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Chemical Synthesis of Magnetic Nano Particles

Chemical Synthesis of Magnetic Nano Particles

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Chemical synthesis of magnetic nanoparticles
Taeghwan Hyeon
 National Creative Research Initiative Center for Oxide Nanocrystalline Materials and School of Chemical Engineering, Seoul National University, Seoul 151-744, Korea. E-mail: thyeon@plaza.snu.ac.kr 
Received (in Cambridge, UK) 9th September 2002, Accepted 12th November 2002 First published as an Advance Article on the web 3rd December 2002
Recent advances in the synthesis of various magnetic nano-particles using colloidal chemical approaches are reviewed.Typically, these approaches involve either rapid injection of reagents into hot surfactant solution followed by aging at hightemperature, or the mixing of reagents at a low temperature andslow heating under controlled conditions. Spherical cobaltnanoparticles with various crystal structures have been synthe-sized by thermally decomposing dicobalt octacarbonyl or byreducing cobalt salts. Nanoparticles of Fe–Pt and other relatediron or cobalt containing alloys have been made by simultane-ously reacting their constituent precursors. Many differentferrite nanoparticles have been synthesized by the thermaldecomposition of organometallic precursors followed by oxida-tion or by low-temperature reactions inside reverse micelles.Rod-shaped iron nanoparticles have been synthesized from theoriented growth of spherical nanoparticles, and cobalt nano-disks were synthesized from the thermal decomposition of dicobalt octacarbonyl in the presence of a mixture of twosurfactants.
Introduction
The development of uniform nanometer sized particles has beenintensively pursued because of their technological and funda-mental scientific importance.
1
These nanoparticulate materialsoften exhibit very interesting electrical, optical, magnetic, andchemical properties, which cannot be achieved by their bulk counterparts.
2
The synthesis of discrete magnetic nanoparticleswith sizes ranging from 2 to 20 nm, is of significant importance,because of their applications in multi-terabit in
2
2
magneticstorage devices.
3
Such magnetic nanoparticles could also findapplications in ferrofluids, magnetic refrigeration systems,contrast enhancement in magnetic resonance imaging, magneticcarriers for drug targeting and catalysis.
4
In the current article,I will discuss recent advances made in the synthesis of variousmagnetic nanoparticles using colloidal chemical syntheticprocedures. A general review on the synthesis and under-standing of nanostructured magnetic materials up to 1996 isgiven in the article by Leslie-Pelecky and Rieke.
5
The materialscovered in the current article are colloidal systems composed of isolated particles with nanometer-sized dimensions that arestabilized by surfactant molecules and dispersed in solventmedia. In the ideal case, these non-interacting systems derivetheir unique magnetic properties mostly from the reduced sizeof the isolated nanoparticles, and contributions from inter-particle interactions are negligible. The surfactant coating onmagnetic nanoparticles prevents clustering due to steric repul-sion. Dynamic adsorption and desorption of surfactant mole-cules onto particle surfaces during synthesis enables reactivespecies to be added onto the growing particles. Thesenanoparticles can be dispersed in many organic solvents and canbe retrieved as powder forms by removing the solvent.The followings are several key issues of nanoparticlesynthesis.
4
Particle size distribution (uniformity): Can we synthesizemonodisperse nanocrystals?
4
Particle size control: Can we control the particle size of nanocrystals in a reproducible manner?
4
Crystallinity and crystal structure: Can we obtain materialswith satisfactory high crystallinity and the desired crystalstructure?
4
Shape-control: Can we synthesize non-spherical and aniso-tropic nanoparticles?
4
Alignment: For device applications, we should also considerthe alignment of nanoparticles on substrates.In the present article, I am especially interested in thesynthesis of monodisperse magnetic nanoparticles. Mono-disperse nanoparticles are generally considered to be sampleswith standard deviations
@
5% diameter for sphericalparticles. Often nanocrystals are referred to as well-definedcrystalline materials, whereas nanoparticles is a term used moregenerally for particles with diameters of 2–50 nm with variablecrystallinity.Chemical methods have been widely used to producenanostructured materials due to their straightforward nature andtheir potential to produce large quantities of the final product.Realizable particle sizes range in size from nanometers tomicrometers, by controlling particle size during synthesis byusing competition between nucleation and growth. There areseveral synthetic procedures for synthesizing monodispersenanoparticles. It is well known that a short burst of nucleationfollowed by slow controlled growth is critical to producemonodisperse particles. The following describe two representa-
Taeghwan Hyeon received his B. S. (1987) and M. S. (1989) inChemistry from Seoul National University, Seoul, Korea. Heobtained his Ph.D. from the University of Illinois at Urbana-Champaign (1996) under the supervision of Professor KennethS. Suslick. After conducting postdoctoral research with Pro- fessor Wolfgang M. H. Sachtler at Northwestern University, he joined the faculty of the School of Chemical Engineering of Seoul National University in September 1997. He has received several awards including the T. S. Piper Award (University of  Illinois, 1996), Korean Young Scientist Award (Korean Govern-ment, 2002), KCS–Wiley Young Chemist Award (KoreanChemical Society, 2001), and The Scientist of the Month Award (Korean Science and Engineering Foundation, 2002). In July2002, he became the director of the National Creative Research Initiative Center for Oxide Nanocrystalline Materials sup- ported by the Korean Ministry of Science and Technology. Hiscurrent research interests include synthesis of metallic and oxide nanoparticles, synthesis of nanoporous carbon materials,and catalytic applications of nanostructured materials.
This journal is © The Royal Society of Chemistry 2003 
   D   O   I  :   1   0 .   1   0   3   9   /   b   2   0   7   7   8   9   b
927
CHEM. COMMUN.
, 2003, 927–934
 
tive synthetic procedures. In the first synthetic procedure (Fig.1), the rapid injection of the reagents, often organometalliccompounds, into hot surfactant solution induces the simultane-ous formation of many nuclei.
6
Alternatively, reducing agentsare added to metal salt solutions at high temperature. In thesecond procedure, reagents are mixed at low temperature andthe resulting reaction mixtures are slowly heated in a controlledmanner to generate nuclei. Subsequently, particle growth occursby the addition of reactive species. Particle size can be alsoincreased by aging at high temperature by Oswalt ripening, inwhich smaller nanoparticles dissolve and deposit on the biggernanoparticles. The growth of nanoparticles can be stopped byrapidly decreasing the reaction temperature. Nanoparticlesproduced using these synthetic procedures often have particlesize distributions with
~10%. Further size-selection proc-esses can narrow the particle size distribution below
= 5%.The most frequently applied size-selection involves the additionof a poor solvent to precipitate the larger particles. When poorsolvent is added to a mixture containing nanoparticles of various sizes, the biggest particles flocculate first because of their greatest van der Waals attraction. This precipitate can beretrieved by centrifugation. The precipitate can be re-dissolvedin solvent, and further size-selection process can be performedto yield particles with narrower particle size distribution. Veryrecently, Klabunde and coworkers reported the fabrication of extremely monodisperse gold nanoparticles through digestiveripening.
7
The particle sizes of nanoparticles can be controlled bysystematically adjusting the reaction parameters, such as time,temperature, and the concentrations of reagents and stabilizingsurfactants. In general, particle size increases with increasingreaction time, because more monomeric species are generated,and with increasing reaction temperature because the rate of reaction is increased.
Nanoparticles of iron, cobalt and nickel
The Murray group at the IBM Watson research center hasstudied the synthesis of monodisperse metallic magneticnanoparticles intensively.
8,9
They have synthesized cobaltnanoparticles with several different crystal structures usingdifferent synthetic procedures. High temperature reduction of cobalt chloride was employed to synthesize
e
-phase cobaltnanoparticles.
9
a
The injection of superhydride (LiBEt
3
H)solution in dioctyl ether into a hot cobalt chloride solution indioctyl ether (200
°
C) in the presence of oleic acid andtrialkylphosphine induced the simultaneous formation of manysmall metal clusters, which acted as nuclei for nanoparticleformation. Continued heating at 200
°
C induced the growth of these clusters to the nanoparticle level. Particle size wascontrolled by the steric bulkiness of the stabilizing surfactants.Short-chain alkylphosphines allowed faster growth, and re-sulted in the bigger particles, while bulkier surfactants reducedparticle growth and favored production of smaller nano-particles. For example, when bulky trioctylphosphine wasapplied in the synthesis, 2
6 nm sized particles were generated.In contrast, when tributylphosphine was used as a stabilizer7
11 nm sized nanoparticles were produced. A further narrow-ing of particle size distribution was proceeded using a sizeselective precipitation by the gradual addition of alcohol (
e.g.
ethanol) into a hydrocarbon (
e.g.
hexane) dispersion containingnanoparticles with wide size distribution. Monodisperse cobaltnanoparticles organize into two- and three-dimensional super-lattices. Fig. 2 shows a 2D assembly of 9 nm cobaltnanoparticles. A high-resolution transmission electron micro-graph of a single nanoparticle, shown in the inset of Fig. 2,reveals its highly crystalline nature. The X-ray diffractionpattern of these nanoparticles reveals a complex cubic structurerelated to the beta phase of elemental manganese (
e
-Co).Heating the
e
-Co nanoparticles at 300
°
C generated hcp Conanoparticles. The Bawendi group have reported on thesynthesis of 
e
-Co nanoparticle powders from the thermaldecomposition of Co
2
(CO)
8
in TOPO.
10
The Alivisatos grouphave reported on the synthesis of monodisperse
e
-Co nano-particles by the rapid pyrolysis of dicobalt octacarbonyl in thepresence of a surfactant mixture composed of oleic acid, lauricacid and trioctylphosphine.
11
They could synthesize 3
17 nmsized cobalt nanoparticles by controlling the precursor/surfac-tant ratio, the reaction temperature, and the injection time. Black 
et al.
later demonstrated spin-dependent electron transport usingself-assembled 10 nm
e
-Co nanoparticles over 100 nm wideelectrodes.
12
Single electron tunneling was clearly observed forthe two-dimensional hexagonal arrays of cobalt nanoparticles.Similar single electron tunneling in cobalt nanoparticles wasalso reported by Pileni and workers.
13
Hcp cobalt nanoparticles were synthesized by using the so-called polyol process, in which high boiling alcohol is appliedas both a reductant and a solvent.
8
In a typical synthesis,1,2-dodecanediol is added into hydrated cobalt acetate solutiondissolved in diphenyl ether containing oleic acid and trioctyl-phosphine at 250
°
C. Nanoparticles were isolated by size-selective precipitation, and particle size was controlled bychanging the relative concentration of precursor and stabilizer.For example, when a 1
+
1 molar ratio of cobalt acetate and oleicacid was used in the synthesis, 6
8 nm sized cobalt nano-particles were produced, while increasing the concentration of stabilizing surfactants by a factor of two yielded smaller 3
6 nmnanoparticles. Particle size could be also varied by controllingthe steric bulkiness of the phosphine stabilizers, for example,
Fig. 1
Generalized synthesis of monodisperse nanoparticles by the injectionof reagents into hot surfactant solution followed by aging and size-selectiveprocess.
Fig. 2
TEM images of 9 nm
e
-Co nanoparticles (inset, high-resolution TEMimage).
9
a
Reprinted with permission from reference 9(
a
). Copyright 1999American Institute of Physics.
928
CHEM. COMMUN.
, 2003, 927
934
 
using tributylphosphine, 10
13 nm Co nanoparticles weregenerated. Using hydrated nickel acetate as a metal precursor,nickel nanoparticles with particle sizes in the range 8
13 nmwere obtained. Co/Ni alloy nanoparticles were also producedusing a mixture of cobalt acetate and nickel acetate through asimilar synthetic procedure.
8
b
Diehl
et al.
used ferromagneticresonance (FMR) techniques to investigate the detailed mag-netic characteristics of cobalt nanoparticles with differentcrystalline structures.
9
b
The structural characterization of anordered assembly of cobalt nanoparticles using high-resolutiontransmission electron microscopy was reported by Wang
et al.
9
c
They synthesized multiply twinned fcc cobalt nanocrystals fromthe thermal decomposition of dicobalt octacarbonyl in thepresence of a surfactant mixture composed of oleic acid andtributylphosphine. An HRTEM image of the nanoparticlesrevealed complicated interference patterns.
8
Reverse micelles, which are water-in-oil droplets stabilizedby a monolayer of surfactant, have been applied as nanoscalereactors for the synthesis of various nanoparticles.
14
Chen
et al.
and later the Pileni group reported on the synthesis of relativelyuniform cobalt nanoparticles by the reduction of cobalt saltinside reverse micelles.
15
Chen
et al.
synthesized cobaltnanoparticles with particle size in the range 1.8
4.4 nm byreducing CoCl
2
with NaBH
4
in reverse micelles formed usingdidodecyldimethylammonium bromide (DDAB). The Pilenigroup reported the synthesis of cobalt nanoparticles from thereaction between a micellar solution containing NaAOT(sodium bis(2-ethylhexyl)sulfosuccinate) and Co(AOT)
2
, andNaBH
4
dissolved in NaAOT solution.
16
Collisions followed byexchange between micellar droplets induce chemical reaction of cobalt ions and sodium borohydride to generate cobalt nano-particles. The as-synthesized nanoparticles were poorly crystal-line while XRD, after heating at 500
°
C, revealed thecharacteristic pattern of fcc cobalt. The average particle sizemeasured using TEM data was 6 nm with a particle sizedistribution
= 9%. A size selection process involving theextraction of nanoparticles from reverse micelles significantlyreduced the polydispersity of the particle size distribution andthese uniform particles self-assembled to generate two-dimen-sionally hexagonally ordered arrays.
17
Relatively very little work has been done to synthesizeuniform iron nanoparticles. Suslick 
et al.
reported the synthesisof iron nanoparticles from the sonochemical decomposition of iron pentacarbonyl in the presence of polyvinylpyrrolidone(PVP) or oleic acid.
18
The sonochemical decomposition of volatile organometallic compounds has been applied to synthe-size various nanostructured materials.
19
Transmission electronmicrographs showed that the iron particles ranged in size from3 to 8 nm. Electron diffraction revealed that the particles as-formed are amorphous, and that after
in situ
electron beamheating they crystallized to bcc iron. These iron nanoparticleswere readily oxidized to FeO when exposed to air. Gedankenand coworkers reported the synthesis of amorphous cobaltnanoparticles by sonicating Co(CO)
3
(NO) in decane solution inthe presence of oleic acid.
20
Spherical 5
10 nm sized amor-phous nanoparticles were produced. One drawback of thesonochemical process in the synthesis of nanoparticles is itsinability to control particle size.Very recently, our research group synthesized monodisperseiron nanoparticles from the high temperature (300
°
C) aging of an iron
oleic acid metal complex, which was prepared by thethermal decomposition of iron pentacarbonyl in the presence of oleic acid at 100
°
C.
21
We were able to synthesize monodispersenanoparticles with sizes ranging from 4 to 20 nm without usingany size selection process. Initially, the iron oleate complex wasprepared by reacting Fe(CO)
5
and oleic acid at 100
°
C. Ironnanoparticles were then generated by aging the iron complex at300
°
C. A TEM image of the iron nanoparticles revealed that thenanoparticles were monodisperse and the electron diffractionpattern showed that the nanoparticles were nearly amorphous.The XRD pattern of the sample after being heat-treated in anargon atmosphere at 500
°
C revealed a bcc
a
-iron structure. Theparticle size could be controlled from 4 to 11 nm by usingdifferent molar ratios of iron pentacarbonyl to oleic acid. Fig.3(a) and (b) show TEM images of iron nanoparticles withparticle sizes of 7 and 11 nm, respectively, which were preparedusing 1
+
2 and 1
+
3 molar ratios of Fe(CO)
5
+
oleic acid. In orderto produce nanoparticles larger than 11 nm, a reaction mixturewith a 1
+
4 molar ratio of Fe(CO)
5
and oleic acid was usedduring the synthesis. However, the particle size of the resultingnanoparticles was still around 11 nm. We could produce ironnanoparticles with particle sizes bigger than 11 nm by addingmore iron oleate complex to previously prepared 11 nm ironnanoparticles, and then aging at 300
°
C. Using this syntheticprocedure, we were able to tune the particle sizes of thenanoparticles from 11 to 20 nm.Using a similar synthetic procedure, we prepared moderatelymonodisperse cobalt nanoparticles and successfully appliedthem to recyclable catalysts for Pauson
Khand reactions, whichinvolve the cycloaddition of alkynes, alkenes and carbonmonoxide to synthesize cyclopentenones.
22
We also usedaqueous colloidal cobalt nanoparticles stabilized by sodiumdodecyl sulfate, which were synthesized by the reverse micellemethod described above, for use as recyclable aqueous-phasePauson
Khand catalysts.
23
Nanoparticles of alloys of cobalt and iron
Sun
et al.
synthesized monodisperse iron
platinum nano-particles by the simultaneous reduction of platinum acet-ylacetonate (Pt(acac)
2
) and the thermal decomposition of ironpentacarbonyl (Fe(CO)
5
) in the presence of oleic acid and oleylamine.
24
a
The composition was adjusted by changing the molarratio of the two precursors. Using a 3
+
2 molar ratio of Fe(CO)
5
to Pt(acac)
2
, Fe
48
Pt
52
nanoparticles were produced, while using4
+
1 mixtures Fe
70
Pt
30
nanoparticles were formed. The particlesize could be varied from 3 to 10 nm by adding more precursorsto previously synthesized 3 nm particles, which acted as nuclei.When the solvent was evaporated slowly, three-dimensionalsuperlattices are generated, and by controlling the chain lengthsof the stabilizing surfactants, inter-particle spacing could betuned. For example, 6 nm Fe
48
Pt
52
nanoparticles were arranged
Fig. 3
TEM images of iron nanoparticles: (a) three-dimensional array of 7nm Fe nanoparticles and (b) 11 nm Fe nanoparticles.
CHEM. COMMUN.
, 2003, 927
934
929

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