Storing abundant solar energy in synthetic fuels is key to ensure a sustainable energy future by replacing fossil fuels and reducing global warming emissions. Practical implementation of the solar-to-fuel technology is predicated on finding new materials with higher efficiency and lower operation temperature than state-of-the-art materials. We use criteria aimed for designing such efficient solar-to-fuel conversion materials in the perovskite system. Based on thermodynamic considerations, the first perovskite solute–solution series, La0.6Sr0.4Cr1−xCoxO3−δ, is investigated to gain fundamental understanding on the role of B-site cationic doping in water and CO2 splitting to produce synthetic fuel. Notably, all of the novel material compositions operate in a strongly lowered temperature regime of 800–1200 °C compared to state-of-the-art binary oxides in the field. We found an optimum in doping for fuel production performance, namely La0.6Sr0.4Cr0.8Co0.2O3−δ, which viably splits both CO2 and H2O. Based on thermogravimetric analysis, we show that the highest performing perovskite splits 25 times more CO2 compared to the current state-of-the-art material, ceria, for two-step thermochemical cycling at 800–1200 °C. No adverse formation of carbonates in a CO2 atmosphere or cation segregation was observed in near and long range structural investigations, which highlight the durability and potential of these solid solutions. These new perovskite compositions enable lowering of the standard solar-to-fuel reactor temperature by 300 °C. The lowered operating temperature has tremendous implications for solar-synthesized fuels in a reactor in terms of lowered heat loss, increased efficiency, and reactor materials.
Titanium nitride is a well-known conductive ceramic material that has recently experienced resumed attention because of its plasmonic properties comparable to metallic gold and silver. Thus, TiN is an attractive alternative for modern and future photonic applications that require compatibility with the Complementary Metal-Oxide-Semiconductor (CMOS) technology or improved resistance to temperatures or radiation. This work demonstrates that polycrystalline TiNx films sputtered on silicon at room temperature can exhibit plasmonic properties continuously from 400 nm up to 30 μm. The films’ composition, expressed as nitrogen to titanium ratio x and determined in the Secondary Ion Mass Spectroscopy (SIMS) experiment to be in the range of 0.84 to 1.21, is essential for optimizing the plasmonic properties. In the visible range, the dielectric function renders the interband optical transitions. For wavelengths longer than 800 nm, the optical properties of TiNx are well described by the Drude model modified by an additional Lorentz term, which has to be included for part of the samples. The ab initio calculations support the experimental results both in the visible and infra-red ranges; particularly, the existence of a very low energy optical transition is predicted. Some other minor features in the dielectric function observed for the longest wavelengths are suspected to be of phonon origin.