SYNTHESIS AND CHARACTERIZATION OF CRYSTALLINE IRON

NANOCUBES FROM ZEROVALENT IRON SANDWICH COMPLEXES

Anh Nguyen, Alvaro Duarte-Ruiz, Jonathan G. Mehtala, and Alexander Wei
Department of Chemistry, Purdue University, West Lafayette, IN 47907-2084

ABSTRACT: We present a solvothermal method for synthesizing crystalline iron nanocubes, based on the thermal decomposition of iron–
arene sandwich complexes (cyclopentadienyl(Fe0)cyclohexadienes or CpFe(benz-H) in the presence of Oleylamine (OAm) and
Oleylamine.HCl (OAm.HCl) as surfactants and n-decane as a solvent. These nanoparticles are comprised of Fe cores with Fe-oxide shells,
as characterized HR-TEM analysis. The reaction parameter such as reaction temperature and surfactant concentration had effects on to the
size and shape of the iron nanoparticles.
Introduction. Magnetic nanoparticles are of great technological importance, and
iron is the most abundant and practical source of ferromagnetic materials.1 Effect of surfactant concentrations
However, iron is oxidatively sensitive, and Fe particles smaller than 8 nm will be
completely oxidized in the presence of water and oxygen.2 Larger Fe NPs form a
Reducing the surfactant concentration appears to accelerate the rate of growth, but
relatively stable, 3-4 nm oxide shell of , protecting the metal core from immediate
result in less uniform size and shape compared with nanoparticles prepared at a
oxidation.
threefold higher ratio of surfactant to CpFe(benz-H).
Several synthetic methods of metallic iron NPs have been developed.2-4 Recently, 130 ºC
25
130 ºC
Tilley and co-workers reported a method using an organoiron sandwich complex for 20

15
the synthesis of crystalline Fe/Fe3O4 core/shell nanoparticles.2 In this poster, we

Counts
Figure 2. Left, TEM images of Fe nanoparticles synthesized in
10
further investigate the synthesis of iron NPs based on this work, with variations in 0.25 M OAm/8.3 mM OAm.HCl; right, particle size analyses at
5
different reaction temperatures.
choice of surfactant, reaction temperature and reagent concentrations. 0
2 6 10 14 18 22 26
Diameter [nm]

Synthesis of crystalline Iron NPs

150 ºC 40
35 150 ºC Table 2. Size of Fe nanoparticles prepared in 0.25 M
30
25
OAm/8.3 mM OAm.HCl at different temperatures .

Counts
20
15
Synthesis of CpFe(benz-H) (Scheme 1): Ferrocene is treated in refluxing benzene 10
5
Reaction Particle diameter Rel. Std.
for 1 hour with AlCl3 (3 equiv), and shredded Al (1 equiv), then poured over ice and 0
2 6 10 14 18 22 26 30
temperature (nm) Dev. (%)
washed with hexanes. The aqueous solution is then treated with KPF6 (1.23 equiv) Diameter [nm]
(oC)
to precipitate the CpFe–benzene salt. The green solid is suspended in dry THF and 170 ºC 35 130 15.3 ± 1.9 (N=113) 12.4
30
170 ºC
reduced with LiAlH4 (2.5 equiv). After 1 hour, the reaction is cooled to 0 ºC and 25 150 17.1 ± 1.8 (N=133) 10.5

Counts
20
quenched with water. The orange/red reaction mixture is diluted with H2O and 15 170 15.2 ± 1.9 (N=141) 12.5
10
extracted with hexanes, which are dried over NaSO4 then concentrated to a red 5
0
solid. This is purified by sublimation, with overall yields of 50% from ferrocene. 2 6 10 14 18
Diameter [nm]
22 26

PF6–
HR-TEM and FFT analysis
1. AlCl3, Al
benzene,
reflux LiAlH4
Structural and compositional information of the nanocubes was obtained using
2. KPF6 THF
Fe NPs HRTEM image analysis (Figure 3, left). FFT analysis of a single nanocube (inset,
dashed square) revealed several well-defined reciprocal lattice peaks (Figure 3, right).
Scheme 1. Reaction sequence for preparing crystalline iron nanocubes. Inverse FFT analysis of bcc-Fe lattices peaks #1 and #2 coincided with the core region
Nanoparticle synthesis: The vessel was flame-dried to remove moisture prior to of the nanocube, whereas that of lattice peaks #3−#7 indicated formation of crystalline
adding CpFe(benz-H) (150 mg, 250 mM) and oleylamine.HCl (OAm.HCl) (22.8 mg, iron oxide in the shell region (Figure 4).
25 mM). The reaction vessel was flushed 3 times with vacuum and argon, then
treated with oleylamine (OAm) (740 µL, 750 mM) and solvent (3 mL) , then flushed
with argon for 1 hour. The reaction vessel was sealed placed in an oil bath pre-
heated to 130 oC for 48 hours.
Characterization: TEM were taken on a Tecnai T20 at 200 kV.

Effect of Reaction Temperature Figure 3. Left, HRTEM image of Fe nanocubes prepared at 130 oC; right, FFT analysis of the nanocube outlined in
dashed square.
The TEM image of Fe nanoparticles indicated that most of these particles were
#1 #2 #3
cubic. These Fe nanocubes had dark cores and surrounded by lighter shells,
consistent with an iron core coated with iron oxide. When the reaction temperature
Figure 4. Inverse FFT
was increased from 130 to 150 or 170 oC, the average NP size increased by 10 or analysis of the seven lattice
20%, respectively. peaks identified in Figure 3.
130 ºC 50
45 130 ºC
40
35
30 Figure 1. TEM images and size
Counts

25
20 distribution analysis of Fe nanocubes
15
10 synthesized at 130; 150 and 170 ºC. #4 #5 #6 #7
5
0
2 4 6 8 10 12 14 16 18 20
Diameter [nm]

150 ºC 25
150 ºC
20

15
Table 1. NP size vs. Reaction temperatures
Counts

10

5 Reaction Particle diameter Rel. Std.

0 temperature (nm) Dev. (%)
2 4 6 8 10 12 14 16 18 20
Diameter [nm] (oC) Table 3. Lattice analysis of core/shell nanoparticles based on FFT image in Figure 3.
170 ºC 45 130 11.8 ± 0.8 (N=148) 6.8 Lattice d values (Å) d values (Å)
40 Measured d
35
170 ºC Peak JCPDS #6-0696 hkl (%) JCPDS #19-0629 hkl (%)
30 150 12.4 ± 1.0 (N=105) 8.1
#
spacing (Å)
(bcc-Fe) (Fe3O4)
Counts

25

14.4 ± 1.3 (N=120) 9.0

20
15 170 1, 2 2.02, 1.95 2.026 110 (100)
10
2.54, 2.45,
5
3, 4, 5, 7 2.53 311 (100)
0
2 6 10 14 18 22 26 2.59, 2.53
Diameter [nm]
6 2.98 2.97 220 (30)
References Acknowledgments
1. Huber, D. L. Small 2005, 1, 482 –501 This work is supported by a grant from the National Science Foundation (CHE-0957738).
2. Cheong, S., et al. Angew. Chem. Int. Ed. 2011, 50, 4206–4209
Anh Nguyen acknowledges the Vietnam Education Foundation.
3. Dumestre, F., Chaudret, B., Amiens, C., Renaud, P., Fejes, P. Science 2004, 303, 821-823.
4. Shavel, A., Gonzalez B. R., Spasova, M., Farle, M., Liz-Marzan, L. Adv. Funct. Mater. 2007, 17, 3870-3876.