Catalyst in DMFC

Like in PEMFC, platinum is the standard catalyst used in the electrode and Nafion polymer electrolyte interface of DMFC for low temperature levels. Catalyst development effort for DMFC involves the search for an alternative to the Pt-Ru catalyst for enhanced anode oxidization reaction. 

Estimate the water content, proton conductivity, water diffusion coefficient, and electro-osmotic drag coefficient for a Nafion membrane under humidity conditions with water activity a = 0.9 and an operating temperature of 80°C. 

Badwal, S. P. S. and K. Foger. Materials for solid oxide fuel cell. Materials Forum 21 183-220,1997. 

Badwal, S. P. S., F. T. Ciacchi, S. Rajendran and J. Drenan. An investigation of conductivity, microstructure and stability of electrolyte compositions in the system 9 mol% (Sc203-Y203)-Zr02(Al203). Solid State Ionics 109 167-186,1998. 

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Most of the catalysts employed in PEM and direct methanol fuel cells, DMFCs, are based on Pt, as discussed above. However, when used as cathode catalysts in DMFCs, Pt containing catalysts can become poisoned by methanol that crosses over from the anode. Thus, considerable effort has been invested in the search for both methanol resistant membranes and cathode catalysts that are tolerant to methanol. Two classes of catalysts have been shown to exhibit oxygen reduction catalysis and methanol resistance, ruthenium chalcogen based catalysts " " and metal macrocycle complexes, such as porphyrins or phthalocyanines. ... 

In this chapter, we reviewed the structure-controlled syntheses of CNFs in an attempt to offer better catalyst supports for fuel cell applications. Also, selected carbon nanofibers are used as supports for anode metal catalysts in DMFCs. The catalytic activity and the efficiency of transferring protons to ion-exchange membranes have been examined in half cells and single cells. The effects of the fiber diameter, graphene alignment and porosity on the activity of the CNF-supported catalysts have been examined in detail. 

The influence of the mesopore size of carbon aerogels on ORR using Pt-doped carbon aerogels has also been reported by other authors [86]. They found practically no influence of pore texture on Pt dispersion. However, they indicate that the ORR activity increased when the mean mesopore size increased, reaching the best ORR performance for a mesopore size of 18.5 nm. Pt-based catalysts have also been used as anodic catalysts in DMFC systems, since Pt is able to activate the C-H bond cleavage in the temperature range of fuel cell operation (298 to 403 K). Thus, different Pt, Pt-Ni, and Pt-Ru catalysts supported on carbon xerogels have been used as catalysts in DMFC systems [87-90]. 

Other property that could be relevant for the durability of DAFC is the ruthenium crossover, that is, the dissolution of Ru from anode catalysts containing Ru (a typical anode catalyst in DMFC) and its re-precipitation in the cathode [14]. The water and methanol permeability was expected to have an effect on Ru crossover, but the only study available on this seems to indicate that differences is not the case [15]. 

One should note that poisoning of PEMFC anode catalysts by CO is also a severe problem as CO is found to some extent in most H2 gas supplies, as H2 is usually produced by steam reforming of CH4 (and CO is a by-product). It has been reported that a CO content as low as 10 ppm in H2 fuel will result in the poisoning of Pt electrocatalysts [74], As shown in Eqs. 17.8 and 17.9, the formation of OHads by water oxidation at the Pt surface is necessary for the oxidative removal of adsorbed CO. However, the formation of Pt-OH only occurs appreciably above 0.8 V vs. RHE [75]. This factor is considered to be the origin of the high overpotentials for the MOR and COOR and, often, a second metal that can provide oxide species at low potentials is added to Pt electrocatalysts to reduce such overpotentials. For example, Pt-based alloys containing elements such as Ru, Mo, W, and Sn have been used in attempts to speed up the electrocatalysis of methanol [70,76,77]. The Pt-Ru alloy (1 1 atomic ratio) is the most active binary catalyst and is most frequently used as the anode catalyst in DMFCs [78]. Ru is more easily oxidised than Pt and is able to form Ru-oxide adsorbates at 0.2 V vs. RHE, thereby promoting the oxidation of CO to CO2, as summarised in Eqs. 17.11-17.13 ... 

Catalytic activity is closely dependent on the method of preparation, so considerable attention has been focused upon new preparation methods to improve the performance of carbon-supported platinum alloy catalysts in DMFC applications. The simultaneous reduction of metal salts [86-88], microwave-assisted reactions [89, 90], micro-emulsion-based synthesis [91-93], and the reduction of single-source molecular precursors [94-99] have been used to various extents. 

Fig. 2.4 I-V curves comparing the performance of Pt-Ru nanocomposites at a loading of 1.5 mg cm with (triplicate) and without (solid line) CNF supports as anode catalysts in DMFCs (Reprinted from Guo et al. [53], Copyright 2006, with permission from Elsevier)...

Although ORR catalysts for DMFCs are mostly identical to those for the PEM fuel cell, one additional and serious drawback in the DMFC case is the methanol crossover from the anode to the cathode compartment of the membrane electrode assembly, giving rise to simultaneous methanol oxidation at the cathode. The... 

Waszczuk et al., 2001b Tong et al., 2002]. Because Ru is deposited as nanosized Ru islands of monoatomic height, the Ru coverage of Pt could be determined accurately. In that case, the best activity with regard to methanol oxidation was found for a Ru coverage close to 40-50% at 0.3 and 0.5 V vs. RHE. However, the structure of such catalysts and the conditions of smdy are far from those used in DMFCs. Moreover, the surface composition of a bimetallic catalyst likely depends on the method of preparation of the catalyst [Caillard et al., 2006] and on the potential [Blasini et al., 2006]. 

Such bimetallic alloys display higher tolerance to the presence of methanol, as shown in Fig. 11.12, where Pt-Cr/C is compared with Pt/C. However, an increase in alcohol concentration leads to a decrease in the tolerance of the catalyst [Koffi et al., 2005 Coutanceau et ah, 2006]. Low power densities are currently obtained in DMFCs working at low temperature [Hogarth and Ralph, 2002] because it is difficult to activate the oxidation reaction of the alcohol and the reduction reaction of molecular oxygen at room temperature. To counterbalance the loss of performance of the cell due to low reaction rates, the membrane thickness can be reduced in order to increase its conductance [Shen et al., 2004]. As a result, methanol crossover is strongly increased. This could be detrimental to the fuel cell s electrical performance, as methanol acts as a poison for conventional Pt-based catalysts present in fuel cell cathodes, especially in the case of mini or micro fuel cell applications, where high methanol concentrations are required (5-10 M). 

The hnding of very substantial amounts of incomplete oxidation products for methanol and formaldehyde oxidation can have considerable consequences for technical applications, such as in DMFCs. In that case, the release of formaldehyde at the fuel cell exhaust has to be avoided not only from efficiency and energetic reasons, but in particular because of the toxicity of formaldehyde. While in standard DMFC applications the catalyst loading is sufficiently high that this is not a problem, i.e., only CO2 is detected [Arico et al., 1998], the trend to reducing the catalyst loading or applications in micro fuel cells may lead to situations where the formation of incomplete oxidation products could indeed become problematic (see also Wasmus et al. [1995]). For such purposes, one could dehne a maximum space velocity above which formation of incomplete oxidation products may become critical. 

The development of MeOH-tolerant cathode catalysts for DMFC is a key component for certain system arrangements. In particular, it is critical for... 

Pt/Ru electrocatalysts are currently used in DMFC stacks of a few watts to a few kilowatts. The atomic ratio between Pt and Ru, the particle si2 e and the metal loading of carbon-supported anodes play a key role in their electrocatalytic behavior. Commercial electrocatalysts (e.g. from E-Tek) consist of 1 1 Pt/Ru catalysts dispersed on an electron-conducting substrate, for example carbon powder such as Vulcan XC72 (specific surface area of 200-250 m g ). However, fundamental studies carried out in our laboratory [13] showed that a 4 1 Pt/Ru ratio gives higher current and power densities (Figure 1.6). 

Over the last decade, novel carbonaceous and graphitic support materials for low-temperature fuel cell catalysts have been extensively explored. Recently, fibrous nanocarbon materials such as carbon nanotubes (CNTs) and CNFs have been examined as support materials for anodes and cathodes of fuel cells [18-31], Mesoporous carbons have also attracted considerable attention for enhancing the activity of metal catalysts in low-temperature DMFC and PEMFC anodes [32-44], Notwithstanding the many studies, carbon blacks are still the most common supports in industrial practice. 

This chapter presents the design and application of a two-stage combinatorial and high-throughput screening electrochemical workflow for the development of new fuel cell electrocatalysts. First, a brief description of combinatorial methodologies in electrocatalysis is presented. Then, the primary and secondary electrochemical workflows are described in detail. Finally, a case study on ternary methanol oxidation catalysts for DMFC anodes illustrates the application of the workflow to fuel cell research. 

Combinations of platium catalyst and Fe-teteraphenylparpherine complex increased the efficiency of oxygen reduction [21]. The decay product of methanol in DMFC... 

The theoretical cell voltage of a DMFC at standard conditions is 1.20 V. The materials used in DMFCs are similar to those in PEMFCs. Pt, PtRu, and Nafion membrane are used as cathode catalyst, anode catalyst, and proton transfer membranes, respectively. However, the catalyst loading in a DMFC is much higher than the loading used in H2/air fuel cells, because both side reactions are slow (Pt loadings 4 mg/cm2 for a DMFC, 0.8 mg/cm2 for a H2/air fuel cell). 

This chapter has examined a variety of EIS applications in PEMFCs, including optimization of MEA structure, ionic conductivity studies of the catalyst layer, fuel cell contamination, fuel cell stacks, localized impedance, and EIS at high temperatures, and in DMFCs, including ex situ methanol oxidation, and in situ anode and cathode reactions. These materials therefore cover most aspects of PEMFCs and DMFCs. It is hoped that this chapter will provide a fundamental understanding of EIS applications in PEMFC and DMFC research, and will help fuel cell researchers to further understand PEMFC and DMFC processes. 

Reddington et al. (66) reported the synthesis and screening of a 645-member discrete materials library L9 as a source of catalysts for the anode catalysis of direct methanol fuel cells (DMFCs), with the relevant goal of improving their properties as fuel cells for vehicles and other applications. The anode oxidation in DMFCs is reported in equation 1 (Fig. 11.12). At the time of the publication, state-of-the-art anode catalysts were either binary Pt-Ru alloys (67) or ternary Pt-Ru-Os alloys (68). A systematic exploration of ternary or higher order alloys as anode catalysts for DMFCs was not available, and predictive models to orient the efforts were also lacking. 

PEM fuel cells use a solid proton-conducting polymer as the electrolyte at 50-125 °C. The cathode catalysts are based on Pt alone, but because of the required tolerance to CO a combination of Pt and Ru is preferred for the anode [8]. For low-temperature (80 °C) polymer membrane fuel cells (PEMFC) colloidal Pt/Ru catalysts are currently under broad investigation. These have also been proposed for use in the direct methanol fuel cells (DMFC) or in PEMFC, which are fed with CO-contaminated hydrogen produced in on-board methanol reformers. The ultimate dispersion state of the metals is essential for CO-tolerant PEMFC, and truly alloyed Pt/Ru colloid particles of less than 2-nm size seem to fulfill these requirements [4a,b,d,8a,c,66j. Alternatively, bimetallic Pt/Ru PEM catalysts have been developed for the same purpose, where nonalloyed Pt nanoparticles <2nm and Ru particles <1 nm are dispersed on the carbon support [8c]. From the results it can be concluded that a Pt/Ru interface is essential for the CO tolerance of the catalyst regardless of whether the precious metals are alloyed. For the manufacture of DMFC catalysts, in... 

The modification of platinum catalysts by the presence of ad-layers of a less noble metal such as ruthenium has been studied before [15-28]. A cooperative mechanism of the platinurmruthenium bimetallic system that causes the surface catalytic process between the two types of active species has been demonstrated [18], This system has attracted interest because it is regarded as a model for the platinurmruthenium alloy catalysts in fuel cell technology. Numerous studies on the methanol oxidation of ruthenium-decorated single crystals have reported that the Pt(l 11)/Ru surface shows the highest activity among all platinurmruthenium surfaces [21-26]. The development of carbon-supported electrocatalysts for direct methanol fuel cells (DMFC) indicates that the reactivity for methanol oxidation depends on the amount of the noble metal in the carbon-supported catalyst. 

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