Methanol adsorption surface reaction mechanism

Surface Reaction Mechanism of Methanol Adsorption-Reaction on Oxide Surfaces... 

The conversion of methanol to hydrocarbons (MTHC) on acidic zeolites is of industrial interest for the production of gasoline or light olefins (see also Section X). Upon adsorption and conversion of methanol on calcined zeolites in the H-form, various adsorbate complexes are formed on the catalyst surface. Identification of these surface complexes significantly improves the understanding of the reaction mechanism. As demonstrated in Table 3, methanol, dimethyl ether (DME), and methoxy groups influence in a characteristic manner the quadrupole parameters of the framework Al atoms in the local structure of bridging OH groups. NMR spectroscopy of these framework atoms under reaction conditions, therefore, helps to identify the nature of surface complexes formed. 

Methyl chloride is an important industrial product, having a global annual capacity of ca. 900 000 tons. Its primary use is for the manufacture of more highly chlorinated materials such as dichloromethane and chloroform and for the production of silicone fluids and elastomers. It is usually manufactured by the reaction of methanol with hydrogen chloride with a suitable acid catalyst, such as alumina. To develop a site-specific reaction mechanism and a kinetics model for the overall process, one first needs to identify all the reagents present at the catalyst surface and the nature of their interactions with the surface. The first step in the reaction is dissociative adsorption of methanol to give adsorbed methoxy species. Diffuse reflectance IR spectroscopy (29d) showed the expected methoxy C-H stretch and deformations, but an additional feature, with some substructure, at 2600 cm was... 

The kinetics of methanol oxidation over metal oxide catalysts were elegantly derived by Holstein and Machiels [16], The kinetic analysis demonstrated that the dissociative adsorption of water must be included to obtain an accurate kinetic model. The reaction mechanism can be represented by three kinetic steps equilibrated dissociative adsorption of methanol to a surface methoxy and surface hydroxyl (represented by K,), equilibrated dissociative adsorption of water to two surface hydroxyls (represented by K ), and the irreversible hydrogen abstraction of the surface methoxy intermediate to the formaldehyde product and a surface hydroxyl (the rate determining step, represented by kj). For the case of a fully oxidized surface, the following kinetic expression was derived ... 

On the basis of an infrared study of the adsorption and reaction of methanol and dimethyl ether over alkali metal cation exchanged zeolites, we propose a reaction mechanism for the decomposition of methanol over alkali cation exchanged zeolites. Additionally, formaldehyde adsorption is performed on these molecular sieves and attempts will be made to correlate its adsorption structure with the surface reactivity. 

To summarize these results, it becomes now clear that EMIR Spectroscopy is particularly well suited to follow the fate of the different small adsorbed organic residues, resulting from the chemisorption of small organic molecules, such as CH3OH. The nature and the quantity of adsorbed species depend strongly on the structure of the catalytic surface, on the concentration of methanol in solution, on the adsorption time, on the applied electrode potential,... All these various experimental conditions lead to a great variety of adsorbed species, and control their surface distribution. According to these spectroscopic data, the reaction oxidation mechanisms of methanol adsorption and oxidation at platinum electrodes... 

Other similar cases exist, such as direct electro-oxidation of alcohols such as methanol and formic acid in low-temperature fuel cells. In these cases, an alternative to the BV formulation that accounts for the limiting adsorption and charge transfer steps is appropriate. Two common models for a surface adsorption limited reaction are the Langmuir and Temkin kinetics. In the simpler Langmuir model, the surface adsorption rate constant is independent of surface coverage. In the Temkin model, the adsorption rate constant is modeled as a function of the surface coverage of adsorbed species. In both models, a two-step reaction mechanism is assumed [6] ... 

As was previously mentioned, PtRu alloys exhibit improved performance over pure Pt alloys.117,118 This is primarily a result of the ability of Ru to dissociate H20 for reaction with CO adsorbed on Pt sites.115,116 That CO oxidation on pure Ru is unfavorable indicates that on the bimetallic surface, CO is oxidized only on the Pt sites.119 Thus, CO is oxidized on Pt sites adjacent to Ru sites, where water is activated.120,121 This is known as a bifunctional mechanism. In addition, the presence of Ru atoms reduces the adsorption energy of CO on neighboring Pt atoms, lowering the activation energy of CO oxidation.122 This effect is purely electronic and is less significant than the bifunctional effect of Ru.123 One significant limitation of PtRu is the weak adsorption of methanol on Ru, particularly at room temperature.117,124 The weak adsorption severely hinders methanol decomposition, which is evident in Fig. 7 by the drop in current density for PtRu electrodes with high Ru composition.125... 

Reactions alcohols, 29 36-49 adsorption, 29 36-37 clean surfaces, 29 37-38 ethanol oxidation, 29 44—48 methanol oxidation, 29 38-44 oxidation on copper and silver, 29 38-48 oxidation reaction, silver, 29 48-49 base-catalyzed, of hydrocarbons, 12 117 free radical mechanism in, of hydrogen peroxide, 4 343... 

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