Open Access
Use of clays and pillared clays in the catalytic photodegradation of organic compounds in aqueous solutions
(Taylor & Francis, 2024-02-23) Cardona Rodríguez, Yaneth; Korili, Sophia A.; Gil Bravo, Antonio; Ciencias; Zientziak
Conventional wastewater treatment plants do not currently remove all organic compounds, including some emerging pollutants. This has prompted several efforts to develop new methods and materials —or to improve existing ones— to remove such pollutants. The technologies studied to remove contaminants from water include photochemical processes in which the photons activate a material to produce radicals, which go on to initiate a series of reactions that result in oxidation of the pollutant. Several photocatalysts and catalyst supports have been used; these include clays and pillared interlayered clays (PILC), which have shown interesting results in the photodegradation of several organic contaminants. In this review, we describe the studies that have used both clays and PILC for the photodegradation of organic compounds in aqueous solutions. The results reported are summarized and compared, thus confirming that the findings support the use of these systems as photocatalysts and that they are successful and promising materials for the removal of several organic compounds. In this aspect, new synthesis procedures for PILC materials can be proposed from Heterostructures and MOF based on clays.
Open Access
Recent progress in the application of Ni-based catalysts for the dry reforming of methane
(Taylor & Francis, 2021) Torrez Herrera, Jonathan Josué; Korili, Sophia A.; Gil Bravo, Antonio; Institute for Advanced Materials and Mathematics - INAMAT2
Ni-based catalysts are highly efficient in methane-reforming processes. In the particular case of methane reforming in the presence of carbon dioxide, or dry reforming of methane (DRM), it is necessary to modify and control the initial properties of the catalyst to confer on it resistance to carbon deposition in particular, and to sintering of the Ni metal particles. In this regard, catalytic supports and promoters of different natures have been proposed. Likewise, the addition of small amounts of noble metals to avoid oxidation of the Ni active phase during the reforming reaction has been proposed. Catalyst preparation methods have also been identified as being of particular interest, since they can affect the structure of the Ni metal particles. In this review, the thermodynamic and kinetic aspects of the dry reforming of methane reaction are presented first. The most recent developments in synthetic methods (impregnation, sol-gel, co-precipitation, equilibrium deposition filtration, atomic layer deposition, non-thermal glow discharge plasma, multi-bubble sonoluminescence, 'core-shell' structure) aimed at maximizing the dispersion and thermal resistance of Ni particles are then discussed and compared. The catalytic supports used to promote dispersion of the active metallic phase, the oxygen-storage capacity, and the metal/support interaction are also described. The review then addresses the fact that both the nature of the support and the addition of promoters and other metallic phases that modify the surface properties can control the interaction between the metal and the support, the electronic density of the active phase, and the degree of Ni reduction. Finally, new lines of research focused on the DRM process to make the reaction conditions milder and favor the process at low temperatures are also summarized. © 2021 Taylor & Francis.
Open Access
Effect of the acid activation on a layered titanosilicate AM-4: the fine-tuning of structural and physicochemical properties
(Elsevier, 2020) Timofeeva, Maria N.; Kalashnikova, Galina O.; Shefer, Kristina I.; Mel'gunova, Elena A.; Panchenko, Valentina N.; Nikolaev, Anatoliy I.; Gil Bravo, Antonio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
In this work we investigated the microporous layered titanosilicate AM-4 (Aveiro-Manchester material number 4) of a synthetic analogous the mineral Lintisite having edge-shared brookite-type TiO6 chains. The objective of our work was to verify the effects of the acid activation on the AM-4 properties, treated with 0.0625–0.25 M HNO3. The results of the physicochemical characterization by SEM, XRD, IR and DR UV–vis spectroscopy, nitrogen adsorption/desorption at 77 K have provided evidences that texture, chemical composition, structural and physicochemical properties of AM-4 could be adjusted by treatment with 0.0625–0.25 M HNO3. According to the method of mass titration, surface acidity (pHPZC) of AM-4 roses with increasing HNO3 concentration, which was in accord with the increase of the reaction rate and yield of 1,5-benzodiazepine in the reaction of cyclocondansation between 1,2-phenylenediamine and acetone.
Open Access
Facile synthesis of an Ni/LaAlO3 - perovskite via an MOF gel precursor for the dry reforming of methane
(Elsevier, 2024) Muñoz Alvear, Helir Joseph; Korili, Sophia A.; Gil Bravo, Antonio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
A simple strategy to prepare the pure perovskite phase of lanthanum aluminate (LaAlO3) by calcination of a highly porous, dry MOF precursor gel has been developed. This study demonstrates that the structural and textural properties, such as specific surface area, pore volumes and pore sizes, of precursor-like metal-organic gels (MOG) (MOG-Al-La) based on metal-organic framework (MOF) structures can be modulated by optimizing the solvothermal treatment time. The perovskite obtained after solvothermal treatment at 120º C for 12 h and calcination at 750º C maintained the mesoporous characteristics of the MOF precursor, with a small particle size due to the decrease in crystallization temperature. These properties in the support allowed a good dispersion of the active Ni sites, low reducibility, and a strong interaction between them and the support, thus suppressing sintering under the severe catalytic reaction conditions evaluated (GHSV = 120,000 cm3/g-h) for the dry reforming of methane. The resulting MOX-(12 h)-LaAlO3-750-Ni catalyst gave a CH4 average conversion of 75% and CO2 average conversion of 80% after 20 h of reaction. The improved stability of the catalyst was attributed to suppression of the formation of the dense network of carbon filaments that can stress and subsequently fracture the support, cause attrition of the catalyst granules and hinder diffusion of the reactants both through the pores of the support and the interparticle spaces.
Open Access
A comparative study of acid and alkaline aluminum extraction valorization procedure for aluminum saline slags
(Elsevier, 2022) Jiménez, Alejandro; Rives, Vicente; Vicente, Miguel Ángel; Gil Bravo, Antonio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
A management process for saline slags, one of the wastes from Secondary Aluminum Production, is proposed. The process begins with a grinding step, followed by washing with water, which removed the fluxing salts but provoking the hydrolysis of AlN, yielding Al(OH)3 and ammonia. Sieving of the solid generated an intermediate and a fine fraction. The first one was rich in metallic aluminum, and can also be returned to the Secondary Aluminum Production. The fine fraction was submitted to a extraction process in acid (HCl or HNO3) or alkaline (NaOH, KOH or CsOH) conditions, under reflux at 90 ºC, obtaining an Al(III) solution that can be used in the synthesis of aluminum-based solids. HCl (1-8 mol/L) and NaOH (1-4 mol/L) were used as reference solutions, HNO3, NaOH and KOH were used under specific conditions; the slag fraction:extraction solution solid:liquid ratio was also varied. The optimum extraction conditions were: extraction time 2 h, solid:liquid ratio 3:10, concentration 3 mol/L for the NaOH medium and 4 mol/L for the HCl medium. More than 30% of the aluminum present in the fraction smaller than 0.4 mm was recovered (the remaining aluminum was present as insoluble phases, corundum and spinel). Acid or basic media can be selected depending on the final use of Al(III) solutions, the basic medium leading to an Al(III) solution with a lower amount of impurities. The hazardousness of the solid obtained after the extraction process was greatly decreased, making possible the use of this solid residue in sectors such as construction.
Open Access
Metal-Al layered double hydroxides synthesized from aluminum slags as efficient CO2 adsorbents at pre- and post-combustion temperature
(Elsevier, 2023) Santamaría Arana, Leticia; Korili, Sophia A.; Gil Bravo, Antonio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Layered double hydroxides (LDH) have been proposed as the materials that offer the best performance in the moderate-temperature range, between 200 and 450 °C, for CO2 adsorption, so the effect of some synthesis parameters and surface modification on their adsorption capacities is herein investigated. This work reports the use of M2+ (Co, Mg, Ni and Zn)/Al layered double hydroxides synthesized with a 3:1 molar ratio by the co-precipitation method and using aluminum extracted from saline slags as source of this metal as CO2 adsorbents. The synthesis and use of Zn/TiAl is also reported considering several proportions of Al-Ti. Structural characterization and comparison of the series has been achieved using powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), nitrogen physisorption at single bond196 °C and thermogravimetry measurements (TGA). The performance of calcined LDH as CO2 adsorbents was evaluated in the 50 – 400 °C temperature range and 80 kPa and results show that Ni6Al2 and Mg6Al2 samples present a significant adsorption capacity at low temperature (0.382 and 0.292 mmolCO2/g, respectively). At 400 °C only Mg6Al2 maintains its high adsorption capacity (0.275 mmolCO2/g) compared to the other calcined LDH. Its adsorption capacity at moderate-temperature range was proven to be better than that of a commercial Mg6Al2 sample. In all materials the CO2 adsorption capacity at 200–450 °C increased by incorporating potassium (K2CO3 and KOH as sources) up to 0.58 mmolCO2/g for Mg6Al2 +K2CO3. The addition of the amine TEPA in the low-temperature range worked for Co6Al2 and Mg6Al2 (increment > 40 %). In the case of Zn6Al2, the partial substitution of Al by Ti also increased the CO2 adsorption capacity from 0.177 to 0.244 mmolCO2/g, finding isosteric heats between 17.07 and 23.30 kJ/mol using the Clausius-Clapeyron equation.
Open Access
Visible-light-driven photocatalytic degradation of organic dyes using a TiO2 and waste-based carbon dots nanocomposite
(Elsevier, 2025-05-20) Sendão, Ricardo M.S.; Algarra González, Manuel; Lázaro-Martínez, Juan; Brandão, Ana T.S.C.; Gil Bravo, Antonio; Pereira, Carlos; Esteves da Silva, Joaquim C.G.; Pinto da Silva, Luís; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Herein we report a visible-light-active photocatalytic nanocomposite (NC50:50) prepared from carbon dots (CDs) and TiO2 nanoparticles, which was applied to the photodegradation of organic dyes in water. The CDs incorporated corn stover, a major agricultural waste, and were prepared via hydrothermal treatment. Using a visible-light irradiation source and the dye methylene blue as a representative of the organic dyes class, we observed that a 374% enhancement of the catalytic performance was achieved by adding CDs relative to bare TiO2. This was possible due to increased visible-light absorption and better photonic efficiency. Tests using reactive species scavengers indicated that three active species (superoxide anion, hydroxyl radicals, and electrons) were responsible for the photodegradation process, differing from bare TiO2 in which only the hydroxyl radical has a relevant role. Photocatalytic degradation was also observed toward Rhodamine B, Orange II and Methyl Orange. Finally, we performed a life cycle assessment (LCA) study to assess and analyse the associated environmental impacts of NC50:50 compared with other alternatives, which revealed that NC50:50 is the alternative resulting in the least environmental impacts. In summary, NC50:50 could, under visible-light irradiation, efficiently remove different organic dyes while incorporating organic waste materials and reducing the impacts associated with their use. We expect that this study provides a base for a more environmentally sustainable design of visible-light-active photocatalysts via waste upcycling.
Open Access
Synthesis of high-surface-area C3N4 deposited on halloysite-derived silica nanotubes: enhanced visible light degradation of norfloxacin
(Elsevier, 2024) Santamaría Arana, Leticia; Korili, Sophia A.; Gil Bravo, Antonio; López de Luzuriaga Fernández, José Manuel; Monge Oroz, Miguel; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Silica nanotubes, obtained from halloysite clay nanotubes that were calcined and acid-activated, were used as support for graphitic carbon nitride (g-C3N4) via a simple deposition method. They were chosen in order to avoid any agglomeration issues, as there was an increase of the specific surface area with respect to pristine halloysite. The composite was tested for the degradation of a persistent emerging pollutant in water, namely, antibiotic norfloxacin. Experiments were performed in darkness (until adsorption-desorption equilibrium was attained) and, subsequently under visible light. Comparison of the performance between the photocatalysts shows that the composite was 49% faster than g-C3N4. The introduction of persulfate in the lumen of the nanotubes via vacuum negative-pressure suction and injection was also tested for the generation of .OH radicals that fasten the degradation rate, obtaining a further 47% increase in the degradation rate of norfloxacin thanks to the release of this anion during the photodegradation process. The degradation mechanism of SiO2/g-C3N4 sample was studied with trapping experiments by the use of scavengers that were introduced to quench the photodegradation: triethanolamine for photoexcited holes (h+), tert-butanol for hydroxyl radicals (.OH) and a N2 atmosphere for superoxide radicals (.O2.).
Embargo
A layered titanosilicate AM-4 as a novel catalyst for the synthesis of 1-methoxy-2-propanole from propylene oxide and methanol
(Elsevier, 2019) Timofeeva, Maria N.; Kurchenko, Julia V.; Kalashnikova, Galina O.; Panchenko, Valentina N.; Nikolaev, Anatoliy I.; Gil Bravo, Antonio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
In this paper we report for the first time the catalytic properties of the titanosilicate AM-4 in the synthesis of 1-methoxy-2-propanol (PGME) from methanol and propylene oxide (PO). PGME is widely used as a pollution-free solvent and intermediate in the synthesis of propylene glycol methyl ether acetate, the herbicide metolachlor and in other industrial applications. We found that the catalytic properties of AM-4 could be adjusted by treatment with 0.0625–0.25 M HNO3. Increasing the concentration of HNO3 led to a decrease in basicity, which played a critical role in the reaction rate and the selectivity towards PGME. The yield of PGME decreased with increased acid concentration. The maximum conversion of PO (88.4%) and the selectivity towards PGME (92.3%) were found to be in the presence of AM-4 at 110 °C and 8 mol/mol MeOH/PO. Our results suggest that titanosilicate AM-4 has great potential for application in basic catalysis.
Open Access
A comparative study of the catalytic performance of nickel supported on a hibonite-type La-hexaaluminate synthesized from aluminum saline slags in the dry reforming of methane
(Elsevier, 2022) Torrez Herrera, Jonathan Josué; Korili, Sophia A.; Gil Bravo, Antonio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
In this work, a hibonite-type Ni/La-hexaaluminate (Ni/LHA) synthesized from an industrial waste is used and compared as catalyst in the dry reforming of methane (DRM) at 973 K. The structure, catalytic behavior, and stability during a run time of at least 50 h of three Nicatalysts obtained from two commercial supports and two preparation methods were used for comparison. An aluminum solution (9.40 g/L) obtained from an aluminum saline slag waste by acid extraction was used to synthesize the hexaaluminate by mixing with a stoichiometric amount of lanthanum nitrate and methanol/Peg400/PegMn400 under hydrothermal conditions at 493 K for 16 h. The Ni/LHA catalyst (10 wt% NiO) was obtained by impregnation of the synthesized support, calcined previously at 1473 K for 2 h. The resulting solids were characterized by several techniques as: X-ray diffraction (XRD), N2 adsorption at 77 K, temperature-programmed reduction (TPR), scanning electron microscopy (SEM) and transmission electron microscopy (HR-TEM). In order to compare the catalytic behavior and properties of the Ni/LHA catalyst, three Ni catalysts obtained from two commercial supports (g-Al2O3 and SiO2) and two preparation methods (wet impregnation (I) and precipitation-deposition (PD)) were synthesized. Analysis of the TPR patterns for the catalysts allowed the type of metal support interaction and NiO species to be determined, with a weak interaction with the support being observed in Ni/LHA and NieI/ SiO2. The NiO species observed, with crystallite sizes between 9.7 and 40.4 nm, confirm the X-ray structural analyses. The Ni/LHA catalyst was found to be active and very stable in the DRM reaction after 50 h. The catalytic behavior was evaluated from the CO2 and CH4 conversions, as well as the H2/CO selectivity, with values of 99% over almost all the time range evaluated. The behavior of this catalyst is comparable to that of NieI/Al2O3 and NiPD/SiO2. The results found indicating that the strong interaction of nickel with the support favors the stability of the catalysts in the DRM reaction.