Electro-catalysts

In contrast with the AFC, the PAFC can demonstrate reliable operation with 40 percent to 50 percent system efficiency even when operating on low quality fuels, such as waste residues. This fuel flexibility is enabled by higher temperature operation (200°C vs. 100°C for the AFC) since this raises electro-catalyst tolerance toward impurities. Flowever, the PAFC is still too heavy and lacks the rapid start-up that is nec-essaiy for vehicle applications because it needs preheating to 100°C before it can draw a current. This is unfortunate because the PAFC s operating temperature would allow it to thermally integrate better with a methanol reformer. 

Porous electrodes are commonly used in fuel cells to achieve hi surface area which significantly increases the number of reaction sites. A critical part of most fuel cells is often referred to as the triple phase boundary (TPB). Thrae mostly microscopic regions, in which the actual electrochemical reactions take place, are found where reactant gas, electrolyte and electrode meet each other. For a site or area to be active, it must be exposed to the rractant, be in electrical contact with the electrode, be in ionic contact with the electrolyte, and contain sufficient electro-catalyst for the reaction to proceed at a desired rate. The density of these regions and the microstmcture of these interfaces play a critical role in the electrochemical performance of the fuel cells [1]. 

Principal design parameters of electro-catalysts for PEMFCs... 

Electro-catalysts which have various metal contents have been applied to the polymer electrolyte membrane fuel cell(PEMFC). For the PEMFCs, Pt based noble metals have been widely used. In case the pure hydrogen is supplied as anode fuel, the platinum only electrocatalysts show the best activity in PEMFC. But the severe activity degradation can occur even by ppm level CO containing fuels, i.e. hydrocarbon reformates[l-3]. To enhance the resistivity to the CO poison of electro-catalysts, various kinds of alloy catalysts have been suggested. Among them, Pt-Ru alloy catalyst has been considered one of the best catalyst in the aspect of CO tolerance[l-3]. 

For the support material of electro-catalysts in PEMFC, Vulcan XC72(Cabot) has been widely used. This carbon black has been successfully employed for the fuel cell applications for its good electric conductivity and high chemical/physical stability. But higher amount of active metals in the electro-catalysts, compared to the general purpose catalysts, make it difficult to control the metal size and the degree of distribution. This is mainly because of the restricted surface area of Vulcan XC72 carbon black. Thus complex and careM processes are necessary to get well dispersed fine active metal particles[4,5]. 

The slurries of electro-catalysts were prepared by mixing together the catalysts and appropriate amount of 5wt % Nafion solution(Du Pont) including some kinds of dispersant[8]. The electrodes were made by spraying method with these well mixed inks. Two electrodes and Nafion 112 membrane were hot pressed with the condition of 50kgf/cm, 120°C for 3min to fabricate MEAs(Membrane Electrode Assembly). 

Fig. 1. Performance evaluation of prepared electro-catalysts as an electrode of PEMFC. Cell temperature 70 C, active area 50cm, platinum loading anode(0.3mgPt/cm )/cathode(0.45mg Pt/cm ), fuel utilization H2/O2 = 80%/50%, RH 100% RFl, pressure H2/O2 = 0 psig/0 psig.

When considering the morphology of prepared electro-catalysts are different to each other especially to the commercial one, one can think that the structure of electrode which was optimized to the commercial catalyst may not be optimum. So, the for the better electrode structures was conducted by investigating the effect of NFP. Fig. 2 is a schematic of electrode which depicts the effect of Nafion content[9]. For the conventional electrocatalysts, the range of 30 35 % NFP is reported as optimum value[10]. 

Design parameters of the anode catalyst for the polymer electrolyte membrane fiiel cells were investigated in the aspect of active metal size and inter-metal distances. Various kinds of catalysts were prepared by using pretreated Ketjenblacks as support materials. The prepared electro-catalysts have the morphology such as the sizes of active metal are in the range from 2.0 to 2.8nm and the inter-metal distances are 5.0 to 14.2nm. The electro-catalysts were evaluated as an electrode of PEMFC. In Fig. 1, it looked as if there was a correlation between inter-metal distances and cell performance, i.e. the larger inter-metal distances are related to the inferior cell performance. 

But when the contents of Nafion ionomer was increased from 30 to 45 % to find out the better electrode structures, the Pt-Ru/SRaw, which had showed the lowest single cell performance, became the best electro-catalyst. By this result one can conclude that as long as the structure of the electrode can be optimized for the each of new electro-catalysts, the active metal size is a more important design parameter rather than inter-metal distances. Furthermore, when the electro-catalysts are designed, the principal parameters should be determined in the consideration of the electrode structures which affect on the electron conduction, gas permeability, proton conductivity, and so on. 

Gold is generally considered a poor electro-catalyst for oxidation of small alcohols, particularly in acid media. In alkaline media, however, the reactivity increases, which is related to that fact that no poisoning CO-hke species can be formed or adsorbed on the surface [Nishimura et al., 1989 Tremihosi-Filho et al., 1998]. Similar to Pt electrodes, the oxidation of ethanol starts at potentials corresponding to the onset of surface oxidation, emphasizing the key role of surface oxides and hydroxides in the oxidation process. The only product observed upon the electrooxidation of ethanol on Au in an alkaline electrolyte is acetate, the deprotonated form of acetic acid. The lack of carbon dioxide as a reaction product again suggests that adsorbed CO-like species are an essential intermediate in CO2 formation. 

Song, H Qiu, X., Guo, D., and Li, F. (2008) Role of structural H2O in Ti02 nanotubes in enhancing Pt/C direct ethanol fuel cell anode electro-catalysts. Journal of Power Sources, 178 (1), 97-102. 

The main components of a PEM fuel cell are the flow channels, gas diffusion layers, catalyst layers, and the electrolyte membrane. The respective electrodes are attached on opposing sides of the electrolyte membrane. Both electrodes are covered with diffusion layers, and the flow channels/current collectors. The flow channels collect current from the electrodes while providing the fuel or oxidant with access to the electrodes. The gas diffusion layer allows gases to diffuse to the electro-catalysts and provides electrical contact throughout the catalyst layers. Within the anode catalyst layer, the fuel (typically H2) is oxidized to produce electrons and protons. The electrons travel through an external circuit to produce electricity, while the protons pass through the proton conducting electrolyte membrane. Within the cathode catalyst layer, the electrons and protons recombine with the oxidant (usually 02) to produce water. 

T. Page, R. Johnson, J. Hormes, S. Noding, and B. Rambabu, A study of methanol electro-oxidation reactions in carbon membrane electrodes and structural properties of Pt alloy electro-catalysts by EXAES, J. Electroanal. Chem. 485, 34-41 (2000). 

Various modeling approaches have been used for the catalyst layers, with different degrees of success. The approach taken usually depends on how the other parts of the fuel cell are being modeled and what the overall goal of the model is. Just as with membrane modeling, there are two main classes of models. There are the microscopic models, which include pore-level models as well as more detailed quantum models. The quantum models deal with detailed reaction mechanisms and elementary transfer reactions and transition states. They are beyond the scope of this review and are discussed elsewhere, along with the issues of the nature of the electro catalysts. 

The experimental data presented in this paper demonstrates the potential of CuCl/HCl electrolysis for nuclear hydrogen production. The CuCl/HCl electrolysis reaction requires a cation exchange membrane in order to produce hydrogen at a current density that exceeds 0.1 A-cm-2. In order to carry out the hydrogen production reaction a platinum electro-catalyst is required. The copper(I) oxidation reaction, on the other hand, does not require a Pt catalyst. This reaction proceeds quite readily on Pt-free graphite electrodes. Methods to mitigate the passage of the copper ion species across the membrane need to be developed to maintain the performance of the cell at the desired level. 

With regard to the electro-catalyst the main research issue is to identify a platinum-based catalyst, i.e. a binary, ternary or quaternary catalyst composed of platinum and one or more transition metals that will be more active (and thereby further reducing the applied potential), exhibit an improved lifespan, and have reduced platinum loadings to reduce the cost. The NWU, located in the North-West province of South Africa where the majority of the world s platinum is mined and produced, is currently setting itself up for the synthesis, characterisation and testing of platinum-based electro-catalysts specifically for normal water electrolysis as well as for S02 electrolysis. 

Applications of this electrode material include (i) the anodic formation of hydroxyl radicals, (ii) the anodic formation of ozone and peroxo species, (iii) waste degradation in aqueous solution (hazardous and a range of organic wastes have been broken down without toxic intermediates), (iv) as a mechanically robust electrode for solid state electrochemistry or in the presence of power ultrasound, (v) as a dimensionally stable electrode, (vi) as a IR and Vis transparent electrode material, and (vii) as an inert substrate for electro-catalysts. 

Dispersed Pt formed as a cluster on the Ti02 particles in PtTi-Sl (Fig. 5a) should strongly catalyse the H2 formation, while the compact Pt particles in PtTi-S2 (Fig. 5b) should be the poorer electro catalysts for H2 evolution. From these considerations and the assumption that the reduction of H+ is ratecontrolling for the formation of HCHO in an 02-free suspension, it can be understood why 0hcho on PtTi-Sl is found to be larger than on PtTi-S2 [82]. 

Determination of Reaction Mechanisms Occurring at Fuel Cell Electro catalysts Using Electrochemical Methods, Spectroelectrochemical Measurements and Analytical Techniques... 

This can be reached by using bimetallic and multi-metallic electro-catalysts. 

The Sabatier principle of catalysis also finds extensive application in the area of electrocatalysis reactants should be moderately adsorbed on the catalyst/electro-catalyst surface. Very weak or very strong adsorption leads to low electrocatalytic activity. This has been demonstrated repeatedly in the literature by the use of volcano plots (Figs 23-25). In these plots, the electrocatalytic activity is plotted as a function of the adsorption energy of the key reactant or some other parameter related to it in a linear or near-linear fashion, such as the work function of the metal [5], or the metal—H bond strength when discussing the H2 evolution reaction (Fig. 24) [54] or the enthalpy of the lower-to-higher oxide transition when examining the O2 evolution reaction (Fig. 25) [55]. 

Traditionally, catalysts are divided into homogeneous and heterogeneous catalysts, biocatalysts (enzymes), photocatalysts, and electro-catalysts. In order of number and volume of chemical processes, most use heterogeneous catalysts, that is, in a phase different (typically a solid phase) than that of the reagents and products. We will thus discuss the use of solid catalysts to promote sustainability of chemical processes in... 

H. Takenaka, E. Torikai, Y. Kawami, N. Wakabayashi and T. Sakai, Studies on solid polymer electrolyte water electrolysis II. Preparation methods for membrane-electro-catalyst composite, Denki Kagaku (J. Electrochem. Soc. Jpn.), 1985, 53, 261. 

Besides a direct application of the hydrogen and oxygen electrodes in power sources (fuel cells, metal-air batteries, metal-hydrogen batteries, hydride cells) a application of gasconsuming electrodes consists in the gas-recombination in sealed cells. An application of the electro-catalysts for acidic electrolytes mentioned above could be the elimination of... 

Fig. 5.6-4 Schematic illustration of a supported ionic liquid fuel cell containing the Wacker oxidation system (SMSEC supported molten salt electro-catalyst) for co-generatlon of acetaldehyde and electricity from ethanol [55],...

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