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A simple and efficient way of obtaining silver nanoparticles that are dispersible both in organic and in
aqueous solvents using a single capping agent is described. The silver nanoparticles are initially prepared
in water in the presence of aerosol OT [sodium bis(2-ethylhexyl)-sulfosuccinate, AOT]. Thereafter, transfer
of the AOT-capped silver nanoparticles to an organic phase is induced by the addition of a small amount
of orthophosphoric acid during shaking of the biphasic mixture. The AOT-stabilized silver nanoparticles
could be separated out from the organic phase in the form of a powder. The hydrophobic nanoparticles thus
prepared are stable and are readily resuspended in a variety of other polar (including water) and nonpolar
solvents without further surface treatment. The amphiphatic nature of the silver surface is brought about
by a small orientational change in the AOT monolayer on the silver surface in response to the polarity
of the solvent.
Figure 2. (A) Representative TEM micrograph from a drop-cast film of the as-prepared silver hydrosol. The inset shows the SAED
pattern of the particles indexed to fcc silver. (B) Particle size distribution histogram of the silver nanoparticles. The solid line is
a Gaussian fit to the data. The AOT concentration for the preparation of the sample used in this image is 5 10-3 M.
Figure 3. (A-C) Representative TEM micrographs recorded from drop-cast films of silver organosol in cyclohexane obtained from
the hydrosol prepared with different concentrations of AOT: A, 1 10-2 M; B, 5 10-3 M; and C, 1 10-4 M. The respective particle
size distributions are plotted in the insets. (D) Powder XRD pattern of a film prepared from the sample depicted in Figure 3B.
we have recorded the UV-vis spectra of the solutions that linity of the particles is consistent with the face-centered
we obtained after the brownish powder has been redis- cubic (fcc) structure of silver. The particle size distribution
persed in water and different solvents such as toluene, analysis (Figure 2B) reveals that the particles are poly-
benzene, chloroform, and cyclohexane. Figure 1B, curve disperse with an average size of 12 ( 3 nm.
1, shows the spectrum of the AOT-capped silver nano- When the initial concentration of AOT in water is varied
particle powder now redispersed in water. Curves 2-5 systematically the average particle sizes varied as 6.1 (
correspond to the spectra recorded from the brownish silver 0.9, 12.3 ( 3, and 10.6 ( 1.8 nm for the AOT concentrations
nanoparticle powder after redispersion in chloroform, 1 10-2, 5 10-3, and 1 10-4 M, respectively (Figure
toluene, cyclohexane, and benzene, respectively. The small 3A-C). The critical micelle concentration (cmc) of AOT is
shifts observed in the peak positions approximately follow reported to be 2.5 10-3 M. Around the cmc or below the
a trend as expected from the refractive index changes in cmc the particles tend to be bigger. Micelles are considered
the solvent. This exercise clearly proves that our simple equilibrium structures where the surfactant molecules
method is very effective in getting silver nanoparticles are always coming out and joining the micellar moiety.
dispersed in a variety of solvents, including redispersibility This could explain the larger sizes of particles observed
in water. when we have lower concentrations of the surfactant where
Figure 2A shows a representative TEM picture of the the micelles may not possess very compact structures.
as-prepared AOT-capped silver nanoparticles (AOT con- However, when we take an excess quantity of the
centration ) 5 10-3 M) in water. Different concentrations surfactant compared to the cmc the micelles are packed
of AOT were used to probe its effect on the resulting probably in a more compact manner leading to the smaller
nanoparticle sizes. These changes are reflected better in sizes of particles observed as in the case of the 1 10-2
the TEM images obtained from the organosols and are M concentration. The XRD pattern recorded from a drop-
given in Figure 3. The inset of Figure 2A shows the selected cast film of the silver hydrosol prepared in the presence
area electron diffraction (SAED) pattern recorded from of 5 10-3 M AOT shows a number of strong Bragg
the AOT-capped silver hydrosol. In the figure the dif- reflections corresponding to the (111), (200), (220), and
fraction rings have been indexed and show that crystal- (311) reflections of fcc silver (Figure 3D). The XRD results,
Letters Langmuir, Vol. 21, No. 3, 2005 825
Scheme 1. Schematic Representation of the AOT Orientations on the Silver Nanoparticle Surface in Different
Environments and the Molecular Structure of AOT
at 1729 cm-1 in very good agreement of our hypothesis of moieties are better stabilized if they are directed toward
orientational change in AOT molecules brought about by the solvent resulting in the amphiphatic nature observed
the solvent environment. here.
To get a more distinct picture of the role of phosphoric
acid in the phase transfer process, we have tried other Conclusion
acids to effect the phase transfer of AOT-capped silver A very simple and efficient way where the same molecule
nanoparticles from water to the organic phase. Our results AOT is used for the synthesis, stabilization, and phase
indicate that the extent of phase transfer varies as HClO4 transfer of silver nanoparticles is described. The phase
g H3PO4 > H2SO4 and that addition of HCl destabilizes transfer is actually the most versatile of the reported
the Ag colloid in the aqueous phase itself. While we do not methods so far in that the powder obtained after the
yet have a clear explanation for the role of the phase organic solvent is evaporated can be redispersed in a
transfer agents, the trends are exactly the same as those variety of solvents including water.
observed by Efrima and co-workers for the oleic acid capped
silver nanoparticle phase transfer procedures. Hence, we
Acknowledgment. S.K.A. and T.B. thank the De-
tentatively assume that the hydrogen bonding mechanism
partment of Science and Technology (DST) and Council
proposed by them is operational in our case as well.18 As
for Scientific and Industrial Research (CSIR), New Delhi,
in the Efrima study, it is possible that the capping layer
respectively, for financial assistance. This work was
composed of the phosphoric acid or its anion and functional
partially funded by an internal grant of the National
moieties of the AOT molecule form a net of hydrogen bonds
Chemical Laboratory, Pune, to B.L.V.P., and it is gratefully
and force the functional group of the AOT to turn over
acknowledged.
toward the nanoparticle surface in the organic solvent. In
the aqueous phase, on the other hand, the functional LA047707+