Monometallic surfaces

The evidence, produced already in the early 1980s, that monometallic surface species like Os " or Rh carbonyl fragments, incapsulated into the surface of silica or alumina, may have the necessary mobility to react with each other, since they return quite easily under a CO atmosphere to the original clusters Os3(CO)i2 and Rh6(CO) respectively [26, 27, 31], was the origin of so-called surface mediated organometallic synthesis. 

The potential dependence of the surface relaxation and the stabihty of the Pd film was probed by XRV measurements [32]. Desorption of Hupd caused a slight Pt-Pd contraction, but the surface became expanded again ( 2.5%) after the adsorption of bisulfate anions. At positive potentials, i.e. in the potential region of OH adsorption, there was a significant (but reversible) change in the Pd structure associated with oxide formation. Importantly, if the Pt(lll) monometallic surface had been cycled up to this potential, then a Pt oxide would be formed that would lead to irreversible roughening (which is the precursor to Pt dissolution) of the surface upon reduction. 

The conclusion may be drawn that the data obtained of comparative studies of olefin polymerization by the one-component catalyst (TiCl2) and two-component systems (TiCl2 + AlEtxCl ) confirm the concept of monometallic active centers on the surface of titanium chlorides developed by Cossee and Arlman (170-173). 

From a general point of view, a monometallic catalyst can be considered as surface metal atoms linked together, forming an ensemble on the surface [160]. 

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. 

Bimetallic nanoparticles (including monometallic ones) have attracted a great interest in scientific research and industrial applications, owing to their unique large sur-face-to-volume ratios and quantum-size effects [1,2,5,182]. Since industrial catalysts usually work on the surface of metals, the metal nanoparticles, which possess much larger surface area per unit volume or weight of metal than the bulk metal, have been considered as promising materials for catalysis. 

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. 

Abstract A convenient method to synthesize metal nanoparticles with unique properties is highly desirable for many applications. The sonochemical reduction of metal ions has been found to be useful for synthesizing nanoparticles of desired size range. In addition, bimetallic alloys or particles with core-shell morphology can also be synthesized depending upon the experimental conditions used during the sonochemical preparation process. The photocatalytic efficiency of semiconductor particles can be improved by simultaneous reduction and loading of metal nanoparticles on the surface of semiconductor particles. The current review focuses on the recent developments in the sonochemical synthesis of monometallic and bimetallic metal nanoparticles and metal-loaded semiconductor nanoparticles. 

Li and Armor reported that Co-exchanged zeolites present a very high catalytic performance for the CH4-SCR, even in oxygen excess conditions [1, 3], Bimetallic Pt-and Pd-Co zeolites have revealed an increase of activity, selectivity towards N2 and stability, when compared with monometallic Co catalysts [4-8] even in the presence of water in the feed. Recent works show that these catalytic improvements are due to the presence of specific metal species as isolated metal ions, clusters and oxides and their location inside the cavities or in the external surface of zeolite crystallites [9, 10],... 

Comparison of the Cu K-edge EXAFS signals for the monometallic Cu/Si02 and the bimetallic Ru-Cu/Si02 catalyst, on the other hand, provides clear evidence for the proximity of ruthenium to copper atoms in the latter. This is seen in the different shape of the measured EXAFS signal and the distorted inverse transform of the first coordination shell. Note that the intensity of the latter is weaker for the bimetallic catalyst, while the region between k=8 and k=15 A-1 has become more important, which points to the presence of a scattering atom heavier than copper in the first coordination shell. The reduced intensity in the Cu Fourier transform of the bimetallic catalyst is indicative of a lower coordination of the copper, which is characteristic of surface atoms. 

Catalysts consisting of more than one component are often superior to monometallic samples. Model studies with potassium on Fe surfaces revealed, for example, the role of the electronic promoter in ammonia synthesis. A particularly remarkable case was recently reported for a surface alloy formed by Au on a Ni(lll) surface where the combination of STM... 

As an aside, we should mention that the same principles apply to the formation of bimetallic clusters on a support. In the case of Pt-Re on AI2O3 it has been shown that hydroxylation of the surface favors the ability of Re ions to migrate toward the Pt nuclei and thus the formation of alloy particles, whereas fixing the Re ions onto a dehydroxylated alumina surface creates mainly separated Re particles. As catalytic activity and selectivity of the bimetallic particles differ vastly from those of a physical mixture of monometallic particles, the catalytic performance of the reduced catalyst depends significantly on the protocol used during its formation. The bimetallic Pt-Re catalysts have been identified by comparison with preparations in which gaseous Re carbonyl was decomposed on conventionally prepared Pt/Al203 catalysts. ... 

The classical preparation methods involve co-impregnation or successive impregnation of metalHc precursors (usually inorganic salts) on soHd supports, the surfaces of which are difficult to characterize. Several compositions coexist in the bimetallic phase, even monometallic particles, and, despite its simplicity, this technique usually fails to control the formation of bimetallic phases and is therefore seldom reproducible. 

From the H/M values for the catalysts NiSn-BM (Sn/Ni = 0.29) and PtSn-BM (Sn/Pt = 0.71), and the H/M values for the corresponding monometallic ones, it can be inferred that Sn blocks about 70% of the originally accessible M atoms. For these systems, based on the dispersion measured for Pt and Ni, the atomic ratios Sn/M correspond to values higher than 1. Notably, even in these cases, an important portion of the metallic surface has sites accessible to hydrogen dissociative adsorption, which is essential for the phase to be active in hydrogenation reactions. 

In CO hydrogenation, the achvity and selechvity to C1-C5 oxygenates over the bimetallic samples are higher than those of the monometallic counterparts [187-190]. Bimetallic catalysts also showed improved activity in the hydroformylation of ethylene compared to either of the monometallic catalysts [191]. The promotion for higher alcohol production is proposed to be associated with the adjacent Ru-Co sites. However, the lack of an exhaustive characterization of catalysts does not allow a clear correlation to be established between the characteristics of the active sites and the catalytic behavior. A formyl species bonded to a Ru-Co bimetallic site has been proposed to be the intermediate in the alcohol synthesis in these systems. A subsequent reaction with an alkyl-surface group would lead to the C2-oxygenate production [187]. 

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