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The coordination polymers were analyzed by using FT-IR,
UV-vis, and WAXD measurements. From FT-IR spectroscopy,
we observed a CN stretching band shift from 2045 to 2084 cm-1
after the polymerization,6 indicating the formation of a cyanide
bridge of Fe(II)-CN-Fe(III).7 In UV-vis spectra, a strong
absorption at ca. 670 nm due to the FeII to FeIII CT8 appeared upon
the addition of Fe3+.6 The intensity of this peak increased in
proportion to the amount of Fe3+ added,6 suggesting the added Fe3+
ions were involved in the coordination polymerization. Different
from other solid PB NPs,2,3 we found that MEPP-produced shells
were amorphous probably due to their curved structures.6
Figure 1a shows a typical TEM image of the coordination
polymer nanoshells with a diameter of ca. 65 nm. However, DLS
measurements of the particles in a diluted solution revealed a
diameter of 133 nm. These different results may be caused by
interparticle coordination. As a matter of fact, the connection of
the particles is clearly observed in the TEM image (see Figure 1a).
This interparticle coordination could be alleviated by dropwise
addition of the miniemulsion to Fe3+ aqueous solution instead of
adding the Fe3+ to the miniemulsion.6A TEM image at higher magnification (see Figure 1b) shows
that the particles exhibit a ring-like morphology, typical of hollow
shell structures. The thickness of the ring is ca. 2 nm indicating
the formation of a thin layer of the coordination polymer with anestimated aggregation number of 1106.6 EDX mapping reveals that
carbon and iron elements (see Figure 1c and 1d) are uniformly
distributed over the surface of the shells, confirming the formation
of a shell of an organometallic network. A tapping mode AFM
was performed, and short rods with hemisphere caps are observed
(see Figure 1e). Undeformed shells were also observed from SEM
experiments (see Figure 2). The observed rigidity of the shells could
be attributed to directional coordination interactions.
We next investigated the coordination polymerization with varied
equivalents of Fe3+ with respect to Fe2+ in the surfactants.6 The
resulting samples were dried from the solutions and characterized
using SEM. The SEM images indicated that a minimum of 1 equiv
of Fe3+ is required to preserve the shape of the miniemulsion
droplets6 and hence to generate shell structures.
Synthesis of the shells with varied size using MEPP is possible.
In two experiments, we prepared a miniemulsion using the same
amount of EPE-Fe (0.5% by weight), but with a toluene content of
5% and 20% by weight, respectively. As characterized by TEM,
the particles prepared from the solution containing 20% toluene
are ca. 198 nm, which is about twice as large as those in the system
with 5% toluene.6
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