Microwave-Driven Exsolution of Ni Nanoparticles in A-Site Deficient Perovskites.

Exsolution has emerged as a promising method for generating metallic nanoparticles, whose robustness and stability outperform those of more conventional deposition methods, such as impregnation. In general, exsolution involves the migration of transition metal cations, typically perovskites, under reducing conditions, leading to the nucleation of well-anchored metallic nanoparticles on the oxide surface with particular properties. There is growing interest in exploring alternative methods for exsolution that do not rely on high-temperature reduction via hydrogen. For example, utilizing electrochemical potentials or plasma technologies has shown promising results in terms of faster exsolution, leading to better dispersion of nanoparticles under milder conditions. To avoid limitations in scaling up exhibited by electrochemical cells and plasma-generation devices, we proposed a method based on pulsed microwave (MW) radiation to drive the exsolution of metallic nanoparticles. Here, we demonstrate the H2-free MW-driven exsolution of Ni nanoparticles from lanthanum strontium titanates, characterizing the mechanism that provides control over nanoparticle size and dispersion and enhanced catalytic activity and stability for CO2 hydrogenation. The presented method will enable the production of metallic nanoparticles with a high potential for scalability, requiring short exposure times and low temperatures.

Evaluation of Er Doped CeO2-δ as Oxygen Transport Membrane.

Ceria based materials are robust candidates for a range of applications involving redox reactions and high oxygen activity. The substitution of erbium in the ceria lattice introduces extrinsic oxygen vacancies. Further addition of Co introduces electronic carriers. We have studied the structural and redox behavior of Ce1-xErxO2-δ (x = 0.1 and 0.2) and the influence of adding 2 mol% of Co in the electrochemical properties. A limitation in the solubility of Er cation is found. Diffusion and surface exchange coefficients have been obtained by electrical conductivity relaxation and the DC-conductivity and O2 permeation measurements show the importance of the electronic component in the transport properties, obtaining an oxygen permeation flux of 0.07 mL·min-1·cm-2 at 1000 °C, for a 769 µm thick membrane.

Comparative Study of Epoxy-CsH2PO4 Composite Electrolytes and Porous Metal Based Electrocatalysts for Solid Acid Electrochemical Cells.

Electrochemical cells based on acid salts (CsH2PO4) have attracted great interest for intermediate temperature, due to the outstanding proton conductivity of acid salts. In this work, electrodes and electrolyte were optimized following different strategies. An epoxy resin was added to the CsH2PO4 material to enhance the mechanical properties of the electrolyte, achieving good conductivity, enhanced stability, and cyclability. The electrodes configuration was modified, and Ni sponge was selected as active support. The infiltration of different oxide nanoparticles was carried out to tailor the electrodes resistance by promoting the electrocatalyst activity of electrodes. The selection of a cell supported on the electrode and the addition of an epoxy resin enables the reduction of the electrolyte thickness without damaging the mechanical stability of the thinner electrolyte.

Characterization of post-consumer plastic film waste from mixed MSW in Spain: A key point for the successful implementation of sustainable plastic waste management strategies.

The purpose of this paper is to provide a full characterization of post-consumer plastic film recovered from mixed municipal solid waste (MSW) treatment plants in Spain. Currently, this type of plastic waste is not recycled due to technical or economic barriers and is still sent to landfill. Different types of municipal plastic waste (MPW) from manual and automated sorting were studied: i) colour plastic film recovered by ballistic separators and then manual sorting in different seasons; ii) colour plastic film recovered by automated sorting (air suction); and iii) white plastic film from primary manual sorting process. The samples were characterized by different techniques, including the ultimate and proximate analysis, Higher Heating Value (HHV) and Lower Heating Value (LHV), metal content, Thermogravimetric Analysis (TGA) and Derivative Thermogravimetry (DTG), Fourier Transform Infrared (FT-IR) analysis and Differential Scanning Calorimetry (DSC). The results were compared to those obtained for pretreated colour and white plastic film waste and contrasted with industrial recycled film granules of polyethylene (as a reference material for packaging film). Additionally, pretreated plastic film samples were also characterized by analyzing viscosity, Pressure-Volume-Temperature (PVT) diagram, specific heat capacity and halogen and sulphur contents. Characterization data from this study will contribute to identify and develop potential recycling alternatives for a more sustainable municipal plastic waste management, which is recognized as a priority in the European Circular Economy Action Plan to use resources in a more sustainable way.

Novel Polymeric Thin-Film Composite Membranes for High-Temperature Gas Separations.

Novel selective polymeric thin-film composite membranes (TFCMs) for applications at elevated temperatures were developed. Thin selective layers of the polyimides Matrimid 5218® and 6FDA-6FpDA were cast on a developed polybenzimidazole (PBI) porous support prepared by a phase inversion process. The TFCM properties were investigated with different gases in a wide temperature range, including temperatures up to 270 °C. The membranes showed very high thermal stability and performed well at the elevated temperatures. The development of highly thermally resistant polymeric membranes such as these TFCMs opens opportunities for application in high-temperature integrated processes, such as catalytic membrane reactors for the water-gas shift reaction in order to maximize H2 yield.

Study of the Effect of Inorganic Particles on the Gas Transport Properties of Glassy Polyimides for Selective CO2 and H2O Separation.

Three polyimides and six inorganic fillers in a form of nanometer-sized particles were studied as thick film solution cast mixed matrix membranes (MMMs) for the transport of CO2, CH4, and H2O. Gas transport properties and electron microscopy images indicate good polymer-filler compatibility for all membranes. The only filler type thatdemonstrated good distribution throughout the membrane thickness at 10 wt. % loading was BaCe0.2Zr0.7Y0.1O3 (BCZY). The influence of this filler on MMM gas transport properties was studied in detail for 6FDA-6FpDA in a filler content range from one to 20 wt. % and for Matrimid® and P84® at 10 wt. % loading. The most promising result was obtained for Matrimid®-10wt. % BCZY MMM, which showed improvement in CO2 and H2O permeabilities accompanied by increased CO2/CH4 selectivity and high water selective membrane at elevated temperatures without H2O/permanent gas selectivity loss.

Gas Separation Properties of Polyimide Thin Films on Ceramic Supports for High Temperature Applications.

Novel selective ceramic-supported thin polyimide films produced in a single dip coating step are proposed for membrane applications at elevated temperatures. Layers of the polyimides P84®, Matrimid 5218®, and 6FDA-6FpDA were successfully deposited onto porous alumina supports. In order to tackle the poor compatibility between ceramic support and polymer, and to get defect-free thin films, the effect of the viscosity of the polymer solution was studied, giving the entanglement concentration (C*) for each polymer. The C* values were 3.09 wt. % for the 6FDA-6FpDA, 3.52 wt. % for Matrimid®, and 4.30 wt. % for P84®. A minimum polymer solution concentration necessary for defect-free film formation was found for each polymer, with the inverse order to the intrinsic viscosities (P84® ≥ Matrimid® >> 6FDA-6FpDA). The effect of the temperature on the permeance of prepared membranes was studied for H2, CH4, N2, O2, and CO2. As expected, activation energy of permeance for hydrogen was higher than for CO2, resulting in H2/CO2 selectivity increase with temperature. More densely packed polymers lead to materials that are more selective at elevated temperatures.

Catalytic Layer Optimization for Hydrogen Permeation Membranes Based on La5.5WO11.25-δ/La0.87Sr0.13CrO3-δ Composites.

(LWO/LSC) composite is one of the most promising mixed ionic-electronic conducting materials for hydrogen separation at high temperature. However, these materials present limited catalytic surface activity toward H2 activation and water splitting, which determines the overall H2 separation rate. For the implementation of these materials as catalytic membrane reactors, effective catalytic layers have to be developed that are compatible and stable under the reaction conditions. This contribution presents the development of catalytic layers based on sputtered metals (Cu and Pd), electrochemical characterization by impendace spectroscopy, and the study of the H2 flow obtained by coating them on 60/40-LWO/LSC membranes. Stability of the catalytic layers is also evaluated under H2 permeation conditions and CH4-containing atmospheres.

Zeolite synthesis modelling with support vector machines: a combinatorial approach.

This work shows the application of support vector machines (SVM) for modelling and prediction of zeolite synthesis, when using the gel molar ratios as model input (synthesis descriptors). Experimental data includes the synthesis results of a multi-level factorial experimental design of the system TEA:SiO2:Na2O:Al2O3:H2O. The few parameters of the SVM model were studied and the fitting performance is compared with the ones obtained with other machine learning models such as neural networks and classification trees. SVM models show very good prediction performances and generalization capacity in zeolite synthesis prediction. They may overcome overfitting problems observed sometimes for neural networks. It is also studied the influence of the type of material descriptors used as model output.