Core/shell structure nanoparticles

Xue J, Wang C, Ma Z. A facile method to prepare a series of Si02 Au core/shell structured nanoparticles. Mater Chem Phys 2007 105(2-3) 419. 

Khurshid, H. Kim, S.H. Bonder, M.J. Colak, L. Ali, Bakhtyar Shah, S.I. Kiick, K.L. Hadjipanayis, G.C. (2009), Water dispersible Fe/Fe-oxide core-shell structured nanoparticles for potential biomedical applications. /. Appl. Phys., 105 07B308-07B308-3. 

Yuan-Qing L, Shao-Yun F, Yang Y, Yiu-Wing M (2008) Facile synthesis of highly transparent polymer nanocomposites by introduction of core-shell structured nanoparticles. Chem Mater... 

Thermosensitive, and amphiphilic polymer bmshes optically active polymers consist of helical poly(iV-propargylamide) main chains and thermosensitive poly(iV-iso-propylacrylamide) (PNlPAm) side chains, were prepared via a novel methodology combining catalytic polymerization, atom transfer radical polymerization (ATRP), and click chemistry. The characterization of GPC, FT-IR, and H-NMR measurements indicated the successful synthesis of the novel amphiphilic polymer brashes. For the confirmation of helical structure of the polymers backbones and the optical activity of the final brashes used UV-Vis and CD spectra. The polymer with optically active cores (helical polyacetylenes) and thermosensitive shells (PNlPAm) brashes self-assembled in aqueous solution forming core/shell structured nanoparticles [137]. 

Optically active polymers show another properties namely thermosensitivity, e.g., main chains helical poly(iV-isopropylacrylamide) and thermosensitive part as side chain of poly(A -isopropylacrylamide) (PNlPAm). Such type of polymers synthetic method described elsewhere [137]. The polymer with optically active cores (helical polyacetylenes) and thermosensitive shells (PNlPAm) brashes self-assembled core/shell structured nanoparticles in aqueous solution. Another example of optically active polymer is poly[/V-(L)-(l-hydroxymethyl)-pro-pylmethacrylamide] (P(l-HMPMA)) of lower critical solution temperature and thermosensitivity. Circular dichroism and microcalorimetric measurements of the polymer showed the polymer chains in a state of relatively low hydration compared to that of by racemate synthesized monomers by free-radical reaction formed P(d,l-HMPMA). Thermosensitivity and structural effects were obtained by microscopic observation of aqueous solution of polymers and its hydrogels [138]. 

X. Sun, Y. Li, Ag C core/shell structured nanoparticles Controlled synthesis, characterization, and assembly, Langmuir 21 (2005) 6019-6024. 

Bimetallic nanoparticles, either as alloys or as core-shell structures, exhibit unique electronic, optical and catalytic properties compared to pure metallic nanopartides [24]. Cu-Ag alloy nanoparticles were obtained through the simultaneous reduction of copper and silver ions again in aqueous starch matrix. The optical properties of these alloy nanopartides vary with their composition, which is seen from the digital photographs in Fig. 8. The formation of alloy was confirmed by single SP maxima which varied depending on the composition of the alloy. 

Core/shell-type nanoparticles ovm ated with higher band inorganic materials exhibit high PL quantum yield compared with uncoated dots d K to elimination of surface non-radiative recombination defects. Such core/shell structures as CdSe/CdS [6] and CdSe ZnS [7] have been prepared from organometaHic precursors. 

The synthesis of bimetallic nanoparticles is mainly divided into two methods, i.e., chemical and physical method, or bottom-up and top-down method. The chemical method involves (1) simultaneous or co-reduction, (2) successive or two-stepped reduction of two kinds of metal ions, and (3) self-organization of bimetallic nanoparticle by physically mixing two kinds of already-prepared monometallic nanoparticles with or without after-treatments. Bimetallic nanoparticle alloys are prepared usually by the simultaneous reduction while bimetallic nanoparticles with core/shell structures are prepared usually by the successive reduction. In the preparation of bimetallic nanoparticles, one of the most interesting aspects is a core/shell structure. The surface element plays an important role in the functions of metal nanoparticles like catal5dic and optical properties, but these properties can be tuned by addition of the second element which may be located on the surface or in the center of the particles adjacent to the surface element. So, we would like to use following marks to inscribe the bimetallic nanoparticles composed of metal 1, Mi and metal 2, M2. 

Pt/Pd bimetallic nanoparticles can be prepared by refluxing the alcohol/water (1 1, v/v) solution of palla-dium(II) chloride and hexachloroplatinic(IV) acid in the presence of poly(A-vinyl-2-pyrrolidone) (PVP) at ca. 95 °C for Ih [15,16,48]. The resulting Pd/Pt nanoparticles have a Pt-core/Pd-shell structure with a narrow size distribution and the dispersion is stable against aggregation for several years. The core/shell structure was confirmed by the technique of EAXFS. Composition of Pt/Pd nanoparticles can be controlled by the initially feed amount of two different metal ions, i.e., in this case one... 

Ag-core/Au-shell bimetallic nanoparticles were prepared by NaBH4 reduction method [124]. UV-Vis spectra were recorded and compared with various ratios of AuAg alloy nanoparticles. The UV-Vis spectra of bimetallic nanoparticles suggested the formation of core/shell structure. Furthermore, the high-resolution transmission electron microscopy (HRTEM) image of the nanoparticles confirmed the core/shell type configuration directly. 

In summary the simultaneous reduction method usually provides alloyed bimetallic nanoparticles or mixtures of two kinds of monometallic nanoparticles. The bimetallic nanoparticles with core/shell structure also form in the simultaneous reduction when the reduction is carried out under mild conditions. In these cases, however, there is difference in redox potentials between the two kinds of metals. Usually the metal with higher redox potential is first reduced to form core part of the bimetallic nanoparticles, and then the metal with lower redox potential is reduced to form shell part on the core, as shown in Figure 2. The coordination ability may play a role in some extent to form a core/shell structure. Therefore, the simultaneous reduction method cannot provide bimetallic nanoparticles with so-called inverted core/ shell structure in which the metal of the core has lower redox potential. 

Successive reduction (or two-step reduction) involves the reduction of first metal ions, followed by the reduction of second metal ions. The second metals are usually deposited on the surface of the first metals due to the formation of the strong metallic bond, resulting in core/shell structured bimetallic nanoparticles. 

Our first attempt of a successive reduction method was utilized to PVP-protected Au/Pd bimetallic nanoparticles [125]. An alcohol reduction of Pd ions in the presence of Au nanoparticles did not provide the bimetallic nanoparticles but the mixtures of distinct Au and Pd monometallic nanoparticles, while an alcohol reduction of Au ions in the presence of Pd nanoparticles can provide AuPd bimetallic nanoparticles. Unexpectedly, these bimetallic nanoparticles did not have a core/shell structure, which was obtained from a simultaneous reduction of the corresponding two metal ions. This difference in the structure may be derived from the redox potentials of Pd and Au ions. When Au ions are added in the solution of enough small Pd nanoparticles, some Pd atoms on the particles reduce the Au ions to Au atoms. The oxidized Pd ions are then reduced again by an alcohol to deposit on the particles. This process may form with the particles a cluster-in-cluster structure, and does not produce Pd-core/ Au-shell bimetallic nanoparticles. On the other hand, the formation of PVP-protected Pd-core/Ni-shell bimetallic nanoparticles proceeded by a successive alcohol reduction [126]. 

Yang et al. found that Ag-core/Pt-shell nanoparticles with a core/shell could only be formed by the successive reduction method using Ag nanoparticles as the seeds. Results of measurements of UV-Vis, TEM, EDX, and XPS supported the core/shell structure of the bimetallic nanoparticles. The reverse order of preparation using Pt nanoparticles as the seeds did not provide any core/shell nanoparticles while a physical mixture of Ag nanoparticles and the original Pt seeds was obtained [140]. 

In order to realize the precise control of core/shell structures of small bimetallic nanoparticles, some problems have to be overcome. For example, one problem is that the oxidation of the preformed metal core often takes place by the metal ions for making the shell when the metal ions have a high-redox potential, and large islands of shell metal are produced on the preformed metal core. Therefore, we previously developed a so-called hydrogen-sacrificial protective strategy to prepare the bimetallic nanoparticles in the size range 1.5-5.5nm with controllable core/shell structures [132]. The strategy can be extended to other systems of bi- or multimetallic nanoparticles. 

Reduction of two different precious metal ions by refluxing in ethanol/water in the presence of PVP gave a colloidal dispersion of core/shell structured bimetallic nanoparticles. In the case of Pd and Au ions, e.g., the colloidal dispersions of bimetallic nanoparticles with a Au core/Pd shell structure are produced. In contrast, it is difficult to prepare bimetallic nanoparticles with the inverted core/shell (in this case, Pd-core/Au-shell) structure. The sacrificial hydrogen strategy was used to construct the inverted core/shell structure, where the colloidal dispersions of Pd-cores are treated with hydrogen and then the solution of the second element, Au ions, is slowly added to the dispersions. This novel method, developed by us, gave the inverted core/shell structured bimetallic nanoparticles. The Pd-core/Au-shell structure was confirmed by FT-IR spectra of adsorbed CO [144]. 

Lee et al. [145] succeeded in preparation of Co-based bimetallic nanoparticles with core/shell structure via transmetalation reaction (Figure 3). The Co-core/Au-shell nanoparticles, e.g., were confirmed to be almost the same in particle size with the seeded Co nanoparticle, as shown in Figure 4. 

In summary, we concluded that the successive reduction method easily provides the bimetallic nanoparticles with the core/shell structure according to versatile design. For example, different reducing agents may be used for the first reduction and the second one, respectively, depending on the property of the metal. In some cases of two kinds of metals with much different redox potentials, however, inverted core/shell nanoparticles are difficult to form even in the successive reduction. The inverted core/shell structure can be realized by an... 

Figure 5. Plausible formation mechanism of core/shell structured bimetallic nanoparticles by a physical mixture. (Reprinted from Ref [146], 2005, with permission from American Chemical Society.)...

It is noteworthy that the HRTEM cannot distinguish core and shell even by combining X-ray or electron diffraction techniques for some small nanoparticles. If the shell epitaxially grows on the core in the case of two kinds of metals with same crystal type and little difference of lattice constant, the precise structure of the bimetallic nanoparticles cannot be well characterized by the present technique. Hodak et al. [153] investigated Au-core/Ag-shell or Ag-core/Au-shell bimetallic nanoparticles. They confirmed that Au shell forms on Ag core by the epitaxial growth. In the TEM observations, the core/shell structures of Ag/Au nanoparticles are not clear even in the HRTEM images in this case (Figure 7). 

PtRu nanoparticles can be prepared by w/o reverse micro-emulsions of water/Triton X-lOO/propanol-2/cyclo-hexane [105]. The bimetallic nanoparticles were characterized by XPS and other techniques. The XPS analysis revealed the presence of Pt and Ru metal as well as some oxide of ruthenium. Hills et al. [169] studied preparation of Pt/Ru bimetallic nanoparticles via a seeded reductive condensation of one metal precursor onto pre-supported nanoparticles of a second metal. XPS and other analytical data indicated that the preparation method provided fully alloyed bimetallic nanoparticles instead of core/shell structure. AgAu and AuCu bimetallic nanoparticles of various compositions with diameters ca. 3 nm, prepared in chloroform, exhibited characteristic XPS spectra of alloy structures [84]. 

Chen et al. [123] examined the amount-dependent change in morphology for a series of Au/Pt bimetallic nanoparticles. The EXAFS results confirmed the formation of a core/shell structure and inter-diffusion between Au and Pt atoms. The composition of the shell layer was found to be Pt-enriched AuPt alloy. They also characterized bimetallic Ag-core/Au-shell nanoparticles by the EXAFS [124]. 

We performed CO-IR measurement on Pt/Pd bimetallic nanoparticles with core/shell structures and characterized their structures [132]. Figure 12 showed the CO-IR probe spectra of Pd-core/Pt-shell bimetallic nanoparticles with different Pd Pt ratios. 

Recently, however, the development of nanotechnology may provide the changes on the research and development of practical catalysts. As mentioned in the previous section we can now design and synthesize a metal nanoparticle with not only various sizes and shapes, but also with various combinations of elements and their locations. Thus, we can now design the synergetic effect of two elements. In the case of core/shell structured bimetallic nanoparticles, the shell element can provide a catalytic site and the core element can give an electronic effect (a ligand effect) on the shell element. Since only the atoms on the surface can be attached by substrates, the thickness of the shell should be an important factor to control the catalytic performance. 

In 1989, we developed colloidal dispersions of Pt-core/ Pd-shell bimetallic nanoparticles by simultaneous reduction of Pd and Pt ions in the presence of poly(A-vinyl-2-pyrrolidone) (PVP) [15]. These bimetallic nanoparticles display much higher catalytic activity than the corresponding monometallic nanoparticles, especially at particular molecular ratios of both elements. In the series of the Pt/Pd bimetallic nanoparticles, the particle size was almost constant despite composition and all the bimetallic nanoparticles had a core/shell structure. In other words, all the Pd atoms were located on the surface of the nanoparticles. The high catalytic activity is achieved at the position of 80% Pd and 20% Pt. At this position, the Pd/Pt bimetallic nanoparticles have a complete core/shell structure. Thus, one atomic layer of the bimetallic nanoparticles is composed of only Pd atoms and the core is completely composed of Pt atoms. In this particular particle, all Pd atoms, located on the surface, can provide catalytic sites which are directly affected by Pt core in an electronic way. The catalytic activity can be normalized by the amount of substance, i.e., to the amount of metals (Pd + Pt). If it is normalized by the number of surface Pd atoms, then the catalytic activity is constant around 50-90% of Pd, as shown in Figure 13. 

After our success in preparation of the colloidal dispersions of Pt-core/Pd-shell bimetallic nanoparticles by simultaneous reduction of PdCl2 and H2PtCl6 in refluxing ethanol/water in the presence of poly(V-vinyl-2-pyrroli-done) [15,16] several reports have appeared on the formation of the core/shell-structured bimetallic nanoparticles by simultaneous reactions [5,52,68,183]. 

---