Nickel surface structure

Figure 4.6 Chemisorption of sulphur on nickel surface structures observed by STM Besenbacherefa/. [51] [425]. Reproduced with the permission of the authors.

Figure Bl.19.14. A sequence of STM images taken during tire construction of a patterned array of xenon atoms on a Ni(lOO) surface. Grey scale is assigned according to the slope of the surface. The atomic structure of the nickel surface is not resolved. Each letter is 5 mn from top to bottom. (Taken from [ ], figure 1.)...

An effect which is frequently encountered in oxide catalysts is that of promoters on the activity. An example of this is the small addition of lidrium oxide, Li20 which promotes, or increases, the catalytic activity of dre alkaline earth oxide BaO. Although little is known about the exact role of lithium on the surface structure of BaO, it would seem plausible that this effect is due to the introduction of more oxygen vacancies on the surface. This effect is well known in the chemistry of solid oxides. For example, the addition of lithium oxide to nickel oxide, in which a solid solution is formed, causes an increase in the concentration of dre major point defect which is the Ni + ion. Since the valency of dre cation in dre alkaline earth oxides can only take the value two the incorporation of lithium oxide in solid solution can only lead to oxygen vacaircy formation. Schematic equations for the two processes are... 

Worch, H., Garz, 1. and Schott, W., Influence of Surface Structure and Chemical Composition on the Pitting Corrosion of Nickel Single Crystals , Werkst. Korros., 24, 872 (1973) C.A., 80, 90185... 

Newton s second law, L0 nickel, 49, 665 nickel arsenide structure, 201 nickel surface, 189 nickel tetracarbonyl, 665 nickel-metal hydride cell, 520 NiMH cell, 520 nitrate ion, 69, 99 nitration, 745 nitric acid, 629 nitric oxide, 73, 629 oxidation, 549 nitride, 627 nitriding, 208 nitrite ion, 102 nitrogen, 120, 624 bonding in, 108 configuration, 35 photoelectron spectrum, 120... 

Before any attempt to establish a correlation between the surface structure of the oxidized alloys and their CO conversion activity one must stress that the surface composition of the samples under reaction conditions may not necessarily be Identical to that determined from ESCA data. Moreover, surface nickel content estimates from ESCA relative Intensity measurements are at best seml-quantlta-tlve. This can be readily rationalized If one takes Into consideration ESCA finite escape depth, the dependence of ESCA Intensity ratio... 

A part of Figure 3 in Ref. 207, reproduced on the right, reports radial EXAFS data around the S Is absorption edge for sulfur adsorbed on the (100) plane of a g nickel single-crystal surface. The top trace corresponds to the deposition of atomic S sulfur by dehydrogenation of H2S, while g, the bottom data were obtained by adsorb- M ing thiophene on the clean surface at 100 K. Based on these data, what can be learned about the adsorption geometry of thiophene Propose a local structure for the sulfur atoms in reference to the neighboring nickel surface. 

Fig. 5. Ni(7 911) with adsorbed CO. (a) Proposed structure. The open circles represent Ni atoms and the shaded circles are CO molecules. The numbers refer to the incident azimuthal angle of the primary ion. (b) NiCO intensity versus azimuthal angle of the bombarding Ar ion. The nickel surface was exposed to 0.6 L of CO. The solid line represents the experimental data and the dashed line results from the classical dynamical calculation. The additional peak at = 60° is not yet...

The above findings indicate that two kinds of surface structures exist even on the surface of HNi and one kind can be removed by pretreatment with hydroxy acid. On the surface of RNi, aluminum does not directly participate in the formation of the differentiating site, but must participate in the formation of the surface structure of nickel which is removed by the pretreatment with hydroxy acid. 

In some cases, the step sites have different chemistry, i.e., they break chemical bonds, thereby producing new chemical species on the surface. This happens for example during NO adsorption on a stepped platinum surface l In this circumstance the step effect on ordering is through the new types of chemistry introduced by the presence of steps. Hydrocarbons for example dissociate readily at stepped surfaces of platinum or nickel while this occurs much more slowly on the low Miller-Index surfaces in the absence of a large concentration of steps As a result ordered hydrocarbon surface structures cannot be formed on the stepped surfaces of these metals while they can be produced on the low Miller-Index surfaces. 

So far, the bonding and surface structure aspects of electrocatalysis have been presented in a somewhat abstract sort of way. In order to make electrocatalysis a little more real, it is helpful to go through an example—that of the catalysis of the evolution of oxygen from alkaline solutions onto substances called perovskites. Such materials are given by the general formula RT03, where R is a rare earth element such as lanthanum, and T is a transition metal such as nickel. In the electron catalysis studied, the lattice of the perovskite crystal was replicated with various transition metals, i.e., Ni, Co, Fe, Mn, and Cr, the R remaining always La. 

It is clear that the influence of surface geometry upon catalytic activity is extremely complex and many more studies are required before any definitive relationship between catalytic activity and metal particle size can be established. Such studies will require to take cognisance of such factors as the perturbation of surface structure due to the formation of carbidic residues, as noted by Boudart [289] and by Thomson and Webb [95], and by the modification of catalytic properties on adsorption, as noted by Izumi et al. [296—298] and by Groenewegen and Sachtler [299] in studies of the modification of nickel catalysts for enantioselective hydrogenation. Possible effects of the support, as will be discussed in Sect. 6.3, must also be taken into account. 

The oxidation of carbon monoxide on nickel oxide has often been investigated (4, 6, 8, 9, II, 16, 17, 21, 22, 26, 27, 29, 32, 33, 36) with attempts to correlate the changes in the apparent activation energy with the modification of the electronic structure of the catalyst. Published results are not in agreement (6,11,21,22,26,27,32,33). Some discrepancies would be caused by the different temperature ranges used (27). However, the preparation and the pretreatments of nickel oxide were, in many cases, different, and consequently the surface structure of the catalysts—i.e., their composition and the nature and concentration of surface defects— were probably different. Therefore, an explanation of the disagreement may be that the surface structure of the semiconducting catalyst (and not only its surface or bulk electronic properties) influences its activity. 

The influence of the surface structure upon the catalytic activity is likely to be particularly important in the case of finely divided nickel oxides, prepared at a moderate temperature, which present catalytic activity for this reaction at room temperature. In a previous work, we studied the room-temperature oxidation of carbon monoxide on nickel oxide prepared by dehydration of the hydroxide under vacuum (p = 10"6 torr) at 200°C., by means of a microcalorimetric technique (8, 20). The object of this work is to re-investigate, by the same method, the mechanism of the same reaction on a nickel oxide prepared at 250°C. [NiO(250)] instead of 200°C. [NiO(200)]. 

It has been shown experimentally that ethene combines exothermically (AH° = —60 kcal mole-1) and reversibly with a metal surface. Although the precise structure of the ethene-nickel complex is unknown, the bonding to nickel must involve the electrons of the double bond because saturated hydrocarbons, such as ethane, combine only weakly with the nickel surface. A possible structure with carbon-nickel cr bonds is shown in Figure 11-1. 

Anodic oxidation of a nickel electrode will give a surface structure that can be represented as Ni—surface—Ox Hy (A). Reaction with, say, a dichiorosilane will then follow (equation 29) ... 

The adsorption of albumin from aqueous solution onto copper and nickel films and the adsorption of B-lactoglobulin, gum arabic, and alginic acid onto germanium were studied. Thin metallic films (3-4 nm) were deposited onto germanium internal reflection elements by physical vapor deposition. Transmission electron microscopy studies indicated that the deposits were full density. Substrate temperature strongly Influenced the surface structure of the metal deposits. Protein and/or polysaccharide were adsorbed onto the solid substrates from flowing... 

Characterization of the Surfaces of Catalysts Measurements of the Density of Surface Faces for High Surface Area Supports. - It has always been a tenet of theories of catalysis that certain reactions will proceed at different rates on different surface planes of the same crystal. Experiments with metal single crystals have vindicated this view by showing that the rate of hydrogenolysis of ethane on a nickel surface will vary from one plane to another. In contrast the rate of methanation remains constant for the same planes.4 Because of this structure sensitivity of catalytic processes there is a requirement for methods of determining the number of each of the different planes which a catalyst and its support may expose at their surfaces. Electron microscopy studies of 5nm Pt particles supported upon graphite show them to be cubo-octahedra with surfaces bound by (111) and (100) planes.5 Similar studies of Pd and Pt prepared by evaporation reveal square pyramids of size 60-200 A bounded by incomplete (111) faces.6... 

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