Metal deposits, characterization

Recently, it is reported that Xi02 particles with metal deposition on the surface is more active than pure Ti02 for photocatalytic reactions in aqueous solution because the deposited metal provides reduction sites which in turn increase the efficiency of the transport of photogenerated electrons (e ) in the conduction band to the external sjistem, and decrease the recombination with positive hole (h ) in the balance band of Xi02, i.e., less defects acting as the recombination center[l,2,3]. Xhe catalytic converter contains precious metals, mainly platinum less than 1 wt%, partially, Pd, Re, Rh, etc. on cordierite supporter. Xhus, in this study, solutions leached out from wasted catalytic converter of automobile were used for precious metallization source of the catalyst. Xhe XiOa were prepared with two different methods i.e., hydrothermal method and a sol-gel method. Xhe prepared titanium oxide and commercial P-25 catalyst (Deagussa) were metallized with leached solution from wasted catalytic converter or pure H2PtCl6 solution for modification of photocatalysts. Xhey were characterized by UV-DRS, BEX surface area analyzer, and XRD[4]. 

In the following review we will focus on two classes of systems dispersed metal particles on oxide supports as used for a large variety of catalytic reactions and a model Ziegler-Natta catalyst for low pressure olefin polymerization. The discussion of the first system will focus on the characterization of the environment of deposited metal atoms. To this end, we will discuss the prospects of metal carbonyls, which may be formed during the reaction of metal deposits with a CO gas phase, as probes for mapping the environment of deposited metal atoms [15-19]. 

Until quite recently the very initial stages of metal deposition were difficult to characterize in detail by structure- and morphology-sensitive techniques. As a consequence and for practical purposes - multilayers were more useful for applications than monolayers - the main interest was focussed onto thick deposits. Optical and electron microscopy, ellipsometry and specular or diffuse reflectance spectroscopy were the classic tools, by which the emerging shape of the deposit was monitored [4-7],... 

Beside O P D it is well known that metal deposition can also take place at potentials positive of 0. For this reason called underpotential deposition (UPD) it is characterized by formation of just one or two layer(s) of metal. This happens when the free enthalpy of adsorption of a metal on a foreign substrate is larger than on a surface of the same metal [ 186]. This effect has been observed for a number of metals including Cu and Ag deposited on gold ]187]. Maintaining the formalism of the Nernst equation, deposition in the UPD range means an activity of the deposited metal monolayer smaller than one ]183]. 

Those types are characterized by typical grain sizes of 10 to 100 mn. The deposits are relatively hard and brittle, whereas some are rather ductile. Examples are metals deposited under high-current-density conditions containing hydrated oxides as a consequence. 

Preparation and characterization of the metal deposits. Pt deposit was made by impregnation with PtClg and reduction in H2at 753 K. The Pt particle size distribution was determined by transmission electron microscopy (TEM) (8, 9 ) (Figure 3) and H2, O2 chemisorptions and titrations (43). The Pt particle size distribution was narrow with a surface weighted mean diameter of ca. 2 mn, almost independent of the Pt content between 0.5 and 10 wt (9 ), provided the preparation method, which includes a treatment in O2 before the reduction, was thoroughly followed. 

The surface concentration, size distribution and other properties of metal nanoparticles formed in a dark on the surface of the inert wide-band-gap semiconducting oxides under contact, photocatalytic, or photoelectrochemical deposition depend substantially on the concentration, bulk distribution, and energy characteristics of donor defects in the initial semiconductor substrate. As a rule, the necessary condition for the formation of the smallest-sized particles in the highest surface concentration is the maximum shift of the surface potential of semiconducting matrix from its equilibrium value during metal deposition. This is part of the reason for the experimentally observed fact that the particles formed in the condition of photocatalytic deposition are characterized by less average size and cover superior portion of surface than those obtained under cathodic deposition, all other factors being equal. 

A significant number of studies have characterized the physical properties of eutectic-based ionic liquids but these have tended to focus on bulk properties such as viscosity, conductivity, density and phase behavior. These are all covered in Chapter 2.3. Some data are now emerging on speciation but little information is available on local properties such as double layer structure or adsorption. Deposition mechanisms are also relatively rare as are studies on diffusion. Hence the differences between metal deposition in aqueous and ionic liquids are difficult to analyse because of our lack of understanding about processes occurring close to the electrode/liquid interface. 

This section deals only with solvents whose reduction products are insoluble in the presence of lithium ions. The list includes open chain ethers such as diethyl ether, dimethoxy ethane, and other polyethers of the glyme family cyclic ethers such as THF, 2Me-THF, and 1,4-dioxane cyclic ketals such as 1,3-dioxolane and 1,3-dioxane, esters such as y-butyrolactone and methyl formate and alkyl carbonates such as PC, EC, DMC, and ethylmethyl carbonate. This list excludes the esters, ethyl and methyl acetates, and diethyl carbonate, whose reduction products are soluble in them (in spite of the presence of Li ions). Solutions of solvents such as acetonitrile and dimethyl formamide are also not included in this section for the same reasons. Figure 6 presents typical steady state voltammo-grams obtained with gold, platinum, and silver electrodes in Li salt solutions in which solvent reduction products are formed and precipitate at potentials above that of lithium metal deposition. These voltammograms are typical of the above-mentioned solvent groups and are characterized by the following features ... 

According to the standard electrochemical potentials (Table 1), with Cu/Cu2+ and Ru/Ru3+ couples, the amount of ruthenium deposited on metallic copper will be small, whereas the redox reaction carried out in presence of platinum or gold salts will occur to a large extent. On the other hand, for electrodes of first type (metal immersed in a solution of a salt of that metal), the standard electrochemical potentials as defined by thermodynamics are calculated with regard to a poly-crystalline metallic phase of infinite size. However, in the case of small metallic particles, characterized by metallic atoms of different coordination numbers, the notion of a local potential can be introduced. That no-... 

The correlation of spectroscopic data between model and real catalysts has always been a concern in catalyst characterization. Weiher et al. (2005) tried to address this issue with a cell design that was compatible with both model catalysts (e.g., submonolayer amounts of metals deposited on a silicon wafer) and real catalysts such as high-surface-area supported metals. Moreover, they also wished to have a design in which plug-flow conditions existed for the powder catalyst experiments. 

Nucleation and growth kinetics — Nucleation-and-growth is the principal mechanism of phase transformation in electrochemical systems, widely seen in gas evolution, metal deposition, anodic film formation reactions, and polymer film deposition, etc. It is also seen in solid-state phase transformations (e.g., battery materials). It is characterized by the complex coupling of two processes (nucleation and phase growth of the new phase, typically a crystal), and may also involve a third process (diffusion) at high rates of reaction. In the absence of diffusion, the observed electric current due to the nucleation and growth of a large number of independent crystals is [i]... 

The results presented here demonstrate that static SIMS has unique capabilities for the characterization of the surfaces of polymers that have been modified by metal deposition or by plasma or corona techniques. Especially, the introduction of unsaturation and crosslinking are aspects that in some polymers can be observed directly. The formation of low-molecular oxidized material that can be inferred from XPS studies, can also be observed directly. A limitation of the quadrupole-type instrument, which is still the most widely used, is its limited mass range and mass resolution. It can be expected that a considerably more detailed description of modified polymer surfaces can be obtained by application of the more powerful reflectron-type Time-of-Flight SIMS spectrometers, but such studies have, to date, not yet been published. 

---