Catalysts blacks, surface area

A considerable decrease in platinum consumption without performance loss was attained when a certain amount (30 to 40% by mass) of the proton-conducting polymer was introduced into the catalytically active layer of the electrode. To this end a mixture of platinized carbon black and a solution of (low-equivalent-weight ionomeric ) Nafion is homogenized by ultrasonic treatment, applied to the diffusion layer, and freed of its solvent by exposure to a temperature of about 100°C. The part of the catalyst s surface area that is in contact with the electrolyte (which in the case of solid electrolytes is always quite small) increases considerably, due to the ionomer present in the active layer. 

Due to the ease of preparation, impregnation is one of the most commonly used techniques to fabricate catalysts. High-surface-area carbon black can be impregnated with catalyst precursors by mixing the two in an aqueous solution... 

FIGURE 4-1 (a) Specific and (b) mass activities for the ORR on carbon-supported Pt catalysts, polycrystaUine Pt (shown at "Om /gp") and Pt-black catalysts (Pt surface area 5m /gpi) determined by rotating disk electrode method in Oi-saturated O.IM HQO4 at 0.9V and 60°C. Reprinted from Ref. [4] with permission from Appl. Catal. B - Environ. 

Physical adsorption—surface areas of any stable solids, e.g., oxides used as catalyst supports and carbon black Chemisorption—measurements of particle sizes of metal powders, and of supported metals in catalysts... 

In this article, we will discuss the use of physical adsorption to determine the total surface areas of finely divided powders or solids, e.g., clay, carbon black, silica, inorganic pigments, polymers, alumina, and so forth. The use of chemisorption is confined to the measurements of metal surface areas of finely divided metals, such as powders, evaporated metal films, and those found in supported metal catalysts. 

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]. 

As surface area and pore structure are properties of key importance for any catalyst or support material, we will first describe how these properties can be measured. First, it is useful to draw a clear borderline between roughness and porosity. If most features on a surface are deeper than they are wide, then we call the surface porous (Fig. 5.16). Although it is convenient to think about pores in terms of hollow cylinders, one should realize that pores may have all kinds of shapes. The pore system of zeolites consists of microporous channels and cages, whereas the pores of a silica gel support are formed by the interstices between spheres. Alumina and carbon black, on the other hand, have platelet structures, resulting in slit-shaped pores. All support materials may contain micro, meso and macropores (see text box for definitions). 

We have already referred to the Mo/Ru/S Chevrel phases and related catalysts which have long been under investigation for their oxygen reduction properties. Reeve et al. [19] evaluated the methanol tolerance, along with oxygen reduction activity, of a range of transition metal sulfide electrocatalysts, in a liquid-feed solid-polymer-electrolyte DMFC. The catalysts were prepared in high surface area by direct synthesis onto various surface-functionalized carbon blacks. The intrinsic... 

The platinum concentrations in the platinized carbon blacks are reported to be between 10 and 40% (by mass), sometimes even higher. At low concentrations the specific surface area of the platinum on carbon is as high as lOOm /g, whereas unsupported disperse platinum has surface areas not higher than 10 to 15m /g. However, at low platinum concentrations, thicker catalyst layers must be applied, which makes reactant transport to reaction sites more difficult. The degree of dispersion and catalytic activity of the platinum depend not only on its concentration on the carrier but also on the chemical or electrochemical method used to deposit it. 

It was seen when studying mixed systems Pt-WOj/C and Pt-Ti02/C that with increasing percentage of oxide in the substrate mix the working surface area of the platinum crystallites increases, and the catalytic activity for methanol oxidation increases accordingly. With a support of molybdenum oxide on carbon black, the activity of supported platinum catalyst for methanol oxidation comes close to that of the mixed platinum-ruthenium catalyst. 

In this section, we demonstrate the real ORR activities (apparent rate constant per real active surface area, fe pp) and P(H202) at bulk Pt and nanosized Pt catalysts dispersed on carbon black (Pt/CB) with dp,= 1.6 + 0.4, 2.6 + 0.7, and 4.8 1.0 nm in the practical temperature range 30-110 °C [Yano et al., 2006b]. The use of a channel flow double-electrode (CFDE) cell allowed us to evaluate fe pp and P(H202) precisely. 

In the enantioselective hydrogenation of isophorone in the presence of (-)-DHVIN modifier the best optical purity was afforded by small dispersion (<0,05) Pd black catalyst (up to 55%) (7). The influence of the preparation method of Pd black on the optical yield was reported (8). A correlation was found between the oxidation state of the metal surface and the enantioselectivity, the catalyst having more oxidised species on its surface giving higher enantiomeric excess, while the Pd black with lower surface area was more enantioselective. 

The stability during potential cycling and ORR activity of Pt (20 wt°/o) supported on MWCNTs and carbon black was also investigated [136]. Two different potential cycling conditions were used, namely lifetime (0.5 to 1.0 V vs. RHE) and start-up (0.5 to 1.5 V vs. RHE). Pt supported on MWCNTs catalyst exhibited a significantly lower drop in normalized electrochemically active surface area (ECA) values compared to Pt supported on Vulcan (Fig. 14.10), showing that MWCNTs possess superior stability to commercial carbon black under normal and severe potential cycling conditions [137]. 

The enormous importance of carbon in such diverse fields as inorganic and organic chemistry and biology is well known however, only the aspects of carbon relevant to catalysis will be described here. The main topics we are concerned with are porous activated carbons, carbon black as catalyst supports and forms of coking. Carbon is also currently used as storage for natural gas and to clean up radioactive contamination. Carbon is available at low cost and a vast literature exists on its uses. Coal-derived carbon is made from biomass, wood or fossil plants and its microstructure differs from carbon made from industrial coke. Activated carbons are synthesized by thermal activation or by chemical activation to provide desirable properties like high surface area. 

The anode layer of polymer electrolyte membrane fuel cells typically includes a catalyst and a binder, often a dispersion of poly(tetraflu-oroethylene) or other hydrophobic polymers, and may also include a filler, e.g., acetylene black carbon. Anode layers may also contain a mixture of a catalyst, ionomer and binder. The presence of a ionomer in the catalyst layer effectively increases the electrochemically active surface area of the catalyst, which requires a ionically conductive pathway to the cathode catalyst to generate electric current (16). 

Tests on the activity of LP-produced Fe-based nanopowders for liquefaction of a sub-bituminous coal under high (688 K, 1 h of reaction) and low (658 K, 0.25 h of reaction) severity conditions have been reported.38 The catalysts tested were Fe7C3 (92 m2 g 1 (BET), particle size = 17 nm (XRD))and Fe XS (42 m2 g 1 (BET), particle size = 14 nm (XRD).38 For comparison, a commercial superfine iron oxide catalyst (SFIO, supplied by Mach I, Inc.) whose major phase has been identified in one study as y-Fe20339 (surface area = 195 m2 g 1 (BET), particle diameter = 3 nm (XRD)) and in other study as the ferrihydrite40 was also evaluated under similar conditions. The coal liquefaction experiments were carried out in 50 cm3 horizontal microautoclave reactors loaded with 3 g of sub bituminous Black Thunder coal and 5 g of tetralin used as hydrogen donor. Catalyst loadings of 0.7% and 1.4% of as-received coal... 

---