Crystal faces structure

Certain materials, most notably semiconductors, can be mechanically cleaved along a low-mdex crystal plane in situ in a UFIV chamber to produce an ordered surface without contamination. This is done using a sharp blade to slice tire sample along its preferred cleavage direction. For example. Si cleaves along the (111) plane, while III-V semiconductors cleave along the (110) plane. Note that the atomic structure of a cleaved surface is not necessarily the same as that of the same crystal face following treatment by IBA. 

Using single crystals it has been shown that different low-index crystal faces see Section 20) exhibit different corrosion rates. However, the relative corrosion rate of the different faces varies with the environment and these structural effects are of little practical significance. On the other hand, the fact that polycrystal grains of different crystallographic orientation may corrode at different rates, is of some importance. 

The main problem in the analysis of E vs. 0 plots is that the two quantities are usually measured independently on different samples. It may happen that the surface structure differs somewhat so that for the sample on which E is measured is different from that of the sample used in UHV experiments. This is especially the case with polycrystalline surfaces, whose structural reproducibility is occasional, but it is also the case with well-defined crystal faces if reconstruction phenomena are possible.60 The problem persists also in the absence ofreconstruction since the concentration and/or distribution of surface defects may be differ-... 

While from a structural point of view metal/solution and metal/vac-uum interfaces are qualitatively comparable even if quantitatively dissimilar, in the presence of ionic adsorbates the comparability is more difficult and is possible only if specific conditions are met.33 This is sketched in Fig. 7. A UHV metal surface with ions adsorbed on it is electrically neutral because of a counter-charge on the metal phase. These conditions cannot be compared with the condition of a = 0 in an electrochemical cell, but with the conditions in which the adsorbed charge is balanced by an equal and opposite charge on the metal surface, i.e., the condition of zero diffuse-layer charge. This is a further complication in comparing electrochemical and UHV conditions and has been pointed out in the case of Br adsorption on Ag single-crystal faces.88... 

In situ Fourier transform infrared and in situ infrared reflection spectroscopies have been used to study the electrical double layer structure and adsorption of various species at low-index single-crystal faces of Au, Pt, and other electrodes.206"210 It has been shown that if the ions in the solution have vibrational bands, it is possible to relate their excess density to the experimentally observed surface. 

K. The electrical double-layer structure at Ag single-crystal faces has been studied extensively.6,10,i5,22,24,32,61,63,75,ss, 149-151,177a, 188,250-... 

The value of Emin in the pseudo-stable state has been found to increase in the sequence (111) (100)single-crystal faces in aqueous solutions. It has been concluded that the Au-DMSO interactions vary much more with the atomic structure of the gold surface than the Au-H20 interactions and that the Au-DMSO interactions are stronger than forH20.477 Following Trasatti s relation,7 the values of A(<5 m - have been obtained for different planes of Au. It has been found that the difference (<5/M - S/s) for Au( 110) and Au( 111) planes is greater than 0.5 V.477 It should be noted that the same order of Au( 111) and Au(210) has been found in a 2.5 x 10-3 M KPF6 + AN solution.63,392,477... 

The influence of the surface pretreatment of Bi single-crystal faces has been studied, and a noticeable dependence of Ea=0 on the surface structure has been established.152,133... 

The main problem in Eas0 vs. correlations is that the two experimental quantities are as a rule measured in different laboratories with different techniques. In view of the sensitivity of both parameters to the surface state of the metal, their uncertainties can in principle result of the same order of magnitude as AX between two metals. On the other hand, it is rare that the same laboratory is equipped for measuring both single-crystal face is not followed by a check of its perfection by means of appropriate spectroscopic techniques. In these cases we actually have nominal single-crystal faces. This is probably the reason for the observation of some discrepancies between differently prepared samples with the same nominal surface structure. Fortunately, there have been a few cases in which both Ea=0 and 0 have been measured in the same laboratory these will be examined later. Such measurements have enabled the resolution of controversies that have long persisted because of the basic criticism of Eazm0 vs. 0 plots. 

Almost all that is known about the crystal face specificity of double-layer parameters has been obtained from studies with metal single-crystal faces in aqueous solutions. Studies in nonaqueous solvents would be welcome to obtain a better understanding of the influence of the crystallographic structure of metal surfaces on the orientation of solvent molecules at the interface in relation to their molecular properties. 

A crystalline solid is a solid in which the atoms, ions, or molecules lie in an orderly array (Fig. 5.16). A crystalline solid has long-range order. An amorphous solid is one in which the atoms, ions, or molecules lie in a random jumble, as in butter, rubber, and glass (Fig. 5.17). An amorphous solid has a structure like that of a frozen instant in the life of a liquid, with only short-range order. Crystalline solids typically have flat, well-defined planar surfaces called crystal faces, which lie at definite angles to one another. These faces are formed by orderly layers of atoms (Box 5.1). Amorphous solids do not have well-defined faces unless they have been molded or cut. 

Except for support effects, structure sensitivity has usually appeared in one of two aspects, variation of rate with svirface crystal face or with particle size. In ICC 1 Gwathmey reported in one of the first experiments with single crystal faces that different faces machined fi om Ni single crystal spheres catalyzed the hydrogenation of ethylene at different rates (ICC 1 paper 5). 

FIGURE 14.11 a) Structure of a growing crystal face (i>) face growing on a lattice with a... 

The structure of growing crystal faces is inhomogeneous (Fig. 14.11a). In addition to the lattice planes (1), it featnres steps (2) of a growing new two-dimensional metal layer (of atomic thickness), as well as kinks (3) formed by the one-dimensional row of metal atoms growing along the step. Lattice plane holes (4) and edge vacancies (5) can develop when nniform nucleus growth is disrupted. 

A wide variety of solid materials are used in catalytic processes. Generally, the (surface) structure of metal and supported metal catalysts is relatively simple. For that reason, we will first focus on metal catalysts. Supported metal catalysts are produced in many forms. Often, their preparation involves impregnation or ion exchange, followed by calcination and reduction. Depending on the conditions quite different catalyst systems are produced. When crystalline sizes are not very small, typically > 5 nm, the metal crystals behave like bulk crystals with similar crystal faces. However, in catalysis smaller particles are often used. They are referred to as crystallites , aggregates , or clusters . When the dimensions are not known we will refer to them as particles . In principle, the structure of oxidic catalysts is more complex than that of metal catalysts. The surface often contains different types of active sites a combination of acid and basic sites on one catalyst is quite common. 

Van Hove MA, Koestner RJ, Stair PC, Biberian IP Kesmodel LL, Bartos I, Somorjai GA. 1981. The surface reconstructions of the (100) crystal faces of iridium, platinum and gold, 1. Experimental-observations and possible structural models. Surf Sci 103 189-217. 

Solid metal electrodes with a crystalline structure are different. The crystal faces forming the surface of these electrodes are not ideal planes but always contain steps (Fig. 5.24). Although equilibrium thermal roughening corresponds to temperatures relatively close to the melting point, steps are a common phenomenon, even at room temperature. A kink half-crystal position—Fig. 5.24c) is formed at the point where one step ends and the... 

The electrocrystallization on an identical metal substrate is the slowest process of this type. Faster processes which are also much more frequent, are connected with ubiquitous defects in the crystal lattice, in particular with the screw dislocations (Fig. 5.25). As a result of the helical structure of the defect, a monoatomic step originates from the point where the new dislocation line intersects the surface of the crystal face. It can be seen in Fig. 5.48 that the wedge-shaped step gradually fills up during electrocrystallization after completion it slowly moves across the crystal face and winds up into a spiral. The resultant progressive spiral cannot disappear from the crystal surface and thus provides a sufficient number of growth... 

The adsorption of cyclohexene, cyclohexane, 1,3-cyclohexadiene, 1,4-cyclohexadiene, and benzene on Pt(l 11) was studied with STM [35, 36]. Figure 7.20a shows an STM image of 2 x 10-s Torr cyclohexene on Pt(l 11). The low-pressure structure shows a hexagonal symmetry with a periodicity of approximately 7 A that is rotated approximately 18-20° with respect to the [1 1 0] direction of the Pt crystal face. From prior... 

It may be noted that the statement made above—that the surface potential in the electrolyte phase does not depend on the orientation of the crystal face—is necessarily an assumption, as is the neglect of S s1- It is another example of separation of metal and electrolyte contributions to a property of the interface, which can only be done theoretically. In fact, a recent article29 has discussed the influence of the atomic structure of the metal surface for solid metals on the water dipoles of the compact layer. Different crystal faces can allow different degrees of interpenetration of species of the electrolyte and the metal surface layer. Nonuniformities in the directions parallel to the surface may be reflected in the results of capacitance measurements, as well as optical measurements. 

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