral Fe3+, octahedral Fe3+, and octahedral Fe2+ [7]. |
Static hyperfine magnetic fields. | At RT, fluctuating hyperfine magnetic fields are presented. At 14 K, superparamagnetic relaxation is negligible and two defined sextets are observed. | Hyperfine magnetic fields at RT [1,7]: Isomer shifts at RT K [1,7]: |
Hyperfine magnetic fields at 14 K [30]: | At RT, the appearance of the complex shapes with mixed components that depend on the particle size, anisotropy energies, blocking temperature distributions, and magnetic interactions are observed. At 14 K, if sizes are smaller than 10 nm, strong spin canting behavior occurs, and the hyperfine parameters slightly differ. For sizes bigger than 10 nm, the hyperfine parameters are equal to the bulk expected ones. | perfine magnetic fields at 140 K [35]: bulk Fe3O4 Hyperfine magnetic fields at 140 K [35]: 21 nm Fe3O4 Hyperfine magnetic fields at RT [7]: 5.3 nm Fe3O4 Isomer shifts at RT [1,7]: |
Isomer shifts at 14 K [30]: | For fittings an average <> for each site must be considered. RAA for site A (37.5%) and site B (62.5%). | They showed lines due to Fe2+ at about −3.0 and −0.5 mm/s. Not observed in resolved spectrum of nano-γ-Fe2O3 at 14 K. |
Samples and Chemical Groups | γ-Fe2O3 + As (III) | NPTiO2 + As (III) | NPTiO2 + As (V) | NPGOTiO2 + As (III) | NPGOTiO2 + As (V) | |
---|---|---|---|---|---|---|
Fe-O | 694 | 624.7 | 697 | 662.7 | 714 | |
Ti-O | - | 773 | 754 | 789 | 779 | |
As-O | 818.9 | 837.9 | 828.9 | 834 | 834.9 | |
C-O (alcoxy) | - | - | - | 1024 | 1048 | |
C-O (epoxy) | - | - | - | 1129 | 1137 | |
C-O (carboxy) | - | - | - | 1257 | 1240 | |
C=C | - | - | - | 1591 | 1548 | |
H2O: | O-H | 1644 | 1641 | 1641 | 1647 | 1645 |
O-H | 3469 | 3431 | 3430 | 3414 | 3395 | |
C-OH | - | - | - | 3205 | 3204 |
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Ramos-Guivar, J.A.; Flores-Cano, D.A.; Caetano Passamani, E. Differentiating Nanomaghemite and Nanomagnetite and Discussing Their Importance in Arsenic and Lead Removal from Contaminated Effluents: A Critical Review. Nanomaterials 2021, 11, 2310. https://doi.org/10.3390/nano11092310
Ramos-Guivar JA, Flores-Cano DA, Caetano Passamani E. Differentiating Nanomaghemite and Nanomagnetite and Discussing Their Importance in Arsenic and Lead Removal from Contaminated Effluents: A Critical Review. Nanomaterials. 2021; 11(9):2310. https://doi.org/10.3390/nano11092310
Chicago/Turabian StyleRamos-Guivar, Juan A., Diego A. Flores-Cano, and Edson Caetano Passamani. 2021. "Differentiating Nanomaghemite and Nanomagnetite and Discussing Their Importance in Arsenic and Lead Removal from Contaminated Effluents: A Critical Review" Nanomaterials 11, no. 9: 2310. https://doi.org/10.3390/nano11092310