Impact of Nanoparticle Consolidation on Charge Separation Efficiency in Anatase TiO2 Films

Mesoporous films and electrodes were prepared from aqueous slurries of isolated anatase TiO2 nanoparticles. The resulting layers were annealed in air at temperatures 100°C ≤ T ≤ 450°C upon preservation of internal surface area, crystallite size and particle size. The impact of processing temperature on charge separation efficiency in nanoparticle electrodes was tracked via photocurrent measurements in the presence of methanol as a hole acceptor. Thermal annealing leads to an increase of the saturated photocurrent and thus of the charge separation efficiency at positive potentials. Furthermore, a shift of capacitive peaks in the cyclic voltammograms of the nanoparticle electrodes points to the modification of the energy of deep traps. Population of these traps triggers recombination possibly due to the action of local electrostatic fields attracting photogenerated holes. Consequently, photocurrents saturate at potentials, at which deep traps are mostly depopulated. Charge separation efficiency was furthermore investigated for nanoparticle films and was tracked via the decomposition of hydrogen peroxide. Our observations evidence an increase of charge separation efficiency upon thermal annealing. The effect of particle consolidation, which we associate with minute atomic rearrangements at particle/particle contacts, is attributed to the energetic modification of deep traps and corresponding modifications of charge transport and recombination, respectively.

Van Der Waals gap-rich BiOCl atomic layers realizing efficient, pure-water CO2-to-CO photocatalysis

Photocatalytic CO2 reduction (PCR) is able to convert solar energy into chemicals, fuels, and feedstocks, but limited by the deficiencies of photocatalysts in steering photon-to-electron conversion and activating CO2, especially in pure water. Here we report an efficient, pure water CO2-to-CO conversion photocatalyzed by sub-3-nm-thick BiOCl nanosheets with van der Waals gaps (VDWGs) on the two-dimensional facets, a graphene-analog motif distinct from the majority of previously reported nanosheets usually bearing VDWGs on the lateral facets. Compared with bulk BiOCl, the VDWGs-rich atomic layers possess a weaker excitonic confinement power to decrease exciton binding energy from 137 to 36 meV, consequently yielding a 50-fold enhancement in the bulk charge separation efficiency. Moreover, the VDWGs facilitate the formation of VDWG-Bi-VO••-Bi defect, a highly active site to accelerate the CO2-to-CO transformation via the synchronous optimization of CO2 activation, *COOH splitting, and *CO desorption. The improvements in both exciton-to-electron and CO2-to-CO conversions result in a visible light PCR rate of 188.2 μmol g−1 h−1 in pure water without any co-catalysts, hole scavengers, or organic solvents. These results suggest that increasing VDWG exposure is a way for designing high-performance solar-fuel generation systems.

A Three-Component Hybrid Templated by Asymmetric Viologen Exhibiting Visible-Light-Driven Photocatalytic Degradation on Dye Pollutant in Maritime Accident Seawater

The increasing dangerous chemical pollutants led by shipping accidents call for the new pollutant treatment strategy. In this work, a new three-component hybrid {[(BiI6)I13]·2I3·(H-BPA)4}n (1) can be used in dye degradation in seawater. The highly interesting feature of 1 lies in its unique 1-D Z-shape [(BiI6)I13]n6− infinite chain constructed from the I···I contacts between mono-nuclear (BiI6)3− anions and I133− polyiodide anions. Finally, the hydrogen bonds between [(BiI6)I13]n6− polyanions and H-BPA2+ cations contribute to the formation a quasi-3-D network. Specifically, 1 exhibits the wide absorption zone from ultraviolet to visible regions and high charge-separation efficiency, hinting its application in visible-light catalysis. As expected, 1 represents photocatalytic activity for the degradation of rhodamine B in seawater with degradation ratio of 90%, and the photocatalytic performance is stable. This work might provide new photocatalytic material for pollutant treatment in shipping accidents.