Carbon monoxide oxidation periodic activity

Potentiometric techniques have been used to study autonomous reaction rate oscillations over catalysts and carbon monoxide oxidation on platinum has received a considerable amount of attention43,48,58 Possible explanations for reaction rate oscillations over platinum for carbon monoxide oxidation include, (i) strong dependence of activation energy or heat of adsorption on coverage, (ii) surface temperature oscillations, (iii) shift between multiple steady states due to adsorption or desorption of inert species, (iv) periodic oxidation or reduction of the surface. The work of Sales, Turner and Maple has indicated that the most... 

From 1987 until now only a few years have passed, but in that time a new physiological mediator has been found, NO. In this short time the three enzymes that individually mediate this reaction in mammals have been characterized and the occurrence of similar enzymes in invertebrates have been determined. It is not only new, but surprising, that this physiological agent is a gas that is formed in one cell and spreads its function to nearby cells, but that its function is limited by oxidation. In the case of brain, Verma and coworkers151 have recently suggested that carbon monoxide may be a similar activator of cGMP. The period of surprises is not yet over. 

The analogy goes further if the activity of NiO as an oxidation catalyst is examined closely. In the case of the H2-D2 exchange reaction on ZnO, there was an activation period corresponding to a surface reduction. For NiO, there is a deactivation period also corresponding to surface reduction during the catalytic oxidation of carbon monoxide. 

After activation, the catalyst is intrcxiuced into the polymerization reactor as slurry in a saturated hydrocarbon such as isobutane. The precise mechanism of initiation is not known, but is believed to involve oxidation-reduction reactions between ethylene and chromium, resulting in formation of chromium (II) which is the precursor for the active center. Polymerization is initially slow, possibly because oxidation products coordinate with (and block) active centers. Consequently, standard Phillips catalysts typically exhibit an induction period. The typical kinetic profile for a Phillips catalyst is shown in curve C of Figure 3.1. If the catalyst is pre-reduced by carbon monoxide, the induction period is not observed. Unlike Ziegler-Natta and most single site catalysts, no cocatalyst is required for standard Phillips catalysts. Molecular weight distribution of the polymer is broad because of the variety of active centers. 

Detailed studies of the coadsorption of oxygen and carbon monoxide, hysteresis phenomena, and oscillatory reaction of CO oxidation on Pt(l 0 0) and Pd(l 1 0) single crystals, Pt- and Pd-tip surfaces have been carried out with the MB, FEM, TPR, XPS, and HREELS techniques. It has been found that the Pt(l 0 0) nanoplane under self-osciUation conditions passes reversibly from a catalytically inactive state (hex) into ahighly active state (1 x 1). The occurrence of kinetic oscillations over Pd nanosurfaces is associated with periodic formation and depletion of subsurface oxygen (Osub)- Transient kinetic experiments show that CO does not react chemically with subsurface oxygen to form CO2 below 300 K. It has been found that CO reacts with an atomic Oads/Osub state beginning at temperature 150 K. Analysis of Pd- and Pt-tip surfaces with a local resolution of 20 A shows the availability of a sharp boundary between the mobile COads and Oads fronts. The study of CO oxidation on Pt(l 0 0) and Pd(l 1 0) nanosurfaces by FEM has shown that the surface phase transition and oxygen penetration into the subsurface can lead to critical phenomena such as hysteresis, self-oscillations, and chemical waves. 

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