High-performance, superparamagnetic, nanoparticle-based heavy metal sorbents for removal of contaminants from natural waters.

We describe the synthesis and characterization of high-performance, superparamagnetic, iron oxide nanoparticle-based, heavy metal sorbents, which demonstrate excellent affinity for the separation of heavy metals in contaminated water systems (i.e., spiked Columbia River water). The magnetic nanoparticle sorbents were prepared from an easy-to-synthesize iron oxide precursor, followed by a simple, one-step ligand exchange reaction to introduce an affinity ligand to the nanoparticle surface that is specific to a heavy metal or class of heavy metal contaminants. The engineered magnetic nanoparticle sorbents have inherently high active surface areas, allowing for increased binding capacities. To demonstrate the performance of the nanoparticle sorbents, river water was spiked with specific metals and exposed to low concentrations of the functionalized nanoparticles. In almost all cases, the nanoparticles were found to be superior to commercially available sorbent materials as well as the unfunctionalized iron oxide nanoparticles.

[1]  Gustaaf Borghs,et al.  Silane Ligand Exchange to Make Hydrophobic Superparamagnetic Nanoparticles Water-Dispersible , 2007 .

[2]  T. A. Hatton,et al.  Bilayer Surfactant Stabilized Magnetic Fluids: Synthesis and Interactions at Interfaces , 1999 .

[3]  Yang-Chuang Chang,et al.  Magnetic chitosan nanoparticles: Studies on chitosan binding and adsorption of Co(II) ions , 2006 .

[4]  Guohua Chen,et al.  Removal and recovery of Cr(VI) from wastewater by maghemite nanoparticles. , 2005, Water research.

[5]  J. Greneche,et al.  Coupling Agent Effect on Magnetic Properties of Functionalized Magnetite-Based Nanoparticles , 2008 .

[6]  Xiaogang Peng,et al.  Super‐Stable, High‐Quality Fe3O4 Dendron–Nanocrystals Dispersible in Both Organic and Aqueous Solutions , 2005, Advanced materials.

[7]  M. Stratmann,et al.  A surface analytical and an electrochemical study of iron surfaces modified by thiols , 1992 .

[8]  James E. Hutchison,et al.  Analysis of Nanoparticle Transmission Electron Microscopy Data Using a Public- Domain Image-Processing Program, Image , 2006 .

[9]  D. Leslie-Pelecky,et al.  Iron oxide nanoparticles for sustained delivery of anticancer agents. , 2005, Molecular pharmaceutics.

[10]  L. Di Palma,et al.  Recovery of EDTA and metal precipitation from soil flushing solutions. , 2003, Journal of hazardous materials.

[11]  A. Ulman,et al.  Self-Assembled Monolayers of Alkanesulfonic and -phosphonic Acids on Amorphous Iron Oxide Nanoparticles , 1999 .

[12]  J. T. Mayo,et al.  Low-Field Magnetic Separation of Monodisperse Fe3O4 Nanocrystals , 2006, Science.

[13]  Wassana Yantasee,et al.  Removal of heavy metals from aqueous systems with thiol functionalized superparamagnetic nanoparticles. , 2007, Environmental science & technology.

[14]  R. Silverstein,et al.  Spectrometric identification of organic compounds , 2013 .

[15]  K. R. Koch,et al.  Diethylenetriamine Functionalized Silica Coated Magnetite Nanoparticles for Selective Palladium Ion Extraction from Aqueous Solutions , 2007 .

[16]  S. Reed,et al.  Small, water-soluble, ligand-stabilized gold nanoparticles synthesized by interfacial ligand exchange reactions , 2000 .

[17]  A. Elaissari,et al.  Surface modification of iron oxide nanoparticles by a phosphate‐based macromonomer and further encapsulation into submicrometer polystyrene particles by miniemulsion polymerization , 2008 .

[18]  S. K. Ghosh,et al.  Synthesis of highly stable folic acid conjugated magnetite nanoparticles for targeting cancer cells , 2007 .

[19]  H. Pizem,et al.  Alkyl Phosphonate/Phosphate Coating on Magnetite Nanoparticles: A Comparison with Fatty Acids , 2001 .

[20]  W. Stickle,et al.  Handbook of X-Ray Photoelectron Spectroscopy , 1992 .

[21]  Jun Liu,et al.  Design and synthesis of self-assembled monolayers on mesoporous supports (SAMMS): The importance of ligand posture in functional nanomaterials , 2007 .

[22]  J. Jang,et al.  Thiol containing polymer encapsulated magnetic nanoparticles as reusable and efficiently separable adsorbent for heavy metal ions. , 2007, Chemical communications.

[23]  M. G. Warner,et al.  Solventless syntheses of mesotetraphenylporphyrin: newexperiments for a greener organic chemistry laboratory curriculum , 2001 .

[24]  William H. Hendershot,et al.  Removal of trace metals from contaminated soils using EDTA incorporating resin trapping techniques , 1998 .

[25]  Guohua Chen,et al.  Comparative study of various magnetic nanoparticles for Cr(VI) removal , 2007 .

[26]  Hao Zeng,et al.  Monodisperse MFe2O4 (M = Fe, Co, Mn) nanoparticles. , 2004, Journal of the American Chemical Society.

[27]  Nathan Kohler,et al.  A bifunctional poly(ethylene glycol) silane immobilized on metallic oxide-based nanoparticles for conjugation with cell targeting agents. , 2004, Journal of the American Chemical Society.

[28]  Zhenghe Xu,et al.  Self-Assembled Monolayer Coatings on Nanosized Magnetic Particles Using 16-Mercaptohexadecanoic Acid , 1995 .

[29]  Tina Masciangioli,et al.  Environmental technologies at the nanoscale. , 2003, Environmental science & technology.

[30]  Jin-Sil Choi,et al.  In vivo magnetic resonance detection of cancer by using multifunctional magnetic nanocrystals. , 2005, Journal of the American Chemical Society.

[31]  van Leeuwen DA,et al.  Quenching of magnetic moments by ligand-metal interactions in nanosized magnetic metal clusters. , 1994, Physical review letters.

[32]  Yang-Chuang Chang,et al.  Preparation and adsorption properties of monodisperse chitosan-bound Fe3O4 magnetic nanoparticles for removal of Cu(II) ions. , 2005, Journal of colloid and interface science.

[33]  Yang Gao,et al.  Heteroepitaxial growth of α-Fe2O3, γ-Fe2O3 and Fe3O4 thin films by oxygen-plasma-assisted molecular beam epitaxy , 1997 .

[34]  F. Schüth,et al.  Magnetische Nanopartikel: Synthese, Stabilisierung, Funktionalisierung und Anwendung , 2007 .

[35]  Ralph G. Pearson,et al.  HARD AND SOFT ACIDS AND BASES , 1963 .

[36]  D. Scherson,et al.  Metal-ion adsorption on carboxyl-bearing self-assembled monolayers covalently bound to magnetic nanoparticles. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[37]  S. Banerjee,et al.  Fast removal of copper ions by gum arabic modified magnetic nano-adsorbent. , 2007, Journal of hazardous materials.

[38]  Robert N Grass,et al.  Magnetic EDTA: coupling heavy metal chelators to metal nanomagnets for rapid removal of cadmium, lead and copper from contaminated water. , 2009, Chemical communications.

[39]  V. Cabuil,et al.  Nickel adsorption by magnetic alginate microcapsules containing an extractant. , 2006, Water research.

[40]  Athanasios B. Bourlinos,et al.  Surface Modification of Ultrafine Magnetic Iron Oxide Particles , 2002 .

[41]  Guohua Chen,et al.  Selective removal of heavy metals from industrial wastewater using maghemite nanoparticle: Performance and mechanisms , 2006 .

[42]  M. Joniau,et al.  Mechanistic aspects of the adsorption of phospholipids onto lauric acid stabilized magnetite nanocolloids , 1991 .

[43]  Dong-Hwang Chen,et al.  Rapid removal of heavy metal cations and anions from aqueous solutions by an amino-functionalized magnetic nano-adsorbent. , 2009, Journal of hazardous materials.

[44]  K. Das,et al.  Monolayer Exchange Chemistry of γ-Fe2O3 Nanoparticles , 2002 .

[45]  Wassana Yantasee,et al.  Direct detection of Pb in urine and Cd, Pb, Cu, and Ag in natural waters using electrochemical sensors immobilized with DMSA functionalized magnetic nanoparticles. , 2008, The Analyst.

[46]  A. Lu,et al.  Magnetic nanoparticles: synthesis, protection, functionalization, and application. , 2007, Angewandte Chemie.