Open Access
Hybrid xerogels doped with Tb(III) and Eu (III) and a water soluble Pybox ligand
(2021) Cruz Quesada, Guillermo; Espinal Viguri, Maialen; Garrido Segovia, Julián José; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
Hybrid organic-inorganic siliceous materials (ORMOSiLs) are a key focus within the nanoscience area as they combine advantages of inorganic materials without losing characteristics intrinsic of organic molecules. In the past years, our research group has designed hybrid siliceous xerogels (HSXG) with porosities and surface chemistries on demand for a range of applications, such as coatings for optic fiber sensors [1]. Although hybrid xerogels are mainly amorphous materials, recent studies by our group have demonstrated that introducing specific organic fragments on the precursors can induce selforganization during the sol-gel process to obtain a series of transparent nanostructured HSXG [2]. In the present work, a step forward is taken in the applicability of this type of HSXG by doping them with Tb(III) or Eu (III) cations and a water-soluble pybox-based antenna ligand (Pybox-EG= 2,2′-(4-(2-Ethoxyethoxy)pyridine-2,6-diyl)bis(4,5-dihydrooxazole)). Inclusion of photoluminescence will provide the materials with new properties and therefore new applications in fiber optic sensors (FOS) or in solar cells devices.
Open Access
New hybrid organochlorinated xerogels
(2021) Cruz Quesada, Guillermo; Espinal Viguri, Maialen; López Ramón, María Victoria; Garrido Segovia, Julián José; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
Hybrid silica xerogels (HSXG) combine the properties of organic and inorganic components in the same material, which makes them promising and versatile candidates for multiple applications. These materials can be easily prepared by the sol-gel process, which offers the possibility to obtain different morphologies. The incorporation of organic precursors plays an important role in their properties, hence, allowing the design of materials for specific applications such as coatings for optical fibers [1]. The aim of this work was to study the influence of the alkyl chain and chlorine atom on the morphological and textural properties of various hybrid materials produced by co-condensation. For this purpose, three series of hybrid xerogels were prepared by co-condensation of TEOS and a chloroalkyltriethoxysilane (TEOS:ClRTEOS, R = methyl, ethyl or propyl) at different molar ratios. The influence of the precursors on the structure and textural properties of the xerogels was studied by means of N2 adsorption, XRD (X-ray diffraction), 29Si NMR (nuclear magnetic resonance) and FE-SEM (Field Emission-scanning electron microscope) [2].
Open Access
Novel silica hybrid xerogels prepared by co-condensation of TEOS and ClPhTEOS: a chemical and morphological study
(MDPI, 2022) Cruz Quesada, Guillermo; Espinal Viguri, Maialen; López Ramón, María Victoria; Garrido Segovia, Julián José; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
The search for new materials with improved properties for advanced applications is, nowadays, one of the most relevant and booming fields for scientists due to the environmental and technological needs of our society. Within this demand, hybrid siliceous materials, made out of organic and inorganic species (ORMOSILs), have emerged as an alternative with endless chemical and textural possibilities by incorporating in their structure the properties of inorganic compounds (i.e., mechanical, thermal, and structural stability) in synergy with those of organic compounds (functionality and flexibility), and thus, bestowing the material with unique properties, which allow access to multiple applications. In this work, synthesis using the sol-gel method of a series of new hybrid materials prepared by the co-condensation of tetraethoxysilane (TEOS) and 4-chlorophenyltriethoxysilane (ClPhTEOS) in different molar ratios is described. The aim of the study is not only the preparation of new materials but also their characterization by means of different techniques (FT-IR, 29Si NMR, X-ray Diffraction, and N2/CO2 adsorption, among others) to obtain information on their chemical behavior and porous structure. Understanding how the chemical and textural properties of these materials are modulated with respect to the molar percentage of organic precursor will help to envisage their possible applications: From the most conventional such as catalysis, adsorption, or separation, to the most advanced in nanotechnology such as microelectronics, photoluminescence, non-linear optics, or sensorics.
Open Access
Tuning the sensitivity of photonic sensors toward alkanes through the textural properties of hybrid xerogel coatings
(Wiley, 2025-01-15) Rosales Reina, María Beatriz; López Torres, Diego; Cruz Quesada, Guillermo; Espinal Viguri, Maialen; Elosúa Aguado, César; Reinoso, Santiago; Garrido Segovia, Julián José; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ingeniería Eléctrica, Electrónica y de Comunicación; Ingeniaritza Elektrikoa, Elektronikoa eta Telekomunikazio Ingeniaritza; Institute of Smart Cities - ISC; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
This work exemplifies how incorporating organosilane modifiers into silica matrices allows for tuning the optical response of reflection photonic sensors through customizing the textural properties of hybrid xerogel sensing films. Xerogels with propyl molar percentages 0, 5, and 10% are used to construct photonic probes (OFS0pTEOS, OFS5pTEOS and OFS10pTEOS, respectively) by dip-coating upon optimizing film deposition parameters. The time response of these probes toward a battery of volatile organic compounds (VOCs) comprising species with different functionality, size-shape, and polarity is systematically analyzed through ON/OFF experiments, revealing that a low propyl content makes the poor-responding OFS0pTEOS film highly sensitive toward non-aromatic, large molecules with low-polar or non-polar character in OFS5pTEOS. This sensor is particularly sensitive toward alkanes, with globular cyclohexane (cyHex) outperforming elongated n-hexane. Variable-temperature calibration curves obtained from step-by-step experiments and adsorption-desorption cycles corroborate these observations and allow hysteresis to be quantified. The response to cyHex closely follows VOC concentration changes with the most stable signal among analytes, leading to well-defined curves with low-to-negligible hysteresis. The isosteric enthalpies of cyHex adsorption are obtained for both the bulk material and the sensor, demonstrating labile adsorbate-adsorbent interactions ruling the sensor response and becoming more exothermic for larger VOC concentrations.
Open Access
Tunability of hybrid silica xerogels: surface chemistry and porous texture based on the aromatic precursor
(MDPI, 2023) Rosales Reina, María Beatriz; Cruz Quesada, Guillermo; Padilla-Postigo, Nataly; Irigoyen-Razquin, Marian; Alonso-Martínez, Ester; López Ramón, María Victoria; Espinal Viguri, Maialen; Garrido Segovia, Julián José; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
The interest in new materials with specific properties has increased because they are essential for the environmental and technological needs of our society. Among them, silica hybrid xerogels have emerged as promising candidates due to their simple preparation and tunability: when they are synthesised, depending on the organic precursor and its concentration, their properties can be modulated, and thus, it is possible to prepare materials with à la carte porosity and surface chemistry. This research aims to design two new series of silica hybrid xerogels by co-condensation of tetraethoxysilane (TEOS) with triethoxy(p-tolyl)silane (MPhTEOS) or 1,4-bis(triethoxysilyl)benzene (Ph(TEOS)2 and to determine their chemical and textural properties based on a variety of characterisation techniques (FT-IR, 29Si NMR, X-ray diffraction and N2 , CO2 and water vapour adsorption, among others). The information gathered from these techniques reveals that depending on the organic precursor and its molar percentage, materials with different porosity, hydrophilicity and local order are obtained, evidencing the easy modulation of their properties. The ultimate goal of this study is to prepare materials suitable for a variety of applications, such as adsorbents for pollutants, catalysts, films for solar cells or coatings for optic fibre sensors.
Open Access
Hybrid xerogels: study of the sol-gel process and local structure by vibrational spectroscopy
(MDPI, 2021) Cruz Quesada, Guillermo; Espinal Viguri, Maialen; López Ramón, María Victoria; Garrido Segovia, Julián José; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
The properties of hybrid silica xerogels obtained by the sol-gel method are highly dependent on the precursor and the synthesis conditions. This study examines the influence of organic substituents of the precursor on the sol-gel process and determines the structure of the final materials in xerogels containing tetraethyl orthosilicate (TEOS) and alkyltriethoxysilane or chloroalkyltri-ethoxysilane at different molar percentages (RTEOS and ClRTEOS, R = methyl [M], ethyl [E], or propyl [P]). The intermolecular forces exerted by the organic moiety and the chlorine atom of the precursors were elucidated by comparing the sol-gel process between alkyl and chloroalkyl series. The microstructure of the resulting xerogels was explored in a structural theoretical study using Fourier transformed infrared spectroscopy and deconvolution methods, revealing the distribution of (SiO)4 and (SiO)6 rings in the silicon matrix of the hybrid xerogels. The results demonstrate that the alkyl chain and the chlorine atom of the precursor in these materials determines their inductive and steric effects on the sol-gel process and, therefore, their gelation times. Furthermore, the distribution of (SiO)4 and (SiO)6 rings was found to be consistent with the data from the X-ray diffraction spectra, which confirm that the local periodicity associated with four-fold rings increases with higher percentage of precursor. Both the sol-gel process and the ordered domains formed determine the final structure of these hybrid materials and, therefore, their properties and potential applications.
Open Access
Design of novel photoactive modified titanium silicalites and their application for venlafaxine degradation under simulated solar irradiation
(Wiley, 2024) Cruz Quesada, Guillermo; Sampaio, María J.; Espinal Viguri, Maialen; López Ramón, María Victoria; Garrido Segovia, Julián José; Silva, Cláudia G.; Faria, Joaquim L.; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA18-2022
Titanium silicalites (TS) are well-known materials for their use in industrial oxidation reactions, and although they are used as photocatalysts, their activity is limited. Therefore, numerous synthetic strategies are investigated to improve their photocatalytic activity. Herein, three series of modified titanium silicalites are synthesized using three different organotriethoxysilanes at different molar percentages with the aim of modifying the structure of the zeolite, both at a porous and chemical level, to obtain materials with high photocatalytic activity. The study of their morphological, textural, chemical, and UV–vis light absorption properties through various characterization techniques has allowed the selection of the best candidates to test their photoactivity in the degradation of venlafaxine, an antidepressant drug that persists as a contaminant in wastewater and has serious neurotoxic effects. Materials synthesized using a 5% molar percentage of RTEOS and 10% of PhTEOS (Ph = phenyl) are able to degrade venlafaxine, whereas the reference material does not show any photocatalytic activity. These results lead the way to use this synthetic strategy to develop titanium silicates and optimize their photocatalytic activity in degradation reactions of different pollutants.
Open Access
Organocatalytic Michael addition of unactivated a-branched nitroalkanes to afford optically active tertiary nitrocompounds
(American Chemical Society, 2023) Lorea Revilla, Beñat; García-Urricelqui, Ane; Odriozola Ibarguren, José Manuel; Razkin Lizarraga, Jesús; Espinal Viguri, Maialen; Oiarbide, Mikel; Mielgo, Antonia; García Castillo, Jesús María; Palomo, Claudio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Gobierno de Navarra / Nafarroako Gobernua; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA18- 2022
The direct, asymmetric conjugate addition of unactivated ¿-branched nitroalkanes is developed based on the combined use of chiral amine/ureidoaminal bifunctional catalysts and a tunable acrylate template to provide tertiary nitrocompounds in 55¿80% isolated yields and high enantioselectivity (e.r. up to 96:4). Elaboration of the ketol moiety in thus obtained adducts allows a fast entry to not only carboxylic and aldehyde derivatives but also nitrile compounds and enantioenriched 5,5-disubstituted ¿-lactams.
Open Access
From fundamental materials chemistry to sensing applications: unravelling the water adsorption mechanism of a luminescent optical fibre sensor membrane
(Elsevier, 2024) Cruz Quesada, Guillermo; Rosales Reina, María Beatriz; López Torres, Diego; Reinoso, Santiago; López Ramón, María Victoria; Arzamendi Manterola, Gurutze; Elosúa Aguado, César; Espinal Viguri, Maialen; Garrido Segovia, Julián José; Ciencias; Ingeniería Eléctrica, Electrónica y de Comunicación; Institute for Advanced Materials and Mathematics - INAMAT2; Institute of Smart Cities - ISC; Zientziak; Ingeniaritza Elektrikoa, Elektronikoaren eta Telekomunikazio Ingeniaritzaren; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
This work provides insight into the correlation between the luminescent response of a water-vapour optical fibre sensor and the textural properties of its lanthanide-doped silica coating. To this end, a library of 16 silica xerogels derived from combinations between 2 lanthanide dopants (EuIII, TbIII) and 8 antenna ligands was synthesised and characterised by photoluminescence spectroscopy and N2 and CO2 adsorption-desorption isotherms, among others. Based on the best luminescent response and most-suited porous texture, the material doped with TbIII and 2,2′-(4-(2-Ethoxyethoxy)pyridine-2,6-diyl)bis(4,5-dihydrooxazole) was selected to construct the probe. A film of this material was affixed to a commercial silica fibre by dip-coating and the resulting sensor was tested in a climatic chamber with relative humidity ranging from 20 to 90% to obtain normalised time-response and calibration curves at three temperatures. The response was linear up to certain water-vapour concentrations, beyond which abruptly changed to polynomial, acting against the sensor resolution. The adsorption mechanism was elucidated by comparing the isosteric enthalpies of adsorption calculated from the sensor calibration curves to those determined from the monolith water-vapour isotherms, revealing that capillary condensation in the membrane mesopores was the key phenomenon leading to the response deviating from linearity.