Zinc chemisorption

On experimental level the question regarding the centers of adsorption was addressed in numerous papers. For instance, in [66] the experimental data were used to show that in case of adsorption of hydrogen atoms on the surface of zinc oxide the centers of chemisorption can be provided by regular oxygen ions of the lattice, i.e. the process of chemisorption of H-atoms can be shown as the following sequence of reactions ... 

We should point out that up to now we have considered only polycrystals characterized by an a priori surface area depleted in principal charge carriers. For instance, chemisorption of acceptor particles which is accompanied by transition-free electrons from conductivity band to adsorption induced SS is described in this case in terms of the theory of depleted layer [31]. This model is applicable fairly well to describe properties of zinc oxide which is oxidized in air and is characterized by the content of surface adjacent layers which is close to the stoichiometric one [30]. 

Further investigations of the above discussed effects show that, at fixed temperature of the oxide film (catalyst), the jump in the electric conductivity first increases in amplitude, as the portion of alcohol vapor admitted into the vessel increases. On further increase of the admitted portion of alcohol, the jump amplitude reduces (starting with the pressure of 3.6-10 2 Torr). At the pressure of 3.2-10 Torr, the jump in the electric conductivity of the zinc oxide film is less pronounced. Finally, at still higher pressures, it disappears (Fig.4.9). This effect is not unexpected. On our mind, it is associated with the fact that, as the concentration of alcohol vapor increases, the sum of the rate of interaction of the vapor with adsorbed hydrogen atoms and the rate of surface recombination of hydrogen atoms at the time instant of production becomes higher than the chemisorption rate of these atoms. The latter is responsible for the increase of the electric conductivity of the semiconductor oxide film via the reaction... 

This reduction step can be readily observed at a mercury electrode in an aprotic solvent or even in aqueous medium at an electrode covered with a suitable surfactant. However, in the absence of a surface-active substance, nitrobenzene is reduced in aqueous media in a four-electron wave, as the first step (Eq. 5.9.3) is followed by fast electrochemical and chemical reactions yielding phenylhydroxylamine. At even more negative potentials phenylhydroxylamine is further reduced to aniline. The same process occurs at lead and zinc electrodes, where phenylhydroxylamine can even be oxidized to yield nitrobenzene again. At electrodes such as platinum, nickel or iron, where chemisorption bonds can be formed with the products of the... 

Figure 3 shows the spectrum of zinc oxide in the presence and absence of hydrogen. The background scan shows three strong bands at 3665, 3616, and 3445 cm-1 as well as a weak band at 3635 cm-1 all of these bands are due to residual surface hydroxyls. (We shall reserve the term hydroxyl for bands in the background the term OH shall be used for bands formed by chemisorption.) The spectrum in hydrogen shows two strong bands at 3489 and 1709 cm-1 these bands, first reported by Eischens... 

Butanol, reaction over reduced nickel oxide catalysts, 35 357-359 effect of ammonia, 35 343 effect of hydrogen, 35 345 effect of pyridine, 35 344 effect of sodium, 35 342, 351 effect of temperature, 35 339 over nickel-Kieselguhr, 35 348 over supported nickel catalysts, 35 350 Butanone, hydrogenation of, 25 103 Butene, 33 22, 104-128, 131, 135 adsorption on zinc oxide, 22 42-45 by butyl alcohol dehydration, 41 348 chemisorption, 27 285 dehydrogenation, 27 191 isomerization, 27 124, 31 122-123, 32 305-308, 311-313, 41 187, 188 isomerization of, 22 45, 46 isomers... 

Parravano and Boudart (1S6) have depicted chemisorption of hydrogen on zinc oxide, as occurring through heterolytic splitting on a pair of adjacent zinc-oxygen sites, followed by proton-transfer, e.g.,... 

Reversible chemisorption and hydrogen-deuterium exchange on zinc oxide have been observed (Taylor et al., 136,137 , Harrison and McDowell,... 

In the preceding example it was deliberately assumed that the zinc oxide crystal used as starting material was perfect and thus, in particular, of stoichiometric composition. This was done solely in order to show that the crystal became an impurity semiconductor following the adsorption process otherwise the reasoning did not involve in any way the behavior of the bulk of the crystal, and the mechanism of the adsorption process did not depend upon the existence or nonexistence of semiconductivity prior to the uptake of hydrogen. If this were a general situation, further examination of the effect of semiconductivity on chemisorption and catalysis would hardly seem profitable. However cases where semiconductivity may play a direct role can easily be imagined. 

Because zinc oxide is a relatively well-understood oxide semiconductor, we shall first review its properties as a hydrogenation catalyst in the catalytic hydrogen-deuterium exchange reaction. Since the latter essentially measures the rate of reversible chemisorption of hydrogen at equilibrium, data on the hydrogen chemisorption will be included in this survey. Any theory of hydrogen chemisorption on zinc oxide must explain all the following well-established facts. 

An additional difficulty in studies of slow chemisorption is evidenced by the Taylor-Liang technique of measuring adsorption isobars at successively higher temperatures without pumping between runs, a technique that has been reviewed in an earlier volume of this series (8). The ad-sorption-desorption phenomena observed between room temperature and about 150°C. clearly show in this temperature range the existence on the surface of zinc oxide of two types of hydrogen chemisorption (9). 

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