Activity phases

A piezo-composite consists of a piezoelectric active phase and a passive plastic phase [2]. In the 1-3-configuration adopted in our case, piezoelectric rods parallely aligned in thickness direction are imbedded in a three-dimensional plastic matrix (Fig. 1). The distance between the rods has to be chosen inferior to the half wave length of the shear wave in the matrix material ensuring that the whole compound is vibrating as a quasi-homogeneous material. 

Chen C-FI, Washburn N and Gewirth A A 1993 In situ atomic force microscope study of Pb underpotential deposition on Au(111) Structural properties of the catalytically active phase J.Phys. Chem. 97 9754-60... 

Composite Devices. Composites made of active-phase PZT and polymer-matrix phase are used for the hydrophone and medical imaging devices (see Composite materials, polymer-matrix Imaging technology). A usehil figure of merit for hydrophone materials is the product of hydrostatic strain coefficient dj and hydrostatic voltage coefficient gj where gj is related to the dj coefficient by (74)... 

The catalyst used in the production of maleic anhydride from butane is vanadium—phosphoms—oxide (VPO). Several routes may be used to prepare the catalyst (123), but the route favored by industry involves the reaction of vanadium(V) oxide [1314-62-1] and phosphoric acid [7664-38-2] to form vanadyl hydrogen phosphate, VOHPO O.5H2O. This material is then heated to eliminate water from the stmcture and irreversibly form vanadyl pyrophosphate, (V(123,124). Vanadyl pyrophosphate is befleved to be the catalyticaHy active phase required for the conversion of butane to maleic anhydride (125,126). 

An additional effect of the use of an organic medium in the catalyst preparation is creation of mote defects in the crystalline lattice when compared to a catalyst made by the aqueous route (123). These defects persist in the active phase and are thought to result in creation of strong Lewis acid sites on the surface of the catalysts (123,127). These sites ate viewed as being responsible for the activation of butane on the catalyst surface by means of abstraction of a hydrogen atom. 

Promoters are sometimes added to the vanadium phosphoms oxide (VPO) catalyst during synthesis (129,130) to increase its overall activity and/or selectivity. Promoters may be added during formation of the catalyst precursor (VOHPO O.5H2O), or impregnated onto the surface of the precursor before transformation into its activated phase. They ate thought to play a twofold stmctural role in the catalyst (130). First, promoters facilitate transformation of the catalyst precursor into the desired vanadium phosphoms oxide active phase, while decreasing the amount of nonselective VPO phases in the catalyst. The second role of promoters is to participate in formation of a soHd solution which controls the activity of the catalyst. 

The bulk stmcture of the catalyticaHy active phase is not completely known and is under debate in the Hterature (125,131—133). The central point of controversy is whether (Valone or in combination with other phases is the most catalyticaHy active for the conversion of butane to maleic anhydride. The heart of this issue concerns the role of stmctural disorder in the bulk and how it arises in the catalyst (125,134,135). Most researchers agree that the catalysts with the highest activity and selectivity ate composed mainly of (Vthat exhibits a clustered or distorted platelet morphology (125). It is also generaHy acknowledged that during operation of the catalyst, the bulk oxidation state of the vanadium in the catalyst remains very close to the +4 valence state (125). 

Benzene-Based Catalyst Technology. The catalyst used for the conversion of ben2ene to maleic anhydride consists of supported vanadium oxide [11099-11-9]. The support is an inert oxide such as kieselguhr, alumina [1344-28-17, or sUica, and is of low surface area (142). Supports with higher surface area adversely affect conversion of benzene to maleic anhydride. The conversion of benzene to maleic anhydride is a less complex oxidation than the conversion of butane, so higher catalyst selectivities are obtained. The vanadium oxide on the surface of the support is often modified with molybdenum oxides. There is approximately 70% vanadium oxide and 30% molybdenum oxide [11098-99-0] in the active phase for these fixed-bed catalysts (143). The molybdenum oxide is thought to form either a soUd solution or compound oxide with the vanadium oxide and result in a more active catalyst (142). 

Industrial catalysts are typically complex in composition and stmcture. CatalyticaHy active phases, supports, binders, and promoters comprise the components of the catalyst. 

Most catalyst supports are simply nearly inert platforms that help stabilize the dispersion of the catalyticaHy active phase. Sometimes, however, the supports play a direct catalytic role, as exemplified by the alumina used in supported Pt and RePt catalysts for naphtha reforming. 

In service, supported catalysts frequentiy undergo loss of activity over a period of time. In many cases, such catalyst deactivation is accompanied by the loss of accessible surface area of the active phase by sintering, by the accumulation of poisons, or by conversion of active sites to inactive species. 

There are other methods of preparation that iavolve estabhshing an active phase on a support phase, such as ion exchange, chemical reactions, vapor deposition, and diffusion coating (26). For example, of the two primary types of propylene polymerization catalysts containing titanium supported on a magnesium haUde, one is manufactured usiag wet-chemical methods (27) and the other is manufactured by ball milling the components (28). 

When catalysts are used in a highly exothermic reaction, an active phase may be diluted with an inert material to help dissipate heat and moderate the reaction. This technique is practiced in the commercial oxychlorination of ethylene to dichloroethane, where an alumina-supported copper haUde catalyst is mixed with a low surface area inert diluent. 

This catalyst is noteworthy in that it represents a good example of a Hquid active phase, actually molten at the typical 600° C+ process temperatures, supported on a soHd support. 

The active phase, which is soHd at room temperature, is comprised of mixed potassium and sodium vanadates and pyrosulfates, whereas the support is macroporous siUca, usually in the form of 6—12 mm diameter rings or pellets. The patent Hterature describes a number of ways to prepare the catalyst a typical example contains 7 wt % vanadium pentoxide, 8% potassium added as potassium hydroxide or carbonate, 1% sodium, and 78 wt % siUca, added as diatomaceous earth or siUca gel, formed into rings, and calcined in the presence of sulfur dioxide or sulfur trioxide to convert a portion of the alkah metal salts into various pyrosulfates (81,82). 

In principle the selective dissolution of the less noble component of a singlephase alloy would perhaps be expected and is in fact observed (dezincification of an a-brass, etc.) even though the details of the mechanism by which it occurs is not yet fully understood. In contrast, the preferential attack of the less noble phase of a two-phase alloy is not only expected and observed —the mechanism by which it occurs in practice is also quite clear. Selective dissolution of the more active phase of a two-phase alloy is best exemplified by the graphitic corrosion (or graphitisation) of grey cast iron. 

Elec- Active Phase Potential- Working Selectivity coefficient1 Recom- Tempe- Electrical Recom- Manufacturer ... 

Since the catalytically active phase is frequently quite expensive (e.g. noble metals) it is clear that it is in principle advantageous to prepare catalysts with high, approaching 100%, catalyst dispersion Dc. This can be usually accomplished without much difficulty by impregnating the porous carrier with an aqueous solution of a soluble compound (acid or salt) of the active metal followed by drying, calcination and reduction.1... 

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. 

The second phenomenon, i.e. the change in catalytic activity or selectivity of the active phase with varying catalyst support, is usually termed metal-support interaction. It manifests itself even when the active phase has the same dispersion or average crystallite size on different... 

In all these cases the support has a dramatic effect on the activity and selectivity of the active phase. In classical terminology all these are Schwab effects of the second kind where an oxide affects the properties of a metal. Schwab effects of the first kind , where a metal affects the catalytic properties of a catalytic oxide, are less common although in the case of the Au/Sn02 oxidation catalysts9,10 it appears that most of the catalytic action takes place at the metal-oxide-gas three phase boundaries. 

Most of the electrochemical promotion studies surveyed in this book have been carried out with active catalyst films deposited on solid electrolytes. These films, typically 1 to 10 pm in thickness, consist of catalyst grains (crystallites) typically 0.1 to 1 pm in diameter. Even a diameter of 0.1 pm corresponds to many (-300) atom diameters, assuming an atomic diameter of 3-10 10 m. This means that the active phase dispersion, Dc, as already discussed in Chapter 11, which expresses the fraction of the active phase atoms which are on the surface, and which for spherical particles can be approximated by ... 

This problem can in many cases be overcome by dispersing the active phase on an electronically conductive material (Fig. 12.1). There have been already at least three experimental studies,7 1215 surveyed here and demonstrating this concept. 

Two cases of electrochemical promotion of commercial catalysts have been very recently reported in the literature and, not too surprisingly, in both cases the active phase was conductive, electronically or ionically. 

But, the increasing of the yields, in this case, shows that the catalytic cycle does not involve any radical species which can be trapped. Therefore the hydroquinone inhibition is probably connected with a sensitive redox process in the activation phase. 

Acne in active phase (papulo-pustular lesions) (Fig. 5.2a, b)... 

In the case of a catalytic membrane reactor (CMR), the membrane is (made) intrinsically catalytically active. This can be done by using the intrinsic catalytic properties of the zeolite or by making the membrane catalytically active. When an active phase is deposited on top of a membrane layer, this is also called a CMR because this becomes part of the composite membrane. In addition to the catalytic activity of the membrane, a catalyst bed can be present (PBCMR). The advantages of a CMR are as follows ... 

Apart from the above described core-shell catalysts, it is also possible to coat active phases other than zeolite crystals, like metal nanoparticles, as demonstrated by van der Puil et al. [46]. More examples of applications on the micro level are given in Section 10.5, where microreactors and sensor apphcations are discussed. 

Data from Hasegawa et at. (1992). Determined by hplc on an optically active phase, "rt = room temperature. 

These are a elass of lymphoeytes thought to be distinet from helper and eytolytic T eells. Their funetion is to inhibit the activation phase of the immune responses. Their existenee as a distinet population of cells has been doubted by many investigators, but they may be lymphoeytes that can inhibit immune responses in different ways. 

In conclusion, XPS is among the most frequently used techniques in characterizing catalysts. It readily provides the composition of the surface region and also reveals information on both the oxidation state of metals and the electronegativity of any ligands. XPS can also provide insight into the dispersion of particles over supports, vrhich is particularly useful if the more common techniques employed for this purpose, such as electron microscopy or hydrogen chemisorption, can not discriminate between support and active phase. 

---