0000000000139588
AUTHOR
Lorenzo Fernández
Expanding the atrane route: Generalized surfactant-free synthesis of mesoporous nanoparticulated xerogels
Abstract A diversity of silica-based and non-silica nanoparticulated mesoporous xerogels have been synthesized from aqueous solution using a surfactant-free strategy, and starting from molecular atrane complexes as precursors. This approach constitutes an extension of the “atrane route” previously described for the surfactant-assisted synthesis of mesoporous materials, and allows us to unify the multiplicity of protocols described for the preparation of conventional xerogels. In fact, we have used exactly the same preparative conditions for obtaining all the compositions reported here. The xerogels synthesized in this way include pure silica (UVM-11), aluminosilicates and titanosilicates (M…
Molecular precursors of mesostructured silica materials in the atrane route: A DFT/GIAO/NBO theoretical study
Abstract Quantum chemical calculations using density functional theory have been carried out to investigate two assumed molecular precursors and identified as silatranes (N[OCH2CH2]3Si–OCH2CH2N–(CH2CH2OH)2 and N[OCH2CH2]3Si–OCH2CH2N–(CH2CH2OH)2Na+) which are present in the synthesis of mesoporous silica based material namely “the atrane route”. One of the ways in this synthesis leads to the well-known MCM-41. Additionally, in this work has been also investigated two others molecules such as triethanolamine (TEAH3) and sodatrane which are present in the medium. Gas phase and solution equilibrium geometries of the previous molecules were fully optimized at B3LYP level, modeling solvent effect…
ZnO nanoparticles embedded in UVM-7-like mesoporous silica materials: Synthesis and characterization
Abstract ZnO nanodomains embedded in bimodal mesoporous silica (UVM-7) materials with high Zn content (4≤Si/Zn≤30) have been synthesized by an one-pot surfactant-assisted procedure from a hydro alcoholic medium using a cationic surfactant (CTMABr=cetyltrimethylammonium bromide) as structural directing agent, and starting from molecular atrane complexes of Zn and Si as hydrolytic inorganic precursors. This chemical procedure allows optimizing the dispersion of the ZnO particles in the silica walls. The bimodal mesoporous nature of the final high surface area nano-sized materials is confirmed by XRD, TEM, and N2 adsorption–desorption isotherms. The small intra-particle mesopore system is due …
DFT Study on the Interaction of Tris(benzene-1,2-dithiolato)molybdenum Complex with Water. A Hydrolysis Mechanism Involving a Feasible Seven-Coordinate Aquomolybdenum Intermediate
In the present work, the reactivity of the tris(benzene-1,2-dithiolato)molybdenum complex ([Mo(bdt)3]) toward water is studied by means of the density functional theory (DFT). DFT calculations were performed using the M06, B3P86, and B3PW91 hybrid functionals for comparison purposes. The M06 method was employed to elucidate the reaction pathway, relative stability of the intermediate products, nature of the Mo–S bond cleavage, and electronic structure of the involved molybdenum species. This functional was also used to study the transference of electrons from the molybdenum center toward the ligands. The reaction pathway confirms that [Mo(bdt)3] undergoes hydrolysis, yielding dihydroxo-bis(…
Nanoparticulated Silicas with Bimodal Porosity: Chemical Control of the Pore Sizes
Nanoparticulated bimodal porous silicas (NBSs) with pore systems structured at two length scales (meso- and large-meso-/macropores) have been prepared through a one-pot surfactant-assisted procedure by using a simple template agent and starting from silicon atrane complexes as hydrolytic inorganic precursors. The final bulk materials are constructed by an aggregation of pseudospherical mesoporous primary nanoparticles process, over the course of which the interparticle (textural) large pore system is generated. A fine-tuning of the procedural variables allows not only an adjustment of the processes of nucleation and growth of the primary nanoparticles but also a modulation of their subseque…
Structural incorporation of nitrogen into zeolites, and alpos: ab initio molecular orbital calculations on stability and basicity
Ab initio molecular orbital calculations (HF/6-31G*) are used to obtain thermodynamical information on the possibility to form NH-bridging or NH2-terminal groups in amorphous and crystalline materials containing Si–O–Si and Al–O–P structures, such as for instance, zeolites and aluminophosphates. We have employed dimeric model clusters Si–O–Si and Al–O–P which contain NH2-terminal groups or an oxygen atom substituted by a NH bridging unit. The Bronsted basicity and the softness–hardness of these structures have been determined using the proton affinity and the HOMO energy, respectively. The obtained results indicate that for both Si–O–Si and Al–O–P linkages and from a thermodynamic standpoin…
Layered-Expanded Mesostructured Silicas: Generalized Synthesis and Functionalization
Mesostructured layered silicas have been prepared through a surfactant-assisted procedure using neutral alkylamines as templates and starting from atrane complexes as hydrolytic inorganic precursors. By adjusting the synthetic parameters, this kinetically controlled reproducible one-pot method allows for obtaining both pure and functionalized (inorganic or organically) lamellar silica frameworks. These are easily deconstructed and built up again, which provides a simple way for expanding the interlamellar space. The materials present high dispersibility, which results in stable colloidal suspensions.
Theoretical study of oligomeric alumatranes present in the chemistry of materials from micro to mesoporous molecular sieves and alumina composites
Quantum chemical calculations using density functional theory have been carried out to investigate molecular precursors based on alumatranes which are one of the components with silatranes for the preparation of mesoporous aluminosilicate materials. In the same way, some oligomeric alumatranes of this study take part in chemical syntheses related to materials such as zeolites and alumina composite. Gas phase and solution equilibrium geometries of the alumatrane precursors were fully optimized at B3LYP level, modeling solvent effects using a self-consistent reaction field (SCRF). From these optimized geometries, calculations of the 1 H, 13 C and 27 Al NMR chemical shifts at GIAO/B3LYP/6-31G(…
Supramolecular capping-ligand effect of lamellar silica mesostructures for the one-pot synthesis of highly dispersed ZnO nanoparticles
ZnO?SiO2 lamellar nanocomposites with high zinc content (5?Si/Zn?50) have been synthesized through a one-pot surfactant-assisted procedure from aqueous solution and starting from molecular atrane complexes of Zn and Si as inorganic hydrolytic precursors. This approach allows optimization of the dispersion of the ZnO nanodomains in the silica sheets. The nature of the layered silica materials has been confirmed by x-ray diffraction. Spectroscopic (ultraviolet?visible and photoluminescence) study of these layered silica materials shows that, regardless of the Si/Zn ratio, Zn atoms are organized in well-dispersed, uniform ZnO nanodomains (about 1.2?nm) partially embedded within the silica shee…
Mesosynthesis of ZnO-SiO(2) porous nanocomposites with low-defect ZnO nanometric domains.
Silica-based ZnO-MCM-41 mesoporous nanocomposites with high Zn content (5≤Si/Zn≤50) have been synthesized by a one-pot surfactant-assisted procedure from aqueous solution using a cationic surfactant (CTMABr = cetyltrimethylammonium bromide) as structure-directing agent, and starting from molecular atrane complexes as inorganic hydrolytic precursors. This preparative technique allows optimization of the dispersion of the ZnO nanodomains in the silica walls. The mesoporous nature of the final materials is confirmed by x-ray diffraction (XRD), transmission electron microscopy (TEM) and N(2) adsorption-desorption isotherms. The ZnO-MCM-41 materials show unimodal pore size distributions without …