The adsorption geometries, energies, and vibrational frequencies of methanol on MgO defective surfaces have been calculated by periodic DFT simulations. The results are very comparable with those obtained with water and are also in very good accordance with microcalorimetry and infrared experiments. At low coverage, the dissociation is observed on all defects involving ions in low coordinations. Over and above the coordination number of surface ions, the adsorption energy is strongly governed by the surface topology: dissociation on confined sites gives rise to methoxy groups highly stabilized by bridging two or even three cations. The occurrence of such very strong sites on MgO powder is confirmed by microcalorimetry. The dissociation ability depends on the methanol coverage because it modifies the surface relaxation and the network of H bonds, resulting, for a given defect, in similar adsorption energies for molecular and dissociated species at high coverage. This explains why there are more strong sites (quantified by microcalorimetry) than dissociating sites (quantified by infrared).

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International audienceCO adsorption in Al-rich faujasite zeolite containing copper and alkali cations has been investigated using DFT methods in order to determine how CO interacts and may modify the original position of the cations. Whether a cluster or a periodic model is used, addition of CO induces the formation of stable complexes labeled DI(CO) in which CO interacts by both its C-end and its O-end, resulting from a cooperative rearrangement of cations. In addition to a CuI migration from site II to the supercage, a migration of alkali from site III′ to site III may occur. DI(CO) also induces a downshift of the νCO mode in comparison with the complex containing CO interacting with a single cation, SI(CO). These results suggest a new assignment of the IR spectra of CO adsorbed in YCuI and YNa+: for YCuI, the upshifted signal at ca. 2160 cm-1 in comparison with νCOgas at 2143 cm-1 could be assigned to a SI(CO) structure, whereas the downshifted signal at ca. 2140 cm-1 could be assigned to a DI(CO) complex. For YNa+, the upshifted signal at ca. 2170 cm-1 could be assigned to SI(CO) NaSII · · ·CO and/or to DI(CO) NaSII · · ·OC· · · NaSIII′, whereas the downshifted signal at ca. 2122 cm-1 could be assigned to DI(CO) complex NaSII · · ·CO· · ·NaSIII′. This study shows that the DI(CO) interaction is a key ingredient for understanding the metal-exchanged zeolite properties

Recent reports on proteins and related models show that vibrational spectroscopy in the far-infrared domain is a promising technique to characterize metal sphere coordination in proteins. The low-frequency modes are however complex, and there is a need to develop the analysis of metal sites by means of quantum chemical calculations as a support for useful interpretation of the far-IR data. In this study, we determined vibrational properties for systems containing Cu(II)-N(Imidazole) interactions present in many biological complexes by means of quantum chemical calculations and confronted the normal mode description with available experimental data. Analysis of the [Cu(histamine)]2+ complex led us to conclude that the anharmonic contributions are negligible in the far-IR domain. Geometry optimizations and vibrational frequency calculations of [Cu(hm)]2+ and [Cu(hm)2(ClO4)2] complexes were compared using various hybrid DFT functionals and basis sets. These investigations stressed the need of potential energy distribution calculations (PED) to assign the vibrational modes, to obtain an overall description of the vibration modes, and to efficiently compare the methods. Comparison of calculation methods with the B3LYP/6-31+G(d,p) and B3LYP/6-311+G(2d,2p) methods and with available experimental data showed that the B3LYP/6-31G(d,p) level of theory provides accurate predictions of the normal mode frequencies and assignments. These comparisons also enlighten that theoretical investigations of 2H- and 65Cu-labeled [Cu(hm)2(ClO4)2] complexes give with a very good accuracy the band shifts of the labeled copper-histamine derivatives. The theoretical calculations combined with experimental data allowed us to predict and calculate with good accuracy the values and assignments of the low-frequency IR modes, notably those involving metal contribution.

International audienceThis combined experimental and theoretical study aims at understanding why surface hydroxyl groups may enhance catalytic reactivity of MgO surfaces in basic catalysis, whereas hydroxyls are weakly deprotonating groups. We investigated that reactivity enhancement in the catalytic conversion of 2-methyl-but-3-yn-2-ol (MBOH). Reaction kinetics was experimentally determined on partially hydroxylated MgO: active sites were saturated with the reactant and catalyzed its conversion with an activation energy of 85 kJ·mol–1. Reaction pathways were calculated over fully hydroxylated, partially hydroxylated, and dehydroxylated MgO surfaces by means of first-principles simulations. To highlight the effect of reactant coverage, we also calculated the reaction pathway on MgO precovered with MBOH molecules. The results show that the surface OH groups generated by dissociative adsorption of water induce a lowering in the activation energy barriers when they keep a bare Mg2+-O2– pair available in the vicinity for MBOH to adsorb and react. Interestingly, OH groups do not directly interact with MBOH converting on the surface, but they modify the basic properties of the vicinal bare Mg2+-O2– pair on which MBOH adsorbs and converts. A similar effect is predicted when MBOH converts on a bare Mg2+-O2– pair in the vicinity of a second adsorbed MBOH molecule. The beneficial effect of coadsorbates on the reactivity of active sites is analyzed by means of a thermodynamic model and an electronic structure analysis

A set of CaO samples was prepared from thermal decomposition of several precursors, leading to very different surface properties. During storage, CaO samples rehydrated quickly but reversibly. Before characterization, the samples were pre-treated at 1023 K under nitrogen flow to obtain CaO as the active phase. Although this pre-treatment led to almost the same specific surface areas for all samples, their basic reactivity levels toward 2-methylbut-3-yn-2-ol conversion were different from one preparation to another. In contrast with the properties of MgO pre-treated at the same temperature, the basic reactivity of CaO correlates neither with the concentration of surface defects (exposing ions in low coordination) determined by photoluminescence nor with the deprotonation ability toward methanol. In order to identify the active sites on CaO pre-treated under nitrogen in the temperature range 673 K-1023 K, OH groups were quantified with (1)H NMR: the higher the surface density of OH groups, the higher the basic reactivity. Even after pre-treatment at 1023 K, after which only a few hydroxyls remain, the basic reactivity is governed by the remaining hydroxylation of the surface. The higher reactivity of OH groups of CaO compared to those of Ca(OH)(2) and MgO is discussed.

, et al.. Influence of natural adsorbates of magnesium oxide on its reactivity in basic catalysis. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2013, 15 (45), pp.19870-19878 isomerization and one alcohol conversion (hept-1-ene isomerization and 2-methyl-3-butyn-2-ol conversion). Catalysis experiments showed that carbon dioxide adsorption poisons the catalyst surface and the DRIFT-DFT combination showed that the nature of active sites in the two reactions differs. On the reverse, partial hydroxylation of the surface enhances activity for both reactions. Interestingly hept-1-ene isomerization gives a volcano curve for the conversion as a function of hydroxyl coverage.Calculations of the electronic structure of magnesium oxide surface show that neither Lewis basicity nor Brønstedt basicity of the surface defects (steps for example) are enhanced by hydroxylation.Meanwhile CO 2 adsorption followed by IR spectroscopy shows that (110) and (111) unstable planes are strongly basic and are stabilized by partial surface hydroxylation. That result could explain the volcano curve obtained for the evolution of alkene isomerisation as a function of hydroxyl coverage.present address :

We demonstrate that weak CH…O hydrogen bonds (HBs) are important host-guest interactions in zeolite assemblies involving structure directing organocations. This type of HB are identified between alkyl groups of the organic structure directing agent (OSDA) and the silica framework in assynthesized silicalite-1 of complex topology (MFI) using a combination of experimental and theoretical data obtained at low and room temperatures. The 28 weak CH…O HB, evidenced along dynamics simulation at room temperature, represent 30% of the energy of the Coulomb electrostatic interaction between OSDA and the zeolite framework. The strongest and most stable HB found here connects the OSDA to the [4 1 5 2 6 2 ] cage containing F atoms and should contribute to preserve zeolite topology during crystal growth. An inspection of other as-synthesized zeolites of very different framework topology indicates that the directional CH...O HBs have to be considered when discussing zeolite structure directing phenomena.