Polymer-core/metal-shell

Polymer-Core/Metal-Shell Hybridized Nanocrystals. 161... 

This polymer-core/metal-shell type of the hybridized NCs has an inverse nanostructure of Sect. 3. Our research group has recently estabUshed the unique fabrication process, visible-light-driven photocatalytic reduction method [53], to PDA-core/metal-shell hybridized NCs. 

X-Ray Photoelectron Spectrometry. X-ray photoelectron spectrometry (XPS) was applied to analyses of the surface composition of polymer-stabilized metal nanoparticles, which was mentioned in the previous section. This is true in the case of bimetallic nanoparticles as well. In addition, the XPS data can support the structural analyses proposed by EXAFS, which often have considerably wide errors. Quantitative XPS data analyses can be carried out by using an intensity factor of each element. Since the photoelectron emitted by x-ray irradiation is measured in XPS, elements located near the surface can preferentially be detected. The quantitative analysis data of PVP-stabilized bimetallic nanoparticles at a 1/1 (mol/mol) ratio are collected in Table 9.1.1. For example, the composition of Pd and Pt near the surface of PVP-stabilized Pd/Pt bimetallic nanoparticles is calculated to be Pd/Pt = 2.06/1 (mol/ mol) by XPS as shown in Table 9.1.1, while the metal composition charged for the preparation is 1/1. Thus, Pd is preferentially detected, suggesting the Pd-shell structure. This result supports the Pt-core/Pd-shell structure. The similar consideration results in the Au-core/Pd-shell and Au-core/Pt-shell structure for PVP-stabilized Au/Pd and Au/Pt bimetallic nanoparticles, respectively (53). 

The metal on the left side more easily forms a core than that on the right side and vice versa for a shell. Thus, in the combination of Au and Pd, for example, Au forms the core and Pd the shell, and so on. The question that arises then is how the order of this trend is determined. The question was answered by the in situ UV-Vis spectra measured during the coreduction of Au and Pt ions in alcohol in the presence of PVP. According to precise analyses of spectra, the formation mechanism of core/shell-structured bimetallic nanoclusters has been proposed as shown in Fig. 3.20. Here the difference in the redox potential of both elements and that in the strength of coordination bonds between polymer and atom of both elements are the factors that determine the order of ease in forming the core or shell. 

The chemical composition of particles can be just as varied as their shape. Commercial particles can consist of polymers or copolymers, inorganic constructs, metals and semiconductors, superparamagnetic composites, biodegradable constructs, and synthetic dendrimers and dendrons. Often, both the composition of a particle and its shape govern its suitability for a particular purpose. For instance, composite particles containing superparamagnetic iron oxide typically are used for small-scale affinity separations, especially for cell separations followed by flow cytometry analysis or fluorescence-activated cell sorting (FACS). Core-shell semiconductor particles, by... 

More recently, the scope of using hyperbranched polymers as soluble supports in catalysis has been extended by the synthesis of amphiphilic star polymers bearing a hyperbranched core and amphiphilic diblock graft arms. This approach is based on previous work, where the authors reported the synthesis of a hyperbranched macroinitiator and its successful application in a cationic grafting-from reaction of 2-methyl-2-oxazoline to obtain water-soluble, amphiphilic star polymers [73]. Based on this approach, Nuyken et al. prepared catalyticaUy active star polymers where the transition metal catalysts are located at the core-shell interface. The synthesis is outlined in Scheme 6.10. 

A new class of metal-loaded nanoparticles was developed by Reynolds et al. (95). These materials have a core-shell morphology, where the core is a functionalized polymer with a high affinity to the Gd(III) ions. The core polymer contained monomers with carboxylate pendant arms, such as ethylacrylate, methacrylate, butylacrylate or allylmethacrylate. The shell consisted of a... 

An alcohol reduction method has been applied to the synthesis of polymer-stabilized bimetallic nanoparticles. They have been prepared by simultaneous reduction of the two corresponding metal ions with refluxing alcohol. For example, colloidal dispersions of Pd/Pt bimetallic nanoparticles can be prepared by refluxing the alcohol-water (1 1 v/v) mixed solution of palladium(II) chloride and hexachloro-platinic(IV) acid in the presence of poly(/V-vinyl-2-pyrrolidone) (PVP) at about 90-95°C for 1 h (Scheme 9.1.5) (25). The resulting brownish colloidal dispersions are stable and neither precipitate nor flocculate over a period of several years. Pd/ Pt bimetallic nanoparticles thus obtained have a so-called core/shell structure, which is proved by an EXAFS technique (described in Section 9.1.3.3). 

In conclusion, the order of reduction of metal ions is controlled by their redox potential. This is also true in other pairs of precious metals such as Pd/Pt, Au/Pd, etc. (53). In addition, poly(jV-vinyl-2-pyrrolidone) (PVP) plays an important role for the formation of the core/shell structure. In the case of the Au/Pt system, the aggregation starts from Au but not Pt. This is probably due to the coordinating ability of metals to PVP. The Pt atoms or microclusters coordinating to PVP are more stable than the Au atoms or microclusters, since Au cannot coordinate to PVP. Thus, Au atoms or microcluster aggregate at first after the reduction, and then Pt atoms or microclusters deposit on the Au nuclei. In summary, the core/shell structure is controlled by (1) the redox potential of metal ions, and (2) the coordination ability of metals to PVP, stabilizing polymer. 

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