Bi 3.25 La 0.75 Ti 3 O 12 (BLT) thin films have been grown on n-type Si (100) substrates by metalorganic decomposition method. The structural properties of the films were examined by x-ray diffraction. The BLT films exhibit good insulating property with room temperature resistivities in the range of 1012–1013 Ω cm. The current–voltage characteristics show ohmic conductivity in the lower voltage range and space-charge-limited conductivity in the higher voltage range. The capacitance–voltage characteristic hysteresis curves show that the metal-ferroelectric-semiconductor structure has memory effect. The fixed charge density and the surface state density were also calculated. The results obtained indicate that the present BLT films are suitable for making ferroelectric field effect transistor memories.
Here, noble‐metal‐doped two‐dimensional metal oxide nanosheets are designed to realize selective CO2 photoreduction to CH4. As a prototype, Pd‐doped CeO2 nanosheets are fabricated, where the active sites of Pdδ+ (2<δ<4) and Ce3+−Ov are revealed by quasi in situ X‐ray photoelectron spectra and in situ electron paramagnetic resonance spectra. Moreover, in situ Fourier‐transform infrared spectra of D2O photodissociation and desorption verify the existence of the Pd−OD bond, implying that Pdδ+ sites can participate in water oxidation to deliver H* species for facilitating the protonation of the intermediates. Furthermore, theoretical calculations suggest the Pd doping could regulate the formation energy barrier of the key intermediates CO* and CH3O*, thus making CO2 reduction to CH4 become the favorable process. Accordingly, Pd‐doped CeO2 nanosheets achieve nearly 100 % CH4 selectivity of CO2 photoreduction, with the raising CH4 evolution rate of 41.6 μmol g−1 h−1.
The chemical conversion of CO2 to long‐chain chemicals is considered as a highly attractive method to produce value‐added organics, while the underlying reaction mechanism remains unclear. By constructing surface vacancy‐cluster‐mediated solid frustrated Lewis pairs (FLPs), the 100 % atom‐economical, efficient chemical conversion of CO2 to dimethyl carbonate (DMC) was realized. By taking CeO2 as a model system, we illustrate that FLP sites can efficiently accelerate the coupling and conversion of key intermediates. As demonstrated, CeO2 with rich FLP sites shows improved reaction activity and achieves a high yield of DMC up to 15.3 mmol g−1. In addition, by means of synchrotron radiation in situ diffuse reflectance infrared Fourier‐transform spectroscopy, combined with density functional theory calculations, the reaction mechanism on the FLP site was investigated systematically and in‐depth, providing pioneering insights into the underlying pathway for CO2 chemical conversion to long‐chain chemicals.
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