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Low-coordinated (LC) ions at the MgO surface (noted Mg2+LC and O2-LC with L = 1-5), located on monatomic and diatomic steps, corners, step divacancies, and kinks, have been modeled thanks to periodic density functional theory (DFT) calculations (VASP). Ions of lowest coordination induce the strongest surface geometry relaxation and the highest surface energies. The hydration energies of these sites and thermodynamic stabilities of the resulting surfaces were studied. The factors controlling the interaction strength between water and the surface are the possibility for the hydroxyl group to adopt a bridging geometry between two Mg2+ cations in concave areas of the surface, such as the bottom of the monatomic step, and at second order the surface atomic coordination, and especially the presence of three-coordinated ions. The Lewis basicity and acidity of O2-LC and Mg2+LC, respectively, increase as their coordination number decreases, which implies the same trend for the Brønsted basicity of the Mg2+-O2- pair toward water. However, this trend can be changed if pairs leading to the formation of bridging OH groups are involved, typically on monatomic steps or in step divacancies where O2C-H and O3C-H are obtained, respectively, instead of the expected O1C-H. Thanks to thermodynamic calculations, the state of the surface as a function of temperature can be determined at a given pressure, unraveling the roles of surface topology and ions coordination.

The infrared OH stretching frequencies of the various types of hydroxyl groups on MgO surfaces have been calculated by periodic (VASP) and cluster (Gaussian) DFT simulations. Surface irregularities (mono and diatomic steps, corners, step divacancies, and kinks) have been considered to model the IR spectra of hydroxylated MgO powders. A good correspondence between calculated and experimental frequencies is obtained with the B3LYP functional. Hydrogen-bonding is the parameter which influences most the IR frequency of OH groups, followed by location of OH groups in concave or convex areas of the surface and then oxygen coordination. The evolution of experimental IR spectra upon evacuation at increasing temperature can be rationalized on the basis of calculated thermal stabilities of each kind of OH groups. A new model is finally proposed to help assign the experimental bands, in terms of hydrogen-bonding, local topology of the hydroxylated sites, and coordination of oxygen.

International audienceThe Lewis and Brønsted basic properties of a stoichiometric hydroxyapatite (HAp) were investigated by infrared spectroscopy following the adsorption and desorption processes of a Lewis acidic molecule, CO2, and a Brønsted acidic molecule, C2H2. CO2 interacts with basic OH– and O2– of PO43– groups to form hydrogenocarbonates and surface carbonates, respectively. It also generates surface type A carbonates and related water upon substitution of two neighboring structural OH– groups. Water modifies the basic properties of the HAp by decreasing the surface carbonatation and enhancing the formation of hydrogenocarbonates, and promotes the substitution ability of OH– by carbonates. Due to the affinity of HAp for carbonatation, the thermodesorption experiment of CO2 accounts for the thermal decomposition of bulk type A and B carbonates rather than for the lone surface basicity. As for the acetylene probe, three nondissociative adsorption modes of acetylene on the HAp surface are observed: a π complex interaction with acidic POH, an interaction with an acid–base (POH–OH) pair, and finally, a σ complex interaction with basic OH– that is the most stable upon desorption. There is no evidence of the involvement of basic O2– of PO43– in the interaction with acetylene. It is thus proposed that both acidic POH and basic OH– groups may play a determinant role in acid–base properties of hydroxyapatites

The interaction of water and methanol with MgO samples with different distributions of oxide ions of low coordination has been investigated by physical techniques, particularly in situ photoluminescence. First, the three photoluminescence fingerprints of oxide ions vs their coordination number have been obtained for samples outgassed at 1273 K. By a pseudo quantitative approach, the relative distribution of the oxide ions of low coordination O(2-)LC (where LC = 3C, 4C, and 5C refer to tri-, tetra-, and pentacoordinated oxide ions, respectively) was determined and correlated with the shape and size of MgO particles determined by TEM and XRD. The photoluminescence of surfaces of MgO obtained after outgassing at increasing temperature or after interaction of water or methanol with a clean surface, i.e., obtained by outgassing at 1273 K, was then studied and evidenced three other photoluminescent species assigned to surface OH groups. The nature and mechanism of formation of the hydroxyls groups responsible for these new luminescent species are discussed in relation with their thermal stability and FTIR experiments.

Oxygen vacancies of zinc oxide were followed by photoluminescence (PL) and electron paramagnetic resonance (EPR) spectroscopies. The green PL emission was associated with oxygen vacancies: its intensity is enhanced upon static thermal treatment under inert or under vacuum, whereas it decreases upon oxygen treatment. A unique EPR signal at g = 1.96 was measured at room temperature after thermal in situ treatment under flow of inert or oxygenated atmospheres, its double integration follows the same trends than the green PL emission and its evolution was shown to probe the oxygen vacancy concentrations. The relative concentration of the related paramagnetic species would be increased/decreased upon trapping/release of the electron associated to the formation/filling of oxygen vacancy. The influence of Ti impurities on the PL and RPE signals was investigated. Finally, it is concluded that the EPR signal is related to oxygen vacancies and its position shift could be explained by the involvement of some mixing orbitals. Thanks to static (PL and EPR) and dynamic (EPR) in situ characterizations, the conditions of formation or filling of oxygen vacancies are discussed depending of the atmosphere and temperature of the pretreatment of kadox and ex-carbonate zinc oxide. High temperature treatments, inert atmospheres, and vacuum lead to the formation of new oxygen vacancies. This process is reversible upon oxygenated atmospheres. The efficiency of such filling up depends on the temperature and starts to prevail on the oxygen vacancy formation below 500 K. It is also shown that few native oxygen vacancies can also be filled up.

Solid state 1 H and 31 P NMR spectroscopy was used to characterize wellcrystallized hydroxyapatite samples of different stoichiometry prepared by a precipitation route. The aim of the paper was to investigate the bulk structural features of samples with different stoichiometry and to discriminate signals related to the surface from those related to the bulk. Thanks to the implementation of (i) in situ thermal pretreatment at 623 K, (ii) filling of the NMR rotor in a controlled atmosphere, (iii) relative proton enrichment of the surface performed under controlled isotopic H-D exchanges, and (iv) specific NMR sequences including inversion recovery measurements, two-dimensional HETCOR and DQSQ spectra, new resolved NMR signals originating from the surface and from the bulk were identified alongside already reported signals associated with adsorbed water, structural phosphates, and OH groups. In particular, considering the influence of the stoichiometry, it was possible to identify a specific signature associated with defective hydrogenophosphate groups present in the bulk. Despite the well-ordered surface terminations of the nanoparticles, specific surface signals associated with nonprotonated and protonated surface terminating phosphate groups could be identified. In addition, from the three resolved 1 H signals associated with columnar OH channels, two from the bulk and one from the surface, a structural model describing the relative organization of hydroxyl groups running along the c axis inside the columnar OH channel in the well-crystallized particles is proposed: the two types of bulk hydroxyls are associated with the presence of both up and down orientations of their related protons in a same tunnel. Corresponding 1 H signatures of the surface-terminating hydroxyls or structured water molecules emerging from the OH channels were also identified. Moreover, in addition to the broad 5.1 ppm line associated with water adsorbed on calcium cations and hydrogenophosphate groups, the 1.1 ppm line is ascribed to structured external water molecules stacking in continuity to the OH channels.

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