Platinum surfaces reduction

The additivity principle was well obeyed on adding the voltammograms of the two redox couples involved even though the initially reduced platinum surface had become covered by a small number of underpotential-deposited mercury monolayers. With an initially anodized platinum disk the catalytic rates were much smaller, although the decrease was less if the Hg(I) solution had been added to the reaction vessel before the Ce(lV) solution. The reason was partial reduction by Hg(l) of the ox-ide/hydroxide layer, so partly converting the surface to the reduced state on which catalysis was greater. 

The molecular modelling approach, taking into account the pyruvate—cinchona alkaloid interaction and the steric constraints imposed by the adsorption on the platinum surface, leads to a reasonable explanation for the enantio-differentiation of this system. Although the prediction of the complex formed between the methyl pyruvate and the cinchona modifiers have been made for an ideal case (solvent effects and a quantum description of the interaction with the platinum surface atoms were not considered), this approach proved to be very helpful in the search of new modifiers. The search strategy, which included a systematic reduction of the cinchona alkaloid structure to the essential functional parts and validation of the steric constraints imposed to the interaction complex between modifier and methyl pyruvate by means of molecular modelling, indicated that simple chiral aminoalcohols should be promising substitutes for cinchona alkaloid modifiers. Using the Sharpless symmetric dihydroxylation as a key step, a series of enantiomerically pure 2-hydroxy-2-aryl-ethylamines... 

Panchenko A, Koper MTM, et al. 2004. Ab initio calculations of intermediates of oxygen reduction on low-index platinum surfaces. J Electrochem Soc 151 A2016-A2027. 

Kuzume A, Herrero E, Feliu JM. 2007. Oxygen reduction on stepped platinum surfaces in acidic media. J Electroanal Chem 599 333-343. 

Komanicky V, Menzel A, You H. 2005. Investigation of oxygen reduction kinetics at (111)-(100) nanofaceted platinum surfaces in acidic media. J Phys Chem B 109 23550-23557. 

For forced-convection studies, the cathodic reaction of copper deposition has been largely supplanted by the cathodic reduction of ferricyanide at a nickel or platinum surface. An alkaline-supported equimolar mixture of ferri- and ferrocyanide is normally used. If the anolyte and the catholyte in the electrochemical cell are not separated by a diaphragm, oxidation of ferrocyanide at the anode compensates for cathodic depletion of ferricyanide.3... 

Carbon-supported platinum (Pt) and platinum-rathenium (Pt-Ru) alloy are one of the most popular electrocatalysts in polymer electrolyte fuel cells (PEFC). Pt supported on electrically conducting carbons, preferably carbon black, is being increasingly used as an electrocatalyst in fuel cell applications (Parker et al., 2004). Carbon-supported Pt could be prepared at loadings as high as 70 wt.% without a noticeable increase of particle size. Unsupported and carbon-supported nanoparticle Pt-Ru, ,t m catalysts prepared using the surface reductive deposition... 

Figure 13. Schematic representation of the setup used for the infrared characterization of liquid-solid interfaces [63], The main cell consists of a platinum disk used for adsorption and reaction, a Cap2 prism for guidance of the infrared beam, and a liquid solution trapped between those two elements. The overall arrangement includes gas and liquid sample introduction stages as well as the electronics used for the electrochemical oxidation-reduction cycles needed to preclean the platinum surface.

Promotion and deactivation of unsupported and alumina-supported platinum catalysts were studied in the selective oxidation of 1-phenyl-ethanol to acetophenone, as a model reaction. The oxidation was performed with atmospheric air in an aqueous alkaline solution. The oxidation state of the catalyst was followed by measuring the open circuit potential of the slurry during reaction. It is proposed that the primary reason for deactivation is the destructive adsorption of alcohol substrate on the platinum surface at the very beginning of the reaction, leading to irreversibly adsorbed species. Over-oxidation of Pt active sites occurs after a substantial reduction in the number of free sites. Deactivation could be efficiently suppressed by partial blocking of surface platinum atoms with a submonolayer of bismuth promoter. At optimum Bi/Ptj ratio the yield increased from 18 to 99 %. 

Fourth, the PtC species is further chlorinated to form Pt4 + species which are strongly bound to the surface. This process leads to a completely new spatial distribution of platinum. After reduction there is an entirely new distribution of platinum particle sizes. One caveat is that metal is lost as volatile species and removed from the reactor. Operating conditions must be selected with care. 

Hydrogen gas is bubbled over a platinum surface that is coated with platinum black, an electrolytically deposited coating of colloidal platinum, which is an excellent catalyst for the above equilibrium. The hydrogen electrode has been selected as the standard against which the potentials of other electrodes are measured. Equations of the type of reaction (I) are called half-cell reactions, because they include electrons. Reaction I is a reduction half-cell reaction. 

Nitrous Oxide (N20). In contrast to nitric oxide, N20 is not readily reduced by hydrogen atoms. However, it is a good O-atom transfer reagent and spontaneously reacts with metal surfaces at elevated temperatures. Under alkaline conditions with a freshly formed platinum surface (Pt ), N20 induces a vol-tammetric reduction peak (Figure 11.8) 10... 

Figure 4.12 Current-potential curve for platinum surface oxide formation and reduction in 0.5 M H2S04. (Reproduced with permission from Ref. 38.)...

From these observations it can be concluded that the changes in catalyst properties in water under reductive circumstances especially at high pH are the result of two phenomena 1) Growth of the platinum particles by a process in which the crystallites become mobile 2) Coverage of the platinum surface. The latter can be caused either by coverage with carbonaceous products originating from the support or by disappearance of the mobile platinum particles in between the graphite layers. 

For fuel-cell technology development, it has been important to understand the characteristics and operation of highly dispersed platinum and platinum alloy electrocatalysts. A series of papers on platinum crystallite size determinations in acid environments for oxygen reduction and hydrogen oxidation was published together by Bert, Stonehart, Kinoshita and co-workers.5 The conclusion from these studies was that the specific activity for oxygen reduction on the platinum surface was independent of the size of the platinum crystallite and that there were no crystallite size effects. 

---