Poisoning species

The vital step in the reaction mechanism appears to be the formation of the intermediate ( CHOf s, which facilitates the overall reaction. The kinetics of its further desorption and/or oxidation into reaction products are the key steps of the mechanism, leading to complete oxidation. An alternative path to the spontaneous formation of the poisoning species, Eq. (21), is its oxidation, with OH species arising from the dissociation of water according to the following reactions ... 

Platinum is the only acceptable electrocatalyst for most of the primary intermediate steps in the electrooxidation of methanol. It allows the dissociation of the methanol molecule hy breaking the C-H bonds during the adsorption steps. However, as seen earlier, this dissociation leads spontaneously to the formation of CO, which is due to its strong adsorption on Pt this species is a catalyst poison for the subsequent steps in the overall reaction of electrooxidation of CHjOH. The adsorption properties of the platinum surface must be modified to improve the kinetics of the overall reaction and hence to remove the poisoning species. Two different consequences can be envisaged from this modification prevention of the formation of the strongly adsorbed species, or increasing the kinetics of its oxidation. Such a modification will have an effect on the kinetics of steps (23) and (24) instead of step (21) in the first case and of step (26) in the second case. 

Another very interesting result obtained from these FURS measurements is the difference between adsorbed CO obtained from dissolved CO and that from the dissociation of adsorbed methanol. The shift in wave number is more important with dissolved CO. These shifts may also be correlated with the superficial composition of the alloys, and it was observed that the optimized composition for the oxidation of CO (about 50 at.% Ru) is different from that for the oxidation of methanol (about 15 at.% Ru). FTIR spectra also revealed that the amount of adsorbed CO formed from methanol dissociation is considerably higher on R than on Pt-Ru. For a Ptog-Ru-o i alloy, the amount of linearly adsorbed CO is very small (Fig. 8), suggesting a low coverage in the poisoning species. Moreover, by observing the potentials at which the COj IR absorption band appears, it is possible to conclude that the oxidation of both (CHO)ads and (CO)acis species occurs at much lower potentials on a R-Ru alloy electrode than on pure Pt. 

A long disputed issue of the nature of strongly bound species in this reaction has been recently revived with the vibrational spectroscopy studies of Bewick et al. (30) using EMIRS technique and of Kunimatsu and Kita (31) using polarization modulation IR-reflection-absorption technique. These data indicated the only CO is a strongly bound intermediate. Heitbaum et al. (32) on the other hand advocate COH, and most recently HCO (33), as the poisoning species on the basis of differential electrochemical mass spectroscopy (DEMS). 

To prevent damage to downstream equipments and poisoning of downstream catalysts, the following contaminants have to been removed from the flue gas particulate (ash, char, and fluid bed material) causing erosion, alkali metals (sodium and potassium compounds) responsible for hot corrosion, tars (high molecular weight hydrocarbons and refractory aromatics), and catalyst poisoning species (H2S, HC1, NH3, and HCN). 

The authors assigned the reaction (Re. 3-3) as the only electrochemical reaction, and the removal of the poisonous species, Pt-COH and Pt-CO, requires the chemical reactions(Re. 3—4, 5 and 6) with Pt-OH, as the oxidizing agent. 

Conventional fuel cell systems provide the designer with greater control over operating conditions as compared to the implantable and ambient-fuel categories. For example, the pH of the system can be adjusted well above or below neutral, and the opportunity exists to eradicate all poison species from the system. As previously mentioned, the realm of... 

For these low-temperature fuel cells, the development of catalytic materials is essential to activate the electrochemical reactions involved. This concerns the electro-oxidation of the fuel (reformate hydrogen containing some traces of CO, which acts as a poisoning species for the anode catalyst methanol and ethanol, which have a relatively low reactivity at low temperatures) and the electroreduction of the oxidant (oxygen), which is still a source of high energy losses (up to 30-40%) due to the low reactivity of oxygen at the best platinum-based electrocatalysts. 

We are currently involved in a three phase developmental program to extend the process to other hydrogen containing streams. The program involves screening candidate streams to identify poisonous species for the metal hydrides, developing poison resistant processes for each stream, and demonstrating the process(es) on a pilot scale to establish process economics. 

Other model reactants are simple organic molecules, for example, formic acid [381, 382]. Pt(lll) exerts lower catalytic influence on HCOOH oxidation than do Pt(lOO) and Pt(llO) faces. However, in the presence of Pb adatoms on Pt(lll) a strong catalytic influence has been observed [383]. The poisonous species production in HCOOH oxidation is then inhibited. Electrochemical reduction of CO2 to glycolate/glyoxylate and oxalic acid has been studied [384]. Other products such as formic acid accompanied by CO and methane have also been detected [385]. In the latter case, the efficiency of the competing process of hydrogen evolution has been suppressed to less than 3.5%. 

Amanita verna, another extremely poisonous species. 

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