Effects of Cr Doping and Water Content on the Crystal Structure Transitions of Ba2In2O5

Temperature-dependent crystal structure alterations in the brownmillerite-type material Ba2In2O5 play a fundamental role in its applications: i) photocatalytic CO2 conversion; ii) oxygen transport membranes; and iii) proton conduction. This is connected to a reversible uptake of up an equimolar amount of water. In this study, in situ X-ray and neutron diffraction were combined with Raman spectroscopy and solid-state nuclear magnetic resonance experiments to unravel the effects of Cr doping and water content on the crystal structure transitions of Ba2In2O5(H2O)x over a wide temperature range (10 K ≤ T ≤ 1573 K, x < 1). A mixture of isolated and correlated protons was identified, leading to a highly dynamic situation for the protons. Hence, localisation of the protons by diffraction techniques was not possible. Cr doping led to an overall higher degree of disorder and stabilisation of the tetragonal polymorph, even at 10 K. In contrast, a further disordering at high temperatures, leading to a cubic polymorph, was found at 1123 K. Cr doping in Ba2In2O5 resulted in severe structural changes and provides a powerful way to adjust its physical properties to the respective application.

Electrostatic Field Enhanced Photocatalytic CO2 Conversion on BiVO4 Nanowires

The recombination loss of photo-carriers in photocatalytic systems fatally determines the energy conversion efficiency of photocatalysts. In this work, an electrostatic field was used to inhibit the recombination of photo-carriers in photocatalysts by separating photo-holes and photo-electrons in space. As a model structure, (010) facet-exposed BiVO4 nanowires were grown on PDMS-insulated piezo-substrate of piezoelectric transducer (PZT). The PZT substrate will generate an electrostatic field under a certain stress, and the photocatalytic behavior of BiVO4 nanowires is influenced by the electrostatic field. Our results showed that the photocatalytic performance of the BiVO4 nanowires in CO2 reduction in the negative electrostatic field is enhanced to 5.5-fold of that without electrostatic field. Moreover, the concentration of methane in the products was raised from 29% to 64%. The enhanced CO2 reduction efficiency is mainly attributed to the inhibited recombination loss of photo-carriers in the BiVO4 nanowires. The increased energy of photo-carriers and the enhanced surface absorption to polar molecules, which are CO in this case, were also play important roles in improving the photocatalytic activity of the photocatalyst and product selectivity. This work proposed an effective strategy to improve photo-carriers separation/transfer dynamics in the photocatalytic systems, which will also be a favorable reference for photovoltaic and photodetecting devices.