Microwave-driven Modulation of Redox Properties of Solid-State Ionic Conductors
Jose M. Serra a, Aitor Domínguez-Saldaña a, Alfonso Juan Carrillo a, Joaquin Santos a, Laura Navarrete a, Maria Balaguer a, Beatriz García-Baños b, Pedro Plaza-González b, David Catalán-Martínez a, Jose Manuel Catalá-Civera b
a Instituto de Tecnología Química (Universitat Politècnica de València – Consejo Superior de Investigaciones Científicas), Av. Los Naranjos, s/n, 46022 Valencia, Spain
b Instituto ITACA, (Universitat Politècnica de València), Valencia, Spain
Proceedings of 24th International Conference on Solid State Ionics (SSI24)
Fundamentals: Experiment and simulation
London, United Kingdom, 2024 July 14th - 19th
Organizers: John Kilner and Stephen Skinner
Keynote, Jose M. Serra, presentation 180
Publication date: 10th April 2024

The sustainability of the process industry, transportation, and energy management will rely on low-CO2 technologies and renewable electricity. The volatile nature of renewable energy sources requires new energy-storage tools together with novel, highly efficient methods to electrify unitary steps in the industry. Here, we present a microwave-driven redox activation of solid-state ionic-conducting materials. Ceramic oxides, such as doped CeO2 and ZrO2, can be chemically reduced at unprecedented low temperatures (<220 °C) by the sole application of microwave radiation, leading to an instantaneous outstanding rise in electrical conductivity. Reproducible, reversible and cyclable surface release of O2 is dependent on material, microwave power, and radiation. Evaluation of different trivalent dopants in CeO2 reveals that microwave-driven reduction correlates with lattice and electronic properties. Narrower oxide bandgaps allow for higher electronic conductivity requiring lower temperatures to trigger the microwave-driven reduction, while larger ionic lattice sizes enhance oxygen diffusion and release. The ability of microwave radiation to evolve O2 and transmute the redox catalytic behaviour in oxides can be used in the electrification of several catalytic processes, such as the partial oxidation of methane to produce olefins or syngas, and as a new tool for the formation of catalytic nanoparticles via exsolution. Direct formation of molecular energy carriers, such as H2 and CO, is possible through further reaction of the redox-activated solid material and low-energy molecules via a deoxygenation mechanism.

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