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.

CsH₂PO₄ is a proton conductor pertaining to the acid salts group and shows a phase transition from monoclinic to cubic phase at 232 ± 2 °C under high-steam atmospheres (>30%). This cubic phase gives rise to the so-called superprotonic conductivity. In this work, the influence of the partial substitution of Cs by Ba and Rb, as well as the partial substitution of P by W, Mo, and S in CsH₂PO₄ on the phase transition temperature and electrochemical properties is studied. Among the tested materials, the partial substitution by Rb led to the highest conductivity at high temperature. Furthermore, Ba and S-substituted salts exhibited the highest conductivity at low temperatures. CsH₂PO₄ was used as electrolyte in a fully-assembled fuel cell demonstrating the applicability of the material at high pressures and the possibility to use other materials (Cu and ZnO) instead of Pt as electrode electrocatalyst. Finally, an electrolyzer cell composed of CsH₂PO₄ as electrolyte, Cu and ZnO as cathode and Pt and Ag as anode was evaluated, obtaining a stable production of H₂ at 250 °C.

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.

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 BaCe_0.2Zr_0.7Y_0.1O₃ (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^®—10 wt.% 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.

The integration of mixed ionic–electronic conducting separation membranes in catalytic membrane reactors can yield more environmentally safe and economically efficient processes. Concentration polarization effects are observed in these types of membranes when O₂ permeating fluxes are significantly high. These undesired effects can be overcome by the development of new membrane reactors where mass transport and heat transfer are enhanced by adopting state-of-the-art microfabrication. In addition, careful control over the fluid dynamics regime by employing compact metallic reactors equipped with microchannels could allow the rapid extraction of the products, minimizing undesired secondary reactions. Moreover, a high membrane surface area to catalyst volume ratio can be achieved. In this work, a compact metallic reactor was developed for the integration of mixed ionic–electronic conducting ceramic membranes. An asymmetric all-La_0.6Sr_0.4Co_0.2Fe_0.8O_3–δ membrane was sealed to the metallic reactor by the reactive air brazing technique. O₂ permeation was evaluated as a proof of concept, and the influence of different parameters, such as temperature, sweep gas flow rates and oxygen partial pressure in the feed gas, were evaluated.