Electrocatalyst carbon support materials

Carbon supports strongly affect fuel cell performance. They may influence the intrinsic catalytic activity and catalyst utilization, but also affect mass transport and ohmic losses. This makes analyses of the role of carbon materials rather complicated. Although numerous studies have been devoted to the carbon support improvement, only a few have attempted to establish relationships between the substructural characteristics of carbon support materials and cell performance. The influence of carbon supports on the intrinsic catalytic activity is the subject of Section 12.6.1. In Section 12.6.2 we consider the influence of support on macrokinetic parameters such as the catalyst utilization, mass transport, and ohmic losses. In Section 12.6.3 we review briefly recent data obtained upon utilization of novel carbon materials as supports for fuel cell electrocatalysts. 

In a carbon-supported metal electrocatalyst, the electronic interaction between metal and carbon support has a significant effect on its electrochemical performance [4], For carbon-supported Pt electrocatalyst, carbon could accelerate the electron transfer at the electrode-electrolyte interface, leading to an accelerated electrode process. Typically, the electrons are transferred from platinum clusters to the oxygen species on the surfece of a carbon support material and the chemical bond formation or the charge transfer process occurs at the contacting phase, which is considered to be beneficial to the enhancement of the catalytic properties in terms of activity and stability of the electrocatalysts. Experimentally, the investigation into the electron interaction between metal catalyst and support materials could be realized by various physical, spectroscopic, and electrochemical approaches. The electron donation behavior of Pt to carbon support materials has been demonstrated by the electron spin resonance (ESR) X-ray photoelectron spectroscopy (XPS) studies, with the conclusion that the electron interaction between Pt and carbon support depends on their Fermi level of electrons. It is considered that the electronic structure change of Pt on carbon support induced by the electron interaction has positive effect toward the enhancement of the catalytic properties and the improvement of the stability of the electrocatalyst system. However, the exact quantitative relationship between electronic interaction of carbon-supported catalyst and its electrocatalytic performance is still not yet fully established [4]. 

Recently, rhodium and ruthenium-based carbon-supported sulfide electrocatalysts were synthesized by different established methods and evaluated as ODP cathodic catalysts in a chlorine-saturated hydrochloric acid environment with respect to both economic and industrial considerations [46]. In particular, patented E-TEK methods as well as a non-aqueous method were used to produce binary RhjcSy and Ru Sy in addition, some of the more popular Mo, Co, Rh, and Redoped RuxSy catalysts for acid electrolyte fuel cell ORR applications were also prepared. The roles of both crystallinity and morphology of the electrocatalysts were investigated. Their activity for ORR was compared to state-of-the-art Pt/C and Rh/C systems. The Rh Sy/C, CojcRuyS /C, and Ru Sy/C materials synthesized by the E-TEK methods exhibited appreciable stability and activity for ORR under these conditions. The Ru-based materials showed good depolarizing behavior. Considering that ruthenium is about seven times less expensive than rhodium, these Ru-based electrocatalysts may prove to be a viable low-cost alternative to Rh Sy systems for the ODC HCl electrolysis industry. 

Another material has some importance for oxygen reduction, not as an electrocatalyst but because other properties make it a good supporting material for catalysts that is, carbon, graphite, used with dispersed platinum particles or adsorbed coordination compounds. The main reduction product on carbon itself... 

Phosphoric Acid Fuel Cells (PAFCs) for Utilities Electrocatalyst Crystallite Design, Carbon Support, and Matrix Materials Challenges... 

In chapter 4, Stonehart (a major authority in the field of H2 fuelcell technology and its fundamental aspects) writes, with co-author Wheeler, on the topic of Phosphoric Acid Fuel-Cells (PAFCs) for Utilities Electrocatalyst Crystallite Design, Carbon Support, and Matrix Materials Challenges. This contribution reviews, in detail, recent information on the behavior of very small Pt and other alloy electrocatalyst crystallites used as the electrode materials for phosphoric acid electrolyte fuel-cells. 

Because carbon black is the preferred support material for electrocatalysts, the methods of preparation of (bi)metallic nanoparticles are somewhat more restricted than with the oxide supports widely used in gas-phase heterogeneous catalysis. A further requirement imposed by the reduced mass-transport rates of the reactant molecules in the liquid phase versus the gas phase is that the metal loadings on the carbon support must be very high, e.g., at least lOwt.% versus 0.1-1 wt.% typically used in gas-phase catalysts. The relatively inert character of the carbon black surface plus the high metal loading means that widely practiced methods such as ion exchange [9] are not effective. The preferred methods are based on preparation of colloidal precursors, which are adsorbed onto the carbon black surface and then thermally decomposed or hydrogen-reduced to the (bi)metallic state. This method was pioneered by Petrow and Allen [10], and in the period from about 1970-1995 various colloidal methods are described essentially only in the patent literature. A useful survey of methods described in this literature can be found in the review by Stonehart [11]. Since about 1995, there has been more disclosure of colloidal methods in research journals, such as the papers by Boennemann and co-workers [12]. 

Carbon supported Pt and Pt-alloy electrocatalysts form the cornerstone of the current state-of-the-art electrocatalysts for medium and low temperature fuel cells such as phosphoric and proton exchange membrane fuel cells (PEMECs). Electrocatalysis on these nanophase clusters are very different from bulk materials due to unique short-range atomic order and the electronic environment of these cluster interfaces. Studies of these fundamental properties, especially in the context of alloy formation and particle size are, therefore, of great interest. This chapter provides an overview of the structure and electronic nature of these supported... 

Electronic interaction and synergistic effects between catalysts and the support material have been investigated in the context of fuel-cell electrocatalysts. Electron spin resonance (ESR) has been used to demonstrate the electron donation by Pt to carbon [11] support. This has been further supported by XPS studies [12], which show that the metal acts as an electron donor to the support, their interaction depending on their respective Eermi levels. Bogotsky and Snudkin [13] have shown that the characteristics of the electrical double layer formed between the microdeposit (Pt) and the support depends to a certain extent on the difference in the work function of Pt (5.4 eV) and carbon support (pyrolytic support 4.7 eV), thereby resulting in an increase of the electron density of Pt. However, the rise in the electron density can be significant only when the particle size of the microdeposit is comparable to the thickness of the double layer. 

P. Stonehart and D. Wheeler, Phosphoric Acid Fuel Cells (PAFCs) for vehicles Electrocatalyst Crystalite Design, Carbon Support, and Matrix Materials Challenges in Modem Aspects of Electrochemistry, Vol. 38, Ed. by B. E. Conway, Kluwer/Plenum, New York (2005) Chapter 4, 385. 

By varying the particle size, shapes, separation, and support on planar model electrocatalysts, the influence of these properties on the electrocatal3dic reactions, e.g., on fuel cell electrodes, can be evaluated systematically. Some new challenges arise, such as the adhesion of the catalyst particles on new types of support materials (e.g., glassy carbon). However, most of the procedures and concepts of preparation and characterization are the same as in heterogeneous catalysis and photocatalysis. 

The right choice of a carbon support greatly affects cell performance and durability. The purpose of this chapter is to analyze how structure and properties of carbon materials influence the performance of supported noble metal catalysts in the CLs of the PEMFCs. The review chapter is organized as follows. In Section 12.2 we give an overview of carbon materials utilized for the preparation of the catalytic layers of PEMFC. We describe traditional as well as novel carbon materials, in particular carbon nanotubes and nanofibers and mesoporous carbons. In Section 12.3 we analyze properties of carbon materials essential for fuel cell performance and how these are related to the structural and substructural characteristics of carbon materials. Sections 12.4 and 12.5 are devoted to the preparation and characterization of carbon-supported electrocatalysts and CLs. In Section 12.6 we analyze how carbon supports may influence fuel cell performance. Section 12.7 is devoted to the corrosion and stability of carbon materials and carbon-supported catalysts. In Section 12.8 we provide conclusions and an outlook. Due to obvious space constraints, it was not possible to give a comprehensive treatment of all published data, so rather, we present a selective review and provide references as to where an interested reader may find more detailed information. 

In PEMFCs, carbon materials are exposed to conditions that favor their corrosion. These are the positive values of the electrode potential, the acidic environment (pHelevated temperature (333 to 363 K), but also the presence of electrocatalysts such as metal nanoparticles. Since the electrode potential, water content, and Pt mass fraction are higher at the cathode of a PEMFC, this may explain why stronger degradation of the carbon support is usually reported at this electrode [266]. The rate of corrosion of carbon in PEMFCs has been reported to increase with an increase in the relative humidity [97,255,256], but Borup et al. [273] arrived at the controversial conclusion that the rate of carbon corrosion increases with decreasing relative humidity. 

The most prominent nanostructured materials in fuel cells are the electrocatalysts of low- and medium-temperature fuel cells, which consist of carbon-supported precious metal particles in the range of 1-5 nm. This structure is necessary to increase the surface to volume ratio of the noble metals, thus reducing the costs of the material. 

For polymer electrolyte membrane fuel cell (PEMFC) applications, platinum and platinum-based alloy materials have been the most extensively investigated as catalysts for the electrocatalytic reduction of oxygen. A number of factors can influence the performance of Pt-based cathodic electrocatalysts in fuel cell applications, including (i) the method of Pt/C electrocatalyst preparation, (ii) R particle size, (iii) activation process, (iv) wetting of electrode structure, (v) PTFE content in the electrode, and the (vi) surface properties of the carbon support, among others. ... 

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