Bimetallic characterizing

Returning briefly to CO2 as a ligand in addition to the various mono-C02 complexes referred to above, several bis(rj -CO2) transition-metal adducts are known, e.g. /ran -[Mo( ) -C02)2(PMe3)4] (5) and trans.mer-[Mo( 2-C02)2(PMc3)3(CNPr )].< 22 The first homo-bimetallic bridging-C02 complex has also been structurally characterized by X-ray analysis, viz. [(dppp)(CO)2Re(/x, j 0,0 j C)Re(CO)3(dppp)] (6) [dppp = l,3-bis(diphenyl-phosphino)propanc]. 0 3)... 

Bimetallic silylene-bridged complexes have been known for a long time and numerous articles related to this subject have appeared. Several compounds have been characterized, some of them also by x-ray structure analysis [165-171], For instance, the complex Mn2(CO)8(Si(C6H5)2)2 shows a distorted (MnSi)2 four-membered ring with a Mn-Mn bond [169], In the following section selected examples which have been described recently or are of particular interest in the present context will be discussed. 

Cyclodiphosphazanes(III) 27 shown in Scheme 16 undergo oxidation reactions to give the cyclodiphosphazanes(V) of type 28. These are prospective ligands in catalysis since these ligands due to lack of phosphorus lone-pairs are less susceptible to the destructive cycloreversion of the ligands. Hence they could prevent catalyst deactivation in the process. When treated with trimethyl aluminum the cyclodiphosphazanes form symmetrically substituted bimetallic species of type 29 [90]. Characterization by single-crystal X-ray studies show... 

A MgO-supported W—Pt catalyst has been prepared from IWsPttCOIotNCPh) (i -C5H5)2l (Fig. 70), reduced under a Hs stream at 400 C, and characterized by IR, EXAFS, TEM and chemisorption of Hs, CO, and O2. Activity in toluene hydrogenation at 1 atm and 60 C was more than an order of magnitude less for the bimetallic cluster-derived catalyst, than for a catalyst prepared from the two monometallic precursors. 

MgO-supported model Mo—Pd catalysts have been prepared from the bimetallic cluster [Mo2Pd2 /z3-CO)2(/r-CO)4(PPh3)2() -C2H )2 (Fig. 70) and monometallic precursors. Each supported sample was treated in H2 at various temperatures to form metallic palladium, and characterized by chemisorption of H2, CO, and O2, transmission electron microscopy, TPD of adsorbed CO, and EXAFS. The data showed that the presence of molybdenum in the bimetallic precursor helped to maintain the palladium in a highly dispersed form. In contrast, the sample prepared from the monometallie precursors was characterized by larger palladium particles and by weaker Mo—Pd interactions. ... 

Herein we briefly mention historical aspects on preparation of monometallic or bimetallic nanoparticles as science. In 1857, Faraday prepared dispersion solution of Au colloids by chemical reduction of aqueous solution of Au(III) ions with phosphorous [6]. One hundred and thirty-one years later, in 1988, Thomas confirmed that the colloids were composed of Au nanoparticles with 3-30 nm in particle size by means of electron microscope [7]. In 1941, Rampino and Nord prepared colloidal dispersion of Pd by reduction with hydrogen, protected the colloids by addition of synthetic pol5mer like polyvinylalcohol, applied to the catalysts for the first time [8-10]. In 1951, Turkevich et al. [11] reported an important paper on preparation method of Au nanoparticles. They prepared aqueous dispersions of Au nanoparticles by reducing Au(III) with phosphorous or carbon monoxide (CO), and characterized the nanoparticles by electron microscopy. They also prepared Au nanoparticles with quite narrow... 

Usually bimetallic nanoparticles as well as monometallic ones are characterized by many probing tools such as UV-visible (UV-Vis) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), EXAFS, infrared spectroscopy of adsorbed CO (CO-IR), and so on [1,2]. 

Table 1. Typical preparations and characterizations of bimetallic nanoparticles reported in literatures. 

Principally purification and characterization methods of monometallic nanoparticles are directly applied to those of bimetallic nanoparticles. Purification of metal nanoparticles dispersed in solution is not so easy. So, in classical colloid chemistry, contamination is carefully avoided. For example, people used pure water, distilled three times, and glass vessels, cleaned by steam, for preparation of colloidal dispersions. In addition, the reagents which could not byproduce contaminates were used for the preparation. Recently, however, various kinds of reagents were used for the reaction and protection. Thus, the special purification is often required especially when the nanoparticles are prepared by chemical methods. 

After purification, the bimetallic nanoparticles are offered to characterization. The characterization techniques were well reviewed previously in literatures [1,2]. In this section, we highlight recent reports on the characterization methods of bimetallic nanoparticles after presenting some previous researches again. 

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). 

Endo et al. [96] prepared AuPt, AuPd, and PtPd bimetallic nanoparticles with 2 nm in particle size in order to investigate catalytic activity for reduction of p-nitrophenol in water. The binary features of the nanoparticles were characterized by UV-Vis spectroscopic measurements. 

We investigated on structure of CuPd (2 1) bimetallic nanoparticles by XRD [71]. Since the XRD peaks of the PVP-protected CuPd nanoparticles appeared between the corresponding diffraction lines of Cu and Pd nanoparticles, as shown in Figru e 11, the bimetallic alloy phase was clearly formd to be formed in CuPd (2 1) bimetallic nanoparticles. We also characterized Ag-core/Rh-shell bimetallic nanoparticles, which formed during simple physical mixing of the corresponding monometallic ones, by XRD coupled with TEM [148]. 

The XRD and TEM showed that the bimetallic nanoparticles with Ag-core/Rh-shell structure spontaneously form by the physical mixture of Ag and Rh nanoparticles. Luo et al. [168] carried out structure characterization of carbon-supported Au/Pt catalysts with different bimetallic compositions by XRD and direct current plasma-atomic emission spectroscopy. The bimetallic nanoparticles were alloy. Au-core/Pd-shell structure of bimetallic nanoparticles, prepared by co-reduction of Au(III) and Pd(II) precursors in toluene, were well supported by XRD data [119]. Pt/Cu bimetallic nanoparticles can be prepared by the co-reduction of H2PtClg and CuCl2 with hydrazine in w/o microemulsions of water/CTAB/ isooctane/n-butanol [112]. XRD results showed that there is only one peak in the pattern of bimetallic nanoparticles, corresponding to the (111) plane of the PtCu3 bulk alloy. 

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]. 

By XPS spectra, Endo et al. [96] confirmed that formation of binary structure prevented Pd atoms from oxidation in the AuPd and PtPd bimetallic nanoparticles which exhibited higher catal5hic activity than monometallic ones. Wang et al. [112]. characterized PtCu bimetallic alloy nanoparticles Ijy XPS. XPS revealed that both elements in the nanoparticles are in zero-valence and possess the characteristic metallic binding energy. 

Recently characterization of bimetallic nanoparticles by EXAFS were extensively reported [122-124,176], Structural transformation of bimetallic Pd/Pt nanoparticles, which were prepared by a sequential loading of H2PtClg onto the Pd loaded catalyst, was investigated with EXAFS at high temperatures [176], The results of EXAFS at Pd K and Pt L-III edges showed that Pt was surface-enriched or anchored on the Pd metal core with an increase of the Pt content. The structure of the obtained bimetallic Pd/Pt nanoparticles seemed to be retained upon heating up to 1273 K under ambient condition [176], Pt/ Au bimetallic nanoparticles can be prepared by polyol method and stabilized by PVP [122], XANES and EXAFS studies were also performed on the samples and their results supported the idea of a Pt-core/Au-shell structure with the elements segregated from each other [122],... 

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. 

In Figure 12a (Pd Pt = 1 2) and 12b (Pd Pt = 1 1), only the spectral feature of CO adsorbed on the Pt atoms, i.e., a strong band at 2068 cm and a very weak broad band at around 1880 cm was observed, while that derived from CO adsorbed on Pd atoms at 1941 cm is completely absent, which proved that the Pd-core has been completely covered by a Pt-shell. Recently we also characterized Au-core/Pd-shell bimetallic nanoparticles by the CO-IR [144]. Reduction of two different precious metal ions by refluxing in ethanol/ water in the presence of poly(A-vinyl-2-pyrrolidone) (PVP) gave a colloidal dispersion of core/shell structured bimetallic nanoparticles. In the case of Pd and Au ions, the bimetallic nanoparticles with a Au-core/Pd-shell structure are usually produced. In contrast, it is difficult to prepare bimetallic nanoparticles with the inverted core/shell, i.e., Pd-core/Au-shell structure. A sacrificial hydrogen strategy is useful 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... 

Recently we investigated ferromagnetic properties of CoPt bimetallic nanoparticles [232,233]. CoPt3 nanoparticles can be prepared by a two-step reduction using NaBH4 as a reductant. The bimetallic nanoparticles were characterized by thermogravimetry (TG) and differential thermal analysis (DTA), FT-IR, TEM) and XRD. Structural and spectroscopic studies showed that the bimetallic nanoparticles adopt an fee crystalline structure with an average particle size of 2.6 nm. SQUID studies revealed... 

The latter report demonstrated the unique ability of this technique to resolve surface structure as well as surface composition at the electrified solid-liquid interfaces. In particular, STM has become an important tool for ex situ and in situ characterization of surfaces at the atomic level, in spite its significant limitations regarding surface composition characterization for bimetallic systems, such as the lack of contrast for different elements and the scanned surface area being too small to be representative for the entire surface. To avoid these limitations, STM has been mostly used as a complementary tool in surface characterization. 

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