High crystallite size

Coke materials are generally made by heat-treatment of petroleum pitch or coal-tar pitch in an N2 atmosphere. Coke made from petroleum is called "petroleum coke" and that from coal is called "pitch coke". These materials have the closest-packed hexagonal structures. The crystallinity of coke materials is not so high as that of graphite. The crystallite size of coke along the c-axis (Lc) is small (about 10-20 A) and the interlayer distance (d value about 3.38-3.80 A) is large. 

This conclusion was additionally confirmed by Palczewska and Janko (67) in separate experiments, where under the same conditions nickel-copper alloy films rich in nickel (and nickel films as well) were transformed into their respective hydride phases, which were proved by X-ray diffraction. The additional argument in favor of the transformation of the metal film into hydride in the side-arm of the Smith-Linnett apparatus consists of the observed increase of the roughness factor ( 70%) of the film and the decrease of its crystallite size ( 30%) after coming back from low to high temperatures for desorbing hydrogen. The effect is quite similar to that observed by Scholten and Konvalinka (9) for their palladium catalyst samples undergoing the (a — j8) -phase transformation. 

In the early days of catalysis the porous high surface area support was usually thought to be inert. It soon became obvious, however, that the catalytic activity, or turnover frequency, of a catalytic reaction on a given active phase is quite often seriously affected both by the crystallite size and by the material of the support. 

Ru02 is an important electrode material for industrial anodic processes. Special attention is deserved by the so-called dimensionally stable anodes (DSA) invented by H. B. Beer in 1968. These are formed by a layer of a microcrystalline mixture of Ti02 and Ru02 (crystallite size less thn 0.1 jum) on a titanium support (Fig. 5.26). This material is suitable as anode for chlorine and oxygen evolution at high current densities. For industrial chlorine production, it replaced the previously used graphite anodes. These... 

Some other studies showed that the combination of the three polymorphs with reduced crystallite size and high surface area can lead to the best photocatalysts for 4-chlorophenol degradation [37], or that particles in the dimension range 25-40 nm give the best performances [38]. Therefore, many elements contribute to the final photocatalytic activity and sometimes the increased contribution of one parameter can compensate for the decrease of another one. For example, better photocatalytic activity can be obtained even if the surface area decreases, with a concomitant increase in the crystallinity of the sample, which finally results in a higher number of electron-hole pairs formed on the surface by UV illumination and in their increased lifetime (slower recombination) [39]. Better crystallinity can be obtained with the use of ionic liquids during the synthesis [39], with a consequent increase of activity. 

When both the component metals have reasonably high melting points, as in Pd-Rh alloys, then the variation of crystallite size with composition (60) is limited, despite the use of high substrate temperatures (400°C). 

Lc 1 nm or Lc>20 nm). Highly graphitic materials (<7002 within 0.335 -0.338 nm and Lc>30 nm) show some increase of the capacity when the lowest limit of d002 is achieved and Lc increases. The specific reversible capacity vs crystallite size or vs treatment temperature diagrams are often published. They look as smooth curves with a minimum within medium temperatures or medium crystallite sizes [7,11,17]. 

Oxidative catalysis over metal oxides yields mainly HC1 and C02. Catalysts such as V203 and Cr203 have been used with some success.49 50 In recent years, nanoscale MgO and CaO prepared by a modified aerogel/hypercritical drying procedure (abbreviated as AP-CaO) and AP-MgO, were found to be superior to conventionally prepared (henceforth denoted as CP) CP-CaO, CP-MgO, and commercial CaO/MgO catalysts for the dehydrochlorination of several toxic chlorinated substances.51 52 The interaction of 1-chlorobutane with nanocrystalline MgO at 200 to 350°C results in both stoichiometric and catalytic dehydrochlorination of 1-chlorobutane to isomers of butene and simultaneous topochemical conversion of MgO to MgCl2.53-55 The crystallite sizes in these nanoscale materials are of the order of nanometers ( 4 nm). These oxides are efficient due to the presence of high concentration of low coordinated sites, structural defects on their surface, and high-specific-surface area. 

Supported metal catalysts are used in a large number of commercially important processes for chemical and pharmaceutical production, pollution control and abatement, and energy production. In order to maximize catalytic activity it is necessary in most cases to synthesize small metal crystallites, typically less than about 1 to 10 nm, anchored to a thermally stable, high-surface-area support such as alumina, silica, or carbon. The efficiency of metal utilization is commonly defined as dispersion, which is the fraction of metal atoms at the surface of a metal particle (and thus available to interact with adsorbing reaction intermediates), divided by the total number of metal atoms. Metal dispersion and crystallite size are inversely proportional nanoparticles about 1 nm in diameter or smaller have dispersions of 100%, that is, every metal atom on the support is available for catalytic reaction, whereas particles of diameter 10 nm have dispersions of about 10%, with 90% of the metal unavailable for the reaction. 

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