Oxidation 43 Oxygen reduction

Keywords Hydrogen oxidation, oxygen reduction, nanodispersed diamond, surface, heat-treated treatment, hydrogen electrode, oxygen electrode. 

Kauranen PS, Skou E (1996) Mixed methanol oxidation/oxygen reduction currents on a carbon supported Pt catalyst. J Electroanal Qiem 408 189-198... 

FIGURE 5.33 The three fnel cells in a PEFC with the oxygen in the second half of the anode channel (cf. Figure 5.30). HOR, ORR, and CCR stand for the hydrogen oxidation, oxygen reduction, and carbon corrosion reactions, while the CL abbreviates the catalyst layer. Arrows indicate trajectories of proton (fdled circles) transport. The dashed line is the shape of the membrane phase potential. 

I. Roche, K. Katuri and K. Scott, A microbial fuel cell using manganese oxide oxygen reduction catalysts, J. Appl. Electrochem. 40,2010,13-21. 

Highly protective layers can also fonn in gaseous environments at ambient temperatures by a redox reaction similar to that in an aqueous electrolyte, i.e. by oxygen reduction combined with metal oxidation. The thickness of spontaneously fonned oxide films is typically in the range of 1-3 nm, i.e., of similar thickness to electrochemical passive films. Substantially thicker anodic films can be fonned on so-called valve metals (Ti, Ta, Zr,. ..), which allow the application of anodizing potentials (high electric fields) without dielectric breakdown. 

The y-lactone problem is made easier because the FGs are all based on oxygen. The molecule can therefore be disconnected without FGl except for oxidation or reduction. Let s now look at the synthesis of a molecule with a difficult FG the muscle relaxant baclofen TM 349. What is the difficult FG ... 

Alkaline Fuel Cell. The electrolyte ia the alkaline fuel cell is concentrated (85 wt %) KOH ia fuel cells that operate at high (- 250° C) temperature, or less concentrated (35—50 wt %) KOH for lower (<120° C) temperature operation. The electrolyte is retained ia a matrix of asbestos (qv) or other metal oxide, and a wide range of electrocatalysts can be used, eg, Ni, Ag, metal oxides, spiaels, and noble metals. Oxygen reduction kinetics are more rapid ia alkaline electrolytes than ia acid electrolytes, and the use of non-noble metal electrocatalysts ia AFCs is feasible. However, a significant disadvantage of AFCs is that alkaline electrolytes, ie, NaOH, KOH, do not reject CO2. Consequentiy, as of this writing, AFCs are restricted to specialized apphcations where C02-free H2 and O2 are utilized. 

Several activities, if successful, would strongly boost the prospects for fuel ceU technology. These include the development of (/) an active electrocatalyst for the direct electrochemical oxidation of methanol (2) improved electrocatalysts for oxygen reduction and (2) a more CO-tolerant electrocatalyst for hydrogen. A comprehensive assessment of the research needs for advancing fuel ceU technologies, conducted in the 1980s, is available (22). 

In an oversimplified way, it may be stated that acids of the volcanoes have reacted with the bases of the rocks the compositions of the ocean (which is at the fkst end pokit (pH = 8) of the titration of a strong acid with a carbonate) and the atmosphere (which with its 2 = 10 atm atm is nearly ki equdibrium with the ocean) reflect the proton balance of reaction 1. Oxidation and reduction are accompanied by proton release and proton consumption, respectively. In order to maintain charge balance, the production of electrons, e, must eventually be balanced by the production of. The redox potential of the steady-state system is given by the partial pressure of oxygen (0.2 atm). Furthermore, the dissolution of rocks and the precipitation of minerals are accompanied by consumption and release, respectively. 

The ions, M , formed by this reaction at a rate, may be carried into a bulk solution in contact with the metal, or may form insoluble salts or oxides. In order for this anodic reaction to proceed, a second reaction which uses the electrons produced, ie, a reduction reaction, must take place. This second reaction, the cathodic reaction, occurs at the same rate, ie, = 7, where and are the cathodic and anodic currents, respectively. The cathodic reaction, in most cases, is hydrogen evolution or oxygen reduction. 

If the potential of a metal surface is moved below line a, the hydrogen reaction line, cathodic hydrogen evolution is favored on the surface. Similarly a potential below line b, the oxygen reaction line, favors the cathodic oxygen reduction reaction. A potential above the oxygen reaction line favors oxygen evolution by the anodic oxidation of water. In between these two lines is the region where water is thermodynamically stable. 

Oxidation and reduction reactions can be carried out usiag reformer hydrogen and oxygen from the air. To decide when electroorganic synthesis is likely to be a viable option for a desired product, some opportunity factors are use of cheaper feedstock elimination of process step(s) or a difficult reaction avoidance of waste disposal, toxic materials, and/or abiUty to recycle reagent and abiUty to obtain products from anode and cathode. 

Oxidation and reduction can initiate changes leading to heterocycle-heterocycle conversions. The reaction of tetraphenylfuran with singlet oxygen (Scheme 34) (B-73MI50303) and that of isoxazoles with LAH (Scheme 35) are examples. 

Iron atoms pass into solution in the water as Fe leaving behind two electrons each (the anodic reaction). These are conducted through the metal to a place where the oxygen reduction reaction can take place to consume the electrons (the cathodic reaction). This reaction generates OH ions which then combine with the Fe ions to form a hydrated iron oxide Fe(OH)2 (really FeO, H2O) but instead of forming on the surface where it might give some protection, it often forms as a precipitate in the water itself. The reaction can be summarised by... 

Obviously, it is not very easy to measure voltage variations inside a piece of iron, but we can artificially transport the oxygen-reduction reaction away from the metal by using a piece of metal that does not normally undergo wet oxidation (e.g. platinum) and which serves merely as a cathode for the oxygen-reduction reaction. 

The mechanism of inhibition by the salts of the long chain fatty acids has been examined . It was concluded that, in the case of the lead salts, metallic lead was first deposited at certain points and that at these points oxygen reduction proceeded more easily, consequently the current density was kept sufficiently high to maintain ferric film formation in addition, any hydrogen peroxide present may assist in keeping the iron ions in the oxide film in the ferric condition, consequently the air-formed film is thickened until it becomes impervious to iron ions. The zinc, calcium and sodium salts are not as efficient inhibitors as the lead salts and recent work has indicated that inhibition is due to the formation of ferric azelate, which repairs weak spots in the air-formed film. This conclusion has been confirmed by the use of C labelled azelaic acid, which was found to be distributed over the surface of the mild steel in a very heterogeneous manner. ... 

In acid conditions oxide films are not usually present on the metal surface and the cathodic reaction is primarily that of hydrogen discharge rather than oxygen reduction. Thus, inhibitors are required that will adsorb or bond directly onto the bare metal surfaces and/or raise the overpotential for hydrogen ion discharge. Inhibitors are usually organic compounds... 

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