The interaction of CO2 with sodium-promoted W(011)

Abstract

The activation of CO2 by interaction with Na atoms on tungsten was studied in a joint experimental/theoretical effort combining MIES, UPS (HeII) and first principles calculations. Experimentally, both the adsorption of Na on tungsten, followed by CO2 exposure to the Na-modified surface at 80 K, and the adsorption of CO2 on tungsten, followed by Na exposure to the CO2 covered substrate, were studied. Below about 120 K CO2 physisorbs on pure W(011), and the distance between the three main spectral features is as for gas phase CO2 (E(B) = 8.4, 12.1, 14.1 eV). When offered to a Na monolayer (ML) deposited onto W, CO2 is converted into a chemisorbed species. The spectral pattern is different from physisorbed CO2, and the three spectral features are shifted towards lower binding energies (E(B) = 6.3, 10.7, 13.9 eV). The chemisorption continues until all available Na species are converted into Na+ species. Additional CO2 offered to the system becomes physisorbed on top of the chemisorbed species. When a CO2 monolayer, physisorbed on tungsten at 80 K, is exposed to Na, the interaction leads initially to a decrease of the surface work function and to a rigid, global shift of all CO2 induced features towards larger binding energies by about 2 eV. Only beyond a minimum Na coverage of about 0.5 ML, chemisorbed species can be detected. We conclude that, initially, transfer of the Na(3s) electron to the tungsten substrate takes place. Above 0.5 ML Na coverage, back donation of charge to CO2 takes place whereby the physisorbed carbon dioxide species become converted into chemisorbed ones. The experimental results are interpreted with the help of first principle calculations carried out on suitable slab models. The structures and surface binding mode of the chemisorbed CO2 species are described. The calculated density of states for the most stable situations is in qualitative agreement with experimental data.

Fundamentals of Methanol Synthesis on Metal Carbide Based Catalysts: Activation of CO2 and H2

“…The latter generally implies a catalyst which activates CO 2 through a charge transfer mechanism leading to a highly bent adsorbed molecule. This can be achieved, for instance, through co-adsorption with an alkali metal on a metal surface [8,9], or the catalytic activation by transition metal catalysts with multiple redox states [10].…”

CO2interaction with violarite (FeNi2S4) surfaces: a dispersion-corrected DFT study

“…4 This is, however, a challenging process because CO 2 is extremely stable and most often interacts only weakly with many surfaces. Activation may be achieved by adding promoters to an otherwise inactive surface 5 or by making use of more reactive catalytic materials. In this respect, a significant number of studies have been reported in the literature on the CO 2 adsorption, activation, and conversion on metals, 6,7 metal-oxides, 8,9 and metal organic frameworks.…”

A DFT study of planar vs. corrugated graphene-like carbon nitride (g-C3N4) and its role in the catalytic performance of CO2 conversion

“…non-spontaneous under mild conditions and additional energy/pressure is required to enhance such contact in most of the common materials. Improved strategies have been investigated by Illas and co-workers when interacting CO 2 with cations 15 and novel transition metal carbide materials. 16 Also, Meng et al show that the use of alkali reagents to modify the surface of TiO 2 increases CO 2 adsorption, and also activates the subsequent conversion.…”