On the Comprehensive Precipitation of Hydroxyapatites Unraveled by a Combined Kinetic-Thermodynamic Approach.

The present study combines experimental and theoretical approaches to investigate the competitive precipitation of calcium phosphates (CaPs) in aqueous solution in order to understand and control both the structural and textural properties of the synthesized hydroxyapatites (HAps). Some of the precipitation reactions were followed by in situ Raman spectroscopy or achieved under kinetically controlled conditions. The CaP precursors of HAps were identified as a function of the precipitation pH of the medium and the order of introduction of the precursor ions in the synthesis reactor. Their formation was rationalized by calculations based on a homogeneous nucleation model. Depending on the synthesis conditions, precipitation reaction pathways of HAps are proposed by bringing together the kinetic model developed in the present study and our previous thermodynamic model. HAps are complex materials due to the ease with which large amounts of crystallographic defects, such as carbonates and hydrogen phosphates, can be incorporated in their structure. As these defects play a key role in material sciences (bone substitute, heterogeneous acid-base catalysis, etc.), the present work also includes the analysis of the formation of these crystallographic defects in the apatitic framework, allowing a better control of their incorporation through careful selection of operating parameters.

Incorporation of vanadium into the framework of hydroxyapatites: importance of the vanadium content and pH conditions during the precipitation step.

Even though vanadium-modified hydroxyapatite (V-HAp) samples are very promising systems for oxidative dehydrogenation of propane, the incorporation of vanadium into the hydroxyapatite framework was reported to be limited and to lead to over-stoichiometric compounds. Here, the synthesis of a Ca10(PO4)6-x(VO4)x(OH)2 stoichiometric solid solution using a co-precipitation method is monitored in the whole composition range (0 ≤ x ≤ 6) by controlling the pH of the precipitation medium, with continuous (the first series of samples) or periodic (the second series of samples) addition of NH4OH during the precipitation step or during the maturation step, respectively. It is demonstrated that the changes in pH conditions result in materials of a substantial difference in terms of the final composition. From XRD patterns and Rietveld refinements, a solid solution V-HAp phase was found to be exclusively obtained for the first series of samples for x varying from 0 to 6. This also occurred in the second series of samples but only for x lower than 4. For 4 ≤ x ≤ 5.22, the materials were composed of a mixture of V-HAp and Ca2V2O7, whereas for a x value of 6 only Ca2V2O7 was formed. The predominance of polymeric V species in solution at a high vanadium concentration deduced from the diagram of speciation of vanadium accounts for the preferential formation of Ca2V2O7 under these particular conditions. However, provided that a higher pH value was maintained, isolated VO3(OH)2- species are predominant, which accounts for the incorporation of isolated vanadates into the hydroxyapatite framework and for the well-controlled stoichiometry with Ca/(P + V) ratios found to be close to 1.67. Such a very good accommodation of vanadium in the hydroxyapatite framework is illustrated by the characterization of the local surrounding of phosphorus and vanadium species using 31P and 51V NMR, Raman and UV-vis spectroscopies.

Control of calcium accessibility over hydroxyapatite by post-precipitation steps: influence on the catalytic reactivity toward alcohols.

Hydroxyapatites are increasingly used as heterogeneous catalysts since they present atypical behaviours for many acid base reactions. The aim of this study was to discuss the possible involvement of Ca2+ Lewis and/or PO-H Brønsted acid sites belonging to the hydroxyapatite system in the conversion of 2-methylbut-3-yn-1-ol, a model molecule that is known to account for the acid base properties, and of ethanol into n-butanol. A series of hydroxyapatite samples with similar bulk properties was prepared from a lone precipitation batch, but by varying the conditions of the washing and drying steps. Although the surface depth probed by XPS exhibited similar average composition, ISS analysis revealed a gradient of calcium concentration in the first surface layers. In fact, the different conditions of drying and washing resulted in a modulation of the relative amount of Ca2+ and PO-H accessible on the top surface, as revealed by the adsorption of the CO molecule monitored by FTIR. The conversion in the two alcohol molecules is linearly dependent on the nature of the acid base pairs involved: when accessible on the top surfaces, due to their stronger acidity, the Ca2+ Lewis acid sites are preferentially involved, but they are less efficient than PO-H, as illustrated by the linear decrease of the conversion levels with the increasing relative amount of accessible Ca2+ cations. It is thus concluded that PO-H sites enhance the performances of the catalysts for the two reactions, and that washing and drying conditions allowing us to decrease the calcium accessibility at the benefit of PO-H should be favoured.

Acidic Osteoid Templates the Plywood Structure of Bone Tissue.

Bone is created by osteoblasts that secrete osteoid after which an ordered texture emerges, followed by mineralization. Plywood geometries are a hallmark of many trabecular and cortical bones, yet the origin of this texturing in vivo has never been shown. Nevertheless, extensive in vitro work revealed how plywood textures of fibrils can emerge from acidic molecular cholesteric collagen mesophases. This study demonstrates in sheep, which is the preferred model for skeletal orthopaedic research, that the deeper non-fibrillar osteoid is organized in a liquid-crystal cholesteric geometry. This basophilic domain, rich in acidic glycosaminoglycans, exhibits low pH which presumably fosters mesoscale collagen molecule ordering in vivo. The results suggest that the collagen fibril motif of twisted plywood matures slowly through self-assembly thermodynamically driven processes as proposed by the Bouligand theory of biological analogues of liquid crystals. Understanding the steps of collagen patterning in osteoid-maturation processes may shed new light on bone pathologies that emerge from collagen physico-chemical maturation imbalances.

Influence of natural adsorbates of magnesium oxide on its reactivity in basic catalysis.

Solid materials possessing basic properties are naturally covered by carbonates and hydroxyl groups. Those natural adsorbates modify their chemical reactivity. This article aims to specifically evidence the role of surface carbonates and hydroxyls in basic heterogeneous catalysis on MgO. It compares the catalytic behaviors of hydroxylated or carbonated MgO surfaces for two types of reactions: one alkene 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 surfaces show that neither Lewis basicity nor Brønsted basicity of the surface defects (steps for example) are enhanced by hydroxylation. Meanwhile CO2 adsorption followed by IR spectroscopy shows that (110) and (111) unstable planes are strongly basic and are stabilized by partial surface hydroxylation. These results could explain the volcano curve obtained for the evolution of alkene isomerisation as a function of hydroxyl coverage.

How to determine IR molar absorption coefficients of co-adsorbed species? Application to methanol adsorption for quantification of MgO basic sites.

Methanol adsorption on MgO samples with different morphologies is studied by infrared (IR) spectroscopy coupled to volumetry or thermogravimetry measurements to probe qualitatively and quantitatively the acid-base paired sites. The molar absorption coefficients of ν(OC) vibration of non-dissociated methanol, type I and type II methoxy species are determined by analyzing data obtained under specific adsorption conditions (ε(ND)=2.5 cm µmol(-1); ε(I)=ε(II)=6.1 cm µmol(-1)). Thanks to these results, the amounts of different adsorbed methanol species are evaluated. These various species are formed on surface sites presenting different topologies. Hence, the IR method is the only one allowing us to both discriminate and quantify the defects on the MgO surfaces, in terms of concentrations of convex and concave defective zones. This study reveals that sol-gel preparation leads to a MgO surface presenting a greater amount of concave defective zones than precipitated MgO.

Mechanism and deactivation process of the conversion of methylbutynol on basic faujasite monitored by operando DRIFTS.

The successive steps occurring during conversion of methylbutynol (MBOH) on a basic NaX zeolite catalyst were characterized by combined micro-GC and operando DRIFT spectroscopy, associated to TPD-MS experiments. These techniques permit to reveal a very strong and fast initial decrease in MBOH consumption, associated to some water desorption and to a deficit in acetone that is a product formed together with acetylene, in agreement with the basic route. The origin of deactivation, the nature and reactivity of the adsorbed compounds and their relative strengths of adsorption are discussed on the basis of the evolution of the operando DRIFT spectra with time on stream and next upon keeping the used catalyst in static then under flowing N(2). The FTIR signatures of the three different modes of MBOH adsorption are determined and only the mode involving a zeolite acid-base pair is found reactive. Aldolic condensation is identified but solely to a minor extent in flowing conditions of the reaction whereas it is significantly enhanced in static. Thus, the apparent initial deactivation can be ascribed mainly to MBOH adsorption.

Basic reactivity of CaO: investigating active sites under operating conditions.

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.

Defect-related multicolour emissions in ZnO smoke: from violet, over green to yellow.

The nature of defects in ZnO smoke was studied at different stages of the material's history by combining photoluminescence (PL) and electron paramagnetic resonance (EPR) spectroscopy. In contrast to studies previously reported on ZnO nanopowders, high vacuum conditions (P < 10-5 mbar) have been applied during sample storage, handling and spectroscopic investigations. Two pairs of violet-PL/EPR signals (2.88 eV/ g = 1.956 and 2.80 eV/ g = 1.960) were observed in the as-synthesized ZnO powder and attributed to surface (dominant) and bulk zinc interstitials (Zni+). Upon annealing in O2-poor conditions, green-PL emission (2.41 eV) and EPR signal at g = 2.002 develop along with EPR signals specific of superoxide radicals (O2-). In the absence of any external O2 supply, the oxygen necessary for the creation of a notable amount of O2- is provided by the lattice of ZnO smoke, so that the green emission and its EPR counterpart are unambiguously assigned to singly charged oxygen vacancies (VO+). Annealing at high PO2 results in a broad PL emission (∼2.07 eV) without an EPR counterpart. This yellow emission was assigned to peroxide-like surface species (O22-). Overall, this study shows that the visible emissions in ZnO smoke nanopowders can range from violet, over green to yellow as a function of sample history and that the corresponding PL/EPR fingerprints can serve as guidelines for the recognition of defects in other ZnO types.

Revisiting acido-basicity of the MgO surface by periodic density functional theory calculations: role of surface topology and ion coordination on water dissociation.

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.

Physicochemical and in situ photoluminescence study of the reversible transformation of oxide ions of low coordination into hydroxyl groups upon interaction of water and methanol with MgO.

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.

The genesis of a heterogeneous catalyst: in situ observation of a transition metal complex adsorbing onto an oxide surface in solution.

Understanding the interactions between metal complexes and oxide surfaces is crucial to the synthesis of supported metal catalysts. Recently developed in situ techniques have made it possible to closely characterize the solid/liquid interface. For the first time, the adsorption of platinum complexes on alumina and silica has been probed using a quartz crystal microbalance; we were able to observe the adsorption of metal complexes in real time, and to observe the reversibility of this adsorption.

Infrared characterization of hydroxyl groups on MgO: a periodic and cluster density functional theory study.

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.

Kinetic model of energy transfer processes between low-coordinated ions on MgO by photoluminescence decay measurements.

Photoluminescence decay studies of emitting species on MgO nanocubes at room temperature provide evidence of three surface species characterized by an excitation and emission wavelength couple {lambda(exc);lambda(em)}. Species A corresponds to {lambda(exc)=240 nm; lambda(em)=380 nm}, whereas the couple {lambda(exc)=280 nm; lambda(em)=470 nm} is assigned to two species: B and B', the former is involved in energy transfer from excited state A* and the latter in direct emission from excited state B'*. A simple model for energy transfer from species A* to B is proposed. The numerical resolution of equations corresponding to this model is in good agreement with experimental data. This method quantifies the kinetics of intrinsic emission and energy transfer processes. Lifetime values indicate that phosphorescence is taking place, and species A, B and B' are identified as edge O(2-) (4 C), corner O(2-) (3 C) and kink O(2-) (3 C) oxide ions respectively.