IR spectra of methane adsorbed on MgO

Methane adsorbed on MgO is activated to form CH₃ fragments stabilized on cations and OH groups.

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, MgO CH₃-, OH-.

     

IR spectra of CO and NO adsorbed on CuO

The original heterogeneity of CuO surface is suggested to account for the presence of two states of surface copper cations with different effective charges.

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CuO, . , .

     

Molecular orbital cluster model study of bonding and vibrations of CO adsorbed on MgO surface

The interaction of CO with the MgO(100) surface has been investigated by means of all electron cluster model calculations. The CO molecule is bound on the Mg²⁺ site of MgO with a chemisorption energy of about 0.2 eV. The binding mechanism is electrostatic in nature and arises almost entirely from the interaction of the weak electric field generated by the ionic surface and the CO charge distribution, with negligible contributions from chemical effects as the CO σ donation. When CO is bound through carbon, its vibrational frequency increases with respect to the gas-phase value. This shift, Δ, has been analyzed and decomposed into the sum of different contributions. It is found that the positive Δω does not arise entirely from the field–dipole interaction but is due, in part, to the increase in Pauli repulsion occurring when the C? O molecule vibrates in the presence of the surface “wall.” A stronger electrostatic interaction, bringing the CO adsorbate closer to the surface, increases this wall effect and results in a more pronounced positive ω shift. It is also found that the two CO orientations exhibit opposite shifts in ω_e, thus, the two orientations can be distinguished, in principle, by IR spectroscopy. The analysis of our ab initio cluster wave functions gives a very different picture than the standard view of the metal–CO bond as arising from σ donation and π back donation.     

IR and XPS studies of the reactivity of CO with Ti-H species at the support on Rh/TiO2 catalysts

Incorporation of hydrogen in Rh/TiO₂ samples during high temperature reduction (H₂ at T > 573 K), has been studied by TPD-MS. ESR and NMR data suggest that hydride-like species associated to Ti³⁺ ions at the support are formed, i.e, (Ti-H)³⁺. Rh(3d) XPS peaks (at 311.2, 306.5 eV) remain unchanged after removal of such hydride-like species (by outgassing at 773 K), though it modifies the adsorption capacity for CO and H₂, monitored by i.r. and NMR, thus indicating a SMSI effect which is reversed by outgassing at 773 K the sample. By heating in CO at 373–473 K bands at 1590, 1470 and 1220 cm^-1 are developed only in the samples saturated with hydrogen, while CH₃OH is detected in the gas phase. Experiments using a pulse microreactor in conditions that allow formation of such (Ti-H)³⁺ species, lead to methanol as the only product of syngas reaction. A model is proposed to explain generation of oxygenated compounds on these catalysts, whieh assumes reaction of the hydride-like species at the TiO₂ support with CO molecules either directly interacting with the support or hounded to the rhodium at the metal-support interface.     

IR studies of NO and CO adsorbed on matrix-isolated silver clusters

The interaction of CO and NO on matrix-isolated silver clusters (D ≈ 100 A) causes a red-shift of the vibrational frequency. Compared to matrix-i     

EPR studies of isotopic exchange involving adsorbed oxygen species on MgO

In the EPR spectra of ¹⁷O₂^? adsorbed on MgO, the hyperfine lines due to ¹⁷O(I = $\text{5}\text{2}$) have been used to monitor the isotopic exchange with gas phase oxygen. The predicted behaviour of the different possible mechanisms (place exchange and/or isotopic exchange) is compared with the experimental results which show that, on MgO at room temperature, isotopic exchange occurs via an intermediate species which is tentatively identified as O₄^?.     

Theoretical study of Sn adsorbed on the MgO(100) surface with defects

In this study, the adsorption of Sn atom at various sites on the MgO(100) surface was characterized using a theoretical approach based on density functional theory calculations. Both regular adsorption centers (O^2? and Mg²⁺) and defects (such as neutral and charged O and Mg vacancies) were considered. Several key parameters for these sites with the adsorbed Sn atom were determined to provide its geometric, energetic, and electronic characterization. The interaction between Sn and the Mg vacancy sites is very strong and is associated with a relatively small distance of the adsorbed Sn atom from the surface and with a large electronic charge transfer from Sn to the surface. A much smaller strength of Sn atom adsorption is observed for the O vacancies and regular sites. Among them, the ${{\text{F}}_{\text{s}}}^{\text{0}}$ center binds the Sn atom strongest and, in consequence, this atom acquires a significant amount of electronic charge.     

NMR and IR study of fluorobenzene and hexafluorobenzene adsorbed on alumina

The adsorption of fluorobenzene (C6H5F) and hexafluorobenzene (C6F6) onto the surface of neutral alumina is investigated by reflectance IR spectroscopy, near-IR spectroscopy, and measurement of 19F NMR chemical shift values. Chemical shifts are dependent on surface coverage and reveal multiple peaks where different adsorption environments occur. C6H5F appears to be adsorbed through polar interactions with surface hydroxyls, whereas C6F6 shows separate resonances for the first layer of coverage and outer layers. Available surface areas are estimated, and reorientation of adsorbed hexafluorobenzene is proposed to account for chemical shift behavior and differences between calculated and measured monolayer coverage.     

Carbon dioxide activation by surface excess electrons: an EPR study of the CO2- radical ion adsorbed on the surface of MgO

The CO2- radical anion has been generated at the surface of MgO by direct electron transfer from surface trapped excess electrons and characterized by electron paramagnetic resonance spectroscopy. Both 13C and 17O hyperfine structures have been resolved for the first time, leading to a detailed mapping of the unpaired electron spin density distribution over the entire radical anion. The magnetic equivalence of the two O nuclei has been ascertained allowing a side-on adsorption structure at low-coordinate Mg2+ ions to be proposed for the surface stabilized radical.     

IR spectroscopic study of the reactivity of aromatic 5-acyltetrazoloisoindoles

An IR study of the 5-acyl tetrazoloisoindoles solvent sensitive bands permit to assign the bands associated to the valence mode of the CO bond in the 1700-1500 cm⁻¹ area. This provides an explanation of the unusual stability of these newly synthesised compounds. Moreover, in air exposed solutions we observe the formation of unique degradation products. A mechanism for their formation and their probable structure was proposed with the help of IR spectroscopy.     

Theoretical study of the formation of adsorbed dicarbonyl species

The formation of mono- and dicarbonyl species during CO adsorption has been theoretically studied in order to obtain a mathematical model of the adsorption isotherms. The dependences proposed describe well the results of other authors and allow better utilization of the experimental data.

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- CO . .

     

Comparison of the reactivity of different Pd-O species in CO oxidation

The reactivity of several Pd-O species toward CO oxidation was compared experimentally, making use of chemically, structurally and morphologically different model systems such as single-crystalline Pd(111) covered by adsorbed oxygen or a Pd(5)O(4) surface oxide layer, an oriented Pd(111) thin film on NiAl oxidized toward PdO(x) suboxide and silica-supported uniform Pd nanoparticles oxidized to PdO. The oxygen reactivity decreased with increasing oxidation state: O(ad) on metallic Pd(111) exhibited the highest reactivity and could be reduced within a few minutes already at 223 K, using low CO beam fluxes around 0.02 ML s(-1). The Pd(5)O(4) surface oxide on Pd(111) could be reacted by CO at a comparable rate above 330 K using the same low CO beam flux. The more deeply oxidized Pd(111) thin film supported on NiAl was already much less reactive, and reduction in 10(-6) mbar CO at T > 500 K led only to partial reduction toward PdO(x) suboxide, and the metallic state of Pd could not be re-established under these conditions. The fully oxidized PdO nanoparticles required even rougher reaction conditions such as 10 mbar CO for 15 min at 523 K in order to re-establish the metallic state. As a general explanation for the observed activity trends we propose kinetic long-range transport limitations for the formation of an extended, crystalline metal phase. These mass-transport limitations are not involved in the reduction of O(ad), and less demanding in case of the 2-D Pd(5)O(4) surface oxide conversion back to metallic Pd(111). They presumably become rate-limiting in the complex separation process from an extended 3-D bulk oxide state toward a well ordered 3-D metallic phase.