Methanol electrocatalytic activity

A third way to increase both the active surface area and the number of oxygenated species at the electrode surface is to prepare alloy particles or deposits and then to dissolve the non-noble metal component. This technique, which is similar to that used to prepare Raney-type catalysts, yields very high surface area electrodes and hence some improvements in the electrocatalytic activities compared with those of pure platinum. However, it is always difficult to be sure whether the mechanism of enhancment of the activities is due to this effect or the possible presence of remaining traces of the dissolved metal. Results with PtyCr and PtSFe were encouraging, although the effect of iron is still under discussion. From studies in a recent work on the behavior of R-Fe particles for methanol electrooxidation, it was concluded that the electrocatalytic effect is due to the Fe alloyed to platinum. ... 

In addition to these different types of alloys, some studies were also devoted to alternatives to platinum as electrocatalysts. Unfortunately, it is clear that even if some catalytic activities were observed, they are far from those obtained with platinum. Nickel tungsten carbides were investigated, but the electrocatalytic activity recorded for methanol oxidation was very low. Tungsten carbide was also considered as a possible alternative owing to its ability to catalyze the electrooxidation of hydrogen. However, it had no activity for the oxidation of methanol and recently some groups showed that a codeposit of Pt and WO3 led to an enhancement of the activity of platinum. ... 

Apart from the problems of low electrocatalytic activity of the methanol electrode and poisoning of the electrocatalyst by adsorbed intermediates, an overwhelming problem is the migration of the methanol from the anode to the cathode via the proton-conducting membrane. The perfluoro-sulfonic acid membrane contains about 30% of water by weight, which is essential for achieving the desired conductivity. The proton conduction occurs by a mechanism (proton hopping process) similar to what occurs... 

Hernandez J, Solla-Gullon J, Heirero E, Aldaz A, Feliu JM. 2006. Methanol oxidation on gold nanoparticles in alkaline media Unusual electrocatalytic activity. Electrochim Acta 52 1662-1669. 

Gavrilov AN, Savinova ER, Simonov PA, Zaikovskii VI, Cherepanova SV, Tsirlina GA, Parmon VN. 2007. On the influence of the metal loading on the stmcture of carbon-sup-ported PtRu catalysts and their electrocatalytic activities in CO and methanol electrooxidation. Phys Chem Chem Phys 40 5476-5489. 

Lee, S-A. et al., Nanoparticle synthesis and electrocatalytic activity of Pt alloys for direct methanol fuel cells, J. Elect. Chem. Soc., 149, A1299, 2002. 

Fuel cells o fer important advantages as a power source, such as the potential for high efficiency, clean exhaust gases and quiet operation. In addition, the direct methanol fuel cell offers special benefits as a power source for transportation, such as potential high energy density, no need for a fuel reformer and a quick response. These advantages, however, have not been fully realized yet. One of the problems is the poor performance of the fiiel electrode. Even platimun, which seems the most active single element for methanol oxidation in add media, loses its electrocatalytic activity rapidly by the accumulation of adsorbed partially oxidized products. 

In Chapter 2, the electrochemical oxidation of carbon monoxide, which is considered as the key intermediate for methanol oxidation, is investigated using electrochemical and spectroscopic methods for polycrystalline and single crystal platiniim electrodes. In Chapter 3, the electrochemical oxidation of methanol on the same electrodes was treated. In Chapter 4, electrocatalytic activities of platinum modified by adding secondary elements will be disciissed. 

Probably, the little ciurent in the first few cycles is due to the lack of electrocatalytic activity for the oxidation of methanol to COad on the tin-rich surface, although the svuface has the oxidation capability for COad ot lower potentials as shown in the previous section. As more platinum became exposed, the more COad is likely to form, followed by the early oxidation of COad on Pt-Sn surface. Further removal of tin, however,... 

These results confirmed the enhancement effect of tin on the electrocatalytic activities for the methanol oxidation. As stated before, tin has the main effect on the oxidation of eoCOad (Easily Oxidized COad) using water as the oxygen source while it has little effect on the oxidation of AoCOad (hard to-oxidize COad). which requires Ptr-OH as the oxygen source. This methanol oxidation enhancement effect is. therefore, also likely because of the enhancement of the utilization of water. Although it is not known whether this water utilization is through a path that has eoCOad as an intermediate or another path that has other active intermediates, there is no practical difference between the two because both paths proceed at more cathodic potentials than a path that has hoCOad as an intermediate. 

For the study of the electrocatalytic reduction of oxygen and oxidation of methanol, our approach to the preparation of catalysts by two-phase protocol " provides a better controllability over size, composition or surface properties in comparison with traditional approaches such as coprecipitation, deposition-precipitation, and impregnation. " The electrocatalytic activities were studied in both acidic and alkaline electrolytes. This chapter summarizes some of these recent results, which have provided us with further information for assessing gold-based alloy catalysts for fuel cell reactions. 

The electrocatalytic activity of the nanostructured catalysts was investigated for electrocatalytic reduction of oxygen and oxidation of methanol. Several selected examples are discussed in this section. The results from electrochemical characterization of the oxygen reduction reaction (ORR) are first described. This description is followed by discussion of the results from electrochemical characterization of the methanol oxidation reaction (MOR). 

The electrocatalytic activity of the nanostructured Au and AuPt catalysts for MOR reaction is also investigated. The CV curve of Au/C catalysts for methanol oxidation (0.5 M) in alkaline electrolyte (0.5 M KOH) showed an increase in the anodic current at 0.30 V which indicating the oxidation of methanol by the Au catalyst. In terms of peak potentials, the catalytic activity is comparable with those observed for Au nanoparticles directly assembled on GC electrode after electrochemical activation.We note however that measurement of the carbon-supported gold nanoparticle catalyst did not reveal any significant electrocatalytic activity for MOR in acidic electrolyte. The... 

Figure 14.8 shows a typical set of CV curves obtained for methanol oxidation at AusiPtig/C catalysts in alkaline electrolyte. Electrocatalytic activity of Aug8Pt32/C catalyst was also characterized and is shown in Table 14.2. 

PtMo alloys are not as effective as PtRu for methanol, or ethanol, oxidation. As shown in Figure 29, the d band vacancy per Pt atom for the PtMo/C catalyst continues to increase until 0.6 V vs RHE, in contrast to the behavior of PtRu/C. ° The authors attribute this difference to the lack of removal of the Cl fragments from the particle surface by the oxy-hydroxides of Mo. However, the difference in the electrocatalytic activity of PtRu and PtMo catalysts may be attributed to ensemble effects as well as electronic effects. The former are not probed in the white line analysis presented by Mukerjee and co-workers. In the case of methanol oxidation, en-... 

Metallic NPs are most widely used in catalytic applications due to their inherent properties. Several examples of platinum and gold NPs are apparent in the literature. For example, electrodeposited platinum NPs on porous carbon substrates exhibit electrocatalytic activity for the oxidation of methanol.60 In another example, gold NPs catalyze the electrochemical oxidation of nitric oxide on modified electrodes.61 In general, catalytic NPs provide two distinct functions enhancing an electrochemical reaction and/or increasing electron transfer to an electrode. 

Platinum, ruthenium and PtRu alloy nanoparticles, prepared by vacuum pyrolysis using Pt(acac)2 and Ru(acac)3 as precursors, were applied as anode catalysts for direct methanol oxidation . The nanoparticles, uniformly dispersed on multiwaUed carbon nanotubes, were all less than 3.0 nm in size and had a very narrow size distribution. The nanocomposite catalysts showed strong electrocatalytic activity for methanol oxidation, which can... 

Electrochemical data indicate that self-assembled monolayers of 5 and 6 catalyze the two-electron reduction of O2 to H2O2. The monolayer from 6 is a more effective electrocatalyst for the reduction of O2 than that from 5 [300]. The different reactivity results from different interfacial architecture this is confirmed by infrared, X-ray photoelectron, and visible spectroscopic measurements [300] which revealed coplanar, inclined t -7z stacking of the porphyrin ring in the monolayer of 5 and head-to-tail orientation of the porphyrin ring in the monolayer of 6. Treatment of the monolayer of 8 with Co(OAc)2 in methanol resulted in electrocatalytic activity in the reduction of O2 [300]. In contrast, a monolayer of 7 treated similarly failed to catalyze dioxygen reduction [300], although treatment of a mixed monolayer of 7 and CH3(CH2)3SH with Co(OAc)2 results in electrocatalytic activity similar to that of 6. 

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