Reactive surfaces

Perez R, Payne M C, Stich i and Terakura K 1997 Roie of covaient tip-surface interactions in noncontact atomic force microscopy on reactive surfaces Phys. Rev. Lett. 78 678... 

Chemically the Hquid NaK alloy, usually used as a dispersion and on an inert support, provides more reactive surface area than either potassium or sodium metal alone, thus enhancing the reducing reactivity and permitting reactions to proceed atlower (eg, —12°C) temperatures. NaK alloys are suitable for chemical reactions involving unstable intermediates such as carbanions and free radicals. 

Commercial spectrometers are usually bakeable, can reach ultrahigh-vacuum pressures of better than 10" Torr, and have fast-entry load-lock systems for inserting samples. The reason for the ultrahigh-vacuum design, which increases cost considerably, is that reactive surfaces, e.g., clean metals, contaminate rapidly in poor vacuum (1 atomic layer in 1 s at 10 Torr). If the purpose of the spectrometer is to always look at as-inserted samples, which are already contaminated, or to examine rather unreactive surfaces (e.g., polymers) vacuum conditions can be relaxed considerably. 

Raman spectroscopy has provided information on catalytically active transition metal oxide species (e. g. V, Nb, Cr, Mo, W, and Re) present on the surface of different oxide supports (e.g. alumina, titania, zirconia, niobia, and silica). The structures of the surface metal oxide species were reflected in the terminal M=0 and bridging M-O-M vibrations. The location of the surface metal oxide species on the oxide supports was determined by monitoring the specific surface hydroxyls of the support that were being titrated. The surface coverage of the metal oxide species on the oxide supports could be quantitatively obtained, because at monolayer coverage all the reactive surface hydroxyls were titrated and additional metal oxide resulted in the formation of crystalline metal oxide particles. The nature of surface Lewis and Bronsted acid sites in supported metal oxide catalysts has been determined by adsorbing probe mole-... 

The relatively low temperature rise of during plating allows the coating of temperature-sensitive materials. Furthermore, composite articles, even those having porous and otherwise reactive surfaces, can be successfully plated. 

The synthesis of end functional polymers by NMP, ATRP and RAFT has already been discussed in Section 9.7. The "grafting to approach involves the covalent attachment of an end-funetionalized polymer with reactive surface groups on the substrate. The approach is inherently limited by the crowding of chains at the surface and the limit this places on the final graft density. 

While it is inherently probable that product formation will be most readily initiated at sites of effective contact between reactants (A IB), it is improbable that this process alone is capable of permitting continued product formation at low temperature for two related reasons. Firstly (as discussed in detail in Sect. 2.1.1) the area available for chemical contact in a mixture of particles is a very small fraction of the total surface (and, indeed, this total surface constitutes only a small proportion of the reactant present). Secondly, bulk diffusion across a barrier layer is usually an activated process, so that interposition of product between the points of initial contact reduces the ease, and therefore the rate, of interaction. On completion of the first step in the reaction, the restricted zones of direct contact have undergone chemical modification and the continuation of reaction necessitates a transport process to maintain the migration of material from one solid to a reactive surface of the other. On increasing the temperature, surface migration usually becomes appreciable at temperatures significantly below those required for the onset of bulk diffusion within a product phase. It is to be expected that components of the less refractory constituent will migrate onto the surfaces of the other solid present. These ions are chemisorbed as the first step in product formation and, in a subsequent process, penetrate the outer layers of the... 

A very useful analysis of catalytic reactions is provided for by the construction of so-caUed volcano plots (Figure 1.2). In a volcano plot, the catalytic rate of a reaction normahzed per unit reactive surface area is plotted as a function of the adsorption energy of the reactant, product molecule, or reaction intermediates. 

It was previously reported that magnesium oxide with a moderate basicity formed reactive surface carbonate species, which reacted with carbon deposited on foe support by foe methane decjomposition [6]. Upon addition of Mg to foe Ni/HY catalyst, reactive carbonate was formed on magnesium oxide and carbon dioxide could be activated more easily on the Mg-promoted Ni/HY catal t. Reactive carbonate species played an important role in inhibiting foe carbon deposition on the catalyst surface. 

In general, the increase of preparation or calcination temperature helps to increase the crystallite size of anatase titania. However, anatase phase is thennally unstable and is easily converted to rutile phase. Moreover, reactive surface area decreases with increasing the... 

Zeolites have reactive surfaces, o ving to the incorporation of AP" on sites vhere normally a Si" " ion resides. This property, in addition to the crystalline system of micropores, enables several applications of zeolites, e.g. in... 

AES and TPD on these surfaces confirm that the reactive surface contains less than a monolayer of carbon while the unreactlve surface has multilayers of carbon. 

To confirm this formation of reactive surface oxygen species and oxygen vacancies, thermoprogrammed oxidations and reductions have been performed on Pd/Zr02. 

Polyelectrolytes form the basis of those modern cements which are distinguished by their ability to adhere to reactive surfaces. At present the main use of such cements lies in the medical field, principally in dental surgery. They adhere permanently to biological surfaces where they have to withstand adverse conditions of wetness, chemical attack, the stress of biological activity, and chemical and biological changes within the substrate. Nevertheless, adhesive bonds are maintained. 

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