The application of density functional theory to calculate adsorption properties, reaction pathways, and activation energies for surface chemical reactions is reviewed. Particular emphasis is placed on developing concepts that can be used to understand and predict variations in reactivity from one transition metal to the next or the effects of alloying, surface structure, and adsorbate-adsorbate interactions on the reactivity. Most examples discussed are concerned with the catalytic properties of transition metal surfaces, but it is shown that the calculational approach and the concepts developed to understand trends in reactivity for metals can also be used for sulfide and oxide catalysts.

Theoretical surface science and catalysis—calculations and concepts

The interaction of water with solid surfaces: Fundamental aspects

Oxidation into CO2 is a major solution to CO abatement in air depollution treatments. The development of catalytic converters led to an extraordinary high number of publications on metal catalysts during the last fifty years. Due to the increasing price of noble metals and to remarkable progresses in oxide syntheses, catalytic oxidation of carbon monoxide over oxide catalysts has recently gained in interest, even if some oxides are known to present remarkable activity since the beginning of the 20th century. In this Review, the kinetics and mechanism of CO oxidation on single and mixed oxides are examined, alongside the catalyst structures

Catalytic Oxidation of Carbon Monoxide over Transition Metal Oxides

Water-gas shift reaction: finding the mechanistic boundary

Although the vast majority of hydrocarbon fuels and products are presently derived from petroleum, there is much interest in the development of routes for synthesizing these same products by hydrogenating CO2. The simplest hydrocarbon target is methane, which can utilize existing infrastructure for natural gas storage, distribution, and consumption. Electrochemical methods for methanizing CO2 currently suffer from a combination of low activities and poor selectivities. We demonstrate that copper nanoparticles supported on glassy carbon (n-Cu/C) achieve up to 4 times greater methanation current densities compared to high-purity copper foil electrodes. The n-Cu/C electrocatalyst also exhibits an average Faradaic efficiency for methanation of 80% during extended electrolysis, the highest Faradaic efficiency for room-temperature methanation reported to date. We find that the level of copper catalyst loading on the glassy carbon support has an enormous impact on the morphology of the copper under catalytic con...

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Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst

One of the important physical-chemical properties that characterizes the interaction of solid surfaces with gases is the bond energy of the adsorbed species. The determination of the bond energy is usually performed indirectly by measuring the heat of adsorption (or heat of desorption) of the gas [1, 2], In order to define the heat of adsorption, let us consider the chemisorption of a diatomic molecule, X2, onto a site on a uniform solid surface, M. The molecule may adsorb without dissociation to form MX2. M represents the adsorption site where bonding occurs to a cluster of atoms or to a single atom. In this circumstance, the heat of adsorption, ΔHads, is defined as the energy needed to break the MX2 bond:

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I. Toyoshima

Papers

Heats of Chemisorption of O2, H2, CO, CO2, and N2 on Polycrystalline and Single Crystal Transition Metal Surfaces