Fuel cell electrocatalysis concepts

M. Watanabe, New CO-tolerant catalyst concepts, in Handbook of Fuel Cells, Electrocatalysis, John Wiley and Sons, Chichester, 2003, Vol. 2. 

The term electrocatalysis was first introduced by Grubb in 1963 [1] in connection with the anodic and cathodic charge-transfer reactions in fuel cells. However, the first systematic experimental investigations of various electrocatalysts had been carried out in the 1920s by Bowden and Rideal [2] and the concept and first interpretation of electrocatalysis had been introduced in the 1930s by Horiuti and Polanyi [3]. Their theory and its extensions and improvements have been analyzed lucidly by Bockris [4-6]. Recent reviews of progress in electrocatalysis can be found in more general [6-8] or specialized books [9-11]. 

Although in situ infrared spectroscopy has been applied widely in terms of the systems studied, the reflective electrodes employed have been predominantly polished metal or graphite, and so an important advance has been the study of electrochemical processes at more representative electrodes such as Pt/Ru on carbon [107,122,157], a carbon black/polyethylene composite employed in cathodic protection systems [158] and sol-gel Ti02 electrodes [159]. Recently, Fan and coworkers [160] took this concept one step further, and reported preliminary in situ FTIR data on the electro-oxidation of humidified methanol vapor at a Pt/Ru particulate electrode deposited directly onto the Nafion membrane of a solid polymer electrolyte fuel cell that was mounted within the sample holder of a diffuse reflectance attachment. As well as features attributable to methanol, a number of bands between 2200 and 1700 cm were observed in the spectra, taken under shortoperating conditions, the importance of which has already been clearly demonstrated [107]. 

This chapter will cover major topics of CL research, focusing on (i) electrocatalysis of the ORR, (ii) porous electrode theory, (iii) structure and properties of nanoporous composite media, and (iv) modern aspects in understanding CL operation. Porous electrode theory is a classical subject of applied electrochemistry. It is central to all electrochemical energy conversion and storage technologies, including batteries, fuel cell, supercapacitors, electrolyzers, and photoelectrochemi-cal cells, to name a few examples. Discussions will be on generic concepts of porous electrodes and their percolation properties, hierarchical porous structure and flow phenomena, and rationalization of their impact on reaction penetration depth and effectiveness factor. 

These preliminary results are a first demonstration that the shape-selected particles concept may work in a realistic fuel cell environment. Future research will focus on degradation and stability tests of the novel materials as well as their application in other fuel cell types, as for instance direct methanol fuel cells and high-temperature pol)uner electrolyte membrane fuel cells. Moreover, the effect of the surfactant requires special attention, as the surfactant molecules may also influence the electrocatalysis by a ligand effect or an ensemble effect directing the adsorption of reactants to specific surface sites. 

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