Electrocatalysts fuel cell studies

In order to get answers to these questions, the ability to better characterize catalysts and electrocatalysts in situ under actual reactor or cell operating conditions (i.e., operando conditions) with element specificity and surface sensitivity is crucial. However, there are very few techniques that lend themselves to the rigorous requirements in electrochemical and in particular fuel cell studies (Fig. 1). With respect to structure, in-situ X-ray diffraction (XRD) could be the method of choice, but it has severe limitations for very small particles. Fourier transform infra red (FTTR), " and optical sum frequency generation (SFG) directly reveal the adsorption sites of such probe molecules as CO," but cannot provide much information on the adsorption of 0 and OH. To follow both structure and adsorbates at once (i.e., with extended X-ray absorption fine stmcture (EXAFS) and X-ray absorption near edge stmc-ture (XANES), respectively), only X-ray absorption spectroscopy (XAS) has proven to be an appropriate technique. This statement is supported by the comparatively large number of in situ XAS studies that have been published during the last decade. 16,17,18,19,20,21,22,23,24,25 highly Versatile, since in situ measme-... 

Zhou, Z.H. (2003) Direct methanol fuel cells studies on the preparation of highly dispersed Pt based electrocatalysts with high loading. PhD thesis. Dalian Institute of Physical Chemistry. 

Table 3.1 lists some of the anodic reactions which have been studied so far in small cogenerative solid oxide fuel cells. A more detailed recent review has been written by Stoukides46 One simple and interesting rule which has emerged from these studies is that the selection of the anodic electrocatalyst for a selective electrocatalytic oxidation can be based on the heterogeneous catalytic literature for the corresponding selective catalytic oxidation. Thus the selectivity of Pt and Pt-Rh alloy electrocatalysts for the anodic NH3 oxidation to NO turns out to be comparable (>95%) with the... 

Markovic NM, Ross PN. 2002. Surface science studies of model fuel cell electrocatalysts. Surf Sci Rep 45 121-229. 

Maniguet, S. EXAFS studies of carbon supported fuel cells electrocatalysts. Ph.D. Thesis, University of Southampton, 2002. 

Another prospect for eflBcient energy conversion is the fuel cell. The diflFerent types of fuel cells presently under study or development were reviewed by G. Belanger of Hydro-Quebec, who concluded that commercial availability of such units is now in sight. However, the need to develop cheap, efficient electrocatalysts for oxygen reduction remains. 

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. 

Strasser, P., Fan, Q., Devenney, M., Weinberg, W. H., Combinatorial Exploration of ternary fuel cell electrocatalysts for DMFC anodes — a comparative study of PtRuCo, PtRuNi and PtRuW systems, AIChE fall meeting, 2003, San Francisco. 

The recent study by Lakshmi et al. [63] is just one example of the very extensive research efforts devoted to the improvement of performance of fuel cells by increasing the dispersion of the electrocatalyst on the carbon support by virtue of carbon surface functionalization [64], Without acknowledging their familiarity with the most relevant prior studies, they did note that the point of neutral charge evaluation helps in identifying the platinum complex to be used for electrocatalyst synthesis based on their charge, in the sense that, for example, if the carbon surface is positively charged an anionic platinum complex is needed (see Section 5.2.1). 

The SECM capacity for rapid screening of an array of catalyst spots makes it a valuable tool for studies of electrocatalysts. This technique was used to screen the arrays of bimetallic or trimetallic catalyst spots with different compositions on a GC support in search of inexpensive and efficient electrocatalytic materials for polymer electrolyte membrane fuel cells (PEMFC) [126]. Each spot contained some binary or ternary combination of Pd, Au, Ag, and Co deposited on a glassy carbon substrate. The electrocatalytic activity of these materials for the ORR in acidic media (0.5 M H2S04) was examined using SECM in a rapidimaging mode. The SECM tip was scanned in the x—y plane over the substrate surface while electrogenerating 02 from H20 at constant current. By scanning... 

In situ polarization studies using an entire fuel cell. This method provides information on the behaviour of the electrocatalyst in actual exploitation conditions. However, little data may be available on mechanistic aspects. 

For fuel-cell technology development, it has been important to understand the characteristics and operation of highly dispersed platinum and platinum alloy electrocatalysts. A series of papers on platinum crystallite size determinations in acid environments for oxygen reduction and hydrogen oxidation was published together by Bert, Stonehart, Kinoshita and co-workers.5 The conclusion from these studies was that the specific activity for oxygen reduction on the platinum surface was independent of the size of the platinum crystallite and that there were no crystallite size effects. 

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