The role of subsurface oxygen in the silver-catalyzed, oxidative coupling of methane

Journal Article · Mon Nov 15 04:00:00 EST 1999 · Journal of Catalysis

DOI:https://doi.org/10.1006/jcat.1999.2651· OSTI ID:20003851

Nagy, A J; Mestl, G; Schloegl, R

The silver-catalyzed, oxidative coupling of methane to C{sub 2} hydrocarbons (OCM) is shown to be an extremely structure-sensitive reaction. Reaction-induced changes in the silver morphology lead to changes in the nature and extent of formation of various bulk and surface-terminating crystal structures. This, in turn, impacts the adsorption properties and diffusivity of oxygen in silver which is necessary to the formation of subsurface oxygen. A strongly bound, Lewis basic, oxygen species which is intercalated in the silver crystal structure is formed as a which a intercalated in the silver crystal structure is formed as a result of these diffusion processes. This species is referred to as O{sub {gamma}} and acts as a catalytically active crystal structure is formed as a result of these diffusion process. This species is referred to as O{gamma} and acts a catalytically active site for the direct dehydrogenation of a variety of organic reactants. It is found that the activation energy for methane coupling over silver of 138 kJ/mol is nearly energy for methane coupling over silver of 138 kJ/mol is nearly identical to the value of 140 kJ/mol for oxygen diffusion in silver measured under similar conditions. This correlation between the diffusion kinetics of bulk-dissolved oxygen and the reaction kinetics of the oxidative coupling of methane to C{sub 2} hydrocarbons suggests that the reaction is limited by the formation of P{gamma} via surface segregation of bulk dissolved oxygen. Catalysis over fresh silver catalysts indicates an initially preferential oxidation of CH{sub 4} to complete oxidation projects. This is result of the reaction of methane with surface bound atomic oxygen which forms preferentially on high-index terminating crystalline planes. Reaction-induced facetting of the silver results in a restructuring of the catalysts from one which initially catalyzes the complete oxidation of methane to CO{sub x} and water to a catalyst which preferentially catalyzes the formation of coupling products. This represents an extremely dynamic situation in which a solid-state restructuring of the catalyst results in the formation of a Lewis-basic, silver-oxygen species which preferentially catalyzes the dehydrogenation of organic molecules.

• Research Organization: Dept. of Inorganic Chemistry, Berlin (DE)
• OSTI ID: 20003851
• Journal Information: Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: 1 Vol. 188; ISSN 0021-9517; ISSN JCTLA5
• Country of Publication: United States
• Language: English

Related Subjects

03 NATURAL GAS
10 SYNTHETIC FUELS
ACTIVATION ENERGY
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
METHANE
OXIDATION
REFORMER PROCESSES
SILVER