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The paper puts forward the concept of a double-redox electrochemical capacitor operating in an aqueous electrolyte. The redox activity of sulphur from insoluble Bi2S3 nanocrystals embedded in the negative electrode material (up to 10 wt%) operating in 1 mol L−1 Li2SO4 electrolyte is demonstrated. It is also shown that the performance is significantly boosted using MPA (3-mercaptopropionic acid) as a ligand attached to the surface of the nanocrystals, which allows for more efficient use of Bi2S3 redox active species. This redox activity is combined with the reactions of iodides, which occur at the opposite electrode with 1 mol L−1 NaI. This enables the formation of a discharge voltage plateau that effectively boosts the capacitance (275 F g−1), and thus specific energy of the device owing to the relatively high cell voltage of 1.5 V. This performance is possible due to the advantageous electrode mass ratio (m− : m+ = 2 : 1), which helps to balance the charge. The rate capability test of the device demonstrates its capacitance retention of 73% at 10 A g−1 of the discharge current. The different states of the redox species ensure their operation at separate electrodes in an immiscible manner without a shuttling effect. The specific interactions of the redox active species with carbon electrodes are supported by operando Raman spectroscopy.

Well-characterized and reproducible nanostructured layered sulfide/carbon composites with optimized properties for their incorporation in energy storage devices including go/no-go criteria for any considered composition

Chapter 1 - Bismuth-based nanomaterials for energy applications

Final report on nanostructured electrodes for energy storage systems based on novel layered sulfide/substrate composites (composition and preparation methods)

Minutes of the final meeting 2022

WP3presentation final project meeting 21/07/2022

Keynote presentation from Elżbieta Frąckowiak at Carbon 2022 Conference "Carbon for a Cleaner Future". London3 - 8 July 2022

Resumen del trabajo presentado a la XXXVIII Reunión Bienal de la Real Sociedad Española de Química, celebrada en el Palacio de Congresos de Granada, del 27 de junio al 30 de junio de 2022., Authors acknowledge the M-ERA.NET (NOEL) project, PCI2019-103637 funded by MCIN/AEI/10.13039/501100011033.

WP3 presentation Progress Meeting 23/03/22.

WP3 presentation Progress Meeting 23/03/22.

Minutes of the 2nd annual meeting 2021

WP3 presentation 2nd Annual Meeting 13/09/21.

WP3 presentation Progress Meeting 21/04/21

WP3 presentation Progress Meeting 16/11/20.

WP3 presentation.1st annual meeting 10/09/2020

Kick-off meeting NOEL-WP3

Deliverable report template

NOEL project website

Minutes of Consortium Annual Meeting (September 2020)

1st generation of nanomaterials (NC or NW) for energy storage applications

Milestone 4:Well-characterized and reproducible nanostructured layered sulfide/carbon composites

Milestone report template

Electrospray was used as a one-step technique to generate inhalable ciprofloxacin-loaded chitosan sub-micron particles with potential use in the treatment of pulmonary infections. The effect of operating parameters was studied and the preparation method optimized. The final sizes of ciprofloxacin-loaded particles were 386.1 ± 248.5 nm and 501.1 ± 276.3 nm for high and low molecular weight chitosan, respectively. The high surface charge of the particles formed, around +45 mV, enhances their mucoadhesive properties. The particles were biocompatible with alveolar cell line (A549), and showed a high antimicrobial activity against two of the most common respiratory pathogens Staphylococcus aureus and Pseudomonas aeruginosa., Financial support from Nanbiosis platform and Biomedical Research Networking Center in Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN). B. Arauzo thanks DGA predoctoral fellowship for personal researcher (2017–2021). Authors thank the “Advanced Microscopy Laboratory” of the “Institute of Nanoscience and Materials of Aragon - University of Zaragoza”, LMA-INMA, for access to their instruments.

A volume in Solar Cell Engineering., The development of energy-harvesting and energy-storage devices based on renewable sources will be fundamental for the deployment of autonomous or isolated systems like emerging internet-of-things (IoT) applications. This chapter will focus on the use of bismuth nanomaterials in energy-related applications. These materials fulfill the requirements of being composed of abundant and non-toxic elements and therefore can be considered environmentally friendly functional materials. The specific applications that will be covered are: energy-harvesting devices including solar cells and thermoelectrics, electrochemical energy storage devices such as batteries and supercapacitors, and photocatalysts for solar hydrogen production. For each technology, we will discuss the state of the art, challenges, and the focus areas for current research., Authors acknowledge Fundación Iberdrola España; Programa Operativo FEDER Aragón 2014–2020, “Construyendo Europa desde Aragón” (Ref. LMP35_18); and M-ERA.NET network, project "NOEL" (reference PCI2019–103637) funded by the Agencia Estatal de Investigación through the PCI 2019 call.

The increasing presence of nanotechnology on the market entails a growing probability of finding ENMs in the environment. Nanoparticles aerosols are a yet unknown risk for human and environmental exposure that may normally occur at any point during the nanomaterial lifecycle. There is a research gap in standardized methods to assess the exposure to airborne nanoparticles in different environments. The controllable generation of nanoparticle aerosols has long been a challenging objective for researchers and industries dealing with airborne nanoparticles. In this work, a versatile system to generate nanoparticulate aerosols has been designed. The system allows the production of both i) instantaneous nanoparticle clouds and ii) continuous nanoparticle streams with quasi-stable values of particle concentration and size distribution. This novel device uses a compressed-air pressure pulse to disperse the target material into either the testing environment (instantaneous cloud formation) or a secondary chamber, from which a continuous aerosol stream can be drawn, with a tunable nanoparticle concentration. The system is robust, highly versatile and easy to operate, enabling reproducible generation of aerosols from a variety of sources. The system has been verified with four dry nanomaterials: TiO2, ZnO, CuO and CNT bundles.

The release of nanosized particles from fluidized beds of ceramic oxide nanopowders, namely, TiO2 (P25), Al2O3 (AluC) and SiO2 (A130) has been assessed for the first time. Previous models and experiments for processing engineered nanoparticles (ENP) using fluidized beds reported only the formation of micron-sized cluster agglomerates in the gas phase. In this work, aerosol spectrometry techniques such as scanning mobility particle sizing (SMPS) and optical particle counting (OPC) have been combined with powder technologies, such as the borescope high-speed camera system, to determine the particle size distribution from 5 nm to 1 mm above a fluidized bed. Furthermore, the morphology of nanoparticulate aerosol at different locations in the bed was determined by offline electron microscopy. The results demonstrate that free nano- and micron-sized particles are released from fluidized beds. Since the structures found above the bed are also expected to be present within fluidized beds, a revision of existing nanoparticle fluidization models, and improved safety and control measures in reactors for gas-phase ENP processing are needed to avoid nanoparticle release.

The deposition of airborne nanosized matter onto surfaces could pose a potential risk in occupational and environmental scenarios. The incorporation of fluorescent labels, namely fluorescein isotiocyanate (FITC) or tris-1,3-phenanthroline ruthenium (II) chloride (Ru(phen)3Cl2), into spherical 80-nm silica nanoparticles allowed the detection after the illumination with LED light of suitable wavelength (365 or 405 nm respectively). Monodisperse nanoparticle aerosols from fluorescently labeled nanoparticles were produced under safe conditions using powder generators and the deposition was tested into different surfaces and filtering media. The contamination of gloves and work surfaces that was demonstrated by sampling and SEM analysis becomes immediately clear under laser or LED illumination. Furthermore, nanoparticle aerosols of about 105 nanoparticles/cm3 were alternatively fed through a glass pipe and personal protective masks to identify the presence of trapped nanoparticles under 405 nm or 365 nm LED light. This testing procedure allowed a fast and reliable estimation of the contamination of surfaces with nanosized matter, with a limit of detection based on the fluorescence emission of the accumulated solid nanoparticles of 40 ng of Ru(phen)3@SiO2 of silica per mg of non-fluorescent matter.

Silica-metal nanohybrids are common materials for applications in biomedicine, catalysis or sensing. Also, hollow structures are of interest as they provide additional useful features. However, in these materials the control of the size and accessibility to the inner regions of the structure usually requires complex synthesis procedures. Here we report a simple colloidal procedure for synthesizing hollow silica-metal nanohybrids, driven by the diffusion of metal precursors through the porous silica shell and subsequent reduction in aqueous solutions. The formation of hollow nanoparticles is controlled by the colloidal conditions during synthesis, which affect the ripening of hollow nanoparticles in presence of organosilanes. The modification of the conditions during synthesis affected the growth of silica precursors in presence of fluorescein isothiocyanate (FITC). The limited access to water molecules during the hydrolysis of silica precursors is attributed to the hydrophobicity of organic fluorescent molecules linked to the condensing silica clusters at the initial stages of nanoparticle formation and to the limitation of water content in the microemulsion method used. Finally, the growth of metal nanoseeds at the core of hollow nanoparticles can be easily achieved though a simple method in aqueous environment. The pH and thermal conditions during the reduction process affect the formation of metal-silica nanohybrids and their structural features.

The combination of complementary characterization techniques such as SEM (Scanning Electron Microscopy), T-SEM (Scanning Electron Microscopy in Transmission Mode), EDX (Energy Dispersive X-ray Spectroscopy) and SAM (Scanning Auger Microscopy) has been proven to be a powerful and relatively quick characterization strategy for comprehensive morphological and chemical characterization of individual silica and titania nanoparticles. The selected “real life” test materials, silica and titania, are listed in the OECD guidance manual as representative examples because they are often used as commercial nanomaterials. Imaging by high resolution SEM and in the transmission mode by T-SEM allows almost simultaneous surface and in-depth inspection of the same particle using the same instrument. EDX and SAM enable the chemical characterization of bulk and surface of individual nanoparticles. The core–shell properties of silica based materials are addressed as well. Titania nominally coated by silane purchased from an industrial source has been found to be inhomogeneous in terms of chemical composition.

The release of hazardous nanoparticulate matter in accidental situations was simulated in a specially designed 13-m3 stainless steel airtight chamber, which allowed the dispersion analysis of airborne matter in a practically particle-free environment (less than 2 #/cm3) and in presence of background atmospheric aerosols. A fast recovering of the initial situation was achieved by means of a tandem HEPA-filtered air and deionized water system. Both unintended spilling of silica-based nanoparticulate powders and continuous emission of 100-nm SiO2 nanoparticles were used as aerosol generation events. The emission of airborne nanoparticles was analyzed in terms of particle number concentrations (PNC), size distributions and source strengths. The emission of nanoparticulate aerosols reached peak PNC for particles in the range from 5 nm to 1 μm with source strengths about 108 #/h in a background-filled environment and 1010 #/h in a practically particle-free atmosphere. No agglomeration was noticed for the released nanoparticles, suggesting that PNC was low enough to prevent coagulation and that particle diameters were over 80 nm. Results indicate that emitted matter was within the range of the most penetrating particle sizes and with source strengths similar to accidental scenarios.

A long-lasting generator of continuous silica nanoparticle aerosols based in a fluidized bed of glass beads coated with nanosized silica has been developed. The attrition resulting from the bubbling fluidized bed regime progressively detaches the silica coating from the glass beads, giving rise to a steady production of silica nanosized aerosols with median diameters from 100 to 250 nm depending on the initial size of the coating nanoparticles. Continuous aerosol production could be maintained for more than 12 h, and the nanoparticle concentration can be easily tuned in the range of 2000 to 14,000 #/cm3 by adjusting the fluidization and/or dilution flow rates. Copyright 2013 American Association for Aerosol Research

This is the peer reviewed version of the following article :Lobera Gonzalez, MP.; Escolastico Rozalen, S.; Serra Alfaro, JM. (2011). High Ethylene Production through ODHE Membrane Reactors based on Fast Oxygen-Ion Conductors. ChemCatChem. 3:1503-1508. doi:10.1002/cctc.201100055, which has been published in final form at http://dx.doi.org/10.1002/cctc.201100055. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

A two-zone fluidized bed reactor (TZFBR) is employed for propane dehydrogenation over a Pt−Sn−K/γ-Al2O3 catalyst. This type of reactor constitutes an alternative to the use of two separate reactors with solid circulation between them or of a single reactor with periodic operation and allows continuous operation with in situ catalyst regeneration. The effect of the main TZFBR operating variables is studied and the reactor performance compared with results obtained in other works using Pt−Sn based catalysts, showing that a steady state is reached with similar selectivity to that reported in the literature for other reactors which suffer the problem of catalyst deactivation.

Correction for ‘Modeling the size distribution in a fluidized bed of nanopowder’ by Andrea Fabre et al., Environ. Sci.: Nano, 2017, 4, 670–678.

[EN] An intensification process for the selective oxidation of hydrocarbons integrates a catalytic reactor and an oxygen separation membrane. This work presents the study of oxidative dehydrogenation of ethane at 1123 K in a catalytic membrane reactor based on mixed ionic-electronic conducting (MIEC) membranes. The surface of a membrane made of Ba0.5Sr0.5Co0.8Fe0.2O3-d has been activated using different porous catalytic layers based on rare earth-doped cerias (fluorite structure) and the porous catalytic coating was deposited by screen printing (coating around 15 mu m). The different catalyst formulations were developed by partial substitution of Ce and were synthesized by co-precipitation followed by cobalt impregnation when required. Specifically, seven different catalysts based on the system Ce1-xLnxO2-d (x=0.1 or 0.2; Ln=Tb, Pr, Er, Gd, and Tb+Er), including the effect of cobalt addition (2?% molar) in Ce0.8Tb0.2O2-d, were studied. The ceria catalysts were studied by XRD, SEM, DC-conductivity as a function of oxygen partial pressure, and the high-temperature stability in a CO2 environment was assessed using thermogravimetry. Then, the influence of the ceria catalytic coating on the oxygen permeation flux through the MIEC membrane was studied using argon and methane as the sweep gas in the permeate side. Finally, oxidative dehydrogenation of ethane reaction tests were performed at 1123 K, as a function of the ethane concentration in the feed. The use of a disk-shaped membrane in the reactor made it possible to prevent the direct contact of gaseous oxygen and hydrocarbons and thus to increase the ethylene yield. High ethylene yields (up to approximate to 84?%) were obtained using a catalytic coating based on 20?% Tb-doped ceria including macropores produced by the addition of graphite platelets in the screen printing ink. The high yields obtained in this kind of catalytic membrane are attributed to the combination of: the high catalytic activity; the control of the oxygen concentration in the gas phase (reaction chamber); and the appropriate fluid dynamics, enabling the fast ethylene evacuation., Financial support by the Spanish Ministry for Science and Innovation (ENE2011-24761 FPI BES-2009-015835 grants), EU through FP7 NASA-OTM Project (NMP3-SL-2009-228701), and the Helmholtz Association of German Research Centres through the Helmholtz Alliance MEM-BRAIN (Initiative and Networking Fund) is kindly acknowledged.

[EN] Ceramic oxygen transport membranes (OTMs) enable selective oxygen separation from air at high temperatures. Among several potential applications for OTMs, the use in (1) oxygen production for oxyfuel power plants and (2) the integration in high-temperature catalytic membrane reactors for alkane upgrading through selective oxidative reactions are of special interest. Nevertheless, these applications involve the direct contact of the membrane surface with carbon-rich atmospheres. Most state-of-the-art permeable membranes are based on perovskites, which are prone to carbonation under operation in CO2-rich environments and/or decomposition in reducing gas environments. The oxygen flux through supported thin film membranes of Ce-0.9Gd0.1O1.95-delta (CGO) with 2 mol.% of cobalt was measured for oxygen separation in oxyfuel processes and in syngas production and degradation was compared to perovskite membranes. The CGO membranes consist of a 27 mu m-thick gastight CGO layer supported on a porous CGO substrate. The flat surface of the membrane was coated using two different porous catalytic layers aiming to improve the oxygen activation rate on the permeate side while the porous substrate was infiltrated with an oxygen reduction catalyst. Oxygen separation was studied using air as feed and argon/CO2 or argon/CH4 mixtures as sweep gas in the temperature range 750-1000 degrees C. The supported membrane exhibited a maximum oxygen flux of ca. 5 ml min(-1) cm(-2) at 1000 degrees C when diluted methane was used as sweep gas. The CGO membrane showed high stability in CO2 (in contrast to tests on La0.6Sr0.4Co0.2Fe0.8O3-delta (LSCF) membranes) and no detrimental effect on the oxygen flux is observed when CO2 is present in the sweep gas even at temperatures below 800 degrees C. Moreover, the SEM analysis showed that membrane integrity remained stable after the permeation tests using CO2. (C) 2011 Elsevier B. V. All rights reserved., Financial support by the Spanish Ministry for Science and Innovation (Project ENE2008-06302) and by the EU through FP7 NASA-OTM Project (NMP3-SL-2009-228701) is kindly acknowledged.

[EN] Process intensification by the integration of membranes and high-temperature reactors offers several advantages with regard to conventional process schemes, that is, energy saving, safe operation, reduced plant/unit size, and higher process performance, for example, higher productivity, catalytic activity, selectivity, or stability. We present the study of oxidative dehydrogenation of ethane at 850 8C on a catalytic membrane reactor based on a mixed ionic¿electronic conducting membrane. The surface of the membrane made of Ba0.5Sr0.5Co0.8Fe0.2O3 d has been activated by using different porous catalytic layers based on perovskites. The layer was deposited by screen printing, and the porosity and thickness was studied for the catalyst composition. The different catalyst formulations are based on partial substitution of A- and B-site atoms of doped strontium ferrite/cobaltites (A0.6Sr0.4Co0.5Fe0.5O3 d and Ba0.6Sr0.4BO3 d) and were synthesized by an ethylenediaminetetraacetic acid¿citrate complexation route. The use of a disk-shaped membrane in the reactor enabled the direct contact of gaseous oxygen and hydrocarbons to be avoided, and thus, the ethylene content increased. High ethylene yields (up to 81%) were obtained by using a catalytic coating based on Ba0.5Sr0.5Co0.8Fe0.2O3 d, which included macropores produced by the addition of graphite platelets into the screen-printing ink. The promising catalytic results obtained with this catalytically modified membrane reactor are attributed to the combination of 1) the high activity, as a result of the high temperature and oxygen species diffusing through the membrane; 2) the control of oxygen dosing and the low concentration of molecules in the gas phase; and 3) suitable fluid dynamics, which enables appropriate feed contact with the membrane and the rapid removal of products., Financial support by the Spanish Ministry for Science and Innovation (Project ENE2008-06302, ENE2011-24761 and FPI Grant JAE-Pre 08-0058), the EU through the FP7 NASA-OTM Project (NMP3-SL-2009-228701), and the Helmholtz Association of German Research Centres through the Helmholtz Alliance MEM-BRAIN (Initiative and Networking Fund) is kindly acknowledged. We thank S. Jimenez for material preparation, M. Fabuel for TPD experiments, and Forschungszentrum Julich for SEM analysis of BSCF catalytic layer.

[EN] Ceramic mixed ionic¿electronic conducting (MIEC) membranes enable very selective oxygen separation from air at high temperatures. Two major potential applications of oxygen-transport membranes are: i) oxygen production for oxyfuel power plants, and, ii) integration within high-temperature catalytic membrane reactors for methane or alkane upgrading by selective oxidative conversions. However, these applications involve contact with carbon-bearing atmospheres and most state-of-the-art highly permeable MIEC membranes do not tolerate operation under CO 2 -rich environments due to carbonation processes. The present contribution shows our ¿ rst attempts in the development of ceria-based protective thin layers on monolithic LSCF membranes. Gd-doped ceria (CGO) deposition is carried out by air blast spray pyrolysis on mirror-polished LSCF disc membranes. The layer thickness is maintained below 0.4 ¿ m in order to prevent the formation of cracks during thermal cycling and minimize limitations caused by the reduced oxygen permeability through the ceria layer. After optimization of the spraying process, smooth crack-free dense coatings are obtained with high crystallinity in the as-deposited state. The layers are characterized by XRD, SEM, AFM, DC-conductivity measurements, interferometry and optical microscopy. Oxygen separation is studied on coated LSCF using air as the feed and argon/CO 2 mixtures as the sweep gas in the temperature range 650¿1000 ° C. The protected membrane exhibits a higher stability than the uncoated LSCF membrane, although the nominal oxygen ¿ ux is slightly reduced at temperatures below 850 ° C due to the limited ambipolar conductivity of doped ceria in the range of oxygen partial pressures investigated. Moreover, the protective layer (250 nm thickness) remains stable after the permeation testing., Financial support by the Spanish Ministry for Science and Innovation (Project ENE2008-06302 and FPI Grant JAE-Pre 08-0058), the EU through FP7 NASA-OTM Project (NMP3-SL-2009-228701), and the Helmholtz Association of German Research Centers through the Helmholtz Alliance MEM-BRAIN (Initiative and Networking Fund) is kindly acknowledged.