Ceria-based electrospun fibers for renewable fuel production via two-step thermal redox cycles for carbon dioxide splitting

Abstract

Zirconium-doped ceria (Ce_1−xZr_xO₂) was synthesized through a controlled electrospinning process as a promising approach to cost-effective, sinter-resistant material structures for high-temperature, solar-driven thermochemical redox cycles. To approximate a two-step redox cycle for solar fuel production, fibrous Ce_1−xZr_xO₂ with relatively low levels of Zr-doping (0 < x < 0.1) were cycled in an infrared-imaging furnace with high-temperature (up to 1500 °C) partial reduction and lower-temperature (∼800 °C) reoxidation via CO₂ splitting to produce CO. Increases in Zr content improve reducibility and sintering resistance, and, for x ≤ 0.05, do not significantly slow reoxidation kinetics for CO production. Cycle stability of the fibrous Ce_1−xZr_xO₂ (with x = 0.025) was assessed for a range of conditions by measuring rates of O₂ release during reduction and CO production during reoxidation and by assessing post-cycling fiber crystallite sizes and surface areas. Sintering increases with reduction temperature but occurs primarily along the fiber axes. Even after 108 redox cycles with reduction at 1400 °C and oxidation with CO₂ at 800 °C, the fibers maintain their structure with surface areas of ∼0.3 m² g⁻¹, higher than those observed in the literature for other ceria-based structures operating at similarly high temperature conditions. Total CO production and peak production rate stabilize above 3.0 mL g⁻¹ and 13.0 mL min⁻¹ g⁻¹, respectively. The results show the potential for electrospun oxides as sinter-resistant material structures with adequate surface area to support rapid CO₂ splitting in solar thermochemical redox cycles.