Desireé M. de los Santos

New Nanomaterials for Consolidating Stone

A novel sol-gel synthesis, in which a surfactant acts to make the pore size of the gel network more coarse and uniform, is shown to provide an effective alternative for the consolidation of stone. The new mesoporous silica avoids the main inconvenience of current commercial consolidants, which is their tendency to crack inside the pores of the stone. Since the cracking of xerogels is a well-known drawback of the sol-gel process, the synthesis presented here can be extended to other applications. Finally, preliminary studies of the effectiveness of the novel surfactant-templated sol in consolidating a typical biocalcareous stone are also discussed.

Surfactant-Synthesized Ormosils with Application to Stone Restoration

A challenging objective in monumental stone restoration is to synthesize crack-free silica materials for application as consolidants. Hydrophobicity is also a valuable property for such products; it is important to prevent the penetration of water because water is the main vehicle by which the agents of decay enter the pore structure of the stone. We report the development of a hydrophobic crack-free nanomaterial with application to stone restoration. Specifically, organically modified silicate (ormosil) has been synthesized by the co-condensation of tetraethoxysilane (TEOS) and hydroxyl-terminated polydimethylsiloxane (PDMS) in the presence of a nonionic surfactant (n-octylamine). The role played by the surfactant in the assembly of the organic-inorganic hybrid silica gel was investigated. We also prepared a crack-free material using the same synthesis but without adding PDMS to the starting sol. Finally, the effectiveness of the nanomaterials synthesized as a consolidant and hydrophobic protective treatment was evaluated on a particular widely used monumental stone. The high hydrophobicity of the organic-inorganic hybrid product synthesized in our laboratory is discussed as a function of the surface roughness of the material.

New Nanomaterials for Protecting and Consolidating Stone

The sol-gel process has been found to be successful in applications for the conservation and restoration of stone. However, a well-known drawback of the materials obtained by this process is their tendency to crack during drying inside the pores of the treated stone. In this article, we present an overview of our current research centred on producing crack-free sol-gel materials for consolidating and protecting building stone. A novel synthesis, in which a surfactant acts as a template to make the pore size of the gel network coarser and more uniform, is shown to provide an effective alternative for preventing the cracking of consolidants. We also highlight an alternative pathway, in which we add an organic component to the silica precursor in the presence of the surfactant. The hybrid organic-inorganic gel prepared in our laboratory provides excellent waterproofing to the stones under study.

Introducing “UCA-FUKUI” software: reactivity-index calculations

A new software (UCA-FUKUI) has been developed to facilitate the theoretical study of chemical reactivity. This program can calculate global parameters like hardness, softness, philicities, and Fukui condensed functions, and also local parameters from the condensed functions. To facilitate access to the program we have developed a very easy-to-use interface. We have tested the performance of the software by calculating the global and local reactivity indexes of a group of representative molecules. Finite difference and frontier molecular orbital methods were compared and their correlation tested. Finally, we have extended the analysis to a set of ligands of importance in coordination chemistry, and the results are compared with the exact calculation. As a general trend, our study shows the existence of a high correlation between global parameters, but a weaker correlation between local parameters.

Electronic and structural properties of highly aluminum ion doped TiO(2) nanoparticles: a combined experimental and theoretical study.

This study presents the experimental and theoretical study of highly internally Al-doped TiO2 nanoparticles. Two synthesis methods were used and detailed characterization was performed. There were differences in the doping and the crystallinity, but the nanoparticles synthesized with the different methods share common features. Anatase to rutile transformation occurred at higher temperatures with Al doping. X-ray photoelectron spectroscopy showed the generation of oxygen vacancies, which is an interesting feature in photocatalysis. In turn, the band-gap energy and the valence band did not change appreciably. Periodic density functional calculations were performed to model the experimentally doped structures, the formation of the oxygen vacancies, and the band gap. Calculation of the density of states confirmed the experimental band-gap energies. The theoretical results confirmed the presence of Ti(4+) and Al(3+) . The charge density study and electron localization function analysis indicated that the inclusion of Al in the anatase structure resulted in a strengthening of the TiO bonds around the vacancy.

TiO2 and pyrochlore Tm2Ti2O7 based semiconductor as a photoelectrode for dye-sensitized solar cells

This study presents the use of TiO2 nanoparticles with Tm as photoelectrodes in DSSCs. The nanoparticles were annealed at 1173 K and the predominant TiO2 phase was rutile. XRD and Raman spectroscopy revealed the presence of a crystalline pyrochlore phase of the mixed oxide Tm2Ti2O7. In turn, XPS confirmed the presence of Ti4+ and Tm3+, so the inclusion of Tm did not affect the oxidation state of the Ti. UV–Vis spectra showed that the presence of the pyrochlore phase led to new electronic states in the band gap. The use of the pyrochlore phase in the photoelectrode had a positive effect, improving the efficiency of the pure TiO2 cells. The efficiency increased by between 2.32% and 3.16% when pure TiO2 was replaced with a mixture of rutile TiO2 and pyrochlore Tm2Ti2O7, so the controlled use of a pyrochlore phase can produce good results in dye-sensitized solar cells. Another important effect of the pyrochlore phase was to increase the open-circuit voltage values by around 7% and can be explained by the flat band voltage values. The samples with Tm showed two flat band voltage values, which generated two possible electronic injection mechanisms in the cells.

Convergent study of Ru–ligand interactions through QTAIM, ELF, NBO molecular descriptors and TDDFT analysis of organometallic dyes

We report a theoretical study of a series of Ru complexes of interest in dye-sensitised solar cells, in organic light-emitting diodes, and in the war against cancer. Other metal centres, such as Cr, Co, Ni, Rh, Pd, and Pt, have been included for comparison purposes. The metal–ligand trends in organometallic chemistry for those compounds are shown synergistically by using three molecular descriptors: quantum theory of atoms in molecules (QTAIM), electron localisation function (ELF) and second-order perturbation theory analysis of the natural bond orbital (NBO). The metal–ligand bond order is addressed through both delocalisation index (DI) of QTAIM and fluctuation index (λ) of ELF. Correlation between DI and λ for Ru–N bond in those complexes is introduced for the first time. Electron transfer and stability was also assessed by the second-order perturbation theory analysis of the NBO. Electron transfer from the lone pair NBO of the ligands toward the antibonding lone pair NBO of the metal plays a relevant role in stabilising the complexes, providing useful insights into understanding the effect of the ‘expanded ligand’ principle in supramolecular chemistry. Finally, absorption wavelengths associated to the metal-to-ligand charge transfer transitions and the highest occupied molecular orbital (HOMO)--lowest unoccupied molecular orbital (LUMO) characteristics were studied by time-dependent density functional theory.

Hybrid Perovskite, CH3NH3PbI3, for Solar Applications

The effect of the incorporation of NH4+ into the CH3NH3+ sites of the tetragonal perovskite CH3NH3PbI3 is analysed. Also, how it affects the introduction of Cd2+ cations into Pb2+ sites for a perovskite with 25źat.% of NH4+ is addressed. The incorporation of NH4+ into perovskite leads to a dramatic loss of crystallinity and to the presence of other phases. Moreover, the NH4PbI3 was not found. The less formation of perovskite when NH4+ is incorporated is due to geometrical factors and not changes in the chemical state bonding of the ions. Also, the samples where perovskite is formed show similar band gap values. A slight increase is observed for samples with x=0.5 and 0.75. For the sample with x=1, a drastic increase of the band gap is obtained. Periodic-DFT calculations agree with the experimental structural tendency when NH4+ is incorporated and the density of states analysis confirmed the experimental band gap. The perovskite with 25źat.% of NH4+ was selected for studying the effect of the concentration of Cd on the structural and electronic properties. The theoretical band gap values decreased with the Cd concentration where the narrowing of Cd s-states in the conduction band plays an important role.

Reinforced silica-carbon nanotube monolithic aerogels synthesised by rapid controlled gelation

AbstractThis work introduces a new synthesis procedure for obtaining homogeneous silica hybrid aerogels with carbon nanotube contents up to 2.50 wt.%. The inclusion of nanotubes in the highly porous silica matrix was performed by a two-step sol–gel process, resulting in samples with densities below 80 mg/cm3. The structural analyses (N2 physisorption and SEM) revealed the hierarchical structure of the porous matrix formed by nanoparticles arranged in clusters of 100 and 300 nm in size, specific surface areas around 600 m2/g and porous volumes above 4.0 cm3/g. In addition, a relevant increase on the mechanical performance was found, and an increment of 50% for the compressive strength and 90% for the maximum deformation were measured by uniaxial compression. This reinforcement was possible thanks to the outstanding dispersion of the CNT within the silica matrix and the formation of Si–O–C bridges between nanotubes and silica matrix, as suggested by FTIR. Therefore, the original synthesis procedure introduced in this work allows the fabrication of highly porous hybrid materials loaded with carbon nanotubes homogeneously distributed in the space, which remain available for a variety of technological applications.

MoS2/Cu/TiO2 nanoparticles: synthesis, characterization and effect on photocatalytic decomposition of methylene blue in water under visible light

Photodegradation processes are of great interest in a range of applications, one of which is the photodecomposition of pollutants. For this reason, analysing nanoparticles that improve the efficiency of these processes under solar radiation are very necessary. Thus, in this study, TiO2 was doped with Mo and Cu using low-temperature hydrolysis as the method of synthesis. Pure TiO2 and x%MoS2/Cu/TiO2 nanoparticles were prepared, where x is the theoretical quantity of MoS2 added (0.0%, 1.0%, 5.5%, 10.0%), setting the nominal quantity of Cu at 0.5 wt.%. The samples obtained were characterized by X-ray diffraction, Raman spectroscopy, X-ray electron spectroscopy and UV-Vis spectroscopy in diffuse reflectance mode. The results suggest that the TiO2 structure was doped with the Mo6+ and Cu2+ ions in the position of the Ti4+. The x%MoS2/Cu/TiO2 samples presented lower band gap energy values and greater optical absorption in the visible region than the pure TiO2 sample. Lastly, the photocatalytic activity of the samples was assessed by means of the photodegradation of methylene blue under visible light. The results show that when the quantity of Mo in the co-doped samples increased (x%MoS2/Cu/TiO2) there were significant increases of up to 93% in the photocatalytic activity.