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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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