Zinc oxide adsorption

Because the sulfur compounds in natural gas are nonaromatic and of low molecular weight, HDS can be performed at lower H2 partial pressures, 1-lOkPa, and temperatures of 200-300 °C depending on the catalyst and the sulfur specia-tion.46 Zinc oxide adsorption capacities for H2S in industrial applications are reported to be high, typically 150-200 mg-S/g sorbent.47... 

Gases which are high in FIjS are subject to a de-sulphurisation process in which H2S is converted into elemental sulphur or a metal sulphide. There are a number of processes based on absorption in contactors, adsorption (to a surface) in molecular sieves or chemical reaction (e.g. with zinc oxide). 

Comparison of specific surface of anatase and zinc oxide determined by electron microscopy A ) and by nitrogen adsorption A )... 

Adsorption Processes. The processes based on adsorption of hydrogen sulfide onto a fixed bed of soHd material are among the oldest types of gas treating appHcations (4). Two common sorbent materials for low concentration gas streams are iron oxide and zinc oxide. 

Surface Barrier Effects in Adsorption, Illustrated by Zinc Oxide S. Roy Morrison... 

Nagoe, M. Morimoto, T. (1969). Differential heat of adsorption and entropy of water absorbed on zinc oxide surface. Journal of Physical Chemistry, 73, 3809-14. 

The same Chapter contains results of studies of effects of adsorption of atom particles as well as simplest free radicals on electric conductivity of semiconductor zinc oxide films. 

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 ... 

On the contrary, in paper [197] the investigation of adsorption of O2 on the surface of monocrystal zinc oxide by methods of contact po-... 

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]. 

The low energy of activation of the change in electric conductivity of zinc oxide observed during adsorption of H-atoms ( 0.08 eV) [102] can correspond to the ionization energy of (0-H) -groups formed during direct interaction of H-atoms with O -ions of the lattice. 

To dissociate molecules in an adsorbed layer of oxide, a spillover (photospillover) phenomenon can be used with prior activation of the surface of zinc oxide by particles (clusters) of Pt, Pd, Ni, etc. In the course of adsorption of molecular gases (especially H2, O2) or more complex molecules these particles emit (generate) active particles on the surface of substrate [12], which are capable, as we have already noted, to affect considerably the impurity conductivity even at minor concentrations. Thus, the semiconductor oxide activated by cluster particles of transition metals plays a double role of both activator and analyzer (sensor). The latter conclusion is proved by a large number of papers discussed in detail in review [13]. The papers cited maintain that the particles formed during the process of activation are fairly active as to their influence on the electrical properties of sensors made of semiconductor oxides in the form of thin sintered films. 

The experiment was carried out in a reaction cell shown in Fig. 3.3 with inner walls covered by a zinc oxide film having thickness 10 pm [20]. The surface area of the measuring film on the quartz plate was about 1/445 of the total film area on the wall of the vessel. The results of direct experimental measurements obtained when the adsorbent temperature was -196 C and temperature of pyrolysis filament (emitter of H-atoms) 1000°C and 1100°C, are shown on Fig. 3.4. One can see a satisfactory linear dependence between parameters A r (the change in film conductivity) and APh2 (reduction of hydrogen pressure due to adsorption of H-atoms), i.e. relations... 

To resolve the problem applying methods of collimated atom beams, equilibrium vapour as well as radioactive isotopes, the Hall effect and measurement of conductivity in thin layers of semiconductor-adsorbents using adsorption of atoms of silver and sodium as an example the relationship between the number of Ag-atoms adsorbed on a film of zinc oxide and the increase in concentration of current carriers in the film caused by a partial ionization of atoms in adsorbed layer were examined. 

Besides the experimental data mentioned above, the kinetic dependencies of oxide adsorption of various metals are also of great interest. These dependencies have been evaluated on the basis of the variation of sensitive element (film of zinc oxide) conductivity using tiie sensor method. The deduced dependencies and their experimental verification proved that for small occupation of the film surface by metal atoms the Boltzman statistics can be used to perform calculations concerning conductivity electrons of semiconductors, disregarding the surface charge effect as well as the effect of aggregation of adsorbed atoms in theoretical description of adsorption and ionization of adsorbed metal atoms. Considering the equilibrium vapour method, the study [32] shows that... 

It was first shown in study [37] that adsorption of N-atoms on films of zinc oxide reduces its conductivity to a certain stationary value which depends, as with oxygen atoms, both on the stationary concentration of particles in the volume adjacent to the sensor s film and on the temperature. 

Figure 3.15 shows the validity of above simplest equation for adsorption of O-atoms provided that there are different concentrations of interstitial zinc atoms on the zinc oxide surface. In case of oxygen atoms the experiment has been carried out in absence of molecular oxygen so that effect of its adsorption on change in conductivity was ruled out. O-atoms were produced by means of pyrolysis of carbon dioxide. From this figure we notice that zinc atoms (superstoichiometric) applied onto the surface of the zinc oxide film are the active centres of adsorption of... 

Our comments on adsorption of oxygen and nitrogen atoms lead to conclusion that practically under all conditions the initial rate of variation of conductivity of zinc oxide film due to adsorption of acceptor particles discussed in this section is proportional to the concentration of particles in the space adjacent to the surface of oxide film. This is similar to the case of donor particles. This means that the following equation is applicable ... 

Fig. 3.17. Kinetics of conductivity of a zinc oxide film in the process of adsorption of CH2-biradicals at 100 C. The radicals have been produced by means of photol)rsis ketene vapour at pressure P = 0,5 Torr. a - after adsorption of Zn-atoms b - prior (/) and after adsorption of (2) Zn-atoms.

It was shown in a number of works [29] that impurity conductivity of thin zinc oxide films are extremely sensitive to adsorption of atoms of various metals (see Chapters 2 and 3). Using this feature of oxide films, we first employed the sensor method to study evaporation of superstechiometric atoms of metals from metal oxide surfaces, zinc oxide in particular [30]. 

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