Pd-Pt core-shell

Wang H, Xu C, Cheng E, Zhang M, Wang S, Jiang SP (2008) Pd/Pt core-shell nanowire arrays as highly effective electrocatalysts for methanol electrooxidation in direct methanol fuel cells. Electrochem Commun 10(10) 1575-1578... 

Kotmigsmaim C, Santnlli AC, Gmig K, Vukmirovic MB, Zhou W-P, Sutter E, Wong SS, Adzic RR (2011) Enhanced electrocatalytic performance of processed, ultrathin supported Pd-Pt core-shell nanowire catalysts fm the oxygen reduction reactiorr J Am Chem Soc 133 9783—9795... 

Harpeness et al. reported the synthesis of roughly spherical Au-Pd core-shell NCs by the MW-polyol-assisted simultaneous reduction of gold and palladium salts. In this case the largely different Au + or Au+ and PdJ redox potentials firstly ensured gold reduction and the formation of metal seeds which in turn promoted heterogeneous nucleation of Pd [255] (Fig. 10.11a). In a similar fashion Pd-Pt core-shell NCs consisting of cubic Pd NC evenly decorated by Pt pellets was very recently described [256] (Fig. 10.11b). 

A series of PfML/Pd/C core-shell samples with varying nominal Pt shell thickness have also been prepared via a proprietary chemical method and explored using X AS and electrochemical techniques [26]. Analysis of EXAFS at the Pd K and ft L3 edges for catalyst pellet samples revealed the expected increase in ft-ft and decrease in Pd-ft and Pt-Pd neighbors with increasing nominal ft coverage from 0.5 to 2 monolayers of ft (calculated based on catalyst surface area of the Pd/C cores). Further EXAFS measurements under electrochemical control in liquid electrolytes revealed an increase in average Pd-Pd bond distance to 2.780 A at 0.0 V for the 0.5 of... 

Slawinski, G.W. and Zamborini, F.P. (2007) Synthesis and alignment of silver nanorods and nanowires and the formation of Pt, Pd, and core/shell structures by galvanic exchange directly on surfaces. Langmuir, 23,10357. 

Similarly, Pd, Ag, and Pd-Ag nanoclusters on alumina have been prepared by the polyol method [230]. Dend-rimer encapsulated metal nanoclusters can be obtained by the thermal degradation of the organic dendrimers [368]. If salts of different metals are reduced one after the other in the presence of a support, core-shell type metallic particles are produced. In this case the presence of the support is vital for the success of the preparation. For example, the stepwise reduction of Cu and Pt salts in the presence of a conductive carbon support (Vulcan XC 72) generates copper nanoparticles (6-8 nm) that are coated with smaller particles of Pt (1-2 nm). This system has been found to be a powerful electrocatalyst which exhibits improved CO tolerance combined with high electrocatalytic efficiency. For details see Section 3.7 [53,369]. 

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... 

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],... 

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... 

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. 

This means that the improvement of catalytic activity of Pd nanoparticles by involving the Pt core is completely attributed to the electronic effect of the core Pt upon shell Pd. Such clear conclusion can be obtained in this bimetallic system only because the Pt-core/Pd-shell structure can be precisely analyzed by EXAFS and Pd atoms are catalytically active while Pt atoms are inactive. 

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]. 

Recently five monometallic (Au, Pd, Pt, Ru, Rh) nanoparticles were investigated as electron mediators together with four core/shell bimetallic (Au/Pd, Au/Pt, Au/Rh, Pt/ Ru) nanoparticles [53,194-196]. The linear relationship was observed between the electron transfer rate coefficients and the hydrogen generation rate coefficient as shown in Figure 15. 

Another electro-oxidation example catalyzed by bimetallic nanoparticles was reported by D Souza and Sam-path [206]. They prepared Pd-core/Pt-shell bimetallic nanoparticles in a single step in the form of sols, gels, and monoliths, using organically modified silicates, and demonstrated electrocatalysis of ascorbic acid oxidation. Steady-state response of Pd/Pt bimetallic nanoparticles-modified glassy-carbon electrode for ascorbic acid oxidation was rather fast, of the order of a few tens of seconds, and the linearity was observed between the electric current and the concentration of ascorbic acid. 

It has been predicted that a Pd skin on a PdsFe core would sit close to the top of the activity/O binding energy "volcano" curve and thus have significantly higher activity than Pt and Pt/Pd core-shell materials. If these materials could be shown to be stable to long-term PEM conditions, then these could represent viable replacements for Pt. As with other alternative non-Pt catalysts, very few stability studies have been reported. 

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