Nickel catalysts surface structures

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... 

Vanadium also promotes dehydrogenation reactions, but less than nickel. Vanadium s contribution to hydrogen yield is 20% to 50% of nickel s contribution, but vanadium is a more severe poison. Unlike nickel, vanadium does not stay on the surface of the catalyst. Instead, it migrates to the inner (zeolite) part of the catalyst and destroys the zeolite crystal structure. Catalyst surface area and activity are permanently lost. 

The single crystal results are compared in Fig. 2 with three sets of data taken from Ref. 13 for nickel supported on alumina, a high surface area catalyst. This comparison shows extraordinary similarities in kinetic data taken under nearly identical conditions. Thus, for the Hj-CO reaction over nickel, there is no significant variation in the specific reaction rates or the activation energy as the catalyst changes from small metal particles to bulk single crystals. These data provide convincing evidence that the methanation reaction rate is indeed structure insensitive on nickel catalysts. 

Nickel and other transition metal catalysts, when modified with a chiral compound such as (R,R)-tartaric acid 5S), become enantioselective. All attempts to modify solid surfaces with optically active substances have so far resulted in catalysts of only low stereoselectivity. This is due to the fact that too many active centers of different structures are present on the surface of the catalysts. Consequently, in asymmetric hydrogenations the technique of homogeneous catalysis is superior to heterogeneous catalysis56). However, some carbonyl compounds have been hydrogenated in the presence of tartaric-acid-supported nickel catalysts in up to 92% optical purity55 . 

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. 

Nature of Active Sites. There is no apparent correlation between the increase of catalytic activity and a modification of the electronic structure of nickel oxide, since the electrical properties of both catalysts are identical. It is probable that local modifications of the nickel oxide surface are responsible for the change of its activity and of the reaction mechanism. It should be possible to associate these structural modification with local modifications of the height of the Fermi level, but it would be difficult to explain the results by the electronic theory of catalysis which considers only collective electrons or holes. A discussion based only on the influence of surface defects seems, therefore, to be more straightforward. 

The best example of a study of this type of intermediate is found in the oxidation of CO over a nickel-nickel oxide catalyst 24). The latter term is used because there is doubt as to the specific nature of the catalyst surface. The spectrum in Fig. 14 was obtained during the oxidation of CO over nickel-nickel oxide at 35° C. The band at 4.56 u is tentatively attributed to an intermediate complex having the structure Ni- 0 C rr.O. The bands at 6.5 and 7.2 u are due to C02 chemisorbed on the catalyst surface. This C02 is considered to be adsorbed product rather than as a reaction intermediate because these bands remain after the reaction is completed. The 4.56- u band in Fig. 14 is attributed to the asymmetrical 0—C—0 vibration rather than to the C—O vibration of chemisorbed CO. This interpretation implies that there should be a second band due to the symmetrical vibration. The symmetrical 0—C—O vibration of C02 produces a Raman band at 7.2 ju. The symmetrical 0—C—0 vibration of Ni - -O—C=0 would be expected to produce an infrared band near 6 or 7 u- Thus far this band has not been observed. This failure is not considered a serious obstacle to the structure assignment,... 

Metallic monoliths made of both rhodium ([HCR 1]) and FeCrAlloy (72.6% Fe, 22% Cr and 4.8% Al ([HCR 3]) carrying micro channels of 120 pm x 130 pm cross-section at various length (5 and 20 mm) were applied. The monoliths were prepared of micro structured foils by electron beam welding. After bonding, the FeCrAlloy was oxidized in air at 1 000 °C for 4 h to form an a-alumina layer, which was verified by XRD. Its thickness was determined as < 10 pm by SEM/EDX. The alumina layer was impregnated with rhodium chloride and alternatively with a nickel salt solution. The catalyst loading with nickel (30 mg) was much higher than that with rhodium (1 mg) (see Table 2.4). The amount of rhodium on the catalyst surface was determined as 3% by XPS. 

XPS and TEM measurements indicate that after fluorination, zinc and nickel, on the surface of these catalysts is present as ZnF2 or NiF2, respectively and these findings support the idea that the Zn(II) and Ni(II) species on doped fluorinated chromias do not become integrated into the surface structure but are, in fact, distinct phases on the surface. 

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