Surface-type catalysis

Surface-type catalysis is ordinary heterogeneous catalysis, whereby the reactions take place on the two-dimensional surface (on the outer surface and pore walls) of solid catalysts. The reaction rate is proportional to the catalyst surface area. 

It is noteworthy that in the two industrial processes to produce methacrylic acid, both involving catalysis by H3PM012O40 and its alkali salts, one involves bulk type II catalysis and the other, surface type catalysis, as described in the following section. 

It has been demonstrated that three different types of catalysis are possible for solid HPAs (211,212) (a) surface type, (6) pseudoliquid or bulk type (I), and (c) bulk type (II) catalysis (Fig. 19). In surface-type catalysis, the catalytic events occur, as for many other solid catalysts, on the outer surface and consequently, the reaction rate for acid-catalyzed reactions should be, in principle, proportional... 

EfiBdent hydrogen supply iiom decalin was only accomplished by the si terheated liquid-film-type catalysis under reactive distillation conditions at modaate heating tempaatures of 210-240°C. Caibcm-supported nano-size platinum-based catalysts in the si ietheated liquid-film states accelerated product desorption fixjm file catalyst surface due to its temperature gradient under boiling conditions, so that both hi reaction rates and conversions were obtained simultaneously. 

In our own lab experiments with various cyano compounds and nickel catalysts, we concluded on a 2-site L.H type catalysis [67] but we had to introduce corrective parameters for substrate interactions, indicating failure of the basic assumption of surface ideality, i.e equal adsorption energy whichever coverage is reached. 

In this section, these influences will be described. Besides the acidic properties, the absorption properties of solid heteropolyacids for polar molecules are often critical in determining the catalytic function in pseudoliquid phase behavior. This is a new concept in heterogeneous catalysis by inorganic materials and is described separately in Section VI. With this behavior, reactions catalyzed by solid heteropoly compounds can be classified into three types surface type, bulk type I, and bulk type II (Sections VII and IX). Softness of the heteropolyanion is important for high catalytic activity, although the concept has not yet been sufficiently clarified. 

There are three prototypes of heterogeneous catalysis with heteropoly compounds as shown in Fig. 2 [4, 5]. Actual cases could be intermediate and vary by the kind of heteropoly compounds, reacting molecules, and reaction conditions. Ordinary heterogeneous catalysis is the surface type, where the catalytic reaction takes place on a two-dimensional surface. Bulk type I is the reaction in the pseudoliquid phase. The secondary structure (Fig. lb) of certain HPAs is flexible and polar molecules are readily absorbed in interstitial positions of the solid bulk to form the pseudoliquid phase. Bulk type II has been demonstrated for several catalytic oxidations at relatively high temperatures. The reaction fields for the bulk types are three-dimensional. 

For acid catalysis, the rates of bulk-type reactions show close correlations with the bulk acidity, while the catalytic activities for surface-type reactions are related to the surface acidity which is sensitive to the surface composition and often change randomly. Similarly, in the case of oxidation catalysis, good correlations exist between the oxidizing ability of catalyst and the catalytic activity for oxidation in both bulk-type and surface-type reactions. Acid and redox bifunctionality is another characteristic of HPAs. For example, the acidity and oxidizing ability work cooperatively for the oxidation of mcthacrolcin, whereas they function competitively for the oxidative dehydrogenation of isobutyric acid [5]. Interestingly, the former is of surface type and the latter of bulk type. 

Figure 2. Three types of heterogeneous catalysis for heteropoly compounds (a) surface type (b) bulk type I (pseudoliquid) (c) bulk type II.

The redox properties can also be controlled by the formation of salts. However, the relationship between these properties and the catalytic activity for oxidation is not sufficiently clarified. For example, it was reported that the activity order for alkali salts was reversed by the reaction temperature [35]. Nevertheless, good correlations are obtained if the concept of surface- and bulk-type catalysis is appropriately considered [4, 36-38]. The reduction by H2 of free acid and group A salts proceeds both on the surface and in the... 

In all these three types of surface-controlled catalysis, it is advisable to check the adsorption inferences reached by interpretation of the experimental kinetic law. Wherever possible, independent adsorption experiments should be carried out with the individual substances concerned. Alternatively, or in addition, infrared and preferably FTIR measurements will often reveal useful information on the presence and state of adsorbed species. 

Porous materials with large internal surface areas have attracted considerable attention in surface chemistry, catalysis and chromatography. In principle, a vast choice of porous materials is available. While some inspiration can indeed be drawn from chemical applications, the choices for useful photovoltaic substrate materials are considerably narrowed by the requirement to have thin-film constituency, transparency and electronic conductivity. Indeed, these requirements are so stringent that only a few substrate types and materials have so far been found suitable. Sintered nanocrystalline oxide films are one major class of these. Much development work on these materials has been reported in the context of dye-sensitised cells, and this is... 

Fundamental correlations between redox properties and catalytic activity have successfully been established for the hydrogen form and alkali salts of 12-molybdophosphoric acid [1]. Provided that the contributions of surface- and bulk-type catalysis are properly taken into account, good monotonic relationships are obtained between the catalytic activity for oxidation and the reducibihty (or the oxidizing power) of the catalyst. The rate of oxidation of aldehydes, a surface-type reaction, correlates linearly with the surface reducibility of the catalyst, and the rate of oxidative dehydrogenation of cyclohexene, a bulk-type reaction, with the bulk reducibility [2]. 

While the acid strength of HPAs is high, they have a limitation in their use in catalysis, and this is due to their low surface area in the solid state (SlOm g- ), which corresponds to the external surface area of the crystal. When the reactants have a polar character, however, HPAs can take up polar molecules in amounts that correspond to more than 100 surface layer, and in this case their catalytic behaviour has been called bulk type catalysis [31"). Therefore, in the case of catalytic reactions involving polar molecules, they occur not only at the surface but also in the bulk solid of certain HPAs. The practical effect is that the catalytic system behaves like a highly concentrated solution, and this explains why these solids have been named pseudoliquids [31 j. Under the pseudoliquid conditions all acid sites are accessible to reactants, and the benefits of the system have been used commercially for reactions such as the hydration of propylene and n-butenc, separation of isobutene, and polymerization of tetrahydrofuran 20, 31". ... 

Methanol dehydrogenates to methyl formate over fresh WC and P-W2C powders with selectivities higher than 90% (109,110). The dominant side reaction is the decomposition to synthesis gas. Over WC and P-W2C modified with oxygen, methanol selectively dehydrates to dimethylether at 473 K and at higher reaction temperatures, C2-C4 olefins are produced (47). Thus, the dehydrodimerization of methanol apparently requires WC sites. These sites are titrated by chemisorbed oxygen. Thus, oxygen on the surface inhibits the formation of methyl formate and introduces a surface acid function WO that catalyzes dehydration by carbenium-ion type catalysis. 

The acid catalysis of heteropoly compounds in the solid state is classified into bulk-type and surface-type reations. The former type reactions proceed in the catalyst bulk and the latter only on the surface. Dehydration reactions of alcohols belong to the former and isomerization of butene to the latter. So the classification is closely related to the adsorption property of reactants. The activities for the surface-type reactions are more sensitive to pretreatment. 

Qualitative examples abound. Perfect crystals of sodium carbonate, sulfate, or phosphate may be kept for years without efflorescing, although if scratched, they begin to do so immediately. Too strongly heated or burned lime or plaster of Paris takes up the first traces of water only with difficulty. Reactions of this type tend to be autocat-alytic. The initial rate is slow, due to the absence of the necessary linear interface, but the rate accelerates as more and more product is formed. See Refs. 147-153 for other examples. Ruckenstein [154] has discussed a kinetic model based on nucleation theory. There is certainly evidence that patches of product may be present, as in the oxidation of Mo(lOO) surfaces [155], and that surface defects are important [156]. There may be catalysis thus reaction VII-27 is catalyzed by water vapor [157]. A topotactic reaction is one where the product or products retain the external crystalline shape of the reactant crystal [158]. More often, however, there is a complicated morphology with pitting, cracking, and pore formation, as with calcium carbonate [159]. 

It would be difficult to over-estimate the extent to which the BET method has contributed to the development of those branches of physical chemistry such as heterogeneous catalysis, adsorption or particle size estimation, which involve finely divided or porous solids in all of these fields the BET surface area is a household phrase. But it is perhaps the very breadth of its scope which has led to a somewhat uncritical application of the method as a kind of infallible yardstick, and to a lack of appreciation of the nature of its basic assumptions or of the circumstances under which it may, or may not, be expected to yield a reliable result. This is particularly true of those solids which contain very fine pores and give rise to Langmuir-type isotherms, for the BET procedure may then give quite erroneous values for the surface area. If the pores are rather larger—tens to hundreds of Angstroms in width—the pore size distribution may be calculated from the adsorption isotherm of a vapour with the aid of the Kelvin equation, and within recent years a number of detailed procedures for carrying out the calculation have been put forward but all too often the limitations on the validity of the results, and the difficulty of interpretation in terms of the actual solid, tend to be insufficiently stressed or even entirely overlooked. And in the time-honoured method for the estimation of surface area from measurements of adsorption from solution, the complications introduced by... 

Structure Modification. Several types of stmctural defects or variants can occur which figure in adsorption and catalysis (/) surface defects due to termination of the crystal surface and hydrolysis of surface cations (2) stmctural defects due to imperfect stacking of the secondary units, which may result in blocked channels (J) ionic species, eg, OH , AIO 2, Na", SiO , may be left stranded in the stmcture during synthesis (4) the cation form, acting as the salt of a weak acid, hydrolyzes in aqueous suspension to produce free hydroxide and cations in solution and (5) hydroxyl groups in place of metal cations may be introduced by ammonium ion exchange, followed by thermal deammoniation. 

Catalytic Properties. In zeoHtes, catalysis takes place preferentially within the intracrystaUine voids. Catalytic reactions are affected by aperture size and type of channel system, through which reactants and products must diffuse. Modification techniques include ion exchange, variation of Si/A1 ratio, hydrothermal dealumination or stabilization, which produces Lewis acidity, introduction of acidic groups such as bridging Si(OH)Al, which impart Briimsted acidity, and introducing dispersed metal phases such as noble metals. In addition, the zeoHte framework stmcture determines shape-selective effects. Several types have been demonstrated including reactant selectivity, product selectivity, and restricted transition-state selectivity (28). Nonshape-selective surface activity is observed on very small crystals, and it may be desirable to poison these sites selectively, eg, with bulky heterocycHc compounds unable to penetrate the channel apertures, or by surface sdation. 

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