Electrocatalysts characterization

From the above discussion it becomes apparent that some conflicting experimental evidence exists on hydrocarbon adsorption and on surface intermediates. This arises primarily from the use of electrocatalysts of varying histories and pretreatments. It should be stressed that many adsorption studies were performed on anodically pretreated platinum. The removal of surfaces oxides from such electrodes may have not been always accomplished when the surface was cathodically reduced in some experiments, as outlined in Section IV,D. Obviously, different surface species could exist on bare or on oxygen-covered electrocatalysts. Characterization of surface structure and activity and of adsorbed species using modern spectroscopic techniques would provide useful information for fuel cell and selective electrocatalytic oxidations and reductions. 

For surface structure studies, perhaps the most popular technique has been LEED (373). Elastically diffracted electrons from a monoenergetic beam directed to a single-crystal surface reveal structural properties of the surface that may differ from those of the bulk. Some applications of LEED to electrocatalyst characterization were cited in Section IV (106,148,386). Other, less specific, but valuable surface examination techniques, such as scanning electron microscopy (SEM) and X-ray microprobe analysis, have not been used in electrocatalytic studies. They could provide information on surface changes caused by reaction, some of which may lead to catalyst deactivation (256,257). Since these techniques use an electron beam, they can be coupled with previously discussed methods (e.g. AES or XPS) to obtain a qualitative mapping of the structure and composition of a catalytic surface. 

Gochi-Ponce Y, Alonso-Nunez G, Alonso-Vante N (2006) Synthesis and electrochemical characterization of a novel platinum chalcogenide electrocatalyst with an enhanced tolerance to methanol in the oxygen reduction reaction. Electrochem Commun 8 1487-1491... 

Specific Activity (SA) and Mass Activity (MA) of Pt Electrocatalysts Supported on Different Carbon Powders Characterized by Specific Surface Area (S) and Particle Size (d)... 

Markovic NM, Radmilovic V, Ross PN. 2003. Physical and electrochemical characterization of bimetallic nanoparticle electrocatalysts. In Wieckowski A, Savinova E, Vayenas C, eds. Catalysis and Electrocatalysis at Nanoparticle Surfaces. New York Marcel Dekker, pp. 311-342. 

Fernandez JL, White JM, Sun YM, Tang WJ, Henkelman G, Bard AJ. 2006. Characterization and theory of electrocatalysts based on scanning electrochemical microscopy screening methods. Langmuir 22 10426-10431. 

Lalande G, Cote R, Tamizhmani G, Guay D, Dodelet JP. 1995. Physical, chemical and electrochemical characterization of heat-treated tetracarboxylic cobalt phthalocyanine adsorbed on carbon black as electrocatalyst for oxygen reduction in polymer electrolyte fuel cells. Electrochim Acta 40 2635-2646. 

Schmidt TJ, Gasteiger HA, Stab GD, Urban PM, Kolb DM, Behm RJ. 1998. Characterization of high-surface area electrocatalysts using a rotating disk electrode configuration. J Electrochem Soc 145 2354-2358. 

Attwood PA, McNicol BD, Short RT. 1980. Electrocatalytic oxidation of methanol in acid electrolyte—Preparation and characterization of noble-metal electrocatalysts supported on pretreated carbon-fiber papers. J Appl Electrochem 10 213-222. 

C.G. Tsiafoulis, P.N. Trikalitis, and M.I. Prodromidis, Synthesis, characterization and performance of vanadium hexacyanoferrate as electrocatalyst of H202. Electrochem. Commun. 7, 1398 (2005). 

The elemental composition, oxidation state, and coordination environment of species on surfaces can be determined by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) techniques. Both techniques have a penetration depth of 5-20 atomic layers. Especially XPS is commonly used in characterization of electrocatalysts. One common example is the identification and quantification of surface functional groups such as nitrogen species found on carbon-based catalysts.26-29 Secondary Ion Mass spectrometry (SIMS) and Ion Scattering Spectroscopy are alternatives which are more surface sensitive. They can provide information about the surface composition as well as the chemical bonding information from molecular clusters and have been used in characterization of cathode electrodes.30,31 They can also be used for depth profiling purposes. The quantification of the information, however, is rather difficult.32... 

Synchotron based techniques, such as surface X-ray scattering (SXS) and X-ray absorption spectroscopy (XAS), have found increased use in characterization of electrocatalysts during electrochemical reactions.37 These techniques, which can be used for characterization of surface structures, require intricate cell designs that can provide realistic electrochemical conditions while acquiring spectra. Several examples of the use of XAS and EXAFS in non-precious metal cathode catalysts can be found in the literature.38 2... 

This review will focus on the applications of XAS in the characterization of low temperature fuel cell catalysts, in particular carbon supported Pt electrocatalysts, Pt containing alloys for use as anode and... 

XAS has been successfully employed in the characterization of a number of catalysts used in low temperature fuel cells. Analysis of the XANES region has enabled determination of the oxidation state of metal atoms in the catalyst or, in the case of Pt, the d band vacancy per atom, while analysis of the EXAFS has proved to be a valuable structural tool. However, the principal advantage of XAS is that it can be used in situ, in a flooded half-cell or true fuel cell environment. While the number of publications has been limited thus far, the increased availability of synchrotron radiation sources, improvements in beam lines brought about by the development of third generation sources, and the development of more readily used analysis software should increase the accessibility of the method. It is hoped that this review will enable the nonexpert to understand both the power and limitations of XAS in characterizing fuel cell electrocatalysts. 

Kirchnerova J Klvana D. Preparation and characterization of high surface perovskite electrocatalysts. Int. J. Hydrogen Energy., 1994, Volume 19, Issue 6, 501-506. 

As a demanding reaction, it is very sensitive to the structural and compositional details of the anode materials. For this reason, research on anodes for O2 evolution calls for close characterization of electrocatalysts, especially from the point of view of materials chemistry and physics. 

The definition of the electrochemical Thiele modulus [Eq. (9b)J characterizing the degree of electrocatalyst utilization is a prerequisite for properly tailoring the micromorphology of porous electrocatalytic electrode coatings and fuel cell electrodes, as it allows matching of the coating or catalyst particle dimension to the catalytic activity of the material ... 

Structural and compositional characterization of individual elements of a combinatorial library can be important for the initial validation of a particular combinatorial synthesis method. Many earlier reports on combinatorial synthesis and screening of electrocatalysts fall short of reporting the complete structural and compositional characterization of individual library elements of interest. The workflow described here includes catalyst characterization before and after screening, thereby establishing an activity-composition-structure-stability relationship for electrocatalysts. This can be relevant in light of the extreme conditions present in a conventional fuel cell environment. 

Fig. 11.8 Schematic of the automated primary high-throughput electrochemical workflow employed at Symyx Technologies for the combinatorial development of new fuel cell catalysts. Individual steps of the workflow include choice of catalyst concept, design of appropriate materials library using Library Studio [31], synthesis of electrocatalyst library on electrode array wafer, XRD and EDX characterization of individual electrocatalysts before screening, high-throughput parallel electrochemical screening of library, XRD and EDX characterization of catalysts after screening, data processing and evaluation.

Structural and compositional characterization of high surface-area catalysts is crucial for evaluating whether the secondary synthesis of a particular electrocatalyst was successful. Similar to the primary screening workflow, XRD is used for the structural characterization of catalyst powders, while SEM/EDX is employed for the compositional characterization of electrocatalyst powders before and after electrochemical screening. 

Characterization of Alloy Electrocatalysts by Combined Low-Energy Ion Scattering Spectroscopy and Electrochemistry... 

---