Carbonaceous, generally structures

Great promise exists in the use of graphitic carbons in the electrochemical synthesis of hydrogen peroxide [reaction (15.21)] and in the electrochemical reduction of carbon dioxide to various organic products. Considering the diversity in structures and surface forms of carbonaceous materials, it is difficult to formulate generalizations as to the influence of their chemical and electron structure on the kinetics and mechanism of electrochemical reactions occurring at carbon electrodes. 

In modern terms, asphaltene is conceptually defined as the normal-pentane-insoluble and benzene-soluble fraction whether it is derived from coal or from petroleum. The generalized concept has been extended to fractions derived from other carbonaceous sources, such as coal and oil shale (8,9). With this extension there has been much effort to define asphaltenes in terms of chemical structure and elemental analysis as well as by the carbonaceous source. It was demonstrated that the elemental compositions of asphaltene fractions precipitated by different solvents from various sources of petroleum vary considerably (see Table I). Figure 1 presents hypothetical structures for asphaltenes derived from oils produced in different regions of the world. Other investigators (10,11) based on a number of analytical methods, such as NMR, GPC, etc., have suggested the hypothetical structure shown in Figure 2. 

The largest class of meteorite finds is stony meteorites, made principally of stone. The general stony classification is divided into three subclasses called chondrites, carbonaceous chondrites and achondrites, and it is at this level of distinction at which we will stop. Before looking at their mineral and isotopic structure in more detail, it is useful to hold the composition of the Earth s crust in mind here for comparison. The Earth s crust is 49 per cent oxygen, 26 per cent silicon, 7.5 per cent aluminium, 4.7 per cent iron, 3.4 per cent calcium, 2.6 per cent sodium, 2.4 per cent potassium and 1.9 per cent magnesium, which must have formed from the common origin of the solar system. 

Carbonaceous char barriers may be formed by the normal mode of polymer burning, and besides representing a reduction in the amount of material burned, the char may act as a fire barrier. The relationship of char yield, structure, and flame resistance was quantified by Van Krevelen (5) some years ago. For polymers with low char-forming tendencies, such as polyolefins, one approach to obtain adequate char is to add a char-forming additive. Such additives generally bear a resemblance to intumescent coating ingredients (6, 7). 

This section provides a comprehensive overview of recent efforts in physical theory, molecular modeling, and performance modeling of CLs in PEFCs. Our major focus will be on state-of-the-art CLs that contain Pt nanoparticle electrocatalysts, a porous carbonaceous substrate, and an embedded network of interconnected ionomer domains as the main constituents. The section starts with a general discussion of structure and processes in catalyst layers and how they transpire in the evaluation of performance. Thereafter, aspects related to self-organization phenomena in catalyst layer inks during fabrication will be discussed. These phenomena determine the effective properties for transport and electrocatalytic activity. Finally, physical models of catalyst layer operation will be reviewed that relate structure, processes, and operating conditions to performance. 

Apart from these general characteristics, each association presents its own peculiarities determined by the origin of the carbonaceous material, the original structures, its mechanical history, and the time of introduction of the radioactive elements. These peculiarities are most important from a geological and geochemical point of view. The few cases described hereafter were chosen according to their diversity and exemplary value. 

Experimental data were obtained on the carbonaceous residue (char), and sulfur distribution was calculated for the solid and gaseous products from the pyrolysis of model compounds. Sharp differences were observed in the quantity of char and the sulfur distribution for the different substances studied. The quantity of volatile matter varied from 21 to 43%. The sulfur retained by the char varied from 21 to 74% of the total present in the compound pyrolyzed (see Table I). The raw data show a possible relationship between the volatile matter and sulfur retention which indicates that as volatile matter decreases, sulfur retention generally increases (Table I). Neither structural features nor the molecular size of the various model compounds appear to have a significant relationship to sulfur distribution. 

On Earth, the Ti(m) oxidation state is unstable. However, Ti3+-bearing minerals are well-characterized in some meteorites and Moon rocks, generally coexisting with Ti4 in such phases as calcic pyroxene, ulvospinel, hibonite and ilmenite. In hibonite, CaAlI20I9, a refractory phase in carbonaceous chondrites, EPR and optical spectral data indicate that Ti3+ ions are present (Hunger and Stolper, 1986 Live et al., 1986). The trivalent Ti ions may be stabilized in the five-coordinated trigonal bipyramidal M5 site of the hibonite structure... 

However, while from these general considerations it is clear that both acidity and pore structure of a zeolite affect the rate of formation of carbonaceous compounds (other factors being held constant), it is generally impossible to quantify the effect of each of these parameters because of the difficulty in obtaining zeolite samples with identical acidities and with different pore structures or vice-versa. Having said that, some examples are given below which illustrate within these limitations the respective roles of acidity and of pore structure. 

Highly porous carbons can be produced from a variety of natural and synthetic precursors [11, 12]. Relatively inexpensive activated carbons are useful adsorbents, but generally their surface and pore structures are exceedingly complex [11, 13]. However, it is now possible to prepare a number of more uniform carbonaceous adsorbents. For example, molecular sieve carbons (MSCs) are available with narrow distributions of ultramicropores, which exhibit well-defined molecular selectivity [11], and carbon nanotubes, aerogels, and membranes are also amongst the most interesting advanced materials for research and development [12, 14]. 

---