Artículos (Instituto de Ciencia de Materiales de Sevilla (ICMS) – CIC Cartuja)
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Artículo Textile microfibers valorization by catalytic hydrothermal carbonization toward high-tech carbonaceous materials(American Association for the Advancement of Science, 2024-11-18) Parrilla Lahoz, Silvia; Zambrano, Marielis C.; Pawlak, Joel J.; Venditti, Richard A.; Ramírez Reina, Tomás; Odriozola Gordón, José Antonio; Duyar, Melis S.; Universidad de Sevilla. Departamento de Química Inorgánica; Ministerio de Ciencia e Innovación (MICIN). España; Agencia Estatal de Investigación. España; Next Generation EuropeMicroplastics fibers shed from washing synthetic textiles are released directly into the waters and make up 35% of primary microplastics discharged to the aquatic environment. While filtration devices and regulations are in development, safe disposal methods remain absent. Herein, we investigate catalytic hydrothermal carbonization (HTC) as a means of integrating this waste (0.28 million tons of microfibers per year) into the circular economy by catalytic upcycling to carbon nanomaterials. Herein, we show that cotton and polyester can be converted to filamentous solid carbon nanostructures using a Fe-Ni catalyst during HTC. Results revealed the conversion of microfibers into amorphous and graphitic carbon structures, including carbon nanotubes from a cotton/polyethylene terephthalate (PET) mixture. HTC at 200°C and 22 bar pressure produced graphitic carbon in all samples, demonstrating that mixed microfiber wastes can be valorized to provide potentially valuable carbon structures by modifying reaction parameters and catalyst formulation.Artículo The impact of interfacial quality and nanoscale performance disorder on the stability of alloyed perovskite solar cells(Nature Research, 2024-10-30) Frohna, Kyle; Chosy, Cullen; Al-Ashouri, Amral; Scheler, Florian; Chiang, Yu-Hsien; Dubajic, Milos; Anaya Martín, Miguel; Stranks, Samuel D.; Universidad de Sevilla. Departamento de Física de la Materia Condensada; European Union (UE). H2020; Engineering Physical Sciences Research Council (EPSCR) U. K.Microscopy provides a proxy for assessing the operation of perovskite solar cells, yet most works in the literature have focused on bare perovskite thin flms, missing charge transport and recombination losses present in full devices. Here we demonstrate a multimodal operando microscopy toolkit to measure and spatially correlate nanoscale charge transport losses, recombination losses and chemical composition. By applying this toolkit to the same scan areas of state-of-the-art, alloyed perovskite cells before and after extended operation, we show that devices with the highest macroscopic performance have the lowest initial performance spatial heterogeneity—a crucial link that is missed in conventional microscopy. We show that engineering stable interfaces is critical to achieving robust devices. Once the interfaces are stabilized, we show that compositional engineering to homogenize charge extraction and to minimize variations in local power conversion efciency is critical to improve performance and stability. We fnd that in our device space, perovskites can tolerate spatial disorder in chemistry, but not charge extraction.Artículo Revisiting Stability Criteria in Ball-Milled High-Entropy Alloys: Do Hume–Rothery and Thermodynamic Rules Equally Apply?(Willey, 2024-10-07) Blázquez Gámez, Javier Sebastián; Manchón Gordón, Alejandro F.; Vidal Crespo, Antonio; Caballero Flores, Rafael; Ipus Bados, Jhon Jairo; Conde Amiano, Clara Francisca; Universidad de Sevilla. Departamento de Física de la Materia Condensada; Junta de Andalucía; Universidad de SevillaStability descriptors for the formation of solid solutions can be divided into two categories: inspired by Hume–Rothery rules (HRR) and derived from thermodynamic approaches. Herein, HRRs are extended from binary to high-entropy alloys (HEAs) focusing on compositions prepared by ball milling. Parameters describing stability criteria are interrelated and implicitly account for the microstrains’ storage energy, more determinant than entropy increase in stabilization of HEAs and more effective in bcc structures than close-packed ones (fcc and hcp). An effective temperature, Teff, is defined as the ratio between increase in metallic bonding energy of solid solutions with respect to segregated pure constituents and configurational entropy. This versatile parameter is used as a threshold for stabilization of HEAs at equilibrium and out of equilibrium. When Teff is below room temperature, HEA would be stable at equilibrium. When Teff is below melting temperature, HEA would be obtained by rapid quenching. Limitations related to electronegativity differences remain valid in mechanically alloyed solid solutions. However, ball milling broadens the allowed differences in atomic size to form HEA. Moreover, thermodynamic criteria can be surpassed in these systems, allowing the formation of single-phase solid solutions beyond the compositional range predicted by those criteria.Artículo Navigating the Legislative Interventions, Challenges, andOpportunities in Revolutionizing Textile Upcycling/RecyclingProcesses for a Circular Economy(American Chemical Society (ACS), 2024) Saif, Maria; Blay Roger, Ruben; Zeeshan, Muhammad; Bobadilla Baladrón, Luis Francisco; Ramírez Reina, Tomás; Nawaz, Muhammad Asif; Odriozola Gordón, José Antonio; Universidad de Sevilla. Departamento de Química Inorgánica; Ministerio de Ciencia e Innovación (MICIN). España; European Union (UE)Embracing a circular economy in the textile industry represents a crucial steptoward sustainability, where fashion and textile sectors contribute significantly to CO2emissions. However, transitioning from a linear “take-make-waste” model to circularity,poses multifaceted challenges, that highlight the staggering volume of annual textile wastesurpassing industry predictions, thus emphasizing the urgent need for comprehensivestrategies. Despite advancements in recycling technologies, challenges persist in collectingand sorting textile waste, where fragmentation in waste management and recycling processeshinders effective management of post-consumer waste. Addressing these challenges demandselevated efforts in collection, sorting, and pre-processing, alongside regulatory interventions todrive enhanced waste collection and circular business models. Efforts are underway to promotesustainable textile recycling, with initiatives like the EU’s Sustainable and Circular TextilesStrategy aiming to reduce reliance on virgin resources. However, achieving a circular textilemarket in the near future requires collaborative action and innovative solutions. Thoughchallenges in scaling and technological limitations still remain, recent breakthroughs in textile-recycling technologies offer promise,signaling a shift toward scalable and sustainable alternatives to virgin fibers, where bio-based chemical processes, andthermochemical recycling processes present transformative opportunities. Where, bold scaling targets, collaborative efforts, andshort-term funding support narrated in this perspective article are imperative to accelerate the transition to a circular textileeconomy, thus delving into the pivotal role of textile recycling, tracing the evolution of recycling technologies, and addressing criticalchallenges hindering widespread adoption.Artículo Magnetostructural transformation and magnetocaloric response in Mn(Fe)NiSi(Al) alloys(Elsevier, 2024-09-30) Khan, Aun N.; Moreno Ramírez, Luis Miguel; Law, Jia Yan; Franco García, Victorino; Universidad de Sevilla. Departamento de Física de la Materia Condensada; Ministerio de Ciencia e Innovación (MICIN). España; Agencia Estatal de Investigación. España; Oficina de Investigación Científica de la Fuerza Aérea. EE. UU.; European Innovation Council. E. U,An efficient magnetocaloric refrigerant must have certain characteristics such as a sharp transition near the desired working temperature, a large cyclic magnetocaloric response, and the use of raw materials with reduced costs and low environmental consequences. In this sense, this work focuses on a series of rare-earth- and Co-free Mn0.5Fe0.5NiSi1-xAlx alloys (x = 0.0525, 0.060, 0.0685) with promising magnetocaloric properties. The alloys were synthesized using combined arc melting and induction melting techniques, as this synthesis route provides improved control on the sample composition and homogeneity. We investigated how the heat treatment temperature and Al content affect the magnetostructural and magnetocaloric properties of the alloys. On the one hand, it is found that annealing at 1173 K for 7 days leads to a sharp magnetostructural transformation with no traces of impurities for the alloy with x = 0.0525. Under these conditions, a large isothermal entropy change of –11.5 J kg−1 K−1 for 1 T is obtained near room temperature, significantly improving the value of the as-cast sample. On the other hand, following this optimal heat treatment, the influence of Al content is studied: upon increasing the Al concentration the magnetostructural transformation shifts to lower temperatures, ranging from 320 K for x = 0.0525 to 220 K for x = 0.0685 (measured upon heating).Artículo Interplay between connectivity and passivating agents in perovskite quantum dot networks(Royal Society of Chemistry, 2024-10-02) Morán Pedroso, María; Tiede, David O.; Romero-Pérez, Carlos; Calvo, Mauricio E.; Galisteo López, Juan F.; Míguez, Hernán; Universidad de Sevilla. Departamento de Física de la Materia Condensada; Ministerio de Ciencia e Innovación (MICIN). España; Agencia Estatal de Investigación. España; Unión Europea NextGeneration; Junta de AndalucíaIntroducing quantum dots (QDs) as the active element of an optoelectronic device demands its incorporation in the shape of interconnected arrays that allow for some degree of electronic coupling in order to inject/extract charge carriers. In doing so, beyond reducing the degree of quantum confinement, carriers are exposed to an enhanced defect landscape as they can access adjacent QDs, which is at the origin of the strong reduction of photoluminescence observed in QD solids when compared to that of the isolated QDs. In this work we demonstrate how a proper defect passivating strategy or atmospheric treatment can greatly enhance charge diffusion in a QD film, needed for an optimal carrier injection/extraction demanded for optoelectronic applications, and also improved its stability against external radiation. From a fundamental perspective, we provide evidence showing that trap density distribution, rather than QD size distribution, is mostly responsible for the observed variations in emission decay rates present in the QD networks under analysis.Artículo Influence of the chemical activation with KOH/KNO3 on the CO2 adsorption capacity of activated carbons from pyrolysis of cellulose(Elsevier, 2024-10-07) Lamata Bermejo, Irene; Alba, María D.; Ramírez Rico, Joaquín; Universidad de Sevilla. Departamento de Física de la Materia Condensada; Junta de Andalucía; European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER)Plant biomass is an attractive precursor to prepare activated carbons with high surface area for CO2 adsorption due to its low-cost and easy regeneration. Despite this interest, there are still remaining questions regarding the optimal processing conditions and the choice of activating agent. Moreover, since plant biomass shows a highly variable proportion of different biopolymers (cellulose, hemicellulose, lignin), it is important to understand the activation effect on each constituent. In this work, carbons obtained from pyrolysis of cellulose were activated using two potassium salts, using two different activation temperatures. The samples were characterized to elucidate the influence of the activation conditions on their CO2 adsorption capacity. In general, all the carbons activated at higher temperature showed higher adsorption capacity. These results are comparable with other carbons derived from biomass described in the bibliography. Among the activated carbons studied, the carbon activated only with KOH exhibits the highest CO2 adsorption capacity at 1 bar meanwhile the highest adsorption capacity at saturation pressure belongs to the carbon activated with larger ratio of KNO3.Artículo Compositional Gradient of Mixed Halide 2D Perovskite Interface Boosts Outdoor Stability of Highly Efficient Perovskite Solar Cells(Willey, 2023-12-23) Degani, Matteo; Pallotta, Riccardo; Pica, Giovanni; Karimipour, Masoud; Mirabelli, Alessandro; Frohna, Kyle; Anaya Martín, Miguel; Grancini, Giulia; Universidad de Sevilla. Departamento de Física de la Materia Condensada; European Research Council (ERC); European Union (UE). H2020; Engineering and Physical Sciences Research Council (UK)Interface engineering using self-assembled 2D perovskite interfaces is a consolidated route to efficient and durable perovskite solar cells. Whether the 2D perovskite forms a homogeneous conformal layer or is heterogeneously distributed on the surface, interface defects are passivated, leading to a general improvement in the device's open circuit voltage (VOC) and stability. Here, an innovative strategy is developed for manipulating the composition of the 2D/3D perovskite interface that results in the formation of a gradient halide distribution, which extends from the surface to the bulk. The use of a bromide-based 2D perovskite triggers a progressive Br/I exchange, affecting not only the surface but also the perovskite underneath. As a result, not only the device VOC improve, as expected, but also the photogenerated current is boosted, leading to a device efficiency of up to 24.4%. Such mixed halide gradient effectively passivates surface and bulk defects making the perovskite active layer more efficient and robust, as demonstrated by the superior device stability showing zero losses in performances upon 36 days (more than 800 h) test in outdoor conditions, those ones relevant for a marketable product.Artículo Better together: Monolithic halide perovskite@metal-organic framework composites(Cell Press, 2024-12-04) Ávila, Elena; Salway, Hayden; Ruggeri, Edoardo; Çamur, Ceren; Rampal, Nakul; Doherty, Tiarnan A. S.; Moseley, Oliver D. I.; Stranks, Samuel D.; Fairen Jiménez, David; Anaya Martín, Miguel; Universidad de Sevilla. Departamento de Física de la Materia Condensada; Ministerio de Ciencia, Innovación y Universidades (MICIU). España; Agencia Estatal de Investigación. EspañaA few years ago, we theoretically studied the production of a stellar neutron spectrum at kT 30 keV using a shaped proton beam impinging on a thick lithium target. Here, we first measure the proton distribution to better control the produced neutron spectrum. Then, we measure the forward-emitted angle-integrated neutron spectrum of the 7Li(p,n)7Be reaction via time-of-flight neutron spectrometry with such proton distribution. The result resembles a stellar neutron spectrum at kT 30 keV. This method avoids in activation experiments the need for spectrum correction. In the case of spherical samples, no knowledge of the crosssection of the isotope being measured by activation would be necessary. Therefore, the present method is of interest for isotopes with unknown or poorly known cross-sections, such as branching points in astrophysics. The key point of our method is the experimental control of the proton distribution that impinges on the lithium target.
Artículo Design of catalysts for selective CO2 hydrogenation(Springer Nature, 2025-02-27) Ye, Runping; Ding, Jie; Ramírez Reina, Tomás; Duyar, Melis Seher; Li, Haitao; Luo, Wenhao; Zhang, Rongbin; Fan, Maohong; Feng, Gang; Sun, Jian; Liu, Jian; Universidad de Sevilla. Departamento de Química Inorgánica; Natural Science Foundation of Jiangxi Province; National Natural Science Foundation of China; National Key Research and Development Program of ChinaCO2 hydrogenation with green hydrogen is a practical approach for the reduction of CO2 emissions and the generation of high-value-added chemicals. Generally, product selectivity is affected by the associated reaction mechanisms, internal catalyst identity and structure, and external reaction conditions. Here we examine typical CO2 hydrogenation reaction pathways, which can provide insight useful for the atomic-level design of catalysts. We discuss how catalyst chemical states, particle sizes, crystal facets, synergistic effects and unique structures can tune product selectivity. Different catalysts, such as Fe-, Co-, Ni-, Cu-, Ru-, Rh-, Pd-based and bifunctional structured catalysts, and their influence on CO2 hydrogenation products (such as CO, methane, methanol, ethanol and light olefins) are discussed. Beyond catalyst design, emerging catalytic reaction engineering methods for assisting the tuning of product selectivity are also discussed. Future challenges and perspectives in this field are explored to inspire the design of next-generation selective CO2 hydrogenation processes to facilitate the transition towards carbon neutrality. (Figure presented.)Artículo Tailoring of Self-Healable Polydimethylsiloxane Films for Mechanical Energy Harvesting(American Chemical Society, 2024) Ghosh, K.; Morgan, A.; García Casas, Xabier; Kar-Narayan, S.; Universidad de Sevilla. Departamento de Electrónica y Electromagnetismo; European Union (UE). H2020; Newton International Fellowships. U.K.; Ministerio de Ciencia e Innovación (MICIN). EspañaTriboelectric nanogenerators (TENGs) have emerged as potential energy sources, as they are capable of harvesting energy from low-frequency mechanical actions such as biological movements, moving parts of machines, mild wind, rain droplets, and others. However, periodic mechanical motion can have a detrimental effect on the triboelectric materials that constitute a TENG device. This study introduces a self-healable triboelectric layer consisting of an Ecoflex-coated self-healable polydimethylsiloxane (SH-PDMS) polymer that can autonomously repair mechanical injury at room temperature and regain its functionality. Different compositions of bis(3-aminopropyl)-terminated PDMS and 1,3,5-triformylbenzene were used to synthesize SH-PDMS films to determine the optimum healing time. The SH-PDMS films contain reversible imine bonds that break when the material is damaged and are subsequently restored by an autonomous healing process. However, the inherent stickiness of the SH-PDMS surface itself renders the material unsuitable for application in TENGs despite its attractive self-healing capability. We show that spin-coating a thin layer (≈32 μm) of Ecoflex on top of the SH-PDMS eliminates the stickiness issue while retaining the functionality of a triboelectric material. TENGs based on Ecoflex/SH-PDMS and nylon 6 films show excellent output and fatigue performance. Even after incisions were introduced at several locations in the Ecoflex/SH-PDMS film, the TENG spontaneously attained its original output performance after a period of 24 h of healing. This study presents a viable approach to enhancing the longevity of TENGs to harvest energy from continuous mechanical actions, paving the way for durable, self-healable mechanical energy harvesters.Artículo Size-tailored Ru nanoparticles deposited over γ-Al 2 O 3 for the CO 2 methanation reaction(Elsevier, 2019-07-31) Navarro Jaén, Sara; Navarro de Miguel, Juan Carlos; Bobadilla Baladrón, Luis Francisco; Centeno Gallego, Miguel Ángel; Laguna Espitia, Óscar Hernando; Odriozola Gordón, José Antonio; Universidad de Sevilla. Departamento de Química Inorgánica; Ministerio de Economía y Competitividad (MINECO). EspañaBy means of the polyol method, a series of 5 wt% Ru/Al 2 O 3 catalysts was synthesized controlling the particle size of the ruthenium species. The physico-chemical characterization demonstrated the successful particle size control of the Ru species, in such a way that higher the Ru/PVP ratio, higher the Ru particle size. Moreover, there are evidences that suggest preferential growth of the RuO 2 clusters depending on the Ru/PVP ratio. Regarding the catalytic activity during the CO 2 methanation, the total conversion and the CH 4 yield increased with the particle size of Ru. Nevertheless, a considerable enhancement of the catalytic performance of the most active system was evidenced at 4 bar, demonstrating the improvement of the thermodynamics (superior total conversion) and kinetics (superior reaction rate) of the CO 2 methanation at pressures above the atmospheric one. Finally, the in situ DRIFTS study allowed to establish that CO 2 was dissociated to CO* and O* species on the metallic Ru particles, followed by the consecutive hydrogenation of CO* towards CHO*, CH 2 O*, CH 3 O*, and finally CH 4 molecules, which were further desorbed from the catalyst. Thus from the mechanistic point of view, a suitable particle size of the Ru nanoparticles along with the high-pressure effects results in the enhancement of the availability of hydrogen and consequently in the formation of CH x O species that enhance the cleavage of the C–O bond, which is the rate-determining step of the overall CO 2 methanation process.Artículo Trapping of Gas Bubbles in Water at a Finite Distance below a Water-Solid Interface(American Chemical Society, 2019-03-01) Esteso Carrizo, Victoria; Carretero-Palacios, S.; Thiyam, P.; Míguez, H.; Parsons, D. F.; Brevik, I.; Boström, M.; Universidad de Sevilla. Departamento de Física de la Materia Condensada; Research Council. Norway; Ministerio de Ciencia, Innovación y Universidades (MICIU). España; Agencia Estatal de Investigación. EspañaGas bubbles in a water-filled cavity move upward because of buoyancy. Near the roof, additional forces come into play, such as Lifshitz, double layer, and hydrodynamic forces. Below uncharged metallic surfaces, repulsive Lifshitz forces combined with buoyancy forces provide a way to trap micrometer-sized bubbles. We demonstrate how bubbles of this size can be stably trapped at experimentally accessible distances, the distances being tunable with the surface material. By contrast, large bubbles (≥100 μm) are usually pushed toward the roof by buoyancy forces and adhere to the surface. Gas bubbles with radii ranging from 1 to 10 μm can be trapped at equilibrium distances from 190 to 35 nm. As a model for rock, sand grains, and biosurfaces, we consider dielectric materials such as silica and polystyrene, whereas aluminium, gold, and silver are the examples of metal surfaces. Finally, we demonstrate that the presence of surface charges further strengthens the trapping by inducing ion adsorption forces.Artículo Natural abundance 17 O MAS NMR and DFT simulations: New insights into the atomic structure of designed micas(Elsevier, 2019-08) Pavón González, Esperanza; Osuna, Francisco J.; Alba Carranza, María Dolores; Delevoye, Laurent; Universidad de Sevilla. Departamento de Física de la Materia Condensada; Université de Lille; Junta de Andalucía; Agencia Estatal de Investigación. EspañaCombining 17 O Magic-Angle Spinning (MAS) NMR at natural abundance with DFT calculations is a promising methodology to shed light on the structure and disorder in tetrahedral sheets of designed micas with enhanced properties. Among brittle micas, synthetic mica is an important alternative to natural ones with a swelling sheet-like structure that results in many applications, by exploiting unique characteristics. Lowenstein's rule is one of the main chemical factor that determines the atomic structure of aluminosilicates and furthermore their properties. In the present article, 17 O MAS NMR spectroscopy is used to validate (or not) the agreement of the Lowenstein's rule with the distribution of Si and Al sites in the tetrahedral sheets of synthetic micas. 17 O MAS spectra of synthetic high-charged micas exhibit two regions of signals that revealed two distinguishable oxygen environments, namely Si-O-X (with X = Si, Al tet , Mg) and Al tet -O-Y (Y=Mg or Al tet ). DFT calculations were also conducted to obtain the 17 O chemical shift and other NMR features like the quadrupolar coupling constant, C Q , for all of the oxygen environments encountered in the two model structures, one respecting the Lowenstein's rule and the other involving Al tet -O-Al tet and Si-O-Si environments. Our DFT calculations support the 17 O assignment, by confirming that Al tet -O-3Mg and Al tet -O-Al tet oxygen environments show chemical shifts under 30 ppm and more important, with quadrupolar coupling constants of about 1 MHz, in line with the spectral observation. By quantifying the 17 O MAS NMR spectra at natural abundance, we demonstrate that one of the synthetic mica compositions does not meet the Lowenstein's rule.Artículo Titania Modifications with Fluoride, Sulfate, and Platinum for Photochemical Reduction of Chromium (VI)(Universidad de Antioquia, 2024) Murcia, J. J.; Hernández Laverde, M.S.; Correa Camargo, I. A.; Rojas Sarmiento, H. A.; Navío Santos, José Antonio; Hidalgo López, M. D.; Universidad de Sevilla. Departamento de Química Inorgánica; Ministerio de Ciencia, Tecnología e Innovación (MINCIENCIAS). Colombia; Universidad Pedagógica y Tecnológica de Colombia (UPTC); Ministerio de Ciencia e Innovación (MICIN). EspañaIn this work, Titania was modified by sulfation or fluorination and platinum on the surface to improve the Cr (VI) reduction efficiency compared to the bare TiO2 material synthesized by the sol-gel method. The synthesized materials were characterized by XRD, SBET, UV-Vis DRS, XRF, TEM, FTIR, and XPS. The modifications led to higher stability in the Anatase phase and surface area of this semiconductor. The addition of F and Pt in TiO2 led to absorption increases in the visible region of the electromagnetic spectrum. A correlation between the new physicochemical properties obtained after TiO2 modification and the photocatalytic performance of this material was observed. The best result in chromium reduction was obtained using Pt-S-TiO2 as the photocatalyst; this material showed a suitable combination of surface area, high UV-Vis absorption, high hydroxylation, and the existence of Pt nanoparticles on the surface, which favors an increased electron-hole pair half-life. Different reaction parameters were also evaluated, which demonstrated that the best photocatalytic performance was obtained under an N2 atmosphere, a light intensity of 120 W/m2, and 2 hours of total reaction time. Likewise, it was noted that an increase in reaction time from 2 to 5 hours, had a detrimental effect on reducing Cr (VI) efficiency.Artículo Stability and Performance of BTC-based MOFs for Environmental Applications(Elsevier, 2024) Rodríguez Esteban, Corina; Ayala Espinar, Regla; López Cartes, Carlos; Universidad de Sevilla. Departamento de Química Inorgánica; Ministerio de Ciencia, Innovación y Universidades (MICIU). España; Junta de AndalucíaTwo series of open metal site MOFs, HKUST-1 and MIL-100(Fe), have been successfully prepared using different methods of synthesis. Their features depend on the synthetic route as well as their role play in different environmental applications. The stability and performance of these BTC-based MOFs have been tested bearing in mind Congo Red (CR) removal, humidity adsorption and iodine capture and release. HKUST-1 and MIL-100(Fe) samples could offer a remarkable role in the adsorption of CR from aqueous solutions. However, the lability of HKUST-1 in water is revealed as a drawback for its reutilization in both static and agitation conditions. The former contrasts to the stability under ambient moisture. MIL-100(Fe) shows promising properties in both CR adsorption in aqueous solutions and humidity adsorption. Nonetheless, the performance largely depends on the synthesis conditions. Although CR removal is based on surface interaction, there is a relation between the adsorpted quantity and the specific surface area. The size and nature of iodine allows the diffusion in the pores of both HKUST-1 and MIL-100(Fe) MOFs. This way, the uptake of iodine is driving by the porosity and surface area of samples rather than their inherent nature. As a rule, the results of this work indicate that not only is it important the specific nature of the MOF chosen for a given application but also the way in which it has been synthesized and the conditions in which they are used. MIL-100(Fe)-R is revealed as the best suitable candidate to be used as a sorbent for CR in aqueous solutions, moisture and I2 gas.Artículo Redefining the Symphony of Light Aromatic Synthesis Beyond Fossil Fuels: A Journey Navigating through a Fe-Based/HZSM-5 Tandem Route for Syngas Conversion(American Chemical Society, 2024) Nawaz, Muhammad Asif; Blay Roger, José Rubén; Saif, Maria; Meng, F. H.; Bobadilla Baladrón, Luis Francisco; Ramírez Reina, Tomás; Odriozola Gordón, José Antonio; Universidad de Sevilla. Departamento de Química Inorgánica; Ministerio de Ciencia e Innovación (MICIN). EspañaThe escalating concerns about traditional reliance on fossil fuels and environmental issues associated with their exploitation have spurred efforts to explore eco-friendly alternative processes. Since then, in an era where the imperative for renewable practices is paramount, the aromatic synthesis industry has embarked on a journey to diversify its feedstock portfolio, offering a transformative pathway toward carbon neutrality stewardship. This Review delves into the dynamic landscape of aromatic synthesis, elucidating the pivotal role of renewable resources through syngas/CO2 utilization in reshaping the industry’s net-zero carbon narrative. Through a meticulous examination of recent advancements, the current Review navigates the trajectory toward admissible aromatics production, highlighting the emergence of Fischer-Tropsch tandem catalysis as a game-changing approach. Scrutinizing the meliorated interplay of Fe-based catalysts and HZSM-5 molecular sieves would uncover the revolutionary potential of rationale design and optimization of integrated catalytic systems in driving the conversion of syngas/CO2 into aromatic hydrocarbons (especially BTX). In essence, the current Review would illuminate the path toward cutting-edge research through in-depth analysis of the transformative power of tandem catalysis and its capacity to propel carbon neutrality goals by unraveling the complexities of renewable aromatic synthesis and paving the way for a carbon-neutral and resilient tomorrow.Artículo Reactive Surface Explored by NAP-XPS: Why Ionic Conductors Are Promoters for Water Gas Shift Reaction(American Chemical Society, 2024) García Moncada, Nuria; Penkova, Anna Dimitrova; González Castaño, Míriam; Odriozola Gordón, José Antonio; Universidad de Sevilla. Departamento de Química Inorgánica; Ministerio de Ciencia e Innovación (MICIN). EspañaNear-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) experiments have been carried out in N2 and N2-H2O atmospheres on a Pt-based catalyst physically mixed with an Eu-doped ZrO2 ionic conductor as a function of temperature under realistic conditions of the water gas shift (WGS) reaction. This work aims to demonstrate the significant effect of having active H2O on the ionic conductor surface at reaction temperatures to provide it to Pt metal sites. The ionic conductor, Eu-doped zirconia matrix, presents defects (oxygen vacancies, Ov) that allows upon H2O dissociation the formation of a hydrogen-bonded molecular water layer favoring diffusion through a Grotthuss mechanism below 300 °C. In the presence of H2O, the Ov are occupied by hydroxyl species as observed in the Eu 4d spectra, which differentiate two types of Eu oxidation states. The Eu3+-to-Eu2+ atomic ratio increases with the occupancy of the Ov by hydroxyls. Moreover, while the Pt-based catalyst alone is unable to create Pt-OH bonds, the physical mixture of the Pt-based catalyst and the ionic conductor allows the formation of Pt-OH bonds from room temperature up to 300 °C. These data demonstrate that the increase in molecular water concentration on the ionic conductor surface up to 300 °C acts as a reservoir to provide water to the Pt surface, enhancing the catalyst performance in the WGS reaction, supporting the importance of the surface H2O concentration in the reaction kinetics.Artículo Levofloxacin Degradation, Antimicrobial Activity Decrease, and Potential for Water Disinfection Using Peroxydisulfate Activation by Ag/TiO2 under Sunlight(Multidisciplinary Digital Publishing Institute (MDPI), 2024) Jojoa Sierra, S. D.; Jaramillo Páez, C.; Serna Galvis, E. A.; García Rubio, I.; Hidalgo, M. C.; Navío Santos, José Antonio; Ormad, M. P.; Torres Palma, R. A.; Mosteo, R.; Universidad de Sevilla. Departamento de Química Inorgánica; European Union (UE); Ministerio de Ciencia, Tecnología e Innovación (MINCIENCIAS). Colombia; Ministerio de Ciencia, Tecnología e Innovación (MINCIENCIAS). ColombiaWater quality and usability are global concerns due to microbial and chemical pollution resulting from anthropogenic activities. Therefore, strategies for eliminating contaminants are required. In this context, the removal and decrease in antibiotic activity (AA) associated with levofloxacin (LEV), using TiO2 and Ag/TiO2 catalysts, with and without sunlight and peroxydisulfate, was evaluated. Additionally, the disinfection capacity of catalytic systems was assessed. The catalysts were synthesized and characterized. Moreover, the effect of Ag doping on visible light absorption was determined. Then, the photocatalytic treatment of LEV in water was performed. The materials characterization and EPR analyses revealed that LEV degradation and AA decrease were ascribed to a combined action of solar light, sulfate radical, and photocatalytic activity of the TiO2-based materials. Also, the primary byproducts were elucidated using theoretical analyses (predictions about moieties on LEV more susceptible to being attacked by the degrading species) and experimental techniques (LC-MS), which evidenced transformations on the piperazyl ring, carboxylic acid, and cyclic ether on LEV. Moreover, the AA decrease was linked to the antibiotic transformations. In addition, the combined system (i.e., light/catalyst/peroxydisulfate) was shown to be effective for E. coli inactivation, indicating the versatility of this system for decontamination and disinfection.Artículo Impact of the Biogas Impurities on the Quality of the Precipitated Calcium Carbonate in the Regenaration Stage of a Chemical Absorption Biogas Upgrading Unit(Elsevier, 2024) Salinero González, Jesús; Gallego Fernández, Luz Marina; Portillo Estévez, Esmeralda; González Arias, Judith; Baena-Moreno, Francisco M.; Navarrete Rubia, Benito; Vilches Arenas, Luis Francisco; Universidad de Sevilla. Departamento de Química Inorgánica; Universidad de Sevilla. Departamento de Ingeniería Química y Ambiental; Ministerio de Ciencia e Innovación (MICIN). EspañaCombining Carbon Capture and Storage (CCS) with producing competitive secondary raw materials is key to decarbonizing industry and reducing resource extraction. Biogas upgrading to biomethane stand out as an alternative, but a significant gap remains in integrating this process within a circular economy framework. This issue has been recently addressed by a process that integrates biogas upgrading via caustic absorption with the production of Precipitated Calcium Carbonate (PCC) and the recovery of sodium hydroxide from waste brine solution using membrane technologies. The profitability of this approach depends on the quality of the PCC, a critical factor that this work addresses. By characterizing PCC is determined whether trace compounds in biogas contaminate the PCC and potentially affect its commercial value. It also examines the CO2 absorption process and analyzes the aqueous samples from the filtration phase of the PCC slurry. Results confirm the high purity of PCC obtained from biogas treatment using Raman spectroscopy, X-Ray Diffraction (XRD), and Scanning Electron Microscopy (SEM). The analyses show that the PCC is pure calcium carbonate, mainly in the stable calcite form, with a typical tetrahedral morphology and no detectable impurities. Characterization of aqueous solutions revealed organic trace compounds from biogas, with TOC concentrations of 9.7 (± 6.4) and 16.0 (± 8) mg C/l. Silicon measurements showed similar concentrations in the absorbent solution and filtrated PCC slurry. Additionally, ammonia escapes as gas, and hydrogen sulfide in the biogas likely contributed to sulfate salt formation. Analysis of the CO₂ absorption shows a first-order reaction with OH-, where the amount of CO₂ absorbed (46.3–50.0 g) closely matches the theoretical value of 48 g. The study reveals that most of the biogas impurities dissolve into the aqueous solution, being crucial for future studies and downstream membrane treatments, and the PCC is unaffected by these impurities with a purity suitable for commercial applications.