(Super)paramagnetic nanoparticles as platform materials for environmental applications: From synthesis to demonstration

Highlights

• The fabrication of monodisperse, (super)paramagnetic nanoparticles is summarized.

• Monolayer and bilayer surface coating structures are described.

• Mono/bilayer coated nanoparticles showed high sorption capacities for U, As, and Cr.

Abstract

Over the past few decades, engineered, (super)paramagnetic nanoparticles have drawn extensive research attention for a broad range of applications based on their tunable size and shape, surface chemistries, and magnetic properties. This review summaries our recent work on the synthesis, surface modification, and environmental application of (super)paramagnetic nanoparticles. By utilizing high-temperature thermo-decomposition methods, first, we have broadly demonstrated the synthesis of highly monodispersed, (super)paramagnetic nanoparticles, via the pyrolysis of metal carboxylate salts in an organic phase. Highly uniform magnetic nanoparticles with various size, composition, and shape can be precisely tuned by controlled reaction parameters, such as the initial precursors, heating rate, final reaction temperature, reaction time, and the additives. These materials can be further rendered water stable via functionalization with surface mono/bi-layer coating structure using a series of tunable ionic/non-ionic surfactants. Finally, we have demonstrated platform potential of these materials for heavy metal ions sensing, sorption, and separation from the aqueous phase.

Graphical abstract

Keywords

Superparamagnetic nanoparticles / Surface functionalization / Environmental sensing / Heavy metal ion sorption

References

[1] Adeleye A S, Conway J R, Garner K, Huang Y, Su Y, Keller A A (2016). Engineered nanomaterials for water treatment and remediation: Costs, benefits, and applicability. Chemical Engineering Journal, 286: 640–662

[2] Ambashta R D, Sillanpää M (2010). Water purification using magnetic assistance: A review. Journal of Hazardous Materials, 180(1–3): 38–49

[3] An K, Kwon S G, Park M, Na H B, Baik S I, Yu J H, Kim D, Son J S, Kim Y W, Song I C, Moon W K, Park H M, Hyeon T (2008). Synthesis of uniform hollow oxide nanoparticles through nanoscale acid etching. Nano Letters, 8(12): 4252–4258

[4] Ashiq M N, Javed Iqbal M, Hussain Gul I (2011). Effect of Al-Cr doping on the structural, magnetic and dielectric properties of strontium hexaferrite nanomaterials. Journal of Magnetism and Magnetic Materials, 323(3–4): 259–263

[5] Cabot A, Puntes V F, Shevchenko E, Yin Y, Balcells L, Marcus M A, Hughes S M, Alivisatos A P (2007). Vacancy coalescence during oxidation of iron nanoparticles. Journal of the American Chemical Society, 129(34): 10358–10360

[6] Chandra V, Park J, Chun Y, Lee J W, Hwang I C, Kim K S (2010). Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. ACS Nano, 4(7): 3979–3986

[7] Chinnasamy C N, Narayanasamy A, Ponpandian N, Chattopadhyay K, Shinoda K, Jeyadevan B, Tohji K, Nakatsuka K, Furubayashi T, Nakatani I (2001). Mixed spinel structure in nanocrystalline NiFe₂O₄. Physical Review. B, 63(18): 184108

[8] Chowdhury S R, Yanful E K (2010). Arsenic and chromium removal by mixed magnetite-maghemite nanoparticles and the effect of phosphate on removal. Journal of Environmental Management, 91(11): 2238–2247

[9] Cornell R M, Schwertmann U (2003). The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses. Weinheim: WILEY-VCH

[10] Dave P N, Chopda L V (2014). Application of iron oxide nanomaterials for the removal of heavy metals. Journal of Nanotechnology, 2014: 1–14

[11] Faraji M, Yamini Y, Rezaee M (2010). Magnetic nanoparticles: Synthesis, stabilization, functionalization, characterization, and applications. Journal of the Iranian Chemical Society, 7(1): 1–37

[12] Gupta K, Khandelwal N, Darbha G K (2020). Removal and recovery of toxic nanosized cerium oxide using eco-friendly iron oxide nanoparticles. Frontiers of Environmental Science & Engineering, 14(1): 15

[13] Gupta V K, Agarwal S, Saleh T A (2011). Chromium removal by combining the magnetic properties of iron oxide with adsorption properties of carbon nanotubes. Water Research, 45(6): 2207–2212

[14] Hao R, Xing R, Xu Z, Hou Y, Gao S, Sun S (2010). Synthesis, functionalization, and biomedical applications of multifunctional magnetic nanoparticles. Advanced Materials, 22(25): 2729–2742

[15] Hsu R S, Chang W H, Lin J J (2010). Nanohybrids of magnetic iron-oxide particles in hydrophobic organoclays for oil recovery. ACS Applied Materials & Interfaces, 2(5): 1349–1354

[16] Hyeon T, Chung Y, Park J, Lee S S, Kim Y W, Park B H (2002). Synthesis of highly crystalline and monodisperse cobalt ferrite nanocrystals. Journal of Physical Chemistry B, 106(27): 6831–6833

[17] Hyeon T, Lee S S, Park J, Chung Y, Na H B (2001). Synthesis of highly crystalline and monodisperse maghemite nanocrystallites without a size-selection process. Journal of the American Chemical Society, 123(51): 12798–12801

[18] Jiang Y, Peng B, Wan Z, Kim C, Li W, Fortner J (2020). Nanotechnology as a key enabler for effective environmental remediation technologies. In: Jiang G, Li X, eds. A New Paradigm for Environmental Chemistry and Toxicology: From Concepts to Insights. Singapore: Springer Singapore, 197–207

[19] Kang E, Park J, Hwang Y, Kang M, Park J G, Hyeon T (2004). Direct synthesis of highly crystalline and monodisperse manganese ferrite nanocrystals. Journal of Physical Chemistry B, 108(37): 13932–13935

[20] Kim C, Lee S S, Lafferty B J, Giammar D E, Fortner J D (2018a). Engineered superparamagnetic nanomaterials for arsenic(v) and chromium(vi) sorption and separation: quantifying the role of organic surface coatings. Environmental Science. Nano, 5(2): 556–563

[21] Kim C, Lee S S, Li W, Fortner J D (2020). Towards optimizing cobalt based metal oxide nanocrystals for hydrogen generation via NaBH4 hydrolysis. Applied Catalysis A, General, 589: 117303

[22] Kim C, Lee S S, Reinhart B J, Cho M, Lafferty B J, Li W, Fortner J D (2018b). Surface-optimized core–shell nanocomposites (Fe₃O₄@Mn_xFeyO₄) for ultra-high uranium sorption and low-field separation in water. Environmental Science. Nano, 5(10): 2252–2256

[23] Kim J, Lee J E, Lee S H, Yu J H, Lee J H, Park T G, Hyeon T (2008). Designed fabrication of a multifunctional polymer nanomedical platform for simultaneous cancer-targeted imaging and magnetically guided drug delivery. Advanced Materials, 20(3): 478–483

[24] Koo B, Xiong H, Slater M D, Prakapenka V B, Balasubramanian M, Podsiadlo P, Johnson C S, Rajh T, Shevchenko E V (2012). Hollow iron oxide nanoparticles for application in lithium ion batteries. Nano Letters, 12(5): 2429–2435

[25] Laurent S, Forge D, Port M, Roch A, Robic C, Vander Elst L, Muller R N (2008). Magnetic iron oxide nanoparticles: synthesis, stabilization, vectorization, physicochemical characterizations, and biological applications. Chemical Reviews, 108(6): 2064–2110

[26] Lee S S, Li W, Kim C, Cho M, Catalano J G, Lafferty B J, Decuzzi P, Fortner J D (2015a). Engineered manganese oxide nanocrystals for enhanced uranyl sorption and separation. Environmental Science. Nano, 2(5): 500–508

[27] Lee S S, Li W, Kim C, Cho M, Lafferty B J, Fortner J D (2015b). Surface functionalized manganese ferrite nanocrystals for enhanced uranium sorption and separation in water. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 3(43): 21930–21939

[28] Lee S S, Zhang C G, Lewicka Z A, Cho M J, Mayo J T, Yu W W, Hauge R H, Colvin V L (2012). Control over the diameter, length, and structure of carbon nanotube carpets using aluminum ferrite and iron oxide nanocrystals as catalyst precursors. Journal of Physical Chemistry C, 116(18): 10287–10295

[29] Li W, Hinton C H, Lee S S, Wu J, Fortner J D (2016a). Surface engineering superparamagnetic nanoparticles for aqueous applications: design and characterization of tailored organic bilayers. Environmental Science. Nano, 3(1): 85–93

[30] Li W, Lee S S, Mittelman A M, Liu D, Wu J, Hinton C H, Abriola L M, Pennell K D, Fortner J D (2016b). Aqueous aggregation behavior of engineered superparamagnetic iron oxide nanoparticles: effects of oxidative surface aging. Environmental Science & Technology, 50(23): 12789–12798

[31] Li W, Lee S S, Wu J, Hinton C H, Fortner J D (2016c). Shape and size controlled synthesis of uniform iron oxide nanocrystals through new non-hydrolytic routes. Nanotechnology, 27(32): 324002

[32] Li W, Liu D, Wu J, Kim C, Fortner J D (2014). Aqueous aggregation and surface deposition processes of engineered superparamagnetic iron oxide nanoparticles for environmental applications. Environmental Science & Technology, 48(20): 11892–11900

[33] Li W, Mayo J T, Benoit D N, Troyer L D, Lewicka Z A, Lafferty B J, Catalano J G, Lee S S, Colvin V L, Fortner J D (2016d). Engineered superparamagnetic iron oxide nanoparticles for ultra-enhanced uranium separation and sensing. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 4(39): 15022–15029

[34] Li W, Troyer L D, Lee S S, Wu J, Kim C, Lafferty B J, Catalano J G, Fortner J D (2017a). Engineering nanoscale iron oxides for uranyl sorption and separation: optimization of particle core size and bilayer surface coatings. ACS Applied Materials & Interfaces, 9(15): 13163–13172

[35] Li W, Wu J, Lee S S, Fortner J D (2017b). Surface tunable magnetic nano-sorbents for carbon dioxide sorption and separation. Chemical Engineering Journal, 313: 1160–1167

[36] Li Z, Wei L, Gao M Y, Lei H (2005). One-pot reaction to synthesize biocompatible magnetite nanoparticles. Advanced Materials, 17(8): 1001–1005

[37] Liu C, Zou B S, Rondinone A J, Zhang J (2000a). Chemical control of superparamagnetic properties of magnesium and cobalt spinel ferrite nanoparticles through atomic level magnetic couplings. Journal of the American Chemical Society, 122(26): 6263–6267

[38] Liu C, Zou B S, Rondinone A J, Zhang Z J (2000b). Reverse micelle synthesis and characterization of superparamagnetic MnFe₂O₄ spinel ferrite nanocrystallites. Journal of Physical Chemistry B, 104(6): 1141–1145

[39] Lu A H, Salabas E L, Schüth F (2007). Magnetic nanoparticles: synthesis, protection, functionalization, and application. Angewandte Chemie International Edition, 46(8): 1222–1244

[40] Ngaboni Okassa L N, Marchais H, Douziech-Eyrolles L, Cohen-Jonathan S, Soucé M, Dubois P, Chourpa I (2005). Development and characterization of sub-micron poly(D,L-lactide-co-glycolide) particles loaded with magnetite/maghemite nanoparticles. International Journal of Pharmaceutics, 302(1–2): 187–196

[41] Pan Z, Zhu X, Satpathy A, Li W, Fortner J D, Giammar D E (2019). Cr(VI) adsorption on engineered iron oxide nanoparticles: exploring complexation processes and water chemistry. Environmental Science & Technology, 53(20): 11913–11921

[42] Park J, Lee E, Hwang N M, Kang M, Kim S C, Hwang Y, Park J G, Noh H J, Kini J Y, Park J H, Hyeon T (2005). One-nanometer-scale size-controlled synthesis of monodisperse magnetic iron oxide nanoparticles. Angewandte Chemie International Edition, 44(19): 2872–2877

[43] Su C (2017). Environmental implications and applications of engineered nanoscale magnetite and its hybrid nanocomposites: A review of recent literature. Journal of Hazardous Materials, 322(Part A): 48–84

[44] Sun S H, Zeng H (2002). Size-controlled synthesis of magnetite nanoparticles. Journal of the American Chemical Society, 124(28): 8204–8205

[45] Sun S H, Zeng H, Robinson D B, Raoux S, Rice P M, Wang S X, Li G X (2004). Monodisperse MFe₂O₄ (M= Fe, Co, Mn) nanoparticles. Journal of the American Chemical Society, 126(1): 273–279

[46] Tang S C N, Lo I M C (2013). Magnetic nanoparticles: Essential factors for sustainable environmental applications. Water Research, 47(8): 2613–2632

[47] Trivedi P, Axe L (2000). Modeling Cd and Zn sorption to hydrous metal oxides. Environmental Science & Technology, 34(11): 2215–2223

[48] U.S.EPA (2001). Arsenic and Clarifications to Compliance and New Source Monitoring Rule: A Quick Reference Guide.Washington D.C.: Environmental Protection Agency, 2

[49] Wei G, Zhang J, Luo J, Xue H, Huang D, Cheng Z, Jiang X (2019). Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene. Frontiers of Environmental Science & Engineering, 13(4): 61

[50] Wiltshire M C K, Pendry J B, Young I R, Larkman D J, Gilderdale D J, Hajnal J V (2001). Microstructured magnetic materials for RF flux guides in magnetic resonance imaging. Science, 291(5505): 849–851

[51] Xu P, Zeng G M, Huang D L, Feng C L, Hu S, Zhao M H, Lai C, Wei Z, Huang C, Xie G X, Liu Z F (2012). Use of iron oxide nanomaterials in wastewater treatment: A review. Science of the Total Environment, 424: 1–10

[52] Yavuz C T, Mayo J T, Yu W W, Prakash A, Falkner J C, Yean S, Cong L L, Shipley H J, Kan A, Tomson M, Natelson D, Colvin V L (2006). Low-field magnetic separation of monodisperse Fe₃O₄ nanocrystals. Science, 314(5801): 964–967

[53] Yu W W, Falkner J C, Yavuz C T, Colvin V L (2004). Synthesis of monodisperse iron oxide nanocrystals by thermal decomposition of iron carboxylate salts. Chemical Communications, 20: 2306–2307

[54] Yuan P, Liu D, Fan M, Yang D, Zhu R, Ge F, Zhu J, He H (2010). Removal of hexavalent chromium [Cr(VI)] from aqueous solutions by the diatomite-supported/unsupported magnetite nanoparticles. Journal of Hazardous Materials, 173(1–3): 614–621

[55] Zeng H, Rice P M, Wang S X, Sun S H (2004). Shape-controlled synthesis and shape-induced texture of MnFe₂O₄ nanoparticles. Journal of the American Chemical Society, 126(37): 11458–11459

[56] Zhou Z H, Wang J, Liu X, Chan H S O (2001). Synthesis of Fe₃O₄ nanoparticles from emulsions. Journal of Materials Chemistry, 11(6): 1704–1709

Acknowledgements

This work was supported by American Chemical Society’s Petroleum Research Fund (#52640-DNI10), the US National Science Foundation (CBET, #1236653 and #1437820), and US Army Corps of Engineers (W912HZ-13-2-0009-P00001).

RIGHTS & PERMISSIONS

2020 Higher Education Press