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Scientific Papers in SCI



2023


Química de Superficies y Catálisis

Multicomponent graphene based catalysts for guaiacol upgrading in hydrothermal conditions: Exploring "H2-free" alternatives for bio-compounds hydrodeoxygenation

Parrilla-Lahoz, S; Jin, W; Pastor-Perez, L; Duyar, MS; Martinez-Quintana, L; Dongil, AB; Reina, TR
Catalysis Today, 422 (2023) 114235

 

Catalytic hydrodeoxygenation (HDO) is a critical technique for upgrading biomass derivatives to deoxygenated fuels or other high-value compounds. Phenol, guaiacol, anisole, p-cresol, m-cresol and vanillin are all monomeric phenolics produced from lignin. Guaiacol is often utilised as a model lignin compound to deduce mechanistic information about the bio-oil upgrading process. Typically, a source of H2 is supplied as reactant for the HDO reaction. However, the H2 supply, due to the high cost of production and additional safety precautions needed for storage and transportation, imposes significant economic infeasibilities on the HDO process's scaling up. We investigated a novel H2-free hydrodeoxygenation (HDO) reaction of guaiacol at low temperatures and pressures, using water as both a reaction medium and hydrogen source. A variety of Ni catalysts supported on zirconia/ graphene/with/without nitrogen doping were synthesised and evaluated at 250 degrees C and 300 degrees C in a batch reactor, with the goal of performing a multi-step tandem reaction including water splitting followed by HDO. The catalysts were characterised using H2-TPR, XRD, TEM and XPS to better understand the physicochemical properties and their correlation with catalytic performance of the samples in the HDO process. Indeed, our NiZr2O/Gr-n present the best activity/selectivity balance and it is deemed as a promising catalyst to conduct the H2-free HDO reaction. The catalyst reached commendable conversion levels and selectivity to mono-oxygenated compounds considering the very challenging reaction conditions. This innovative HDO approach provides a new avenue for cost-effective biomass upgrading.


November, 2023 | DOI: 10.1016/j.cattod.2023.01.027

Materiales Ópticos Multifuncionales

Enhancement of upconversion photoluminescence in phosphor nanoparticle thin films using metallic nanoantennas fabricated by colloidal lithography

Ngo, TT; Viaña, JM; Romero, M; Calvo, ME; Lozano, G; Miguez, H
Materials Advances, 4 (2023) 6381-6388

Lanthanide-doped upconversion nanoparticles (UCNPs), as multifunctional light sources, are finding utility in diverse applications ranging from biotechnology to light harvesting. However, the main challenge in realizing their full potential lies in achieving bright and efficient photon upconversion (UC). In this study, we present a novel approach to fabricate an array of gold nanoantennas arranged in a hexagonal lattice using a simple and inexpensive colloidal lithography technique, and demonstrate a significant enhancement of UC photoluminescence (UCPL) by up to 35-fold through plasmon-enhanced photoexcitation and emission. To elucidate the underlying physical mechanisms responsible for the observed UCPL enhancement, we provide a comprehensive theoretical and experimental characterization, including a detailed photophysical description and numerical simulations of the spatial electric field distribution. Our results shed light on the fundamental principles governing the enhanced UCNPs and pave the way for their potential applications in photonic devices.


November, 2023 | DOI: 10.1039/D3MA00775H

Materiales de Diseño para la Energía y Medioambiente

A technological approach based on engineered nanoclay composites for cesium and iodine retention

Osuna, FJ; Pavon, E; Alba, MD
Chesmosphere, 341 (2023) 140128

 

The development of effective and environmentally friendly methods for separating hazardous radionuclides from waste poses a significant technological challenge. 137Cs and 131I are among the most important radionuclides discharged into the environment by nuclear power plants. One of the best ways to eliminate them involves adsorption on clay minerals. In this regard, studies have demonstrated that organofunctionalized clay minerals are effective adsorbents. Thus, this study investigates the capability of organofunctionalized synthetic design clay minerals to jointly eliminate cesium and iodine. The adsorbents studied are a range of organofunctionalized clay minerals with alkylammonium cations of different alkyl chain lengths (2, 3 and 18) and some physical mixtures of raw clay minerals and octadecylammonium compounds. Organofunctionalized synthetic swelling highly charged micas are effective adsorbents for the simultaneous adsorption of cesium and iodine. In addition, the optimal system is a mixture of Na-M4 with octadecylammonium (50% w/w).


November, 2023 | DOI: 10.1016/j.chemosphere.2023.140128 | Digital CSIC: http://hdl.handle.net/10261/354918

Fotocatálisis Heterogénea: Aplicaciones

Bismuth ferrite as innovative and efficient photocatalyst for the oxidation of As(III) to As(V) under visible light

Chianese, L; Murcia, JJ; Hidalgo, MC; Vaiano, V; Iervolino, G
Materials Science in Semiconductor Processing, 167 (2023) 107801

The presence of As in drinking water is a problem felt all over the world. In particular, arsenic is present in +3 (As(III)) and +5 (As(V)) oxidation states. However, As(III) is the most toxic and difficult to remove with conventional adsorption processes. A pre-oxidation process is therefore necessary. In this work, we report, for the first time, the use of BiFeO3 as a visible-light active photocatalyst for the complete and fast oxidation of As(III) to As(V) in water. In particular, the influence of annealing temperature for BiFeO3 preparation was studied and the prepared photocatalysts were characterized through XRD, N2 adsorption at −196°C, TEM, XPS, Raman and UV–Vis DRS spectroscopy. The best photocatalytic activity was achieved with BiFeO3 calcined at 550°C. The influence of catalyst dosage and the role of the main oxidizing species was evaluated, evidencing the key role of h+ in the photooxidation reaction of As(III) to As(V). Moreover, the efficiency of the photocatalyst was also evaluated in the case of drinking water contaminated by arsenic. The results demonstrated that, despite the presence of dissolved salts in the drinking water, the photocatalyst maintained its activity. The results obtained in this work prove that BiFeO3 calcined at 550°C evidenced photocatalytic performances better than different photocatalyst formulations studied for the photooxidation of As(III) to As(V) under visible light.


November, 2023 | DOI: 10.1016/j.mssp.2023.107801

Reactividad de Sólidos

Negative emissions power plant based on flexible calcium-looping process integrated with renewables and methane production

Ortiz, C; García-Luna, S; Carro, A; Chacartegui, R; Pérez-Maqueda, L
Renewable & Sustainable Energy Reviews, 185 (2023) 113614

This paper provides a review of negative carbon capture technologies. Based on these technologies, here it is proposed an innovative negative emissions power plant combining the generation and storage of energy from biomass, photovoltaic, and concentrated solar power, capturing and recovering CO2 by producing H2 or CH4 as green energy carriers. The main features of the system are i) large-scale energy production system with negative CO2 emissions; ii) 100% renewable system based on biomass and solar energy with the possibility of integrating other renewables; iii) synergistic integration of processes and systems; iv) recovery of O2 generated by photovoltaic-driven electrolysis within the process of partial biomass oxycombustion and v) solar-driven limestone calcination. A detailed model of the entire plant is developed to evaluate the integration of the process. The model performance is assessed on an hourly basis throughout the whole year. The base case results show an energy consumption from 1 to 2.1 MJ/kg CO2 to capture 60–77% of CO2 emitted from the biomass plant and green methane production of more than 7500 tons/year. The negative emissions associated with the process are -612 kg CO2/MWh. It justifies the interest in the proposed negative emissions power plant.


October, 2023 | DOI: 10.1016/j.rser.2023.113614

Química de Superficies y Catálisis

Low-temperature reverse water gas-shift reaction over highly efficient Cu-hydrotalcites: Mechanistic insights on the role of malachite phase

Alvarez-Hernandez, D; Marin-Sanchez, M; Lobo-Andrades, L; Azancot, L; Bobadilla, LF; Ivanova, S; Centeno, MA
Catalysis Today, 422 (2023) 114235

Carbon dioxide (CO2) transformation into valuable fuels and chemicals is in most cases a challenge far from readiness nowadays. One possible route for its conversion is the reverse water gas shift reaction (rWGS), crucial for syngas generation and required for the chemical conversion of CO2 to fuels and platform chemicals. In this paper, well organized Cu/Zn/Al structures were proposed as efficient catalysts for rWGS reaction at low tem-peratures. The results of in situ XRD revealed the formation of layered structures such malachite and hydro-talcite. The operando DRIFTS-MS studies of those structure suggests a participation of Cu2+/Cu+ pair in the reaction, promoting the redox mechanism and enhancing the activity at lower temperature. This work also provides a new strategy to design Cu-based rWGS catalysts able to prevent the sintering of active phase.


October, 2023 | DOI: 10.1016/j.cattod.2023.114235

Química de Superficies y Catálisis

Guaiacol hydrotreatment in an integrated APR-HDO process: Exploring the promoting effect of platinum on Ni-Pt catalysts and assessing methanol and glycerol as hydrogen sources

Jin, W; Gandara-Loe, J; Pastor-Perez, L; Villora-Pico, JJ; Sepulveda-Escribano, A; Rinaldi, R; Reina, TR
Renewable Energy, 215 (2023) 118907

This study presents an integrated approach combining aqueous phase reforming (APR) and hydrodeoxygenation (HDO) for the hydrotreatment of guaiacol, a model compound representing lignin-derived phenols in pyrolysis bio-oils. The APR process enables in-situ H2 generation, eliminating the need for an external hydrogen source. We examine the interplay between metal species, the Pt-promoting effect on Ni-Pt catalyst supported on activated carbon (AC), and the choice of hydrogen source (methanol or glycerol). Amongst the monometallic catalysts, a 1% Pt/AC catalyst notably achieved over 96% guaiacol conversion at 300 degrees C with either hydrogen source. Interestingly, when 0.5-1% of the Ni loading is replaced with Pt, the resulting bimetallic Ni-Pt/AC catalysts demonstrate a significant improvement in guaiacol conversion, reaching 70% when methanol is employed as the hydrogen source. Surprisingly, no comparable enhancement in guaiacol conversion is observed when employing glycerol as the hydrogen source. This observation underlines one of the pivotal effects of the hydrogen source on catalyst performance. X-ray photoemission spectroscopy (XPS) pinpointed strong Ni-Pt interactions in the catalyst. It also revealed distinctive electronic features of Ni-Pt/AC, which are favourable for steering selectivity towards cyclohexanol rather than phenol when Pt loading is increased from 0.5 to 1%. Moreover, Pt enhanced catalyst stability by inhibiting the oxidation of Ni sites and mitigating Ni-Pt phase sintering. Overall, our findings offer important insights into integrating APR and HDO processes, the promotion effect of Pt, and the importance of hydrogen source selection in terms of guaiacol conversion and catalyst stability.


October, 2023 | DOI: 10.1016/j.renene.2023.118907

Reactividad de Sólidos

Influence of Long-Term CaO Storage Conditions on the Calcium Looping Thermochemical Reactivity

Amghar, N; Perejón, A; Ortiz, C; Maqueda, LAP; Sánchez-Jiménez, PE
Energy & Fuels, 37 (2023) 16904-16914

Long-term storage capability is often claimed as one of the distinct advantages of the calcium looping process as a potential thermochemical energy storage system for integration into solar power plants. However, the influence of storage conditions on the looping performance has seldom been evaluated experimentally. The storage conditions must be carefully considered as any potential carbonation at the CaO storage tank would reduce the energy released during the subsequent carbonation, thereby penalizing the round-trip efficiency. From lab-scale to conceptual process engineering, this work considers the effects of storing solids at low temperatures (50–200 °C) in a CO2 atmosphere or at high temperatures (800 °C) in N2. Experimental results show that carbonation at temperatures below 200 °C is limited; thus, the solids could be stored during long times even in CO2. It is also demonstrated at the lab scale that the multicycle performance is not substantially altered by storing the solids at low temperatures (under CO2) or high temperatures (N2 atmosphere). From an overall process perspective, keeping solids at high temperatures leads to easier heat integration, a better plant efficiency (+2–4%), and a significantly higher energy density (+40–62%) than considering low-temperature storage. The smooth difference in the overall plant efficiency with the temperature suggests a proper long-term energy storage performance if adequate energy integration is carried out.


October, 2023 | DOI: 10.1021/acs.energyfuels.3c02652

Materiales para Bioingeniería y Regeneración Tisular

Sol–Gel Technologies to Obtain Advanced Bioceramics for Dental Therapeutics

X. Song; J.J. Segura-Egea; A.Díaz-Cuenca
Molecules, 28 (2023) 6967

The aim of this work is to review the application of bioceramic materials in the context of current regenerative dentistry therapies, focusing on the latest advances in the synthesis of advanced materials using the sol–gel methodology. Chemical synthesis, processing and therapeutic possibilities are discussed in a structured way, according to the three main types of ceramic materials used in regenerative dentistry: bioactive glasses and glass ceramics, calcium phosphates and calcium silicates. The morphology and chemical composition of these bioceramics play a crucial role in their biological properties and effectiveness in dental therapeutics. The goal is to understand their chemical, surface, mechanical and biological properties better and develop strategies to control their pore structure, shape, size and compositions. Over the past decades, bioceramic materials have provided excellent results in a wide variety of clinical applications related to hard tissue repair and regeneration. Characteristics, such as their similarity to the chemical composition of the mineral phase of bones and teeth, as well as the possibilities offered by the advances in nanotechnology, are driving the development of new biomimetic materials that are required in regenerative dentistry. The sol–gel technique is a method for producing synthetic bioceramics with high purity and homogeneity at the molecular scale and to control the surfaces, interfaces and porosity at the nanometric scale. The intrinsic nanoporosity of materials produced by the sol–gel technique correlates with the high specific surface area, reactivity and bioactivity of advanced bioceramics.


October, 2023 | DOI: 10.3390/molecules28196967

Fotocatálisis Heterogénea: Aplicaciones - Nanotecnología en Superficies y Plasma

Mechanistic aspects of the reduction of rutile titanium dioxide and its Re-oxidation. Development and destruction of crystallographic shear structures

Bickley, RI; Garside, GR; González-Carreño, T; González-Elipe, AR; Navío, JA
Journal of Solid State Chemistry, 326 (2023) 124174

A model is presented giving the mean dimensions of acicular octadecahedral microcrystallites of a rutile titanium dioxide powder. Reduction at 823 K, in conjunction with ESR, electrical conductivity and controlled re-oxidation has enabled the model to be applied to reduced microcrystallites. At 300 K they contain <0.1% of paramagnetic [Ti3+↑ VO: Ti3+] reduced edge sites and >99.9% of reduced spin-paired [Ti3+↑↓ Ti3+ VO:] sites. These sites are situated on the external crystal faces and on polygonal bulk crystallographic shear (CS) structures inclined to the microcrystal four-fold symmetry axis. CS structures are quantum-sized [Ti4O7VO:] environments which broaden the paramagnetic signals at 78 K. Temperature programmed reduction in H2(g) reveals atomic hydrogen as a precursor to CS structure formation via a lattice template formed on microcrystallite faces. Shear structures are oxidised on their polygonal perimeters at differing rates on the respective microcrystallite faces by anionic vacancy transfer from sub-surface regions.


October, 2023 | DOI: 10.1016/j.jssc.2023.124174

 

 

 

 

 

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