Methanol anode catalysts

Improvement on Methanol Anode Catalysts and Methanol Tolerant Cathode Catalysts... 

The transient response of DMFC is inherently slower and consequently the performance is worse than that of the hydrogen fuel cell, since the electrochemical oxidation kinetics of methanol are inherently slower due to intermediates formed during methanol oxidation [3]. Since the methanol solution should penetrate a diffusion layer toward the anode catalyst layer for oxidation, it is inevitable for the DMFC to experience the hi mass transport resistance. The carbon dioxide produced as the result of the oxidation reaction of methanol could also partly block the narrow flow path to be more difScult for the methanol to diflhise toward the catalyst. All these resistances and limitations can alter the cell characteristics and the power output when the cell is operated under variable load conditions. Especially when the DMFC stack is considered, the fluid dynamics inside the fuel cell stack is more complicated and so the transient stack performance could be more dependent of the variable load conditions. 

Dinh FIN, Ren X, Garzon FTF, Zelenay P, Gottesfeld S. 2000. Electrocatalysis in direct methanol fuel cells in-situ probing of FTRu anode catalyst surfaces. J Electroanal Chem 491 ... 

Lei HW, Suh S, Gurau B, Workie B, Liu R, Smotkin ES. 2002. Deuterium isotope analysis of methanol oxidation on mixed metal anode catalysts. Electrochim Acta 47 2913-2919. 

Rao V, Simonov PA, Savinova ER, Plaksin GV, Cherepanova S V, Kryukova GN, Stimming U. 2005. The influence of carbon support porosity on the activity of PtRu/Sibunit anode catalysts for methanol oxidation. J Power Sources 145 178-187. 

This survey focuses on recent developments in catalysts for phosphoric acid fuel cells (PAFC), proton-exchange membrane fuel cells (PEMFC), and the direct methanol fuel cell (DMFC). In PAFC, operating at 160-220°C, orthophosphoric acid is used as the electrolyte, the anode catalyst is Pt and the cathode can be a bimetallic system like Pt/Cr/Co. For this purpose, a bimetallic colloidal precursor of the composition Pt50Co30Cr20 (size 3.8 nm) was prepared by the co-reduction of the corresponding metal salts [184-186], From XRD analysis, the bimetallic particles were found alloyed in an ordered fct-structure. The elecbocatalytic performance in a standard half-cell was compared with an industrial standard catalyst (bimetallic crystallites of 5.7 nm size) manufactured by co-precipitation and subsequent annealing to 900°C. The advantage of the bimetallic colloid catalysts lies in its improved durability, which is essential for PAFC applicabons. After 22 h it was found that the potential had decayed by less than 10 mV [187],... 

Steigerwalt, S.E. et al., A Pt-Ru/graphitic carbon nanofiber nanocomposite exhibiting high relative performance as a direct-methanol fuel cell anode catalyst, J. Phys. Chem. B., 105, 8097, 2001. 

Mu, Y., et al., Controllable Ptnanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells. The Journal of Physical Chemistry B, 2005.109(47) ... 

R. X. Liu, and E. S. Smotkin, Array membrane electrode assemblies for high throughput screening of direct methanol fuel cell anode catalysts, J. Electroanal. Chem. 535, 49-55 (2002). 

Influence of PTFE content in the anode DL of a DMFC. Operating conditions 90°C cell temperature anode at ambient pressure cathode at 2 bar pressure methanol concentration of 2 mol dm methanol flow rate of 0.84 cm min. The air flow rate was not specified there was a parallel flow field for both sides. The anode catalyst layer had 13 wt% PTFE, Pt 20 wt%, Ru 10 wt% on Vulcan XC-73R carbon TGP-H-090 with 10 wt% PTFE as cathode DL. The cathode catalyst layer had 13 wt% PTFE, Pt 10 wt% on carbon catalyst with a loading 1 mg cm Pt black with 10 wt% Nafion. The membrane was a Nafion 117. (Reprinted from K. Scott et al. Journal of Applied Electrochemistry 28 (1998) 1389-1397. With permission from Springer.)... 

Cao, D., Bergens, S.H. 2004. Pt-Ru j , nanoparticles as anode catalysts for direct methanol fuel cells. J Power Sources 134 170-180. 

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. 

Since high current density at the maximum power density and the cost of the noble metals are important parameters for the commercialization of DMECs, H-CNE-supported Pt-Ru alloys maybe classified among the most efficient and cost-effective anode catalysts. It is also worth mentioning that the CNF-supported catalysts feature superior catalytic activity at the high temperatures where the mass transfer of methanol and oxygen is more favorable due to the fibrous network of CNEs. 

This section addresses the role of chemical surface bonding in the electrochemical oxidation of carbon monoxide, CO, formic acid, and methanol as examples of the electrocatalytic oxidation of small organics into C02 and water. The (electro)oxidation of these small Cl organic molecules, in particular CO, is one of the most thoroughly researched reactions to date. Especially formic acid and methanol [130,131] have attracted much interest due to their usefulness as fuels in Polymer Electrolyte Membrane direct liquid fuel cells [132] where liquid carbonaceous fuels are fed directly to the anode catalyst and are electrocatalytically oxidized in the anodic half-cell reaction to C02 and water according to... 

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. 

In addition to the slow methanol oxidation kinetics, methanol that crosses over from the anode to the cathode side through the membrane can react with 02 at the cathode catalyst, leading to a mixed potential at the cathode side and thereby reducing cell performance. To solve this problem, methanol-tolerant catalysts as well as membranes with low methanol permeability have been investigated. However, these materials are still in the research stages and commercial applications have not been developed. 

In a fuel cell, inductance is usually caused by the adsorbed species on the electrode surface. For example, in a direct methanol fuel cell, adsorption of CO on the anode catalyst can at low frequencies result in an inductance loop. 

The medium-frequency arc, the size of which is strongly dependent on the anode potential, corresponds to methanol electrooxidation kinetics. Note that different anode catalyst compositions and operating conditions of the DMFC can be evaluated by assessing their effects on anode performance. 

Havranek A, Wippermann K (2004) Determination of proton conductivity in anode catalyst layers of the direct methanol fuel cell (DMFC). J Electroanal Chem 567(2) 305-15... 

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. 

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... 

This survey focuses on recent catalyst developments in phosphoric acid fuel cells (PAFC), proton exchange membrane fuel cells (PEMFC), and the previously mentioned direct methanol fuel cell (DMFC). A PAFC operating at 160-220 °C uses orthophosphoric acid as the electrolyte the anode catalyst is Pt and the cathode can... 

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