On platinum

Tully J C 1980 Dynamics of gas-surface interactions reactions of atomic oxygen with adsorbed carbon on platinum J. Chem. Phys. 73 6333... 

Ultraviolet photoelectron spectroscopy (UPS) results have provided detailed infomiation about CO adsorption on many surfaces. Figure A3.10.24 shows UPS results for CO adsorption on Pd(l 10) [58] that are representative of molecular CO adsorption on platinum surfaces. The difference result in (c) between the clean surface and the CO-covered surface shows a strong negative feature just below the Femii level ( p), and two positive features at 8 and 11 eV below E. The negative feature is due to suppression of emission from the metal d states as a result of an anti-resonance phenomenon. The positive features can be attributed to the 4a molecular orbital of CO and the overlap of tire 5a and 1 k molecular orbitals. The observation of features due to CO molecular orbitals clearly indicates that CO molecularly adsorbs. The overlap of the 5a and 1 ti levels is caused by a stabilization of the 5 a molecular orbital as a consequence of fomiing the surface-CO chemisorption bond. 

Figure A3.10.24 UPS data for CO adsorption on Pd(l 10). (a) Clean surface, (b) CO-dosed surface, (c) Difference spectrum (b-a). This spectrum is representative of molecular CO adsorption on platinum metals [M].

Freunscht P, Van Duyne R P and Schneider S 1997 Surface-enhanced Raman spectroscopy of trans-stilbene adsorbed on platinum- or self-assembled monolayer-modified silver film over nanosphere surfaces Chem. Phys. Lett. 281 372-8... 

A pletliora of different SA systems have been reported in tire literature. Examples include organosilanes on hydroxylated surfaces, alkanetliiols on gold, silver, copper and platinum, dialkyl disulphides on gold, alcohols and amines on platinum and carboxyl acids on aluminium oxide and silver. Some examples and references can be found in [123]. More recently also phosphonic and phosphoric esters on aluminium oxides have been reported [124, 125]. Only a small selection out of tliis number of SA systems can be presented here and properties such as kinetics, tliennal, chemical and mechanical stability are briefly presented for alkanetliiols on gold as an example. 

Kolb D M, Kdtz R and Yamamoto K 1979 Copper monolayer formation on platinum single crystal surfaces Optical and... 

If an appreciable amount of residue remains, note its colour. Add a few drops of water and test the solution (or suspension) with htmus or with Universal indicator paper. Then add a httle dilute hydrochloric acid and observe whether efiervesceiice occurs and the residue dissolves. Apply a flame test with a platinum wire on the hydrochloric acid solution to determine the metal present. (In rare cases, it may be necessary to subject a solution of the residue to the methods of qualitative inorganic analysis to identify the metal or metals present.) If the flame test indicates sodium, repeat the ignition of the substance on platinum foil. 

Cyclopropane rings are opened hydrogenolytically, e.g., over platinum on platinum dioxide (Adam s catalyst) in acetic acid at 2 - 4 bars hydrogen pressure. The bond, which is best accessible to the catalyst and most activated by conjugated substituents, is cleaved selectively (W.J. Irwin, 1968 R.L. Augustine, 1976). Synthetically this reaction is useful as a means to hydromethylate C—C double bonds via carbenoid addition (see p. 74f. Z. Majerski, 1968 C.W. Woodworth, 1968). 

PGM catalyst technology can also be appHed to the control of emissions from stationary internal combustion engines and gas turbines. Catalysts have been designed to treat carbon monoxide, unbumed hydrocarbons, and nitrogen oxides in the exhaust, which arise as a result of incomplete combustion. To reduce or prevent the formation of NO in the first place, catalytic combustion technology based on platinum or palladium has been developed, which is particularly suitable for appHcation in gas turbines. Environmental legislation enacted in many parts of the world has promoted, and is expected to continue to promote, the use of PGMs in these appHcations. 

Pla.tinum, Platinum plating has found appHcation in the production of platinised titanium, niobium, or tantalum anodes which are used as insoluble anodes in many other plating solutions (see Metalanodes). Plating solutions were often based on platinum "P" salt, which is diamminedinitroplatiniim (IT). A dinitroplatinite sulfate—sulfuric acid bath has been used to plate direcdy onto titanium (129). This bath contains 5 g/L of the platinum salt, pH adjusted to 2.0 with sulfuric acid. The bath is operated at 40°C at 10—100 A/m. Other baths based on chloroplatinic acid have been used in both acid and alkaline formulations the acid bath uses 20 g/L of the platinum salt and 300 g/L hydrochloric acid at 65° C and 10—200 A/m. The alkaline bath uses 10 g/L of the platinum salt, 60 g/L of ammonium phosphate and ammonium hydroxide to give a pH of 2.5—9.0. The alkaline bath can be plated directly onto nickel-base alloys acid baths require a gold strike on most metals. 

Nickel on nickel Gold on gold Platinum on platinum Copper on copper Indium on indium Lead on lead Aluminium on aluminium Silver on silver Iron on iron Tin on tin Steel on tin alloy Steel on steel Steel on Pb alloy Steel on Al. bronze Steel on cast iron Steel on brass Steel on bronze Steel on Pb. brass... 

Although considerable study has been devoted to oxygen chemisorption (mainly on platinum) there is considerable ambiguity in the surface stoichiometry of the reaction. In some cases Pt20 is formed, in others PtO, the particular compound... 

M. Ehsasi et al. Steady and nonsteady rates of reaction in a heterogeneously catalyzed reaction Oxidation of CO on platinum, experiments and simulations. J Chem Phys 97 4949-4956, 1989. 

H. P. Kaukonen, R. M. Nieminen. Computer simulations studies of the catalytic oxidation of carbon monoxide on platinum metals. J Chem Phys 97 4380- 386, 1989. 

The lowest wettable surface known = 6 dyne/cm) is a monolayer of perfluoro-launc acid on platinum, whose surface is made up of closely packed CF3 groups [20] Fluonnated graphite, (C2FJ and (CF) , also have surface tensions approachmg 6 dyne/cm [21] Perfluorinated materials, however, are not required tor low surface energies only the outermost surface groups must be perfluorinated [20, 22]... 

Carbon and Hydrogen.—Carbon compounds are frequently inflammable, and when heated on platinum foil take fipe or char and burn away. A safer test is to heat the substance with some easily reducible metallic oxide, the oxygen of which forms carbon diovide with the carbon present. Take a piece of soft glass tube about 13 cm. (5 in.) long, and fuse it together at one end. Heat a gram or two of fine copper oxide in a porcelain crucible for a few minutes to drive off the moisture, and let it cool in a desiccator. Mix it with about one-tenth of its bulk of powdered sugar in a mortar. Pour the mixture into the tube, the open end of which is now drawn out into a wide capillary and oeni. at the same time into the form Fig. i. 

The Action of Heat.—We will assume in the first 1 ic,. S7. plate that the substance is homogeneous and consists of a single individual. Heat a portion on platinum foil and notice if it volatilises, chars, or burns with a clear, luminous, non-Iuminous (aliphatic), or smoky (aromatic) flame. Determine the nature of the residue, if any, when the carbon has burnt away. 

We clearly demonstrated that, in going from a bulk CusPt to an overlayer on platinum, the influence of the substrate reflects in the photoemission spectra and that its consideration improves the agreement with the experimental data. 

Until about 40 years ago, these elements were referred to as "inert gases" they were believed to be entirely unreactive toward other substances. In 1962 Neil Bartlett, a 29-year-old chemist at the University of British Columbia, shook up the world of chemistry by preparing the first noble-gas compound. In the course of his research on platinum-fluorine compounds, he isolated a reddish solid that he showed to be 02+(PtFB-). Bartlett realized that the ionization energy of Xe (1170 kJ/mol) is virtually identical to that of the 02 molecule (1165 kJ/mol). This encouraged him to attempt to make the analogous compound XePtF6. His success opened up a new era in noble-gas chemistry. 

It has a chain structure, with one unpaired electron per tetramer unit ( eff = 1.81 B) and can be regarded as a Pt Pt111 compound. ESR data suggest that the unpaired electron resides in a MO based on platinum 5dz2 orbitals directed along the tetramer chain. 

Purely parallel reactions are e.g. competitive reactions which are frequently carried out purposefully, with the aim of estimating relative reactivities of reactants these will be discussed elsewhere (Section IV.E). Several kinetic studies have been made of noncompetitive parallel reactions. The examples may be parallel formation of benzene and methylcyclo-pentane by simultaneous dehydrogenation and isomerization of cyclohexane on rhenium-paladium or on platinum catalysts on suitable supports (88, 89), parallel formation of mesityl oxide, acetone, and phorone from diacetone alcohol on an acidic ion exchanger (41), disproportionation of amines on alumina, accompanied by olefin-forming elimination (20), dehydrogenation of butane coupled with hydrogenation of ethylene or propylene on a chromia-alumina catalyst (24), or parallel formation of ethyl-, methylethyl-, and vinylethylbenzene from diethylbenzene on faujasite (89a). 

Infrared absorption studies of CO on platinum shows two bands near... 

Breiter, M. W. Adsorption of Organic Species on Platinum Metal Electrodes 10... 

E. Lamy-Pitara, S.E. Mouahid, and J. Barbier, Effect of anions on catalytic and electrocatalytic hydrogenations and on the electrocatalytic oxidation and evolution of hydrogen on platinum, Electrochim. Acta 45, 4299-4308 (2000). 

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