Nitrogen oxide chemisorption

Numerous quantum mechanic calculations have been carried out to better understand the bonding of nitrogen oxide on transition metal surfaces. For instance, the group of Sautet et al have reported a comparative density-functional theory (DFT) study of the chemisorption and dissociation of NO molecules on the close-packed (111), the more open (100), and the stepped (511) surfaces of palladium and rhodium to estimate both energetics and kinetics of the reaction pathways [75], The structure sensitivity of the adsorption was found to correlate well with catalytic activity, as estimated from the calculated dissociation rate constants at 300 K. The latter were found to agree with numerous experimental observations, with (111) facets rather inactive towards NO dissociation and stepped surfaces far more active, and to follow the sequence Rh(100) > terraces in Rh(511) > steps in Rh(511) > steps in Pd(511) > Rh(lll) > Pd(100) > terraces in Pd (511) > Pd (111). The effect of the steps on activity was found to be clearly favorable on the Pd(511) surface but unfavorable on the Rh(511) surface, perhaps explaining the difference in activity between the two metals. The influence of... 

TABLE XI. Carbon Monoxide, Di-Nitrogen and Nitric Oxide Chemisorption on Metals... 

Total smface areas were measured by nitrogen adsorption at -196 C, using an automated instrument (Omnisorp lOOCX, Coulter Electronics Limited). The cross sectional area of the nitrogen molecule was assumed to be 16.2 x 10 m. Pore type and volume data were also obtained by this method, using t-plot analysis. Metal areas were measured by selective chemisorption of hydrogen at 30 °C in the same instrument. Copper surface areas were measured in a flow system by nitrous oxide chemisorption at 60 C. 

V.I. Tsivenko, Investigation of Chemisorption of Nitrogen Atoms on Semiconductor Oxides of Metals, Doctorate thesis (Chemistry), Moscow, 1971. 

Of crucial significance in deciding between various models have been estimates of the number of copper atoms required to transform the surface into a (2 x 3)N phase. This was the approach adopted by Takehiro et al 2 in their study of NO dissociation at Cu(110). They concluded that by determining the stoichiometry of the (2 x 3)N phase that there is good evidence for a pseudo-(100) model, where a Cu(ll0) row penetrates into the surface layer per three [ll0]Cu surface rows. It is the formation of the five-coordinated N atoms that drives the reconstruction. The authors are of the view that their observations are inconsistent with the added-row model. The structure of the (2 x 3)N phase produced by implantation of nitrogen atoms appears to be identical with that formed by the dissociative chemisorption of nitric oxide. 

Results of Hydrogen Chemisorption/Pulse Reoxidation Measurements over Activated Silica-Supported Cobalt Catalysts Calcined at 350°C Using either Flowing Air or 5% Nitric Oxide in Nitrogen... 

Clearly the molecular events with iron were complex even at 80 K and low NO pressure, and in order to unravel details we chose to study NO adsorption on copper (42), a metal known to be considerably less reactive in chemisorption than iron. It was anticipated, by analogy with carbon monoxide, that nitric oxide would be molecularly adsorbed on copper at 80 K. This, however, was shown to be incorrect (43), and by contrast it was established that the molecule not only dissociated at 80 K, but NjO was generated catalytically within the adlayer. On warming the adlayer formed at 80 K to 295 K, the surface consisted entirely of chemisorbed oxygen with no evidence for nitrogen adatoms. It was the absence of nitrogen adatoms [with their characteristic N(ls) value] at both 80 and 295 K that misled us (43) initially to suggest that adsorption was entirely molecular at 80 K. 

Br0nsted acid sites depends on the structure of the amine. Chemisorption data for amorphous oxides (54) show that 2,6-dimethylpyridine (which contains methyl groups that hinder coordination of the nitrogen atom with Lewis acids) is a more selective reagent for the determination of Br0nsted acidity than an unhindered amine such as pyridine. Jacobs and Heylen (44) arrived at a similar conclusion on the basis of an infrared study of amines chemisorbed on Y zeolite. They also found that the poisoning effectiveness of 2,6-dimethylpyridine is much greater than that of pyridine for the catalytic titration of Y zeolite. 

The surface hydrides, surface oxides, and other surface compounds, mentioned above, need not be formed by the action of free atoms with free valencies on metal surfaces, but, just as in normal chemical reactions, these compounds may result from the reaction of the metal surfaces with molecules. The chemisorption of an H2 molecule on a metal surface may lead to the chemisorption of two separate hydrogen atoms and so may the action of an 02 molecule on a metal surface lead to the chemisorption of two oxygen atoms, the action of an N2 molecule to the chemisorption of two nitrogen atoms, etc. Surface hydrides, oxides, and nitrides are, then, the result of normal chemical reactions of these gases with the surfaces of the metals. 

Sulfur compounds adsorb onto surface-active metal (or metal oxide) sites, causing deactivation in a large number of petroleum, petrochemical, and chemical catalytic applications. Acidic catalysts such as zeolites and promoted aluminas are poisoned by nitrogen compounds by chemisorption onto active sites also located on the surface. 

Metals or metal alloys are suitable as ammonia catalysts - especially those metals in the transition-metal group. Metals or metal compounds whose chemisorption energy of nitrogen is neither too high nor too low show the greatest effectiveness. Most catalysts are complex and contain other metal oxides that are hard to reduce. This promotes the activity of metallic iron74. 

The chemisorption and reactivity of the oxides of nitrogen on metal surfaces are of great environmental interest because of their connection to the reaction with carbon monoxide, leading to innocuous products, e.g. 

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