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Magnetic Nanoparticles Synthesis, Protection, Functionalization, And Application

Magnetic Nanoparticles Synthesis, Protection, Functionalization, And Application

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Magnetic Nanoparticles
DOI: 10.1002/anie.200602866
Magnetic Nanoparticles: Synthesis, Protection,Functionalization, and Application
 An-Hui Lu, E. L. Salabas, and Ferdi Schüth*
 Angewandte
Chemie
Keywords:
magnetic properties · nanoparticles ·synthetic methodsF. Schüth et al.
Reviews
1222
2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed.
2007
,
46
, 12221244
 
1.
Introduction
Magnetic nanoparticles are of great interest for research-ers from a wide range of disciplines, including magneticfluids,
[1]
catalysis,
[2,3]
biotechnology/biomedicine,
[4]
magneticresonance imaging,
[5,6]
data storage,
[7]
and environmentalremediation.
[8,9]
While a number of suitable methods havebeen developed for the synthesis of magnetic nanoparticles of various different compositions, successful application of suchmagnetic nanoparticles in the areas listed above is highlydependent on the stability of the particles under a range of different conditions. In most of the envisaged applications, theparticles perform best when the size of the nanoparticles isbelow a critical value, which is dependent on the material butis typically around 10–20 nm. Then each nanoparticlebecomes a single magnetic domain and shows superparamag-netic behavior when the temperature is above the so-calledblocking temperature. Such individual nanoparticles have alarge constant magnetic moment and behave like a giantparamagnetic atom with a fast response to applied magneticfields with negligible remanence (residual magnetism) andcoercivity (the field required to bring the magnetization tozero). These features make superparamagnetic nanoparticlesvery attractive for a broad range of biomedical applicationsbecause the risk of forming agglomerates is negligible at roomtemperature.However, an unavoidable problem associated with par-ticles in this size range is their intrinsic instability over longerperiods of time. Such small particles tend to form agglomer-ates to reduce the energy associated with the high surface areato volume ratio of the nanosized particles. Moreover, nakedmetallic nanoparticles are chemically highly active, and areeasily oxidized in air, resulting generally in loss of magnetismand dispersibility. For many applications it is thus crucial todevelop protection strategies to chemically stabilize thenaked magnetic nanoparticles against degradation during orafter the synthesis. These strategies comprise grafting of orcoating with organic species, including surfactants or poly-mers, or coating with an inorganic layer, such as silica orcarbon. It is noteworthy that in many cases the protectingshells not only stabilize the nanoparticles, but can also be usedfor further functionalization, for instance with other nano-particles or various ligands, depending on the desiredapplication.Functionalized nanoparticles are very promising forapplications in catalysis, biolabeling, and bioseparation.Especially in liquid-phase catalytic reactions, such small andmagnetically separable particles may be useful as quasi-homogeneous systems that combine the advantages of highdispersion, high reactivity, and easy separation. In thefollowing, after briefly addressing the magnetic phenomenaspecific for nanoparticles, we focus mainly on recent develop-ments in the synthesis of magnetic nanoparticles, and variousstrategies for the protection of the particles against oxidationand acid erosion. Further functionalization and application of such magnetic nanoparticles in catalysis and bioseparationwill be discussed in brief. Readers who are interested in amore detailed treatment of the physical properties andbehavior of these magnetic nanoparticles, or biomedical andbiotechnology applications, are referred to specificreviews.
[10–18]
2.
Special Features of Magnetic Nanoparticles
Two key issues dominate the magnetic properties of nanoparticles: finite-size effects and surface effects whichgive rise to various special features, as summarized in
[*] Dr. A.-H. Lu, Dr. E. L. Salabas, Prof. Dr. F. SchüthMax-Planck-Institut für Kohlenforschung45470 Mülheim an der Ruhr (Germany)Fax: (
+
49)208-306-2395E-mail: schueth@mpi-muelheim.mpg.de
his review focuses on the synthesis, protection, functionalization, andapplication of magnetic nanoparticles, as well as the magnetic prop-erties of nanostructured systems. Substantial progress in the size and shape control of magnetic nanoparticles has been made by developingmethods such as co-precipitation, thermal decomposition and/or reduction, micelle synthesis, and hydrothermal synthesis. A major challenge still is protection against corrosion, and therefore suitable protection strategies will be emphasized, for example, surfactant/po-lymer coating, silica coating and carbon coating of magnetic nano- particles or embedding them in a matrix/support. Properly protectedmagnetic nanoparticles can be used as building blocks for the fabri-cation of various functional systems, and their application in catalysisand biotechnology will be briefly reviewed. Finally, some future trendsand perspectives in these research areas will be outlined.
From the Contents
1.
Introduction
1223
2.
Special Features of Magnetic Nanoparticles
1223
 3.
Synthesis of Magnetic Nanoparticles
1227 
 4.
Protection/Stabilization of  Magnetic Nanoparticles
1232
 5.
Functionalization and  Applications of Magnetic Nanoparticles
1237 
6.
Summary and Perspectives
1240 
Magnetic Nanoparticles
Angewandte
Chemie
1223
 Angew. Chem. Int. Ed.
2007
,
46
, 1222–1244 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 
Figure 1. Finite-size effectsresult,for example, fromthequantum confinement of the electrons, whereas typi-cal surface effects arerelated to the symmetrybreaking of the crystalstructure at the boundaryof each particle. Withoutattempting to be exhaustive,these two issues will beaddressed in Section 2.1and 2.2. More completereviews on magnetism innanoscale systems can befound elsewhere.
[19,20]
Because there is no generalagreement on the size limitsfor nanoparticles, in the fol-lowing we use this term forparticles with diametersranging from 1 to 100 nm.
2.1.
Finite-Size Effects
The two most studiedfinite-size effects in nano-particles are the single-domain limit and the super-paramagnetic limit. Thesetwo limits will be brieflydiscussed herein. In largemagnetic particles, it is wellknown that there is a multi-domain structure, where regions of uniform magnetizationare separated by domain walls. The formation of the domainwalls is a process driven by the balance between themagnetostatic energy (
D
MS
), which increases proportionallyto the volume of the materials and the domain-wall energy(
dw
), which increases proportionally to the interfacial areabetween domains. If the sample size is reduced, there is acritical volume below which it costs more energy to create adomain wall than to support the external magnetostaticenergy (stray field) of the single-domain state. This criticaldiameter typically lies in the range of a few tens of nano-meters and depends on the material. It is influenced by thecontribution from various anisotropy energy terms.The critical diameter of a spherical particle,
D
c
, belowwhich it exists in a single-domain state is reached when
D
MS
=
dw
, which implies
D
c
%
18
 ffiffiffiffiffiffiffiffi
 A
eff 
0
2
, where
A
is the
 An-Hui Lu received his B.S. in Chemical Engineering from Taiyuan University of Tech-nology (China) in 1996 and his Ph.D. fromthe Institute of Coal Chemistry, Chinese Academy of Sciences in 2001. After post-doctoral work (as a Max-Planck research fellow and Alexander von Humboldt fellow)in the group of Prof. F. Schüth at the Max-Planck-Institut für Kohlenforschung, he waspromoted to group leader in 2005. Hisresearch interests include synthesis and func-tionalization of nanostructured materialsand magnetically separable catalysts, and their use in heterogeneous catalytic reac-tions.Elena Lorena Salabas¸ (nØe Bîzdoacaˇ  )received her B.S. (1996) and M.S. (2000)degrees in physics from the University of  Bucharest, Romania. She obtained her Ph.D. in Physics from the University Duis-burg-Essen, Germany in 2004. She wasawarded the Lev Falicov Student Award (Denver-Colorado, 2002) of the AmericanVacuum Society for the Best Student Paper  Award in the Magnetic Interfaces and Nano-structure Division. Currently she has a post-doctoral fellowship in the group of Prof. F.Schüth at the Max-Planck-Institut für Koh-lenforschung, Mülheim. Her research focuses on the magnetism of nano-structured materials and exchange-biased systems.
Figure 1.
The different magnetic effects occurring in magnetic nanoparticles. The spin arrangement in a) aferromagnet (FM) and b) an antiferromagnet (AFM);
D
=
diameter,
D
c
=
critical diameter. c) A combination of two different ferromagnetic phases (magenta arrows and black arrows in (a)) may be used for the creation of novel functional nanomaterials, for example, permanent magnets, which are materials with high remanencemagnetization (
M
r
) and high coercivity (
H
C
), as shown schematically in the magnetization curve (c), d) Anillustration of the magnetic moments in a superparamagnet (SPM). A superparamagnet is defined as anassembly of giant magnetic moments which are not interacting, and which can fluctuate when the thermalenergy,
B
, is larger than the anisotropy energy. Superparamagnetic particles exhibit no remanence orcoercivity, that is, there is no hysteresis in the magnetization curve (d). e) The interaction (exchange coupling;linked red dots) at the interface between a ferromagnet and an antiferromagnet produces the exchange biaseffect. In an exchange-biased system, the hysteresis is shifted along the field axis (exchange bias field(
H
eb
))and the coercivity increases substantially. f) Pure antiferromagnetic nanoparticles could exhibit super-paramagnetic relaxation as well as a net magnetization arising from uncompensated surface spins (bluearrows in (b)). This Figure, is a rather simplistic view of some phenomena present in small magnetic particles.In reality, a competition between the various effects will establish the overall magnetic behavior.
F. Schüth et al.
Reviews
1224
2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed.
2007
,
46
, 12221244

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