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Biopolymer-Based Films Reinforced with FexOy-Nanoparticles

Abdullah, JAA; Jimenez-Rosado, M; Benitez, JJ; Guerrero, A; Romero, A
Polymers, 14 (2022) 4487
Materiales de Diseño para la Energía y Medioambiente


Nowadays, natural polymer-based films are considered potentially environmentally friendly alternatives to conventional plastic films, due to many advantageous properties, including their easy processability, high flexibility, non-toxicity, low cost, high availability, and environmental safety. However, they are limited in their application by a number of shortcomings, including their high water solubility and vapor permeability as well as their poor opacity and low mechanical resistance. Thus, nanoparticles, such as green FexOy-NPs, can be used to overcome the drawbacks associated with these materials. Therefore, the aim of this study was to develop three different polymer-based films (gelatin-based, cellulose acetate-based and chitosan-based films) containing green synthesized FexOy-NPs (1.0% w/w of the initial polymer weight) as an additive to improve film properties. This was accomplished by preparing the different films using the casting method and examining their physicochemical, mechanical, microstructural, and functional characteristics. The results show that the incorporation of FexOy-NPs into the different films significantly enhanced their physicochemical, mechanical, and morphological properties as well as their antioxidant characteristics. Consequently, it was possible to produce suitable natural polymer-based films with potential applications across a wide range of industries, including functional packaging for food, antioxidants, and antimicrobial additives for pharmaceutical and biomedical materials as well as pesticides for agriculture.

Noviembre, 2022 | DOI: 10.3390/polym14214487

Transparency of polymeric food packaging materials

Guzman-Puyol, Susana; Benitez, Jose J; Heredia-Guerrero, Jose A
Food Research International, 161 (2022) 111792
Materiales de Diseño para la Energía y Medioambiente


Transparency is a very important technical parameter to evaluate and validate certain food packaging materials. In the recent scientific literature, several methods (i.e. transmittance, opacity, haze, and absorbance) have been used and such variety hinders a direct comparison of results from different authors. In this Review, we describe and discuss the most widely employed methods to measure transparency, with special emphasis on two main parameters: transmittance and opacity. Moreover, a comparison of the different techniques is addressed and the typical values of transmittance and opacity of common transparent food packaging materials are provided. Our current opinion is that transparency should be expressed as transmittance in the visible range due to both the quickness and easiness of the measurement and the standardization of data. This information should be accompanied by the thickness value and a graphical image of the analysed samples for a useful and complete characterization.

Noviembre, 2022 | DOI: 10.1016/j.foodres.2022.111792

Insights into the Impact of Activators on the 'Catalytic' Graphitization to Design Anode Materials for Lithium Ion Batteries

Hanhart, V; Frankenstein, L; Ramirez-Rico, J; Diozios, V; Winter, M; Gomez-Martin, A; Placke, T
Chemelectrochem, 9 (2022) e202200819
Materiales de Diseño para la Energía y Medioambiente


In this work, we systematically investigate the 'catalytic' graphitization of a biomass precursor (coffee ground) using 10-60 wt.% of the activator iron (III) chloride hexahydrate in a temperature range of 1000 degrees C-2400 degrees C. Special focus is put on the correlation of synthesis conditions, e.g., heat treatment temperature and mass fraction of iron chloride, with the electrochemical performance in carbon vertical bar vertical bar Li metal cells. The structural investigations of the materials reveal a positive impact of an increasing heat treatment temperature and/or mass fraction of inserted activator on the degree of graphitization and the delithiation capacity. However, a saturation point regarding the maximum degree of graphitization at 2000 degrees C and reversible capacity by the 'catalytic' graphitization approach using iron (III) chloride has been found. A maximum degree of graphitization of approximate to 69% could be reached by applying 2000 degrees C and 40 wt.% FeCl3 center dot 6H(2)O, resulting in a reversible capacity of 235 mAh g(-1).

Noviembre, 2022 | DOI: 10.1002/celc.202200819

Effective photocatalytic conversion of formic acid using iron, copper and sulphate doped TiO2

Zouheir, M; Tanji, K; Navío, JA; Hidalgo, MC; Jaramillo-Paez, CA; Kherbeche, A
Journal of Central South University, 29 (2022) 3592-3607
Fotocatálisis Heterogénea: Aplicaciones


In this paper, the combined addition of copper or iron and sulphate ions onto TiO2 prepared by a simple sol-gel method is studied for formic acid photocatalytic conversion. A wide structural and morphological characterization of the different photocatalysts was performed by X-ray diffraction (XRD), N2-physisorption for BET surface area measurements, scanning and transmission electronic microscopies (SEM and TEM), UV-Vis diffuse spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS), in order to correlate the physico-chemical properties of the materials to their photocatalytic efficiencies for formic acid oxidation. Results have shown important differences among the catalysts depending on the metal added. Sulphated TiO2/Cu (1%Cu) was the best photocatalyst obtaining about 100% formic acid conversion in only 5 min. The appropriate physico-chemical features of this photocatalyst, given by the addition of combined copper and sulphate ions, explain its excellence in photocatalytic reaction.

Noviembre, 2022 | DOI: 10.1007/s11771-022-5172-9

Monitoring the Simultaneous Implantation of Ti and Tb Cations to a Sacrificial Template and the Sol-Gel Synthesis of Tb-Doped TiO2 (Anatase) Hollow Spheres and Their Transition to Rutile Phase

Colomer, MT; Vattier, F
International Journal of Molecular Sciences, 23 (2022) 13162


Tb-doped TiO2 (anatase) micro-hollow spheres (HSs) with nano-shells, in the range 0.00-3.00 at.% Tb, were successfully synthesized by a simultaneous chemical implantation route of both Ti and Tb cations from chlorides to a poly-styrene (PST)-co-poly-divinyl benzene (PDVB) sacrificial template, followed by controlled hydrolysis and polycondensation reactions. After water addition to the mixture of the precursors with the template, a decrease in the intensity and a shift to lower wavenumbers of the C=O absorption band in the IR spectra can indicate not only the anchoring of Ti and Tb ions to the carbonyl group of the template but also the hydrolysis of the implanted precursors. This latter process can involve a proton attack on the Ti-Cl, Tb-Cl and C=O bonds, the occupation of a vacant site by a water molecule, and then the dissociation of the dangling Ti-Cl, Tb-Cl ligands and C=O bonds. It gives rise to Ti1-xTbx[(OH)(4-u)Cl-v]@PST-PDVB and Ti1-xTbx[(OH)(4-y)]@PST-PDVB complexes (x = 0.00, 0.0012, 0.0170 and 0.030). Finally, polycondensation of these species leads to Ti1-xTbxO2-w'@PST-PDVB compounds. After subsequent thermal removal at 550 degrees C of the template, the IR bands of the core (template) totally vanished and new bands were observed in the 400-900 cm(-1) region which can be attributed to the metalloxane bondings (M-O, M'-O, M-O-M, M-O-M' and/or M'-O-M', being M and M' = Ti and Tb, respectively, i.e., mainly vibration modes of anatase). Then, micron-sized HSs of TiO2 and Tb-doped-TiO2 (anatase) were obtained with nano-shells according to field emission gun scanning electron microscopy (FEG-SEM) and transmission electron microscopy (TEM) observations. Furthermore, X-ray photoelectron spectroscopy (XPS) measurements confirmed the presence of Tb4+ (38.5 and 41.2% for 1.70 and 3.00 at.% Tb, respectively) in addition to Tb3+ in the resulting HSs, with increasing Tb4+ content with both Tb doping and higher calcination temperatures. Then, these HSs can be considered as rare earth (RE) co-doped systems, at least for 1.70 and 3.00 at.% Tb contents being the transition to rutile phase favored by Tb doping for those compositions. Finally, diffusion of Tb from the inner parts to the surface of the HSs with the calcination treatments was also observed by XPS.

Noviembre, 2022 | DOI: 10.3390/ijms232113162

Morphologically diverse CaCO3 microparticles and their incorporation into recycled cellulose for circular economy

Guerra-Garces, J; Garcia-Negrete, CA; Pastor-Sierra, K; Arteaga, GC; Barrera-Vargas, M; de Haro, MJ; Fernandez, A
Materials Today Sustainability, 19 (2022) 100166
Materiales Nanoestructurados y Microestructura


The main raw material for manufacture of paper is cellulose fibers that can be virgin or recycled. Globally, 70% of the Tetra Pak packages sold are not recycled and remain as unused wastes. Therefore, the development of alternatives to promote greater recycling and sustainable use of these packages is of great interest. In this study, the formation of precipitated calcium carbonates (PCC) in the presence of carboxymethyl cellulose (CMC) is studied at different temperatures, and the morphologically diverse particles obtained are explored as filler for composites based on cellulosic fibers recovered from Tetra Pak containers. It was found that the addition of filler does not lead to deterioration of either tensile strength or thermal and stability of the obtained composite samples. Results also suggest that the morphological diversity of the filler contributes to a more efficient filling of the interfibrillar spaces of cellulosic fibers and, in turn, to the fiber and filler compatibility.

Noviembre, 2022 | DOI: 10.1016/j.mtsust.2022.100166

Boosting the photocatalytic properties of NaTaO3 by coupling with AgBr

Puga, F; Navío, JA; Hidalgo, MC
Photochemical & Photobiological Sciences (2022)
Fotocatálisis Heterogénea: Aplicaciones


AgBr/NaTaO3 composites, with different molar % of NaTaO3 (Br/NTO(X%)), have been synthesized by simple precipitation methods; bare NaTaO3 was synthesized by hydrothermal procedure, while AgBr was synthesized by a precipitation procedure using cetyl-tri-methyl-ammonium bromide (CTAB) and AgNO3. Samples have been characterized by X-ray diffraction (XRD), N2 adsorption, UV–vis diffuse reflectance spectroscopy (DRS), Fourier-transform infrared spectroscopy (FT-IR), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of the as-prepared photo-catalysts was evaluated through photocatalytic degradation of rhodamine B (RhB), methyl orange (MO) and caffeic acid (CAFA) under UV and visible illumination. Single AgBr material and Br/NTO(X%) composites displayed the ability to absorb light in the visible region, while NaTaO3 is only photoactive under UV irradiation. Based on the position of conduction and valence bands of AgBr and NaTaO3, the heterojunction between these two photo-catalysts corresponds to a type II junction. In the case of photocatalytic degradation of RhB and CAFA, Br/NTO(x%) composites have highest photocatalytic activity than that obtained by both parental materials under the same operational conditions. AgBr and Br/NTO(x%) composites achieve a fast degradation of MO, together with a considerable adsorption capacity, attributed to the presence of a remaining amount of residual CTAB on the AgBr surface. In summary, coupling AgBr with NaTaO3 improves the photocatalytic activity under both UV and visible illumination with respect to the parental components, but the performance of the composites is highly dependent on the type of substrate to be degraded and the illumination conditions.

Noviembre, 2022 | DOI: 10.1007/s43630-022-00334-9

Enhanced red-UC luminescence through Ce3+ co-doping in NaBiF4:Yb3+/Ho3+(Er3+)/Ce3+ phosphors prepared by ultrafast coprecipitation approach

Giordano, L; Du, H; Castaing, V; Luan, F; Guo, D; Viana, B
Optical Materials X, 16 (2022) 100199
Materiales Ópticos Multifuncionales


Series of Yb3+/Ho3+(Er3+)/Ce3+ co-doped NaBiF4 phosphors were synthesized through an ultrafast co-precipitation reaction technique at room temperature. The effect of the Ce3+ ions on the crystal structure and upconversion (UC) luminescence properties of the studied samples were investigated in detail. FTIR and XPS demonstrated the pre-formation of NaBiF4 and the introduction of Yb3+, Ho3+, Er3+ and Ce3+ all as dopants in the host materials. Under 980 nm excitation, NaBiF4:Yb3+,Ho3+(Er3+),Ce3+performed the characteristic emission of the activator ion, and the introduction of Ce3+ did not change the emission wavelengths, only the relative intensities. Due to partial good energy overlap when 2F7/2 Ce3+ manifold is populated, raising Ce3+ ions concentration enhanced the red UC emission versus green UC emission but also lead to significant decrease in the average lifetimes of all monitored emissions for Ho3+ and Er3+. These lifetime decreases are explained by the energy loss in non-radiative pathways after the introduction of Ce3+. In addition, the green to yellow color emission change through addition of Ce3+ was explored in NaBiF4: Yb3+,Ho3+,Ce3+ to propose a novel application in two-level anti-counterfeiting.

Octubre, 2022 | DOI: 10.1016/j.omx.2022.100199

Highly efficient electrical discharge machining of yttria-stabilized zirconia ceramics with graphene nanostructures as fillers

Muñoz-Ferreiro, C; Lopez-Pernia, C; Moriche, R; Gommeringer, A; Kern, F; Poyato, R; Gallardo-Lopez, A
Journal of the European Ceramic Society, 42 (2022) 5943-5952
Reactividad de Sólidos


Electrical-discharge machining (EDM) of advanced ceramics allows the miniaturization of parts with complex shapes. Since electrical conductivity is required, non-conductive ceramics need a conductive second phase. This work assesses the feasibility of industrial EDM in advanced yttria-stabilized tetragonal zirconia (3YTZP) composites with 20 vol% graphene nanostructures with different morphology using different EDM energies. The structural integrity of the graphene nanostructures, the roughness of the machined surfaces and the geometrical tolerances have been evaluated by Raman spectroscopy, confocal microscopy and scanning electron microscopy, showing that it is possible to obtain a stable and efficient EDM process in these composites using low electrode energies. The use of the largest and thickest graphene nanostructures led to the best performance in terms of EDM machinability, the smallest nanostructures produced the best surface finish for low electrode energy and the thinnest nanostructures allowed the highest material removal rate at medium energy in the composites.

Octubre, 2022 | DOI: 10.1016/j.jeurceramsoc.2022.06.037

Design and Characterization of ITO-Covered Resonant Nanopillars for Dual Optical and Electrochemical Sensing

Tramarin, L; Casquel, R; Gil-Rostra, J; Gonzalez-Martinez, MA; Herrero-Labrador, R; Murillo, AMM; Laguna, MF; Banuls, MJ; Gonzalez-Elipe, AR; Holgado, M
Chemosensors, 10 (2022) 393
Nanotecnología en Superficies y Plasma


In this work we present a dual optical and electrochemical sensor based on SiO2/Si3N4 resonant nanopillars covered with an indium tin oxide (ITO) thin film. A 25-30 nm thick ITO layer deposited by magnetron sputtering acts as an electrode when incorporated onto the nanostructured array, without compromising the optical sensing capability of the nanopillars. Bulk sensing performances before and after ITO deposition have been measured and compared in accordance with theoretical calculations. The electrochemical activity has been determined by the ferri/ferrocyanide redox reaction, showing a remarkably higher activity than that of flat thin films of similar ITO nominal thickness, and proving that the nanopillar system covered by ITO presents electrical continuity. A label-free optical biological detection has been performed, where the presence of amyloid-beta has been detected through an immunoassay enhanced with gold nanoparticles. Again, the experimental results have been corroborated by theoretical simulations. We have demonstrated that ITO can be a beneficial component for resonant nanopillars sensors by adding potential electrochemical sensing capabilities, without significantly altering their optical properties. We foresee that resonant nanopillars coated with a continuous ITO film could be used for simultaneous optical and electrochemical biosensing, improving the robustness of biomolecular identification.

Octubre, 2022 | DOI: 10.3390/chemosensors10100393

Pre-Roman and Republican amphorae (III-I centuries b.C.) from production contexts of the Guadalquivir Basin: technical and compositional characterization

Moreno-Megías, V.; García-Fernández, F.J.; Martín-del-Río, J.J.; Borreguero-Cid, M.; Sánchez-Soto, P.J.
Boletín de la Sociedad Española de Cerámica y Vidrio, 61 (2022) 498-515
Materiales Avanzados


The present work consists of an archaeometric investigation concerning ceramic samples, mostly unpublished, of the III-I centuries b.C. They were found in connection with kilns of the city of Sevilla (Archbishop's Palace) and the countryside (Arrabal zone, Carmona). They are identified with evolved variations of Iron Age amphorae of Punic and Turdetanian tradition, or already Roman typologies. The main objectives of this research include their technological and compositional characterization as well as the comparison of the characteristics of each manufacture tradition.

An assemblage of 13 samples has been studied through petrographic analysis of thin sections, chemical analysis (X-ray fluorescence) and mineralogical analysis (X-ray diffraction). The chemical results showed the silico-aluminous and calcitic character of the samples, with variable contents of iron oxide as well as other minor elements and traces. The statistical treatment of the data by multivariant analysis has differentiated 3 conglomerates and one sample as an outsider. The mineralogical analysis has identified 8 crystalline phases, several of them already present in the raw materials and others formed by thermal treatment. It is interesting to note the illite, identified as dehydroxylated phase, anorthite, diopside and gehlenite. The petrographical analysis has identified 3 different petro-groups, which are correlated by a compositional point of view with the original context of the samples. Thus, according to these results, it has been possible to distinguish the manufactures of Sevilla from the Roman shapes, the common ware and the imitation types of Carmona.

It has been discussed the possible solid-state reactions which yielded the crystalline phases identified by X-ray diffraction, besides an estimation of firing temperatures between 820-850 degrees C in an oxidant atmosphere. Finally, the possible sources for the raw materials used in the fabrication of these amphorae have been proposed in the Guadalquivir River valley, considering their illitic-calcitic characteristics. 

Septiembre, 2022 | DOI: 10.1016/j.bsecv.2021.03.008

Sol-Gel Synthesis of Endodontic Cements: Post-Synthesis Treatment to Improve Setting Performance and Bioactivity

Song, X; Diaz-Cuenca, A
Materials, 15 (2022) 6051
Materiales para Bioingeniería y Regeneración Tisular


The sol-gel process is a wet chemical technique that allows very fine control of the composition, microstructure, and final textural properties of materials, and has great potential for the synthesis of endodontic cements with improved properties. In this work, the influence of different sol-gel synthesis variables on the preparation of endodontic cement based on calcium silicate with Ca/Si stoichiometry equal to 3 was studied. Starting from the most optimal hydraulic composition selected, a novel second post-synthesis treatment using ethanol was essayed. The effects of the tested variables were analyzed by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen physisorption, and Gillmore needles to determine the setting time and simulated body fluid (SBF) immersion to measure the bioactive response in vitro. The results indicated that the sol-gel technique is effective in obtaining bioactive endodontic cements (BECs) with high content of the hydraulic compound tricalcium silicate (C3S) in its triclinic polymorph. The implementation of a novel post-synthesis treatment at room temperature using ethanol allows obtaining a final BEC product with a finer particle size and a higher CaCO3 content, which results in an improved material in terms of setting time and bioactive response.

Septiembre, 2022 | DOI: 10.3390/ma15176051

Influence of the carbon incorporation on the mechanical properties of TiB2 thin films prepared by HiPIMS

Sala, N; Abad, MD; Sanchez-Lopez, JC; Crugeira, F; Ramos-Masana, A; Colominas, C
International Journal of Refractory Metals & Hard Materials, 107 (2022) 105884
Tribología y Protección de Superficies


Nanostructured TiB2 and TiBC thin films with carbon contents up to 11 at. % were prepared by physical vapor deposition using high power impulse magnetron sputtering (HiPIMS) technology. The influence of carbon incorporation during the deposition of TiB2 coatings was investigated on the chemical composition, microstructure and mechanical properties by means of scanning electron microscopy, atomic force microscopy, x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), nanoindentation, scratch test, calotest and adhesion Daimler-Benz test. The results indicated that small additions of carbon up to 3 at. % improved the mechanical behavior and increased the adhesion of the TiB2 thin films. Hardnesses up to 37 GPa were reached and the adhesion of the coating to AISI D2 steel substrates increased from 11 to 18 N. XRD and XPS results showed that the carbon atoms are either occupying interstitial sites within the hexagonal structure of the TiB2 or forming bonds with titanium and boron atoms. The preferred orientation of the films determined by XRD also changed with the increasing carbon content in the (001) crystalline plane.

Septiembre, 2022 | DOI: 10.1016/j.ijrmhm.2022.105884

Multiscale Kinetic Monte Carlo Simulation of Self-Organized Growth of GaN/AlN Quantum Dots

Budagosky, JA; García-Cristobal, A
Nanomaterials, 12 (2022) 3052
Nanotecnología en Superficies y Plasma


A three-dimensional kinetic Monte Carlo methodology is developed to study the strained epitaxial growth of wurtzite GaN/AlN quantum dots. It describes the kinetics of effective GaN adatoms on an hexagonal lattice. The elastic strain energy is evaluated by a purposely devised procedure: first, we take advantage of the fact that the deformation in a lattice-mismatched heterostructure is equivalent to that obtained by assuming that one of the regions of the system is subjected to a properly chosen uniform stress (Eshelby inclusion concept), and then the strain is obtained by applying the Green's function method. The standard Monte Carlo method has been modified to implement a multiscale algorithm that allows the isolated adatoms to perform long diffusion jumps. With these state-of-the art modifications, it is possible to perform efficiently simulations over large areas and long elapsed times. We have taylored the model to the conditions of molecular beam epitaxy under N-rich conditions. The corresponding simulations reproduce the different stages of the Stranski-Krastanov transition, showing quantitative agreement with the experimental findings concerning the critical deposition, and island size and density. The influence of growth parameters, such as the relative fluxes of Ga and N and the substrate temperature, is also studied and found to be consistent with the experimental observations. In addition, the growth of stacked layers of quantum dots is also simulated and the conditions for their vertical alignment and homogenization are illustrated. In summary, the developed methodology allows one to reproduce the main features of the self-organized quantum dot growth and to understand the microscopic mechanisms at play.

Septiembre, 2022 | DOI: 10.3390/nano12173052

Optimization of anion exchange membrane water electrolyzers using ionomer-free electrodes

Lopez-Fernandez, E; Gomez-Sacedon, C; Gil-Rostra, J; Espinos, JP; Brey, JJ; Gonzalez-Elipe, AR; de Lucas-Consuegra, A.; Yubero, F
Renewable Energy, 197 (2022) 1183-1191
Nanotecnología en Superficies y Plasma


This work is carried out in the context of the anion exchange membrane water electrolysis (AEMWE) and pursuits to determine the influence of different cell components on the global electrochemical performance. Ionomer-free electrodes consisting of anodic Ni-Fe and cathodic Ni electrocatalysts deposited by magnetron sputtering in an oblique angle deposition configuration were utilized for this study. In addition to the characteristics and equivalent thickness of the electrocatalysts, other factors affecting the efficiency that have been considered in this study encompass the type of gas diffusion layer (GDLs), including carbon paper and stainless-steel fiber paper supports, and several commercial anion exchange membranes. The electrocatalytic performances in both a threeelectrode and complete single cell AEMWE set-ups, together with the physico-chemical characterization of the electrodes before and after operation, have served to select the optimum components for the utilized cell configuration. Thus, current densities of 670 mA cm-2, at polarization voltage of 2.2 V, 1.0 M KOH electrolyte and 40 degrees C were obtained in a membrane electrode assembly. A seven days chronopotentiometry experiment at a fixed current of 400 mA cm-2 demonstrated a noticeable stability of this type of AEMWE cells incorporating ionomer-free electrodes.

Septiembre, 2022 | DOI: 10.1016/j.renene.2022.08.013

Oxygen production routes assessment for oxy-fuel combustion

Garcia-Luna, S; Ortiz, C; Carro, A; Chacartegui, R; Perez-Maqueda, LA
Energy, 254 (2022) 124303
Reactividad de Sólidos


Oxyfuel combustion is a promising alternative to decarbonize the power sector. However, the main barrier to commercial deployment of the technology is the high energy consumption associated with oxygen production (-200-300 kWh per ton of O-2), which penalizes the thermal-to-electric efficiency of 8.5-12% compared to traditional air combustion plants. Typically, oxygen is obtained from a cryogenic air separation process. However, other technologies have been gaining momentum in recent years, such as membrane technologies, chemical looping air separation, and renewable-driven electrolysis. The present work evaluates all these options for O-2 production to retrofit a 550 MWe coal-fired power plant with oxyfuel combustion. A techno-economic assessment is carried out to estimate the energy penalty, the O-2 production cost (V/ton) and the Levelized Cost of Electricity. The best results are obtained by combining oxygen transport membranes and electrolysis since the energy consumption has been reduced to 98.56 kWh/ton of O(2, )decreasing by 59.31% the cryogenic distillation energy consumption (242.24 kWh/ ton O2), reducing the overall energy penalty compared to cryogenic air separation from 8.88% points to 7.56%points. The oxygen transport membrane presents the lowest cost of electricity in retrofitting cases, 51.48 $/MWh, while cryogenic distillation estimated cost is 52.7 $/MWh. Their costs of avoided CO2 are 31.79 $/ton CO2 and 34.15 $/ton CO2 respectively.

Septiembre, 2022 | DOI: 10.1016/

Ni-Phosphide catalysts as versatile systems for gas-phase CO2 conversion: Impact of the support and evidences of structure-sensitivity

Zhang, Q; Pastor-Perez, L; Villora-Pico, JJ; Joyce, M; Sepulveda-Escribano, A; Duyar, MS; Reina, TR
Fuel, 323 (2022) 124301
Química de Superficies y Catálisis


We report for the first time the support dependent activity and selectivity of Ni-rich nickel phosphide catalysts for CO2 hydrogenation. New catalysts for CO2 hydrogenation are needed to commercialise the reverse water-gas shift reaction (RWGS) which can feed captured carbon as feedstock for traditionally fossil fuel-based processes, as well as to develop flexible power-to-gas schemes that can synthesise chemicals on demand using surplus renewable energy and captured CO2. Here we show that Ni2P/SiO2 is a highly selective catalyst for RWGS, producing over 80% CO in the full temperature range of 350-750 degrees C. This indicates a high degree of suppression of the methanation reaction by phosphide formation, as Ni catalysts are known for their high methanation activity. This is shown to not simply be a site blocking effect, but to arise from the formation of a new more active site for RWGS. When supported on Al2O3 or CeAl, the dominant phase of as synthesized catalysts is Ni12P5. These Ni12P5 catalysts behave very differently compared to Ni2P/SiO2, and show activity for methanation at low temperatures with a switchover to RWGS at higher temperatures (reaching or approaching thermodynamic equilibrium behaviour). This switchable activity is interesting for applications where flexibility in distributed chemicals production from captured CO2 can be desirable. Both Ni12P5/Al2O3 and Ni12P5/CeAl show excellent stability over 100 h on stream, where they switch between methanation and RWGS reactions at 50-70% conversion. Catalysts are characterized before and after reactions via X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), temperature-programmed reduction and oxidation (TPR, TPO), Transmission Electron Microscopy (TEM), and BET surface area measurement. After reaction, Ni2P/SiO(2 )shows the emergence of a crystalline Ni12P5 phase while Ni12P5/Al2O3 and Ni12P5/CeAl both show the crystalline Ni3P phase. While stable activity of the latter catalysts is demonstrated via extended testing, this Ni enrichment in all phosphide catalysts shows the dynamic nature of the catalysts during operation. Moreover, it demonstrates that both the support and the phosphide phase play a key role in determining selectivity towards CO or CH4.

Septiembre, 2022 | DOI: 10.1016/j.fuel.2022.124301

Unraveling the Mo/HZSM-5 reduction pre-treatment effect on methane dehydroaromatization reaction

Lopez-Martin, A; Caballero, A; Colon, G
Applied Catalysis B-Environmental, 312 (2022) 121382
Materiales y Procesos Catalíticos de Interés Ambiental y Energético


Reduction pre-treatment at different temperatures were performed over Mo/HZSM-5 system before methane dehydroaromatiztion reaction. We have shown the crucial effect of reduction temperature on the final catalytic performance. Outstanding improvement in the aromatics conversion has been attained. Thus, H-2 formation form methane cracking reaction seems to be hindered for pre-treated catalysts. As a consequence, the deposition of coke in these samples appeared also notably suppressed. The optimum performance has been achieved for reduction pre-treatment at 550 degrees C. For this temperature, we have observed that the fraction of reduced Mo species is higher.

Septiembre, 2022 | DOI: 10.1016/j.apcatb.2022.121382

Sustainable routes for acetic acid production: Traditional processes vs a low-carbon, biogas-based strategy

Martin-Espejo, JL; Gandara-Loe, J; Odriozola, JA; Reima, TR; Pastor-Pérez, L
Science of the Total Environment, 840 (2022) 156663
Química de Superficies y Catálisis


The conversion of biogas, mainly formed of CO2 and CH4, into high-value platform chemicals is increasing attention in a context of low-carbon societies. In this new paradigm, acetic acid (AA) is deemed as an interesting product for the chemical industry. Herein we present a fresh overview of the current manufacturing approaches, compared to potential low-carbon alternatives. The use of biogas as primary feedstock to produce acetic acid is an auspicious alternative, representing a step-ahead on carbon-neutral industrial processes. Within the spirit of a circular economy, we propose and analyse a new BIO-strategy with two noteworthy pathways to potentially lower the environmental impact. The generation of syngas via dry reforming (DRM) combined with CO2 utilisation offers a way to produce acetic acid in a two-step approach (BIO-Indirect route), replacing the conventional, petroleum-derived steam reforming process. The most recent advances on catalyst design and technology are discussed. On the other hand, the BIO-Direct route offers a ground-breaking, atom-efficient way to directly generate acetic acid from biogas. Nevertheless, due to thermodynamic restrictions, the use of plasma technology is needed to directly produce acetic acid. This very promising approach is still in an early stage. Particularly, progress in catalyst design is mandatory to enable low-carbon routes for acetic acid production.

Septiembre, 2022 | DOI: 10.1016/j.scitotenv.2022.156663

Hydrogen production from landfill biogas: Profitability analysis of a real case study

Vidal-Barrero, F; Baena-Moreno, FM; Preciado-Cardenas, C; Villanueva-Perales, A; Reina, TR
Fuel, 324 (2022) 124438
Química de Superficies y Catálisis


Hydrogen is not only considered as a cornerstone within renewable energy portfolio but it is also a key enabler for CO2 valorisation being a central resource for industrial decarbonization. This work evaluates the profitability of hydrogen production via combined biogas reforming and water-gas shift reaction, based on a real case scenario for landfill biogas plant in Seville (Spain). A techno-economic model was developed based on a process model and the discounted cash-flow method. A biogas flow of 700 m(3)/h (input given by the landfill biogas plant) was used as plant size and the analysis was carried out for two different cases: (1) use of already available energy sources at the industrial plant, and (2) solar energy generation to power the process. The economic outputs obtained showed that under the current circumstances, this hydrogen production route is not profitable. The main reason is the relatively low current hydrogen prices which comes from fossil fuels. A revenues analysis indicates that hydrogen from biogas selling prices between 2.9 and 5.7 euro/kg would be needed to reach profitability, which are considerably higher than the current hydrogen cost (1.7 euro/kg). A subsidy scheme is suggested to improve the competitiveness of this hydrogen production process in the short-medium term. A cost analysis is also performed, revealing that electricity prices and investment costs have a high impact on the total share (23-40% and 8-22%, respectively). Other potential costs reduction such as catalyst, labour and manteinance & overhead are also evaluated, showing that cutting-down production costs is mandatory to unlock the potential of hydrogen generation from biogas. Our work showcases the techno-economic challenge that green energy policies face in the path toward sustainable societies.

Septiembre, 2022 | DOI: 10.1016/j.fuel.2022.124438