Influence of synthesis parameters on iron nanoparticle size and zeta potential

  • Nikki Goldstein
  • Lauren F. GreenleeEmail author
Research Paper


Zero valent iron nanoparticles are of increasing interest in clean water treatment applications due to their reactivity toward organic contaminants and their potential to degrade a variety of compounds. This study focuses on the effect of organophosphate stabilizers on nanoparticle characteristics, including particle size distribution and zeta potential, when the stabilizer is present during nanoparticle synthesis. Particle size distributions from DLS were obtained as a function of stabilizer type and iron precursor (FeSO4·7H2O or FeCl3), and nanoparticles from 2 to 200 nm were produced. Three different organophosphate stabilizer compounds were compared in their ability to control nanoparticle size, and the size distributions obtained for particle volume demonstrated differences caused by the three stabilizers. A range of stabilizer-to-iron (0.05–0.9) and borohydride-to-iron (0.5–8) molar ratios were tested to determine the effect of concentration on nanoparticle size distribution and zeta potential. The combination of ferrous sulfate and ATMP or DTPMP phosphonate stabilizer produced stabilized nanoparticle suspensions, and the stabilizers tested resulted in varying particle size distributions. In general, higher stabilizer concentrations resulted in smaller nanoparticles, and excess borohydride did not decrease nanoparticle size. Zeta potential measurements were largely consistent with particle size distribution data and indicated the stability of the suspensions. Probe sonication, as a nanoparticle resuspension method, was minimally successful in several different organic solvents.


Nanoparticles Zero valent iron Particle size distribution Stabilizer Organophosphate Carboxymethyl cellulose Water treatment Environmental effects 



The authors acknowledge Roy H. Geiss for obtaining TEM images (Online resource 1). LF Greenlee acknowledges the National Research Council and NIST for a postdoctoral fellowship.

Supplementary material

11051_2012_760_MOESM1_ESM.doc (740 kb)
Supplementary material 1 (DOC 740 kb)


  1. Agrawal A, Tratnyek PG (1996) Reduction of nitro aromatic compounds by zero-valent iron metal. Environ Sci Technol 30(1):153–160CrossRefGoogle Scholar
  2. Alayoglu S, Eichhorn B (2008) Rh–Pt bimetallic catalysts: synthesis, characterization, and catalysis of core-shell, alloy, and monometallic nanoparticles. J Am Chem Soc 130(51):17479–17486. doi: 10.1021/ja8061425 CrossRefGoogle Scholar
  3. Alessi DS, Li ZH (2001) Synergistic effect of cationic surfactants on perchloroethylene degradation by zero-valent iron. Environ Sci Technol 35(18):3713–3717CrossRefGoogle Scholar
  4. Duan WB, Oota H, Sawada K (1999) Stability and structure of ethylenedinitrilo poly(methylphosphonate) complexes of the alkaline-earth metal ions in aqueous solution. J Chem Soc Dalton Trans 17:3075–3080CrossRefGoogle Scholar
  5. Franco AP, Mercê ALR (2006) Complexes of carboxymethylcellulose in water. 1: Cu2+, VO2+ and Mo6+. React Funct Polymers 66(6):667–681. doi: 10.1016/j.reactfunctpolym.2005.10.018 CrossRefGoogle Scholar
  6. Glavee GN, Klabunde KJ, Sorensen CM, Hadjapanayis GC (1992) Borohydride reductions of metal ions—a new understanding of the chemistry leading to nanoscale particles of metals, borides, and metal borates. Langmuir 8(3):771–773CrossRefGoogle Scholar
  7. Glavee GN, Klabunde KJ, Sorensen CM, Hadjipanayis GC (1993) Borohydride reduction of cobalt ions in water-chemistry leading to nanoscale metal, boride, or borate particles. Langmuir 9(1):162–169CrossRefGoogle Scholar
  8. Glavee GN, Klabunde KJ, Sorensen CM, Hadjipanayis GC (1995) Chemistry of borohydride reduction of iron(II) and iron(III) ions in aqueous and nonaqueous media—formation of nanoscale Fe, FeB, and Fe2B powders. Inorg Chem 34(1):28–35CrossRefGoogle Scholar
  9. Greenlee LF, Hooker S (2011) Characterization of stabilized zero valent iron nanoparticles. In: Boellinghaus T, Lexow J, Kishi T, Kitagawa M (eds) Materials challenges and testing for supply of energy and resources, pp 173–188Google Scholar
  10. Greenlee LF, Hooker SA (2012) Development of stabilized zero valent iron nanoparticles. Desalination Water Treat 37:114–121CrossRefGoogle Scholar
  11. Greenlee LF, Testa F, Lawler DF, Freeman BD, Moulin P (2010a) The effect of antiscalant addition on calcium carbonate precipitation for a simplified synthetic brackish water reverse osmosis concentrate. Water Res 44(9):2957–2969. doi: 10.1016/j.watres.2010.02.024 CrossRefGoogle Scholar
  12. Greenlee LF, Testa F, Lawler DF, Freeman BD, Moulin P (2010b) Effect of antiscalants on precipitation of an RO concentrate: metals precipitated and particle characteristics for several water compositions. Water Res 44(8):2672–2684. doi: 10.1016/j.watres.2010.01.034 CrossRefGoogle Scholar
  13. He F, Zhao DY (2005) Preparation and characterization of a new class of starch-stabilized bimetallic nanoparticles for degradation of chlorinated hydrocarbons in water. Environ Sci Technol 39(9):3314–3320. doi: 10.1021/es048743y CrossRefGoogle Scholar
  14. He F, Zhao DY (2007) Manipulating the size and dispersibility of zerovalent iron nanoparticles by use of carboxymethyl cellulose stabilizers. Environ Sci Technol 41(17):6216–6221. doi: 10.1021/es0705543 CrossRefGoogle Scholar
  15. He F, Zhao DY (2008) Hydrodechlorination of trichloroethene using stabilized Fe–Pd nanoparticles: reaction mechanism and effects of stabilizers, catalysts and reaction conditions. Appl Catal B Environ 84(3–4):533–540. doi: 10.1016/j.apcatb.2008.05.008 CrossRefGoogle Scholar
  16. He F, Zhao DY, Liu JC, Roberts CB (2007) Stabilization of Fe–Pd nanoparticles with sodium carboxymethyl cellulose for enhanced transport and dechlorination of trichloroethylene in soil and groundwater. Ind Eng Chem Res 46(1):29–34. doi: 10.1021/ie0610896 CrossRefGoogle Scholar
  17. Jonasson RG, Rispler K, Wiwchar B, Gunter WD (1996) Effect of phosphonate inhibitors on calcite nucleation kinetics as a function of temperature using light scattering in an autoclave. Chem Geol 132(1–4):215–225CrossRefGoogle Scholar
  18. Kim JH, Tratnyek PG, Chang YS (2008) Rapid dechlorination of polychlorinated dibenzo-p-dioxins by bimetallic and nanosized zerovalent iron. Environ Sci Technol 42(11):4106–4112. doi: 10.1021/es702560k CrossRefGoogle Scholar
  19. Martell AE, Smith RM, Motekaitis RJ (2004) NIST critically selected stability constants of metal complexes, version 8. Texas A and M University, TexasGoogle Scholar
  20. Ng JD, Lorber B, Witz J, TheobaldDietrich A, Kern D, Giege R (1996) The crystallization of biological macromolecules from precipitates: evidence for Ostwald ripening. J Cryst Growth 168(1–4):50–62CrossRefGoogle Scholar
  21. Nurmi JT, Tratnyek PG, Sarathy V, Baer DR, Amonette JE, Pecher K, Wang CM, Linehan JC, Matson DW, Penn RL, Driessen MD (2005) Characterization and properties of metallic iron nanoparticles: spectroscopy, electrochemistry, and kinetics. Environ Sci Technol 39(5):1221–1230CrossRefGoogle Scholar
  22. Pang SY, Jiang J, Ma J (2011) Oxidation of sulfoxides and arsenic(III) in corrosion of nanoscale zero valent iron by oxygen: evidence against ferryl ions (Fe(IV)) as active intermediates in Fenton reaction. Environ Sci Technol 45(1):307–312. doi: 10.1021/es102401d CrossRefGoogle Scholar
  23. Phenrat T, Liu YQ, Tilton RD, Lowry GV (2009) Adsorbed polyelectrolyte coatings decrease Fe-0 nanoparticle reactivity with TCE in water: conceptual model and mechanisms. Environ Sci Technol 43(5):1507–1514. doi: 10.1021/es802187d CrossRefGoogle Scholar
  24. Ponder SM, Darab JG, Bucher J, Caulder D, Craig I, Davis L, Edelstein N, Lukens W, Nitsche H, Rao LF, Shuh DK, Mallouk TE (2001) Surface chemistry and electrochemistry of supported zerovalent iron nanoparticles in the remediation of aqueous metal contaminants. Chem Mater 13(2):479–486. doi: 10.1021/cm000288r CrossRefGoogle Scholar
  25. Popov K, Ronkkomaki H, Lajunen LHJ (2001) Critical evaluation of stability constants of phosphonic acids (IUPAC technical report). Pure Appl Chem 73(10):1641–1677CrossRefGoogle Scholar
  26. Reddy MM, Hoch AR (2001) Calcite crystal growth rate inhibition by polycarboxylic acids. J Colloid Interf Sci 235(2):365–370CrossRefGoogle Scholar
  27. Sawada K, Miyagawa T, Sakaguchi T, Doi K (1993) Structure and thermodynamic properties of aminopolyphosphate complexes of the alkaline-earth metal ions. J Chem Soc Dalton Trans 3777–3784Google Scholar
  28. Sawada K, Duan WB, Ono M, Satoh K (2000) Stability and structure of nitrilo(acetate-methylphosphonate) complexes of the alkaline-earth and divalent transition metal ions in aqueous solution. J Chem Soc Dalton Trans 6:919–924CrossRefGoogle Scholar
  29. Sun YG, Xia YN (2002) Shape-controlled synthesis of gold and silver nanoparticles. Science 298(5601):2176–2179CrossRefGoogle Scholar
  30. Tang YM, Yang WZ, Yin XS, Liu Y, Yin PW, Wang JT (2008) Investigation of CaCO3 scale inhibition by PAA, ATMP and PAPEMP. Desalination 228(1–3):55–60CrossRefGoogle Scholar
  31. Tratnyek PG, Salter-Blanc AJ, Nurmi JT, Amonette JE, Liu J, Wang C, Dohnalkova A, Baer DR (2011) Reactivity of zero valent metals in aquatic media: effects of organic surface coatings in aquatic redox chemistry (ed) American Chemical Society, vol 1071, 381–406Google Scholar
  32. Wang CB, Zhang WX (1997) Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs. Environ Sci Technol 31(7):2154–2156CrossRefGoogle Scholar
  33. Wang Y, Wong JF, Teng XW, Lin XZ, Yang H (2003) “Pulling” nanoparticles into water: phase transfer of oleic acid stabilized monodisperse nanoparticles into aqueous solutions of alpha-cyclodextrin. Nano Lett 3(11):1555–1559. doi: 10.1021/nl034731j CrossRefGoogle Scholar
  34. Yang QF, Liu YQ, Gu AH, Ding J, Shen ZQ (2001) Investigation of calcium carbonate scaling inhibition and scale morphology by AFM. J Colloid Interf Sci 240(2):608–621CrossRefGoogle Scholar
  35. Zhang W-X (2003) Nanoscale iron particles for environmental remediation: an overview. J Nanopart Res 5:323–332CrossRefGoogle Scholar
  36. Zheng ZH, Yuan SH, Liu Y, Lu XH, Wan JZ, Wu XH, Chen J (2009) Reductive dechlorination of hexachlorobenzene by Cu/Fe bimetal in the presence of nonionic surfactant. J Hazard Mater 170(2–3):895–901. doi: 10.1016/j.jhazmat.2009.05.052 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. (outside the USA) 2012

Authors and Affiliations

  1. 1.Materials Reliability DivisionNational Institute of Standards and TechnologyBoulderUSA

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