RESUMEN
Low temperature ionic conducting materials such as OH- and H+ ionic conductors are important electrolytes for electrochemical devices. Here we show the discovery of mixed OH-/H+ conduction in ceramic materials. SrZr0.8Y0.2O3-δ exhibits a high ionic conductivity of approximately 0.01 S cm-1 at 90 °C in both water and wet air, which has been demonstrated by direct ammonia fuel cells. Neutron diffraction confirms the presence of OD bonds in the lattice of deuterated SrZr0.8Y0.2O3-δ. The OH- ionic conduction of CaZr0.8Y0.2O3-δ in water was demonstrated by electrolysis of both H218O and D2O. The ionic conductivity of CaZr0.8Y0.2O3-δ in 6 M KOH solution is around 0.1 S cm-1 at 90 °C, 100 times higher than that in pure water, indicating increased OH- ionic conductivity with a higher concentration of feed OH- ions. Density functional theory calculations suggest the diffusion of OH- ions relies on oxygen vacancies and temporarily formed hydrogen bonds. This opens a window to discovering new ceramic ionic conducting materials for near ambient temperature fuel cells, electrolysers and other electrochemical devices.
RESUMEN
The production of conjugated C4-C5 dienes from biomass can enable the sustainable synthesis of many important polymers and liquid fuels. Here, we report the first example of bimetallic (Nb, Al)-atomically doped mesoporous silica, denoted as AlNb-MCM-41, which affords quantitative conversion of 2-methyltetrahydrofuran (2-MTHF) to pentadienes with a high selectivity of 91 %. The incorporation of AlIII and NbV sites into the framework of AlNb-MCM-41 has effectively tuned the nature and distribution of Lewis and Brønsted acid sites within the structure. Operando X-ray absorption, diffuse reflectance infrared and solid-state NMR spectroscopy collectively reveal the molecular mechanism of the conversion of adsorbed 2-MTHF over AlNb-MCM-41. Specifically, the atomically-dispersed NbV sites play an important role in binding 2-MTHF to drive the conversion. Overall, this study highlights the potential of hetero-atomic mesoporous solids for the manufacture of renewable materials.